Coatings For High Temperature Environments Anti Corrosion and Anti-2024

Engineering Materials
Amirhossein Pakseresht
Kamalan Kirubaharan Amirtharaj Mosas Editors
Coatings
for High-Temperature
Environments
Anti-Corrosion and Anti-Wear
Applications
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Indexed at Compendex (2021) and Scopus (2022)
Amirhossein Pakseresht ·
Kamalan Kirubaharan Amirtharaj Mosas
Editors
Coatings
for High-Temperature
Environments
Anti-Corrosion and Anti-Wear Applications
Editors
Amirhossein Pakseresht Kamalan Kirubaharan Amirtharaj Mosas
FunGlass—Centre for Functional FunGlass—Centre for Functional
and Surface Functionalized Glass and Surface Functionalized Glass
Alexander Dubček University of Trenčín Alexander Dubček University of Trenčín
Trenčín, Slovakia Trenčín, Slovakia
ISSN 1612-1317 ISSN 1868-1212 (electronic)

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Preface
Materials are exposed to temperatures that change their physical and chemical prop-
erties due to environmental reactions with the material and its surface. The science
and technology of surface modification of materials have become more important
over the past few decades. The best way to protect materials from oxidation and hot
corrosion is through the application of coatings. Researchers thought that applying a
suitable coating can be a good strategy to protect the underlying material by acting as
a potential barrier between the material and the environment, so it has been constantly
improved and developed.
High-temperature coatings are a technologically significant, cost-effective, and
rapidly expanding field. Over the past few decades, coatings have come a long
way and are now used for protection against high-temperature oxidation and wear.
While limiting the heat exposure of structural components, these coatings protect
those parts that are exposed to high temperatures, extending the life of the compo-
nents, and lowering oxidation, thermal fatigue, wear, hot corrosion, and erosion.
There are different kinds of coatings made from ceramics, intermetallics, cermets,
organosilicon polymers, and other materials with good thermal stability. These kinds
of coatings are an important part of how different coating techniques are developed.
There is much useful information available regarding anti-wear and anti-corrosion
coatings for high-temperature environments and how they perform. However, this
knowledge is spread through conference proceedings, book chapters, monographs,
journals, and published industrial reports. The authors decided to put this collec-
tive information together under the theme of coatings for high-temperature envi-
ronments. This book covers coatings used for high-temperature environments, espe-
cially corrosion and wear applications. In addition, this book also addresses the
basic understanding of materials and their selection, basic principles of physical and
chemical metallurgy, design considerations, manufacturing methods, performance
upgrades, and different methods for evaluating the coating microstructure and appli-
cation. This book covers coatings for high-temperature environments, especially for
corrosion and anti-wear applications. It also includes fundamental studies, including
creating coating architecture, methods of preparation, and coating performances for
the temperature range of applications.
v
vi Preface
Organization of the Chapter
Corrosion-resistant materials are becoming increasingly in demand. The fundamental

concepts of corrosion and materials used for corrosion under insulation are discussed
in Chapter “Corrosion Under Insulation for Hot Structural Components”. Chapter
“Development of Coating-Resistant Materials at High Temperatures for Waste-to-En-
ergy Plant Application” discusses the development of coating-resistant materials at
high temperatures for waste-to-energy plant applications. The development of suitable
software for such applications that can effectively protect against corrosion is studied
in this chapter. Recent investigations of silicon carbide- and silicon nitride-based
composite enamel coatings for thermal shock and chloride corrosion coupled envi-
ronments are discussed in Chapter “Composite Enamel Coatings for Thermal Shock
and Chloride Corrosion Coupled Environments”. Chapter “Polycrystalline Diamond
and Cr Double Coatings Protect Zr Nuclear Fuel Tubes Against Accidental Temper-
ature Corrosion in Water-Cooled Nuclear Reactors” discusses the combinations of
polycrystalline diamond and magnetron-sputtered Cr double coating for their ability
to protect nuclear fuel tubes against corrosion at accident temperatures in a water-
cooled nuclear reactor environment. Silicon-based technology and the application of
silicon-based coatings to protect metallic alloys from high temperatures are discussed
in Chapter “Silicon-Based Technologies for High-Temperature Coatings and Their
Corrosion Behaviours”.
Chapter “A New Solution to Save Production Costs in the Deposition
of the Wear-Resistant Coating” focused on the updated achievements with air plasma
spraying using the Fe-based amorphous coating to deposit a competitive wear resis-
tance coating. The methodology for the evaluation of wear resistance coatings,
standards, and their relationship between wear, hardness, and friction is briefly
described in Chapters “A New Solution to Save Production Costs in the Deposi-
tion of the Wear-Resistant Coating” and “Wear/Erosion Resistant High-Temperature
Coatings”. The protection requirement for wear-resistant coatings at high tempera-
ture using high-entropy alloys is discussed in Chapter “Research on Anti-Oxidation
and Wear-Resistance Co–Cr–Fe–Nb–Ni High Entropy Alloys Coatings Prepared
by Laser Cladding”. The effect of the addition of elements with respect to the
microstructure and hardness is discussed in this chapter.
Boride-based coatings are stable at high temperatures due to their high melting
point, which allows them to maintain their hardness and oxidation resistance up to
1000 °C, with the possibility of increasing the high-temperature wear resistance of
metallic materials. Various boriding methods for the formation of boride coatings
on high-temperature metallic materials to improve their performance for diverse
high-temperature applications are discussed in Chapter “The Boriding Process
for Enhancing the Surface Properties of High-Temperature Metallic Materials”.
The properties such as wear, adhesion, oxidation, corrosion, and tribo-corrosion
of borided materials are explained well in this chapter. Finally, Chapter “Tribolog-
ical Characterization of Electroless Nickel Coatings at High Temperatures” presents
various aspects of high-temperature tribological characterization of electroless nickel
coatings.
Preface vii
Chapter “Thin Chromium-Based Coatings for Internal Combustion Automobile

Engine Valve Protection” presents the latest findings concerning the impact of various
liquid fuel types on the course of high-temperature corrosion on internal combustion
engine valves and a method to increase the heat resistance by applying chromium-
based metallic coatings. The corrosion behavior of automobile engine valve steels
under an air atmosphere and combustion gases was discussed. High-temperature
thermoelectric materials for a variety of high-temperature applications are discussed
in Chapter “Protective Coatings for High-Temperature Thermoelectric Materials”.
Chapter “Electrically Insulating Corrosion-Resistant Tritium Permeation Barrier
Coatings for High Temperature Liquid Metal Breeders of Nuclear Fusion Reac-
tors” examines the experimental investigations on AlPO4 -bonded Al2 O3 coatings to
assess the deposition feasibility, electrical insulation integrity, and thermal/chemical
stability in static molten lead–lithium (PbLi) alloy materials for fusion reactor appli-
cations. The use of different types of silicone-based coatings for high-temperature
applications is discussed in Chapter “Silicone-Based Coatings for High-Tempera-
ture Applications”. The factors affecting the performance of the coatings were also
briefly discussed. Chapter “Heat Resistant Coatings—An Overview” summarizes an
overview of ceramic materials used for heat resistance coatings, their properties, and
their processing methods.
Conclusion
The main aim of the book, “Coatings for high temperature environments: Anti-
corrosion and anti-wear applications”, is to offer a comprehensive overview of the
advancements, potential challenges, and applications of a wide variety of materials
in the field of high-temperature coatings. By the contribution of leading researchers,
engineers, and industrial experts in this book, we hope that this book will serve as
a valuable resource for academicians, students, researchers, and industrial experts
seeking to improve their knowledge in the field of high-temperature coatings.
Trenčín, Slovakia Amirhossein Pakseresht

Acknowledgements
We would like to extend our heartfelt thanks and appreciation to all the contributing
authors who have shared their knowledge and expertise in this book. This book
would not be possible without their dedication and excellent contributions in their
respective disciplines. The editors would like to thank the reviewers for their helpful
contributions in improving the chapter contents, cohesion, and narrative of each
chapter. The majority of the contributing authors also worked as reviewers, and
we would like to thank them for their tireless efforts in completing the reviewing
process in such a short period of time. The editors would like to thank the readers of
the high-temperature coating community for providing inspiration for this work. We
feel this book will be extremely beneficial to their studies and research. Finally, we
would like to thank the Springer Nature publisher personnel for their assistance from
the beginning of the book proposal submission process. This would not have been
feasible without their prompt assistance. We would also like to thank the editorial and
production teams for their dedicated efforts and for making the publication possible.
Finally, the editors would like to express their gratitude to the FunGlass center at
Alexander Dubcek University in Trencin, Slovakia, for providing us with a dynamic
environment in which to complete this book. This work is a part of dissemination
activities of project FunGlass. This project has received funding from the European
Union’s Horizon 2020 research and innovation program under grant agreement No.
739566. Also, this work was supported by the VEGA grant no. 1/0171/21 and APVV
grant no. APVV-22-0070.
Trenčín, Slovakia Amirhossein Pakseresht

ix
About This Book
This book addresses the recent trends in high-temperature coatings that are used to
provide oxidation and wear resistance to metallic/ceramic components in extreme
environments. Ceramics, intermetallics, organosilicon polymers, cermets, and other
materials with great thermal stability have long been recognized for these applica-
tions. This book introduces the state of the art in coating materials and processes
for high-temperature environments and identifies areas for improvement in mate-
rials selection, performance upgrades, design considerations, and manufacturing
methods. The book covers a variety of high-temperature coatings prepared through
various synthesis processes such as thermal spraying, physical vapor deposition, elec-
trodeposition, and sol–gel methods. It covers corrosion/oxidation, phase stability,
and thermal and mechanical behavior of high-temperature coating materials having
greater thermal stability.
With contributions from international researchers active in the field, this edited
book features the most recent and up-to-date literature references for a broad read-
ership consisting of academic and industrial professionals. It is suitable for graduate
students as well as scientists and engineers working in the area of anti-corrosion-
and anti-wear-resistant high-temperature coatings for industrial applications.
xi
Contents
Corrosion Resistant Coatings for High Temperature Environment

Corrosion Under Insulation for Hot Structural Components . . . . . . . . . . . 3
I-Tseng Liu, Yi-Chen Weng, and Ying-Chih Liao
Development of Coating-Resistant Materials at High Temperatures
for Waste-to-Energy Plant Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
Ankita Kumari, Priyanka Sati, and Sudesh Kumar
Composite Enamel Coatings for Thermal Shock and Chloride
Corrosion Coupled Environments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
Dongming Yan and Hao Qian
Polycrystalline Diamond and Cr Double Coatings Protect Zr
Nuclear Fuel Tubes Against Accidental Temperature Corrosion
in Water-Cooled Nuclear Reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
Irena Kratochvílová, Petr Ashcheulov, Jakub Luštinec, Jan Macák,
Petr Sajdl, and Radek Škoda
Silicon-Based Technologies for High-Temperature Coatings
and Their Corrosion Behaviours . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
Priyanka Sati, Ankita Kumari, and Sudesh Kumar
High Temperature Wear Resistance Coatings

A New Solution to Save Production Costs in the Deposition
of the Wear-Resistant Coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
Trung Dao Duy and Vu Duong
Wear/Erosion Resistant High-Temperature Coatings . . . . . . . . . . . . . . . . . . 161
S. Arulvel, D. Dsilva Winfred Rufuss, Jayakrishna Kandasamy,
P. Kumaravelu, R. Prayer Riju, and P. U. Premsuryakanth
xiii
xiv Contents
Research on Anti-Oxidation and Wear-Resistance

Co–Cr–Fe–Nb–Ni High Entropy Alloys Coatings Prepared
by Laser Cladding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
Jin Zhang and Minyu Ma
The Boriding Process for Enhancing the Surface Properties
of High-Temperature Metallic Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
I. E. Campos Silva, A. Günen, M. Serdar Karakaş,
and A. M. Delgado Brito
Tribological Characterization of Electroless Nickel Coatings
at High Temperatures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
Arkadeb Mukhopadhyay, Tapan Kumar Barman, and Prasanta Sahoo
Heat Resistant Coatings

Thin Chromium-Based Coatings for Internal Combustion
Automobile Engine Valve Protection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
Zbigniew Grzesik and Grzegorz Smoła
Protective Coatings for High-Temperature Thermoelectric
Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
S. Nanthini, Pandiyarasan Veluswamy, and H. Shankar
Electrically Insulating Corrosion-Resistant Tritium Permeation
Barrier Coatings for High Temperature Liquid Metal Breeders
of Nuclear Fusion Reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
Abhishek Saraswat, Chandrasekhar Sasmal, Ashokkumar Prajapati,
Rajendraprasad Bhattacharyay, Paritosh Chaudhuri,
and Sateesh Gedupudi
Silicone-Based Coatings for High-Temperature Applications . . . . . . . . . . . 385
T. Dharini, Anand Krishnamoorthy, and P. Kuppusami
Heat Resistant Coatings—An Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
A. Anitha, A. Hemalatha, and P. Udhayakumar
Corrosion Resistant Coatings for High
Temperature Environment
Corrosion Under Insulation for Hot
Structural Components
I-Tseng Liu, Yi-Chen Weng, and Ying-Chih Liao
Abstract Corrosion under insulation (CUI) is a common issue for hot structural
components covered by thermal insulation materials and aluminum cladding for
energy-saving and anti-scalding purposes. Environmental and human factors causing
CUI are discussed in this chapter, providing readers deep insights into CUI preven-
tion. Even though CUI is difficult to manage simply through visual inspection,
on-site non-destructive testing (NDT) methods can facilitate detection process and
provide clear guidelines for finding high-risk components under claddings. More-
over, the concepts of recognized and generally accepted good engineering practices
(RAGAGEPs) and process safety management (PSM) can serve as the rule of thumb
for diminishing the risk of CUI. CUI prevention strategies are also summarized in
this chapter. Among them, anti-CUI coatings before cladding are the most feasible
strategy due to the acceptable cost and easy processing. Anti-CUI coatings are formu-
lated with proper resin and pigment system based on the operating temperature of
hot structural components and followed by standard laboratory tests, such as ASTM
G189-07(2021) and ISO 19277:2018 elaborated in this chapter. These test methods
can provide meaningful performance evaluations of anti-CUI coatings, and give
helpful guidelines for both formulation development and screening of commercially
available coatings.
Keywords Corrosion under insulation (CUI) · Non-destructive testing ·

RAGAGEPs · Anti-CUI coatings · Polymer and metallic pigmented coatings ·
Standard laboratory test
I-T. Liu · Y.-C. Weng · Y.-C. Liao (B)

Department of Chemical Engineering, National Taiwan University, Taipei, Taiwan
e-mail: liaoy@ntu.edu.tw
© The Author(s), under exclusive license to Springer Nature Switzerland AG 2024 3

A. Pakseresht and K. K. Amirtharaj Mosas (eds.), Coatings for High-Temperature
Environments, Engineering Materials, https://doi.org/10.1007/978-3-031-45534-6_1
4 I-T. Liu et al.
Abbreviation Explanation
AMPP Association for Materials Protection and Performance
API American Petroleum Institute
ASTM American Society for Testing and Materials International
CDU Crude Distillation Unit
CoC Cost of Corrosion
CR Computed Radiography
CTE Coefficient of Thermal Expansion
CUI Corrosion Under Insulation
DFT Dry Film Thickness
IMPM Inert Multi-polymeric Matrix
IR Infrared
ISO International Organization for Standardization
LGO Light Gas Oil
MIO Micaceous Iron Oxide
NACE National Association of Corrosion Engineers
NDT Non-destructive Testing
PEC Pulsed Eddy Current
PSM Process Safety Management
PTFE Polytetrafluoroethylene
PVC Pigment Volume Concentration
RAGAGEPs Recognized and Generally Accepted
Good Engineering Practices
ROI Return on Investment
SCC Stress Corrosion Cracking
SGP Saturate Gas Plant
SSPC Steel Structures Painting Council
TMIC Titanium-Modified Inorganic Copolymer
TSA Thermal Sprayed Aluminum
UT Ultrasonic Technology
1 Introduction
The annual cost of corrosion (CoC) is approximately estimated to be US$ 2.5 trillion,
which is 3.4% of the world’s GDP [1]. Statistics illustrate that 40–60% of piping
maintenance expenditures are related to corrosion under insulation (CUI) or other
relevant issues [2]. Corrosion control is an intuitive method to avoid economic loss,
but lessons are learned after disastrous events, accidents, shutdowns, and production
Corrosion Under Insulation for Hot Structural Components 5
Scheme 1 Corrosion types
loss. Battling for corrosion protection and treatment is a never-ending war. Corrosion
is an electrochemical reaction between electrolytes (e.g., water and water-leachable
ions) and electrode pairs (e.g., metal surface), and can be classified into seven types by
mechanism (Scheme 1): uniform corrosion [3, 4], galvanic corrosion [5, 6], crevice
corrosion [7, 8], pitting corrosion [9, 10], intergranular corrosion [11, 12], erosion
corrosion [13, 14], and stress corrosion cracking [15, 16].
CUI is the external corrosion that occurs on carbon steel, low-alloy, and austenitic/
duplex stainless-steel equipment (e.g., piping systems, pressure vessels, tanks, and
reactors) which are covered with thermal insulation materials [17]. Hot structural
components at certain conditions are prone to suffer from CUI issue. There are
three main causes for CUI: (1) insulation materials satiated with water (rainfall and
condensation from cooling towers), (2) corrosive ions (from surroundings or thermal
materials themselves), and (3) periodic change of temperature and humidity (envi-
ronmental conditions or processing). CUI is a corrosion phenomenon specified in
hot structural components covered by insulation materials. Practically, CUI is the
combination of different corrosion types mentioned above. Based on practical expe-
riences, temperature is the most critical factor for CUI. As indicated in professional
guidelines (Table 1), CUI is not limited to high-temperature conditions (i.e., it also
happens under cryogenic conditions). For example, CUI could happen on insulated
carbon steel at temperatures ranging from −12 to 177 °C with high possibility. On
the other hand, CUI on austenitic/duplex stainless steel occurs at higher temperatures
ranging from 50 to 205 °C [17–20]. Due to page limitation, in this chapter, we will
focus on high-temperature conditions.
Corrosion at high temperatures has a unique characteristic among all kinds of
corrosion. At high temperatures, small molecules (e.g., chlorides, sulfides, and
hydrogen) can easily diffuse into metals, and may accumulate or precipitate in the
6 I-T. Liu et al.
Table 1 Temperature range

Guideline Temperature range
for CUI occurrence
Carbon steel ( °C) Stainless steel ( °C)
API 510/570 −12 ~ 177 60 ~ 205
EFC 55 −4 ~ 175 >60
NACE SP0198 −4 ~ 175 50 ~ 175
API: American Petroleum Institute
EFC: European Federation of Corrosion
NACE: National Association of Corrosion Engineers (NACE
and SSPC merged into AMPP at 2021)
grain boundaries of metal. As a result, stress accumulation occurs in metal parts, and
therefore CUI is often accompanied by stress corrosion cracking (SCC). Because
high-temperature (>100 °C) processing and fabrication are commonly used in petro-
chemical industries, heat loss, energy consumption, and personnel anti-scalding are
inevitable issues when handling hot structural components. Before the 1970s, thermal
insulation was mainly used for components over 150 °C. At these temperatures,
nearly no moisture is present on the insulated metal surfaces. Thus, CUI is limited
because of the low-humidity environment. Things changed upon the rise of oil and gas
industries in the 1970s when insulation materials were widely installed on compo-
nents below 150 °C for energy-saving purposes [21]. Since then, CUI became a
prevalent issue.
In general, thermal insulation materials like fiberglass, mineral wool, and calcium
silicate are covered directly on hot components and followed by aluminum cladding
for waterproofing considerations [21]. Practically, aluminum cladding will deform
and unseal due to human trampling and silicone sealant aging. These issues reduce
the water protection capability of the insulated parts. Thus surrounding moisture can
penetrate through pinholes or gaps and be absorbed by insulation materials. From
experience, insulation materials can absorb water about three to five times their
original weight [22]. The satiated insulation materials not only provide moisture
sources for corrosion on metals but also incubate a great environment for CUI,
because water evaporation is prohibited even under temperatures higher than the
boiling point of water (100 °C) between metal and insulation layers. Meanwhile, it
is nearly impossible to observe and diagnose corrosion by visual inspection without
removing the insulation materials.
2 Case Studies of Corrosion Under Insulation (CUI)
CUI has caused devastating accidents in the past decades. On April 16, 2001, a serious
fire explosion incident happened at ConocoPhillips Humber Refinery [23]. From the
investigation report, CUI occurred at an elbow connected to a section of pipes on
the saturate gas plant (SGP), downstream of a water-into-gas injection point. The
corrosion led to pipe connection failure, and high-pressure flammable gas (ethane/
propane/butane) leaked out from the corroded 6-inch pipe. After leaking for 20–30 s,
flammable gas ignited into a catastrophic explosion as shown in Fig. 1a. Damage to
the SGP and adjacent plants is shown in Fig. 1b, c. Fortunately, upon the explosion,
most of the employees were inside buildings preparing for shift handover, and only
a few employees were on-site. Thus, no serious injury occurred. There was only a
short-term impact on the operation after this accident.
Another case for CUI is Chevron’s crude unit fired on August 6, 2012 [24, 25].
The light gas oil (LGO) sidedraw from a crude distillation unit (CDU) deviated from
Fig. 1 a The fire and secondary fireball, b damage to the SGP, c adjacent plant. Courtesy Public
report of the fire and explosion at the ConocoPhillips Humber refinery, Health and Safety Exec-
utive, 2001. https://www.yumpu.com/en/document/view/22334776/public-report-of-the-fire-and-
explosion-at-the-conocophillips-hse
8 I-T. Liu et al.
the routine process. LGO leaked out from the rupture of the serving pipeline and
the leakage was ignited 2 min later. After the explosion, the burned oil resulted in a
vast amount of black smoke, which can be seen miles away (Fig. 2). Unfortunately,
19 company employees lose their lives in this accident, and approximately 15,000
people from neighboring communities suffered from respiratory problems in the
following years. Investigation revealed that critical factors for this accident were:
(1) inadequate design standard (ASTM A53) before 1985, which did not specify
the silicon content in carbon steel pipe. (2) Failure to identify and monitor the high
corrosion rate, which was due to the combination of CUI and high silicon content of
the pipe. (3) Improper operation by firefighters. Insulation materials were removed
immediately and caused severe chemical leaking from the unwrapped pipe. These
devastating accidents show the importance of CUI material selection for chemical
leakage prevention, and continuous CUI monitoring can help preventing hazardous
explosion.
Besides material mismatch, CUI issues may also occur even under regular opera-
tions. The following case of CUI can be attributed to improper annual maintenance.
As shown in Fig. 3a, compressed propylene leakage from a pipe was identified on-
site. The main leakage component was a pipe connected to the inlet of a propylene
reactor. From annual inspections, no decrease in pipe wall thickness was observed
by guided wave ultrasonic technology (UT) testing. However, from metallographic
analysis, transgranular cracks grew dendritically from the pipe surface into the pipe
(Fig. 3b), illustrating stress corrosion at the leakage area. Moreover, from the SEM
image, crack morphology was characterized in a brittle fracture manner and chlo-
ride deposition was found near the crack. From the elemental analysis, silicon and
calcium were also found (Fig. 3c). Those images give clear evidence that leach-
able ions were carried out by water from the calcium silicate insulations. In theory,
however, severe corrosion from the leached ions was impossible for this piping area,
because the regular working temperature was 37 °C, much lower than the corrosion
Fig. 2 Chevron’s crude unit fire. a Seconds after ignition, b Rupture of pipe component (with
insulation removal). Courtesy Final investigation report-Chevron Richmond refinery pipe rupture
and fire, U.S. Chemical Safety and Hazard Investigation Board, 2012. https://www.csb.gov/che
vron-refinery-fire/
Fig. 3 a Propylene leakage from an inlet pipe (with insulation removed), b Crack morphology and
growth direction from metallographic analysis, c SEM image and EDX analysis for the crack area.
Courtesy The failure analysis on the inlet pipe of propadiene reactor of low-temperature unit in
naphtha cracking plan, Linyuan Petrochemical Plant, 2011
occurring temperature. However, the reactor maintenance required a catalyst regen-

eration process every year. During the regeneration, the temperature of the inlet pipe
turned out to be 100 °C, a temperature high enough to trigger corrosion. This periodic
high-temperature processing was the major reason for this CUI accident, and was
found in many other reactors in this plant [26].
3 Fundamental Concepts of Corrosion and CUI
Corrosion is an electrochemical oxidation–reduction reaction. The reaction is

composed of metal oxidation and water reduction. For example, the corrosion of
iron is a stepwise oxidation reaction (i.e., from Fe to Fe2+ and further to Fe3+ ), while
the corrosion of aluminum is a single-step oxidation reaction (i.e., Al–Al3+ ). Mean-
while, volume or density changes (expansion for most cases) are often accompanied
by corrosion. This phenomenon gives rise to more metal surface exposure to mois-
ture or air, and favors continuing oxidation. But few materials, such as aluminum
10 I-T. Liu et al.
and stainless steel, can form dense oxidation layers to stop further oxidation reac-
tions. In the corrosion process, reduction/oxidation products may vary according
to the redox reaction conditions, such as alloy composition, temperature, moisture,
water-leachable ions, and pH value [27, 28]. Major factors are discussed below in
the detail.
3.1 Environmental Factors
3.1.1 Temperature
Temperature plays an important role in the corrosion process because it affects the
chemical reactions both thermodynamically and kinetically. From a kinetics perspec-
tive, an increase in temperature will increase the reaction rates of corrosion, including
the diffusion of the ions and the corrosion products. There is a rule of thumb that the
corrosion rate of a metal doubles for every 10 °C increase in temperature [28]. Theo-
retically, from a thermodynamics perspective, free energy (G) is the driving force for
a reaction. Free energy is governed by enthalpy (H), entropy (S), and temperature
(T ) as
G = H − T S (1)
For most reactions, entropy generation S is positive, and therefore free energy
decreases with increasing temperature. In other words, high temperature leads to
more negative free energy so that corrosion reaction is thermodynamically favorable
and spontaneous at high temperatures.
Ellingham diagrams are often adopted to determine the temperature dependence
of the stability of metal oxides. An Ellingham diagram illustrates how the free energy
changes with the temperature and pressure of oxygen [29]. The higher stability of the
metallic oxide is shown at the lower position of the lines in the Ellingham diagram
(i.e., low temperature and oxygen pressure). Ellingham diagram for common metal
oxides is shown in Fig. 4 [29].
3.1.2 Moisture
Moisture can interact with metals through the following reaction:
M(s) + H2 O(g) → MO(s) + H2(g) (2)
If oxygen is present in the environment, hydrogen would be oxidized to water

vapor and thus corrosion of metal keeps happening until oxygen or metal is consumed.
Moreover, some metal oxides even form volatile products when reacting with water
vapor, such as ferrous oxide and ferric oxide:
Fig. 4 Ellingham diagram for several common metal oxides [29]
FeO(s) + H2 O(g) → Fe(OH)2(g) (3)
2Fe2 O3(s) + 4H2 O(g) → 4Fe(OH)2(g) + O2(g) (4)
These metal hydroxides evaporate and cannot form a protection layer for the
interior metals. Furthermore, from Le Chatelier’s principle, formation of evaporative
hydroxides in an open environment might quickly reduce the oxide’s thickness and
deteriorate the corrosion.
12 I-T. Liu et al.
3.1.3 Ion Effect
The presence of ions can accelerate corrosion reactions. Particularly, chloride-

induced corrosion [30] has drawn lots of attention because chloride ions not only
dissolve many metals (e.g., iron and chromium) but also break down the passive layer
(e.g., Fe2 O3 or Fe3 O4 ) of steels. For rebar, chloride ions are adsorbed in the passive
layer and react with iron to form chlorides and hydroxides through the following
reactions [30]:
Fe → Fe2+ + 2e− (5)
Fe2+ + 2Cl− → FeCl2 (6)
FeCl2 + 2H2 O → Fe(OH)2 + 2H+ + 2Cl− (7)
Because the chloride ion, as a catalyst, changes the reaction routes, the corrosion
reaction would continue once the passive layer is destroyed.
3.1.4 pH Value
A Pourbaix diagram, or a potential-pH diagram, is useful for determining the stability

of metals [31] because most of the oxidation reactions are affected by pH value. The
Pourbaix diagram of Fe–H2 O system, for example, is shown in Fig. 5 [31]. The pH
value is plotted against the redox potential concerning the standard hydrogen elec-
trode calculated by the Nernst equation. In this diagram, the vertical line represents
a pH-dependent reaction, while the horizontal line represents a potential-dependent
reaction involving electron transfer. In addition, a Pourbaix diagram can be divided
into three major regions, which represent three possible states of a metallic material:
(1) immunity, (2) passivity, and (3) corrosion. In the immunity region, metals are
immune from corrosion and thus are safe to use. In the passivity region, oxides or
hydroxides tend to form on the surface of metals, protecting the metals from expo-
sure to the environment. No corrosion will happen in this region. Nonetheless, in the
corrosion region, a metal is thermodynamically favorable in transforming to its ionic
or soluble species.
3.2 Other Factors
Corrosion rate is strongly affected by temperature for both open and closed systems
[20]. In general, the corrosion rate decreases at higher temperatures in an open system,
but increases in a closed system (CUI) as shown in Fig. 6.
Fig. 5 Pourbaix diagram for iron at 25 °C [31]
3.2.1 Insulation Materials
Insulation materials are used to retard the heat flow and thus reduce energy loss and
consumption. In general, insulation materials can be divided into two categories: (1)
fibers or blankets (e.g., fiberglass and mineral wool) and (2) cells (e.g., cellular glass,
phenolic foam, and nitrile rubber). Once thermal insulation materials are adopted,
the pipeline system will change from an open system to a closed system, and CUI
becomes an inevitable issue. A small amount of water that goes inside the insulation
system will cause severe corrosion. Things become worse when materials are prone
to absorb water. Trapped water inside gaps can leach contaminants like chlorides
and sulfides from thermal insulation materials. These ions accelerate and change the
mechanism of corrosion. Even though thermal insulation materials are covered by
aluminum cladding, moisture will not go inside the system in most circumstances.
However, some human factors may be overlooked and incubate CUI.
14 I-T. Liu et al.
Fig. 6 Temperature dependence of corrosion rate of steel. Corrosion rates for closed system, open
system, and CUI are shown in solid line, dashed line, and hollow circles, respectively. Courtesy
NACE SP0198-Control of corrosion under thermal insulation and fireproofing materials-a systems
approach, 2017 edition
3.2.2 Human Factors
Insulation materials are covered with aluminum cladding for structural and water-
proof consideration. However, human factors caused by incorrect usage may increase
the risk of CUI. Human trampling is common due to a lack of safety consciousness
and discipline, which cause deformation and gaps in the aluminum cladding. Water
from surroundings, such as rainfall and cooling towers, will be absorbed by insu-
lation materials and cause CUI. Moreover, a mismatch for silicone sealants under
certain environments may cause potential risks for aging. Practically, the edges and
gaps of aluminum cladding are sealed with incorrect silicone sealants, which are
prone to age and crack under UV exposure and highly humid conditions. Moisture
penetrates the insulation materials through the cracks thereafter. Fortunately, the risk
of CUI can be diminished by proper personnel training and regulations. Also, some
non-destructive testing (NDT) methods can help with corrosion management.
3.3 On-Site Non-destructive Testing (NDT) Methods for CUI
CUI is difficult, or even impossible, to manage by only visual inspections. At

the same time, insulation removal for inspection is not feasible due to high costs
(scaffolding and non-reusable insulation), time limit (annual shut down for mainte-
nance), and huge manpower requirements. Therefore, NDT methods are beneficial
for CUI management [32]. From a safety perspective, occupational safety, mechan-
ical integrity, and process safety are three foundations of process safety management
(PSM). Among them, mechanical integrity is often overlooked with lowest priority.
As a result, CUI issues will only be aware until near-miss events or accidents occur.
The ideas for NDT methods are to identify CUI from two aspects: (1) corrosion
reaction. Corrosion is an endothermic reaction, which can be recognized by infrared
(IR) thermography. (2) Wall thickness of structural components: corrosion usually
leads to decreases in wall thickness, which can be recognized by pulsed eddy current
(PEC) testing for instance. With these tools, CUI can be managed without insulation
removal. Once the NDT methods are applied, resource configuration for maintenance
and protection can be optimized. Some of the proven and generally accepted NDT
methods are [33–38].
• IR thermography.
• Neutron backscatter.
• Guided wave UT.
• Profile radiography.
• Computed radiography (CR).
• PEC testing.
4 Concepts and Methods for CUI Protection
CUI is quite complex and strongly depends on environmental conditions and the
temperature profiles of structural components. Therefore, some guidelines and
concepts of process safety management (PSM) are essential and referred to as
recognized and generally accepted good engineering practices (RAGAGEPs). These
practices are commonly used to reduce mistakes.
16 I-T. Liu et al.
4.1 Recognized and Generally Accepted Good Engineering

Practices (RAGAGEPs)
American Petroleum Institute (API) and Association for Materials Protection and
Performance (AMPP) are the common RAGAGEPs addressing general problems of
CUI cases. AMPP was created when the National Association of Corrosion Engineers
(NACE) and Steel Structures Painting Council (SSPC) united in 2021 after more than
145 combined years of corrosion control and protective coatings. Guidelines for CUI
and corrosion-related issues are listed below. Readers can check out the details by
looking into the standard documents.
• API 583, Corrosion Under Insulation and Fireproofing.
• API 571, Damage Mechanism Affecting Fixed Equipment in the Refining
Industry.
• API 570, Piping Inspection Code: In-service Inspection, Rating, Repair, Alterna-
tion, of Piping System.
• API RP 580, Risk-Based Inspection.
• API RP 581, Risk-Based Inspection Technology.
• API 585, Pressure Equipment Integrity Incident Investigation.
• NACE SP0198, Control of Corrosion Under Thermal Insulation and Fireproofing
Materials-A System Approach.
4.2 Modified Thermal Insulation Structures
Practically, fiberglass, mineral wool, and calcium silicate are commonly used as
insulation materials. However, these materials are prone to uptake and trap moisture
inside metal/insulation gaps, even in the circumstances that the working tempera-
ture of components is higher than the boiling point of water. The absorbed water
will further leach corrosive ions (e.g., chlorides) from insulation materials. Water-
leachable ions facilitated corrosion thereafter. Also, the thermal conductivity of
thermal insulation materials significantly decreases after water uptake (70% increase
in thermal conductivity with 4% water uptake by volume). Therefore, water removal
is the most effective way to prevent hot structural components from CUI. Nowadays,
improvements in thermal insulation materials are made to diminish water absorption
amount and residence time in closed pipeline/insulation systems.
4.2.1 Insulation Cladding
Aerogel Blankets
Aerogels are naturally mesoporous (porosity > 90%) materials and have high specific
surface area (S BET = 600–1000 m2 /g), low bulk density (ρ = 0.0030–0.35 g/cm3 ),
and low thermal conductivity (k = 0.015–0.14 W/m K) [39]. Aerogels are made
from precursors such as water glass or alkylsilane via the sol–gel method. Precursors
hydrolyze in acid conditions (e.g., HCl) to form sol, followed by being base-catalyzed
(e.g., NH4 OH) to form a cross-linked network of alcogels thereafter. The solvent in
alcogels can be removed by ambient drying, freeze drying, or supercritical drying
process. Aerogel monoliths are obtained after the processes mentioned above [40].
However, aerogel monoliths are brittle and limited in a few specific engineering appli-
cations [41]. Thus, aerogels are commonly incorporated with blankets to enhance
their flexibility. In the manufacturing process, blankets are immersed completely in
precursor solutions, and the gelling reaction is triggered after the immersion process.
Then, blankets are immersed in a solvent (e.g., ethanol) for aging and a drying process
is followed to remove the residue solvents. Aerogel blankets exhibit low thermal
conductivity (0.013–0.014 W/m K) when compared with conventional thermal insu-
lation material (rock wool: 0.033–0.045 W/m K, calcium silicate: 0.045–0.065 W/
m K, and glass wool: 0.03–0.045 W/m K) [42]. Therefore, a thinner insulation design
is possible with the same level of thermal management. Also, aerogel blankets have
low water uptake under high temperature (>300 °C) and thus can be used with
long-term stability. Nonetheless, the high price of aerogel blankets leads to practical
concerns for their applications.
Waterproof Enhancement of Insulation Materials
To diminish water uptake, insulations can be modified by water repellent agents,

which reduces the risk of CUI. Water repellent agents can be classified into three
types: (1) mineral oil-based additives, (2) silicone oil-based additives, and (3) inor-
ganic resin additives. For mineral oil-based additives, the agent starts to decompose
at 150 °C and the degradation products can be removed easily by water. Therefore,
long-term usage is not recommended. As a result, silicone oil-based additives are
developed to enhance thermal stability. The silicone oil-based insulation materials
have excellent waterproof performances below 250 °C. However, for conditions of
higher temperature, silicone oil undergoes phase separation in the insulation mate-
rials. This phenomenon leads to local defects, such as pinholes or channels on insu-
lations, resulting in higher water uptake. Therefore, silicone oil-based additives are
not favorable in insulation materials for temperature higher than 250 °C. Last but
not least, inorganic resin additives own the highest thermal stability (~250 °C) and
are immobile in insulations under high temperature.
Non-contact Insulation System
To reduce the residence time of water, non-contact insulations are designed. The idea
is to achieve fast moisture/water evaporation through the separation of the insulation
and hot components by creating cavities. The non-contact system is a combination
18 I-T. Liu et al.
Fig. 7 Non-contact (or

distance-insulation)
insulation system [21]
of polytetrafluoroethylene (PTFE) spacers and perforated aluminum plates as shown

in Fig. 7 [21]. With this design, the initiation of CUI and corrosion rate can be
controlled.
4.2.2 Thermal Insulation Coatings
Although modified insulation cladding can reduce the risk of CUI issues, the existing
gaps between insulation materials and structural components still allow water ingress
to a certain degree. By using insulation coating, these gaps no longer exist and water
uptake can be reduced significantly. With proper material design, thermal insulation
coatings can stop moisture from reaching structural metal components. Insulation
coatings are formulated by pigments, binders, and additives for dispersing and rheo-
logical consideration. Pigments of low thermal conductivity, such as (hollow) ceramic
pigment and silica aerogel powder or granulates, are commonly used. Meanwhile,
UV resistance and thermal shock resistance are important concerns for outdoor appli-
cations. Acrylic (silicone-acrylic and acrylic urethane) resin and silicate are suitable
polymeric binding materials. As a rule of thumb, acrylic insulation coating should be
used for conditions below 170 °C, while silicate should be used below 205 °C [43].
Practically, the coefficient of thermal expansion (CTE) is a crucial parameter for
thermal shock resistance. Dry film thickness (DFT) per coat is a critical consideration
for cost. Silicate is limited for its low DFT per coat. Among all commercial products,
waterborne acrylic resin with silica aerogel is the most commonly used. Due to the
high thermal conductivity of ceramic pigments, high pigment volume concentration
(PVC) is usually formulated for better thermal insulation property. However, ceramic
pigment coating with high PVC is limited for its poor thermal shock resistance, which
often leads to coating cracks.
Because of the water impermeability (or relatively low permeability), thermal

insulation coatings on pipes are feasible for both hot and cold (anti-sweating) condi-
tions. Compared with conventional insulation materials, insulation coating only
needs one-step application. But the coating thickness is constrained to approximately
0.5–20 mm (20–790 mil). Besides the simple one-step process, insulation coatings
can also be combined with an anti-corrosive primer to reach a longer lifetime [20].
4.3 Anti-CUI Coatings
Insulation coatings are limited by DFT per coat and are costly due to high pigment
fractions. From an economic perspective, the return on investment (ROI) of insulation
coating expenditure against energy saving is debatable in different countries and
regions. Therefore, the alternative solution for CUI protection is applying anti-CUI
coatings inside insulation claddings. Coatings for this application must be highly
thermal resistant. Therefore, epoxy resin (e.g., phenolic and novolac) and an inorganic
copolymer or inert multi-polymeric matrix (IMPM) are suitable materials. Because
solar radiation is blocked by the outside insulation claddings, UV resistance is not a
critical issue for coatings of this design.
Pigments such as aluminum powder, micaceous iron oxide (MIO), and mont-
morillonite are commonly formulated with the aforementioned polymeric resins
to improve corrosion resistance. Aluminum powder can provide cathodic protec-
tion, while layered MIO and montmorillonite can provide tortuous paths, which can
diminish ion diffusivity and increase the service life of coated metal components. In
general, phenolic and novolac epoxy resin coating (2K) should be used for condi-
tions below 170 and 205 °C, respectively, while inorganic copolymer and IMPM
(1K) can reach up to 400–650 °C. However, inorganic copolymer and IMPM are
not the ones for all solutions even though the price is comparable to novolac epoxy.
For high-temperature corrosion protection, water and oxygen solubility dominate
the corrosion rate below 200 °C. Notice should be taken that inorganic copolymer or
IMPM is not recommended for conditions below 200 °C due to the higher moisture
permeability than that of phenolic and novolac epoxy. As a rule of thumb, phenolic
and novolac epoxies are preferred for operating temperatures below 205 °C, and
inorganic copolymer or IMPM is preferred above 205 °C.
Last but not least, from a material perspective, chloride content in insulation mate-
rials is also crucial for CUI protection. The chloride extraction method is guided by
ASTM C871 [44] and the acceptable level is guided by ASTM C795 [45]. Generally,
chloride extraction from insulation materials should be lower than 10 ppm.
In this section, several methods are mentioned for either trying to reduce the
water uptake or dredging the moisture. Conventional thermal insulation systems are
modified to enhance the water-repelling property and reduce the water absorption
rate (I.). Others are dedicated to creating channels or spacers in insulations for water
removal convenience (II.). For coatings, thermal insulation coatings can replace insu-
lation materials for conditions below 170°C (III.). For higher temperature, anti-CUI
20 I-T. Liu et al.
Fig. 8 Strategies for CUI protection
coating before insulation materials cladding is more applicable. High thermal resis-
tance and low moisture permeability of anti-CUI coating can prevent moisture from
reaching components (IV). Strategies for CUI protection are shown in Fig. 8.
5 Materials of Anti-CUI Coatings
Corrosion at high-temperature conditions involves the participation of moisture.

Therefore, covering a moisture barrier over metal components can greatly reduce the
risks of corrosion. To serve as diffusion barriers for moisture and corrosive ions, coat-
ings must possess certain barrier properties, such as high thermal shock resistance,
proper CTE, high-transition glass temperature (T g ), high decomposition tempera-
ture, etc. For instance, crosslinking materials are commonly used for high T g and
high decomposition temperature consideration. However, if the crosslinking density
is too high, thermal shock resistance and CTE would be too low, resulting in cracks
after a short operating period. Therefore, materials suitable for CUI protection are
very limited due to the trade-off between the contradicting properties mentioned
above. Nonetheless, materials for anti-CUI coatings can be customized according
to operation requirements. The following materials have acceptable properties and
affordable costs for on-site protection and maintenance.
5.1 Polymer Coatings
5.1.1 Epoxy
Conventional epoxies pigmented with aluminum spheres or flakes have been used for
decades. Diglycidyl ether of bisphenol-A (DGEBA) and diglycidyl ether of bisphenol
F (DGEBF) are commonly used epoxy compounds. However, regular epoxy materials
can only work for operating temperatures around 120–150 °C. For higher operation
temperatures, either phenolic or novolac epoxy is adopted.
5.1.2 Phenolic/Novolac Epoxy
Phenolic/novolac epoxies are better in thermal stability than conventional epoxies.

This property can be attributed to the benzene structure in the crosslinking network.
The tailored phenolic/novolac epoxy coatings can reach a high maximum operating
temperature up to 230 °C [46]. Aside from epoxies, hardeners also play important
roles in thermal resistance. For reaction consideration, polyamines, anhydrides, and
polyamides are most commonly used [47]. Among them, polyamines are widely
used for open time/pot-life of 1–2 h, which is feasible for on-site operation at room
temperature (25 °C). The functionality of hardeners can also affect coating properties
significantly by changing the crosslinking density of polymer networks. For example,
polymer networks with high crosslinking density show better chemical resistance and
lower flexibility, and vice versa. However, thick coatings usually show unreleased
stress during curing, and thus coating cracks are commonly observed at the corner of
components during temperature cycling operations. Practically, total DFT is regularly
controlled below 250 μm.
5.1.3 Silicone/Silicate
Silicone/silicate coatings are prepared when inorganic silicone pigments are added
to a coating. The working temperature of silicone/silicate can reach up to 400 °C.
However, they are quite expansive and vulnerable to acids, alkalis, and warm moisture
conditions, resulting in a short lifetime of corrosion protection. Besides, cracks are
commonly observed if silicone/silicate-based materials are designed for high DFT
operation. Once cracks appear, the corrosion resistance declines significantly due to
moisture/water and ion penetration. Therefore, silicone/silicate coatings are generally
applied with DFT of 25 μm.
22 I-T. Liu et al.
5.1.4 Organic–Inorganic Hybrid
This type of coating was first introduced in the 1990s for higher thermal stability
aspirations. The modified organic–inorganic hybrid CUI coatings are widely used in
the late 1990s and are dominated by two types:
• TMIC, titanium-modified inorganic copolymer.
• IMPM, inert multi-polymeric matrix.
The higher bond energy of Si–O (454.2 kJ/mol) than C–C (355.6 kJ/mol) leads to
better thermal stability [48]. Meanwhile, the materials can also be used for cryogenic
(e.g., −196 °C) conditions. From a cost perspective, commercially available anti-
CUI coatings of organic–inorganic hybrid are close to or slightly higher than coatings
of phenolic/novolac epoxy.
On the other hand, a mismatch between organic–inorganic hybrid can easily lead
to microcracks in these coating materials. Thus, the hybrid materials might have
lower performances than original expectations even at temperatures below 200 °C.
At this temperature range, moisture permeability (solubility × diffusivity) dominates
the corrosion resistance, while the thermal stability of resin dominates the corrosion
resistance for temperature above 200 °C. Since organic–inorganic hybrids gener-
ally have relatively higher moisture permeability than epoxies, it is highly recom-
mended that organic–inorganic hybrid materials should not be used in the moisture
permeability-dominated CUI preventions.
5.2 Metallic Pigment Coatings
5.2.1 Zinc Coating
Zinc (rich) coatings are widely used for atmospheric corrosion protection due to
their higher oxidation potential than carbon steel. Nowadays, off-shore (e.g., wind
turbines) and photovoltaic brackets (e.g., agro-photovoltaics) protection are drawing
people’s attention due to the booming demand for green/renewable energy. However,
zinc-pigmented coatings are seldom or even prohibited in anti-CUI coatings, because
zinc and carbon steel undergo polarity inversion at about 60 °C [49], and thus zinc
will no longer protect carbon steel from corrosion beyond this temperature. What’s
worse, zinc will corrode carbon steel and shorten the lifetime of metallic components
instead.
5.2.2 Thermal Sprayed Aluminum (TSA)
TSA is a protection method that applied molten aluminum on metallic compo-

nents [50]. TSA has a maximum operating temperature of 660 °C (melting point
of aluminum). A dense protective layer of Al2 O3 is formed on the surface of the
aluminum and can slow down or even stop the corrosion reaction. Notice should be
taken that, in general, TSA has a porosity of 5–15 %, and sealer paints are often
applied thereafter.
TSA possesses a long lifetime that can reach up to 20 years without any mainte-
nance. Nonetheless, TSA might accompany fire and spark during operation, and is
prohibited in most on-site applications. As a result, TSA is only applicable in certain
special circumstances.
6 Standardization Laboratory Test for Anti-CUI Coatings
Coating formulations designed for CUI protection need to be qualified by stan-

dard lab tests before being applied to field operations. Standard lab tests can give
clear insights into coating properties and can be classified into two sections: (1)
instrumental analysis tests, such as thermal, mechanical, and chemical resistance;
(2) corrosion resistance under high temperature, such as multi-phase CUI simulation
test. Several test methods are summarized in Table 2.
Instrumental analysis tests are well established both in test methodology and
equipment. These tests can tell preliminary properties but are not able to give
clear insights into CUI protection. As a result, multi-phase CUI simulation tests
are proposed to simulate the periodic temperature and moisture changes in regular
Table 2 Test methods for anti-CUI coatings

Characteristics Standardization Descriptions
Dry heat ASTM D2485B • Test panels are exposed in muffle furnace at an agreed
resistance temperature for 24 h
• Panels are allowed to cool under ambient or water to
room temperature
• If no deterioration is observed, the panels are exposed in a
natural salt spray (ASTM B117) for 24 h
ASTM E2402 • TGA
Thermal shock ISO 19277 • Test panels are exposed in muffle furnace at agreed
resistance temperature and quenched in water
– 150 °C for phenolic and novolac epoxy
– 400 °C for inorganic copolymer and IMPM
• Repeat test cycle for 20 times and ranking thermal shock
resistance by visual inspection (ISO 4628)
Corrosion ASTM G189-07 CUI simulation cell
resistance • Monitored by electrochemical current flow and weight
loss
ISO 19277 Multi-phase CUI cyclic corrosion test
ISO 19277 Cyclic insulated pipe test (CIPT)
24 I-T. Liu et al.
on-site operations. Unfortunately, no single equipment or instruments are commer-

cially available. Nonetheless, ASTM G189-07(2021) [51] and ISO 19277:2018 [52]
standards can be general guidance for simulation test setup.
6.1 ASTM G189-07(2021)
ASTM G189-07(2021) can simulate moisture effect on CUI potential. The apparatus
designed in ASTM G189-07(2021) is composed of two parts: (1) CUI simulation
cell and (2) heat oil circulation as shown in Fig. 9a. For the CUI simulation cell,
the coating is applied on the outer surface of metallic rings, which are electrically
isolated by PTFE compartments with each other as shown in Fig. 9b labeled by the
yellow arrows [53]. Metallic rings are covered by insulations, which have an inlet
and outlet for 0.01 wt% (100 ppm) NaCl solution (or acidified by H2 SO4 –pH 6 if
needed) on top and bottom, respectively, as shown in Fig. 9c [53]. Corrosive liquid
can be controlled by a peristaltic pump for facilitated corrosion tests. Simulation
conditions are also suggested in ASTM G189-07(2021) as shown in Fig. 9 d. For
most situations, the testing temperature is set at 175 °C during the test; however, these
conditions are not mandatory. Temperature and NaCl solution flow rate can both be
specified by the user’s needs. The CUI resistance of the coatings is monitored by
electrochemical current flow and weight loss of metallic rings. The corrosion rate
can be calculated by the following equation [51]:
Corrosion Rate = (K × M)/( A × T × D) (8)
where K is a constant (3.45 × 106 mil/year; 8.76 × 104 mm/year), M is the mass
loss ([=] g) calculated by pre-exposure mass (M i ) minus the post-exposure (after
cleaning) mass (M f1 ) for the ring specimens, A is the exposed area ([=] cm2 ), T is
the time of exposure ([=] h), and D is the density of ring specimens ([=] g/cm3 ).
Corrosion rate change with specified conditions is shown in Fig. 9e. Because
ASTM G189-07(2021) does not consider the effect of thermal stress and thermal
shock resistance on CUI, these tests usually need to be combined with other
instrumental analyses to evaluate the possibility of on-site CUI.
6.2 ISO 19277:2018
ISO 19277:2018 provides two different methods for high-temperature CUI simula-
tion: (1) multi-phase CUI cyclic corrosion test and (2) vertical pipe test.
Fig. 9 a CUI-cell design, b, c cell without insulations showing spacers, samples, and dam [53],
d suggested simulation conditions, e corrosion rate for metallic rings protected by coatings. Courtesy
ASTM G189-07(2021)-Standard Guide for Laboratory Simulation of Corrosion Under Insulation,
2021 edition
6.2.1 Multi-phase CUI Cyclic Corrosion Test
This testing cycle is composed of three stages: (1) hot–dry, (2) hot and wet, and (3)
ambient environment, which corresponds to the conditions of dry heat, wet heat,
thermal shock, intermittent boiling water, steam interface, and shutdown time. The
test chamber is made up of 316 stainless steel and filled with 5 wt% NaCl solution
and a heating conduit in the center of the chamber. Anti-CUI coatings are applied on
the outer surface of metallic square rings, which is similar to ASTM G189-07(2021).
The coated rings are scribed with an X-cut on all four sides and worn in series on
the heating conduit, in which hot oil is circulated, and all coating rings are heated by
the conduits as shown in Fig. 10a [43].
Test rings undergo 15 cycles of 4 h of hot–wet and 4 hours of hot–dry stages,
followed by 48 hours of ambient cooling, with the entire cycle repeated 6 times (6
weeks). Temperature for hot stages can be set as 150 and 175 °C for CUI-2 and CUI-3
classification, respectively. The test procedures are shown in Fig. 10b [52]. Coatings
at the interface of liquid and gas phases can illustrate CUI resistance, because of
immersion in NaCl solution and the hot–dry condition. Coatings before and after 6
weeks of testing are shown in Fig. 10c [43].
26 I-T. Liu et al.
Fig. 10 Equipment design, b test procedures defined in ISO 19277:2018, c coatings before and after
6 weeks of testing (Courtesy for a and c: CUI, practical approach from a coating perspective, The
10th Tank & Refinery Conference, PPG, 2017. Courtesy for b: ISO 19277:2018-Petroleum, Petro-
chemical and Natural Gas Industries-Qualification Testing and Acceptance Criteria for Protective
Coating Systems Under Insulation, 2018)
6.2.2 Vertical Pipe Test
The vertical pipe test is designed to test the resistance of anti-CUI coatings for simu-
lated CUI conditions. The process includes temperature cycling for high temperatures
and periods of shutdown. Because the hotplate is placed at the bottom of the pipe,
the corrosion resistance of anti-CUI coatings is non-uniform along the specimen due
to the temperature gradient. Meanwhile, 1 wt% NaCl solution uptake by insulation
materials is also considered. A schematic diagram of the vertical pipe test is shown
in Fig. 11.
At the beginning of the test, 1 liter of 1 wt% NaCl solution is poured into the
insulated pipe from the top. The pipe is placed onto a hotplate at 500 °C (or specified
temperature) for 8 h. After that, the pipe is transferred to another vessel. Fresh 1 wt%
NaCl solution is poured into the pipe and kept cooling under ambient conditions for
another 16 h. The testing cycle is repeated 5 days per week for 6 weeks. After testing,
the pipe is cut into 11 sections from the bottom 50 mm and rated by the guidance
Fig. 11 Sectional view of

vertical pipe test
of ISO 4628-2, 4628-3, 4628-4, and 4628-5. The limitation is that systematic error
may exist due to the variance of the solution composition along the pipe.
7 Summary
Corrosion under insulation (CUI) is a corrosion reaction in closed system and draws
wide attention after devastating accidents in the past decades. Three case studies are
discussed at the beginning of this chapter. Fundamental concepts of corrosion are
reviewed to help readers understand the effects of environmental and human factors
on CUI. Even though CUI is almost impossible to be managed by visual inspection,
on-site non-destructive testing (NDT) methods can give clear clues about which
components are of high risk under claddings. Moreover, guidance of recognized
and generally accepted good engineering practices (RAGAGEPs) and process safety
management (PSM) is highly recommended.
In insulation system design, modification of insulation materials can be dedi-
cated to reducing the risks of CUI. Also, applying anti-CUI coating before insu-
lation cladding is another applicable and affordable method. As a rule of thumb,
resin systems of anti-CUI coatings are determined by the operating temperature
of hot structural components. Some coatings with high thermal resistance, such
as IMPM, may not be recommended in low temperature (i.e., <200 °C) and high
humidity conditions. Standardization laboratory tests, such as ASTM G189-07(2021)
and ISO 19277:2018 for anti-CUI coatings, are also elaborated in this chapter.
These test methods can provide meaningful evaluations for anti-CUI coatings perfor-
mance, and give useful guidelines in both formulation development and screening
of commercially available coatings.
28 I-T. Liu et al.
Acknowledgements This work was supported by the “Advanced Research Center for Green Mate-
rials Science and Technology” from the Featured Area Research Center Program within the frame-
work of the Higher Education Sprout Project by the Ministry of Education (111L9006), the National
Science and Technology Council in Taiwan (NSTC 109-2221-E-002-064-MY3, NSTC 111-2622-
E-002-042, NSTC 111-2634-F-002-016), and National Taiwan University (NTU-CC-111L890903
and NTUCC-111L4000-1).
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Development of Coating-Resistant
Materials at High Temperatures
for Waste-to-Energy Plant Application
Ankita Kumari, Priyanka Sati, and Sudesh Kumar
Abstract Higher efficiency by the use of thermal waste recycling technologies

has recently become more well known. Corrosion-resistant materials are becoming
more and more in demand. To complete a challenging job avoidance boiler that
burns waste and is capable of producing steam, harshly corrosive environments are
important technologies that must be combined with corrosion avoidance strategies
in plant design and engineering. The distinctiveness of elements influencing high-
temperature corrosion and corrosion action on the waterwall and superheater tubes
of waste-to-energy boilers is explained for the first time in this research. The devel-
opment and application of high-temperature coatings and corrosion-resistant boiler
tubing is then summarised as the present status of this. Several coating techniques,
such as metal-spraying over welding, employ alloys that include corrosion-resistant
components. Also, research of corrosion processes and the assessment process using
a real boiler have great repeatability. Crucial for the creation of new materials. Coat-
ings and corrosion-resistant materials are crucial technologies for waste-to-energy
(WTE) plant maintenance cost reduction and control production competence growth.
Super heaters that operate at high temperatures also created coatings with great tough-
ness using ceramic and cermet materials. The significant developments and uses in
WTE plants over the years are covered in this chapter, along with the mechanisms
of alloy corrosion, the deterioration of spray coating layers, and potential future
research areas for the development of corrosion-resistant sources and coatings. The
development and demand for corrosion avoidance technology is reportedly highly
influenced by the usage of appropriate materials at reasonable costs. Corrosion-
resistant CRM, CRC (corrosion-resistant coatings) technology advancements have
improved the performance and durability of WTE plants. One of the areas for further
study is the development of software for WTE boilers that can effectively apply
corrosion protection. Engineers and researchers from CRM and CRC should be able
to handle the difficulties.
Keywords Pyrolysis · Corrosion · Monitoring · Testing
A. Kumari · P. Sati · S. Kumar (B)

Department of Chemistry, Banasthali Vidyapith, Banasthali 304022, India
e-mail: sudeshneyol@gmail.com

32 A. Kumari et al.
1 Introduction
Global regulations prohibiting the combustion of biomass and waste are intended
to promote high-level recycling and reduce environmental load, such as NOx , SOx
and heavy metals. Biomass/waste-to-energy (WTE) plants are at the heart of stable
renewable energy sources in many countries. Furthermore, the efficiency of biomass/
WTE plants in generating electricity has increased to around 20–30%. Municipal
solid wastes, including refuse derived fuels (RDF), are commonly used as a fuel in
WTE plants, and a few types of industrial wastes are occasionally mixed into the
fuel, whereas biomass power generation plants burn biomass such as wood wastes,
agricultural wastes, sewage and so on collected from areas near the plant site. As a
result, the applied fuels and thus boiler conditions vary depending on the country or
region.
The two objectives of waste recycling promotion are high levels of material recir-
culation and a reduction in environmental burdens like CO2 and dioxins. Power plants
for ash melting and waste gasification are key components of waste-to-energy (WTE)
plants with higher efficiency. With respect to WTE boilers, the standard steam condi-
tion of 300 C/2.9 MPa has been significantly improved to 400 C/3.9 MPa, and Japan’s
first plant producing steam at 500 C/9.8 MPa has been running continuously for more
than 5 years [1]. In recent years, SHTs made of corrosion-resistant materials (CRMs)
have been used more frequently to minimise maintenance. Corrosion-resistant coat-
ings (CRCs), such as highly corrosion-resistant Ni-base alloy metal spray coatings
and weld overlays made of alloy 625, have been used extensively on water wall tubes
to reduce maintenance (WWTs). Furthermore, thanks to the advancement of pyrol-
ysis and gasification-melting furnaces, new dioxin-reducing combustion systems, as
well as numerous novel waste treatment methods, are now available. Future develop-
ments in this research will cover the effects of alloying elements, corrosion processes
in WTE boilers and current advancements in the use of CRM and CRC technologies
in difficult HTC environments.
1.1 WTE Boiler Corrosion Environment
The majority of WTE facilities use steam at a condition of 300–4500 C/2.9–5.8 MPa
to ensure stable operation and avoid corrosion damage to boiler tubes and other
components. The characteristics of waste and how the WTE plant runs have changed
as a result of significant changes in life and production styles brought about by
technological and economic development:
1. Strict pollution control measures are used to stop the production of NOx
and dioxins, such as increased plant running rates, high combustion chamber
temperatures and low O2 operation.
Development of Coating-Resistant Materials at High Temperatures … 33
2. Saving energy and efficiently using waste heat: A harsh environment that is more
likely to experience corrosion due to increased heat efficiency, such as boilers
that operate at high temperatures and pressures (400–500 °C/3.9–9.8 MPa).
3. The development of next-generation plants, like pyrolysis gasification-melting
furnaces [2] and oxygen-enriched combustion, is a result of the need to reduce
ash volume and produce non-polluting ash.
4. Lower operating costs and innovations in maintenance-free operation, like
cutting-edge combustion in control and monitoring technology, are examples
of cost-performance improvements.
Waste contains a variety of materials, including combustibles and incom-
bustibles like wood, paper, plastics and other materials. In addition, the combustion
gas produces significant amounts of low melting point deposits with high chlo-
ride contents, which increases the variability in gas temperature and composition
compared to boilers burning fossil fuels [3]. Even alloys with high corrosion resis-
tance can be attacked by molten adherent ash, which also causes general corrosion,
intergranular corrosion and localised corrosion to the metals [4]. By lowering the
combustion gas temperature supplied into the SHTs to less than 6500 C, it is possible
to reduce temperature fluctuation as well as the adhesion of dust elements, such as
extremely corrosive chlorides and sulphates. By cooling the gas, it is possible to
maintain the stability of the protective oxide layer on the metal surface. However, it
is well known that the use of soot blowers, which are used to remove heat-reflecting
deposits, causes severe thermal cycling and can even cause the protective oxide layer
to disintegrate.
2 HTC-Resistant Materials and Coatings Technological

Advances
In response to the aforementioned extremely corrosive conditions, new CRMs and

CRCs, corrosion resistance testing and assessment techniques and methods for
corrosive environment analysis have all improved.
2.1 CRCs for WWTs
The metal temperatures of the WWTs can be as low as 230–3300 C depending on the
steam pressure (2.9–9.8 MPa). CRCs are used in the application, such as metal spray
coatings, weld overlay, or cladding with a high CRM content, on the base material
of carbon steel.
34 A. Kumari et al.
2.1.1 Spray Coating
CRM metal spray coatings can be applied quickly and affordably on-site to thick-
nesses of 150–500 m [5]. Flame spray coating on WWTs, primarily made of Al/
80Ni20Cr alloy, started to be used in 1985 [6]. Using high-velocity oxygen fuel
(HVOF), NiCrSiB alloy spraying has also been developed [7]. Over 50 WTE plants
in Japan have used HVOF coatings. Real-world plants in Europe and the US were
used to test WWTs and SHTs [8–12]. Workability, corrosion environment severity,
required lifetime and cost are taken into consideration when choosing spray coating
systems (applied both off-site and on-site). Widespread use of HVOF is present.
Recently, a ZrO2 /Ni-base alloy plasma jet coating system was created and applied
to SHT boilers running at 500 °C/9.8 MPa WTE [13].
2.1.2 Weld Overlay
Because they can create a thick, chemically bonded coating layer that can be several
millimetres thick and is applied over the base metal thick, weld overlays are more
durable than thermal spray coatings. Alloy 625 weld overlays have excellent welding
workability and corrosion resistance. The durability is said to be at least 10 years,
and the application started around 1990, primarily on-site [14]. List of weld overlay
procedures and materials in use today [15–19]. For both in-shop and on-site appli-
cations, a lot of WWTs use shielded arc welding and MIG automatic welding. For
SHTs, plasma powder welding (PPW) and MIG welding are used, and tube bending
is possible even after weld overlay. Under metal temperatures of 330 °C, the 2-year
field tests have shown that the maximum corrosion loss rate for the 500 °C/9.8 Mpa,
high efficiency boiler WWT is approximately 0.1–0.2 mm/year. It has been confirmed
that these coatings are durable for at least 15 years [20].
2.1.3 Composite Tubing
In Europe, composite tubings with an outer tube made of CRMs and an inner tube
made of carbon steel are frequently used for WWTs and SHTs. Base alloys with high
Cr-high Mo–Ni content, like Alloy 625 (Sanicro 63), have a lot of application expe-
rience; a thorough assessment of the durability of these systems based on reported
experience is available [21].
2.1.4 Refractory Materials
Refractory tiles with higher SiC content and occasionally higher Al2 O3 are used
because they have a longer lifespan than traditional castable refractory materials.
The tiles are essentially attached to the outside of the WWTs by hanging or fastening
them there, and their surfaces reach temperatures of about 900 °C or lower. The
materials, production method, form and installation method are chosen based on the
evaluation of the high-temperature combustion gas’s resistance to oxidation, thermal
shock, etc.
2.2 Alloy Tubes with Corrosion Resistance and Superheater

Coatings
The alloy design of seamless tubes used in SHTs boiler construction takes into
account both heat resistance and corrosion resistance. Temperatures of 350 °C or
lower are typically used for carbon steel [22]. Fe-base and Ni-base austenitic mate-
rials are tested and used in high-temperature environments with a requirement for
strong corrosion resistance, temperatures of 400 °C or more. Field corrosion tests
have shown that the corrosion resistance of Ni–Cr–Fe alloys containing the alloying
elements Mo, Nb and Si is increased.
2.2.1 Alloys with a High Cr–Ni–Fe Content as the Base Alloy
The most common austenitic stainless steels used in 400 °C/3.9 MPa boilers are the
25Cr–14–20 Ni alloys 309S and 310S [23], or the modified 310S alloys 310HCbN and
NF709 [24]. Due to their lower cost, 310S and modified 310S are preferred because
the difference in Ni–Cr–Fe alloys’ corrosion resistance at steam temperatures below
450 °C is not as significant as it is for other materials [25]. Alloy 825 and Sanicro 28
(composite tube) of 20–30 Cr–30–40 Ni alloys are occasionally used in high thermal
efficiency plants in Europe, the US and Southeast Asia [26, 27].
2.2.2 Alloy with a High Cr-High Mo–Ni–Based
Alloy 625 and Sanicro 63 (composite tube) exhibit excellent corrosion resistance
under high-temperature steam conditions of 450 °C or higher. Additionally, it is well
known that alloys with higher Mo contents than Alloy 625, such as HC-22 and JH 24,
have superior corrosion resistance. When choosing materials for these alloys with
high Mo content, it is important to keep in mind that material age deterioration at
high metal temperatures is a possibility.
2.2.3 Alloys Containing a High Si–Cr–Ni Content
The 310S alloys QSX3 and QSX5 have been altered by the addition of about 3%
Si. Widely used in industry, Nicrofer 45TM has a high level of corrosion resistance.
Additionally, MAC-F and MAC-N alloys with high Cr, high Ni, high Fe and 4% Si
36 A. Kumari et al.
have undergone a 4-year test period in 500 C/9.8 MPa SHTs [28–38]. However, these
MAC-F, N alloys have shown good performance through alloying element optimiza-
tion for metals used in WTE boilers. High Si alloys present some challenges in terms
of tube manufacturability, weldability and micro-structural stability. Depending on
where a material is located in a superheater, where different corrosion environments
exist, a material’s corrosion resistance varies. Making the best use of the materials
in light of the corrosion environment is therefore crucial.
2.2.4 CRCs for Superheaters
Corrosive conditions are worse in SHTs than in WWTs due to higher metal temper-
atures and the presence of molten salts. The TiO2 –Al2 O3 /625 cermet HVOF coating
microstructures were exposed to WTE superheaters for about 2 years. Amazingly
low thickness loss, corrosive matter penetration and long-term durability of more
than 3 years were all noted. Furthermore, the ZrO2 /625 dual-layer system applied
by plasma jet process demonstrated high bonding strength after 2 years of exposure
in 500 °C high-temperature SHTs. The durability of spray coatings is thought to be
improved by the use of ceramics.
3 Materials and Coatings Corrosion Mechanisms
3.1 Resources Corrosion Mechanisms
Below is a description of how the main combustion gas side factors affect corrosion
rate. This type of corrosion is known as “molten salt induced corrosion” because
the corrosion reaction becomes active when the number of deposits increases and
some of the deposits melt [39]. The corrosion rate is temperature dependent. Gas
temperature is believed to be the primary determinant of deposition rate and deposit
composition. The concentration of chloride in the deposits is high in areas where
DT (gas temperature–metal temperature) is high because this temperature gradient
is what drives the condensation and deposition of the vapour components in the gas.
Additionally, it is well known that the concentrations of Cl, SO4 , alkaline and heavy
metals influence the physical characteristics of the deposits, including the proportion
of molten phase, permeability and so forth [40]. As the corrosion peak appears around
10% of chloride concentration, the penetration of corrosive gas through the deposits
and the presence of oxidising constituents like O2 are thought to be essential for the
maintenance of the corrosion reaction. In addition, rapid thermal cycling takes place
on the tube surface in real plants as a result of variations in gas temperature and the
use of soot blowers. Deposits and oxide layer regeneration and falling off are both
ongoing processes. The development of cracks in the layer of alloy 625 oxides as a
result of thermal variation in the area affected by soot blow. Cl, S and other elements
are thought to penetrate cracks onto the corrosion interface, raising the partial pres-
sures of S and Cl beneath deposits. However, molten salt corrosion is thought to
happen early on in the corrosion process when the oxide layer is thin. It is presum-
able that as the oxide layer thickens, the corrosion brought on by the direct reaction
of molten salt gradually changes to the gas reaction. Recent research [41] quantified
the degree to which important factors, such as temperature gradient, temperature
fluctuation, amount of molten ash and so forth, affect the rate of corrosion. Char-
acteristic intergranular corrosion is a result of both material-side (impurities, grain
boundary precipitates, etc.) and environmental-side (stress, molten salt, etc.) factors
[42].
3.2 Spray Coatings Deterioration Mechanisms
The spray coating layer’s gradual deterioration over time. Corrosive gases (HCl,
etc.) that penetrate the base material/coating layer interface cause the base metal
to corrode and the coating to deteriorate. This causes the coating layer to “swell”,
accelerate the loss of adhesive strength and peel. Since dense coating is needed to
increase lifetime, supersonic flame spray coating (HVOF), in which the alloy powder
is sprayed at supersonic speed while still in a semi-molten state, is preferred. The
material characteristics that determine durability are the coating material’s resistance
to corrosion, the base material’s adhesiveness, the thermal properties, including the
thermal expansion coefficient and the residual stress. A quantitative lifetime evalua-
tion method for the coating layer is necessary because the spraying conditions have
a significant impact on the physical properties of the coating. Future life evaluation
research and development is anticipated.
4 Corrosion-Resistant Substances and Coatings:

Application Trends
The materials used to make WWT tubes are typically carbon steels and CrMo steels,
which prevent localised corrosion inside the tube. Depending on the water/steam
pressure, metal temperatures in WWTs range from 250 to 320 °C, whereas surface
metal temperatures in SHTs range from 300 to 550 °C. As temperature, pressure and
power generation efficiency rise, the corrosive environment gets worse. Development
and application of CRM and CRC are therefore crucial issues. Trends in the creation
and use of sophisticated CRMs and CRCs, as well as corrosion resistance and tech-
niques for evaluating environmental factors. The use of materials and coatings on
biomass/WTE boiler WWTs and SHTs has recently followed the trends mentioned
below.
38 A. Kumari et al.
4.1 Coatings for Waterwall Tubes
In the extremely corrosive environments of the combustion furnace outlet position,

WWT corrosion rates of 0.2–4.0 mm/year have been noted. As was previously
mentioned, depending on the water/steam pressure, the metal temperatures of the
WWTs are relatively low. The most typical CRCs used to safeguard carbon steel and
CrMo steel tube materials are thermal spray coatings, weld overlays, claddings and
ceramic tile.
4.1.1 Metal Spray Coatings
CRM thermal spray coatings have a thickness of 150–800 m and can be applied
quickly on-site, depending on the spraying process. Various spray processes used
on boilers are compared in terms of spray speed. Around 1985 [6], Al/80Ni20Cr
alloy flame spray coating was first applied to WWTs. To assess coating durability,
numerous field tests in WTE boilers were conducted [43]. Despite being in a harsh
corrosive environment with higher metal temperatures in WTE boilers, SHTs have
not demonstrated durability for longer than 3 years. Depending on the particular
environment of the boiler, the durability varies. For instance, it has been claimed that
spray coatings in WTE plants have decent durability, as displayed below:
(a) High durability has been demonstrated for self-fluxing (NiCrSiB) alloys (not
fused), Ni base alloys like alloy 625, and modified 625 alloys sprayed with a
dense film using the High-Velocity Oxygen Fuel (HVOF) process.
(b) European biomass and WTE boilers sprayed with the modified plasma spray
process use corrosion-resistant alloys, such as alloy 625 [44] (Fig. 1).
Fig. 1 Comparison of the spray speeds for various boiler thermal spray systems [41]
Based on workability, repair time, necessary lifetime and total cost-performance,

thermal spray coating systems (applied both in-shop and on-site) are selected. Perfor-
mance and durability of cold or hot spray processes have recently been investigated
[45], with strong bonding and defect-free surfaces being crucial. It is anticipated
that applications and development for high-temperature corrosion protection will
continue. As-sprayed coatings are convenient in terms of working time and applica-
tion speed, but because there are open defects in the layer, they are less durable than
completely dense coatings. Micro-pores and oxide inclusions are examples of small-
scale flaws that are challenging to completely eliminate. Therefore, it is known that
interface corrosion in the coating/base material brought on by corrosive gases that
have seeped through such flaws results in accelerated blister and peel-off formations
of the coating layer. At low metal temperatures, the thickness loss of the coating layer
during the deterioration process in WWTs is relatively small. The HVOF procedure
is now applied more frequently as a result (Table 1).
Recently, self-fluxing (NiCrSiB) alloy coatings fused by automatic induction
heating have been applied successfully to WWTs. With a thickness that can be
chosen between 0.5 and 2.5 mm, this coating has a smooth surface, a chemical bond
and no dilution to the substrate material [46]. There are a variety of shapes available
for large panels for WWTs and SHTs in corrosive conditions. Future improvements
in simplicity of application are anticipated.
4.1.2 Weld Overlays
A dense, thick coating layer that is chemically bonded to the base metal can be
created by weld overlays. Weld overlays made of alloy 625 have been used for at
least 10 years [47]. For both in-shop and on-site applications of WWTs, automatic
MIG and shielded arc welding have frequently been used [48]. For single tubes for
SHTs, shops have primarily used MIG welding and plasma powder welding (PPW),
where tube bending and welding can be done on overlaid tubes. The WWTs in the
500 °C/9.8 MPa high efficiency boiler had a maximum corrosion rate of about 0.1–
0.2 mm/year, according to 2-year field tests [49]. In terms of coating layer quality,
laser welding is superior to traditional MIG welding because it allows for a wide
range of materials and low, controlled heat input. Laser-clad tubes and panels are
gradually being added to actual boilers [44]. In WTE boilers, friction welded tubes
are also being developed and tested [50]. Future cost-performance gains and wise
material choices to increase durability are anticipated. Wires, powders and more
recently cored wires are all readily available welding supplies. As a result, it is
simple to supply materials that are suitable for corrosive environments, and quick
material development is feasible.
40 A. Kumari et al.
Table 1 List of the performance requirements for applied materials, developed materials and
materials anticipated for use in waste incineration boilers [41]
Material Equipment Required material Materials processes Materials expected to
and parts performance applied materials be developed
Furnace Grate Heat resistance Heat- and • Corrosion- and
(stoker-type) corrosion corrosion-resistant wear-resistant
air dispersion resistance wear castings (ferritic and coatings (weld
nozzle (fluid resistance austenitic) overlay, etc.)
bed) Corrosion Fire brick (SiC-type, • Corrosion- and
Refractory resistance Chamotte-type) heat-resistant
materials Wear resistance Plastics, castables castings
Heat resistance • Ceramics
Erosion resistance • Ceramics tiles (si
C-type, etc.)
• Highly durable
refractory materials
Boiler Waterwall Corrosion Carbon steels, • Highly
tube resistance stainless corrosion-resistant
Superheater Heat resistance Composite tube Composite tube
tube Corrosion Corrosion-resistant • Corrosion-resistant
Tube shield resistance coatings coatings
Heat resistance (metal spray, 625 • Highly
Corrosion overlayed) corrosion-resistant
resistance Carbon steel, CrMo alloys (high Cr, Ni,
steel, Austenitic Mo alloys, etc.)
stainless steels • Highly
High Cr-high Ni corrosion-resistant
alloys (825, etc.) coatings
Carbon steel, • Highly
austenitic corrosion-resistant
Stainless steels alloys
• Ceramics shield
Others Protection Heat resistance Stainless steels, Ni • Highly
tube Corrosion base alloys, corrosion-resistant
Small welded resistance Ceramics, etc. alloys
parts (Thermal-shock Carbon steel, • Ceramics shield
resistance) low-alloyed steels, • Ni-base alloys, etc.
stainless steels, etc.
4.1.3 Clad Tubes Co-extruded
In Europe, co-extruded composite tubes with carbon steels and low alloy steels as
the inner tube and CRMs as the outer tube have primarily been used for WWTs
and SHTs. High Cr-high Mo–Ni–based alloys, like Sanicro 63, have been used in
a variety of applications [51]. However, it has recently been discovered that weld
overlays and metal spray coatings perform better in terms of applicability and cost.
4.1.4 Diffusion Coatings
Diffusion coatings on boilers have a longer history of use than thermal spray coat-
ings. Due to the following factors, the use of many diffusion processes, including
chromizing, siliconizing and aluminizing, in WTE and biomass boilers is currently
uncommon.
(a) This kind of coating has a thin effective thickness, between 10 and 100 m.
Additionally, on-site repairs are not possible.
(b) The application temperature and exposure time cause a gradual change in the
coating layer’s composition.
(c) Some coating layers become brittle as a result of the formation of intermetallic
compounds.
As a result, in highly corrosive environments, localised corrosion from coating
defects is possible [52]. Such coatings are designed and painted in multiple layers to
control surface atmosphere and form corrosion-resistant diffusion layers, which are
heated during services. The positive outcomes have been documented [53].
4.1.5 Refractory Ceramic Linings and Tile System
The high gas temperature zones of the furnace are lined with common fireclay linings,
such as alumina-silica refractory materials, at a temperature of about 1100 °C [54].
Refractory materials have microstructures that are relatively coarse and inhomoge-
neous when compared to coatings made of metal and ceramic. Therefore, selecting
and evaluating materials can be difficult [55].
4.2 Superheaters Corrosion-Resistant Alloys and Coatings
When designing an alloy for SHTs, corrosion and heat resistance should both be
taken into account [56]. Boiler construction also requires good plastic workability
and weldability. Carbon steel is typically used at steam temperatures of around 400 °C
or less, while, depending on the corrosive environments, CrMo steels, austenitic stain-
less steels, or Ni base alloys are used in the high-temperature region of more than
400 °C [57]. According to field corrosion tests, the addition of alloying elements like
Mo, Nb (Cb) and Si to Ni–Cr–Fe alloys is thought to be effective in reducing the
corrosion rate [58]. Additionally, SHTs with higher temperatures and more corro-
sive environments are subjected to CRCs. According to each coating process, various
coating materials like alloys, cermets and ceramics are chosen based on their prop-
erties, ease of fabrication, cost, etc. Below is a description of the various CRMs and
CRCs that are currently used with WTE boilers.
42 A. Kumari et al.
4.2.1 High Cr-High Ni–Fe Base Alloys
For 400 °C/3.9 MPa boilers, austenitic stainless-steel tubes made of 25Cr–14–20Ni
steels like 309S, 310S, 310HCbN and NF709—alloys that are modified versions
of 310S—are typically used due to their corrosion resistance and cost-effectiveness
[59]. This is because the corrosion resistance of Ni–Cr–Fe alloys and Ni base alloys
is similar under steam conditions below 450 °C. In WTE and biomass boilers, alloy
825, Sanicro 28 (composite tube) of 20–30–Cr–30–40–Ni alloys, is occasionally used
for highly corrosive environments [27]. Low-grade austenitic stainless steels with
18Cr–8Ni systems have a high rate of intergranular corrosion and are therefore not
used. Austenitic stainless steels are also rarely used as coatings because of their poor
weldability and thermal fatigue caused by an improper thermal expansion coefficient,
among other issues.
4.2.2 High Cr-High Mo–Ni–Based Alloys
Under 450 °C or higher high-temperature steam conditions, alloy 625 and Sanicro
63 (composite tube) exhibit good corrosion resistance. Additionally, it is well known
that alloy 622 (HC-22), which has a higher Mo content than alloy 625, exhibits
exceptional corrosion resistance. For these high Mo alloys, applications involving
high metal temperatures greater than 500 °C must take ageing deterioration into
account. Many biomass/WTE boiler WWTs and SHTs have been coated with alloy
625 and alloy 622 weld overlays, which have grown to be the most popular and
convenient coatings (Fig. 2).
4.2.3 High Si-High Cr-High Ni Alloys
Modified 310S alloys with about 3% Si additions are QSX3 and QSX5 . Additionally,
for 4 years [60], MACF and MAC alloys containing 21–28% Cr, 3.2–4.2% Si, Ni
and Fe were used in 500 °C/9.8 MPa SHTs in a WTE boiler. Depending on where
a material is located in the SHTs, where corrosive environments differ, a material’s
corrosion resistance varies. As a result, it’s crucial to choose the best materials you
can give the corrosive surroundings.
4.2.4 Cermet Coatings
In a working commercial plant that uses steam at 5000 C/9.8 MPa, cermet spray
coatings were applied: 50% TiO2 50% 625 (TiO2 625) (TiO2 625). In secondary
SHTs affected by soot blowing for 1.3–2 years at the metal temperature of 432–
4480 C, spray coating by HVOF and Cr3C275Ni25Cr (CrC–NiCr) spray coating by
ultrasonic plasma jet process were evaluated [61]. On the other hand, after 4 months
of exposure, the CrCNiCr coating, used to prevent E-C in SHTs in WTE boilers,
Fig. 2 Corrosion mechanisms in Ni–Cr–Mo–(Nb, Fe) alloy [28]
showed peeling with numerous hexagonal patterned cracks, particularly in the soot
blower affected position. To lessen erosion and E-C damage, these cermet-coated
layers were applied to FBC boilers. They are hard and corrosion-resistant.
(a) High-velocity continuous combustion (HVCC)-sprayed WC-NiCrB cermet
coatings exhibit good durability in USA biomass BFBC boilers that experience
severe corrosion and sand erosion conditions at 316 °C [62].
(b) In CFBC sludge boilers, coatings made of WC/Cr carbide-Ni–Fe cermet and
Cr carbide-stainless steel that were sprayed using the high-velocity arc contin-
uous spray (HVAC) or the high-velocity air fuel (HVAF) process exhibit good
durability [63].
4.2.5 Ceramic Coatings
Ceramic coatings were used to stop severe corrosion in biomass/WTE boilers and
demonstrated good durability in SHTs, but there aren’t many examples of their use
because of practical issues and cost constraints (Table 2).
For long durability and to control the different thermal expansion properties, bond-
coatings of CRMs are typically required under ceramic layers. The WTE plant has
exposed two different types of dual-layer coatings with alloy 625 or NiCrSiB alloy
under-coats and yttria-stabilised zirconia (ZrO2 –8% Y2 O3 , here in after abbreviated
as YSZ) coating as the top-coat [64] (Table 3).
44 A. Kumari et al.
Table 2 Standard microstructures and test conditions for YSZ/Ni base alloy and Cr3 C2 75Ni25 Cr
cermet coatings [64]
Test positions Third superheater Third superheater steam Second superheater
steam inlet outlet steam outlet
Tube materials Alloy 625 Alloy 625 310HCbN
Steam temp 445 °C 500 °C 450 °C
Gas temp 62 °C 510 °C 488 °C
Under/top coating • 625/YSZ • 625/YSZ • 625/YSZ
materials • NiCrSiB/YSZ • NiCrSiB/YSZ • NiCrSiB/YSZ
• Cr3 C2 · 75Ni25 Cr
Test bundles • On-site (for used • First tube in no. 2, 3, 4 –
tube) bundles
• In-shop (for new • First tube in no. 9
tube) bundle
Table 3 After 1.3 years of exposure, the lifetime prediction of YSZ/Ni base alloy coatings [64]
Test Gas/steam Max. S/b affected Coating Lifetime of Lifetime of
positions temp. (°C) corrosion materials coatings S/ coatings S/
(materials) rate (mm/ B not B affected
year) S/B affected
not affected
Secondary 488/450 0.41 0.64 YSZ/625 >3 >3
SH steam YSZ/ >3 >3
outlet (310 NiCrSiB <0.3 <0.3
HCbN) Cr3 C2 -NiCr
Tertiary SH 510/500 0.59 1.1 YSZ/625 >3 –
steam YSZ/ >3 –
outlet NiCrSiB
(Alloy 625)
Tertiary SH 621/445 1.82 3 YSZ/625 >3 >1.5
steam inlet YSZ/ >3 >1.5
(Alloy 625) NiCrSiB
5 Decline Mechanisms and Design of Coatings
5.1 Formation and Breakdown of Protective Oxides Layer
The gas temperature, in particular, the temperature gradient T (the difference between
the gas temperature and the metal temperature), is thought to be the primary cause
of the condensation and depositing of the corrosive vapour components in the gas
[47]. The deposits with high T have a high chloride content and are more likely to
produce low melting deposits than other deposits. Furthermore, it is well known that
the amounts of Cl, SO4 , alkalis and heavy metals affect the deposits’ corrosiveness as
well as their physical properties, such as their permeability and the volume of molten
phase [40]. It is believed that corrosive gas components must penetrate the deposits
and oxidising elements like oxygen must be present in order to maintain the corrosion
processes. Additionally, in actual plants, the use of soot blowers and changing gas
temperatures result in significant thermal cycling that affects the surface of the tubes.
This type of corrosion is referred to as “molten salt induced corrosion” [65] because
the gaseous corrosion process becomes active as the amount of deposits increases and
a portion of the deposit’s melts. If the protective oxide layer breaks down, corrosive
material will get into the base material and scale lamellae will form as a result of the
partial gaseous state fluctuating. CRMs must have the capacity to form and self-heal
a robust protective oxide layer, which is comparable to a ceramic coating film, when
used in harsh, corrosive environments. Based on the structure and properties of the
corrosion products that disperse as chlorides, sulphates and oxides from the flue gas
side to the corrosion interface, it is believed that steady-state corrosion is caused by
high-temperature gaseous reactions, specifically chlorination/suffixation/oxidation.
The effects of critical factors like temperature gradient, temperature fluctuation and
the amount of molten ash on corrosion rates were quantitatively examined in coating
experiments [65, 66].
5.2 Erosion and Erosion/Corrosion-Resistant Materials

and Coatings
As the primary systems for the combustion of mixed, inhomogeneous solid fuels like
waste and biomass, FBC boilers are gaining popularity. The bubbling fluidized bed
combustor (BFBC) and the circulating fluidized bed combustor are two examples of
commonly used furnace types. Because solid fuels combine with sand flow, which
is typically maintained in the furnace at a temperature of 800–900 °C, erosion or
E-C damages on WWTs, SHTs and heat exchanger tubes placed in the furnace have
been noted. These damages are impacted by the movement of sand and ash particles.
The combined effects of mechanical erosion and corrosion almost always result in
damage rates that exceed a few millimetres per month.
(1) Damage to protective oxide layers, such as that brought on by soot blower assault
on SHTs and low-velocity solid particle erosion on furnace tubes, speeds up the
corrosion process. It is essential to increase materials’ corrosion resistance and to
fortify protective oxide coatings in order to prevent damage in this circumstance.
(2) Material surfaces can be eroded or abraded mechanically. The speed of degrada-
tion is controlled by this mechanical fracture at the surface. This kind of damage
is frequently influenced by high-velocity combustion gas flow, which moves at
few 10–100 m/s and contains solid sand and ash particles.
(3) The scenario in the middle of (a) and (b) is mixing of corrosion and erosion,
and it is thought that flue gas moving at just a few tens of metres per second
or less has an impact on it. It is assumed that this type of accelerated corrosion
causes a lot of tube damage in actual boilers.
46 A. Kumari et al.
Mechanical erosion is thought to be severe at particle speeds greater than a few

m/s; however, damage processes switch to E-C at relatively low particle speeds and
severely corrosive conditions [65, 66]. When selecting the applied coatings for actual
FBC boilers, field tests are frequently the most reliable method of estimating lifespan.
As an illustration, various hard CRC materials, as seen below, have been used for a
variety of applications, most notably FBC boilers.
(a) Weld Overlays: High Cr martensitic stainless steels, hard facing materials.
(b) Laser Claddings: WC-Co, WC-NiCr, Cr carbide-NiCr, WCr carbide–NiCr.
(c) Thermal Sprays: WC-NiCr, WC/Cr carbide–NiCr, WC-NiCrB, NiCrSiB, WC/
Cr carbide–Ni–Fe, etc.
(d) Ceramic Linings: Al2 O3 -rich, SiC-rich refractories and fine ceramics.
The most important factor (a) is weldability, and by utilising current cored wire
and nano-powder technologies, various types of ceramic materials may be used in
(b) and (c). For achieving excellent coating qualities, it’s important to consider the
powder and wire design in addition to the coating process. Calculating and assessing
the damage to FBC boilers’ extent is challenging. As a result, the coatings were
frequently selected while taking availability, cost and performance into account based
on the outcomes of field tests. Furthermore, E-C phenomena and damage rates are
challenging to realise in condensed laboratory tests because the various contribu-
tions of corrosion and erosion are unknown. The creation of testing and assess-
ment technologies is considered to be one of the most crucial issues for upcoming
advancements.
5.3 Durability of Alloy and Ceramic Spray Coatings
The ways that spray coating layers that have spent a lot of time in corrosive envi-
ronments like boilers deteriorate. Corrosive gases like HCl and Cl2 penetrating the
coating/base material interaction lead to the degradation of the covering layer and
corrosion of the basic material. The adhesive strength is subsequently decreased, the
coating layer “swells” or “cracks” and eventually the peel comes off (Fig. 3).
Durability is governed by material factors such as open porosity, CRC corro-
sion rate, base material bonding strength, thermal expansion coefficient and residual
stress. The physical properties of the coating are significantly influenced by the
spraying conditions. Recently, using tiny electric resistance methods, a quantitative
lifespan evaluation approach for boilers based on these degradation mechanisms was
developed and implemented [56].
Fig. 3 Mechanisms of
coating layer deterioration
from thermal spraying in an
extremely corrosive
environment (Redrawn) [9]
6 Conclusion
In recent years, a slew of new requirements, such as pollution control, improved

power generation efficiency, material recycling and so forth, have been placed on
WTE plants. A more complex and varied HTC environment for the plants is the
result of different combustion techniques and plant system implementations. It is
believed that a key focus in the creation and application of corrosion prevention
technologies is the use of the proper material in the right place at an affordable
price. The performance and durability of WTE plants have increased thanks to the
development of corrosion-preventing CRM and CRC technologies. The creation of
software to successfully apply these corrosion prevention techniques to WTE boilers
is one of the future research topics. These difficulties must be overcome by the
engineers and researchers developing CRMs and CRCs.
Recent performance standards for biomass and WTE facilities include those for
material recycling, high electric power generating efficiency and pollution suppres-
sion. Due to the use of various combustion methods and plant systems, the high-
temperature corrosive environment of the plants is growing and diversifying. The
primary fundamental mechanisms that underlie high-temperature corrosion and E-C
are thought to be constant across all plants. CRMs and CRCs are believed to have
been created and implemented with the objective of placing the appropriate mate-
rial in the appropriate location at a reasonable total cost. High-temperature parts
now perform and last longer thanks to improvements in coating, CRM and CRC
technologies. To achieve long lifetime, it is necessary for material information and
plant design/operation to work together. Future research on corrosion and erosion
in harsh high-temperature environments is expected to cover a wide range of topics,
and engineers and scientists are expected to rise to the challenge of using CRMs and
CRCs to find a solution.
48 A. Kumari et al.
Acknowledgements It is my proud privilege and special appreciation towards Department of

Chemistry, Vigyan Mandir, Banasthali Vidyapith, Rajasthan. We are also thankful to reviewers for
their most valuable suggestions, guidance and constructive criticism that made it possible for the
work to get published.
Conflict of Interest No conflict of interest.
Research Funding No funding available.
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(2013)
Composite Enamel Coatings for Thermal
Shock and Chloride Corrosion Coupled
Environments
Dongming Yan and Hao Qian
Abstract In some special cases, steel substrates may suffer the coupled threats of
chloride corrosion and elevated temperature, requiring both high-temperature and
corrosion protection. Enamel coating has been utilized to protect metallic substrates
against corrosion and has proven to be effective. Recently, silicon carbide and silicon
nitride were added to pure enamel coating and the composite enamel coatings were
developed. Results showed that the composite enamel coatings had excellent thermal
shock resistance, good corrosion resistance, and sufficient cracking resistances. Due
to these improvements, the composite enamel coating became a candidate material
for applications in thermal shock and chloride corrosion coupled environments.
Keywords Composite enamel · High-temperature coating · Corrosion protection ·

Thermal shock · Residual stress · Corrosion mechanism · Microstructure
1 Introduction
Corrosion, a pervasive challenge in civil engineering, industry, and daily life, induces
significant structural damage and substantial economic costs. Particularly, some
distinctive scenarios, like offshore launch towers and related facilities, boilers, chim-
neys, ship engines, etc., expose steel structures to the combined hazards of chloride
corrosion and elevated temperature. Enamel coatings have been employed to miti-
gate corrosion of metallic substrates, exhibiting commendable efficacy. However, the
conventional enamel coatings exhibit constrained resistance to thermal shock and
insufficient damage tolerance due to the presence of rigid covalent or ionic bonds.
Consequently, these limitations significantly undermine the anti-corrosion perfor-
mance of such coatings and restrict their practicality in engineering applications
subjected to environments featuring both thermal shock and chloride corrosion.
Composite coatings have usually been considered to be an attractive option for
improving some technical properties of coatings. Recently, silicon carbide or silicon
D. Yan (B) · H. Qian

College of Civil Engineering and Architecture, Zhejiang University, Hangzhou 310058, China
e-mail: dmyan@zju.edu.cn

54 D. Yan and H. Qian
nitride was added to pure enamel and the composite enamel coating was developed
for applications in thermal shock and chloride corrosion coupled environments. In
the present chapter, silicon nitride/enamel composite coatings with 0, 1.5, 2.5, 3.5,
5, and 7.5 wt.% silicon nitride content (N0, N1.5, N2.5, N3.5, N5, and N7.5, respec-
tively) and silicon carbide/enamel composite coatings with 0, 2.5, 5, and 7.5 wt.%
silicon nitride content (S0, S2.5, S5, and S7.5, respectively) were investigated, and
their microstructure, mechanical properties, thermal shock tolerance, and corrosion
resistance were reviewed in detail.
2 Surface and Microstructural Characterization

of Composite Enamel Coatings
2.1 Silicon Nitride/Enamel Composite Coatings
2.1.1 Surface Morphology and Contact Angle
Figure 1 shows the surface morphology and the water contact angles of the different
composite coatings. From Fig. 1a, with increasing silicon nitride content, there is
a noticeable color change from dark blue of N0 to gray of N7.5. For micro view,
however, it should be noted that the images exhibited unrealistic colors due to the
lighting conditions of digital microscope. N0 presents microcracks on its surface,
resulting from the thermal damage when cooling. Silicon nitride not only helps
mitigate the microcracks’ formation but also introduces significant porosity as well
as visible open pores when redundancy, as observed for N7.5 (Fig. 1a).
Figure 1b presents the 3D surface morphologies and corresponding surface rough-
ness data of different samples. Evidently, the incorporation of silicon nitride signif-
icantly reduces surface smoothness. Quantitatively, the average surface roughness
(Ra) of N0 is 1.51 μm, which undergoes an increase to 4.07 μm, 6.22 μm, and
10.36 μm for N2.5, N5, and N7.5, respectively. This observed rise in roughness can
be attributed to the elevated viscosity of the molten enamel caused by the presence of
silicon nitride, which hampers effective leveling [1]. Physically, such an increase in
roughness contributes to enhanced hydrophobicity of the material [2–4]. Indeed, our
findings demonstrate an escalation in the contact angle, which is 55.7° for N0 and
progresses to 67.6°, 77.6°, and 76.8° for N2.5, N5, and N7.5, respectively (Fig. 1c).
Enamel coatings that have higher contact angles offer improved resistance against
water penetration, thus proving advantageous for corrosion protection [5].
Composite Enamel Coatings for Thermal Shock and Chloride Corrosion … 55
Fig. 1 Surface morphology and contact angle of different enamel coatings: a Macro and micro
images of N0, N1.5, N2.5, N3.5, N5, and N7.5; and 3D morphologies b and contact angles c of N0,
N2.5, N5, and N7.5 [1]
2.1.2 Phase Structure
Figure 2 gives the X-ray diffraction (XRD) patterns obtained for samples. The XRD
pattern of all samples exhibits a characteristic hump in the range of 20°–40°, indi-
cating the presence of amorphous phases within the enamel. The diffraction peaks
primarily correspond to apatite (Ca5 (PO4 )3 [F, OH]), which is an inorganic compo-
nent found in the hard tissue of human. Apatite possesses favorable attributes such as
low solubility and excellent acid resistance [6, 7], contributing to the capabilities of
the enamel coating for corrosion prevention. Despite the inclusion of a bit of silicon
nitride (1.5 wt.%, N1.5), distinct diffraction peaks attributable to silicon nitride are
evident in the XRD patterns. Notably, the XRD signals’ intensity of the silicon nitride
progressively intensifies as the silicon nitride content increases (Fig. 2). There is
no indication that the silicon nitride underwent any chemical reactions during the
sintering process at 530 °C, as evidenced by the XRD patterns.
Fig. 2 XRD results of

Si3 N4 , N0, N1.5, N2.5,
N3.5, N5, and N7.5 [1]
2.1.3 Microstructure
Figure 3 displays the cross-sectional morphologies of the enamel coatings with

varying silicon nitride contents, along with the extracted pore phase. The powder
electrostatic spraying ensures a uniform coating thickness of approximately 200 μm
for all samples. All coating phases exhibit complete sintering. Notably, the incorpora-
tion of CoO and NiO as adhesion promoters facilitates a strong adhesion at enamel/
steel substrate interface [8, 9]. XRD analysis (Fig. 2) confirms pore formation in
enamels attributed to the physical effect that silicon nitride makes molten enamel
more viscous [1]. Consequently, the escape of sintering-induced gases (H2 , H2 O,
CO2 , CO, etc.) is limited [1, 9].
Figure 4 shows the distribution of porosity for all coatings. The incorporation
of silicon nitride induces significant alterations in the pore distribution. The total
porosity and the maximum pore size both exhibit notable increases with the augmen-
tation of silicon nitride amount. For instance, the initial total porosity of N0 is 6.04%,
which raised to 26.14%, 39.75%, 44.80%, 59.42%, and 55.75% for N1.5, N2.5,
N3.5, N5, and N7.5, respectively. The dominant pore size is 0–20 μm for N0, which
enlarges to 20–40 μm, 20–40 μm, 40–60 μm, 60–80 μm, and 60–80 μm for N1.5,
N2.5, N3.5, N5, and N7.5, respectively. Similarly, the maximum pore size is 20–
40 μm for N0, which enlarges to 40–60 μm, 40–60 μm, 60–80 μm, 100–120 μm,
and 100–120 μm in N1.5, N2.5, N3.5, N5, and N7.5, respectively. Notably, pores with
a diameter greater than 100 μm demonstrate a higher likelihood of interconnection
(Fig. 3e, f), which can be detrimental to corrosion protection efforts.
Fig. 3 Cross-sectional view of SEM and pore images of different samples: a N0, b N1.5, c N2.5,
d N3.5, e N5, and f N7.5 [1]
Fig. 4 Porosity distribution

against equivalent pore
diameter for different
coatings [1]
2.2 Silicon Carbide/Enamel Composite Coatings
2.2.1 Phase Composition
Figure 5 presents the XRD results of silicon carbide and all enamel coatings. All
diffraction peaks observed for silicon carbide only corresponded to the character-
istic peaks of Moissanite-6H (α-SiC), indicating high purity. In contrast, the enamel
coatings displayed an amorphous phase between 20° and 40°. The diffraction peaks
observed in S0 can be indexed to CaF2 and Ca5 (PO4 )3 [F, OH]. Besides the same
diffraction peaks observed in S0, the diffraction peaks corresponding to silicon
Fig. 5 XRD patterns of

silicon carbide, S0, S2.5, S5,
and S7.5 [13]
carbide were clearly present for S2.5, S5, and S7.5, and the intensity of these silicon
carbide diffraction peaks exhibited a gradual increase as the silicon carbide content
increased. In addition, not any new phases were detected. These findings indicate
that as results of the excellent thermal and chemical stability [10–12], silicon carbide
never underwent any chemical reaction throughout the entire sintering.
2.2.2 Surface Morphology
The surface morphologies of coated samples are shown in Fig. 6. Clearly, S0 exhibits
significant microcracks on its surface, with approximately 4 μm in width (Fig. 6a).
These microcracks have been previously identified as potential pathways for aggres-
sive ions, leading to reduced corrosion resistance during early immersion stages
[1]. The presence of microcracks is attributed to that the enamel and steel had a
mismatched coefficient of thermal expansion (CTE), which results in considerable
residual stress within the coating matrix. Notably in Fig. 6b, the addition of 2.5
wt.% silicon carbide in S2.5 demonstrates marked improvements, with decreased
the width (<1 μm) and number of microcracks. Further enhancement is observed
in S5, and remarkably, no microcracks were found in S7.5, indicating a favorable
thermal expansion match between the enamel and the steel.
2.2.3 Cross-Sectional Microstructure
Figure 7a–d displays the cross-sectional backscattered electron (BSE) images of

different coatings. Notably, as the content of silicon carbide increases, composite
coatings show a substantial increase in pore volume. The XRD results in Fig. 5
confirm the absence of any chemical reactions between silicon carbide and enamel.
Fig. 6 SEM results of different enamel surfaces: a S0, b S2.5, c S5, and d S7.5 at (1) 150× and
(2) 2400× [13]
The observed increase in porosity is due to the dual effect of the silicon carbide, that
is, the mechanical presence and the modification of the matrix [1]. Consequently,
the molten composites presented a raised viscosity during the sintering process,
impeding the escape of gases and leading to the formation of pores [1]. These findings
align with previous research on the silicon nitride-modified enamel [1]. However,
because silicon carbide has a smaller size (d90 = 7.699 μm) than silicon nitride
(d90 = 28.464 μm), the silicon carbide induces isolated pores smaller than 40 μm
in diameter, whereas silicon nitride induces interconnected pores up to 100 μm in
diameter.
For BSE images, phases exhibit brighter appearance with elements having higher
average atomic number [14, 15]. Figure 7e gives a magnified morphology and
elements of identified phases. Notably, the darkest region corresponds to the pore.
The dominant phase (point 1) is characterized by the elements of aluminum (Al),
sodium (Na), silicon (Si), oxygen (O), phosphorus (P), and potassium (K), indicating
its association with the matrix phase, likely corresponding to the amorphous phases
identified from XRD analysis (Fig. 5). The medium brightness phases encompass
elements of oxygen (O), phosphorus (P), and calcium (Ca) elements (point 2), or
fluorine (F), calcium (Ca), and oxygen (O) (point 3), suggesting their composition as
calcium compounds (Ca5 (PO4)3 [F, OH], CaF2 ), which in accordance with the XRD
(Fig. 5). The brightest phases exhibit the presence of nickel (Ni) and oxygen (O)
elements (point 4) and zirconium (Zr) and oxygen (O) elements (point 5), which can
be attributed to the agglomeration of NiO and ZrO2 , respectively. Notably, the silicon
carbide is undetectable as results of its tight bonding and similar atomic number to
matrix.
The gray threshold-based separation method using Image J software was
employed to distinguish different phases. The distribution maps of the pore phase,
Ca compounds, [Zr, Ni] oxides, and matrix phase for different coatings are shown
in Fig. 8a–d. Generally, apart from some agglomerated [Zr, Ni] oxides, all phases
exhibited a uniform distribution across the coatings. Figure 8a–d shows the content
Fig. 7 BSE results of cross section: a S0, b S2.5, c S5, and d S7.5; e Magnified images and elements
of various phases: (1) matrix, (2) Ca5 (PO4 )3 [F, OH], (3) CaF2 , (4) Ni oxides, and (5) Zr oxides [13]
of every phase, with a summary plot shown in Fig. 8e. S0 had a matrix content of
67.55%, which reduced to 58.66%, 58.39%, and 56.40% for S2.5, S5, and S7.5,
respectively. Correspondingly, S0 had a total porosity of 6.21%, which increased
to 17.54%, 20.65%, and 26.31% for S2.5, S5, and S7.5, respectively. The [Zr, Ni]
oxides remained relatively stable content at around 0.4–0.5% in all coatings, which
was much lower than the content in the raw materials (approximately 2% in volume).
This observation can be attributed to the fact that only the agglomerated portion
was calculated, while the evenly distributed sections were so small that cannot be
distinguished, and a few Ni oxides were enriched in the transition layer (Fig. 9a).
Furthermore, because of the presence of silicon carbide and the increase in porosity,
the content of Ca compounds reduced from 25.80% (S0) to 23.33% (S2.5), 20.45%
(S5), and 18.00% (S7.5). If calculates the percentage of Ca-compounds in the pure
solid phases (except for silicon carbide), all coatings had a similar value of ~27%
(Fig. 8e). These suggest that silicon carbide may only impact the pores’ creation of
rather than the crystallization of CaF2 and Ca5 (PO4 )3 [F, OH].
Figure 8f presents the distribution of pores for all samples. Clearly, the increase in
pore number of S2.5, S5, and S7.5 result in the overall increase in porosity. However,
the dominating diameter of pores remained rather stable, indicating that the size distri-
bution of the pores did not change significantly. Furthermore, all the pores observed
in the composite coatings were still isolated and not interconnected. Notably, the
greatest diameter of pores remained less than 40 μm in all samples, accounting for
Fig. 8 Phase distributions extracted from BSE images: a S0, b S2.5, c S5, d S7.5; (1) for pore, (2)
for Ca compounds, (3) for [Ni, Zr] oxides, and (4) for matrix phase; e phase content; f pore size
distribution [13]
Fig. 9 a Interfacial BSE morphology between enamel and steel; b EDS of steel (point 1), transition
layer (point 2), and Co/Ni enrichment (point 3); and c the XPS spectrum of Fe 2P in transition layer
[13]
roughly one-fifth of the coating thickness. This finding suggests a low probability of
forming penetrating defects within the coatings.
2.3 Enamel/Steel Interface Analysis
Figure 9a and b show the morphology and elemental analysis of the interface between
composite enamel and steel. As marked by the red dotted lines, a transition layer was
presented, which had a thickness between 0.5 and 1 μm. This transition layer appears
as a medium brightness phase. EDS analysis at point 2 reveals the elements of Fe,
P, O, Al, Si, Na, and K in the transition layer, suggesting that it forms through
elemental interdiffusion of the iron (Fe, point 1) from the steel substrate and the
elements (Al, P, O, Si, Na, K, etc., as seen in Fig. 7) from the enamel matrix when
iron is oxidized. Furthermore, white particles, which contain elements of P, O, Na,
Al, Si, and a significant amount of Ni and Co, are observed near the transition layer
(point 3). This indicates that the Ni and Co have enriched elements in the transition
layer. These observations align with previous findings on pure enamel coating [16],
suggesting that the presence of silicon carbide has no influence on the formation of
the transition layer.
Fig. 10 Tensile stress–strain

curves of enamel-coated and
bare steel bars
The valence state of iron in the transition layer was determined using X-ray
photoelectron spectroscopy (XPS) investigation of Fe 2P peaks. The Fe 2P peaks
were deconvoluted using parameters from references [17, 18]. Figure 9c shows the
XPS spectrum with fitting results. The sample exhibits ferromagnetism and lacks
prominent satellite peaks corresponding to Fe3 O4 [17]. The ratio of Fe2+ and Fe3+
was 0.23:0.27, exceeding the ratio typically observed in Fe3 O4 (0.33:0.67). This
suggests the presence of FeO in addition to Fe3 O4 in the transition layer. Therefore,
iron oxide can be identified as a combination of Fe3 O4 and FeO, formed as a result
of limited oxygen supply at the interface of enamel and steel.
3 Mechanical Properties of Composite Enamel Coatings
3.1 Strength of Coated Steel
Figure 10 shows the stress–strain curve of the enamel-coated rebar. Clearly, regard-
less of the HRB600 high-strength steel bars or HPB300 ordinary steel bars, the
stress–strain curves of coated and uncoated rebars are basically unchanged, which
means that the sintering process of 530 °C for enamel coating will not influence the
mechanical properties of steel bars. Among them, the elastic modulus, yield strength,
and ultimate strength of the enamel-coated HRB600 are 200.5 GPa, 652.5 MPa, and
818.3 MPa, respectively. The elastic modulus, yield strength, and ultimate strength of
the enamel-coated HPB300 are 196.7 GPa, 306.3 MPa, and 401.8 MPa, respectively.
3.2 Adhesion of Coating to Steel Substrate
A pull-off test was used to investigate the adhesion at enamel coating/steel substrate
interface, and Fig. 11 displays the fracture appearances of the three coatings. It is
Fig. 11 Fracture surfaces of a SC, b DC, and c TC, with (1) for test plate and (2) for test bar
evident that all three types exhibit mixed failure modes. For single-coated (SC)
samples, the failure mode involves the breaks at interfaces of epoxy/test plate,
epoxy/coating, and coating/substrate. For double-coated (DC) and triple-coated (TC)
samples, the failure mode involves the breaks at the interfaces of epoxy/coating and
coating/substrate. To quantify the adhesion strengths σ (unit: MPa), the breaking load
F (unit: N) and cross-sectional area A (unit: mm2 ) of the test bar were used, with
the formula σ = F/A. The calculation indicated that SC had the maximum adhesion
strength of 5.72 ± 0.77 MPa, while the DC and TC had adhesion strength values
of 3.12 ± 0.43 and 3.05 ± 0.52 MPa, respectively. The thickness’s impact on adhe-
sion was minimal since the DC and TC had similar adhesion strengths. Furthermore,
the extensive size of coating/substrate interface failure suggests that the interface
transition layer is critical for the adhesion of DC and TC.
Previous studies have suggested that the formation of an iron oxide layer through
diffusion and precipitation can enhance the chemical adhesion at the enamel/steel
interface [8, 19]. However, the results obtained from the pull-off tests presented a
different outcome. It was observed that the SC exhibited significantly higher adhesion
strength compared to the DC and TC. Surprisingly, the transition layer decreased the
adhesion strength. For DC and TC, although the transition layer and enamel interface
exhibited strong chemical bonding, the mechanical properties of the transition layer
itself were found to be weak. This led to the fracture occurring within the transition
layer, resulting in reduced adhesion strength. The presence of residual oxide on
the fracture surface (Fig. 11b and c) further confirmed the internal breakage of the
transition layer. As a result, DC and TC showed little difference in adhesion strength.
3.3 Hardness and Indentation Cracking Resistance
Figure 12 illustrates the relationship between microhardness, crack probability, and

crack length for enamel coatings with varying silicon nitride amounts and under
different indentation loads. The indentation load will influence the microhardness,
with smaller loads resulting in higher microhardness values (Fig. 12a). For the N0
coating, the microhardness is approximately 450 HV. However, with increasing
silicon nitride, the microhardness significantly decreases. The N1.5, N2.5, N3.5,
N5, and N7.5 coatings exhibit average microhardness values of around 250, 130, 50,
25, and 25 HV, respectively. The decrease in microhardness with increasing silicon
nitride content can be attributed to the coarsened porous structure observed in the
enamel coatings (Fig. 7). This coarsening decreases the net section area as well as
apparent strength of the coatings [20, 21].
In the Vickers indentation test, each indentation produces four apex angles. To
assess the crack probability, the number of cracked and uncracked indentation apex
angles (CIA and UIA) were taken into account. The crack probability was calculated
using the formula NCIA /(NCIA + NUIA )×100%, where NCIA and NUIA represents the
number of cracked and uncracked indentation apex angles, respectively. Figure 12b
Fig. 12 Indentation results of enamel coatings, under various silicon nitride content and indentation
loads: a Microhardness, b crack probability, and c crack length [1]
illustrates the crack probability of enamel coatings with varying indentation loads.
It is observed that increasing the indentation load significantly increases the crack
probability for composite coating with silicon nitride by less than 5%. However,
this trend fails to capture the data for N5 and N7.5, indicating the exceptionally high
tolerance of these enamel coatings to indentation. When considering the same inden-
tation load, crack probabilities consistently decrease with increasing silicon nitride
content. This suggests that the silicon nitride enhances the resistance to cracking.
Using a crack probability threshold of 20%, the approximate crack initiation loads
are 0.98 N, 0.98 N, 2.94 N, and 4.90 N for N0, N1.5, N2.5, and N3.5, respectively.
N5 and N7.5 showed no signs of cracking.
Figure 12c presents the average crack lengths corresponding to various silicon
nitride amounts. Similar to the crack probability results, the crack length is affected
by the indentation loads and increases with higher loads. However, with increasing
silicon nitride, the crack lengths are reduced. This indicates that the silicon nitride
enhances the enamel coatings’ resistance against the crack propagation induced by
indentation loads. The data on crack length provides valuable insights into the crack
propagation behavior of the enamels. The consistent trend observed in Fig. 12c
supports the notion that the inclusion of silicon nitride improves the enamel coatings’
crack resistance.
3.4 Impact Resistance
Figure 13 depicts the surface appearances of different enamel coatings after impact.
In the case of N0 (without silicon nitride addition), spallation and cracking are evident
around the impact craters, indicating the fragility and susceptibility to damage.
However, for silicon nitride-modified enamels, no additional spalling or cracking
occurs around the craters. This observation suggests that the inclusion of silicon
nitride significantly mitigates the fragility of the enamel coatings, making them more
resistant to damage caused by impacts. The results shown in Fig. 13 support the
notion that silicon nitride addition improves the mechanical robustness and impact
resistance of the enamel coatings.
Fig. 13 Impact morphology of different enamel coatings after an impact of 3 J energy [1]
4 Thermal Shock Resistance of Composite Enamel

Coatings
4.1 Thermal Shock Damages
Figure 14 illustrates the surface appearances of the enamel coatings after thermal
shocks. Surprisingly, N0 is completely compromised at 19 thermal shock cycles,
with an extensively damaged coating/substrate interface (Fig. 14a). This failure of
N0 under a relatively low number of thermal cycles can be attributed to a combi-
nation of enamel cracking and steel oxidation. Thermal shocks induce the cracking
of the enamel, creating pathways for oxide penetration. This, in turn, facilitates the
oxidation of the substrate, leading to a reduction in the adhesion between the coating
and substrate. Consequently, the coating peels away from the substrate [22].
Enamels containing silicon nitride showed no visible macrocracks at 19 cycles,
prompting further testing up to 100 cycles. After 100 cycles, significant cracks were
observed on the surfaces of N1.5, N2.5, and N3.5, indicating the occurrence of
thermal shock-induced damage (Fig. 14b, c, and d). However, no noticeable spalling
or detachment of the coatings from the steel substrate was observed, suggesting the
presence of good bonding at the enamel/steel interface. Comparatively, the crack
width of N1.5, N2.5, and N3.5 (100 thermal cycles) was found to be thinner than that
of N0 after only 19 cycles. In addition, their cracks exhibited a more tortuous path, and
part of cracks were arrested before interconnecting with others (Fig. 14d). Moreover,
the areas enclosed by cracks in N1.5, N2.5, and N3.5 were considerably smaller (<1
Fig. 14 Enamel surface morphology following 19 cycles of 400 °C thermal shocks for a N0 and
100 cycles for b N1.5, c N2.5, d N3.5, e N5, and f N7.5 [1]
mm2 ) compared to N0 (ranging from 1 to 8 mm2 ). The reduced crack-enclosed area,

indicative of higher crack density, suggests an enhanced fracture energy capable of
counteracting the thermal strains experienced during heating and cooling. Addition-
ally, the presence of pores within the enamels offers space for the release of thermal
stresses accumulated during the thermal shock process. Remarkably, for high silicon
nitride additions (N5 and N7.5), no cracks were observed up to 100 thermal cycles,
highlighting their exceptional thermal resistance (Fig. 14e, f).
4.2 Dilatometric Analysis
Figure 15a shows the dilatometric curves of different composite coatings and steel
substrates. These curves of enamels exhibit a characteristic pattern commonly
observed in amorphous materials, characterized by a linear region following a signif-
icant peak. The glass transition temperature (T g ) and softening temperature (T s ),
which are the main characteristic temperatures of amorphous materials, were deter-
mined based on the knee point [23, 24] and the largest expansion, respectively
(Fig. 15a). Table 1 shows the coefficient of thermal expansion (CTE) averaged from
100 to 300 °C. It can be observed from Fig. 15a that the T g initially decreases as
the silicon carbide content increases. The T g of S0 was 346 °C, which decreased to
327 °C for S2.5. Subsequently, the T g gradually increases to 343 °C for S5 and 351 °C
for S7.5. A similar trend is observed for T s , which decreases from 389 °C for S0 to
361 °C for S2.5 and then increases to 373 °C for S5 and 385 °C for S7.5. The reduc-
tion of T g and T s for S2.5 results from the raised porosity observed in the enamel
coatings (Fig. 8). This porosity weakens the supportability of the enamel, resulting
in a partial offset of the expansion due to self-weight deformation. This interpreta-
tion is supported by the relatively weak T s peak observed for S2.5 (Fig. 15a). The
reinforcement effect of silicon carbide enhances the viscosity of composite enamels,
resulting in increased T g and T s of S5 and S7.5 [23, 25]. The results of T s also
confirm that a 530 °C sintering is feasible, which is approximately 150 °C above T s .
This higher sintering temperature allows for enamel flow and the production of the
uniform thickness (Fig. 7). Additionally, the CTE(100–300 °C) decreases from 16.3 ×
10–6 /°C (S0) to 14.3 × 10–6 /°C (S7.5), approaching the CTE of the steel (13.4 ×
10–6 /°C). This finding suggests the silicon carbide’s beneficial effects. The theory of
multiphase materials’ CTE also states that the second phase, which comprises pores
or low-CTE materials, will decrease the overall CTE of multiphase material [26].
To study the temperature dependence of CTE, it was determined up to T g at 10 °C
intervals. As given in Fig. 15b, the CTE does not exhibit a linear relationship with
temperature. Similar observations were also reported in previous studies [27, 28].
With increasing temperature, the CTE curve of enamel shows three stages: (i) a
rapidly increasing stage at initial temperature; (ii) a gradually increasing stage with a
linear trend at moderate temperatures; and (iii) a rapidly increasing stage around T g .
Stage III corresponds to the enamel’s viscoelastic behavior, which allows the glass
network with enough movement to relieve thermal stress within the enamel coating
Fig. 15 Dilatometric curves a and temperature-dependent CTE b of steel, S0, S2.5, S5, and S7.5
[13]
Table 1 Thermal and mechanical parameters of different composite coatings [13]

T g (°C) T s (°C) CTE (100–300 °C) E c (GPa) σc (MPa)
(×10–6 /°C)
S0 346 389 16.3 79.78 98.14
S2.5 327 361 15.8 66.49 80.63
S5 343 373 15.1 63.08 62.38
S7.5 351 385 14.3 57.11 35.19
[22, 29]. Consequently, only stages I and II were taken into consideration for the
calculation of residual stress in Sect. 4.3.
4.3 Residual Stress Analysis
The following assumptions were made:

(i) The coating and substrate are isotropic and homogeneous.
(ii) The bending deformation and moment can be neglected.
(iii) Stress is distributed equally across the thickness.
(iv) All deformation occurs within the elastic range.
We can proceed to calculate the residual stress using Fig. A1 and the above
assumptions.
As temperature changes from T1 to (T1 + dT ), we can express the deformation
coordination as Eq. (1):
εT ,c + ε F,c = εT ,s + ε F,s (1)

Fig. 16 Mismatched
thermal deformation
between coating and
substrate-induced residual
stress [13]
The complete form can be given by
dσc dσ s
αc (T1 )dT + (1 − vc (T1 )) = αs (T1 )dT + (1 − vs (T1 )) (2)
E c (T1 ) E s (T1 )
where εT and ε F denotes the strains that resulted from thermal and force, respectively.
α denotes the thermal expansion coefficient. σ denotes the residual stress. E denotes
the elastic modulus. v denotes the Poisson’s ratio. The subscripts c and s present the
coating and substrate, respectively.
The force balance equation can be stated as
F = ts bdσ s = −tc bdσ c (3)
According to Eqs. (2) and (3), from temperature T1 to temperature T2 , the coating’s
residual stress (σc ) could be represented as follows:
T2
αs (T ) − αc (T )
σc = 1−vc (T )
dT (4)
E c (T )
+ E s (T )ts (1
tc
− vs (T ))
T1
In the case of tc << ts , Eq. (4) can be simplified as
T2
E c (T ) · (αs (T ) − αc (T ))
σc = dT (5)
1 − vc (T )
T1
If the E c and vc are believed to be temperature independent, then Eq. (5) was
simplified to Eq. (6), which is consistent with the findings of reference [30].
T2
Ec
σc = (αs (T ) − αc (T ))dT (6)
1 − vc
T1
where σc can be compressive or tensile, depending on the relative values of

αc and αs .
If αs > αc , the coating will be compressed, and when σc > f c,c , the coating will
fail in compression.
If αs < αc , the coating will be tensioned, and when σc > f c,t , the coating will
fail in tension.
Noted that the following equation must be satisfied to prevent shear failure
between coating and substrate:
F = τ I bl > f c tc b (7)
where τ I denotes the interface shear strength.

For a specific material, thinner coating can easily meet the requirements.
tc
τI > fc (8)
l
The determination of Young’s modulus for composite coatings involved two steps,
first the silicon carbide strengthening and subsequently the pore weakening. To inves-
tigate the influence of second particles on Young’s modulus, the Halpin–Tsai model
[31] was used, as shown in Eqs. (9) and (10).
E m 1 + 2sq V pa
E dc = (9)
1 − q V pa
E pa
Em
−1
q= (10)
E pa
Em
+ 2s
where E dc denotes the Young’s modulus of composite when dense; E m denotes

Young’s modulus of the pure enamel matrix, which was 87.7 GPa in this study,
calculated using the Oliver–Pharr method [20]; E pa denotes the Young’s modulus
of SiC, assumed to be 447 GPa [21]; V pa and s denotes the volume fraction and the
aspect ratio of SiC, respectively.
As for the influence of pores on Young’s modulus, pores were considered to be a
second phase with zero Young’s modulus. Equations (9) and (10) can be converted
to Eq. (11).
E dc 1 − V po
Ec = (11)
1+ 1
V
2s po
where E c and V po denote Young’s modulus and volume porosity of porous composite
coatings, respectively.
Young’s modulus of pure and composite enamel coatings was determined using
Eqs. (9)–(11), as shown in Table 1. The results clearly show a decrease in Young’s
modulus as follows: S0 has a value of 79.78 GPa, while S2.5, S5, and S7.5 have values
of 66.49 GPa, 63.08 GPa, and 57.11 GPa, respectively. This decrease suggests that
the weakening impact caused by porosity plays a significant role in determining
Young’s modulus, owing to its higher change proportion.
The coating’s residual stress plays a crucial role in determining its susceptibility
to cracking during the cooling process. To calculate the residual stress, a simplified
form Eq. (12), consistent with the approach reported in reference [30], was employed.
T2
Ec
σc = (αs (T ) − αc (T ))dT (12)
1 − vc
T1
where αs and αc are the CTEs of substrate and coating, respectively; vc is the Poisson’s
ratio of the coating, as reported to be 0.27 for enamel [30].
Table 1 shows the obtained residual stress values for all coatings. It is evident
that the silicon carbide results in a significant decrease in residual stress. The values
decrease from 98.14 MPa for S0 to 80.63 MPa, 62.38 MPa, and 35.19 MPa for S2.5,
S5, and S7.5, respectively. For S0, where the residual stress exceeded its tensile
strength, presents numerous microcracks (Fig. 6a). With silicon carbide addition,
the residual stress decreased, and microcracks’ number and width decreased for S2.5
and S5, eventually no microcracks for S7.5 (Fig. 6b–d). As discussed in Sect. 2.3,
a transition layer, consisting of a mixture of enamel and iron oxides, occurs due
to the interdiffusion at the enamel/steel interface. This transition layer possesses
an intermediate CTE between the enamel and steel, facilitating thermal deforma-
tion compatibility. Additionally, the temperature-dependent nature of the enamel
coating’s Young’s modulus, as indicated by Wachtman’s equation [32], suggests a
potential decrease in actual residual stress at high temperatures. Therefore, the actual
residual stress is even lower than the calculated values for composite coatings.
4.4 Microstructure-Dependent Thermal Shock Resistance
The addition of silicon nitride in this study has demonstrated several benefits for
enamels, including a decrease in the possibility of cracking, reduction in crack length,
and increased tolerance to impacts and thermal shocks. These improvements can be
attributed to alterations in the microstructure, particularly the pores, which play
a significant role. For crack initiation and propagation, the driving force is typi-
cally external loads or thermal stresses. When this driving force exceeds a certain
threshold, initial cracks nucleate. If the elastic energy at the fracture tips of initial
cracks is adequate to provide the needed surface energy, these nucleated cracks
will keep propagating and dissipating energy [33, 34]. The presence of pores has a
considerable effect on the mechanical behavior of enamels. Pores can significantly
decrease the elastic modulus (E) [35], thereby reducing the elastic energy stored at
the fracture site [33]. Additionally, pores have advantages in terms of energy release,
passivation of the crack tip, and reduction of stress concentration [36, 37]. Conse-
quently, enamels with increased porosity exhibit shorter indentation crack lengths
(Fig. 12c). Moreover, crack length reduction and hardness decrease (Fig. 12a and
c) both indicate an increase in fracture toughness (K I c ), as described in the formula
[38]. Due to the critical indentation load being directly proportional and inversely
proportional to the fourth power of fracture toughness and the third power of mate-
rial’s hardness, respectively, it also raises with porosity (Fig. 12b) [39]. Furthermore,
the porous enamels exhibit the ability to absorb a greater amount of thermal shock
energy and can release more thermal stress induced by the mismatch of enamel and
steel [40, 41]. In addition, the presence of a porous structure is typically related to a
lower global in-plane elastic modulus, that enhances the material’s strain tolerance
and, consequently, improves its thermal shock resistance (Fig. 14) [42].
5 Corrosion Resistance of Composite Enamel Coatings
5.1 Corrosion Morphology Evolution
Figure 17 shows the corrosion evolution of composite enamel coatings. Upon initial
immersion (1 day), no corrosion is observed, although microcracks are evident in N0
and open pores are present in N7.5. After 30 days of immersion, rust spots begin to
appear in the cracks of N0 and pores of N7.5 (Fig. 17). In contrast, the other samples
still exhibit no noticeable signs of corrosion. At 105 days, clear rust spots are visible
for N0, N5, and N7.5, whereas a significant portion of N2.5 remains unaffected by
the corrosive effects of the 3.5 wt.% NaCl solution.
5.2 Electrochemical Study
Figure 18 illustrates the corrosion behaviors of coated and bare steels at an immersion
age of 1 and 105 days (3.5 wt.% NaCl solution). The saturated calomel electrode
(SCE) was used as a reference electrode. After 1 day of immersion, noticeable differ-
ences in cathodic and anodic behavior were found between the coated and uncoated
samples, as well as among the different composite coatings. For anodic polarization,
Fig. 17 Corrosion surface of composite coatings after 1, 30, and 105 days immersing in 3.5 wt.%
NaCl solution [1]
bare steel exhibits a distinct passivation from −0.9 to −0.7 V versus SCE, followed
by the onset of pitting higher than −0.7 V versus SCE (Fig. 18a). In contrast, the
samples coated with enamels demonstrate an increase in corrosion potential (E corr )
and a reduction of current density (I corr ) compared to the bare sample, indicating
an enhanced corrosion resistance [43]. Notably, N0 presents an I corr value that is
roughly one magnitude smaller than bare steel. Moreover, the I corr values of the
silicon nitride-modified samples exhibit a reduction of around 5–10 times compared
to N0.
For 105 days’ immersion tests, bare steel as well as N0, N2.5, N5, and N7.5
were investigated, as presented in Fig. 18b. It was observed that the Icorr values for
all coated samples converged to a similar value of approximately 10–6 A/cm2 . This
value is nearly one order of magnitude smaller than the bare steel (10–5 A/cm2 ).
Furthermore, the slopes of the anodic polarization curves exhibited a decreasing
trend with increasing silicon nitride content, indicating an expansion in the defect
area [44].
Tafel extrapolation [45, 46] was employed to obtain the Icorr for a quantitative
comparison. The extracted E corr and I corr are shown in Fig. 18c, d, respectively. For
Fig. 18 Polarization curves of coated and uncoated samples, at 1 day a and 105 days, b immersing
in 3.5 wt.% NaCl solution; extracted, c corrosion potential and d corrosion current density [1]
N0, the E corr increased and I corr decreased after 105 days’ immersion, indicating that
the pure enamel coating provides continuous corrosion resistance enhancement. By
contrast, though N5 and N7.5 presented best at 1 day, they had the largest degen-
eration (E corr decreases and I corr increases) at 105 days. The N2.5, which has a low
silicon nitride concentration, only showed a slight degeneration. This suggests that
the enamel coating’s corrosion barrier properties were dominated by its microstruc-
ture, with great pore size and amount (N5 and N7.5) resulting in severe deterioration,
whereas individual microcracks (N0) exhibiting enhanced corrosion protection with
prolonged time (discussed in Sect. 5.4).
Figure 19 presents the electrochemical curves of UC, S0, S2.5, S5, and S7.5 at
1 day’s immersion. From Fig. 19a, the OCP value of S0 (−0.680 V versus SCE)
was more positive compared to UC (−0.750 V versus SCE). For composite coat-
ings, the OCP values further shifted to −0.635, −0.609, and −0.568 V versus SCE
for S2.5, S5, and S7.5, respectively. This indicates that the amount of electrolyte
solution entering the coating/steel interface has decreased [47]. Figure 8b–d shows
the EIS results for all samples, with both Nyquist and Bode plots. From Fig. 8d,
with silicon carbide increasing, the high-frequency phase angle rose and the low-
frequency phase angle decreased. In addition, when composite coatings contained
more silicon carbide, the capacitive arc expanded, and the impedance rose (Fig. 8b,
Fig. 19 Electrochemical data of different samples, immersing in 3.5 wt.% NaCl solution for 1 day:
a OCP; b nyquist plots; c modulus; d phase angle; and e |Z|0.01 versus Rp [13]
c), suggesting an improved corrosion resistance. Figure 8e compares the EIS (|Z|0.01 )
and LPR (Rp ) data. It can be seen that the average |Z|0.01 of UC was 1.9 × 103
cm2 , and it increased to 8.9 × 103 , 1.0 × 105 , 1.1 × 105 , and 6.8 × 105 cm2
for S0, S2.5, S5, and S7.5, respectively. Additionally, the Rp of UC was 2.7 × 103
cm2 , which rose to 4.1 × 104 , 1.9 × 105 , 1.8 × 105 , and 8.1 × 105 cm2 for
S0, S2.5, S5, and S7.5 respectively, suggesting that silicon carbide improved the
enamel coating’s corrosion protection. Though |Z|0.01 was a bit lower than Rp , they
had similar trends. Therefore, |Z|0.01 may be utilized to undertake a semi-quantitative

evaluation of corrosion protection behavior [48–50].
Composite coatings’ corrosion behavior was found to be closely associated with
their microstructure, particularly the presence of surface microcracks. In the case of
S0, the observed microcracks (Fig. 6a) served as pathways for the corrosive elec-
trolyte to penetrate, resulting in a relatively low Rp value, which was only around
15 times compared to UC. However, with the silicon carbide addition (S2.5 and S5),
the number and width of microcracks reduced (Fig. 6b and c), leading to an increase
in the Rp value and an enhancement in corrosion protection. Remarkably, S7.5 was
free of any microcracks (Fig. 6d) because of its thermal expansion matched with
steel. Consequently, S7.5 exhibited the best corrosion protection, surpassing the UC
by around 300 times and the S0 by 20 times in terms of Rp .
5.3 Salt-Spray Test
A neutral salt-spray test was conducted to investigate the anti-corrosion behavior of

all coated rebars. Figure 20 shows the optical corrosion morphology evolutions of
PE, S2.5, S5, and S7.5 with exposure time. The UC sample suffered severe corrosion
with the corrosion products thoroughly covering the surface within 8 days, therefore
not shown here. Overall, all coatings provided adequate corrosion protection for steel
rebars. For PE, S2.5, and S5, slight signs of corrosion located at the defects were
observed at 8 days, and the corrosion area gradually enlarged with the exposure
time. However, they suffered different extents of corrosion and S5 was still superior
to PE and S2.5. For S7.5, corrosion signs appeared as late as 60 days, and the
corrosion was almost located at the edge, which was probably due to the undesirable
sealing. According to the weight changes shown in Fig. 20b, the UC sample generally
followed a linear weight increase trend with the rate of 2.99 mg/(cm2 d). For all
coated samples, the weight rapidly increased before 30 days due to the water uptake
of enamel coatings and not sufficiently dried before weighing. Following that, the
coated samples showed slow weight increase trends with rates of 0.18–0.25 mg/
(cm2 d), which was approximately 10–15 times lower than that of the UC sample.
Overall, significant improvements could be seen for coatings with higher silicon
carbide addition, which was consistent with the morphology observations.
5.4 Corrosion Evolution Mechanism
For coated steel in a 3.5 wt.% NaCl solution, the anodic and cathodic reactions involve
the oxidation of iron and the reduction of oxygen, respectively. Corrosion occurs if a
corrosive medium penetrates the steel surface, and the corrosion is primarily driven
by the localized active dissolution of iron. It is evident that the corrosion protection
Fig. 20 Optical corrosion morphology evolutions (a) and weight changes (b) of UC, PE, S2.5, S5,
and S7.5, with increasing exposure time under 35 °C and 5 wt.% NaCl neutral salt-spray condition
of the enamel coating is significantly affected by the defects, particularly through

defects that serve as pathways for the penetration of corrosive ions [44, 51].
Figure 21 illustrates the corrosion evolution process for enamel coatings with
cracks and pores. For N0, initial microcracks were present on its surface (Fig. 1).
These microcracks act as pathways for corrosive medium’s penetration, leading to
the poor corrosion resistance during the early immersion, despite having the smallest
porosity (Fig. 4). As corrosion progressed (Fig. 21), corrosion products accumulated
within microcracks and expanded in both directions, exerting compressive forces on
the coating. However, for N0, because of the high hardness and compressive strength
(Fig. 12a), and relatively small crack spacing, the expansion forces of corrosion
products were insufficient to cause coating damage. Instead, the corrosion products
compacted within the crack, obstructing the penetration of corrosive ions. Conse-
quently, an improvement in corrosion resistance of N0 was observed after immersing
for 105 days (Fig. 18d).
For N5 and N7.5 with pores, their superior hydrophobicity (Fig. 1c) made them
more resistant to infiltration. Therefore, during the initial stage of immersion, they
remained unwetted with pores in the form of air chambers (Fig. 21), enhancing the
physical barrier performance. However, with immersing, corrosive ions penetrated
across the coating arriving at the steel surface, leading to corrosion reactions and the
accumulation of rust within the pores. Unlike the corrosion products in microcracks,
the corrosion products within the pores exerted radial expansion forces, resulting in
the coating in tension. This expansion stress exceeds the tensile strength ( f t ) easily,
as f t is significantly lower than f c for brittle enamel materials [52]. Additionally, large
porosity of coating reduces its entire hardness and apparent strength, indicating the
presence of connecting pores. Consequently, the porous coating was more susceptible
to destruction caused by the expansion of corrosion products, and the corrosion
products were more prone to diffusion. This explains why N5 and N7.5 initially
Fig. 21 Corrosion process for enamel coatings with cracks and pores: at early, middle, and late
stages immersing in 3.5 wt.% NaCl solution [1]
exhibited the best physical barrier but experienced the most significant deterioration
over time. Notably, N2.5 only suffered minimal degradation due to its less pores,
smaller pore diameter (Fig. 3), and greater strength and hardness (Fig. 12a) when
compares to N5 and N7.5.
6 Summary
Engineering structures such as offshore launch towers and industrial facilities such as
boilers and chimneys are susceptible to the coupled threats of chloride corrosion and
high temperature. The silicon carbide/enamel and silicon nitride/enamel composite
coatings were developed, and the results showed that (i) the coating’s cracking resis-
tances against indentation and impact loads were greatly improved; (ii) the composite
enamel coatings can withstand more than 100 thermal shocks cycles; and (iii) the
composite enamel coated steel kept at least 10 times lower corrosion rate compared to
the uncoated one. Due to these improvements, the composite enamel coating became
a candidate material for applications in thermal shock and chloride corrosion coupled
environments.
Acknowledgements Financial support to complete this chapter by the National Key Research and
Development Program of China (No. 2022YFE0109200), the National Natural Science Foundation
of China (Nos. 51522905, 51778570, and 51879230), and China Postdoctoral Science Foundation
(No. 2022M722789) are greatly appreciated.
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Polycrystalline Diamond and Cr Double
Coatings Protect Zr Nuclear Fuel Tubes
Against Accidental Temperature
Corrosion in Water-Cooled Nuclear
Reactors
Irena Kratochvílová , Petr Ashcheulov, Jakub Luštinec, Jan Macák,

Petr Sajdl, and Radek Škoda
Abstract The chapter proposes a new strategy for protecting Zr alloy nuclear fuel
tubes from accidental temperature corrosion in water-cooled nuclear reactors. Protec-
tion of the zirconium alloy fuel tubes against accidental temperature corrosion in
water-cooled nuclear reactors is important for the safety and efficiency of nuclear
power plants, as corrosion in fuel tubes can lead to accidents and reduce the lifespan of
the fuel. The new strategy of zirconium alloy fuel tubes from accidental temperature
corrosion presented here involves a combination of polycrystalline diamond (PCD)
and chromium (Cr) layers. The PCD layer prevents direct interaction between the Zr
alloy surface and the hot water environment of the reactor and releases carbon into the
underlying Zr material to alter conditions for the penetration of oxygen and hydrogen.
The Cr layer helps to reduce corrosion by forming carbides and improving adhesion
of the coatings to the Zr alloy substrate. The chapter also discusses the importance
of the order of the Cr and PCD layers and the parameters affecting the corrosion
of coated ZIRLO tubes. Overall, this new strategy has the potential to significantly
improve nuclear safety.
I. Kratochvílová (B) · P. Ashcheulov · J. Luštinec

Institute of Physics of the Czech Academy of Sciences, Na Slovance 2, 182 21 Prague, Czech
Republic
e-mail: krat@fzu.cz
I. Kratochvílová · J. Luštinec
Faculty of Nuclear Sciences and Physical Engineering, Czech Technical University in Prague,
Břehová 78/7, 115 19 Prague, Czech Republic
J. Macák · P. Sajdl
Faculty of Environmental Technology, Department of Power Engineering, University of
Chemistry and Technology Prague, Technická 1903/3, 166 28 Prague, Czech Republic
R. Škoda
Robotics and Cybernetics, Czech Technical University in Prague, Czech Institute of Informatics,
Jugoslávských partyzánů 1580/3, 160 00 Prague, Czech Republic

84 I. Kratochvílová et al.
Keywords Polycrystalline diamond layer · accident tolerant fuel · Corrosion in

water-cooled nuclear reactors · ZIRLO fuel tubes surface corrosion · Plasma
enhanced chemical vapor deposition · Magnetron-sputtered Cr
1 Introduction
Nuclear energy does not emit carbon dioxide or other greenhouse gases during elec-
tricity generation, making it a low-carbon source of energy. Overall, the use of nuclear
energy needs to be carefully managed to ensure that its benefits are maximized while
minimizing any negative environmental impacts. Nuclear power plants also have the
advantage of being able to generate large amounts of electricity from a single unit,
which reduces the need for multiple power generation facilities in a single location.
However, nuclear energy also has its drawbacks. One of the main concerns is the
potential for accidents, which can result in devastating consequences for both human
life and the environment. The nuclear industry has implemented numerous safety
measures and regulations to minimize the risk of accidents, but accidents such as
Chernobyl and Fukushima have highlighted the need for continued improvements
in safety procedures [1, 2]. Many countries around the world continue to invest in
nuclear energy as a key part of their energy mix. The development of advanced nuclear
technologies, such as small modular reactors and fusion reactors, could potentially
address some of the concerns associated with traditional nuclear power plants and
contribute to a sustainable future energy system. Base-load nuclear power plants
operate at maximum capacity for roughly 90% of the time during a given year. This
is around two times that of coal or natural gas fossil power plants and almost three
times as much as solar or offshore wind power plants. This high load factor can be
achieved as nuclear plants require little maintenance and are designed to operate for
up to several years between refueling [3–7].
The fuel rods are assembled into fuel assemblies, and these assemblies are loaded
into the reactor core. During operation, the uranium dioxide fuel pellets undergo
fission, generating heat which is used to produce steam to generate electricity. As
the fuel is burned, fission products build up in the fuel and eventually the fuel must
be replaced.
The zirconium alloy cladding provides both mechanical support for the fuel pellets
and acts as a barrier to the release of radioactive fission products into the reactor
coolant. The cladding is exposed to high temperatures and corrosive environments
during normal operation, and the buildup of corrosion products can limit the heat
transfer from the fuel to the coolant. This can lead to overheating of the fuel and
ultimately, failure of the fuel rod. Therefore, managing corrosion of the cladding is
critical to the safe and efficient operation of nuclear reactors.
The majority of commercial nuclear reactors today are light water reactors: either
pressurized water reactors (PWRs) or boiling water reactors (BWRs). Because of this
important function, cladding integrity during fuel and reactor operation is crucial
for nuclear safety. Various degradation processes—including grid-to-rod fretting,
Polycrystalline Diamond and Cr Double Coatings Protect Zr Nuclear … 85
debris-induced failures, localized corrosion, waterside corrosion, and hydriding—

may challenge the integrity of the cladding tube [1, 2, 8–11]. In particular, zirconium
alloys are not only used as a material for nuclear fuel tubes but also for other structural
elements in fuel assemblies and the core internals of nuclear reactors, such as spacer
grids or complete pressure channels. The main reason for their use is the low para-
sitic absorption of neutrons and high resistance against radiation damage. Zirconium
alloys also possess very good mechanical properties, namely high melting tempera-
ture, and corrosion stability, which are maintained even during long-term exposure
to the extreme conditions produced in nuclear reactors, especially high neutron flux,
and high pressures [1, 11–15]. However, there is also a significant disadvantage:
during the reaction with Zr alloy fuel rod surface the water molecules are dissociated
and both oxygen and hydrogen ions penetrate into the Zr alloy [6, 8]. At temperatures
around 850 °C the α phase of zirconium changes to β phase which is more prone
to oxygen/hydrogen diffusion. The zirconium alloys changed by oxygen/hydrogen
diffusion are less dense and are mechanically weaker than the original material—their
formation results in blistering and finally cracking of the cladding. So as zirconium
alloys oxidize and zirconium hydrides are formed the ductility of the nuclear rod
is decreased. Oxygen and hydrogen uptake into the Zr alloy change the mechanical
properties of the core components and are an important criterion for nuclear fuel
licensing. In nuclear devices Zr alloys have to serve faultlessly and without main-
tenance, but even if their environmental parameters can become very extreme. The
extensive production of hydrogen gas can result in hydrogen-air chemical explosions.
Intense heat and pressure can trigger a reaction between the nuclear fuel Zr cladding
and the surrounding water stream causing the production of explosive hydrogen gas
resulting in several explosions as happened in Fukushima [2, 16–18]. This resulted
in the intensive research and accident-tolerant fuel (ATF) development programs
launched all around the world.
During high-temperature corrosion of ZIRLO, the ZrO2 phase is formed on the
surface of the alloy. ZrO2 is a ceramic material that has high thermal stability and
oxidation resistance. The ZrO2 phase can exist in several crystal structures, including
the tetragonal, monoclinic, and cubic phases. At high temperatures, ZrO2 can trans-
form from its metastable tetragonal phase to the more stable monoclinic phase.
This phase transformation is accompanied by a volume increase, which can lead to
cracking and spalling of the ZrO2 layer, exposing the underlying alloy to further
oxidation and corrosion [19, 20].
One of the approaches to address the corrosion and oxidation issues with zirco-
nium alloy fuel tubes is to apply a protective coating on their surface. The coating
material should have high corrosion resistance and adhere well to the substrate.
Thin coatings are expected to have a minimal effect on the behavior of the Zr-
based cladding during normal operation, i.e., high neutron irradiation stability and
high corrosion resistance. The coating should also have high thermal conductivity to
maintain heat transfer from the fuel to the coolant. By applying a protective coating,
the chemical reactions and physical interactions that cause corrosion and oxidation
of the fuel tube surface can be minimized, improving the overall performance and
safety of the fuel.
Various coating materials have been investigated, including pure metals, alloys,
ceramics, and MAX phases [21]. Among them, MAX phases such as Zr3 AlC2 ,
Ti3 SiC2 , and Cr2 AlC have shown promise as protective coatings due to their excel-
lent irradiation damage and corrosion resistance. However, these coatings may not
be suitable for use as ATF claddings due to their low oxidation resistance at elevated
temperatures. FeCrAl coatings have also been studied as protective coatings, and
they are adequate for normal conditions. However, they can undergo rapid degrada-
tion in high-temperature steam due to severe inter-diffusion between the coating’s
iron element and the zirconium substrate. Therefore, researchers are still exploring
various coating materials and designs to find suitable alternatives for use as ATF
claddings [17].
Chromium (Cr) coatings have been shown to exhibit high corrosion resistance in
supercritical water by forming a stable Cr2 O3 protective scale [15, 17]. However,
long-term steam oxidation of Cr coatings can lead to the generation of massive
structural defects such as bubbles and cracks due to the significant growth stress
caused by the large volume difference between Cr2 O3 and Cr [15, 16, 18]. This
can compromise the effectiveness of the coating as a protective barrier. Therefore,
researchers are investigating methods to reduce the growth stress and improve the
durability of Cr coatings, such as using multilayer coatings or incorporating other
materials to buffer the stress [10].
Several studies have shown that coating zirconium alloy surfaces with polycrys-
talline diamond (PCD) of nanocrystalline structure (NCD) layers grown using a
Linear Antenna Microwave Plasma-Enhanced Chemical Vapor Deposition (MW-
LA-PECVD) apparatus can effectively protect against oxygen and hydrogen uptake
in water-cooled nuclear reactor environments, both at normal operating and acci-
dent temperatures. Diamond has several desirable properties, such as high thermal
conductivity, resistance to chemical degradation, and low neutron absorption cross
section, making it an attractive coating material for nuclear fuel cladding. However,
more research is needed to optimize the growth processes. The composition of thin-
layer polycrystalline diamond (PCD) is not homogeneous, and it typically contains
both sp3-hybridized diamond (96%) and sp2-hybridized carbon phases. This compo-
sition enables PCD layers to have suitable thermal expansion properties even over a
wide range of temperatures, which helps to prevent delamination of the coating from
the substrate. The main function of PCD as a corrosion-protective coating is based
on the fact that the carbon from PCD can change the surface electrochemistry and
semiconductivity of the ZrO2 surface, which can enhance the corrosion resistance of
the zirconium alloy substrate [22].
ZIRLO fuel tubes were coated with a new double-layered coating consisting of a
technologically easily accessible and inexpensive PCD grown in an MW-LA-PECVD
apparatus and magnetron-sputtered Cr. Two double-layered coatings of ZIRLO fuel
tubes were used: one with a Cr layer as the bottom and a PCD layer as the top coating
and the other with Cr as the top and PCD as the bottom coating. Both protective
coatings have different and complementary anti-corrosion functions. The ability of
the coating to protect Zr nuclear fuel tubes against emergency temperature corrosion
has been tested at temperatures above 800 °C at which the so-called high-temperature
rapid corrosion occurs.
2 PCD Coating on ZIRLO Substrate: History

of Application
Due to its exceptional electrical, thermal, and optical properties, diamond is a very
attractive material for radiation detection [23, 24]. In [23] a device based on detector-
grade polycrystalline CVD diamond plate with graphite electrical contacts was
presented.
In [22, 25–27], a new polycrystalline diamond layer application was presented: the
composite thin polycrystalline/nanocrystalline diamond (PCD/NCD) coating signifi-
cantly reduced corrosion of Zr alloy nuclear fuel tube surfaces [28]. Tests have shown
that PCD coatings reduce oxidation and penetration of H into Zr alloy both with short-
term elevated emergency temperatures up to 1100 °C and long-term maintenance
temperatures (autoclave at 360 °C, resulting in 40% lower oxidation in PCD-coated
samples). This prolongs the use of fuel that is removed from the reactor mainly due
to surface corrosion rather than sufficient burning and thus improves nuclear safety.
The PCD layer is quasi-elastic and can withstand thermal loads, preventing direct
contact of the Zr alloys with the corrosive environment of the reactor. In addition,
carbon from the PCD layer penetrates the underlying Zr material, changing it to
significantly slow the corrosion process. The specific technology of PCD formation
results in high-layer adhesion to the surface. Fuel cells covered by PCD are being
tested for long-term use in the Halden Norwegian reactor and have been selected by
Westinghouse as fuel-resistant [28].
The study in [28] discusses the behavior of PCD-coated Zr alloys in a neutron
flux environment, which was simulated using Fe ion beam irradiation. The results
show that the NCD films grown using the MW-LA-PECVD method exhibit structural
integrity after Fe2+ beam irradiation and hot steam processing. The effects of neutron
irradiation on chemical vapor-deposited diamonds were also investigated, and despite
an increase in unit-cell volume, the crystalline structure remained stable.
The PCD layers grown using the MW-LA-PECVD method consist of diamond and
inclusions of anisotropic graphite. The study [29] shows that PCD layers of different
thicknesses (300–700 nm) can decrease oxygen and hydrogen uptake into ZIRLO
fuel tubes and plates processed in hot water at 360 °C for more than 100 days under
primary circuit conditions in Pressurized Water Reactors (PWR) according to ASTM
standard procedures. The protective performance of PCD layers was also evaluated in
hot steam at 400 °C for 4 days and at extremely high hot steam temperatures of 900–
1100 °C for 1 h and at 1200 °C for 30 min [25, 27, 29]. It was explained that the carbon
from the PCD layer enters into the underlying Zr alloy, resulting in a significant
change in its structural, chemical, and physical parameters, leading to a lower uptake
of hydrogen and oxygen into the material and resulting in a lower degradation of
ZIRLO fuel tubes and ZIRLO plates in hot steam or water environments. Overall,
the study suggests that protective PCD layers can prolong nuclear cladding lifetime
and enhance nuclear fuel burnup.
3 Growth of PCD Layer on ZIRLO Substrate
As the number of possible applications for polycrystalline increases, there is constant

development and enhancement of the film properties. Polycrystalline diamond has
further advantages if in the form of a thin film (compared to a thicker polycrystalline
layer), such as a smoother surface, less deposition time, and less light absorption.
PCD thin films can have tailored properties, including controlled grain size and orien-
tation, and can be synthesized with other materials to form composites with enhanced
properties. PCD thin films are also highly resistant to wear and chemical corrosion,
making them suitable for various applications in harsh environments. Overall, the
development of PCD thin film technology has greatly expanded the potential appli-
cations of diamond in various fields, including electronics, biomedicine, energy, and
aerospace [30, 31].
PCD films can be synthesized using a chemical vapor deposition (CVD) technique.
In this method, a substrate is placed in a reactor chamber and heated to a high
temperature. A gas mixture containing a carbon source, such as methane, and a
hydrogen carrier gas is then introduced into the chamber. RF energy or a microwave
discharge is used to dissociate the gas mixture and create a plasma. The carbon atoms
in the plasma then deposit onto the substrate surface and form diamond crystals. By
controlling the deposition conditions, such as gas composition, pressure, temperature,
and deposition time, the microstructure, morphology, and properties of the PCD films
can be tailored to meet specific requirements for various applications [32, 33].
The suitability of PCD for various applications depends on material parameters
like substrate nature, substrate dimensions, the possibility of nonplanar geometries,
surface morphology, electrical conductivity, the capability of device fabrication, elec-
trochemical properties (given by the sp3 /sp2 ratio) and favorable cost. PCD diamond
films have advantages compared to single-crystalline forms (like low-cost and large
area) thus a variety of applications were meanwhile expanded beyond the clas-
sical mechanical use of diamond. These applications include PCD polycrystalline
diamonds for optical, electronic, and electrochemical applications, PCD diamond
grades for thermal management, and PCD films for a number of further advanced
applications [33].
Industrial applications of the polycrystalline diamond grown on large area
substrates, 3D shapes, at low substrate temperatures, and on standard engineering
substrate materials require novel plasma concepts. One of them is the application of
the non-MW-LA-PECVD apparatus for polycrystalline diamond growth (see Fig. 1).
The MW-LA-PECVD apparatus consists of a vacuum system, a growth chamber, a
pressure control system, a process gas delivery control system, a microwave power
controller and delivery system, a water cooling system and an air cooling system. The
MW-LA-PECVD apparatus is capable of producing both continuous wave and pulsed

microwaves, with maximum powers of 3 kW and 10 kW, respectively. Microwave
power is controlled by the use of a pulse generator, magnetron heads, rectangular
tunable waveguides, and coaxial power distributors. Microwaves are delivered into
the growth chamber in a linear form by four pairs of antennas enclosed in quartz
envelopes. The linear microwave plasma sources are arranged parallelly to one
another above the substrate holder.
Temperature of the samples can be estimated during the diamond deposition by
a Williamson Pro 92-38 infrared thermometer capable of measurements in the 400–
1000 °C range. The samples (e.g., Zr alloy tubes/rods) are usually immersed/spin-
coated in a dispersion containing nanodiamond particles, which act as seeds and
therefore induce nucleation sites for PCD growth. The samples are then mounted
on a substrate or on a specially designed sample holder to ensure that the whole
circumference of the sample/tube is exposed to plasma, and placed into the reactor
chamber.
The MW-LA-PECVD apparatus chamber allows for the deposition of PCD on
substrates with sizes as large as 50 × 30 cm2 using a gas mixture of H2 + CH4 +
CO2 at low process pressures (<1 m Bar). Due to its diffuse plasma properties (due
to a combination of low process pressures and high-frequency pulsed microwaves
Fig. 1 Photograph of Zircaloy2 rods during PCD deposition. Above the Zircaloy2 rods the linear
antennas (from which diffuse plasma is formed) can be seen housed inside quartz tubes which
act as air/vacuum interfaces. The apparatus is capable of producing both continuous waves (at a
maximum of 3 kW) and tunable pulsed microwaves (at a maximum of 10 kW). The growth chamber
potentially allows the deposition on substrates up to the size of 500 mm × 300 mm [25]
Fig. 2 Secondary electron

micrographs of the
PCD-covered Zircaloy2
surface [25]
while maintaining high concentrations of atomic hydrogen), the MW-LA-PECVD

system enables growth on 3D objects with good homogeneity over large areas, even
if the object is held static during the deposition.
The PCD films were grown on ZIRLO substrates in MW-LA-PECVD system
using a gas mixture of H2 , CH4 , and CO2 at various ratios and low process pressures
ranging from 0.5 to 2 mbar. The microwave power used was up to 10 kW pulsed,
and the growth time was up to 8 h. The average substrate temperature during growth
was measured to be ca. 500 °C. The final protective layer is therefore a homogenous
polycrystalline diamond layer that is formed using the chemical vapor deposition
method. Such layers are usually characterized by their thickness, which ranges from
100 nm to 50 μm, and the size of the crystalline cores in the layer, which ranges
from 10 to 500 nm. The PCD coating typically consists of sp3 and sp2 carbon phases,
with a high crystalline diamond content of 96%. Usually, various techniques are
used to analyze the quality of PCD-coated ZIRLO surfaces (before and after hot
steam/water processing), which include Raman spectroscopy, optical microscopy,
Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM),
Electrochemical Impedance Spectroscopy (EDS), Secondary Ion Mass Spectroscopy
(SIMS), X-Ray Diffraction (XRD), X-Ray Photoelectron Spectroscopy (XPS), and
Electrochemical Impedance Spectroscopy (EIS) (as presented on Figs. 2 and 3).
4 Cr Coating on ZIRLO Substrate
The physical sputtering process is a method for physically vaporizing atoms from a
solid surface by using energetic particles, typically ions of a gaseous material that are
accelerated in an electric field. This process is commonly used for depositing metals,
Fig. 3 Raman spectra of the PCD-coated Zircaloy2 sample (a), PCD-coated Zircaloy2 sample after
hot steam oxidation at 950 °C. The 1332 cm−1 peak is typical of diamond. The broadband visible at
1400–1550 cm−1 is a signature of amorphous carbon located within the grain boundaries, the band
at ~1580 cm−1 was assigned to graphite, and the ~1620 cm−1 peak was attributed to the presence
of “graphite-like” disordered carbon [25]
alloys, and compound textiles, among other materials, onto a substrate material to
form a metallic film [34–36].
In plasma-based sputtering, which is the most common form of sputtering, a
plasma is present and positive ions are accelerated toward the target, which is at a
negative potential with respect to the plasma. At low pressures, these ions reach the
target surface with an energy that is determined by the potential drop between the
surface and the point in the electric field at which the ion is formed. At higher pres-
sures, however, the ions undergo physical collisions and charge exchange collisions,
leading to a spectrum of energies of the ions and neutrals bombarding the target
surface.
Magnetron sputtering coating is a vacuum coating process that falls under the
category of physical vapor deposition (PVD) and is mainly used for depositing metals,
alloys, compound textiles, and other materials with a thickness of up to 5 μ. A target
or a metal precursor, that is desired to be deposited, is bombarded with energetic
ions of inert gases (e.g., argon or helium). The forceful collision of these energetic
ions with the target ejects target metal atoms into space. These metal atoms are then
deposited on the substrate material forming a metallic film. The target is cooled by
water so that little radiation heat is generated. A wide range of metals including
silver, copper, brass, titanium, silicon, silicon nitride, and carbon nitride can be used
[37].
In [22], the fabrication of Cr coatings on ZIRLO fuel tubes was done through a
magnetron sputtering process in a vacuum chamber. The process involved the use of
a chromium target with a diameter of 50 mm, which was cleaned of native oxides
and contaminants through pre-sputtering for 2 min before deposition. The vacuum
chamber was evacuated to a pressure of 5·10–5 Pa, and an argon environment was
introduced into the deposition chamber via a flow controller. The gas pressure was
adjusted to 1 Pa by adjusting the argon flow to 20 sccm, and a DC voltage of 400 V

was applied to the sputtered target to generate plasma discharge in the deposition
chamber. The DC power was set to 200 W. To prevent deposition during the cleaning
process, a shutter was used in front of the sputtered target. The Cr coating was grown
on a ZIRLO tube that was placed 5 cm away from the target, with the tube’s axis
parallel to the target surface. The tube was rotated at a rate of 10 turns per minute
during the deposition process to ensure even coverage. The deposition process took
100 min, and the thickness of the completed Cr coating was approximately 3–4 μm.
5 Hot Steam Oxidation
In [22], the high-temperature steam corrosion of the PCD-coated ZIRLO (ZIRLO/

PCD), Cr-coated ZIRLO (ZIRLO/Cr), and PCD and Cr double-layer-coated ZIRLO
were compared. In the case of double coating, ZIRLO was coated either by PCD
(300 nm thick) as the bottom layer and Cr (3–4 μm thick) as the top layer (ZIRLO/
PCD/Cr) or with Cr (3–4 μm thick) as the bottom layer and PCD (300 nm thick) as
the top layer (ZIRLO/Cr/PCD). Coated and bare ZIRLO fuel cladding tubes were
placed in hot steam furnaces. Two devices were used: 1. Netzsch STA449 F3 Jupiter
(NETZSCH-Gerätebau GmbH, Selb, Germany) installed in the Institute for Applied
Materials, Karlsruhe Institute of Technology, Germany for the hot steam oxidation
kinetics and 2. the resistance furnace installed in the Institute of Nuclear Fuels, Prague
Czech Republic (UJP Praha), for standard hot steam oxidation measurements.
The Netzsch STA449 F3 Jupiter was used in [22] to perform hot steam oxidation
kinetics experiments on four different materials: ZIRLO, ZIRLO/PCD, ZIRLO/Cr,
and ZIRLO/PCD/Cr. The heating and cooling rates were 20 °C/min and 100 °C/
min, respectively, and the steam injection started 5 min after reaching the isothermal
plateau and continued until the end of the isothermal phase. The atmosphere during
the oxidation phase was a mixture of 2 g/h H2 O and 50 ml/min Ar, which corre-
sponded to a PH2 O of 0.45 bar. The chamber pressure was approximately 1 bar.
The steam flow conditions were fixed in the experimental equipment to ensure
comparability across the different materials tested.
The resistance furnace was used to perform hot steam tests on ZIRLO, ZIRLO/
Cr, ZIRLO/PCD/Cr, and ZIRLO/Cr/PCD samples. The tests were conducted at a
constant temperature and low pressure (0.1 MPa) according to standard method-
ology. The temperature was measured using B-type thermocouples placed next to
the specimen surface. After the test, the specimens were quenched in ice water,
deburred, cleaned, and weighed. The weight gain of the samples was calculated
as the difference between the sample weight before and after oxidation, including
the weight of the material released during the hot steam/autoclave treatments. The
weight gain was normalized to the relevant/coated area of the tube surface, taking
into account that the PCD layer was unable to fully penetrate the tube’s internal
structure. The weight gain of the coated parts of the tubes (fully covering the outer
surface and covering 40% of the inner surface) was then recalculated to obtain the
weight gain of the coated parts of the samples in mg dm−2 .
5.1 Hot Steam Oxidation of PCD-Coated ZIRLO
It should be noted that the protective effect of PCD coating consisting of sp3 and
sp2 carbon phases with a high crystalline diamond content (96%) on ZIRLO fuel
tubes may vary depending on the specific conditions and parameters of the oxidation
process [22, 27, 29, 38]. However, studies have consistently shown that the PCD
coating can provide significant protection against oxidation and hydrogen uptake
in ZIRLO fuel tubes, even when the coating is cracked. Additionally, the carbon
from PCD coating has been found to penetrate the ZrO2 layer during hot steam or
hot water processing, providing active protection [27]. Studies have also shown that
PCD-coated ZIRLO tubes exhibit reduced oxidation compared to uncoated ZIRLO
tubes under similar hot steam processing conditions. Specifically, after 40 min at
850 °C in a hot steam furnace, the oxidation of 500 nm thick PCD-coated ZIRLO
tubes was reduced by 11% compared to that of uncoated ZIRLO tubes treated under
the same conditions. The weight gain of hot steam processed PCD-covered ZIRLO
was 0.33 g/dm2 , while the weight gain of the bare ZIRLO hot steam processed sample
(40 min at 850 °C) was 0.37 g/dm2 .
PCD coating reduces Zr nuclear fuel cladding oxidation compared to that of
uncoated ZIRLO samples with the same treatment: at operating temperatures, oxida-
tion was typically reduced by 40%; under treatment at 1000 °C for 30 min, oxidation
was typically reduced by 17–20%, and hydrogen uptake into the Zr alloy was also
reduced.
In [27], SIMS suggests that carbon from the PCD layer effectively diffuses into
the ZrO2 layer. The study also found that the carbon content in the ZrO2 layer
decreased with increasing distance from the surface, indicating that the carbon was
not homogeneously distributed within the layer. Furthermore, it was found that the
concentration of carbon in the ZrO2 layer was highest for samples coated with PCD
alone, and lower for samples coated with a combination of PCD and other coatings,
such as Cr or PCD. This suggests that the presence of other coatings may inhibit
the diffusion of carbon into the ZrO2 layer. Overall, these findings suggest that the
incorporation of carbon into the ZrO2 layer through the use of PCD coatings can
significantly reduce Zr oxidation and improve the performance of Zr-based nuclear
fuel cladding in high-temperature and high-pressure environments; Figs. 4 and 5.
During high-temperature corrosion of ZIRLO, the ZrO2 phase is formed on the
surface of the alloy. But at high temperatures, ZrO2 can transform from its metastable
tetragonal phase to the more stable monoclinic phase. This phase transformation can
lead to cracking and spalling of the ZrO2 layer, exposing the underlying alloy to
further oxidation and corrosion. Proper carbon amount in ZrO2 diffused from PCD
coating can change the ZrO2 tetragonal phase transformation process [38] so that the
a) b)
1 2 3
1 2 3
Fig. 4 a TEM micrograph of a section cut from a PCD-coated ZIRLO tube showing the (1) diamond
layer and (2) Zr oxide layer on top of the (3) Zr alloy. b TEM image showing the presence of an
amorphous carbon layer between the PCD and the Zr oxide layer after oxidation [27]
Fig. 5 SIMS data from o

NCD/PCD-coated ZIRLO C, 1000 C NCD coated ZIRLO
tube after 60 min at 1000 °C C, NCD coated ZIRLO
in a hot steam environment, a 3000
peak in carbon content was
within the ZrO2 layer 2 μm
13C (counts/s)
below the sample surface. 2000

NCD/PCD coating on the
ZIRLO sample was 0.5 μm
thick. The carbon depth 1000
profiles are plotted from the
sample surface [27]
0
0 1000 2000 3000 4000

Depth (nm)
tetragonal ZrO2 protectivity against ZIRLO corrosion is extended in time under the
given conditions, or works up to high temperatures.
The Zr alloy surface has a Zr oxide film with many defects, specifically oxygen
vacancies, which cause it to have n-type semi-conductivity. This means that there
are electron donor defects in the dielectric ZrO2 , which are located in the forbidden
gap close to the conductivity band.
Mott–Schottky tests were performed on ZIRLO samples that were exposed
to high-temperature steam. The non-coated samples showed plain n-type semi-
conductive behavior, while the PCD-coated samples showed mixed n- and p-type
semi-conductivity. The corresponding donor and acceptor densities were 2–3 ×
1016 cm−3 and 4.4 × 1016 cm−3 , respectively.
The Zr/ZrO2 behaves like a metal/n-type semiconductor junction, creating a space-
charge area on the interface. Due to the n-type semi-conductive oxidized layer,
oxygen anions originating from water dissociation are attracted by the positive charge
of the depletion layer at the n-semiconductor/Zr interface. However, oxygen anions

have a lower probability of passing electrons through the n-type semi-conductive
ZrO2 /Zr alloy interface.
On the other hand, the n-semiconductor/Zr interface enables oxygen anions to be
absorbed by oxygen vacancies at the ZrO2 /Zr interface. This reaction results in the
interaction of the zirconium and oxygen to form ZrO2 and oxygen vacancies.
In references, it was found that diamond-coated Zr nuclear fuel rods are protected
against accidental high-temperature steam/water corrosion. This protection is due
to the fact that carbon diffuses from the diamond coating into ZrO2 , changing its
physical properties and making it a compensated semiconductor with mixed n- and
p-type characteristics. As a result, oxygen anions from water dissociation are not
strongly attracted to the Zr/ ZrO2 interface, and their interaction with zirconium
vacancies is reduced. This disruption of the oxidation process on the anodic side of
the corrosion loop provides protection against corrosion.
This protection is stronger at higher temperatures and/or longer exposure times,
as more carbon from the diamond coating is released and penetrates deeper into the
ZrO2 . The authors in [38] calculated that the addition of carbon from the diamond
coating into ZrO2 reduces the electric field generated by the space charge at the Zr/
ZrO2 interface from 1.445 × 10–7 to 1.083 × 10–7 V.
Chemical and electrochemical changes caused by diamond coating were also
investigated [38]. ZrOC and ZrC groups were found to be formed on the ZIRLO
surface, which attract hydrogen and create H+ and ZrOC, H+ and ZrC complexes. The
strong absorption of H+ on ZrOC and ZrC disrupts the water dissociation equilibrium,
reducing the oxidation process. Additionally, ZrOC and ZrC groups contribute to the
limited hydrogen incorporation into the ZIRLO rod surface. The uptake of hydrogen
into uncoated ZIRLO was found to be an order of magnitude higher than the hydrogen
uptake into carbon-coated ZIRLO samples after all tested hot steam treatments [38].
Carbon can react with ZrO2 to form a carbide phase, which can increase the
stability of the tetragonal ZrO2 phase at high temperatures [27, 29]. The presence of
carbon can also lead to the formation of ZrC, which can act as a nucleation site for
the formation of the tetragonal ZrO2 phase. However, excessive carbon can also lead
to the formation of a monoclinic phase, which is less stable at high temperatures.
Therefore, the effect of carbon on phase transformation in ZrO2 depends on the
amount of carbon present and the conditions under which the material is exposed to
high temperatures [38].
In [38], according to accidental temperature tests, the corrosion of the coated
ZIRLO began to be affected by carbon diffusion (changing chemical and physical
ZrO2 properties) approximately after 2.5 min in 900 °C steam. After 20 min at
900 °C in a hot steam furnace, the oxidation of the diamond coated ZIRLO rod
was strongly affected by carbon diffusion: coated ZIRLO corrosion was reduced by
~20% compared to that of the uncoated ZIRLO rod treated under the same conditions.
Coating had also a stabilizing effect on the tetragonal ZrO2 phase and reduced the
number of cracks in the ZrO2 layer.
At very high temperatures, such as 1000 °C and above, the protective effect of
the diamond coating on the ZIRLO rods is reduced. This is because the hydrogen
complexes formed with ZrOC and ZrC groups in the diamond coating may become
unstable at these high temperatures. Water dissociation on ZrC and ZrOC is more
likely to occur than on the H+ /ZrOC or H+ /ZrC complexes or even ZrO2 molecule,
which can lead to changes in the formation and disintegration of all the complexes
and the rate of carbon diffusion. These dynamic changes, which are dependent on
temperature and diamond content in the coating, can affect the conditions for acci-
dental temperature water dissociation and may reduce corrosion of ZIRLO fuel rods.
In previous tests [25, 29], it was found that the corrosion of diamond-coated nuclear
rods was lower than that of uncoated rods when subjected to high-temperature steam/
water treatments up to 1200 °C.
The ability of the diamond coating to protect ZIRLO against hot steam corro-
sion depends on the fraction of the sp2 carbon phase in the coating. Soft, sp2
carbon controls the amount of the ZrOC/ZrC complexes and thus the electrochem-
ical balance. If more soft carbon is available to make more H+ /ZrOC and H+ /ZrC
complexes, the hydrogen ions are released from complexes at temperatures round
1000 °C and thus the rate of water dissociation is increased. When the ZIRLO nuclear
fuel rod surface was coated by PCD layer containing >95% of the diamond phase,
the corrosion was reduced by 25% after a 60 min exposition in 1000 °C hot steam
[38].
5.2 Corrosion of ZIRLO Coated by Magnetron-Sputtered Cr
The Cr coating on the ZIRLO surface provides protection against hot steam corro-
sion by forming a dense layer of Cr2 O3 , which acts as a diffusion barrier for oxygen
and reduces the oxidation rate in high-temperature steam environments. The inter-
action between Cr and Zr produces a Cr–Zr interdiffusion layer that improves the
adhesion between the coating and the Zr substrate. When the chromium oxide layer
grows to a certain extent, Zr diffuses upward, reducing the Cr2 O3 oxide and creating
monoclinic ZrO2 , which creates paths for further oxygen uptake into the Zr alloy
substrate. In our study, the Cr-coated Zr alloy surface had a layered phase struc-
ture, with a Cr-rich sublayer on the surface, followed by chromium oxide (Cr2 O3 ),
residual metallic Cr, and the Zr–Cr intermetallic phase and oxidized Zr-αZr(O) in
the inward direction. The characterization of the coated surface was performed using
techniques such as SEM, Raman spectroscopy/optical microscopy, and electrochem-
ical impedance spectroscopy (EDS). The results indicate that the Cr coating provides
effective protection against hot steam corrosion of ZIRLO.
5.3 Hot Steam Oxidation of PCD and Cr-Coated ZIRLO
Additionally, in the results of accidental-temperature water/steam tests, ZIRLO/PCD

were also compared to ZIRLO/Cr and double coated of ZIRLO: ZIRLO/PCD/Cr and
ZIRLO/Cr/PCD (Fig. 6). Coated and bare ZIRLO fuel cladding tubes were placed
for 30 min in a 900 °C hot steam furnace followed by 40 min in a 1000 °C hot steam
furnace. The measured weight gains were caused by oxidation and hydrogen uptake
into the hot steam-tested samples.
The hot steam oxidation kinetics of different coatings on ZIRLO fuel cladding
tubes were measured using a hot steam furnace. The initial oxidation stage (<5 min)
was affected by carbon diffusion, with the polycrystalline diamond (PCD) coating
diffusing carbon into the zirconium alloy and the Cr coating acting as a water-
impermeable barrier. After longer exposure times, the Cr coating showed stronger
anti-corrosion effects compared to the PCD coating. After 30 min at 900 °C and
40 min in a 1000 °C hot steam furnace, the PCD-coated ZIRLO tubes showed a
5% reduction in oxidation compared to uncoated ZIRLO tubes, while the Cr coating
reduced oxidation by 39%, and the PCD/Cr double-layer coating reduced corrosion
by 25% (Table 1 and Fig. 7).
It appears that the double-coated ZIRLO samples with both PCD and Cr layers
exhibited the best resistance to hot steam oxidation, with a reduction in corrosion
ranging from 25 to 47% compared to uncoated ZIRLO samples. The specific arrange-
ment of the coatings, with the Cr layer either on the top or bottom and the PCD layer
Table 1 Relative weight gains of the ZIRLO samples with protective coatings after the hot steam
furnace tests (Netzsch STA449 F3 Jupiter). The results are expressed in % of uncoated ZIRLO
weight gain and in g dm−2 . Samples were subjected to hot steam at a temperature of 900 °C for
30 min and 1000 °C for 40 min each (full time)
Sample ID 900 °C for 30 min 900 °C for 30 min and 1000 °C for
40 min
Rel. (% wt) Abs. (g dm−2 ) Rel. (% wt) Abs. (g dm−2 )
ZIRLO 100 0.62 100 1.23
ZIRLO/PCD 85 0.53 95 1.07
ZIRLO/PCD/Cr 65 0.40 75 0.92
ZIRLO/Cr 39 0.24 61 0.75
Fig. 6 a SEM micrographs of the ZIRLO/PCD/Cr surface, b hot steam-tested ZIRLO/Cr surface,
and c hot steam-tested ZIRLO/PCD/Cr surface [22]
Fig. 7 The hot steam oxidation kinetics of ZIRLO samples oxidizing under accident conditions of
a reactor: 900–1000 °C in a hot steam furnace (Netzsch STA449 F3 Jupiter). After 30 min of heating
at 900 °C (a), the corrosion increased in all cases: ZIRLO, Cr-coated ZIRLO, and Cr/PCD-coated
ZIRLO. Raising the temperature of hot steam up to 1000 °C caused a further increase in ZIRLO
corrosion in all cases [22]
grown on either seeded or unseeded surfaces, had a significant impact on the effec-
tiveness of the coating. The results suggest that the combination of PCD and Cr layers
can provide effective protection against hot steam corrosion in ZIRLO nuclear fuel
cladding tubes, Table 2.
Table 2 Relative weight

Sample ID 900 °C for 30 min and 1000 °C for
gains of the ZIRLO samples
40 min
with protective coatings after
the hot steam resistance Rel. (% wt) Abs. (g dm−2 )
furnace tests (the resistance ZIRLO 100 0.540
furnace installed in the
Institute of Nuclear Fuels, ZIRLO/PCD/Cr 80 0.432
Prague Czech Republic). The ZIRLO/Cr/PCD 53 0.286
results are expressed in % of ZIRLO/Cr/PCD* 58 0.315
uncoated ZIRLO weight gain
and in g dm−2 . Samples were ZIRLO/Cr 69 0.372
subjected to hot steam at a
temperature of 900 °C for
30 min and 1000 °C for
40 min each (full time)
5.3.1 Corrosion of ZIRLO Coated by PCD (Bottom) and Cr (Top)

Layers
The double-layer coating with PCD (300 nm thick) as the bottom layer and Cr (3–
4 μm thick) as the top layer reduced the hot steam-tested ZIRLO tube corrosion
by 20–25% compared to unprotected hot steam-tested ZIRLO. Though our recent
results demonstrate the successful application of PCD and PCD/CrAlSiN double
coating for the protection of ZIRLO tubes [27], the protection ability of the PCD as
bottom and Cr layer as top layer was less effective, than in the case of Cr as bottom
and PCD as top coating and even just Cr single-layer coating.
The EDS analysis of the hot steam-tested ZIRLO/PCD/Cr sample shows atomic
percent profiles similar to those in the case of the hot steam-tested ZIRLO/Cr sample.
The profiles show the presence of chromium oxide (Cr2 O3 ), residual metallic Cr,
carbon-rich layer, Zr–Cr interdiffusion layer, Cr2 O3 , and oxidized Zr (ZrO2 ). SEM
and energy-dispersive spectroscopy have detected a narrow carbon-rich layer above
the Zr–Cr interdiffusion layer, and XPS has shown a relatively small amount of Cr
carbides.
The amount of Cr carbides is an essential factor in reducing ZIRLO corrosion, as
they are effective in improving the oxidation resistance of the substrate. However, in
the case of the hot steam-tested ZIRLO/PCD/Cr sample, the chromium sputtered on
the PCD coating creates only a small amount of Cr carbides, which are too far from
the sample surface. As a result, the oxidized Cr takes part in the standard Cr-coated
ZIRLO corrosion loop, where Zr reduces the Cr2 O3 oxide, creating monoclinic ZrO2 ,
and making paths for further oxygen uptake into the Zr alloy substrate.
Furthermore, SEM and optical microscopy have revealed poor adhesion of Cr to
the PCD layer. Overall, the protection ability of the PCD as the bottom layer and Cr
as the top layer was found to be less effective than the Cr as the bottom layer and
PCD as the top layer, and even just the Cr single-layer coating.
5.3.2 Corrosion of ZIRLO Coated by Cr (Bottom) and PCD (Top)

Layers
The double-layer coating with Cr as the bottom layer and PCD as the top layer
exhibited the best ability to slow down the oxidation process and protect the ZIRLO
cladding against hot steam oxidation. This was demonstrated by a 47% reduction in
overall corrosion compared to bare ZIRLO. The thickness of the oxidized ZIRLO
substrate was less than 3 μm. The EDS analysis of hot steam-tested ZIRLO/Cr/
PCD revealed a more homogeneous distribution of carbon under the top Cr2 O3
layer compared to hot steam-tested ZIRLO/PCD/Cr. XPS analysis found the highest
number of Cr–C complexes under the top chromium oxide layer, and the material
just below Cr2 O3 is mainly composed of Cr and Cr carbides. The enhanced Cr
carbides were formed due to the technological aspects of the PCD production when
the previously prepared Cr coating was subjected to an intense microwave plasma
discharge. Chromium carbide, which is known for its hardness, chemical resistance,
and refractory properties, acted as an effective diffusion barrier and improved the
oxidation resistance of the substrate by preventing the oxidation of Zr.
6 Summary
The combination of polycrystalline diamond and magnetron-sputtered Cr double

coating was investigated for its ability to protect ZIRLO nuclear fuel tubes against
corrosion at accident temperatures in a water-cooled nuclear reactor environment.
The combination of Cr magnetron sputtering and microwave plasma chemical vapor
deposition of PCD reduced Zr corrosion of the substrate significantly. The order of
the layers in the double coating strongly affected the ability to protect ZIRLO fuel
tubes against hot steam corrosion. The lowest corrosion at accident temperatures
steam was observed for double-layer-coated ZIRLO with the Cr layer on the bottom
and the PCD on the top. This double-layer coating significantly reduced ZIRLO tube
corrosion by 42–47% compared to unprotected ZIRLO. In contrast, the double-layer
coating with PCD as the bottom layer and Cr as the top layer reduced the accident
temperatures steam ZIRLO tube corrosion by 20–25% compared to unprotected
ZIRLO.
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08.015
Silicon-Based Technologies
for High-Temperature Coatings
and Their Corrosion Behaviours
Priyanka Sati, Ankita Kumari, and Sudesh Kumar
Abstract Polymers based on silicon make excellent materials for coating applica-
tions in industrial sectors, manufacturing, energy sector, transportation, waste reme-
diation, nuclear, space, etc. Coatings that withstand high temperatures offer compati-
bility with the environment as well as substrates play a crucial role. Strong adherence
to the majority of surfaces, as well as good chemical, thermal and UV resistance, are
only a few of these compounds’ outstanding qualities. In some situations, chemical
processes or radiation can also be used to turn them into ceramic materials, in addi-
tion to heat treatment. Since they were first used in specialised, high-performance
coatings, silicon-based technologies have become widely used in the coatings sector
along with solar applications, functional qualities and high-temperature stability are
also required for coatings. The current chapter examines several silicon-based tech-
nology high-temperature applications and corrosion mitigation where coatings play
a crucial role and the parameters influencing their selection and processing step
have been elaborated. Components that run at extremely high temperatures, such as
gas turbines, jet engines and industrial plants, are subject to a phenomenon known
as high-temperature corrosion. Every aspect of our existence is affected by corro-
sion, including buildings, bridges, utilities, as well as automobiles, trains and other
moving vehicles. A crucial method of corrosion mitigation is coating. In most cases,
corrosion happens when conductive ions, water and oxygen form an electrochemical
cell on the metal surface. The formulator can lengthen the lifespan of the coated
object and increase the longevity of a paint layer by limiting the penetration of these
corrosion-causing substances. More formulators are able to meet stringent applica-
tion requirements thanks to customised chemistries and efficient performance. This
chapter examines the range of silicon-based technologies and the recent upsurge
in silicon-based products. This chapter ends by discussing new surveys on coating
qualities, providing advice to coatings formulators on how to employ silicon-based
technology to improve their products and discussing the application of silicon-based
coating to protect metallic alloys from high temperatures.
Keywords Silicon-based · Coatings · Corrosion · High-temperature · Ceramics
P. Sati · A. Kumari · S. Kumar (B)

Department of Chemistry, Banasthali Vidyapith, Rajasthan 304022, India
e-mail: sudeshneyol@gmail.com
104 P. Sati et al.
Abbreviations
EBCs Environmental Barrier Coatings

CVD Chemical Vapour Deposition
SBT Silicon-Based Technology
PVD Physical Vapour Deposition
1 Introduction
The first silicon-based technology (SBT) application was developed in 1935, using
glass tapes saturated with resin to offer superior insulation and protection for elec-
trical wiring on U.S. Navy submarines. The usefulness of silicon-based technology
has grown over the previous few decades to encompass most coatings markets in
addition to classic applications. There have been at least 3,000 patents issued in
the previous 5 years that relate to its application in protective paints, varnishes and
finishes. Using chemical abstracts, we can see that the number of paint patents stating
the usefulness of silicon-based technology steadily increased from 1945 to 2001 [1].
Traditional advantages of silicon-based technological materials, such as weathering
and heat resistance, continue to attract attention. However, there has been an increase
in the number of patents filed for novel applications of silicon-based technologies.
Our ever-evolving culture constantly tests the capabilities of new materials in
search of improved functionality, lower costs, longer lifespans and less environ-
mental impact. It is not uncommon for property needs to exceed the capabilities of
single material systems, requiring the implementation of more complicated systems
that make use of multiple materials. However, for many applications, it is sufficient to
produce significantly better performance by simply modifying the surface qualities
by means of suitable coatings. Coatings can be used to make a substrate more durable
against the elements, to provide new capabilities to a system by altering its surface
qualities or to merely alter its appearance [2]. Polymers, metals, ceramics and glasses
can all be used to make coatings. In general, polymers’ low material and processing
costs, as well as their ease of deposition, are advantageous, but they also have rela-
tively poor hardness and limited chemical and thermal stability. Metallic coatings
have excellent electrical and thermal conductivity but are typically more difficult
and expensive to manufacture than polymeric coatings and have poor corrosion and
oxidation resistance. Ceramic coatings, on the other hand, are stable against corro-
sion and oxidation and have high levels of hardness, wear resistance and temperature
resistance [3]. The main downsides of these coatings are their brittleness and the
greater production costs compared to polymeric and metallic coatings. In the end,
the coating material used will be determined by the desired qualities, environmental
conditions during application and processing, substrate compatibility and material
and processing costs. In the light of these considerations, polymers based on silicon
are the best option for coatings. When compared to conventional organic coatings,
Silicon-Based Technologies for High-Temperature Coatings and Their … 105
coatings based on these compounds excel in both thermal stability and chemical
resistance [4].
For this reason, polymer deposition techniques can also be used to generate
ceramic coatings after the polymer has been converted into ceramic. Thus, in addition
to the benefits in the polymer state, silicon polymers allow for a simpler fabrication
of ceramic coatings, lowering processing costs in contrast to methods like physical
vapour deposition (PVD), chemical vapour deposition (CVD), thermal spraying and
sol-gel procedures [5, 6].
2 Types of Silicon-Based Coating
Coatings made from silicone are widely employed in manufacturing. Coatings made
from silicone are used by tyre producers, for instance, because of the reliability
with which they work during the moulding process, thereby guaranteeing product
quality. Traditional antifouling paints contain hazardous ingredients, whereas paints
with silicone additions improve vessel efficiency (faster speed and lower fuel use).
Silicones are used in industrial paints to increase their tackiness, waterproofness and
durability. Coatings that contain silicon are described in detail below.
2.1 Protective Coating
Protecting silicone rubber from the elements may be necessary. To extend the useful
life and durability of a silicone keyboard or other silicone device, a protective coating
can be put over it. When it comes to silicone rubber, the SiCoat coating technique
is the way to go because of its abrasion resistance. Even under extreme conditions,
this compound prevents silicone rubber from deteriorating.
2.2 Conductive Coating
An advantage of conductive coatings for silicone keypad goods is the cross-link

bond they provide. A conductive coating is essential for optimal keypad performance
under any and all conditions. Every keypad is designed for a distinct purpose, so it’s
beneficial to think whether or not your device could benefit from a conductive silicone
coating.
106 P. Sati et al.
2.3 Bond Coating
Technology has advanced to the point where bond coating can be used to adhere
rubber to polyester switches. Mechanical bonding of keypads and switches is far more
costly and time-consuming than bond coating. When developing silicone keypads,
the bond coating procedure is now required due to its superior efficiency, ease of use
and low cost.
2.4 Dip Coating
Coatings based on silicon polymers are typically developed using either dip coating
or spin coating, two of the earliest coating technologies to see widespread commer-
cial application. In this deposition method, a layer is grown on a substrate’s surface,
while it is removed from a liquid bath [7]. For this reason, the film can be produced
onto all exposed sides of the substrate simultaneously, which is useful in some situ-
ations. The ability to selectively deposit coatings by masking off sections improves
coating quality but may also degrade the coatings themselves due to the mask’s
effect on film development. There isn’t a lot of complicated machinery involved in
the dip coating process, and there aren’t even that many variables to worry about. It’s
important to find the sweet spot between the liquid’s viscosity, density and surface
tension. Also, if fillers are employed, they need to be evenly distributed throughout
the liquid. Dip-coating is a straightforward procedure that requires only the regu-
lation of immersion time and withdrawal speed when using a slurry with the right
properties. The technique has the benefit of low waste, with evaporative losses being
the most significant source of waste but being easily mitigated by storing solutions
in containers with narrow openings [8].
When homogeneity of coating thickness is required, the process is limited to
simple geometries like sheets, plates, cylinders, tubes and slightly irregular shapes
[9]. It is feasible to deposit coatings onto substrates with more complex shapes, but
this often results in coatings that are not uniform in thickness because of fluctuations
in the flow of the coating solution during withdrawal [3]. Additionally, edge effects
have a significant impact on thickness homogeneity in dip coating. These edge effects
often have an impact on the area between 8 and 15 mm inwards from the top and
bottom edges, and 15 mm inwards from the sides. It is difficult to deposit uniform
coatings onto small surfaces because these effects worsen with increasing withdrawal
speed yet are independent of substrate size [10]. The coating solution used in this
method must be applied in very large quantities. Since a number of precursors degrade
in the presence of oxygen and moisture, investing in specialised storage facilities and/
or equipment to maintain the coating solution’s quality over extended periods of time
can significantly boost production costs. The use of more viscous liquids or liquids
with fillers also presents challenges due to the inhomogeneous flow of the liquid. The
parameters of the liquid, such as its surface tension, viscosity, density and volatility,
as well as the rate of withdrawal, determine the thickness of the resulting film.
2.5 Spin Coating
For the deposition of silicon-based polymers, spin coating is another popular coating
process. In the manufacturing sector, it has found widespread application in the
coating of silicon wafers for use in electronic devices [11]. This method utilises the
centrifugal force created by spinning the substrate to distribute the coating solution,
which is typically placed in the middle of the substrate, outwards towards the edges
[3]. It’s easy to replicate results with the spin coating equipment, and the technique
is reliable. To coat the same substrate, far less coating solution is needed in spray
coating than in dip coating. Spin coating, on the other hand, wastes a lot more coating
solution. Additionally, deposition may only be performed in one face at a time, hence
it is best suited for flat or slightly curved surfaces. Furthermore, deposition of more
viscous solutions is challenging and typically results in coatings with surface flaws
[12].
Particularly difficult for coatings that incorporate fillers, this presents a significant
problem. Spin coating is similar to dip coating in that the coating thickness is affected
by the rotational speed and the liquid’s characteristics; however, in spin coating,
higher rotational speeds result in thinner coatings. Coatings typically have a thickness
between a few nanometres and a few micrometres. Deposition of many consecutive
layers can result in thicker coatings, similar to what can be achieved with dip coating,
so long as the prior layer is not re-dissolved [13].
2.6 Spray Coating
Spray coating is widely used in both large-scale manufacturing and laboratory

settings. The method operates on the premise that tiny droplets of coating solu-
tion are atomised and carried towards the substrate, where they collide to create
a film. Pressure, a pressurised carrier gas, a supercritical process, an electrostatic
technique or rotation are all viable options for achieving atomisation [14]. Spray
nozzles are used to apply coatings using a pressured carrier gas, usually air, and the
coating solution is introduced into the gas stream as it exits the nozzle [15]. The
usage of highly reactive polymers and the preparation of oxygen-free coatings are
both thwarted by the fact that air is necessary for deposition, even though inert gases
can be utilised as carrier gas. Spray deposition contains many more variables than
dip and spin coating, such as carrier gas pressure, spray nozzle aperture, nozzle-
to-substrate distance, impact angle, spray jet shape and relative nozzle-to-substrate
velocity. However, the development of the coating process is made more difficult by
the large number of parameters involved. However, this allows for a wider variety of
108 P. Sati et al.
coating solutions to be deposited, as well as greater control over coating attributes

such as thickness and surface structure, by adjusting a number of factors.
Most coating formulations are solvent-borne and contain filler particles, therefore
spraying equipment consists of a pressurised gas source, a solution container, the
spray nozzle and an exhaust system [16]. Coating with a spray gun can be done
with only your hands and arms. The talents of the operator, however, will have
a significant impact on reproducibility and uniformity. The procedure can be more
reliably replicated using more complex systems with mechanical or electronic control
during operation. Spray coating uses a small amount of coating solution per area of
substrate, yet produces a considerable amount of waste owing to overspray [17].
2.7 Preceramic Polymers
Metalorganic components including silicon, carbon, nitrogen, oxygen and some-

times even metals like boron and aluminium make up the backbone of preceramic
polymers. Mostly organic supplementary units are linked to the main structure. H,
Alkyl, Vinyl, Aryl, etc., are all examples of common side groups. In addition, the
physicochemical behaviour of a precursor can be modified by modifying it or adding
new groups, which is essential for cross-linking and polymer-to-ceramic conversion
[18, 19]. The monomeric silicon-based compounds used as adhesion promoters in
many multilayered systems belong under a subset of siloxanes while being referred
to as silanes (Fig. 1).
When siloxanes are heated, they change into SiO2 or, in the case of organosilox-
anes, SiCO. Polycarbosilanes, another major family of precursors, are converted
to SiC through thermal treatment in the absence of oxygen [20]. Finally, nitrogen-
containing silicon polymers, including polysilazanes, polycarbosilazanes and polysi-
lylcarbodiimides, have attracted a lot of interest for use as coatings. These mate-
rials can be transformed into Si3 N4 (for polysilazanes) or SiCN ceramics (for
poly(organo)silazanes, polycarbosilazanes and polysilylcarbodiimides) through a
heat treatment in an inert atmosphere. Researchers have looked into variants of
these three basic types of precursors containing boron, aluminium and transition
Polycarbosilanes Polysiloxanes Polysilazanes
Fig. 1 Examples of silicon-based polymers

metals (such as Fe, Co, Ni, Pd, Pt, Cu, Ag and Au). Another group of silicon-based
chemicals that can be utilised to make coatings is called geopolymers [21].
Coatings made from silicon polymers require meeting specific conditions before
they can be prepared, especially if they are to be transformed into ceramic. To begin,
coating deposition in liquid state requires precursors that are liquids or have adequate
solubility in common solvents. A latent reactivity, supplied by the presence of certain
chemical groups that cause cross-linking upon exposure to thermal, radiative or
chemical stimuli, is also necessary and is an important feature of both polymeric and
ceramic coatings [22, 23]. Cross-linking transforms polymers and oligomers, which
are typically liquid or soluble, into thermoset materials that are insoluble and cannot
be melted. This latent reactivity is typically associated with reactive bonds like Si–H
or N–H or unsaturated organic groups like vinyl. Finally, a high enough molecular
weight is necessary to prevent the volatile loss of low molecular weight molecules
during cross-linking and ceramic transformation [24].
2.8 Particle-Filled Coatings
Coatings based on silicon polymers commonly have fillers added to them to increase
their potential applications. Fillers are added to polymeric systems to alter their visual
characteristics, create novel surface structures or impart new capabilities. Ceramic
coatings can have their microstructure and characteristics modified by adding fillers
[25]. Coating fillers can range in size from nanometres to micrometres and can be
made of a variety of materials including polymers, ceramics, glasses and metals.
Based on how they react to heat treatment, these fillers can be broken down into four
categories: Fillers can be either passive or active, while also being either glass or
sacrificial [26]. Passive fillers, as their name implies, do not actively contribute to the
system. The processing and application do not alter their original composition, mass,
or particle size. These fillers constitute the vast majority of those utilised in polymeric
finishes. Certain filler materials are only inert under specific conditions, including an
oxygen-free environment or low temperatures [27]. Organic polymers degrade under
pyrolysis conditions, whereas glasses melt and metals oxidise. That’s why ceramics
are the go-to for passive fillers: they’re inert and don’t conduct electricity. There
is no need for a protective environment over a wide temperature range when using
ceramics like SiC, Si3 N4 , ZrO2 , TiO2 , BN, Al2 O3 and SiO2 . These materials have a
high melting point and temperature stability and are either stable oxides or have strong
oxidation resistance [28]. Because they are inert, coating systems can have large
amounts of filler applied to them to modify the final ceramic’s properties. Precursors
may be employed only as temperature-resistant binders for passive filler particles in
some applications. However, even if the macroscopic shrinkage of the coatings due
to precursor densification during ceramisation is totally avoided, residual porosity
will always persist in the coatings when using medium- to high-volume fractions of
passive filler. Moreover, if the fillers have a narrow particle size distribution, a higher
volume proportion of filler results in a greater level of porosity [29–32].
110 P. Sati et al.
Active fillers are those that react chemically with the coating process. These can
involve interactions with the precursor, with the gaseous products of pyrolysis, or
with the pyrolysis environment, all of which can lead to the formation of new phases.
The high temperatures required for these reactions mean that active fillers are rarely
used in polymeric coating systems [33].
3 Properties of Coating
Coatings with diverse properties are possible due to the vast availability of precur-
sors and processing methods, as well as the adaptability of systems via the incor-
poration of fillers. Therefore, silicon polymer coatings have been created for a
wide variety of uses. Many low-temperature coating methods have made substan-
tial use of polyorganosiloxanes, also known as silicones [34]. These molecules are
composed of silicon and have the structural formula X3 Si(CH2 )nY, where X repre-
sents hydrolysable groups that promote adhesion with the substrate and Y represents
a functional group that has an affinity for the coating material.
Silicones are a fascinating class of polymeric materials that come in a wide variety
of interesting shapes. Because of their unique features, they can be modified to meet
the specific needs of the healthcare and aerospace industries. They have a wide variety
of uses, including sealing, lubricating and more (Table 1).
Table 1 Various properties of silicone

Properties of silicone Description
Chemical reactivity Usually, non-reactive
Thermal conductivity Poor thermal conductivity by design, however this can be
changed by changing the formula
Toxicity FDA-approved medicinal and food grades, non-toxic when
used properly
Water repellence Extremely water repellent
Sealing ability Watertight sealing on smooth surfaces
Ozone, UV, and oxygen resistance Radiation and oxidation-resistant
Electrical conductivity Natural insulator, although fillers can make silicone
conductive
Gas permeability Gas-permeable
Thermal stability Physical and mechanical qualities are stable across a large
temperature range
Organic solvent resistance Chemical-proof
3.1 Permeability
Silicone is a great material because of its high gas permeability and resistance to heat.
Openings in the molecular chains of silicone are large enough to let gas molecules
through, but too small to let water molecules through [35]. Fabrics that are both
water- and air-resistant are now a reality thanks to coatings that combine these two
properties.
Silicone rubbers excel in several areas, but one is thermal stability. Over a wide
temperature range, silicone retains its important mechanical and physical qualities
within specified design limitations. The air service temperature range for silicone
products can be rather wide, from as low as −136 °C to as high as 316 °C.
Silicone has a lot of useful characteristics. A few of the ways in which producers
and consumers alike can make the most of its special qualities are described below:
1. Materials made with silicone are risk-free. They are frequently used as a
component of medical implants.
2. Dimensional stability of silicones is high. They are temperature-resistant and
retain their original form.
3. Silicones do not react with chemicals and can be used in a wide variety of
settings. They are not affected by the presence of water, fuels and oils, extreme
temperatures, cold, salt spray or UV light.
4. Any form can be made from silicone. Silicones can be found in a wide variety of
forms, including liquids, pastes, sheets and even hard, plastic-like solids. Coat-
ings, injection/compression moulded parts, stamping, tubing and lubricants are
just some of the many applications for these materials.
3.2 Adhesion
Silicone’s superior adhesion qualities result from the chemical link between organic
polymer matrices and surfaces that are often difficult to attach to, such as glass,
metal and stone. Silicones are able to stick to surfaces when other goods relying on
physical bonding would fall short because of the chemical link they form. As a result
of this chemical relationship, silicone-based adhesives are much more durable than
those based on other adhesion promoters, which are more mechanical or physical in
nature [36]. Many goods in the building, auto, air and sea transport industries rely on
silicone-based adhesives to keep vital systems together under extreme conditions.
Physical and chemical linkages are formed between the silicone macromolecules
and the surface atoms during the curing process. Silicone bonds to the surface slowly
but surely. When the curing process is complete, the material has reached its final,
unchangeable condition, at which point it is firmly bound to the surface in question
but has no effect on any other surfaces with which it comes into touch [37] (Fig. 2).
112 P. Sati et al.
Fig. 2 Adhesion of silicone
4 Mechanisms of Adhesion
Good wetting and adhesion between the liquid precursor and the substrate are neces-
sary for film formation in the production of coatings based on silicon polymers. After
solidification, this excellent adhesion must still be preserved. The interfacial tension
between the substrate and the liquid coating material, as well as the surface free
energy of the substrate, are the primary factors determining wetting [38]. Young’s
equation describes this relationship (Eq. 1) as
γSG − γSL
cosθ = (1)
γLG
where θ is the contact angle between the liquid and the solid surface, γSG is the solid’s
surface free energy at the interface with the surrounding atmosphere and γSL is the
surface tension of the liquid in contact with the atmosphere. At the triple point, the
contact angle is the angular separation between the solid’s surface and the tangent to
the contour of a droplet resting on the surface (interface between solid, liquid and gas
phases). In one significant way that Eq. 1 can be understood, a short contact angle
results from a combination of a solid’s high surface free energy and a liquid’s low
surface tension [39] (Fig. 3).
The work of adhesion is another attribute given by the relationships between the
surface energy/tension of the substrate, coating and interface. This is a measurement
of the effort required to remove a coating from its substrate in the absence of any
chemical or mechanical interactions [40]. By combining Eqs. (1) and (2), we obtain
Eq. (3), often known as the Young–Dupré equation, which characterises the connec-
tion between the work of adhesion and the contact angle, and by extension, between
Fig. 3 Representation of the

contact angle of a liquid with
a solid surface
the adhesion strength and the wetness. According to the Young–Dupré equation,
larger adhesion forces result from narrower contact angles. Coating precursors have
so lower adhesion to polymers than to ceramics, glasses and metals.
W A = γSG + γLG − γSL (2)
W A = γLG (1 + cosθ ) (3)
Strong adherence to substrates is not guaranteed, but adequate wetting in the liquid
state is necessary for obtaining such coatings. It is the mechanical aspects and, more
crucially, the chemical interactions between the coating and the substrate that ulti-
mately determine the coating’s adherence strength for solid coatings [41]. Coating
and substrate may become mechanically interlocked depending on the substrate’s
morphology, which is related to the mechanical interactions that occur due to the
substrate’s surface roughness. Since silicon polymer deposition occurs predomi-
nantly in the liquid phase, surface cavities on the substrate can be filled by the coating
material. The coating material is clamped within the cavity after solidification, which
increases the adhesion strength [42].
When the liquid precursor and the substrate are well-wetted, an increase in surface
roughness boosts adhesion strength by increasing the interfacial area and mechanical
interlocking between the two [43]. The adherence of silicon polymers and the ceramic
coatings formed from them to the substrates is essentially the result of chemical
interactions, in addition to the mechanical effects.
5 Properties of Silicon-Based Technology and Their

Application
Coatings with diverse properties are possible due to the vast availability of precur-
sors and processing methods, as well as the adaptability of systems via the incor-
poration of fillers. Therefore, silicon polymer coatings have been created for a wide
variety of uses. In particular, polyorganosiloxanes, also known as silicones, have
seen widespread use in a variety of low-temperature coating systems [44]. These
114 P. Sati et al.
molecules are composed of silicon and have the structural formula X3 Si(CH2 )nY,
where X is a hydrolysable group that promotes adhesion to the substrate and Y is a
functional group that is selectively attracted to the coating.
Coatings made from silicon-based precursors have several uses, but dielectrics
for electrical devices stand out as one of the most well-established and widespread.
Isolating the various components of an electronic system from one another, dielectrics
are typically SiO2 layers created using (chemical vapour deposition). Miniaturisation
of circuits with ever-increasing power has, however, resulted in systems with gaps of
a few nanometres in width and a high aspect ratio between the different structures.
Device encapsulation is another area where this technology has found use in the
electronics industry. Plastic foils are often used for encapsulation; however, they
allow water vapour and oxygen to degrade the devices inside [45]. However, gas
barrier coatings made from silicon-based polymers can improve the foils’ perfor-
mance. Precursor-based coatings are useful for preventing degradation caused by
atomic oxygen when used in low Earth orbit. In the case of solar cells, in particular,
coatings have been engineered to have certain functional qualities. For instance, high-
emissivity coating systems are used to manage the temperature of space-based solar
cells, silicon solar cells are passivated to prevent recombination and boost efficiency
and absorbing coatings are utilised to enhance solar collector performance.
In the coatings industry, environmental barrier coatings made from silicon poly-
mers are the current focus of most research (EBCs). Ceramics are particularly well
suited for such systems due to their inherent high stability in hostile settings (Fig. 4).
Coatings made from silicone are indestructible, long-lasting and add both prac-
ticality and aesthetic appeal to their respective surfaces [46]. They’re superior to
alternatives because of their technical and mechanical properties and adaptability:
1. Provided in a wide range of formats, from liquids to elastomers, their versatility
and ease of use are enhanced.
2. To meet the demands of industry and satisfy customer needs, it must be non-toxic
and safe.
Fig. 4 Applications of silicon-based coatings

3. Weather resilient.
4. Non-sticky.
5. Durable in the face of harsh elements and chemical exposure.
6. Water repellent.
Coatings made of silicone are quite useful due to their adaptability:
Coatings made from silicon-based precursors have several uses, but dielectrics
for electrical devices stand out as one of the most well-established and widespread.
Dielectrics, typically SiO2 layers formed using CVD, serve to separate the various
elements of an electrical system. Miniaturisation of circuits with ever-increasing
power has, however, resulted in systems with gaps of a few nanometres in width and
a high aspect ratio between the different structures.
Photocatalysis, radiation shielding, thermal barrier coatings, diffusion barriers,
surfaces with tailored IR-emissivity for defence and thermal management appli-
cations, glass and ceramic strengthening and protection [47], photochromism, light
conversion, sensors, fire protection, buffer layers for diamond coating, cathode mate-
rial for fuel cells, thin-film electrolytes and water purification are all other uses for
silicon-based polymeric and ceramic coatings.
5.1 Primers
As such, silicates and alkoxy silanes can be used in primer formulation for a wide
range of metal and siliceous substrates. Primers based on alkoxy silanes are well
known for boosting adhesion, but they also have other useful properties, such as
regulated hydrophobicity, high UV and thermal stability, surface activity, chemical
resistance and corrosion protection. Specifically, zinc-rich primers and chromium
substitution are of interest [48]. Hexavalent chromium is present in several metal
surface preparations [49]. It’s because of the new rules that people are looking for
alternatives to chromium. Paintability, degrease resistance and corrosion resistance
were all improved upon by using a primer made of acrylic copolymer, epoxy resin,
silica sol and trialkoxysilane compound. This discovery was made in 1983. It wasn’t
until 12 years later that it was discovered that acrylic copolymer- and epoxy resin-free
wash primer could achieve the same results.
5.2 Heat-Resistant Coatings
In the late 1940s, for a few very demanding applications, SBT resins were used as
the principal binder in high-temperature coatings [50]. Coatings made from silicone–
organic copolymers and cold blends now offer a range of high-performance features.
The coating’s performance hinges on picking the right SBT resin and colouring.
116 P. Sati et al.
5.3 Industrial Maintenance Coatings
Coatings that combine the UV and chemical resistances of SBT with the physical
properties and cure mechanisms of organic resins can be formulated using cold blends
and copolymers of SBT and organic resins [51]. New technologies based on silicon
are being developed to address the drawbacks of conventional materials like silicone
and organic homopolymers.
Acid equilibration of siloxane precursors with organic polyols prior to hydrolysis
to produce resins with a unique combination of hardness, flexibility and solvent
resistance [52] is one method used to improve the physical attributes of UV- and heat-
resistant coatings. These patents were largely concerned with enhancing the physical
qualities of what is primarily a siloxane resin by means of a modest modification
degree of organic cross-linking. SBT is used as a modifier in systems where organic
resins serve as the principal binder.
5.4 Hygienic Coatings
Coatings that provide frequent and simple washing or active sterilisation of the
surface are in high demand due to rising hygiene standards in hospitals and food
processing plants. Demand for cleanliness is on the rise, yet there may be fewer
ways to address the issue [53]. A closer look is being taken at biocides. Costly
testing and documentation are necessary before new biocidal-active compounds can
be commercialised. In contrast, sanitary surfaces can be attained with less effort by
employing passive bio-contamination management, which is accomplished through
the use of easy-clean coatings. Exposure to UV light is one of the most widely used
techniques for sanitising surfaces. Coatings can easily lose their protective qualities
due to typical wear, abrasive cleansers and chemical disinfectants, and UV radiation
degradation of organic resin paint binders is only one more factor [54].
5.5 Abrasion-Resistant Coatings
While most coatings are designed with abrasion resistance in mind, one area of
technology based on sol-gel chemistry is laser-focused on the property. Polysiloxane
polyether copolymer, when added to an aqueous anti-reflective coating formulation,
helps with flow and cuts down on flaws. Protective and optical coatings, passivation
and planarisation layers, sensors, high or low dielectric films, inorganic membranes,
electro-optical and nonlinear optical films, electrochromics, semiconducting anti-
static coatings, superconducting films, strengthening layers and ferroelectrics are
just some of the many modern uses for anti-reflective coating thin-film coatings
[55]. The compound can be applied to a variety of substrates, including wood, metal,
printed surfaces, glass and ceramics, but it shows the most promise when used on
sheets of soft plastic. The clearcoat compositions used in automobiles have gained a
lot of interest.
6 Benefits of Silicon-Based Additives
Si is the second most common element in the earth’s crust. The varied good and detri-
mental impacts of chemical fertiliser have been the focus of extensive study. The use
of chemical fertilisers has the potential to pose risks to the biosphere, particularly the
agricultural ecology. Silicon (Si) fertiliser has been shown to have positive economic
and environmental impacts when used in agriculture. Adding Si fertiliser to your
garden or farm can help reduce both natural and human-caused stresses on your
crops [56]. Si fertiliser’s role in agriculture and environmental clean-up is crucial,
so learning about it is important. Its agricultural application improves silicon uptake
by plants, buffers plant responses to salt and drought and removes Al, As, Cd, Cu,
Zn and Cr.
Both the types of fertilisers used and how they are administered to crops were taken
into account. The use of foliar sprays has been shown to increase crop growth and
yield while simultaneously decreasing the impact of biotic and abiotic stresses. The
material comprised of silicon nanoparticles offers promising possibilities. Silicon’s
effects on the environment, and whether or not it is a good additive, are still unclear,
but further study and research are planned to shed light on the topic.
7 High-Temperature Corrosion-Resistant Ceramic Coating
Exhaust coating, header coating or high heat coating are all common names for high-
temperature ceramic coating. Anti-corrosion coatings for exhaust systems and engine
parts are developed for use at high temperatures. What we call corrosion occurs when
an object’s vital properties deteriorate after being exposed to atmospheric moisture
[57]. The high-temperature coating product is safe to use at temperatures over 1200°,
and some coatings are safe to use at temperatures over 1600°. Exhaust systems might
benefit from the high-temperature coating process in more ways than one. With a
thickness of 2–4 mils, this ceramic coating provides a tough, corrosion- and chip-
proof surface. Both the adhesion and abrasion resistance of this coating method are
exceptional (Fig. 5).
Advantages of using high-temperature ceramic coating:
1. The most effective corrosion prevention of any coating used in exhaust systems.
2. Base metal temperatures of over 900°F and exhaust gas temperatures of over
1200°F were successfully reached and maintained during testing.
3. Use on any surface that can tolerate a cure temperature of 250°F.
118 P. Sati et al.
Fig. 5 Applications of heat-temperature coatings
4. Offers exceptional protection against corrosion.

5. Helps to protect engine electronics by lowering under-hood temperatures by 30
degrees or more.
6. Improved performance and increased power (over a 3% increase in horsepower
has been recorded).
There is a wide range of hues for high-temperature ceramic coatings, from black
velvet to stoplight red. You can choose from a variety of gloss levels, from semi-to
highly reflective. Moreover, a selection of satin metallic finishes is also available.
8 Corrosion-Resistant Coatings for High-Temperature

Applications
In order to achieve higher efficiencies, devices used in the conversion of energy have
had to be operated at higher and higher temperatures. As a result, metals and other
low-temperature materials will have to be replaced by their ceramic counterparts.
High-temperature corrosion from combustion gases, air pollutants or the operating
medium is a problem for many of these ceramics. High-temperature protective coat-
ings need to fulfil a number of criteria in order to provide adequate, long-term protec-
tion. They need to seal off the corrosive substance, stay put on the surface and provide
protection. Therefore, a number of coating-related difficulties, such as thermome-
chanical stability, thermochemical stability and interfacial adhesion, are brought to
the fore by these specifications [58]. There must be some give and take between
these features because practically all solutions will be inadequate. Consequently, the
characteristics of protective coatings can be broken down into three distinct classes:
Chemical and thermal stability at high temperatures:
1. Constant adhesion and bending strength;
2. Anti-oxidation and corrosion properties;
3. Hermeticity;
4. Its producibility, dependability and affordability;
5. Tolerant failure mode.

Significant strides have been made in the direction of solving some extremely
difficult issues in high-temperature corrosion protection. Obviously, it’s a really
challenging task to find a way to protect Si-based ceramics so they may be used
in combustion conditions. Yet, protective coatings made of mullite have shown
promising resistance to alkali attack, safeguarding the ceramic substrate beneath
them.
9 Conclusions and Future Outlook
Polymers based on silicon have exceptional characteristics and can be utilised to

make both polymeric and ceramic coatings. Coatings can be deposited in liquid
form since the majority of these chemicals are either liquids themselves or soluble
in widely available solvents. Cross-linking of polymer chains occurs in response to
heat, chemical reaction, radiation or a combination of these treatments, resulting in
coatings that are both unmeltable and insoluble. There is a wide selection of precur-
sors available for purchase. Numerous coating systems are feasible due to the fact that
the qualities and composition of polymeric and ceramic coatings are determined by
the composition and chemical structure of the precursors, which in turn determines
the behaviour of the polymers during processing. Silicon-based polymers have supe-
rior adherence to most substrates and fillers, which is one of their main advantages
over their organic counterparts. This happens because the precursor molecules react
with the –OH groups on the surface of the substrates and filler particles, resulting in
chemical bonds. Similarly, inorganic polymer layers can be transformed into highly
adhering ceramic coatings after deposition. There has been a lot of research on
silicon-based polymer coatings, but there is still a lot of room for innovation. Modi-
fication of polymers, hybrid materials, novel processing techniques and strategies to
reduce stresses originating during conversion into ceramic coatings should lead to
enhanced coating systems with excellent attributes in the future.
Acknowledgements It is my proud privilege and special appreciation towards my supervisor,

Dr. Sudesh Kumar, professor of Chemistry, Banasthali Vidyapeeth, Department of Chemistry,
Rajasthan, under his guidance for his keen enthusiastic interest and valuable guidance which made
it possible to complete this work.
Conflict of Interest We have no conflict of interest.

120 P. Sati et al.
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High Temperature Wear Resistance
Coatings
A New Solution to Save Production Costs
in the Deposition of the Wear-Resistant
Coating
Trung Dao Duy and Vu Duong
Abstract Plasma spray processes are widely applied in industry. The inert gases
are the monoatomic ones that provide the plasma stream at a high temperature but
not too high enthalpy. The merit of the inert gas is the elimination of feedstock and
the deposition from oxidation. Very few research publications have focused on the
use of ordinary air for plasma generation. However, air is the most recommended
plasma generation gas since its cost is competitive, and especially in spraying ceramic
material, it has a definite advantage. To save on production costs, it is useful to find
substitutes for expensive traditional powder materials and inert gases (e.g., argon and
helium). They can be amorphous materials, especially Fe-based amorphous mate-
rials. This chapter focused on the updated achievements with air plasma spraying
using the Fe-based amorphous coating to deposit a competitive wear resistance.
Keywords Cohesion bond · Fe-based materials · Particle velocity · Plasma

power · Tribology test · And average enthalpy
1 Introduction
Coatings, which control a sizable portion of the market, are the key solutions in the
struggle against the problem of protecting the surface in numerous harsh industrial
settings. It should be mentioned that the total worldwide revenue was $7.58 billion
in 2015 and is anticipated to increase by 7.79% annually to reach $11.8 billion
by 2021 [1] to promote creative development. It is vital to concentrate on both
innovative material systems and cutting-edge machinery in order to overcome this
obstacle. In this field, thermal spray technology has been shown to be effective
thanks to its adaptability and flexibility, as well as its respectable output. Thermal
T. D. Duy
National Research Institute of Mechanical Engineering, Hanoi 100000, Vietnam
V. Duong (B)
School of Engineering and Technology, Duy Tan University, Danang City 550000, Vietnam
e-mail: vuduong@duytan.edu.vn
126 T. D. Duy and V. Duong
spray coatings provide a number of advantages over many other methods, including
the ability to give a thorough thickness to substrate surfaces with particular and
complicated features at affordable prices. Due to a number of factors, the industry
is widely recognized for adopting the plasma spraying method in the environment
to eliminate aggressive degradation from the working conditions. Some of these
uses include improving the frictional coefficient and increasing corrosion resistance
in the cylinder bore of internal combustion engines with particular coatings; it is
advised to increase corrosion resistance all around by up to 50% [2]. Numerous parts,
including a gas turbine, a fossil chamber, and others, experience heated corrosion-
erosive material deterioration [3]. It effectively boosts the components’ abrasion
resistance, hardness, wear resistance, and high-temperature corrosion resistance by
depositing the nanostructured coating over the component’s bare substrate surface.
Wear resistance has long been known to reduce production costs and lengthen the
operational life of components.
The durability of a component determines whether it has to be overhauled or
replaced. Because of this, improving wear resistance is crucial to understanding any
mechanical system [4]. The utilization of specific materials to achieve a very low
thermal conductivity when subjected to high heat flow is often illustrated by thermal-
barrier coatings (TBCs). TBCs draw a specific worldwide effort from researchers
and management because of the necessity for improved performance of machine
components working in heavy circumstances for application in the power, aerospace,
and automotive sectors [5].
This market is being strengthened and expanded by the creation of new atmo-
spheric plasma spraying (APS) and thermal spray applications. Superhydrophobic
coatings, coatings used as heating components, biomedical coatings, and coatings
for electronics are among the novel functional coatings on this list. Over the last
10 years, several efforts have been made to decrease energy losses in the industry
through the development of innovative wear-resistant materials. This field encom-
passes design innovation, property research, and the creation of novel, wear-resistant
materials, including enhanced wear-resistant materials.
Tungsten carbide (WC), aluminum oxide ceramic (Al2 O3 ), titanium carbide (TiC),
and Cr2 O3 make up the first conventional group of wear-resistant materials made of
oxide ceramic. The tungsten carbide coating has a hardness rating of 70 HRC. This
coating is a great substitute for rough chrome plating since it also has the advantage
of grinding mirror surfaces. When the temperature is lower than 450 °C, particle
erosion and cavitation conditions utilize chrome oxide ceramic coatings. Due to its
insolubility in acids and alkalis, this coating’s other recommendation is for use in
harsh chemical environments. When sealed, the aluminum oxide ceramic coating is
a perfect material for wear resistance and serves as a heat barrier.
The next class of cutting-edge wear-resistant materials falls under the “cermet”
name. This differs somewhat from the carbide family. A composite material called
Cermet is made of a ceramic core that is mostly in the form of carbide and is reinforced
by a metallic binder. The introduction of this sort of material into a wear-resistant
substrate is made possible by its composition and structure, which provide a novel
mix of toughness and hardness. Cermet materials also perform exceptionally well
A New Solution to Save Production Costs in the Deposition … 127
in corrosive environments [6]. Unusual performance in terms of strong wear resis-

tance, super erosive resistance, and high mechanical strength at high temperatures
is provided by a newly developed cermet (TiC, N)-based product from this family.
Due to the entire solid-solution structure of cermet, it has superior fracture toughness
to cemented carbide [7]. They do, however, have certain disadvantages because of
their intrinsic brittleness and limited resistance to oxidation at high temperatures,
despite having unique features. The definition of cermet states that this problem is
still unresolved for any acceptable metal component to offer enough ductility and heat
conductivity. Up to 80% of the volume of a hard ceramic phase typically consists of
a metal-binding phase [8]. Recent publications are a useful addition to the ongoing
improvement of the performance of cermet materials because they support novel
manufacturing techniques, advanced technologies, and cutting-edge research while
also promoting theoretical and experimental investigations [9–12].
Amorphous wear-resistant materials, a new class of extremely sophisticated mate-
rials, can be distinguished from crystalline materials by their distinguishing charac-
teristics because they lack crystal defects such as grain boundaries and dislocations.
Due to their excellent use of a high elongation limit, exceptional wear resistance, high
corrosion resistance, and high strength and stiffness, they have a wide variety of appli-
cations in the industry. What is the precise makeup of the deposition coating created
using the thermal spray technology? Amorphous alloys may often be formed by quick
solidification. Authors in [13] found that Fe-based amorphous material is considered
a cheap surface protective coating after thoroughly examining the corrosion resis-
tance of the Fe–Cr–Mo–C–B alloy feedstock for HVAF coating [13]. Researchers in
[14] looked into the connection between the FeCoCrNiMo0.2 coatings’ wear char-
acteristics and plasma spraying power. There are a few factors that contribute to the
extensive literature on the use of Fe instead of Co in amorphous systems. On the one
hand, the probable scarcity and high price fluctuation of CO prompt the search for
an alternative. On the other hand, the International Agency for Research on Cancer
(IARC) determined in 2009 that cobalt metal with tungsten carbide was probably
harmful to humans in the Report on Carcinogens—Background Paper for Cobalt-
Tungsten Carbide: Powder and Hard Metal (Group 2A). The cobalt-tungsten carbide
combination may possess special toxicological characteristics, according to some
[15]. Techniques and technology for thermal spray have progressed dramatically.
Due to the competitive market, the industry puts pressure on several research insti-
tutions and colleges to respond (in terms of profitability, quality, and reliability). In
addition to the current thermal spray methods, new ones in development provide solu-
tions for overcoming these difficulties. The cold spray is a novel feature of thermal
spray technologies. The particle’s velocity may be increased using a De Laval nozzle
up to 1000 m/s. According to recent publications, the mechanical characteristics of
the deposition and the metallurgical bonding with the surfaces of the components
are mostly enhanced by the kinetic energy of the particles [16]. The low-temperature
green technique is the cold spray procedure. The military, aerospace, and nuclear
energy sectors have all identified uses for cold spray [17–19]. Aerosol deposition is
suggested in the electronics sector as a low-cost technology for flexible substrates
and coated materials in Masco’s manufacturing. The unique characteristic of this
process is the mixing of very small, nanoscale particles with the gas that produces
the aerosol. At a very low pressure (apsi = 1 10 Pa or 1 kPa), this aerosol is discharged
through a specific nozzle [20, 21]. Although cold spray has not yet proven effective
in depositing ceramic coatings, in theory it is quite similar to aerosol deposition since
it uses a low-temperature and high particle velocity. We haven’t yet talked about the
model for how little solid particles collide to produce coatings. Due to the influence
of inertia, the importance of particle size is being debated [22, 23].
The newly discovered method for depositing extremely thin coatings with high
density and quality is plasma spraying at low pressure. In this procedure, the thick-
ness ranges from 1 to 100 µm. The modified approach is advised for the quick
deposition of thin, uniform coatings over extremely wide surface areas, in contrast to
plasma spraying at low pressure. The conventional thermal spray or vapor deposition
methods cannot deposit such coatings (CVD, PVD). Therefore, this procedure may be
regarded as a fundamentally novel and developing technique for thermal spray tech-
nologies. The very low-pressure plasma spraying systems work at significantly lower
pressures of 100–500 Pa as compared to low-pressure plasma spraying, which oper-
ates at chamber pressures of 5–20 kPa. Since extremely low-pressure plasma spraying
offers a significant improvement over conventional methods, thermal-barrier coat-
ings, photocatalytic coatings, and wear-resistant coatings are the main applications
of this method [24].
Since the solid particle size in the suspension reaches a range of a few nanometers
to 5 µm, the complete novel method employing liquid feedstocks of suspensions for
thermal spraying places a sophisticated restriction on the thickness of the coating.
The nanostructured coatings used in this method work better for a wide range of
applications, including those in biomedicine as well as industry. The fast development
of suspension thermal spraying technology is addressing a significant number of
inventions with regard to intellectual property. The equipment, feedstock material
system, and applications are all covered by the inventions in this method [25, 26].
These coatings guarantee a huge number of emitters produced on an industrial basis.
Certain functional coatings can be applied using the suspension spray [27, 28].
For many applications, the essential part of the thermal spray system is an arc
plasma torch. The design of the plasma torch in general and several specific torch
components in particular have seen a lot of innovation in the previous 10 years. Their
conceptualization, strength, and capability range greatly. In close cooperation with
the universities and institutes, all researchers and builders made contributions to the
attempt to increase the effectiveness of coating deposition. The papers concentrated
on the following topics: arc stability, plasma flow concentration, velocity distribution,
deposition efficiency, as well as cathode and anode contour design. Ghorui and Das
[29] first proposed their original idea—evolving mechanical design from numerical
modeling. The modern direct current plasma torch functions on a self-adjusting arc
length. The primary disadvantage of this kind of torch is the large-scale arc shunting
that limits its voltage. The variation in the plasma power flow profile was also brought
on by the shunting of the arc. The coating quality is reduced by this erratic plasma
flow. To create an axisymmetric heterogenous plasma flow, Viktor Kuzmin [30] and
colleagues developed a supersonic plasma torch with sectioned inter-electrode inserts
and an annular input component of powder feedstock. The torch’s maximum power
is 95 kW [30]. It should be mentioned that the 100 kW plasma torch developed
by Indian researchers Bhardwaj et al. was reported [31]. A special plasma torch
with two chambers for high-velocity plasma spraying that can deposit CoNiCrAlY
powder at a speed of 500 m/s was created by Caliari [32]. This torch’s 50 kW output
displayed improved voltage and reduced arc current, extending the electrode’s life
[32]. Rotundo et al. [33] modified the cathode insert to increase its endurance since
the electrode life has a substantial impact on the continuous and steady deposition
process. They discovered the nuanced impact of several factors on the cathode’s
degradation and emittance [33]. The anode’s weight loss and erosion position are
influenced by the plasma current, gas feeding rate, anode length, and plasma torch
power. This discovery may encourage plasma torch design optimization to provide
the highest-quality plasma deposition [34]. When modifying the primary parameters
of the spraying process utilizing Al2 O3 particles for design and testing, Kui Wen
et al. offered extremely interesting and important results for the comparison between
the two types of the inner contour of the anode [35].
Positive findings were reported in connection with the twin torch, three torch, and
connected plasma torch because the power of the plasma torch affects the energy
of the plasma flow, which in turn controls the particle influence on the performance
of the sprayed coating [36–38]. Modern multi-electrode torches for better particle
heating and process stability are another addition made by Marques et al. [39].
They also suggested a whole new design for the plasma torch with three anodes and
three cathodes; however, the idea is now just in the primary design stage utilizing
simulation [39]. In general, as chemical-plasma technologies, all high-power AC
plasma torches have a special use in the chemical sector. Their maximum power is
500 kW, and their service life in continuous air operation is 2000 h [40–42]. The
application of the AC plasma torch for spraying has not yet been documented. The
following key industries are growth drivers for thermal spray deposition: aerospace
and aviation; heavy industry; petroleum and chemical industries; and healthcare. In
2024, it is anticipated that this industry will generate approximately $13 billion in
total worldwide revenue [43]. The manufacturing cost in thermal spray deposition
deals with the materials, technique, and end-use industry. These positions and an
outline of the key elements relating to deposition coatings serve as the foundation
for the chapter, which focuses on the current state, a paradigm, and trends in thermal
spray coatings in order to improve wear resistance in high-temperature and corrosive
environments while finding ways to reduce production costs.
2 Definitions and Phenomena
2.1 Thermal Spray
According to the definition of “thermal spray process,” the term “thermal” refers
to the role that temperature plays in heating or melting the feedstock before it is
sprayed onto the substrate. However, this tendency is shifting due to more advanced
procedures, including the spraying of HVOF and HVAF, in which the thermal energy
is outweighed by the kinetic energy of the particles. The function of temperature and
spray stream kinetics in each of the methods is depicted in Fig. 1.
2.2 Tribology
Wear, lubrication, and friction are some of the major topics covered by the
phenomenon of tribology, which is defined as the interaction of surfaces in rela-
tive movements. Tribology is generally regarded as an interdisciplinary field that
connects dynamics, chemistry, and materials. Designing coatings with a high level
of wear resistance while taking the operational environment into account is a key
goal. Tribology is a challenging interdisciplinary subject since wear is often covered
by material science and metallurgy, friction is frequently covered by mechanical
engineering, and lubrication is typically covered by chemistry.
2.3 Lubrication and Lubricant
Lubrication is a method in which a lubricant is utilized to minimize wear and friction

in contact between two surfaces. This phenomenon is interpreted as a way to supply
an element with grease or oil to help it function more efficiently. The lubrication
will assist in lowering the amount of friction created by touching surfaces. Due to
its feel and the relatively basic structure of machine elements, grease lubrication
Fig. 1 The correlation

between temperature and
velocity in different thermal
processes
(a) (b)
Fig. 2 Types of lubrication, a oil lubrication; b dry lubrication
is the preferred option for replenishing over an extended period. In the event of
high-speed rotation and high temperatures, oil lubrication is specified (Fig. 2a). The
right designation of oil lubrication and grease lubrication in industries depends on
the operating circumstances. When the use of oil or grease draws dust and filth, a
dry lubricant is a sophisticated solution (Fig. 2b). A lubricant is a component of the
lubrication system that works to lessen friction when two surfaces come into contact.
The lubricant functions as a force transmitter, a carrier of foreign particles, and a
surface coolant.
2.4 Wear and Wear Resistance
When the two sliding components are moving as a result of the mechanical contact
under stress, wear is primarily thought of as a material loss from the surface in
mechanical engineering. The utilization of thermal spray technology and the wide
range of coating materials make this technique a practical and profitable tool for
resolving a wear issue. There are several forms of wear and recognizing them can
help to select the best material for the application.
Adhesive wear occurs when two metallic surfaces slide against each other in a
relative motion (Fig. 3). The compatibility of the materials in contact under the load
conditions affects how long an adhesive will last. A material’s capacity to endure mass
loss from its surface as a result of mechanical impacts is known as wear resistance.
The ambient conditions, the kind of wear, and the load are the three key determinants
of wear resistance.
If the hard particles on one surface are dragged against and move along the second
surface, the wear can be adhesive, abrasive, and erosive accordingly (Fig. 3a–c).
When a solid surface is struck by hard particles suspended in gases or fluids,
simultaneous chemical, thermal, and dynamic effects cause a significant loss of the
original surface. Erosion is what this clothing is. While frictional and abrasive wear
is aided by chemical or electrochemical corrosion, corrosive wear frequently results.
A specific sort of damage in high-speed applications, such as trailing propellers,
pump impellers, and other hydraulic systems, is known as cavitation erosion. The
(a) (b) (c)
Fig. 3 a, b, c: a Adhesive wear; b Abrasive wear; c Erosive wear
primary factor that leads to a vapor bubble collision is high-velocity liquid flow in
an environment with a rapid change in pressure. Some parameters for selecting a
material in spraying technology should be taken into account depending on each
location and circumstance. Typically, weight loss or volume loss is used to quantify
wear. However, sometimes it is challenging to quantify the mass loss. It may instead
be indirectly inferred by looking at the size of the wear scar geometry or the quantity
of wear debris on a surface. For a precise measurement, the sliding wear test should
last as long as feasible.
2.5 Gas Generation Plasma
When the ionization process is triggered by the ongoing collision of discharged

particles, plasma is the particular state of matter. A plasma is a volumetric mass of
charged molecules that may have the appearance of an ionized cloud or gas. It is
necessary to start the ionization of gas and expose it to a strong electromagnetic field
in order to produce plasma. Because it is made up of ions and electrons, plasma may
carry electricity. In plasma spraying, the plasma-generated gases often contain pure
or a combination of argon, hydrogen, nitrogen, or helium. Since it is the simplest to
start a plasma with and is often less aggressive toward the electrode and feedstock,
argon is typically utilized as the main plasma gas. In general, secondary gases like
nitrogen, hydrogen, and helium are employed. Among the noble gases are argon and
helium. Despite the cost savings and benefits of some particular depositions, there is
a paucity of literature on the subject of air plasma spraying that uses ordinary air for
the plasma formation. However, with the advancement in torch design and the best
spraying settings, regular air may now be advised for the wear-resistant coating of
ceramic materials, particularly Fe-based amorphous alloys [44, 45]. Argon plasma
offers several benefits, but it has lower thermal conductivity and enthalpy than binary
gases. Because the molecular gases require more energy for the dissociation before
the first ionization, air plasma produced by ordinary air has a greater enthalpy and
thermal conductivity than plasma produced by argon. As a result, the plasma that
is activated by regular air has a greater enthalpy and thermal conductivity. This
argument made a sense to think of how plasma spraying uses common air in place
of noble and inert gases.
(a) (b) (c) (d)
Fig. 4 Transition state of the metal; a Crystalline metal; b Amorphous alloy; c Amorphous
transition; d Impact and rapid cooling of particle
2.6 Amorphous Alloy
The amorphous alloy may be produced via a very quick temperature change from
a liquid to a solid state. For the amorphous transition to occur, a rapid cooling
rate is required. As a result, the microstructure of an amorphous alloy has a short-
range order, which sets it apart from ordinary crystalline metal (Fig. 4a). Since the
rapid crystallization of the amorphous alloy (Fig. 4b) gives it a distinctive struc-
ture, it performs better than a crystalline alloy of the same composition. Numerous
papers have demonstrated that thermal spraying may be used to create amorphous
coatings that are based on Fe and other self-fluxing materials. Because they offer
exceptional corrosion and wear resistance at a relatively low material cost, Fe-based
amorphous materials are among the most appealing coatings [46–49]. Amorphiza-
tion—the transition from crystalline to amorphous (Fig. 4c, d)—is influenced by a
variety of variables, including mechanically induced deformation defects, the ther-
modynamic stability of crystalline phases, and the diffusion process that alters the
chemical composition of the crystalline and amorphous phases. However, at the
nanoscale, this amorphous transition and the metastable solid solution are competing
processes, and it is likely that the various situations are caused by microstructural
stability under extreme plastic deformation.
2.7 Coefficient of Friction
The friction coefficient is calculated by dividing the friction force by the normal
force. The kind of contacting materials, surface shape, and lubrication conditions all
affect the friction coefficient’s value. The coefficient of friction is a number without
dimensions. Depending on the applied force, the friction force will move in the
opposite direction. (Fig. 5).
Ff = μ × N (1)
where: The friction force, F f , is expressed in Newton.

Fig. 5 Scheme of friction

force
The friction coefficient is a dimensionless value.

The normal force is N and is measured in Newtons.
The two forms of friction coefficient—static and kinetic friction coefficients—
need to be distinguished. The ratio of the highest static friction force divided by the
normal force before movement begins in contact with surfaces is used to compute
the static friction coefficient. The friction force is divided by the normal force felt
by a body moving over a rough, dry surface to get the kinetic friction coefficient.
In contrast, because it impacts the item before it begins to move, static friction is
referred to as rolling friction and kinetic friction as sliding friction.
2.8 Enthalpy
Enthalpy is a thermodynamic phenomenon that shows how much heat is present in

the system overall. This amount is calculated by adding the system’s internal energy
to the result of multiplying pressure by volume. Enthalpy changes depend on a
chemical reaction occurring at a certain volume. The general formula for calculating
this amount is
H = E + p × V (2)
H stands for enthalpy. E is the system’s internal energy, while p stands for pressure.
V stands for volume. It is important to distinguish between heat and enthalpy. On
the one hand, heat is a type of energy, but enthalpy specifies the quantity of heat
transported at a constant pressure. While heat is not an inherent feature of a system,
enthalpy describes the state of the system. Enthalpy is a function of the state; hence,
the defined system’s initial and ultimate states are the only conditions on which its
amount depends. Thermal spraying, particularly plasma spraying, causes some of the
enthalpy loss for heating a system, including particle and torch cooling. The compu-
tation of the heat energy transmitted to the feedstock stream might be done using
the average mass enthalpy in general. This energy is used to activate the substrate
surface, melt the particle stream, and improve plastic deformation.
2.9 The Adhesion and Cohesion Bond
The crucial element for ensuring the coatings’ quality is the bonding power between
a coating and a substrate. When using thermal spray, the type of adhesive strength
between the molten or melt particles and the substrate surface is primarily determined
by a mechanical, chemical, and metallurgical mechanism depending on the two main
energy sources: the heat source and the kinetic source, forming sprayed layers with the
particular structure containing un-melted particles, oxides, and pores. Each energy
source’s dominant contribution is influenced by the torch’s architecture, the feedstock
material’s properties, and the spraying procedure. For instance, the high-velocity
oxygen-fuel (HVOF) process exhibits both considerable heat energy and high kinetic
energy. The crucial factor for good bonding in the coating is difficult to measure. Due
to the intricacy of the physical, chemical, and mechanical interactions during short-
term flight via the torch onto the substrate, the impact of the powder shape on the
bonding is also up for consideration in this context. The mechanical interlocking is
what primarily creates the bonding strength between the coating and the surface. The
secondary contributions come from the Van der Waals force (molecular attraction)
and elemental diffusion (metallurgical process). The strength of the link between a
deposited layer and a substrate surface is referred to as the adhesion phenomenon.
The term “cohesion strength” refers to the coating’s stress state under strain that is
typical for the surfaces. For simplicity, cohesion is defined as the material strength,
while adhesion is defined as mechanical interlocking. Both adhesion and cohesion
have a direct impact on the coating’s performance and lifetime.
2.10 Deposition Coating
Spray deposition is a method of depositing a layer of bulk material onto a substrate

by directing a stream of molten particle droplets onto it. The porosity, infusion of
particles, and fissures are some of the common inherent flaws of thermal spray. It is
frequently observed that the deposition’s quality has declined (Fig. 6).
Fig. 6 Typical scheme of thermal spray deposition
3 Materials for High-Temperature Coating
3.1 The Improvement of Wear-Resistant Materials
3.1.1 Coating
Surface engineering and matrix strengthening are two important approaches for
enhancing wear resistance in coatings. If desirable surface qualities and their perfor-
mance for mechanical components in service operation are to be achieved, surface
engineering may be thought of as the field that deals with those processes. Engi-
neering parts can be identified by certain functionalities, such as wear resistance,
corrosion resistance, and heat barrier. The thermal spraying approach is the most prac-
tical and cost-effective method for addressing these needs among the standard surface
engineering methods. Hardness is regarded as a significant component affecting wear
resistance. The composition and microstructure of coatings have a significant impact
on how hard they are. Because of recent advancements in amorphous materials and
coatings, which have exceptional mechanical and tribological qualities, they are
highly recommended as wear-resistant materials. To demonstrate the importance
of the Fe or Co components in the wear-resistant amorphous layer, Yanxu et al.
employed three raw powder materials in a plasma spray welding experiment [48].
The content of the replacement components (Fe or Co) can vary greatly, as can be
shown in Table 1. The higher hardness and wear resistance of carbides are evident.
They may be viewed as a hard phase in the matrix that improves the layer’s wear
resistance. The microhardness can be increased to 650–750 HV. The shape of the worn
coating demonstrated the coating’s tendency to become harder as the mass percentage
of the Fe-based amorphous alloy increased. Cobalt was identified in health care
literature as genotoxic and a supply concern, and it is advised to research and use other
cobalt substitutes. Along with the element Co, the category of key raw materials also
includes the elements W, Y, and Cr. Recent events have prompted industry managers
and academics to look for another replacement. The HVOF Fe-based coatings for
the automobile sector demonstrated improved hardness and reduced friction [50]. Fe
is a primary mass due to the coatings’ presence, which is shown in Table 2 [50].
A ternary of quaternary systems demonstrated a significant segregation in the
two binary compounds, and they accelerated a process of compositional modulation,
resulting in an improvement in anti-wear capabilities with regard to the compo-
sition of feedstock powder in the spraying [51]. The authors of this paper stated
the appealing chemical compositions of the powdered Fe-based alloys displayed in
Table 3. When compared to the control samples, the heat treatment reduced the tested
sample’s wear rate by 44.90%.
The effect of the HVOF spraying force on the wear resistance of an amor-
phous coating with the following composition was discovered by Ma et al. [52,
53]. The key factors enhancing wear resistance are reported to be increased tribo-
film stability and greater resistance to spallation. The amorphous coating demon-
strated excellent wear resistance in comparison to highly recommended coatings
like Fe48Mo14Cr15Y2C15B6 and Fe49.7Cr18Mn1.9Mo7.4W1.6B15.2C3.8Si2.4,
despite the lack of W and the extremely low Cr and Mo content. The positive
results in [54] validated the development of the amorphous structure using twin
wire arc spraying to deposit the layer with the wear resistance in the investiga-
tion direction. In this experiment, AISI 1018 steel was used as the substrate, and
Praxair Surface Technology’s 140 MXC nanocomposite wire was chosen because of
Table 1 Typical content of elements in powder materials (wt.%) [48]

Powder C Si Mn Cr Mo Ni P S W B Fe Co
42 Cr Mo 0.45 0.37 0.8 1.2 0.25 0.03 0.03 0.03 – – Remain –
Co-based 3.2 1.0 1.0 26.0 – 22.5 – – 5.0 – 3.0 Remain
Fe-based 1.7 1.8 – 4.0 – 7.5 – – – 3.0 Rest –
Table 2 Content of elements in the substrate and depositions [50]

Content (wt%) Fe C B Si S Cr Mn Ni P
Gray cast-iron 94 3.1 1.8 1.32 0.28 0.08 0.26 0.01 0.28
FeSiNiCr 73 – – 15 – 02 – 10 –
FeBCr 59 – 26 – – 15 – – –
Table 3 Content of elements in Fe-based alloy powder (wt.%) [51]

C Si B Cr Ni Fe
0.45 2.5 1.5 13 35 Rest
its higher wear resistance. An iron-rich amorphous phase was discovered by TEM
and RDX investigations. The tungsten and boron carbides are dispersed unevenly
throughout the matrix. It has been reported that the boron carbide phase exists at
the amorphous-crystalline interface. The study’s key finding was that the coatings’
amorphous-crystalline structure was responsible for their enhanced hardness and
lower wear. One observation is that there hasn’t been much research done on the
deposition of Fe-based amorphous coatings using ordinary air in open atmospheric
environments. This technology has various difficulties that restrict the practical use
of wear resistance in terms of reducing manufacturing costs. To tackle this issue,
some encouraging findings are provided in [55]. Table 4 [55] shows the chemical
composition of four types of Fe-based amorphous powder.
The particle size fraction of powders using the device Cilas-1090 is listed in
Table 5.
The main parameters in this experiment were varied according to Table 6.
A series of the experiments are conducted to reveal the oxygen contents in the
dependence of the main plasma spraying parameters (Table 7).
The outcome of this experiment demonstrated enhanced oxygen levels in the
coatings, with the feedstock X-5 having the highest levels. It has been noted that the
plasma jet’s particle oxidation is growing. As a result, since the process takes place
outside and the plasma is created using regular air, the oxygen level in the coatings
must be increased. However, given that there is some correlation between wear
resistance and coating hardness, as previously discussed, the oxygen concentration
may have a bidirectional influence on wear resistance. Because the increased oxygen
concentration in the X-5 powder was noted in Table 7. Additional research will
be required to uncover the new information. In the subsequent set of trials, it is
discovered that wear resistance and adhesive bonding are the key traits for judging
the coating’s quality. The adhesive bonding of the covering increased in step with
the rise in plasma current power. However, the wear resistance of the coating is
dependent on both the plasma current and the normal air flow rate (Table 8) [55].
When the plasma current rose while maintaining the air flow rate, it was observed
that the wear resistance of the coating created by the powder X-5 dropped while the
adhesive bond increased (see Tables 9 and 10) [55].
The wear resistance is complicatedly influenced by the air flow rate. As a result, the
low velocity creates the ideal environment for melting the particle, which results in a
strong link between the particles in the coating and increases wear resistance. Because
Table 4 Chemical composition of powder, % by weight [55]

Brand C Cr B Mo Ni Mn Si Nb V W Fe
code
H-4 0.11 32.9 0.10 3.30 5.0 1.05 0.70 – – – Remain
H-10 0.06 35.3 0.40 3.50 10.5 1.05 0.91 – – – Remain
B-5 0.41 12.5 – 0.70 – 0.54 0.66 0.73 0.35 6.10 Remain
X-5 0.73 5.0 0.25 4.20 – 1.25 0.84 0.54 1.20 – Remain
Table 5 Fraction distribution of 4 powder particle sizes [55]
Brand code Mean diameter (µm) Content of articles upon size fraction, %
0–1.0 1–1.5 1.5–2.0 12–16 16–24 24–32 32–48 48–64 64–96 96–128 128–192
H-4 53.9 7.7 18.9 14.1 – – – – 24.9 24.7 3.2 6.1
H-10 69.2 – 10.4 16.5 – – – – 16.3 40.8 3.1 12.6
B-5 66.4 – 14.0 21.5 – – – – 11.6 35.5 4.0 13.1
X-5 72.5 0.9 0.2 0.6 0.5 – – 14.5 4.5 43.4 5.0 13.8
A New Solution to Save Production Costs in the Deposition …
139
Table 6 The condition of the spraying modes

Series of experiment
1 Current I = 120 A Voltage U = 200 V Flow rate of air G = Spraying distance =
1.19 g/s 120 mm
2 Current I = 180 A Voltage U = 190 V Flow rate of air G = Spraying distance =
1.25 g/s 120 mm
Table 7 The comparison of the content of oxygen in the feedstock material and in the deposition
[56]
Powder brand code Spraying mode content of the oxygen, %
In feedstock powder (before In deposited coating (after
spraying) spraying)
H-4 1 0.19 1.70
2 0.19 1.14
B-5 1 0.30 1.33
2 0.30 0.07
H-10 1 0.18 1.24
2 0.18 0.90
X-5 1 0.14 2.15
2 0.14 1.60
Table 8 The wear resistance of the coating X-5 in relative units

Sample Current of plasma-I, Flow rate of gas-, Wear resistance in Adhesion bond of
A G, g/s relative units coating, MPa
1 150 0.55 21 22
2 150 1.13 53 41
3 150 1.76 38 35
4 150 2.42 65 30
5 180 0.75 28 45
6 180 1.42 68 56
7 180 1.76 42 54
8 180 1.95 60 30
the melting conditions are poor, if the flow rate of gas is continuously increased while
maintaining the same current, the cohesion bond will weaken and wear resistance
will drop. The cohesion and adhesion bonds are favorably impacted by the particles’
continued increase in velocity from the particle threshold value, which significantly
improves wear resistance since the velocity factor (kinetic energy) starts to predom-
inate. With the exception of extremely low air flow rates, wear resistance rises in
lockstep with air flow rate, nearly coinciding with the change in adhesion bond. It
Table 9 Shows how the wear resistance of the coating X-5 varies with plasma current and gas flow
rates
Sample Current of plasma-I, Flow rate of air-G, Wear resistance in Adhesion bond of
A g/s relative units coating, MPa
1 150 0.55 21 22
2 150 1.13 53 41
3 150 1.76 38 35
4 150 2.42 65 30
5 180 0.75 28 45
6 180 1.42 68 56
7 180 1.76 42 54
8 180 1.95 60 30
Table 10 Wear resistance and adhesion bond of coatings X-5 [55]

Sample number Current of Flow rate of Wear resistance in Adhesion bond,
plasma-I, A gas-G, g/s relative unit MPa
1 120 1,42 58 36
2 150 1,42 53 41
3 180 1,42 42 54
can be explained by the following factor, most likely: Low velocity impairs both
excellent coherence and adhesion bonds. The results in Table 7 show that while
the coating’s oxygen content has increased, this has had a bilateral effect on wear
resistance. If the coating improves wear resistance, it could, in certain situations,
have a beneficial impact. However, if the coating is bending or tugging, this has a
detrimental effect since concentrators and an uneven structure might act as crack
initiators. In order to more thoroughly investigate the impact of this component,
the following experiment was presented: the measurement of the friction coefficient
and the consideration of the morphology of contacting surfaces. The findings from
Tables 7 through 10 were analyzed to help explain some occurrences. Due to the low
plasma power and low particle kinetic energy, which result in a low coating density,
the wear resistance is often low when the gas flow rate is very low. The wear resis-
tance changes in a complicated way as the flow rate rises. First, the slow velocity
created the ideal environment for melting the particles, promoting an increased cohe-
sive link between particles in the coating, and improving wear resistance. Second, the
cohesive bond in the coating will weaken due to poor melting conditions caused by
the ongoing rise in gas flow rate without a corresponding change in current. It has a
detrimental impact on wear resistance. On the other hand, when velocity continues to
rise, cohesion and adhesion bonds are favorably impacted, enhancing wear resistance.
This situation occurred when the heating effect started to lose ground to the velocity
factor (kinetic energy) [57]. Due to their advantageous wear, self-flux materials are
utilized extensively throughout a wide range of sectors. The fundamental flaws in
the NiCrBSi coatings, such as their porosity and weak adhesive bond, prevent them
from performing well in harsh industrial environments. Heat treatment of the coat-
ings improved both the bonding strength and wear resistance [58, 59]. The melting
temperature of this self-flux alloy was around 1110 °C. When a powder particle
flies through a plasma arc with a high temperature and collides with a substrate, the
particle melts or partially melts, and the quick cooling causes the particle to transi-
tion to an amorphous state. However, several studies [60–62] have shown that the
NiCrBSi coatings crystallize during the heat treatment at a relatively low tempera-
ture. The microstructure and phase transitions of the as-sprayed NiCrBSi coatings
would be impacted by the annealing at the predetermined temperatures. The smaller
contacting area was mostly caused by the coatings’ increased hardness, which also
reduced deformation and decreased the wear volume and friction coefficient. The
time required to achieve maximum hardness and improve the wear resistance of
NiCrBSi coatings decreases with increasing annealing temperatures. This partic-
ular mixed microstructure consists of both crystalline and amorphous phases. The
quick cooling rate of partially melted and fully melted particles after deposition and
impact is what causes the heterogeneous microstructure. A heat treatment reverses
the coatings’ declining hardness and wear resistance trend.
3.1.2 Grain Size of Particle and Nanoscale Effect
According to the varied tribological conditions, the findings of the studies [63, 64]
showed an opposing influence on the wear resistance of WC–Co and Mo coatings.
When sliding distance and speed are increased, the wear resistance of Mo coatings
also rises. The results of the experiment showed that even if the hardness increases,
the wear resistance increases when the grain size is reduced from 40–90 to 15–40
µm. This demonstrates the complexity of the wear phenomenon since it depends
not only on hardness but also on other factors, such as the coating’s microstruc-
ture, the load being applied, the sliding speed, and the lubrication conditions. The
matrix microstructures significantly affect the coatings’ ability to resist wear. In this
instance, the size of the grains, the morphology of the grain boundaries, and the
material’s dislocations all have a significant role in how they behave. It has a notice-
able impact on how well the material wears. The amount of nanoparticles present,
grain size, grain boundary structure, and dislocation type all play a role in anti-wear
effectiveness. For instance, in [65], the author looked at various ratios of tough B4 C
nanoparticles with a size range of 10–50 nm as reinforced argents in the matrix of
Fe–based amorphous powders. The following are the ratios: 0, 5, 10, 15, 20, and
25%. According to reports, adding more B4 C nanoparticles increases the composite
coatings’ nano-hardness, but at 20% B4 C concentration and higher, their fracture
toughness starts to decline. Because of this, the changes in the deposited materials’
mechanical characteristics were in line with those in the transition from a brittle to a
ductile state. The results of experiments reported by Wang et al. in [62] revealed an
intriguing tendency regarding the grain size effect of nanoparticles on wear resistance
in the case of WC–Co under various tribological conditions: the grain size had an
opposite effect on the wear resistance in a dry sliding environment, with the excep-
tion of the ultrafine grain size of WC–Co powder, which has not only extremely high
hardness but also good fracture toughness. The role of interfacial bonding between
carbide grains and metallic binders can be used to elucidate this idea. Rather than
hardness, this impact is more pronounced on wear resistance [66]. Although nanos-
tructured coatings are still in the development stage, they hold great promise for the
high-tech industry in the near future, particularly in the defense industry given the
huge investment needed for turbine blade thermal-barrier coatings, rotating compo-
nent wear resistance and corrosion resistance in heavy operation environments, and
camouflage stealth coating in high-tech weapon systems. In terms of sustainable and
green development, the nanostructured coatings will support industries by enhancing
their strength, toughness, wear resistance, and thermal barrier, which will lower the
cost of production, repair, maintenance, and overhaul.
3.1.3 Influence of the Spraying Process
The wear resistance is impacted by the spray procedures. As of right now, spraying
an amorphous iron-based coating is advised using the plasma spray, HVOF spray,
and detonation spray. In comparing the three, studies evaluated the differences in
microstructure and wear performance. The raw materials used as feedstock were
amorphous powders with the following formula: Fe48Mo14Cr15Y2C15B6 (at%).
The powder has a nominal size of 50–80 µm. The results of the wear test and
microstructure analysis both indicated that the wear rate increases as the sliding
velocity rises. Compared to HVOF and plasma spray, detonation spray generated the
least amount of wear. Because the plasma coating in this case has a lower density
than the remaining approaches, the wear rate is lowest when compared to the HVOF
and detonation procedures [67, 68]. It is interesting that plasma spray, HVOF spray,
and detonation spray have amorphous contents of 79.39%, 85.26%, and 88.14%,
respectively. The plasma jet has a working temperature range of 6000–10000 °C,
which is significantly greater than the other two spray types. Before the powder and
substrate collided, a portion of the powder solidified in flight. As a result, the plasma
spray coating contains the least amount of amorphous material.
3.2 Relation Between the Wear and Hardness
The resistance of the material to persistent deformation is referred to as “hardness.”

By bending, scratching, or resisting identification, the hardness can be assessed. The
capacity of a material to withstand material loss as a result of mechanical action is
referred to as toughness. Due to its toughness, a material may be wear-resistant yet not
very hard. Higher-strength materials are also more resistant to wear. The fragile metal
illustrates the tiny difference. Brittle metals are harder as a result, but less resistant to
wear. The combination of metals’ strength and hardness provides the explanation. The
composition and microstructure of a substance will determine its intrinsic hardness.

Speaking of wear resistance, there are many additional factors that might affect
it, including abrasive qualities, the environment, and the testing procedure. This
relationship is a difficult problem that requires further study, and the best answer
will be determined depending on the operational circumstances. The significance
of toughness in this situation merits consideration. The combination of strength and
ductility that can resist a rupture is called toughness. In this scenario, plastic or elastic
deformation is possible. So, which is preferable: highly wear-resistant coatings or
really hard materials? The application in the operating environment will determine
the response. Less stiff and harder materials are those with reduced hardness and
strength. This type of material, which has less abrasive wear, has found widespread
use in mechanical applications such as cutting tools and the automotive and aerospace
industries. The hard coating may be more resilient to endure more extreme working
circumstances, such as higher abrasive action or shock situations. The problem is that
strength and hardness by themselves do not improve wear resistance. It is necessary
to take into account some other factors, namely surface roughness, the lubrication
environment, and the coefficient of friction.
3.3 Relation Between the Wear and Friction
The components in mechanical systems are worn out by friction. For this reason,
lubrication is required to reduce friction. Although they are not intrinsic qualities
of the materials, friction and wear are connected to one another in the tribology
environment. Wear and friction are two different types of reactions to the same tribo-
logical environment. They form the distinct functions of the tribology environment
and exhibit a strong link. Because of this, the mechanical system’s tribological perfor-
mance is highly dependent on the variables affecting wear and friction. Because the
coefficient of friction is changing, the substrate’s surface roughness affects how long
thin, soft coatings last. Since the wear of harder materials is less than that of softer
materials if the coefficient of friction is the same, there is a reduction in wear on
that surface until it occurs when the coating on the surface of the substrate is harder
than that of the matching one. Friction and wear are linked to irreversible dissipative
processes that decrease mechanical power and create entropy. Friction supplies the
energy that causes wear. The loss of power caused by the friction force causes the
usable work to be converted to heat. Heat on the morphology has a negative impact
on the mechanical properties of the contacting surfaces. It is accepted that heat and
load led to irreversible plastic deformations that were accompanied by friction force
and energy loss. When the load is normal to the contacting interface between the
two entities, adhesion bonding can occur at least through Van der Waals force. The
friction force is made easier by this sticky action, which also prevents wear. Overall,
wear is defined as the volume of material being removed from a contacting surface.
Other forms of wear resulting from surface damage include material mobility over a
surface and material adhesion from one surface to another. In every situation, wear
causes the surface to deteriorate. Wear, in turn, results in surface deterioration, speeds
up the dissipative processes and has a negative impact on friction. There isn’t always
a consistent mathematical relationship between friction and wear because a number
of other elements may be at play at the same time. For instance, in the case of friction
on the steel surfaces between a steel and a polymer reinforced with minute glass fibers
in the situation of linear sliding contact, the authors [69] found that the elevation of
the friction under the normal load is virtually linear.
4 Methodology for Evaluating the Performance

of the Deposition
The following primary criteria are used to evaluate the effectiveness of thermal
spray coating: the hardness; the enthalpy of the stream; the velocity of the particle;
the porosity; the wear resistance; the corrosion resistance; and the adhesive and
cohesive bonding strength.
4.1 Porosity—Its Influence on the Quality of Coating
The percentage of total space inside a given volume of material is known as porosity.
The percentage of open and closed space inside a coating material’s volume is known
as porosity in the case of thermal spray coating. For all thermal spray techniques,
porosity is an inherent occurrence. Depending on how the coating was applied, the
porosity has advantages and disadvantages [70]. The porosity has a beneficial func-
tion in thermal-barrier coatings [70], but its effects on wear- or corrosion-resistant
coatings vary depending on the loading and lubrication conditions. Due to its biocom-
patibility and resistance to corrosion, the porous titanium implant is highly recom-
mended in medicine [71]. The right biomechanical characteristics and bio-functional
harmony of the implant are emphasized. It is helpful to think about a few techniques
for evaluating porosity in light of this topic. There are three types of porosity: open,
closed, and total.
The following characteristics—pore form, size, distribution, direction of splats,
and size of micro dislocations—define porosity. The spraying parameters, the phys-
ical, mechanical, and chemical interactions between the in-flight particle and the
spraying jet, as well as the substrate contact process, can control all of them. The
direct approach, which involves calculating the bulk volume of the porous sample
and then calculating the volume of skeletal material devoid of pores, is the main tech-
nique for evaluating porosity. As a result, the pore volume is determined by taking the
entire volume and subtracting the covering material volume. Mercury infiltration, gas
adsorption, and water intrusion are the three main components of the direct approach.
The physical processing of samples during measurement is necessary for the direct
procedures. The indirect approaches include sample analysis and picture processing.
All techniques for determining porosity may be categorized and prioritized in [72].
The study of micrographs employing scanning electron microscopy, atomic force
microscopy, transmission electron microscopy, electrochemical impedance spec-
troscopy, neutron scattering, thermometry, and other indirect approaches is among
them. The measuring pore diameter in the mercury intrusion method might increase
to 0.0070 µm. The following equation gives the porosity percentage:
Porosity (%) = ×100 (3)
where V1 is the total volume of mercury in the voids and V2 is the sample’s bulk
volume, porosity (%) is calculated as V1/V2 × 100. Since mercury is unhealthy
for the body, safer substances like gallium and indium can be used as replacements.
The hydrophobic materials are subjected to the water intrusion procedure. The same
concept as mercury intrusion is applied. The mercury approach is less complicated
than this one. There is water surrounding the sample. The sample will absorb the water
because water will diffuse into it when air is forced out of all pores, especially those in
networked pores or microcracks that link capillaries. The volume of pores is directly
related to the weight difference between the sample before and after exposure to water.
Although the enclosed pores cannot be measured using this approach, the apparent
porosity is often as close to the total porosity as is practicable. All indirect techniques
can be regarded as non-destructive. Through the study of cross-section specimens,
microscopy enables a more comparative evaluation of the pore in terms of shape
and geometry. The preferred method for achieving a resolution of 200 nm is optical
microscopy. The SEM, TEM, and AFM are frequently useful at the micrometer and
nanoscale scales. The disadvantage of these techniques is that sample preparation
and analysis require knowledgeable personnel and specific equipment in order to
attain the required resolution. To successfully estimate the 3D porosity of thin films,
a novel method that combines a helium pycnometer, computed micro-tomography
(CMT), and specialized software has been developed [73].
4.2 Measurement of the Wear Resistance
4.2.1 The Standards ASTM G99
The pin-on-disc test, which is very straightforward and has a lot of lubrication, is the
most often used technique in mechanical engineering for measuring wear and friction
of materials. Testing is carried out in accordance with ASTM G99, G133, or F732
standards. This standard establishes the procedures for calculating the sliding wear
of materials in accordance with a pin-on-disk system. Abrasion-free environments
are used to test each pair of materials. The friction coefficient may be calculated
using this method. The system’s applied load, sliding speed, sliding distance, ambient
environment, lubrication conditions, and material qualities will all have an impact on
how much wear occurs in a given system. Predicting the relative ranking of material
combinations is inherent to all wear test methods. The pin-on-disk test technique
does not aim to reproduce all the situations that may be seen in service, thus there
is no guarantee that the test will represent the wear rate of a specific material in
conditions different from those in the test (for example, lubrication, load, pressure,
contact geometry, removal of wear debris, and presence of a corrosive environment).
Now it is frequently observed in practice when the researchers may adhere to all of the
guidelines provided above but assign different test parameters, such as applied load,
sliding speed, materials, and ambient conditions, and therefore achieve different test
results.
4.2.2 The Standards ASTM G133
The process for determining how typical materials and other potentially wear-
resistant materials wear in sliding conditions is governed by ASTM G133. A linear,
reciprocating ball-on-flat-plane mechanism makes up the test’s basic design. The
unique value of this approach is that the direction of the relative motion between
sliding surfaces is switched. Consequently, the slide is moving back and forth in
a straight line. However, this technique may be used to calculate the coefficient of
kinetic friction. The important measurements are the wear volumes of the contacting
ball and flat specimen materials. Both dry and lubricated operations should use
this test technique. This test technique is not appropriate for use when operating in
corrosive environments. As the standard, SI units of measurement are used. When
the identical materials are moved in this manner instead of continually sliding in
one direction, a different wear value may be obtained. According to the particular
application, test loads and speeds should be chosen.
Taber abrasion (ASTM D4060). Taber abrasion is a quick, simple, and cost-
effective way to collect comparative wear data for multi-layer coatings. A set of
specialized taber wheels applies a cyclical abrasive force to the coatings. From the
measurements taken before and after the test, the mass loss may be computed.
The coefficient of friction (ASTM D1894) is determined by measuring the static
and dynamic friction forces applied to the two specified materials. According to
this test, the two primary factors used to calculate the friction coefficient are static
resistance and dynamic resistance.
4.2.3 The Standards ASTMF732-17
For polymeric materials, this standard is advised. This test method is used to evaluate
material combinations in the event that it is determined that the wear is concentrated
on the polymeric prosthetic component. If the sliding distance varies throughout the
polymeric specimen surface due to the complex motion of the patterns, wear may
be reported as a function of wear cycles. Wear is defined as the volume loss of the
specimen as a function of sliding distance. The experimental weight loss divided by
the polymer’s density is used to calculate the volume loss of the polymer specimen.
Wear should be interpreted simply as a function of both the number of wear cycles and
the sliding distance. Because the contact surface and wear movements are simplified,
this test technique only represents a first step in the overall wear recommendation
of a candidate material. Before committing to more expensive and time-consuming
joint simulator testing, the test technique is recommended for screening material
combinations for wear performance in various orthopedic wear applications quickly
and accurately. The measurements are given in SI units or inch-pound units.
4.3 Corrosion Test
For the purpose of determining a material’s resistance to corrosion under certain

environmental circumstances, such as humidity, toxic aluminum concentration (salt
percentage), temperature, and duration, corrosion testing is advised. For a multilateral
application, corrosion testing is connected to a variety of industries. Materials and
equipment may be permanently damaged by corrosion. These losses include dangers
to health and safety, equipment failure that follows, and costs and lifetimes that
are expensive to correct. The key to determining if a material will be suitable for
the settings in which it will be used is to choose the correct material and conduct
corrosion tests. Depending on the materials and environmental circumstances, many
industrial standards are used to evaluate corrosion, including the following:
ASTM A262 Practices A, B, C, E, and F are used to assess the susceptibility against
the intergranular attack in austenitic stainless steels.
• The hazardous intermetallic phase in duplex austenitic and ferritic stainless steels
may be identified using ASTM A923 Method C.
• When performing the aluminum exfoliation test, ASTM G34 is advised.
• For the evaluation of the pitting and track corrosion resistance of stainless steels
and similar alloys, ASTM G48 Methods A, B, C, D, E, and F are used.
• For a visual assessment of the exfoliation corrosion susceptibility of aluminum
alloys from the 5XXX family, ASTM G66-99 (2005) e1 is advised.
• ASTM G28 Methods A and B are suggested for evaluating the susceptibility to
intergranular corrosion in wrought, nickel-rich, chromium-bearing alloys.
• The Humidity Test (AMS 2700), MIL-STD 753, and Methods 102 and 103 of
ASTM A380 and A967 are reliable and efficient tools for passivation tests.
• The ASTM G67-04 Standard and mass loss upon exposure to nitric acid are used
to assess the susceptibility of the 5XXX series of aluminum alloys to intergranular
corrosion.
• The standards for salt spray tests and salt fog include ASTM B117, MIL-STD-
202, MIL-STD-810, and NASM-1312-1. You can use a salt spray environment to
gauge a coating’s corrosion resistance. The military standards are MIL-STD-202
and MIL-STD-810.
• The primary procedures for the test are ASTM D4541-02 and ASTM standard
C633-13.
4.4 Adhesive Test
The adhesive bond between a thermally sprayed coating and the substrate is
frequently a crucial feature, following the ASTM C633-13 standard. The examina-
tion of the tensile load required to separate the coating from the substrate is the most
commonly used technique for determining the adhesive bonding of the coating. The
ratio of the greatest load applied at failure to the cross-sectional area determines the
coating’s tensile strength. When a fracture develops at the coating-substrate contact,
the bond strength is revealed. When the failure occurs fully within the coating, the
cohesive strength of the coating is observed. For the better coatings, the epoxy glue
will frequently fail.
ASTM C633-13 (2021) is the new version applied for the adhesion or cohesion
strength of thermal spray coatings.
This standard is used for acceptance certification and quality control. Designing
or calibrating thermal spray equipment and procedures, as well as assisting in the
creation of novel thermal spray depositions with improved adhesion and integrity,
might be valuable. It is advised to use this standard to compare the adhesion or cohe-
sion strengths of coatings with materials intended for thermal deposition that are
comparable in kind. The test should not be advised for purposes of providing intrinsic
value, such as figuring out whether or not a coating would experience particular envi-
ronmental conditions. The form of the specific coated item, the spraying procedure,
the thickness of the deposition, and other variables all affect the real strength. Addi-
tionally, a coating may be strained in a more complicated way in practice. Regarding
the definition of the bonding strength between the coating and the substrate, the
approach is appropriate for all common thermal spray procedures.
Notice: The vast spectrum of thermal spray coating materials includes ceramics,
cermets, and composite materials. A coating is made up of several spray ingredients
for variety, specifically an oxide layer sprayed on top of a metal-bonding layer.
The substrate is often made of metal; however, it can also be ceramic or graphite.
Typically, this test is run at room temperature. Testing at higher temperatures is not
advised since a proper adhesive bonding agent is needed. It is advised to employ
very low (cryogenic) temperatures in some specialized research. This test is only
applicable to materials thicker than 0.015 inches (0.38 mm). The restriction is put in
place since the test involves the use of an adhesive bonding agent. Thus, the bonding
ingredients tend to penetrate thermal spray coatings and may invalidate the results
of testing. It is expected that new adhesive bonding agents will be developed to aid
in lowering the minimum thickness needed for coatings. The numbers expressed in
inch-pound units are considered the norm.
Tensile and shear testing (ASTM F1147, F1160, and F1044) Mechanical testing
of coatings often requires specimen preparation according to the typical sketch. The
resulting test sample is then tested in tension per ASTM F1147 or shear per ASTM
F1044 until failure. Shear fatigue is also often performed on coating test samples in
accordance with ASTM F1160.
4.5 Thermal Insulation Test
ASTM E1461-13 is a standard test method for thermal diffusivity by the flash
method. A crucial transient thermal feature needed for many applications is thermal
diffusivity. For measuring the thermal diffusivity of a variety of solid materials, the
flash technique is advised. Because of the specimen’s small size, straightforward
geometry, rapid measurement, and simple handling, this approach provides a clear
benefit. A homogeneous, isotropic, opaque solid specimen’s specific heat capacity
may be calculated under precise, exact circumstances. For the purpose of deter-
mining the thermal diffusivity of mostly homogenous, isotropic solid materials, this
test procedure is advised. This test method is appropriate for measurements on almost
completely solid materials that are opaque to the delivered energy pulse (preferred,
but low porosity is acceptable). The values given in SI units are acknowledged as
being the norm. This standard does not include any additional units of measurement.
4.6 Hardness Testing
The Rockwell, Brinell, Vickers, and Knoop hardness tests are the four most
commonly used methods for determining a material’s hardness. For rapid hardness
tests in production control, Rockwell is advised. It is typically used with metallic
materials. After an indenter has been pushed into the specimen material at a certain
weight, the depth of the indent is measured to calculate the Rockwell hardness (HR).
Steel balls or diamond cones are used. When assessing the hardness of larger samples
of materials with coarse or uneven grain structures, Brinell hardness testing is prefer-
able. Using a tungsten carbide ball, the Brinell hardness test (HB) indentation creates
a sizable imprint. The indent’s size may be read visually. The intended users feature
tungsten carbide tips that are spherical. In the microhardness testing range, Knoop
(HK) is a Vickers test substitute. The major purpose of this test is to prevent cracking
in brittle materials. It is ideal for facilitating the testing of thin layers’ hardness.
The lengthy diagonal of the asymmetrical pyramidal diamond used as the indenter
is used to visually measure the indentation. In contrast to the previous two methods,
the Knoop testing method typically employs applied stresses no greater than 1 kgf
to determine microhardness using a specific elongated pyramidal probe tip. Vikers’s
technique of testing, which uses an applied force no larger than 1 kgf, is comparable to
Knoope testing. When a diamond pyramid indenter is introduced with a certain force,
the diagonal lengths of an indent left in the sample material are measured to calculate
the Vickers hardness (HV). Utilizing a table or formula, the microscope measures the
Table 11 Specific requirement

Testing method Applied standard Load range in unit (kgf) Load range in newton
Rockwell ISO 6508 15–150 (147.1–1471 N)
ASTM E18 15–150 (147.1–1471 N)
Brinell ISO 6506 1–3000 (9.807–29420 N)
ASTM E 10 1–3000 kgf (9.807–29420 N)
Vickers ISO 6507 10 to ≤100 (0.0981 to ≤9.807 N)
ASTM E384 1 to ≤1 (0.0098 to ≤9.807 N)
ASTM E384 >1 to ≤120 (>9.807 to ≤1176.800 N)
Knoop ISO 4545 1–1 (0.0098 to ≤9.807 N)
ASTM E 384 1–1 (0.0098 to ≤9.807 N)
indent’s diagonals to establish the hardness. Generally speaking, the material behind
the indent during the hardness test should be indicative of the whole microstructure.
Therefore, a larger impression is advised than for a homogeneous material if the
microstructure is rather coarse and heterogeneous. The following primary factors
should be taken into account when choosing the hardness test method: the type of
material to be tested, whether compliance with a standard is required, the tested
material’s typical hardness, the homogeneity or heterogeneity of the testing mate-
rial, sample size and shape, mounting circumstances, the number of tested samples,
and the degree of result accuracy. There are specific requirements for the different
hardness tests (Table 11).
4.7 Measurement of Enthalpy
An approach called calorimetry is typically used to assess enthalpy. By monitoring the

temperature variations, the heat evolved during the operation is typically computed
using the known heat capacities of the liquid and the calorimeter. Two different
situations are used to conduct these measurements: It is important to remember that
enthalpy and internal energy can be calculated using two different methods: constant
volume, which is referred to as internal energy, and constant pressure, which is
referred to as enthalpy.
– At constant pressure, qp
– At constant volume, qv .
Enthalpy is defined as the energy released at constant pressure. Mathematically,
it is the sum of internal energy with the product of pressure and volume.
H = U + PV (4)
where
H is th enthalpy
U is the internal energy
P is the pressure of the system
V is the volume of the system.
Directly calculating a system’s absolute enthalpy is rather challenging. So, it is
possible to determine the enthalpy around a reference point. As a result, it is used
to calculate enthalpy change. Enthalpy change, or ∆H, is positive for endothermic
processes, whereas it is negative for exothermic ones. Calorimetry methods are used
to measure the change in enthalpy under laboratory circumstances. Enthalpy change
is understood to be the heat change at constant pressure, or ∆H = qp . This approach
involves partially filling the system with a specified amount of water and inserting
a thermometer to gauge the temperature change. The heat generated by a chemical
reaction is absorbed by the water. The quantity of heat that has been absorbed or
developed is determined by the change in water temperature. In this procedure, the
energy change or enthalpy change is computed as
∆H = q p = m · c p · ∆T (5)
where
m mass of water
cp specific heat capacity of water at constant pressure
∆T temperature difference.
4.8 Determination of the Velocity of Particles in Plasma

Spraying
A high-speed imaging camera can capture fast-moving events at high frame rates
and replay the recorded pictures as a slow-motion movie. When choosing a high-
speed camera for your study, there are a number of factors to take into account. This,
of course, has an impact on the intended resolution, so a powerful system is often
required if a particular resolution and frame are desired. Your image’s duration is
determined by the frames per second; a longer movie will be produced at a higher
frame rate. The image size, object velocity, and temporal resolution must all be
taken into consideration when calculating the frame rate. The determination of the
frame rate is greatly influenced by the image size. Because bigger events (events
with larger picture sizes) often last longer throughout the full field of vision, they
tend to have lower frame rates than those recorded at a higher magnification. The
frame rate must be raised to capture a shorter period of time (within a narrower
field of vision). The resolution is the number of pixels for a specific field of vision.
The image resolution determines which features of your image can be resolved. A
photograph with a greater resolution will really be of “better quality.” The greatest
resolution and required frame rate cannot, however, be obtained with all cameras.
It is necessary to first determine the frame rate and then assess the resolution of
potential cameras in order to choose one that will deliver the proper frame rate and
a suitable resolution. The amount of time that a camera’s film (or digital sensor) is
exposed to light is known as exposure time (also known as shutter speed). Motion
blur, also known as the sharpness or blurriness of a picture, is influenced by exposure
duration. A little bit of blurriness in a photograph is usually accepted, but if there is
a lot of motion blur, the subject’s edges look blurry, and it is hard to measure and
distinguish the subject without a clear outline. Due to their high frame rates, high-
speed imaging cameras often have short exposure durations. A shorter exposure time
indicates that less time is needed for light to reach the camera’s sensor. Some cameras
require a manual trigger, which means we must wait for the event to happen before
activating the camera system to start taking pictures. The electronic shutter may be
precisely timed to operate in phase with a timing signal through synchronization. The
Inter-Range Instrumentation Group (IRIG-B) time code with or without phase shift,
the internal camera clock (crystal frequency oscillator), the external clock source
(f-sync signal from a second camera or any source that generates a TTL pulse),
and the video signal are all synchronization instruments (f-sync pulses generated
by the video raster generator). Multiple cameras may be present. A good lens is a
crucial component of a successful photographic setup. There are several factors that
need to be taken into account while choosing lenses. This comprises the following:
sensor size, flange focal distance, field of vision, depth of field, and lens mount.
The lens mount serves as the mechanical (and occasionally electronic) link between
the camera body and the lens. The focal length is the separation between the lens’s
nodal plane and the point at which light waves converge. The opening in the lens
through which light passes is called the aperture (also known as the f-stop). The
aperture controls both the amount of light the camera receives and the angle at which
different wavelengths focus on the picture plane. As was already noted, the image
size is essentially determined by the field of vision. The area of the image that seems
to be reasonably crisp is called the “depth of field” (as opposed to softer portions of
the image, which may appear as a background). The actual dimensions of the image
sensor’s active area make up the sensor’s size. The distance between the picture plane
and the front face of the image camera’s front mount is known as the “flange focal
distance.” The sort of photographs that are needed and the topic that has to be shot
will eventually choose the proper lens, which will deliver a clear and accurate image
of its subject. The price variations between lenses often correspond to the variations
in their speeds. Fast lenses are more expensive and lighter, and they allow us to
photograph in low light with faster shutter speeds. Depending on the application,
choosing between monochrome and color systems is a crucial choice. Color masks
are used in polychrome systems to lower sensitivity by two to three times. As a result,
a polychrome system needs two to three times more light to produce a picture with the
same exposure as a monochrome system. While the ability to discern between hues
may be useful in some applications, it is not always essential in laboratory research
because the drawback of decreased light sensitivity is frequently noticeable. For the
examination of photographs, a variety of tools are available. Manufacturers of high-

speed cameras typically sell their own packages of analysis software. This program
may be used to obtain quantitative quantities, including the subject’s velocity, as well
as to edit pictures and videos. Additionally, there are various free picture analysis
apps that should be taken into consideration.
5 Conclusions
– Spray thermal coatings are used to deposit heated powder droplets onto a
substrate’s surface, creating a coating and giving it a certain surface quality
that it did not have before. As a result, the substrate provides the component’s
bonding and cohesive strength, while coatings improve the surface’s superior
properties, including wear resistance, corrosion resistance, and heat resistance.
The main benefit of thermal spray coatings is that they may provide certain
surface characteristics that are only possible by thermal spraying and operate
well in high-temperature environments. Therefore, for new and reconditioned
sections and components for jet engines and gas turbines, compressors, and
pumps, thermal spray coatings are widely utilized in the aerospace, automotive,
and power generation industries.
– The most commonly used thermal spray technology for coatings is plasma
spraying, which can apply coatings through both inert gases and their mixtures as
well as through regular air. In order to ensure the resourcefulness of the electrodes
and the quality of the coatings, particularly the Fe-based amorphous powder, the
construction of this type of plasma torch and the entire system requires some
specific design. This helps to lower production costs and improve some coating
properties, depending on the working conditions.
– The modernization and creative design of the plasma torch’s construction can
help increase the efficiency of the thermal spray process. These improved solu-
tions focus on stabilizing the plasma stream, which raises the temperature and
velocity of the particle stream. This topic has been the subject of various fasci-
nating investigations, such as those on better laminar or cascaded plasma torches
with swirling units. The internal shape of the anode nozzle, in particular, has
a significant impact on the kinetic and thermal characteristics of the in-flight
particles, which in turn affect the coating quality.
– A unique annular input unit for supplying powder material that coincides with
the Laval inner contour of the anode in the plasma torch was installed in the
cascaded plasma torch to modernize the supersonic plasma jet outflow. A swirl
unit’s vortex movement enhances gas mixing in the arc stream, isolates it from the
plasma channel walls, and raises the voltage of the plasma jet. The plasma torch
will operate more favorably with a longer jet length because the axial temperature
gradient will be improved, the cathode’s lifespan will be increased by a reduction
in plasma current, and the voltage drop may be increased thanks to the changeable
length of the plasma jet.
– Surface engineering and matrix strengthening are the main avenues for enhancing
wear resistance in coatings. This issue can also be taken into account in close
connection to the composition, grain size, and spraying process parameters, partic-
ularly the velocity and temperature of the particle stream. Fe-based amorphous
coatings and other nanocomposite coatings with higher wear resistance can be
found in high-temperature environments. The modern wear resistance capabil-
ities of the surface in a heavy operating environment are made possible by the
right design of the surface coating layer. It is generally acknowledged that a key
factor in determining how resistant a material is to wear is its hardness. However,
depending on the macro- and microscale domains, as well as the lubrication condi-
tions, the stiffness of the surface layer in the substrate plays a variety of roles in
the wear resistance.
– The porosity has advantages and disadvantages depending on how the coating
was applied. The porosity has a beneficial function in thermal-barrier coatings,
but depending on the loading and lubrication conditions, it has a variable impact
on wear- or corrosion-resistant coatings. The thermal insulation of thermal-barrier
coatings is greatly influenced by the size, shape, and distribution of the pores. The
spraying parameters, the physical, mechanical, and chemical interactions between
the in-flight particle and the spraying jet, as well as the substrate contact process,
can control these features.
– It is obviously challenging to suggest a general approach for all coating types given
their diverse uses and operational environments. The most often drawn conclu-
sion from this chapter is how to enhance everything, including the engineering
surface, the substrate layer’s matrix, and the plasma torch’s unique construction,
with the right technological processes and feedstock materials. The quality of the
coatings and the cost of manufacturing are heavily dependent on the managers’
and investors’ wise and prudent decisions.
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018-30090-9
Duong Vu received a Ph.D. in mechanical engineering from Saint Petersburg University, Russia,
in 1993. He graduated from the university in 1980 (Eastern Ukrainian University). His diploma
is in Equipment and Technology of Welding Production. He is currently the vice dean of the
School of Engineering Technology at Duy Tan University in Danang, Vietnam. His interests are in
welding technology, plasma spraying technology, surface treatment, materials science, manufac-
turing processes, applied mechatronics, entrepreneurship, professional starter education, and engi-
neering technology education. He published about 40 works (papers, proceedings of international
conferences, books, and book chapters) and taught courses such as Applied Strength of Materials,
Materials and Manufacturing, Machine Design, Machine Element, and Production Drawing and
CAD.
Wear/Erosion Resistant
High-Temperature Coatings
S. Arulvel, D. Dsilva Winfred Rufuss, Jayakrishna Kandasamy,

P. Kumaravelu, R. Prayer Riju, and P. U. Premsuryakanth
Abstract Numerous mechanical parts, including, rotary vanes, emission and intake
blowers, rotor rings, boiler tubes, steam turbines, gas turbines, pulverized fuel supply
lines, nozzles, and gun barrels, are susceptible to erosive wear. Due to the simulta-
neous effects of various factors such as particle size, velocity, hardness, and impact
angle, this erosive wear phenomenon is extremely complex. To alleviate the prob-
lems caused by erosion, several technical solutions have been proposed. Amongst
these coatings are one such solution. The application of high-temperature coatings
was found to be an efficient technique to reduce erosive wear in extreme environ-
ments. In recent years, many ceramic and metal coatings have both advantages and
drawbacks. Therefore, it is crucial to discuss how different high-temperature coatings
might enhance the erosive wear resistance. The technology development, influencing
variables, properties, and failures of high-temperature erosion-resistant coatings are
therefore highlighted in the current chapter. This could open up new opportunities
for research into cutting-edge high-temperature erosive wear resistance coatings.
Keywords Erosion · Wear · Coatings · High temperature · Failures
Nomenclature
Ti–6Al–4V Alpha-beta titanium alloy

Al2 O3 Alumina
Al Aluminium
AISI American Iron and Steel Institute
ASTM American Society for Testing and Materials
APS Atmospheric plasma spray
B Boron
C Carbon
S. Arulvel (B) · D. Dsilva Winfred Rufuss · J. Kandasamy · P. Kumaravelu · R. Prayer Riju ·

P. U. Premsuryakanth
School of Mechanical Engineering, Vellore Institute of Technology, Vellore 632014, India
e-mail: gs.arulvel.research@gmail.com
162 S. Arulvel et al.
CNTs Carbon nanotubes

CVD Chemical vapour deposition
Cr Chromium
Cr3 C2 Chromium carbide
Co Cobalt
°C Degree Celsius
DC Direct current
g/g Gramme per gramme
HVOF High Velocity Oxygen Fuel
HEA High-entropy alloys
h Hour
HfC Hydrofluorocarbon
K kelvin
Kg Kilogramme
kW kilowatt
LZO Lanthanum zirconium oxide
Q345 low alloy steel
µm Micro metre
mm Millimetre
Mg Milligramme
min Minutes
NASA National Aeronautics and Space Administration
Ni Nickel
NiAl Nickel aluminide
IN625 Nickel-based superalloy
NiCr Nickel-Chromium Alloys
PVD Physical vapour deposition
RF Radio frequency
Gr Roentgenium
SEM Scanning electron microscope
SA210 Seamless medium carbon steel
s Second
Si Silicon
SiC Silicon carbide
SiO2 Silicon dioxide
SPE Solid particle erosion
SS Stainless steel
TaC Tantalum carbide
TBCs Thermal barrier coatings
Ti Titanium
TiN Titanium nitride
MDN321 Titanium stabilized austenitic stainless steel
WC Tungsten carbide
UV Ultraviolet
V Vanadium
Wear/Erosion Resistant High-Temperature Coatings 163
YSZ Yttria stabilized-zirconia

Y Yttrium
ZrC Zirconium carbide
ZrO2 Zirconium dioxide
1 Introduction
Solid particle erosion (SPE) and high-temperature erosion wear are the major issues
in many of the engineering components. This type of erosions has a wider impact
on the failures of components in various applications such as steam turbines, gas
turbines, wind turbines, hydroelectric power plants, and boiler tubes, which leads
to plant shut down and resulting in large economic losses through maintenance
and replacement [1]. The gas turbine engine is a critical part of the aircraft, which
often subjects to the SPE damage. This leads to high maintenance costs, high fuel
consumption, and high emissions problems [2]. In addition, the mission completion
rates, readiness, and safety decrease could produce the catastrophic accidents of
the turbine engines [3]. The wind turbines are also subjects to SPE damage, which
can result in higher cost with decrement in the annual energy production. In other
application like hydroelectric power plants, the corrosion and SPE are the challenging
problems and can result in increased maintenance costs and production losses. So,
it is clear that the erosion wear was the serious drawbacks in the components of
engineering applications [4]. Hence, to enhance the life of the components with
low maintenance costs, an extensive effort has been put up to improve the surface
properties of the materials [5], which is briefly discussed in this chapter.
Materials like titanium, stainless steel, and nickel-based alloys were often used in
the aerospace, automobile, and energy sectors, where the erosive wear is predomi-
nant. So, researchers studied the erosive wear behaviour of titanium, stainless steel,
and nickel alloys at various parameters [6]. Ti6 Al4 V is a commonly used alloy in the
aerospace field, and different authors have studied its solid particle erosion properties
at varying temperatures. Generally, the rate of erosion decreases with the tempera-
ture for all angles of impingement. Accordingly, the similar findings were observed
for the Inconel and SS304 alloys, both of which are used in the aerospace sector.
However, in 1989, Tabakoff reported an increase in erosion rate for both Inconel
alloys and Ti6 Al4 V alloy with the increase in the temperature. This may be due to
the fact that Tabakoff only tested the alloys at 204 and 371 °C for Ti6 Al4 V and
Inconel, respectively, which did not allow for the observation of a downtrend in the
erosion rate [7]. In the case of SS410 alloy, the erosion rate decreased for lower angle
impingements and increased for normal impingement angle (30°) with high temper-
ature. A similar trend was observed for the Al2024 alloy, with decreased erosion
rates for a 20° impinging angle and increased erosion rates for 60°. Here, the rate
of material removal depends on the hardness of the material, as well as the erodent
[8]. Therefore, the hardness of the material plays a vital role in the improvement of
erosion resistance.
During SPE, the particles with the size ranging from 10 to 300 µm collide with
the substrate and transfer their energy to it. This kinetic energy leads to break the
bonds and initiates the cracking process in the brittle substrates or plastic deformation
in the metallic substrates [9]. Furthermore, different material clearance techniques,
including brittle fracture, cutting, and melting, fatigue, might erosive wear even
worse. So in addition to the hardness, the properties like ductility, thermal expansion,
and oxidation resistance are important to control the erosive wear [10].
The machinery components such as turbines, propellers, pumps, and valves
are often subjects to surface degradation like erosion and wear with a significant
economic impact. To address this issue, more advanced materials with superior
surface characteristics are necessary. So, researchers have proposed a wide range
of coatings on the materials to prevent the erosion. These can be categorized as
titanium-based, ferrous, cobalt-based, bulk metallic glass, and nickel-based mate-
rials In the case of ductile ferrous materials (SS304), the erosion increases with the
impact velocity and reaches a critical value. To reduce the impact caused by the
erosion, several surface treatment methods and coatings have been used to improve
surface hardness.
The advanced coating technology such as oxy-fuel powder process, laser surface
alloying, wire arc spraying, physical vapour deposition, detonation-gun spray plasma,
high-velocity oxy-fuel process, and flame spray methods (thermal sprayed coat-
ings) were used to deposit the erosion-resistant coatings. Other protective coatings,
such as polyurethane-based coatings, are frequently used to protect against SPE
damage due to their thermal stability, elasticity, long-term damping, mechanical
strength, excellent UV stability, low toxicity, and chemical resistivity. Besides that,
ceramic coating is environmentally friendly and provides benefits such as afford-
ability, thermal stability, mechanical endurance, corrosion, and wear resistance. In
comparison, the ceramic coatings are frequently employed in a variety of industrial
applications [11] due to their substantial wear resistance, chemical resistance, and
thermal properties.
From the literatures, it is evidenced that the coatings were majorly used to prevent
the high-temperature erosion and wear. However, there is no article or chapter which
focused on the technological advancements, parametrical influence, and failures of
recent high-temperature erosion-resistant coatings. Therefore, the present chapter
elaborates on the advanced coatings and technology developed in recent years, as
well as the failures of the coatings.
2 Technology Advancement in High-Temperature Erosive

Wear Resistance
The history of TBCs for high-temperature erosion resistance application (gas turbine
engines) dates back to 1987. TBCs are advanced coatings that are usually applied to
metallic surfaces operating at higher temperatures, such as gas turbine engines. The
main purpose of TBCs is to shield the surfaces from high-temperature environments
and to enhance their performance. Figure 1 illustrates the gradual increase in the use of
coating technologies for depositing various coatings on material surfaces to withstand
high-temperature erosion, between 1990 and 2023. Different coating techniques such
as PVD, CVD, and electroless coating were utilized between 1990 and 2000s. Each
technique has benefits and drawbacks; for example, electroless NiP coating needs
lower temperatures to deposit metals onto high-temperature wear resistance material
surfaces, whereas CVD and PVD need a temperature of 250 °C and above to begin the
deposition process. From 2001 to 2010, HVOF and thermal spray were commonly
used to deposit high-temperature-resistant coatings like Inconel and titanium. In
recent years, plasma spray and laser cladding techniques have become popular for
controlling the erosive wear at high temperatures. Overall, the advancements of
these coating technologies over the years have contributed the development of more
durable and efficient coatings, thereby enhancing the performance of components
operated at high-temperature conditions.
Fig. 1 Technological road map of high-temperature erosive wear resistance

3 Parameters Influencing Erosive Wear
The parameters that influence the erosive wear are mainly divided into three main
categories: the first one is related to fluid velocity conditions (temperature of liquid,
concentration of particles, flow speed, density of liquid, particle impingement angle,
liquid chemical activity), the second associated with solid particles (their hardness,
size, strength, shape), and the third related to the target material [12] (surface topog-
raphy, toughness, fatigue, yield and ultimate tensile strength, size of the defects, and
microstructure.). Moreover, the material stiffness and hardness have a significant
impact on the rate of material erosion. The higher rate of erosion occurs at a normal
impact angle for brittle materials and at higher impact angle for the ductile materials.
Importantly, the hardness of the eroded particles can also have an impact on the
erosion rate, regardless of the hardness of the material [13].
4 Advance Coating Techniques
4.1 Thermal Spray Techniques
Thermal spray techniques (TSP) are coating processes that deposit various coatings
(metals, ceramics, and polymeric materials) on the surface by using a spray gun that
operates at extremely high temperatures (900–1600 °C range) [14]. TSP are used
to prevent the surfaces from the erosion, corrosion, and wear and can also provide
an electrical insulation or thermal insulation to the surface [15]. The coatings are
applied in layers, and each layer is typically between 0.051 and 0.127 mm thick.
In this process, the TSP material is heated to a very high temperature and sprayed
onto the surface of the substrate through a spray gun. During the coating process, the
particle melts on the surface of the substrate, which allows the coating to strongly
adhere to the substrate. The coating material is then cooled and solidified, forming a
uniform protective layer over the substrate [16].
TSP can be applied to different materials like metals, plastics, ceramics, and
composites. The type of coating material chosen will depend on the application and
the environment in which it will be used. For example, some coatings may be more
resistant to corrosion and wear in wet or salty environments, while the others may be
better suited for use in dry or hot environments. Thermal spray coatings are generally
used to protect the surfaces from erosion caused by wear and tear. The coating acts
as a barrier between the surface of the substrate and the outer atmosphere, protecting
it from the elements and reducing the rate of erosion. The coatings are also hard and
durable layers, which can provide a high resistance to abrasive wear and erosion.
The type of coating, thickness, and the substrate hardness are some of the important
factors that affect the erosive wear resistance of the surface coatings [17].
The various types of thermal spray coating are as follows: Cold Sprayed Coat-
ings, Flame Sprayed Coatings, Plasma Sprayed Coatings, High Velocity Oxy-Fuel
Sprayed Coatings, Arc Sprayed Coatings, Detonation Gun Sprayed Coatings, Laser
Cladding Coatings, Robotic Thermal Spray Coatings, Combustion Powder Flame
Spraying, and Electron Beam Physical Vapour Deposition Coatings. Through the use
of the atmospheric plasma spraying (APS) and high-velocity oxygen fuel (HVOF),
the coatings can offer excellent mechanical properties like hardness, fracture tough-
ness, and cohesive strength. In recent years, the WC–Cr3 C2 –Ni coating has shown
exceptional properties than the other WC-based coatings. However, the WC–Cr3 C2 –
Ni coating lost its ability at temperatures above 500 °C due to catastrophic oxidation.
This coating is known to have superior high-temperature wear and oxidation resis-
tance than other WC compositions, and further, the HVOF process parameters have
been optimized to maximize its bond strength. WC–Cr3 C2 –Ni coating has higher
corrosion, hot corrosion, and high-temperature wear resistance than other WC-based
coatings and hard chrome plating [18]. However, the further research on improving
the high-temperature erosion resistance of WC–Cr3 C2 –Ni coatings could be a great
benefit to the extend the performance of components used in the aerospace, oil-gas,
and power generation industries.
4.1.1 High-Velocity Oxygen Fuel (HVOF)
In HVOF process, the oxygen and fuel are injected into the combustion chamber along
with the coating powder. This creates a high-temperature, high-pressure environment
in the chamber, then propelling the gases through the nozzle at supersonic speeds.
The powder particles are then exposed in the chamber between the temperature
range from 2500 to 3200 °C, depending on the fuel, fuel gas/oxygen ratio, and gas
pressure [19]. Depending on the various factors like flame temperature, the time
spent by the particles, the material’s melting point, and thermal conductivity, the
particles could fully or partly melt. The supersonic jet used in the HVOF process
sets it apart from conventional flame spraying and is responsible for the higher
speed of particle impact on the substrate, leading to improved coating characteristics.
The jet expansion and vaporization of the coating particles at the exit of the gun
further distinguishes the HVOF process (Fig. 2) from flame spraying [20]. The HVOF
process is an attractive method of applying coatings due to its high particle velocity
on impact and reasonable process temperature. The coatings produced are generally
dense, adherent, and contain few oxides, making them well-suited for spraying high-
quality metallic coatings and cermets. Further, its high kinetic energy and low thermal
energy have a beneficial impact on coating properties, making it suitable for spraying
tungsten carbide coatings [21]. This makes the HVOF process ideal for applications
such as bond coats within thermal barrier coating systems.
The main advantage of the HVOF process is its ability to produce coatings with
high hardness and wear resistance. Several studies have been conducted to assess
the wear resistance of HVOF coatings, and it has been observed that the wear resis-
tance of HVOF is better than the other thermal spray coatings [22]. The studies
compared the wear resistance of an HVOF coating (WC–Co–Cr) with an electro-
plated (WC–Co–Cr) coating and found that the HVOF had a minimum wear rate
Fig. 2 Schematic illustration of HVOF coating
under erosive wear conditions. The authors also concluded that the increases in
wear resistance of the HVOF were due to its high hardness and better adhesion [23].
Under simulated turbine circumstances, S. Matthews examined the high-temperature
erosion-oxidation of Cr3 C2 –Ni Cr thermal spray coatings. The Cr3 C2 phase was
highly susceptible to internal oxidation, and the Cr3 C2 –Ni Cr phase boundary served
as a preferred path for oxygen diffusion and oxidation. Additionally, the depth of
internal oxidation increases with the temperature [24]. After repeated re-oxidation
and erosion trials, a similar internal oxidized layer was found, and the depth of
oxidation remained constant after 20, 40, and 60 days of testing. This indicates
the achievement of a steady state, where the internal oxidation has moved into the
HVOF composite coating ahead of the least erosive mass loss. In other studies, the
CrNiAlCY metal powder is coated on AISI401 through HVOF coating. The higher
oxygen flow rate during thermal spraying has allowed the dendritic chromium carbide
grains to embed in an intermetallic aluminium nitride matrix. This results in a reduced
porosity and increased micro-hardness of the coatings, which further improved the
high-temperature wear resistance without any phase segregation, oxidation, or decar-
burization [25]. Table 1 debits the summary of HVOF Coated material with erosive
rate with failure mechanism.
4.1.2 Plasma Spray Coating Process
The plasma spraying process melts the feedstock at a very high temperature, typically
with a primary carrier gas such as argon or argon–hydrogen mixture. The generated
plasma stream can reach temperatures of up to 7720 °C at atmospheric pressure,
Table 1 Summary of HVOF Coated material with erosive rate with failure mechanism
S.no Base material Coatings Erosive wear rate Erosive failure References
mechanism
1 Steel C45 Cr3 C2 –Ni 2.5 mm3 • Tensile residual [26]
stresses
• Fatigue cracks
• Detachment of
material during
erosion
2 SS304 WC–Co 0.00043 g/g • Ductile mode of [27]
erosion
• Micro-cutting
• Ploughing
3 Cast iron Inconel-718, 0.00043 g/g • Brittle erosion [28]
Al2 O3 mode
• Lip formation
• Micro-cutting
• Abrasion
4 SS 316L WC–Cr3 C2 –Ni 0.39 × 10–3 g/g • Ploughing [29]
• Spalling pits
• Abrasive grooving
• Mixed erosion
mechanisms
5 Mild steel Ni–20Cr2 O3 49 mg • Micro-cutting [30]
• Ductile erosion
mechanism
• Lip formation
• Ploughing
which is enough to melt refractory materials or materials with high melting points.
It is also possible to customize the process for high-value coatings in atmospheric
air or a more controlled environment. This process utilizes either direct current (DC)
arcs or radio frequency (RF) discharges to generate plasma [31]. The structure of
a plasma-sprayed coating (Fig. 3) is determined by the temperature, velocity, and
size distribution of the incident particles. Direct measurements of these factors in
a plasma torch have been linked to the formation of the coating. The particles that
strike the substrate may not be completely molten, which can affect the deposition
efficiency and the microstructure of the deposit. When a spherical liquid droplet hits
a flat surface at high velocity, it will flatten and the thin sheet of liquid at the edges
will disintegrate into small droplets [32]. In the case of plasma spraying, the substrate
is below the melting point of the droplet, so solidification interrupts the spreading
and breakup. Then the individual particles are splat quenched with a cooling rate of
around 106 K s−1 . Heat treatments suggest that the interface structure is determined
by distributed contact points within an effectively non-conducting film arising from
entrapped gas. The microstructure of plasma-sprayed coatings is thus linked to the
Fig. 3 Schematic illustration of plasma spray coating
mechanism, including the interfaces between lamellae and the internal structure
created by rapid solidification [33].
Digvijay G. Bhosale investigated the high-temperature solid particle erosion
behaviour of SS 316L with WC–Cr3 C2 –Ni coatings. The coated specimens showed
a variety of erosion processes, while uncoated ones experienced more malleable
effects. At lower angles of impact, the wear of coated samples was mainly caused
by ploughing and cutting caused by the erodent. However, at a direct angle, intense
wear mechanisms such as splintering and delamination were observed in the case of
an APS coating. Table 2 debits the summary of plasma spray coated material with
erosive rate with failure mechanism.
4.1.3 Laser Cladding Process
Laser cladding is a popular technique used for hard facing or surfacing in indus-
trial applications that applies a layer of powder coating onto the substrate surface
(base metal) using a laser beam or arc as a source of heat (Fig. 4). In this process,
a laser beam of different shapes is consistently emitted through different nozzles,
while also combining various powder combinations. These powder combinations
then melt upon contact with the laser beam, resulting in the creation of a coating layer
[39]. Laser cladding offers many advantages over traditional coating methods and its
performance is significantly higher. Firstly, laser cladding allows for precise control
over the coating thickness, resulting in a more uniform and consistent deposition.
Secondly, it enables the use of a wide range of materials, including dissimilar metals,
alloys, and ceramics, offering flexibility in coating selection [40]. Additionally, laser
Table 2 Summary of plasma spray coated material with erosive rate with failure mechanism
S.no Base material Coating Erosive wear rate Erosive failure References
material mechanism
1 SS316l WC 0.71 × 10–3 g/g • Splat [34]
delamination
• Ploughing
• WC pull-outs
• Micro-cutting
2 AISI 304 NiCrSiB/Al2 O3 0.4 × 10–3 g/g • Micro ploughing [35]
• Splat removal and
detachment of
Al2 O3 hard
particles
• Ni softer phases
• Micro-cutting
3 Al Fly as + Al2 O3 17 mg/kg • Local scratching [36]
• Cracks
• Crater formation
• Plastic
deformation
• Micro-cutting
• Extrusion and
chipping of the
coating
4 SA210 GrA1 IN625-bimodal 0.21 × 10–3 g/g • Ploughing [37]
Al2 O3 • Micro-cutting
• Brittle erosion
mode
• Detached splats
• Fracture and
cracks
5 MDN321 NiCrBSiFe and 0.5 × 10–3 g/g • Wrinkles [38]
NiCr • Pitting
• Ductile mode
cladding minimizes heat-affected zones, reducing the risk of distortion or damage

to the substrate. Moreover, it provides excellent metallurgical bonding between the
coating and the substrate, enhancing overall coating integrity. Lastly, laser cladding
offers high deposition rates, enabling efficient and cost-effective coating applica-
tion [41]. It is also an efficient way to repair mechanical parts, as opposed to
other approaches that require more time and energy. Various process parameters
are involved in laser cladding, such as laser energy, the diameter of the laser beam
spot, scanning velocity of the laser, thickness of the pre-powder layer, rate of powder
feed, nozzle angle, and stand-off distance [42].
The effectiveness of the laser cladding process is largely determined by its scan-
ning speed, which can affect the thickness, width, and height of the clad layer. If the
scanning speed is appropriate, the clad layer can exhibit desirable properties such as
Fig. 4 Schematic illustration of laser cladding process
a strong metallurgical bond with the base material, small crystals, and no cracks or
gas cavities. A higher scanning speed generally results in a thinner clad layer, while
a lower scanning speed leads to a thicker layer. Similarly, a higher scanning speed
typically results in a narrower clad width, whereas a lower scanning speed produces
a wider width. These factors are important in laser cladding for several reasons.
First, the thickness of the clad layer determines the desired material properties, such
as hardness or corrosion resistance. Controlling the thickness ensures the coating
meets specific requirements. The width of the clad layer affects the coverage and
area being treated. A wider clad width can cover a larger surface area in a single
pass, increasing the efficiency and reducing the processing time. The height of the
clad layer is crucial for achieving the desired geometry or restoring worn or damaged
parts. Precise control over the height ensures dimensional accuracy and proper fit
with the surrounding components. Optimizing the scanning speed to control these
factors is vital in achieving the desired coating quality, dimensional accuracy, and
overall performance of the laser-cladded component [43]. In one study, the impact
of laser cladding speed on SS 431 was examined, but it was found that increasing the
speed did not improve the hardness and wear properties of the stainless steel coatings.
Other researchers have also investigated the effects of scanning and cladding speed
on the microstructure and hardness of these coatings [44]. The laser power used in
the process is also crucial, as it can cause micro-cracks if too low or reduce wear
resistance if too high. An experiment showed that increasing the laser power from 1.8
to 3.0 kW led to deeper laser melted pools and some micro-cracks, with the best wear
resistance achieved at 2.5 kW. The powder feed rate is another important parameter
that affects the cladding thickness, with an increase in feed rate leading to a propor-
tional increase in coating thickness until a certain limit is reached [45]. Additionally,
research has shown that the hardness and wear resistance of the coating also increase
with a rise in powder feed rate [46]. Several other parameters, such as overlap clad,
direction of clad, preheating, nozzle distance, injection angle, and particle size shape,
have also been studied, but their impact is less significant than the main parameters
discussed above. Nonetheless, their interaction with the quality of the clad surface
should not be disregarded [47].
In the past, steel was the most commonly used material for erosion wear, but
composite materials and alloys are now being used as replacements. As a result,
researchers have studied a variety of materials for erosion wear, including steel,
copper alloys, magnesium alloy, Ti–6Al–4V and its alloys [48]. However, these
materials can be expensive, so researchers have developed erosion-resistant coatings
using low-cost materials such as steel through laser cladding techniques. Different
types of powder materials, such as nickel and cobalt base, tungsten carbide, titanium
and its composite, high chromium cast iron, and some iron base alloys, have been
used to improve corrosion and erosion wear resistance. In a recent study, Stellite 6
clad layers were used on stainless steel as a base material, and the results showed that
the clad surface improved erosion wear resistance by five times compared to bare
stainless steel [49]. Table 3 debits the summary of the laser cladding process coated
material with the erosive rate with failure mechanism.
5 Erosive Wear Resistance of Ceramic Coatings
Ceramic coatings can be effective at controlling high-temperature erosive wear, as

they offer several benefits such as high hardness, thermal stability, thermal shock
resistance, surface seals, erosion resistance, diffusion barriers, sealants, corrosion
resistance, and resistance to chemical and mechanical degradation. These properties
make them suitable for use in high-temperature environments, such as gas turbines
and other combustion engines. Ceramic coatings are the most frequently applied
metallic components to withstand high-temperature environments [54]. Ceramic
coatings exhibit exceptional resistance to the erosive effects of solid particles, such
as abrasion and impact. The erosive wear resistance of ceramic coatings stems from
their inherent properties, including high hardness, high-temperature stability, and
chemical inertness. These properties enable ceramic coatings to withstand the erosive
forces and prevent material loss or degradation. Additionally, the microstructure of
ceramic coatings plays a crucial role in their erosive wear resistance. Fine-grained
ceramics with a dense and uniform structure exhibit enhanced resistance to erosive
wear, as they effectively resist the penetration and removal of material by abrasive
particles. These coatings have demonstrated significant improvements in reducing
erosive wear and extending the service life of components in industries such as
mining, power generation, oil and gas, and aerospace [55].
One of the most commonly used ceramic coatings for controlling high-
temperature erosive wear is thermal barrier coatings (TBCs). TBCs are designed to
protect metal components from the high temperatures generated during combustion
and to reduce the transfer of heat to the underlying substrate. This can help to prevent
Table 3 Summary of laser cladding process Coated material with erosive rate with failure
mechanism
S.no Base Coating material Erosive wear rate Inference References
material
1 SS410 NiCrSiBC + WC 0.02 from • Plastic [50]
0.16 mg deformation
• Worn-out marks
• Micro-cutting
• Minute
ploughing sites
• Lip structures
• Ploughing mark
• Tiny craters
2 Martensitic Ni + 50% Cr3 C2 26.5 g m−2 h−1 • Impact craters [51]
stainless • Deformed lips
steel • Plastic
deformation
3 Martensitic Ni + 50% WC 43.8 • Little [51]
stainless micro-cracks
steel • Ropping holes
• Plastic
deformation
4 AISI 304 Inconel Cr3 C2 0.10 • Microcracks [52]
plate • Transgranular
crack
5 Q345 steel Alx CoCrFeNiTi0.5 0.04 mg/min • Ductile erosion [53]
mode
• Micro-cutting
• Ploughing
thermal fatigue and cracking, which can lead to erosive wear [56]. Other types of
ceramic coatings that can be effective at controlling high-temperature erosive wear
include oxide and carbide coatings. Oxide coatings, such as alumina or zirconia, can
provide excellent resistance to high-temperature corrosion and wear. Carbide coat-
ings, such as titanium carbide or tungsten carbide, are also highly resistant to wear
and can provide excellent protection against erosive wear. Cermet-based coatings
can also be employed in extreme temperatures. Understanding the microstructure
and behaviour of ceramic coatings is critical for optimizing their performance in
controlling high-temperature erosive wear [57]. Furthermore, there is no uniform
testing method that can determine which material is best for varied wear or wear-
corrosion. Numerous studies have also been investigated to find the effectiveness
of ceramic coatings such as ZrO2 , Al2 O3 , SiC, SiO2 , HfC, TaC, and ZrC in high-
temperature environments. These coatings have been explored for their ability to
withstand high temperatures, resist wear and corrosion, and provide thermal insula-
tion to protect underlying materials. Researchers have conducted experiments and
analysed data to determine the properties and performance of these coatings in various
high-temperature conditions, such as in gas turbines, engines, and industrial appli-

cations [58]. When selecting a ceramic coating for controlling high-temperature
erosive wear, it is important to consider factors such as the type of substrate material,
the operating environment, and the specific wear mechanisms that are likely to be
encountered. Proper surface preparation, including cleaning and roughening, is also
critical to ensure good adhesion and performance of these ceramic coating [59].
Based on recent literature it is found that ceramic coatings are effective in control-
ling high-temperature erosive wear by creating a protective layer on metallic compo-
nents. This layer can mitigate or prevent the effects of high-velocity particle impact,
which leads to erosive wear. Microscopic analysis is used to study the formation of
voids in the coating and to understand the impact of temperature on its erosion resis-
tance. Studies have shown that ceramic coatings with 80% ceramic powder exhibit
greater cavitation erosion resistance compared to aluminium alloy references [60].
Fe-based coatings, on the other hand, form oxide scales to protect against oxidation
and corrosion in high-temperature environments. The formation of voids and pores
is one of the major challenges in ceramic coating. The formation of voids in ceramic
coatings is influenced by temperature, void formation increases as the temperature
is raised and as a result it will end up in oxide formation. To understand this effect,
oxidation studies have been performed on cast Co–22Cr–11Al (CoCrAl) coating
alloy at temperatures ranging from 700 to 1000 °C [61]. However, warm-pressing
above 180 °C can produce transparent and void-free monoliths, suggesting that lower
temperatures may reduce void formation [62]. The properties of ceramic layers are
also linked to processing technology, such as sintering temperature and method of
coating. Overall, temperature is a crucial factor affecting the formation of voids
in ceramic coatings, with higher temperatures promoting increased void formation.
Ceramic coatings offer a reliable solution for protecting components from high-
temperature erosive wear by forming a protective layer that reduces the impact of
high-velocity particles [63].
6 Erosive Wear Resistance of Metallic Coatings
Metallic coatings are a viable option for controlling high-temperature erosive wear
in aerospace applications [1]. NiCr-based coatings, such as nimonic coatings, are
commonly used for high-temperature applications to minimize oxidation [64]. Other
metallic coatings, including aluminide, chromide, and MCrAlY, are effective in
protecting superalloys against high-temperature environmental factors. These coat-
ings are applied using either a diffusion or conversion process in which the deposited
material is diffused and/or reacted with the substrate to create a gradual change in
composition. To achieve effective erosion-resistant coatings, thicker coatings with
good mechanical properties are required. The use of cost-effective precursor mate-
rials and innovative coating designs can help achieve the desired coating thick-
ness with low production costs [65]. Metallic coatings have the ability to manage
high-temperature erosive wear through various mechanisms. For instance, Fe-based
coatings form oxide scales to prevent corrosion and oxidation in high-temperature

conditions [60].
Metallic coatings like High Velocity Oxygen Fuel (HVOF) sprayed coatings have
been developed to shield against solid particle erosion [64]. The study also inves-
tigates high-temperature erosion-oxidation mechanisms to understand how ductile
materials undergo material loss due to erosive wear conditions [66]. The tempera-
ture range at which metallic coatings can endure high-temperature erosive wear is
determined by several factors, including the coating type and its specific use. The
temperature range also varies depending on the compressor stage, whereas turbine
blades undergo extreme temperatures of 1000 °C and above [1]. The study of HVOF
sprayed coatings’ erosion behaviour was conducted at a temperature of 900 °C [1].
Cermet compositions are well known for their wear resistance, high-temperature
oxidation resistance, hardness, and abrasion properties. Fe-based coatings have been
found to exhibit wear behaviour, corrosion analysis, and high-temperature resistance
properties [60]. An increase in temperature results in a decrease in the volume loss
of coated samples, and some coatings can perform well even at temperatures as
high as 700 °C [67]. In general, the temperature range at which metallic coatings
can resist high-temperature erosive wear varies depending on multiple factors, but
in some cases, it can be as high as 1000 °C or more. To assess the effectiveness
of metallic coatings in controlling high-temperature erosive wear, researchers use
microstructure studies, micro-hardness tests, and high-temperature oxidation and
erosion tests. When it comes to ceramic coatings, the main obstacle is the formation
of pores, while with metallic coatings, the major hurdle is oxidation [1].
Dervis Ozkan examined how oxidation and wear affect the Cr3 C2 –NiCr hard metal
coatings on stainless steel substrates under various temperature and time conditions.
In recent research, efforts have been made to understand the elevated temperature
erosion behaviour of metals and alloys and to develop new erosion-resistant coatings
which have low erosion–oxidation ratio [68]. NASA worked together with the Allison
Advanced Development Company to enhance erosion coatings for gas turbine fan
and compressor applications. Six different erosion coating systems were tested to
determine their ability to endure intense thermal cycling without spalling. All six
coating systems were able to survive the tests [69].
7 Erosive Wear Resistance of Composite Coatings
Composite coatings are effective in controlling high-temperature erosive wear due

to their high resistance to wear and corrosion, surface toughness, hardness, adhe-
sive strength, and temperature resistance [70, 71]. They have the ability to with-
stand high temperatures and provide erosion resistance to metallic coating [72]. The
composite surface-coating can be made using various coating techniques, such as
chemical vapour deposition, physical vapour deposition, and thermal spray coating
[70]. These coatings provide a protective surface layer that can withstand wear,
corrosion, and erosion problems, while it also increases the mechanical strength
[67]. According to recent studies, composite coatings containing higher amounts of

carbon nanotubes (CNTs) have demonstrated the best resistance to erosive wear [73].
Moreover, research has found that CNT-reinforced Cr2 O3 coatings on ASTM-A36
steel and NiCr coatings on turbine steel exhibit high resistance to hot corrosion and
slurry erosion, respectively [74]. Additionally, CNTs have been shown to enhance the
hardness, corrosion, and wear resistance of coatings [75]. CNTs possess unique prop-
erties, including high strength, stiffness, thermal conductivity, and chemical stability,
making them useful in various industries [76]. Overall, the use of composite coat-
ings containing higher amounts of CNTs can provide superior erosion resistance and
better protection against high-temperature erosive wear.
In aviation turbines, thermal barrier coatings (TBCs) made of composites are
frequently utilized to safeguard nickel-based superalloys against both melting and
thermal cycling. The addition of cool air flow enables TBCs to raise the maximum
gas temperature beyond the melting point of the superal compared to single-phase
thermal barrier coatings (TBCs), phase composite TBCs have shown superior coating
durability, thermal conductivity, and solid particle erosion resistance. Studies on the
erosive wear resistance of LZO and YSZ coatings have found that the coating density
and content significantly affect the coatings’ erosion resistance [77].
Researchers have investigated the impact of heat treatment on the erosion resis-
tance of composite coatings and found that when treated at 600 °C and 90°, erosion
was reduced. This reduction in erosion was attributed to the removal of porosity,
improved coherence of the nickel matrix, and decreased hardness. Composite fibre
materials are employed in a wide range of applications, from everyday appli-
ances to high-tech uses, in order to reduce wear rates. Extensive research has been
conducted on the anti-erosive anti-wear properties of polymers and their compos-
ites [77]. Recent advancements in understanding the methods for controlling erosive
wear have been made for composite coating with the creation of erosion-corrosion
maps showing transitions. In many industrial conditions, composite coating experi-
ences solid particle erosion in corrosive environments leading to degradation, and
controlling the damage can depend entirely on empirical experience.
8 Erosive Wear Resistance of Super Alloy Coatings
Superalloy coatings have been found to exhibit good temperature stability in addition
to their high resistance to wear and erosion. To control high-temperature erosive wear,
super alloy coatings are utilized. Because of the work hardening and temperature
stability of their constituents, these coatings have a high hardness, resulting in lower
volume loss due to erosion and as a result it can withstand extreme heat environment
[67]. There are a variety of erosion-resistant superalloy coatings available, and their
performance is temperature dependent.
NiAl super alloy coating is a type of high-performance coating that is made from
a superalloy consisting of nickel and aluminium. This coating is designed to provide
excellent protection against high-temperature corrosion, oxidation, and wear. It is
commonly used in high-temperature applications, such as gas turbines, power plants,

and aerospace components. NiAl super alloy coatings are known for their outstanding
oxidation resistance, as the aluminium content in the alloy forms a protective oxide
layer at high temperatures, which prevents further oxidation of the substrate material.
Additionally, these coatings offer excellent wear resistance due to their high hardness
and low coefficient of friction.
NiAl intermetallic super alloy coatings can carburize the super alloy coated
substrate at high temperatures as a result increases the hardness and weight of the
component and thereby making the coating substance brittle; hence, it leads to crack
formation resulting in failure [78]. Some common materials used in superalloy coat-
ings include nickel–chromium alloys, titanium alloys, cobalt-chromium alloys, and
stainless steels. These materials offer a range of properties that make them suitable
for different applications, including high strength, corrosion resistance, and thermal
stability [79].
The application of superalloy coatings can be achieved using various techniques,
including thermal spray, electroplating, and chemical vapour deposition. The selec-
tion of a coating technique is determined by the application’s particular require-
ments and the coating material’s characteristics. Thermal spray coating is a signifi-
cant method amongst them. Researchers have developed thermal spray high-entropy
alloy (HEA) coatings to enhance the erosion resistance of Ni-base superalloys under
extreme temperatures. These HEA coatings possess excellent tribological proper-
ties, such as porosity, hardness, and wear resistance. AlSiCrFeCoNi alloys with
the HEA coating process have gained popularity chiefly due to their resistance to
high-temperature oxidation [80].
9 Coatings Failure at High-Temperature Conditions
There are four important coating failures in high-temperature applications, which

include oxidation, hot corrosion, mechanical distress, and solid-state diffusion. In
addition to these failure modes, the cyclic and thermal loads of the component can
also cause the thermomechanical fatigue in the coatings. In advanced turbine engines,
the thermomechanical stress cracking was frequently observed around film-cooling
holes. Later, this is controlled through the application of TBC. The brief discussion
on the different types of failure modes in the coatings is provided below.
9.1 High-Temperature Oxidation
The coatings have been introduced in order to produce a barrier between the substrate
material and the high-temperature gases. The coatings could prevent the formation of
oxide scale at higher temperatures. For example, the chromia scale tends to sublimate
to CrO3 above the higher temperatures (840–870 °C), which provides a low protec-
tion compared to the alumina. The coating and ultimately the substrate are quickly
attacked without the shielding scale. So, recent research has shown the improvement
of oxide layer adhesion, which can further improve the properties of the coatings
at higher temperature. To increase the adherence of the oxide layer, the coatings
are frequently supplemented with oxygen-active materials like hafnium and yttria.
Nonetheless, a solid quantitative knowledge of these consequences is lacking in
controlling the high-temperature oxidation.
9.2 Hot Corrosion
Hot corrosion refers to the attack of molten salts, usually sodium and potassium
sulphates, which enter the turbine hot section as impurities from the air and fuel
and can cause a rapid material loss in the components. It is not quite obvious what
function secondary elements with impurities like chlorine, calcium, and iron from
the local environment serve. Once the scale is lost or penetrated, both the protective
covering and the metal substrate beneath it will quickly deteriorate. This requirement
is for petroleum-based fuels, and either chromia or alumina can typically meet it.
However, alumina coating was better at greater operating temperatures compared to
the chromia.
9.2.1 Mechanical Distress
The impact damage and mechanically induced erosion are two related failure mech-
anisms that require specific attention. Particles in the air stream cause erosion when
they abrade the coating. When a heavy object contacts the coating, the impact could
cause the damages. These failure modes will, however, become more significant
as substrate materials are used in situations where they provide no built-in defence
against the oxidation or other severe failure modes. Even, the retention of TBCs is
heavily influenced by these failure mechanisms. Compared to the metallic coatings,
these ceramic coatings are naturally more susceptible to impact damage and erosion.
9.3 Solid-State Diffusion
The diffusion of the coating with the base metal is another significant degradation
pathway for the coating’s failure at high-temperature conditions. For example, the
concentration of aluminium that is available to produce alumina in the coating is
reduced by the diffusion of aluminium into the base metal. Once the aluminium
concentrations fall below a particular threshold, a protective oxide can no longer
sustain the spallation failure. Hence for better high-temperature coating properties,
the fundamental principles of diffusion should be clear and in control.
10 Summary and Future Scope
The present chapter elaborates on the erosion and wear resistant of high-temperature
coatings with various failure modes. And, also discussed how the coatings overcome
the failures to reduce the erosive wear. Comparatively, the thermal barrier coatings
are frequently used to increase the performance of the turbine and also to reduce
the thermomechanical fatigue cracking in high-temperature operating conditions.
Ceramic coatings are found better than the metallic coatings towards the damage and
erosion resistance. The alumina was better at high operating temperatures compared
to the chromia because of the reduced scaling effects. For an efficient diffusion
process, the optimum quantity of the coating should be used, because the oxide layer
will not prevent the spallation failure if the weight fraction of oxidizing elements falls
below the certain threshold. It is also concluded that the developed coatings should
be more durable and able to withstand the intense heat of the environment. Also,
the coating can be developed that is more resistant to chemical and environmental
damage.
Still, there is a scope for the research in analysing the high-temperature resistance
coatings with various phase constituents. So, in the future, the high-temperature
coatings could be developed with various phase constituents to provide a better
protection from the extreme temperatures. This could uplift the coated materials
in various high-temperature applications like boilers, turbine blades, steam lines,
spacecraft nozzles, and gun barrels, where the erosive wear is predominant.
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https://doi.org/10.1007/s11666-020-01047-0
Research on Anti-Oxidation
and Wear-Resistance Co–Cr–Fe–Nb–Ni
High Entropy Alloys Coatings Prepared
by Laser Cladding
Jin Zhang and Minyu Ma
Abstract Oxidation and wear have been confirmed to be a great threat to the metals
at high temperatures, for instance, in the fields of power, petrochemical industry,
weapon, and aerospace. A novel Co–Cr–Fe–Nb–Ni high-entropy alloy coating was
designed and manufactured by laser cladding, which was composed of toughness
FCC and hardness Laves phase. The Cr atoms dissolved into the FCC phase, while
the Si atoms doped into the Laves phase by replacing the Nb atoms. In the oxidation
process, the coating experienced mainly the selective oxidation of the Cr and Nb.
The oxidation of Si in the Laves phase replaced the Nb, producing a more stable (Cr,
Si)Ox at the interface and delaying the internal diffusion of oxygen. The addition
of Ce improved the compactness and bonding strength of the Cr2 O3 oxide film.
The hardness of Co–Cr–Fe–Nb–Ni coatings was determined by the Laves phase and
the MC phase, which precipitated by the diffusion of Nb and C and decreased the
Laves content. The wear mechanism changed from abrasive wear to oxidation wear
as temperature increased. The Co–Cr–Fe–Nb–Ni HEAs coatings exhibited superior
performance of anti-oxidation and wear resistance compared to electroplated hard
Cr coating at high temperature.
Keywords High-entropy alloys · Laser cladding · Thermal growth oxides ·

Wear · Corrosion
J. Zhang (B)
University of Science and Technology Beijing, Beijing, China
e-mail: zhangjin@ustb.edu.cn
M. Ma
Chongqing University of Technology, Chongqing, China
e-mail: myma2023@cqut.edu.cn
188 J. Zhang and M. Ma
1 Introduction
1.1 Protection Requirement for Oxidation/Wear Resistance

at High Temperature
Thermal power generation is one of the world’s primary forms of electricity produc-
tion. The enhanced efficiency and reduced emissions technology pertaining to
thermal power generation help power plants burn less coal while reducing CO2
emissions. Supercritical steam generator works at supercritical pressure and temper-
ature of water, which is commonly employed in power production. When the water
work enters the generator’s condenser at the temperature and pressure below the
critical point, it results in slightly less fuel consumption. Unlike traditional boilers,
supercritical steam generators operate above the critical temperature of 374 °C and
pressure of 22 MPa.
The density of liquid water decreases smoothly without any phase change and
becomes indistinguishable from steam. The thermodynamic efficiency of power
plants using supercritical steam generators improved significantly. From Carnot’s
theorem, the conversion of higher temperature steam in the turbine is more efficient
at supercritical pressure.
Nowadays, the supercritical power plants can reach efficiencies of 42–45%. The
Rheinhafen-Dampfkraftwerk Block 8 unit in Germany achieved the record-breaking
net efficiency of 47.5% by utilizing the superheated and reheated steam temperatures
of 600/620 °C and pressures of 27.5 MPa [1]. It has been confirmed that the advanced
ultra-supercritical (AUSC) power plants can improve the power generation efficiency
to 50% by improving the temperatures and pressures of steam over 700 °C and 35
MPa, which are anticipated to commence operations within the next 10 years [2, 3].
As the temperature further increased in AUSC power plants, the heated components
become subject to more demanding requirements for high-temperature oxidation
resistance, which is one of the primary factors in the failure of these components [4, 5].
The CO2 and H2 O mixture gas has a great corrosion damage on the structural alloys
of heated components. Also, the high-temperature flue gas with ash particles impacts
on the surface of heat components at high speed, causing erosion and wear [6]. The
erosion resistance of the metals used in boilers in the high-temperature corrosive
atmosphere is an important parameter to ensure the stable operation of power plants.
Currently, with the 700 °C AUSC power plants are expected to be operated, the
oxidation resistance and mechanical properties of the heated components’ materials
are more severely desired.
Also in the automatic weapon, the erosion resistance of the metals used in the
barrel is expected to be improved. The bore surface heated by combustion gas may
reach 1000 °C and decline to half this value in a few milliseconds. The combustion
products by propellants can severely erode and oxidize material surfaces. In addition,
projectiles move forward and gradually squeeze into the rifling, the friction force
produced by the projectiles causes mechanical wear on the bore surface.
Research on Anti-Oxidation and Wear-Resistance Co–Cr–Fe–Nb–Ni … 189
In the above combustion process, the coupling effect of high-temperature oxida-

tion and wear will result in serious damage to the heated components. The mixture
atmosphere can seriously affect the surface condition of the materials. Electroplated
hard Cr coatings provide excellent corrosion and mechanical properties for protecting
the heated components in many industries; however, the viability of the electroplating
process is at risk due to the toxic hexavalent chromium baths. Currently, the materials
with an environmentally friendly, anti-oxidation, and excellent mechanical properties
at high temperature are more severely desired to improve the reliability and service
life of heated structural components.
1.2 High-Entropy Alloy Properties
High-entropy alloys (HEAs) have received a great deal of attention for their
unique mechanisms and excellent properties in challenging service conditions.
Unlike conventional alloys, which contain one and rarely two base elements, HEAs
consisting of four or more elements in an equimolar or near-equimolar composi-
tion to form a solid solution alloy and stimulating significant interest in the field
of material science and engineering [7, 8]. The high mixing entropy effect makes
HEAs exhibit a series of properties different from conventional materials, such as
lattice distortion, slow diffusion, and high-temperature phase stability. According to
Gibbs free energy, the mixing entropy competes with the mixing enthalpy, and the
high mixing entropy plays a dominant role in the free energy of the system, espe-
cially at the high temperature. In the random intercalation state, the high mixing
entropy of the HEAs can greatly reduce the free energy of the system, thus making
it exhibit perfect high-temperature stability. Therefore, HEAs have full potential as
a high-temperature protective material.
CoCrFeNi is one of the most common HEAs with face-centered cubic, exhibiting
high ductility and relatively low strength. The performance of the alloy can be
substantially improved by additional elements. For example, Al can promote the
phase transition of FCC changed to BCC, improving the hardness of HEAs. Addi-
tionally, Al can inhibit the impact of supercooling on grain morphology [9]. Chen
[10] revealed that Ti and Al play a crucial role in the formation of L12 precipitates
and enhance the phase stability in CoCrFeNi HEAs. Yang [11] reported that the
multicomponent Ni3 (Al, Ti)-type nanoparticles have attractive features for strength-
ening HEAs without compromising ductility. The precipitation of multicomponent
Ni3 (Al, Ti)-type nanoparticles provides appealing characteristics for enhancing the
strength of 1.5 GPa without sacrificing the ductility as high as 50% of HEAs. The
addition of the Nb element can form the Laves phase which effectively improving the
wear resistance of FCC HEAs at high temperature [12, 13]. Chromium (Cr) is one
of the most important elements for improving high-temperature properties, as it can
play a role in solid solution strengthening and produce short-range ordered strength-
ening. Additionally, the chromium oxide (Cr2 O3 ) film formed by the Cr element has
excellent high-temperature oxidation resistance.
1.3 Laser Cladding High-Entropy Alloys Coatings
From the economic aspect, the high cost of bulk HEAs is due to the high content
of expensive alloying elements. The surface coatings technologies can achieve a
judicious combination of costs and properties. Moreover, it was reported that HEA
coating performed even better properties compared to the bulk material, which might
be due to the homogeneous microstructure by more precise shaping control [14]. Li
[15] deposited AlCoCrFeNi coatings onto AISI 1045 carbon steel. In contrast to the
bulk HEA material, no discernible Cr-rich interdendritic segregation or nano-sized
precipitates were detected within the dendrites of the HEA coating. The corrosion
current of the HEA-coated specimen was significantly lower than that of the bulk
HEA material. It takes the advantage of fine microstructure, metallurgical bonding,
and less intermixing with the substrate. Furthermore, the rapid solidification rate of
104 –106 K/s can lead to significant effect of non-equilibrium solute trapping, reduce
the nucleation and growth rate of the brittle intermetallic compound, and improve
solubility limitation.
In this work, the Co–Cr–Fe–Nb–Ni HEAs coatings were prepared by laser
cladding. The Cr, Si, C, and Ce were used to improve the high-temperature oxidation
and wear resistance of coatings. A N2 –44CO2 –6H2 O (vol. %) mixture gas at 800 °C
was generated to evaluate the high-temperature oxidation resistance of the HEAs
coatings. The wear tests of HEAs coatings were carried out in dry sliding condition
using a ball-on-disc wear from room temperature (RT) to 800 °C. The 5 mm diameter
grinding balls are made of Si3 N4 . The cylindrical discs dimensions with a diameter
of 20 mm and a height of 10 mm were machined from HEAs coatings. The disc
samples’ surface was ground with 400–2000 grit silicon carbide papers. Wear tests
were carried out with loads of 100 N and sliding velocity of 1 m/s. The role of each
element on oxidation and wear resistance was elaborated.
The HEAs coatings were produced by laser cladding on the surface of Cr–Mo–V
steel. Each specimen was abraded via silicon carbide papers up to 800 #, cleaned with
alcohol, and dried subsequently before cladding. The cladding powders consisted of
Fe, Cr, Co, Ni and Nb, CeO2 particles with a purity >99.5 wt.% and size of 75–150
μm. The Si, C, and Ce were added into the coatings by FeSi, FeCrC, and CeO2 with
the same particle size for reducing the sparks during laser cladding. The powders
were weighed according to the ratio of elements and mixed by a ball mill for 8 h.
The mixed powders were dried over 2 h at 120 °C, then pre-placed on the substrate
steel. The thickness of the pre-placed layer was about 1 mm. A 1.5 kw fiber laser
processing system with a 1.5 mm spot diameter was employed for manufacturing
the HEAs coatings. The laser cladding parameters: 800 W of power, 7 mm/s of the
scanning speed, and an overlapping ratio of 30%. The Argon gas was used to protect
the molten pool during the laser cladding process with a flux of 8 L/min.
2 The Microstructure Co–Cr–Fe–Nb–Ni Coating
2.1 Effect of Cr Content on the Microstructure
Cr is a crucial element in ensuring high-temperature oxidation resistance of metal

due to its dense and stable thermal growth oxides of Cr2 O3 . In the CoCrx FeNb0.5 Ni
HEAs coatings, the coating microstructure mainly consists of FCC and Laves phase,
when the Cr content x from 0.5 increases to 2 (Fig. 1). The Co, Cr, Fe, and Ni have
similar atomic radius and can form FCC solid solutions [16–18]. The atomic radius
ratio of Nb to other atoms concentrated within the range of 1.1–1.3, promoting the
formation of Laves phase [19]. As shown in the XRD patterns, all the diffraction
peak positions of the Laves and FCC phase shift to the lower angle, meaning the
crystal spacing for both phases crystal becomes larger according to Bragg’s Law.
The solution of Cr atoms in both phases results in the lattice distortion.
The microstructure of coatings was observed by scanning electron microscope
(SEM) (Fig. 2) The CoCrx FeNb0.5 Ni HEAs coatings all show a dendritic structure
along the solidification direction, wherein the interdendritic structure becomes more
obvious with the Cr content increased. Additionally, the growth of the dendritic struc-
tures was inhibited in CoCr0.5 FeNb0.5 Ni and CoCrFeNb0.5 Ni coatings. The typical
lamellar eutectic microstructure consists of gray FCC phase and white Laves phase
can be observed in the above two coatings. As the Cr content increased, the gran-
ular microstructure of Laves phase formed in CoCrFeNb0.5 Ni coatings (x = 1.5 and
2). The precipitation of granular structure Laves phases owing to the growth drive
decreased as the consumption of Nb in the molten pool. The chemical composi-
tion of the FCC and Laves phase in CoCr2 FeNb0.5 Ni coating were detected by EDS
Fig. 1 The XRD patterns of CoCrx FeNbNi HEAs coatings. a The diffraction peak of CoCrx FeNbNi
coatings. b The diffraction peak of (200) in the FCC phase. c The diffraction peak of (110) in Laves
phase
(Table 1). The gray region consists of only 4.09 at.% Nb and 44.86 at.% Cr. The
Nb content of the white region reaches 29.27 at.%, implying the white region is the
Laves phase. Additionally, the atomic content of Cr in the FCC phase is much higher
than in the Laves phase, meaning the Cr atoms prefer to dissolve in the FCC phase.
The FCC and Laves phases in the CoCr2 FeNb0.5 Ni coating were further observed
via TEM (Fig. 3). The lamellar structure as well as the granular structure of the Laves
phase can be clearly observed. Due to the fast-cooling rate of the laser cladding and
the “sluggish diffusion effect” of the HEAs, the Laves phases are mostly nano-
sized thickness with a lamellar structure. The diffraction pattern of the FCC phase
(along the [1̄12] crystalline band axis) and the Laves structure (along the [21̄1̄0]
crystalline band axis) further confirm the structure of CoCr2 FeNb0.5 Ni coating. An
inverse Fourier transform of the high-resolution photograph of the FCC phase in the
coating shows a large number of non-parallel white lines, indicating that the lattice
deformation of the FCC phases is caused by distortion. This is consistent with the
results of XRD and electron microscopy energy spectra result.
2.2 Effect of Si Addition on the Microstructure
Si is an important element in the laser cladding process for its strong deoxidation
effect. Also, the SiO2 film formed by Si at high temperature has a protective effect.
The phases of CoCr2 FeNb0.5 NiSix depend on the addition of Si. The XRD result
reveals little change in phase constitution when x is no more than 0.2. The diffraction
peaks of Cr15 Co9 Si6 (M24 Si6 ) were detected with more Si addition. The metal silicide
formed when too much Si was added due to the limited solution of Si in the FCC and
Laves phase. Noteworthy, the diffraction peaks in the FCC phase keep at the same
2θ position, while those of the Laves phase are significantly shifted to a higher angle
in CoCr2 FeNb0.5 NiSi0.2 , meaning the Si dissolved into the Laves phase and affected
the structure of the Laves phase (Fig. 4).
The Laves phase in CoCr2 FeNb0.5 Ni coatings is a hexagonal structure of type
A2 B. Wherein, the Co, Cr, Fe, and Ni atoms randomly occupy A-sites and Nb atoms
mainly occupy the B-sites. The stability of the Laves phase is related to the ratio of
B–A atomic radius. The ideal atomic radius ratio of DB /DA is 1.225, for the tightest
stacks result in the most stable structure [20]. In the CoCr2 FeNb0.5 Ni coatings, the
atomic radius ratio of B–A is close to Cr2 Nb owing to the higher Cr content, which
is smaller than the ideal ratio. The Si will occupy the A-sites, and some of the Nb
at the sites of B will be replaced by Cr, Ni, Co, or Fe when the Si dissolved into the
Laves phase. The DB /DA is closer to 1.225 due to the average atomic radius of A rises
and that of B decreases (Fig. 5). The interplanar spacing of Laves phases becomes
smaller with Si-doped having a more stable structure [21, 22].
The CoCr2 FeNb0.5 NiSi0.2 coating has the similar microstructure compared to
CoCr2 FeNb0.5 Ni. With the increase of Si content, a feathery-like microstructure
appears in the coating, concomitant with the precipitated of fine phases. The eutectic
structure disappeared and more pores defects appear in the coating in laser processing
Fig. 2 Microstructure of CoCrx FeNb0.5 Ni coatings was observed by scanning electron microscope.
a–a1 x = 0.5, b–b1 x = 1, c–c1 x = 1.5, d–d1 x = 2
Table 1 The chemical composition of different regions in CoCr2 FeNb0.5 Ni HEAs coatings in
Fig. 2 (at.%)
Region Phase Co Cr Fe Nb Ni
A FCC 17.17 44.86 17.48 4.09 16.40
B Laves 15.88 23.99 15.97 29.27 14.89
Fig. 3 TEM of
CoCr2 FeNb0.5 Ni coating.
a Microstructure at the
bright field and diffraction
spot of FCC and Laves
phase. b High-resolution
morphology and inverse
Fourier transformation
when the Si atom ratio is above 0.2 (Fig. 6). Pores always be caused by the entrapment
of gas released from the powders. The metal with better fluidity eutectic structure in
the melting process is conducive to the escape of gas. However, the gas in the molten
poor cannot escape in time during the laser cladding process due to the poor melt
fluidity with excessive Si addition [23]. The quality of the coating can be guaranteed
when the Si atomic ratio is less than 0.2.
Fig. 4 The XRD patterns of CoCr2 FeNb0.5 NiSix HEAs coatings. a The diffraction peak of Co–
Cr2 FeNb0.5 NiSix coatings. b The diffraction peak of (110) in the Laves phase
Fig. 5 The structure schematic diagram of A2 B Laves without and with Si-doped in Cr2 FeNb0.5 Ni
coating. a Without Si-doped, b with Si-doped
The chemical composition of FCC and Laves phase in CoCr2 FeNb0.5 Ni and
CoCr2 FeNb0.5 NiSi0.2 were detected (Table 2). It is obvious that Si dissolved in the
Laves phase and the Nb content of Laves phase decreased. The mixing entropy
∆Hmix AB of Fe, Co, Cr, Ni, and Nb between Si are −35 kJ/mol, −38 kJ/mol,
−37 kJ/mol, −40 kJ/mol, and −56 kJ/mol, respectively [24]. Si can preferentially
combine with Nb, forming the Laves during the solidification due to the stronger
affinity of Si and Nb atoms. Therefore, the Si atoms can occupy the A-sites in Laves
Fig. 6 The microstructure

of CoCr2 FeNbNiSix HEAs
coatings. a x = 0, b x = 0.2,
c x = 0.4 and d x = 0.6
Table 2 The chemical composition of different regions in CoCr2 FeNb0.5 NiSix HEAs coatings in
Fig. 6 (at.%)
Coatings Region Phase Co Cr Fe Nb Ni Si
CoCr2 FeNb0.5 Ni A FCC 17.17 44.86 17.48 4.09 16.40 –
B Laves 15.88 23.99 15.97 29.27 14.89 –
CoCr2 FeNb0.5 NiSi0.2 A FCC 17.01 45.38 17.43 3.76 15.71 0.71
B Laves 17.70 20.98 18.04 21.22 17.65 3.59
phase and the Co, Cr, Fe, or Ni can replace the Nb atoms at B site. This results in a
tighter occupation of the atoms, decreasing the interplanar spacing. The interplanar
spacing of the Laves phase decreases from 0.797 to 0.768 nm in CoCr2 FeNb0.5 Ni
and CoCr2 FeNb0.5 NiSi0.2 coatings are observed by inverse Fourier transform (Fig. 7).
The Nb content in the Laves phase also decreases from ~30 to ~20 at.% with the Si
addition. More Nb atoms can expelled in the melt pool, promoting the formation of
Laves phases which results in a higher content of Laves phases in the coating.
2.3 Effect of C Addition on the Microstructure
The addition of Si leads to an increase in defects of the coatings, making it difficult

to improve its mechanical properties. C is a type of interstitial atom often used to
enhance the strength of metallic materials. In the CoCr2 FeNb0.5 NiSi0.2 coatings, the
diffraction peaks of MC can be clearly observed after the addition of C, indicating
that in-situ reaction during solidification produced a reinforced phase of MC (Fig. 8).
The C in the melt pool reacted with the strong carbide-forming element Nb to form
Fig. 7 Transmission electron microscopy and inverse Fourier transformation of

CoCr2 FeNb0.5 NiSix coating prepared by laser cladding. a x = 0 and b x = 0.2
MC phase. The high content of Nb elements in the high-entropy alloys inhibited the
separate reaction of Cr and C, and no other structure carbides were observed. The
typical eutectic structure can still be observed in the dendritic. After the C addition,
some fine spherical phases can be considered as MC are observed in the interdendritic.
Also, the MC phase size grows larger significantly with more C addition (Fig. 9).
Another interesting phenomenon, the edges of the MC phase are very smooth when
the C-atom ratio is 0.1, while the burr structure appears on the surface of MC phase
when the C-atom ratio is 0.3. Also, it is obvious from the distribution of elements that
the MC particles mainly consist of Nb and C in CoCr2 FeNb0.5 NiSi0.2 C0.3 (Fig. 10).
In the TEM pictures of CoCr2 FeNb0.5 NiSi0.2 C0.1 coatings, diffusely distributed
phases with ~100 nm were clearly observed. The selected area electron diffraction
(SAED) with (3̄3̄1) and (2̄4̄2) crystal plane can be identified as NbC (Fig. 11). In
traditional metallic materials, the NbC strengthened phase is mostly irregular such
as granular, petal-like, and polyhedral, mainly because the difference in interfacial
energy of NbC can lead to different growth direction of the crystal plane during
solidification [25, 26]. In the HEAs coatings of this study, the mechanism of NbC
phase growth based on diffusion reactions can be explained by the Oswald ripening.
The high concentration of Nb provides sufficient growth drive for NbC, which does
not undergo oriented growth during the growth process, forming a spherical phase
with minimal surface area for the lowest energy eventually [27, 28]. As the C addition
Fig. 8 The XRD patterns of CoCr2 FeNb0.5 NiSi0.2 HEAs coatings with and without C addition
Fig. 9 The microstructure of CoCr2 FeNb0.5 NiSi0.2 HEAs coatings with and without C addition.
a x = 0, b x = 0.1, c x = 0.2, d x = 0.3
increases, selective orientational growth of the NbC phases since the concentration
of free Nb atoms decreases, therefore burr edges appear on the surface.
Fig. 10 The elements distribution of CoCr2 FeNb0.5 NiSi0.2 C0.3 HEAs coatings
Fig. 11 TEM pictures of CoCr2 FeNb0.5 NiSi0.2 C0.1 coatings. a Microstructure of CoCr2 Fe–
Nb0.5 NiSi0.2 C0.1 coatings. b Microstructure, diffraction spot, and chemical composition of MC
particle
2.4 Effect of CeO2 Addition on the Microstructure
Rare earth elements can purify the molten pool and refine grains, which is an effective
way for enhancing the mechanical properties of laser cladding coatings [29, 30]. Also,
the Ce can decrease the defects at the oxide/metal interface, improving the adhesion
of the thermal growth oxide film. The denser and well adherently oxide film is a
benefit to high-temperature oxidation resistance of metal [31, 32]. Ce is difficult to
exist in the form of elemental powder, therefore, the CeO2 powders with 75 μm
particle size were added into the CoCr2 FeNb0.5 NiSi0.2 C0.1 mixture powders. In the
CoCr2 FeNb0.5 NiSi0.2 C0.1 laser clad coating, the diffraction peaks positions of FCC,
Laves, and NbC phases have little shift after the addition of CeO2 , which implies that
the CeO2 is not participated in the phase solidification reaction. Also, no diffraction
peaks of CeO2 can be observed even when the CeO2 content reaches 3 wt.% (Fig. 12).
Fig. 12 The XRD patterns

of CoCr2 FeNb0.5 NiSi0.2 C0.1
HEAs coatings with CeO2
addition
The microstructure of the coatings after the addition of CeO2 shows a clear refine-
ment (Fig. 13). The flower-like morphology consisted of lamellar structure becoming
smaller and more uniform and dispersible. The CeO2 particles had not been found in
the coating, indicating that they absorbed the energy of the laser beam and melted.
During the laser cladding process, CeO2 with a high laser absorption rate signifi-
cantly increased the absorption rate of the powders and promoted the fluidity of the
molten pool [33]. CeO2 melted in the molten pool, and the Ce atoms could be easily
trapped by defects at the interface. The Ce atoms adsorbed at the grain boundaries
formed new fine CeOx particles with O in the melt pool. The difference between
the surface energy of the interfaces was reduced, and the growth of interfaces with
maximum surface tension was suppressed. The CeOx increased the nucleation sites
of the Laves phase. The growth of the lamellar structure was suppressed due to the
pinning effect of the CeOx , resulting in a finer eutectic structure.
Fig. 13 Microstructure of CoCr2 FeNbNiSi0.2 C0.1 coatings with CeO2 addition. a 0 wt.%, b 0.5
wt.%, c 1 wt.%, d 2 wt.% and f 3 wt.%
3 The Oxidation Behavior of Co–Cr–Fe–Nb–Ni Coatings
3.1 The Role of Cr on Wet Mixture Gas Oxidation
H2 O and CO2 have a significant influence on the oxidation kinetics of coatings.

They are the main atmospheres for high-temperature oxidation in AUSC boilers.
The oxidation test was carried out in a quartz tube furnace filled with mixture gas.
The specimens were cut into 10 × 10 × 1 mm and all the surfaces were polished to 1
μm. Hereafter, the specimens were ultrasonically washed with absolute ethanol and
placed in a corundum crucible, which was used to record weight change. The quartz
tube furnace was pumped into 10 Pa and subsequently filled with the N2 –44CO2 –
6H2 O (vol. %) mixture gas at a flux of 300 mL/min. The furnace was stabilized at
800 °C by heating rate of 20 °C /min. The total exposure time was 320 h and weighted
the specimen every 40 h.
The oxidation kinetic curves clearly show that the oxidation weight gain of the
coating is divided into two main stages (Fig. 14). In the first 100 h, the oxidation
curves grew rapidly for the initial stage of the oxide film growth. The oxidizing
gases reached the surface of the coating, reacting with the epilayer atoms. The rate
of weight gain decreased after 100 h. The surface of the coatings was covered with a
complete oxide film, preventing oxidizing gases from contacting the coating directly.
The diffusion is the main way for oxygen ions to reach the interface between the
coating and the oxide film. At this time, the metal ions in the coating could only diffuse
outwards through the oxide film and further oxidated. The process of oxidation weight
gain is controlled by the reaction to diffusion. The oxidation weight gain curves of
CoCrx FeNb0.5 Ni can be approximated as parabolic laws, which can be fitted using
the equation: (∆m)2 = K p × t, where ∆m is the weight gain per unit area of coating
oxidation, K p is the parabolic rate constant, and t is the oxidation time. The K p
of CoCrx FeNb0.5 Ni is 0.203 mg2 /(cm4 h), 0.174 mg2 /(cm4 h), 0.133 mg2 /(cm4 h),
and 0.086 mg2 /(cm4 h), respectively. The addition of Cr significantly improves the
oxidation resistance of the coating.
The oxidation products on the surface consist of fine-grain and blade oxides
(Fig. 15). In CoCr0.5 FeNb0.5 Ni coating, the oxidized surface morphology is relatively
rough. The clustered spherical structure is composed of fine-grain and blade oxidation
products. With the content of Cr increased, the surface of the oxidation products
becomes relatively flat and the spherical clusters disappear. The blade oxides are
randomly distributed among the fine-grain oxides. The main oxidation products of
CoCrx FeNb0.5 Ni coatings are Cr2 O3 due to the XRD result (Fig. 16). Also, a few
Cr3 O diffraction peaks are also observed, which could form due to the oxidation of
Cr at low oxygen partial pressure [34, 35]. Some diffraction peaks of NbO2 could be
detected in the oxidized CoCr0.5 FeNb0.5 Ni coating.
The interface cross section of oxidized high-entropy alloys coatings can be divided
into four main regions (Fig. 17). The elements composition of these regions was
detected (Table 3). The outer surface (Region A) is a Cr2 O3 oxide film composed of
Cr and O. The region B is the inner oxidation zone (IOZ) at the interface between the
Fig. 14 The oxidation kinetic curves of CoCrx FeNb0.5 Ni HEAs coatings at 800 °C in wet mixture
gas oxidation
Fig. 15 The oxidized surface morphology of CoCrx FeNb0.5 Ni HEAs coatings at 800 °C in wet
mixture gas oxidation after 320 h. a x = 0.5, b x = 1, c x = 1.5 and d x = 2
coating and the oxide film, which consists of Cr, Nb, and O. Combined with the NbO2
and Cr3 O diffraction peaks found in the XRD results, this region can be considered
as mixed oxides of Nb and Cr. The Laves phase and FCC phase existed in the regions
C and D, respectively. The NbO2 is produced by the oxidized Laves phase for the
Fig. 16 X-ray diffraction spectra of oxidized CoCrx FeNb0.5 Ni HEAs coating in mixture gases of
HEAs coatings at 800 °C in wet mixture gas oxidation after 320 h
Nb mainly presents in this phase in the coating. Kirkendall voids can also be clearly
observed at the interface after oxidation. At the later stage of oxidation, the coating
surface was covered by a complete oxide film. At this time, the metal cations in the
coating diffused outward, and the oxygen ions diffused inward. Since the diffusion
rate of cations outward was faster than the diffusion rate of anions inward, Kirkendall
voids were left at the interface [36].
In the N2 –44CO2 –6H2 O (vol.%) mixture gas, N2 is a relatively stable gas. As no
N-containing products were found after exposing to the mixed gas, it can be assumed
that N2 in the atmosphere does not participate in the reaction. The oxidation reaction
of oxygen comes from CO2 and H2 O, and the mainly reaction can be described as
follows [37]:
1
CO2 ⇌ CO + O2
2
2CO ⇌ CO2 + C
Fig. 17 The interface cross section of CoCrx FeNb0.5 Ni HEAs coating at 800 °C in wet mixture
gas oxidation for 320 h. a, e x = 0.5, b, f x = 1, c, g x = 1.5 and d, h x = 2
Table 3 The elements composition of different regions in oxidized CoCrx FeNb0.5 Ni coatings in
Fig. 17 (wt.%)
Coatings Region O Cr Nb Fe Co Ni
CoCr0.5 FeNb0.5 Ni A 64.86 35.14 – – – –
B 60.86 11.97 27.17 – – –
C – 5.59 22.42 26.27 22.18 23.54
D – 9.56 5.32 30.16 27.15 27.81
CoCrFeNb0.5 Ni A 62.47 37.53 – – – –
B 61.97 12.89 25.14 – – –
C – 5.12 23.20 26.13 23.31 22.24
D – 6.98 5.13 30.75 28.38 28.76
CoCr1.5 FeNb0.5 Ni A 64.46 35.54 – – – –
B 58.37 15.53 26.10 – – –
C – 10.24 32.28 21.46 17.82 18.21
D – 14.13 4.77 28.13 26.39 26.58
CoCr2 FeNb0.5 Ni A 61.15 38.85 – – – –
C – 12.15 33.17 19.26 19.81 15.61
D – 22.89 5.00 25.84 23.11 23.16
1
H2 O ⇌ H2 + O2
2
CO + H2 ⇌ H2 O + C
The mixed atmosphere can provide free O and C at the surface of the coating.
At equilibrium in the 800 °C environment, the pO2 (partial pressure of oxygen) in
the atmosphere is 2.6 × 10–7 atm, while the ac (carbon potential) is 1.66 × 10–40 .
The Cr and Nb are the elements that preferentially oxidize in the coating at 800 °C
according to the Ellingham diagram. Carbides of Nb or Cr had not been found, for
the carbide reactions could hardly occur for the extremely low carbon potential [38].
Therefore, the coating reacts preferentially as follows:
4
Cr + O2 ⇌ Cr2 O3 ∆ f GΘ = − 746840 + 170.29T
3
2Nb + O2 ⇌ 2NbO2 ∆ f GΘ = − 786590 + 149.79T
At 800 °C, the free energy of Cr2 O3 and NbO2 is −564.12 and −625.86 kJ/mol.
The NbO2 with more negative free energy is easier to grow in this environment.
However, in the cross-sectional observation of the coating after high-temperature
oxidation, it is obvious that the Cr2 O3 appeared at the outer of the coating, while
NbO2 is observed only in the inner oxidation zone. The high concentration of Cr
enhances the selective oxidation of chromium and Cr2 O3 preferentially formed on

the surface.
3.2 The Role of Si on Wet Mixture Gas Oxidation
The Si was added into the CoCr2 FeNb0.5 Ni coating to improve the quality of lase clad
coating. Also, its oxides contribute to the high-temperature oxidation resistance. The
oxidation kinetics for these samples with and without Si can be approximately fitted
by the parabolic law. The oxidation weight gain of CoCr2 FeNb0.5 NiSi0.2 decreased
compared to CoCr2 FeNb0.5 Ni. It can be found that the weight gain of the above
two coatings is similar at the early stage of oxidation, while decreasing after 200 h
with the Si addition. The effect of Si in improving the oxidation resistance is mainly
demonstrated in the late stage of oxidation. The excessive Si addition decreases the
oxidation resistance of the coatings (Fig. 18). Similar to the CoCr2 FeNb0.5 Ni coating,
the oxides on the surface of the coating with Si addition are still consisted of fine-
grain and blade oxides. Excessive Si addition results in more defects in the coating
(Fig. 19).
The difference between the CoCr2 FeNb0.5 Ni and CoCr2 FeNb0.5 NiSi0.2 oxide
layer is mainly at the interface after 320 h oxidation, which can be observed from
the examined cross section (Fig. 20). The complete outside oxide layer can be iden-
tified as Cr2 O3 , while the interface between coating and oxidation layer is quite
different. Minor oxides at the interface seem different from the Cr2 O3 . The aggre-
gation of Nb disappeared at the interface when Si was added to the coating. Instead,
the aggregation of Si at the interface becomes obvious, indicating the Si diffused
to the interface and reacted with O. The Fe, Co, and Ni are still concentrated in the
coatings. The selective oxidation and the delayed diffusion effect of the high-entropy
alloys inhibited the oxidation of these elements.
The interface of CoCr2 FeNb0.5 NiSi0.2 coating after oxidation was observed more
carefully by TEM (Fig. 21). The corresponding SAED patterns are FCC (red dot)
Fig. 18 The oxidation

kinetic curves of
CoCr2 FeNb0.5 NiSix HEAs
coatings at 800 °C in wet
mixture gas oxidation
Fig. 19 The oxidized surface morphology of CoCr2 FeNbNiSix HEAs coatings at 800 °C in wet
mixture gas oxidation after 320 h. a x = 0, b x = 0.2, c x = 0.4 and d x = 0.6
Fig. 20 The elements distribution mapping of cross-sectional morphology of a CoCr2 FeNb0.5 Ni

and b CoCr2 FeNb0.5 NiSi0.2 HEAs coating after oxidation [39]. Authorized by Elsevier
and the Laves (yellow dot) phases, respectively. The outer oxide layer of SADE with
(001) and (02̄1) crystal plane can be judged as Cr2 O3 . The IOZ (green dot) can be
recognized as the Cr3 O via the SAED pattern with (02̄1̄) and (2̄1̄0) crystal plane.
However, the chemical composition of this zone is mainly 24.71 at.% Cr, 3.63 at.%
Si, 60.91 at.% O and 11.47 at.% Cu. The detected Cu might be polluted during the
focused ion beam (FIB) preparation. The samples were welded to the copper column
after the cut. The Si in both the inner oxide zone and the Laves phases implies that
Si had diffused from the Laves phase to the inner oxide zone. The HRTEM images
of the inner oxide zone shows that the path of internal oxidation is mainly along the
boundary between the Laves and FCC phase (Fig. 22). Broadened diffraction rings
were observed around the Laves phase at the internal oxidation zone by Fourier
transform. Amorphous products were generated by the oxidation of Si and Cr, which
are mainly (Cr, Si)Ox amorphous oxides [40].
SiO2 has a more negative free energy (−717.28 kJ/mol) compared with that of
NbO2 and Cr2 O3 . In the early stage of high-temperature oxidation, oxygen atoms
reached the coating surface and reacted with Cr atoms due to the selective oxidation.
The high concentration of Cr promoted the growth of Cr2 O3 film on the coatings’
surface. After the oxide film completely covers the coating surface, oxygen ions must
diffuse through the oxide film to contact the coating, meanwhile the Cr ions diffused
outward through the film. Kirkendall voids were formed at the interface owing to the
Fig. 21 The elements

distribution mapping of
cross-sectional morphology
of CoCr2 FeNb0.5 NiSi0.2
HEAs coating after oxidation
[39]. Authorized by Elsevier
Fig. 22 High-resolution
transmission electron
microscope image of the
interface between IOZ and
HEAs matrix [39].
Authorized by Elsevier
difference in diffusion rates between anions and cations. The oxygen ions reached
the coating surface and then diffused inward along the interface between the FCC
and the Laves phases, both two phases oxidated slowly. The oxygen partial pressure
at IOZ is low, contributing to the formation of Cr3 O. The Si replaced the oxidation
of Nb since the Laves phase was doped with Si. An extremely thin amorphous (Cr,
Si)Ox oxide layer was formed to cover the Laves phase. It could effectively prevent
the contact between oxygen ions and the Laves phase, since the higher stability of
(Cr, Si)Ox and no grain boundaries of amorphous structure [40]. The reducing the
oxidation rate of the Laves phase helped to improve the high-temperature oxidation
resistance of the coating.
3.3 The Influence of C and CeO2 on High-Temperature

Oxidation
The addition of C can form MC-reinforced particles. However, the high diffusion
rate at high temperature is detrimental to the oxidation resistance of the coating [41].
The oxidation kinetic curve of the CoCr2 FeNb0.5 NiSi0.2 Cx coating reveals that the
addition of C weakens the high-temperature oxidation resistance (Fig. 23). Even
the oxidation products are still Cr2 O3 . The growth drive of Cr2 O3 becomes weaker
since the Cr atoms are immobilized in MC. The oxidation resistance of the coatings
shows a significant decrease, especially at the C-atom ratio of 0.3. The fine-grain and
blade Cr2 O3 can still be observed on the oxidized surface of the coating (Fig. 24).
The blade Cr2 O3 oxides grew with the increase of C content. The oxidized surface
became rather rough when the C-atom ratio reached 0.3. The cross sections clearly
show the differences in the oxide layer. The interface of the coating surface remains
flat, which is different from the previous rough oxide surface. The blade oxides
growth with C addition, leading to more voids between oxide films (Fig. 25). The
Cr atoms could diffuse outward and oxidate more easily since the denseness of the
oxide film decreases. The growth of blade oxides would produce a rough surface and
decrease the oxidation resistance.
The CeO2 was added to the coatings to improve the denseness of the oxide layer.
A significant decrease in oxidation weight gain of the coatings after the addition
of CeO2 (Fig. 26). The surface of the oxidation layer had changed significantly.
The blade oxides disappeared, replaced by whisker-like oxides (Fig. 27). The cross
section of the oxide further illustrates the difference in coating oxidation after CeO2
addition. With the addition of CeO2 , the denseness of the oxide film was significantly
improved. Kirkendall voids at the interface disappeared, and the bonding ability of
the thermal growth oxides layer was enhanced.
The diffusion path of ions became more tortuous since the grain of the coating was
refined after CeO2 addition. During oxidation, Ce ions were released from the CeOx
nanoparticles that were enveloped by the inward-growing oxides from the scale/metal
interface. The pegging effect of intergranular CeOx , which was preferentially formed
at the grain boundaries, reduced the outward diffusion rate of Cr ions. The growth
Fig. 23 The oxidation

kinetic curves of
CoCr2 FeNb0.5 NiSi0.2 HEAs
coatings with C addition in
wet mixture gas oxidation at
800 °C
Fig. 24 The oxidized

surface morphology of
CoCr2 FeNb0.5 NiSi0.2 Cx
HEAs coatings at 800 °C in
wet mixture gas oxidation
after 320 h. a x = 0, b x =
0.1, c x = 0.2 and d x = 0.3
Fig. 25 The cross-sectional

morphology of
CoCr2 FeNb0.5 NiSi0.2 Cx
HEAs coatings at 800 °C in
wet mixture gas oxidation
after 320 h. a x = 0, b x =
0.1, c x = 0.2, and d x = 0.3
Fig. 26 The oxidation weight gain of CoCr2 FeNb0.5 NiSi0.2 C0.1 HEAs coatings at 800 °C in wet
mixture gas
Fig. 27 The cross section and surface morphology of CoCr2 FeNb0.5 NiSi0.2 C0.1 HEAs coatings
with CeO2 addition in wet mixture gas at 800 °C. a, e 0.5 wt.%, b, f 1 wt.%, c, g 2 wt.% and d, h 3
wt.%
process of the thermal oxidation film controlled was changed from Cr ions to oxygen
ions, which inhibited the growth of Cr2 O3 orientation [31, 41–43]. The process of
inward diffusion of oxygen ions through the oxide film became difficult due to the
denser oxide film. The CeOx aggregated at the scale/metal interface, inhibiting the
vacancy aggregation, and Kirkendall voids disappeared. The consumption of Cr ions
for oxidation was reduced as the diffusion of ions became difficult. The oxide film
was more tightly bonded to the coating, and the adhesion was improved. Meanwhile,
the Cr2 O3 film would be further vaporization and redeposition in the wet environment
following the reaction [44]:
Cr2 O3 (s) + 2H2 O(g) + 3/2O2 (g) = 2CrO2 (OH)2 (g)
Further oxidation of Cr2 O3 produced CrO2 (OH)2 vapor by H2 O, which molecule

at the tip of the blades had faster dissociation, favoring the whiskers form [45].
4 The Wear Mechanisms of Co–Cr–Fe–Nb–Ni Coatings
4.1 The Influence of C Addition on Hardness
Hardness is an important indicator of wear resistance. The Laves and MC phases

are important strengthening phases in CoCr2 FeNb0.5 NiSi0.2 with C addition, both
dependent on the content of Nb. The hardness of the coating increases and then
decreases with the addition of carbon. The highest hardness of the coatings can be
obtained at a C-atom ratio of 0.1, reaching 851 HV0.3 (Fig. 28). The content of
FCC, Laves, and MC phase were counted through numerous microstructures. The
content of MC increased, while the Laves decreased with more addition of C. When
the C atomic ratio was 0.3, the increment of the MC phase was only ~5%, while
the reduction of the Laves phase was almost ~10%. (Fig. 29). It illustrates that the
process of MC formation leads to a serious decrease of the Laves phase.
NbC precipitated preferentially by diffusion reaction during solidification because
of the strongest affinity between Nb and C atoms and the high melting point of NbC.
When adding a few C, the little Nb in the melt pool can be captured by the C to form
the NbC reinforced phase without causing a serious drop in the Laves phase. NbC
has a stronger reinforcement effect due to its hardness is ~20 GPa, much higher than
that of the Laves phase (~8 GPa) [46, 47]. The synergistic reinforcement of NbC
and Laves phase improves the hardness of the coating. With more NbC precipitated,
the free Nb atoms in the melt pool were insufficient for the formation of the Laves
phase, and its content decreased. The increased concentration of Fe, Co, Cr, and Ni
resulted in an increase in the FCC phase. The hardness of the coatings decreased
because the strengthening effect of NbC could not compensate for the decrease of
the Laves phase.
Fig. 28 The hardness of

CoCr2 FeNb0.5 NiSi0.2
coatings with C addition
Fig. 29 The phase content

of CoCr2 FeNb0.5 NiSi0.2
coatings with C addition
4.2 The Wear Mechanisms of HEAs Coatings at Elevated

Temperature
Besides the erosion of the high-temperature atmosphere, the heated components also
receive the impact of ash and other particles, which wear out the materials’ surface.
The wear rate was calculated by profile measurement after test [48]. The wear rate
of CoCr2 FeNb0.5 NiSi0.2 coatings with a C addition atom ratio of 0.1 reveals the
optimize wear resistance, which is consistent with the hardness trend of the coatings
(Fig. 30). The wear rates 3.43 × 10–5 (mm/(N m)) and 2.56 × 10–5 (mm/(N m))
increased by 1.25 times and 1.24 times, respectively, compared to the coating without
C addition at RT and 800 °C. The hardness plays a significant effect on the wear
resistance of the coatings at elevated temperatures. The relationship between the wear
rate and hardness of CoCr2 FeNb0.5 NiSi0.2 C0.1 coating was compared at different
temperatures (Fig. 31). The wear rate of the coating increases with the decline of
hardness when the temperature is below 400 °C, indicating that hardness has a direct
effect on the wear resistance. When the temperature exceeds 400 °C, the wear rate
begins to decrease, implying that hardness is no longer the only factor. Noteworthy,
the CoCr2 FeNb0.5 NiSi0.2 C0.1 maintained a hardness higher than 600 HV3 even at
800 °C, thanks to the NbC phase retaining a high hardness at high temperatures [41].
A significant difference can be observed when comparing the wear morphology
of HEAs coatings at different temperatures (Fig. 32). At RT and 200 °C, parallel
grooves along the sliding direction on the surface, which is a typical type of abrasive
wear. The brittle phase of the Laves fractured and became debris, which continuously
micro-cut the coating surface. When C was added to the coating, the MC particles
acted as debris in the wear process. The size of MC particles was small and had a
nearly spherical structure when the C content was low. The cutting effect of debris on
the coating surface was weak, and the grooves were relatively shallow. The grooves
Fig. 30 The wear rate of

CoCr2 FeNb0.5 NiSi0.2
coatings with different C
addition at an evolved
temperature
Fig. 31 The wear rate and

hardness of
CoCr2 FeNb0.5 NiSi0.2 C0.1
coating at different
temperatures
became deeper as the NbC grew larger. The wear mechanism is mainly abrasive wear
at RT and 200 °C.
At 400 °C, some oxides were found on the grooves, showing a certain oxidative
wear and abrasive wear. When the temperature reached 600 °C, oxide layer delamina-
tion could be observed on the worn surface except the grooves. The wear mechanism
is abrasive wear and oxidative wear. With the temperature further improved to 800 °C,
the worn surface becomes flat and only a little debris is observed. Some slight grooves
are observed on the surface of the oxide layer. The wear mechanism is oxidative wear
and slight abrasive wear. The surface morphology of the C0.1 CoCr2 FeNb0.5 NiSi0.2
coatings before wear at elevated temperature was observed (Fig. 33). At 400 °C,
visible processing evidence on the surface of the coating means that oxidation has
not occurred. Some oxides were found after the wear test mainly originated from the
heat resulting from friction during the wear process [49]. At 600°C, the fine gran-
ular oxides do not fully cover the coating surface due to minimal oxidation. During
subsequent friction, the coating undergoes further oxidation. At 800°C, the coating
surface is nearly entirely covered with oxides. Throughout the wear process, the oxide
layer cyclically experiences squeezing, delamination, peeling, and compaction. The
complete oxide film Cr2 O3 may played a protective role for the coating [50].
Fig. 32 The wear morphology of the CoCr2 FeNb0.5 NiSi0.2 Cx coatings at different temperatures.
a1–a5 x = 0, b1–b5 x = 0.1, c1–c5 x = 0.2 and d1–d5 x = 0.3
Fig. 33 The surface morphology of the CoCr2 FeNb0.5 NiSi0.2 C0.1 coating before wear at high-
temperature environment. a 400 °C, b 600 °C and c 800 °C
5 Comparison of HEAs Coatings to Electroplated Hard Cr
5.1 The Oxidation Behavior of Two Coatings
Electroplated hard Cr is often used in a high-temperature environment as a wear and

oxidation-resistant coating in industrial and decorative fields [51]. To realize the Co–
Cr–Fe–Nb–Ni coatings real performance of high-temperature wear and oxidation at
800 °C, the electroplated hard Cr coatings with 50 μm thickness were compared. The
high-temperature oxidation in mixture gas of two coatings was also tested, and the
cross section of the oxide layers was observed. The oxide film thickness of the HEAs
coating is only 2.21 μm, while that of electroplated hard Cr is 20.26 μm, almost 10
times (Fig. 34). Noteworthy, there are numerous voids inside the oxide film of hard
Cr coatings. The oxide film of HEAs coating was denser for better protection. Also,
the weight gain per unit area of electroplated hard Cr was 6.77 mg/cm2 , and that of
the HEAs coating was only 0.43 mg/cm2 , with a decrease of 93%. Some microcracks
were observed in the electroplated hard Cr. In the electroplating process, the unstable
intermediate chromium hydride of β-Cr decomposes to stable pure chromium of α-
Cr, and the hard chromium layers generally crack relieved the internal stresses of
coatings [52]. In high-temperature oxidation, oxidizing gases could travel deeper
into the coating through the cracks, resulting in more oxidation.
Fig. 34 The oxide layer thickness of hard Cr compared to HEAs coating at 800 °C. a HEAs coating
and b electroplated hard Cr
Fig. 35 The wear of the electroplated hard Cr compared to HEAs coating at 800 °C. a The wear
profile of two coatings, 3D wear profile of b HEAs coating and c hard Cr
5.2 The Wear Behavior of Two Coatings
The high-temperature stability of electroplated hard Cr reduces to 600 HV at 600 °C,

which is weaker than that of high-entropy alloys [53]. The wear profile of hard Cr
is almost 60 μm, much deeper than that of the HEAs coating, which is only 15 μm
(Fig. 35). The depth of the wear trace exceeded the thickness of the electroplated
hard Cr coating itself, indicating that the plated hard Cr only has a protective effect in
the early stage of wear. At the later stage of the wear process, the electroplated hard
Cr was worn through and loses the protective effect. The base material was abraded
in the later stage of the wear test. The wear rate of hard Cr was 14.54 × 10–5 mm3 /
(N m). The HEAs coating was 1.47 × 10–5 mm3 /(N m), with 89% reduction relative
to hard Cr. Due to the special effects of HEAs coatings, the stability of HEAs coatings
and thin oxide film might be beneficial to wear resistance at high temperature. HEAs
exhibited superior performance to electroplated hard Cr, both in oxidation and wear
resistance at high temperature.
6 Conclusion
The Co–Cr–Fe–Nb–Ni HEAs coatings prepared by laser cladding show a superior

oxidation and wear resistance at elevated temperature. The Co–Cr–Fe–Nb–Ni HEAs
coatings have eutectic microstructure composed of FCC and Laves phases. Cr can
dissolve into the FCC phase, causing lattice distortion of the FCC phase without
changing the phase composition of the coating. The increment of the Cr can signif-
icantly improve the high-temperature oxidation resistance of the HEAs coatings.
High Cr content enhances the selective oxidation of Cr, and protective Cr2 O3 oxide
film on the surface inhibits the oxidation of the Laves phase. A drop of Si can form a
more compact dimension in the Laves phase with higher stability. In addition, the Si
in the Laves phase replaces the oxidation of Nb, producing a more stable (Cr, Si)Ox
internal oxide layer, which effectively inhibits further internal diffusion of oxygen
ions. The C added in the melt pool can react with the Nb, generating a fine NbC rein-
forcing phase in-situ. The content of NbC and Laves strongly influenced the HEAs
coatings’ hardness, and high hardness benefits the wear resistance. The protective
oxide film may play more impactful on wear resistance at the temperature above
400 °C. The CeO2 melted in the molten pool, and new CeOx adsorbs at the boundary
can effectively inhibit the growth of lamellar structure and refine the coatings. The
active element effect of Ce speeds the short-range diffusion of Cr ions, promoting the
formation of denser Cr2 O3 film. Whether in oxidation or wear at high temperature,
Co–Cr–Fe–Nb–Ni HEAs coatings exhibit more excellent performance compared to
electroplated hard Cr.
In complex mixed atmosphere working conditions, the HEAs coatings with Cr2 O3
protective film seem to be insufficient for it can be further reacted by H2 O above
600 °C. Ion diffusion at phase and grain boundaries is also an important factor in
high-temperature oxidation. The thermal growth oxides should be considered in the
design of HEAs. Also, the coherent, semi-coherent interface and twin crystals may
be introduced into the HEAs coatings to inhibit ion diffusion. In conclusion, the lase
clad HEAs coatings have potential prospects for high-temperature applications. More
HEAs coatings need to be systematically researched in the future. HEAs coatings with
attractive properties are worthy of development from both academic and application
viewpoints.
Acknowledgements This research was supported by the National Natural Science Foundation
of China (Grant No. 51901016), the Fundamental Research Funds for the Central Universities
(FRF-TP-18-031A2, FRF-GF-18-024B), University Innovation Research Group of Chongqing
(CXQT20023), and Scientific Research Foundation of Chongqing University of Technology
(2023ZDZ004).
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The Boriding Process for Enhancing
the Surface Properties
of High-Temperature Metallic Materials
I. E. Campos Silva, A. Günen, M. Serdar Karakaş, and A. M. Delgado Brito
Abstract High-temperature metallic materials operate in environments with a broad

spectrum of mechanical and chemical conditions, originating typical failures such as
steam oxidation, hot corrosion, and wear-corrosion; the service life of the metallic
component is reduced with severe economic losses. The ever-increasing demands
for enhanced component performance require continuous improvements in existing
material systems. In this sense, boriding is a promising thermochemical process used
to increase the surface properties of metallic materials for high-temperature applica-
tions. The resulting boride coating has excellent wear resistance at high temperatures
due to its high hardness, thermal, and chemical stability, and adhesion to the substrate
material. In addition, the boride coating is resistant to corrosion in acidic, alkaline,
and salt media, suitable for use in harsh environments. The mechanical and chemical
properties of the boride coating are preserved at high temperatures (up to 1000 °C);
the probability of the boride coating cracking or spalling at high temperature is negli-
gible. This chapter reviews the various boriding methods as adopted for the formation
of boride coating on high-temperature metallic materials to improve its performance
for diverse high-temperature applications. Wear, practical adhesion, oxidation, corro-
sion, and tribocorrosion properties of borided materials are explained in terms of the
boride coating-substrate system behavior.
Keywords Boriding · High-temperature materials · Boride coatings · Mechanical

properties · Oxidation resistance · Wear-corrosion resistance
I. E. Campos Silva (B)

Instituto Politécnico Nacional, SEPI ESIME Zacatenco, Grupo Ingeniería de Superficies, U.P.
Adolfo López Mateos, 07738 Ciudad de México, Mexico
e-mail: icampos@ipn.mx
A. Günen
Department of Metallurgy and Materials Engineering, Faculty of Engineering and Natural
Sciences, Iskenderun Technical University, 31200 Hatay, Turkey
M. Serdar Karakaş
Department of Metallurgical and Materials Engineering, Faculty of Engineering and Natural
Sciences, Konya Technical University, 42130 Konya, Turkey
A. M. Delgado Brito
TecNM/Tecnológico de Estudios Superiores de Jocotitlán, 50700 Estado de México, Mexico
222 I. E. Campos Silva et al.
1 The Boriding Process
The reactivity of B toward metals leads to various boron compounds widely used for
a variety of tribological and corrosion applications. Introducing boron into metallic
materials is an efficient method to increase physical and chemical properties such as
hardness, wear resistance, corrosion resistance, and oxidation resistance due to the
formation of metal borides on the material’s surface. Usually, the metal borides are
characterized by the combination of covalent, metallic, or ionic bonds, leading to the
development of materials with outstanding properties [1].
Boriding is a thermochemical diffusion-based surface-hardening process applied
to various ferrous, nonferrous, and cermet materials for extending the lifespan of
metal components for high-temperature applications. The resulting boride coating
on the metallic material has high hardness (between 10 GPa and 33 GPa) in combi-
nation with high thermal and chemical stability of the constituent boron compounds,
which make it resistant to wear and corrosion. In fact, the hardness of boride coating
produced on different metallic materials is much greater than those produced by any
other conventional surface hardening treatments and is equivalent to that of tungsten
carbide and many hard PVD coatings [2–4].
The boride coating is stable at high temperatures due to its high melting point,
which allows it to maintain its hardness and oxidation resistance up to 1000 °C,
with the possibility to increase the high-temperature wear resistance of metallic
materials. Also, two key factors contribute to the high-temperature wear resistance
of the boride coating: (i) the formation of a protective oxide layer (H3 BO3 ) over the
borided surface that acts as a solid lubricant during sliding and (ii) the boride coating
has a high Young’s modulus (or stiffness), which increases its deformation resistance
under stress [5].
On the other hand, the boride coating can withstand corrosive environments
such as strong acids, salts, and water steam, even in the presence of corrosive
gases at elevated temperatures and pressures. Notably, when the boride coating is
exposed to high-temperature industrial applications, a stable B2 O3 protective layer
is developed on the borided surface due to the reaction of the coating with O or other
oxidizing agents in the environment, preventing corrosion of the underlying metallic
material [6].
On most engineering alloys and metals used for high-temperature applications,
the boriding process is usually carried out at 700 °C – 1000 °C for 0.5 h –12 h,
forming 10 μm – 150 μm thick coatings. The thickness and the microstructure of
the formed boride coating affect the mechanical and chemical properties of borided
materials. They depend on the boriding temperature, the exposure time, the amount
of B atoms surrounding the surface sample, and the chemical composition of the
material. Therefore, selecting the optimum process parameters is vital to obtain
boride coatings with adequate thicknesses for their intended practical applications
[7].
Some microstructures of boride coatings on materials used for high-temperature
applications are presented in Fig. 1.
The Boriding Process for Enhancing the Surface Properties … 223
Fig. 1 Cross-sectional views of boride coating microstructures: a Fe2 B on low-carbon steel; b Fe2 B
coating with isolated FeB on high-alloy steel; c FeB–Fe2 B on low-alloy steel; d FeB–Fe2 B on
stainless steel; e FeB–Fe2 B combined with borocementite; f cobalt boride coating on Co-base
alloy; g nickel boride coating on Ni-base alloy; h titanium boride coating on Ti-base alloy. Courtesy
of Grupo Ingeniería de Superficies, Instituto Politécnico Nacional
The boriding of low-carbon, low-alloy, and high-alloy steels results in the forma-
tion of a saw-toothed coating consisting of three types of microstructures: (i) Fe2 B
with a tetragonal crystalline structure (Fig. 1a), (ii) tetragonal Fe2 B with an isolated
orthorhombic FeB (Fig. 1b), or (iii) FeB–Fe2 B coating (Fig. 1c). The saw-toothed
microstructure of both FeB and Fe2 B can be explained by dendrite “side-arm”
growth like that observed during the solidification of many metallic systems [8].
Also, Brackman et al. [9] establish that the preferential direction growth of borides
into the substrate exhibits orientations close to or with [001] perpendicular to the
surface.
The substrate’s alloying elements influence the boride coating’s growth and
microstructure. The saw-toothed microstructure of the boride coating becomes less
pronounced as the proportion of alloying elements in the substrate increases (Fig. 1b
and d). The saw-toothed microstructure of the boride coating is reduced due to the
concentration of the alloying elements on the tips of the boride columns, decreasing
the active boron flux in these regions, and inhibiting the growth of the boride coating.
Alloying elements such as C, Si, and Al are insoluble in the boride coating.
They are displaced ahead of the coating, forming a well-defined zone of precipitates
that denominate the diffusion zone. Figure 1e depicts the cross-sectional view of
borided 1018 steel. The boride coating microstructure consists of a FeB–Fe2 B coating
combined with borocementite that develops into the columns of the jagged structure.
The formation of borocementite is associated with the diffusion of C that is displaced
by the boride coating to the bulk material [10].
In contrast, for the variety of borided high-alloy materials (i.e., steels, nickel
alloys, and cobalt alloys), alloying elements such as Cr, Ni, Mo, V, and W tend to
dissolve in the boride coating and form interstitial compounds with B. In addition,
these alloying elements’ presence restricts the boride coating’s growth, developing
a semi-flat boride coating microstructure.
The microstructure of the boride coating on stainless steel (Fig. 1d) involves the
FeB (outer coating) and the Fe2 B (inner coating) combined with CrB and Cr2 B phases
due to Cr substituting Fe to form complex borides. The presence of CrB and Cr2 B
increases the hardness on the outer zone of the borided surface [11]. Underneath the
coating, the diffusion zone is constituted by two zones: a Cr-rich layer (beneath the
boride coating) that enhances the diffusion across the grain boundaries, in addition to
the appearance of a Ni-rich layer between the Cr-rich layer and the substrate [12, 13].
The boriding of Co-base and Ni-base high-temperature alloys develops a flat,
uniform boride coating microstructure with a well-defined diffusion zone under the
coating. The microstructure of the cobalt boride coating mainly consists of CoB-
Co2 B (orthorhombic and tetragonal crystalline structures, respectively) combined
with CrB, Cr2 B, and Mo2 B compounds (Fig. 1f). The formation of the diffusion zone
is related by the primary precipitation of Cr-rich products along the grain boundaries
of the substrate [14, 15]. The coating of borided nickel-base alloys (Fig. 1g) is
mainly composed of nickel borides (orthorhombic Ni4 B3 and tetragonal Ni2 B), iron
borides (FeB, Fe2 B), and chromium borides (CrB, Cr2 B). The diffusion zone is an
intermixture of Ni–B, Fe–B, and Cr–B phases, acting as a diffusion barrier to restrict
the growth of the nickel boride coating [16–19].
Titanium and its alloys are attracting considerable attention because of their poten-
tial use as low-density and high-temperature structural materials. Their inadequate
oxidation resistance (at elevated temperatures >800 °C) and poor tribological perfor-
mance limit their practical applications. Boriding is also applicable to titanium alloys
to improve their mechanical and chemical properties by the formation of a compact,
uniform coating composed of hexagonal TiB2 and orthorhombic TiB compounds
according to the Ti–B phase diagram [20–23]. The coating is characterized by a TiB2
outer coating with a TiB coating containing distributed TiB whiskers mixed with the
microstructure of the base metal, as shown in Fig. 1h. The whiskers growth has been
primarily attributed to the one-way diffusion of B along [010] crystal direction.
Some mechanical properties of boride coatings on high-temperature metallic
materials are presented in Table 1. The mechanical properties of the boride coating
are anisotropic, varying along the depth of the coating/substrate system. In addition,
the properties depend on the coating microstructure, the substrate’s chemical compo-
sition, the boriding techniques used to produce the coatings (temperatures, exposure
time, the boron potential surrounds the material surface, etc.), and the heat treatments
employed after boriding.
Table 1 Mechanical properties of boride coatings on high-temperature metallic materials

Borided Microstructure Hardness Young’s modulus Fracture Residual References
material of boride (H) (GPa) (E) (GPa) toughness stresses
coating (KIC ) (σr ) (GPa)
(MPa
m1/2 )
AISI 4140 FeB, Fe2 B, FeB–Fe2 B FeB–Fe2 B (~313) FeB–Fe2 B FeB–Fe2 B [24–26]
steel* CrB (14–19) (2.9–3.5) (0 to –0.3)
AISI 8620 FeB, Fe2 B FeB (~23) FeB–Fe2 B (~ 292) FeB FeB [27–29]
steel* Fe2 B (2.2–3.6) (+0.6)
(~19) Fe2 B Fe2 B
(2.6–3.9) (–2.7)
AISI H13 FeB, Fe2 B, FeB FeB (350–379) FeB FeB (+0.7 [30, 31]
steel CrB (17–22) Fe2 B (320–334) (1.3–1.4) to +0.9)
Fe2 B Fe2 B Fe2 B
(10–18) (5.0–5.2) (–0.2 to
–0.5)
316L steel FeB, Fe2 B, FeB rich FeB rich zone FeB Outer [32–34]
CrB, Cr2 B, zone (338–341) (1.2–1.6) zone of
Mo2 B, Ni3 B (18–22) Fe2 B rich zone Fe2 B the
Fe2 B rich (256–299) (2.2–3.0) coating
zone (+1.1 to +
(16–18) 1.6)
Inner zone
of the
coating
(–1.2 to
–1.4)
Co-base CoB, Co2 B, CoB rich CoB rich zone CoB rich CoB rich [35–37]
alloys Mo2 B, CrB, zone (300–320) zone zone (+1.1
Cr2 B (18–20) Co2 B rich zone (0.5–0.8) to +1.2)
Co2 B rich (260–290) Co2 B rich Co2 B rich
zone zone zone (–1.2
(16–17) (2.7–4.6) to –0.6)
Nickel-base Ni3 B, Ni2 B, Outer zone Outer zone of the Outer Outer [38, 39]
alloys NiB, Ni4 B3 , of the coating (370–390) zone of zone of
Cr2 B, CrB coating Inner zone of the the the
(21–24) coating (340–360) coating coating
Inner zone (~0.6) (+1.2 to +
of the Inner zone 1.3)
coating of the Inner zone
(15–19) coating of the
(~4.4) coating
(–0.25 to
–1.2)
Ti-base TiB2 , TiB TiB2 (~32) TiB2 (~343) TiB2 –TiB [40–42]
alloy TiB (0.8–4.4)
(23–27)
* Low-alloy steels are often used up to about 650 °C. The prolonged exposure at temperatures above
370 °C may result in graphitization and weakening of the steel

1.1 The Boriding Techniques
The boriding techniques are classified into two groups: chemical and physical, which
are discussed in detail by Kulka [17]. The techniques are divided based on the forma-
tion mechanism of free B atoms diffusing into the metallic substrate. Surface alloying
with B, thermal spraying, detonation spraying, and cladding with B are examples of
physical boriding techniques.
The chemical boriding techniques include solid, liquid, and gaseous media. They
need an activator (reducing agent) and a boriding agent that supplies the B atoms
during the process; the activator and boriding agent react to derive elemental B,
which diffuses into the metal surface, forming the boride coating. In this section, a
greater focus is placed on boriding chemical techniques; a brief overview of some
of them is presented in Table 2.
The concept of “hybrid” boriding (chemical-physical) techniques was used during
the last years, such as ultra-fast boriding, fluidized bed boriding, plasma-paste
boriding, and the pulsed-DC powder-pack boriding [17, 43, 46–50]. The “hybrid”
techniques offer, principally, the reduction of temperature and boriding time (in most
cases, the temperature ranges are between 700 °C and 950 °C with exposure times
around 0.25 h – 4 h), relatively low energy consumption, and they are friendly to
the environment. In addition, the use of plasma and electricity, increases the growth
kinetics of boride coatings on the material’s surface. For example, the fluidized bed
boriding contains a bed of SiC particles, a powder boriding agent, and an N2 –H2
gas mixture. The technique can employ electricity as the heat source. Thus, the bed
serves as a faster heat-transfer medium; the high rates of heating and flow, as well as
direct withdrawal of the parts, provide shorter operating cycle times [4].
On the other hand, ultra-fast boriding involves the preparation of a molten elec-
trolyte consisting of about 90 wt.% borax and ~10 wt.% carbonates of alkaline
and alkaline-earth elements (sodium and/or calcium carbonate) or sodium chloride.
A high-frequency induction furnace containing a graphite crucible gives external
agitation and mixing of electrolytes. In addition, it helps overcome diffusion barriers
in the electrochemical process, developing fast boriding and thick boride coatings
in short processing times (less than an hour). The induction furnace has a positively
charged cathode (to which the samples are attached) and a negatively charged anode;
the furnace is connected to a power source, and ions flow from the anode to the
cathode, depositing B on the cathode and attached samples [46, 51, 52].
Based on the enhancement effect of the direct current field on powder-pack
boriding [53–55], a novel technique called pulsed-DC powder-pack boriding
(PDCPB) was developed [50]. This technique was carried out by generating a direct
current field between two electrodes in the powder mixture (the material to be borided
is collocated among the electrodes). The direct current field promotes an electromi-
gration effect, increasing the B diffusion over the surface of materials. A schematic
diagram of the main parts of the experimental apparatus is shown in Fig. 2a. In this
apparatus, two electrodes with a distance of 10 mm are placed in the powder mixture
in a metallic container and heated in a conventional muffle. The PDCPB employs a
Table 2 Various boriding techniques in solid, liquid, and gas media

Technique Media Examples of the Brief Some References
boriding mixture description advantages and
components’ disadvantages
Powder-pack Solid Boron source: boron The specimens Easy handling, [17, 43]
carbide, ferroboron, are introduced low-cost
and amorphous in a container requirements,
boron (heat-resisting simplicity of the
Activator: NaBF4 , steel or similar) equipment, and
KBF4, Na2 CO3 , and embedded the possibility of
BaF2 and Na2 B4 O into the powder changing the
Diluent: SiC, Al2 O3 mixture. The composition of
sealed container the boriding
is heated to the mixture. The
required powder mixture
temperature can be reused
with or without about 5–6 times
an inert by blending in
atmosphere. 20–50% with
The thickness the new boriding
and mixture
microstructure However, the
of the boride technique is
coating depend limited to only
on the process small-sized
parameters products and
(temperature, requires high
holding time, labor costs in
and so on) and packing and
the composition removing
of the boriding powder after
mixture. After boriding
boriding, the
sealed
container is
cooled to room
temperature
(continued)
Table 2 (continued)
Paste Solid Water-base paste The paste is Used in [17, 44, 45]
containing B4 C applied by high-volume
(boron source), and spraying, production, also
Na3 AlF6 (activator). brushing, or for partial
The ratio of the dipping. The boriding applied
water to the mixture paste thickness locally on parts
of B4 C and Na3 AlF6 over the of the work
is around 1:5. In material’s pieces. The
some cases, a paste surface is manual work
composition of B4 C, controlled involved when
KBF4 , and SiC is using a mold. boriding in
used, combined with After boriding, powder can be
a binder media, the material is drastically
employed for quenched (in reduced.
long-term stability different media) Nevertheless, a
of the paste to room protective
temperature atmosphere, or
in a vacuum, is
necessary to
avoid oxidation
during the
process. The
boron supply by
the atmosphere
is limited
compared to the
powder-pack
Electroless Liquid The bath usually The material is Boriding is [10, 17, 43]
salt-bath contains 70% immersed in the simple and
Na2 B4 O7 and 30% salt bath at economical to
B4 C (by temperatures operate. After
weight)—the B4 C above 900 °C. boriding, excess
content up to 20 After boriding, salt must be
wt.% is replaced by the material is removed,
ferroaluminum to retired from the increasing the
increase the number bath and cooled cost and time
of B atoms in the to room consuming.
bath. A mixture of temperature Maintenance
55% Na2 B4 O7 , 45% cost is high for
ferroboron, and 5% the technique
ferroaluminum is since it requires
also used regular
recharging with
salt due to
increased bath
viscosity
(continued)
Table 2 (continued)
Gaseous Gas Boron halide/ The material is The gas mixture [17, 43]
hydrogen mixture put into a is supplied
combined with chamber or continuously to
organic compounds cylindrical the furnace
((CH3 )3 B and retort of a retort. A
(C2 H5 )3 B) muffle under a constant
protective boriding
atmosphere. atmosphere is
When the maintained
boriding constant on the
temperature is material’s
achieved, the surface,
gas mixture is compared to
activated for the solid and liquid,
desired in which the
exposure time. boron source is
After boriding, exhausted
the material is during boriding.
cooled under a However, gases
protective such as B2 H6 ,
atmosphere to BCl3 , and BF3
room are highly toxic,
temperature cancerogenous,
and explosive/
corrosive
DC power supply coupled with a programmable electronic control device (PECD)

to generate polarity changes in the flux of B+ ions. The pulsed-DC field provides
a uniform B+ ions diffusion, causing the formation of similar boride coating thick-
nesses on both surfaces (anode and cathode) exposed to the current field. Notably, the
PDCPB develops uniform and compact boride coatings (~15 μm) for the boriding
conditions of 700 °C and 0.25 h of exposure.
2 The Adhesion Resistance of Boride Coating on Metallic

Substrates
Adhesion is one of the most critical factors contributing to boride coatings’ relia-
bility. The adhesion of the boride coating to the metallic substrate is of great impor-
tance in the design, functionality, and performance of the borided metallic materials.
In this sense, the wear and the corrosion are intimately related to the extent of
adhesion of the boride coating to the substrate: (i) the boride coating should firmly
Fig. 2 a Schematic representation of the thermoelectrical system used in PDCPB: 1 Power supply, 2
PECD, 3 Container, 4 Electric furnace, 5 Electrodes, 6 Material. Representation of boron diffusion
through several stages: b B atoms dissociation from the boriding media, c transport of B+ ions
through the electric field, d nucleation of borides, and e growth of boride coating
adhere to the substrate to avoid or retard the infiltration of corroding species at the
coating/substrate interface, (ii) scratches produced by abrasive and erosive environ-
ments constantly wear away the borided surface. Both phenomena progressively
compromise the integrity of the surface and may lead to its failure.
The adhesion of boride coating to the metallic substrate is measured in terms of
the force, defining the force of adhesion as the maximum force per unit area exerted
when the coating and substrate are separated; the Daimler-Benz Rockwell C and
scratch tests are the most widely tests used for evaluating the adhesion of boride
coating-substrate system [39, 56–65].
Notably, in the scratch test, a diamond indenter with a spherical tip (typically
a radius = 200 μm, angle of 120°) is scratched over the surface of the specimen
under investigation with the application of a specific load and speed. The load is
often progressively increased during the test, resulting in flaking or chipping of
the coating. After the scratch test, different failure modes (cohesive and adhesive)
are subsequently expressed in terms of critical loads (LC ) and are defined as the
minimum loads under which a certain failure mode occurs. Critical loads are either
obtained by visually inspecting of the specimen either during or after the test, by
monitoring an acoustic emission signal (AE) [66, 67]. Usually, the onset of AE and
the microscopical observations of the first damage occurring in the coating correlate
quite well. In the same manner, the coefficient of friction (CoF) and residual indenter
depth (Rd) are measured during the scratch test as shown in Fig. 3 On the other hand,
typical failure mechanisms (cohesive and/or adhesive) developed by the scratch test
at the surface of borided materials are presented in Fig. 4.
The scratch resistance of the boride coating is a complex phenomenon because
there are many factors involved, including coating parameters (i.e., boriding tech-
nique, boriding temperature, the microstructure of the boride coating, hardness and
Young’s modulus along the depth of the coating, boride coating thickness, distribu-
tion of residual stresses in the coating, and fracture toughness of the boride coating),
scratching conditions (shape and radius size of the indenter, applied load, and
scratching speed), and substrate properties such as hardness and Young’s modulus.
Scratch tests on XC38 borided steel were performed in the work of Allaoui et al.
[57]. This steel is employed in pressure vessels, turbine fasteners, boiler support rods,
and machine tools. The steel was exposed to molten salts of borax (Na2 B4 O7 ) with
different reducing agents (B4 C, Al, and SiC), producing two types of boride coating
microstructures on the surface: the Al and B4 C agents propitiated the formation
of FeB–Fe2 B coating, whereas SiC led to the development of a Fe2 B coating. The
scratch tests revealed that the best adhesion performance was obtained in the steel
Fig. 3 The scratch profile on the surface of borided Inconel 718 obtained during a progressive
load. The scratch properties such as CoF, Rd, and AE were plotted as a function of the indenter
displacement, while LC1 , LC2 , and LC3 correspond to the development of failures at specific points
of the scratch track. Courtesy of Grupo Ingeniería de Superficies, Instituto Politécnico Nacional
Fig. 4 Scratch failure mechanisms on the surface of borided metallic materials: cohesive (tensile
and Hertzian cracks) and adhesive (lateral cracks, spalling and gross spallation). Courtesy of Grupo
Ingeniería de Superficies, Instituto Politécnico Nacional
exposed to boriding with the mixture containing SiC (critical load > 200 N). The
XC38 steel exposed to boriding with the reducing agent of Al revealed fewer effective
results (critical load ~80 N).
The practical adhesion resistance of the boride coating to the substrate can be
modified by post-heat treatments [68]. When a FeB–Fe2 B coating on an AISI 316
L steel is exposed to a diffusion annealing process (DAP), the amount of FeB can
be limited or dissolved completely, increasing the Fe2 B coating thickness. The DAP
leads to a relaxation of residual stresses accompanying both the dissolution of the
FeB and changes in the boride coating-substrate bonding. The scratch test results
demonstrated that the critical load for the detachment of the coating to the substrate
was increased around 3 times for the borided AISI 316 L steel exposed to DAP
(cohesive failure was the predominant mechanism) compared to the borided steel
non-exposed to the post-heat treatment that exhibited an adhesive failure.
The scratch test evaluated the influence of boride coating thicknesses and the
distribution of residual stresses on the practical adhesion resistance of nickel boride
coating to the Inconel 718 [39]. The presence of high tensile stresses at the outer
zone of the boride coating caused the layer to fail on low loads. However, on the
inner zone of the nickel boride coating and for deeper coating thickness, the presence
of compressive residual stresses produced an opposite effect, increasing the critical
loads of the nickel boride coating-substrate system.
Bull and Rickerby [69] established that, in real tribological systems, the working
loads are smaller than the critical load determined by the single-pass scratch test.
Thus, several passes over the same scratch track are needed before cumulative damage
results in film or coating failure. Rodríguez-Castro et al. [70] studied the multi-pass
scratch behavior of Fe2 B coating and FeB–Fe2 B coating on the borided AISI 316 L
steel. Boride coatings, in the thickness range from 4 μm to 18 μm, were formed by
the powder-pack method, employing the interrupted boriding procedure proposed
by Gopalakrishnan et al. [71] to achieve the single (Fe2 B) coating. First, single-pass
scratch tests with a Rockwell C indenter were carried out and critical chipping load
was determined (51 N). Next, 100 unidirectional scratch passes with the 20%, 30%,
and 40% of the critical load were performed. After the multipass-scratch tests, they
found a lower coefficient of friction in the borided samples compared to the untreated
AISI 316 L steel; at the highest load employed, the Fe2 B coating presented the lowest
friction. The boriding process, regardless of single (Fe2 B) or dual-phase (FeB–Fe2 B)
coatings, improved up to five times in wear resistance than that of the untreated AISI
316 L steel. It was also observed that the substrate contributed significantly when
the boride coating was thin (<11 μm), avoiding severe damage, and the presence of
the FeB, in these thin coatings, was even favorable.
Furthermore, Vega-Morón et al. [72] evaluated the multi-pass scratch performance
of borided AISI H13 steel. Boride coatings, from 3 μm to 8 μm, were obtained by the
powder-pack process. In the single-pass scratch, the load was between 3 N and 80 N,
and the chipping critical load was estimated at 24 N. Then, with the same Rockwell
C indenter used in single-pass, unidirectional multi-pass scratch tests, from 25 to 100
passes, were performed to evaluate the evolution of friction and cumulated damage
during these stages; 35% and 50% of the chipping critical load were applied in the
tests. It was found that the number of cracks inside the scratch track increased as the
tests proceeded, as well as the severity of the chipping failures at the edges of the
track. Considering the highest applied load, the borided AISI H13 steel presented a
lower coefficient of friction and residual depth after the 100 scratch passes compared
to the untreated AISI H13 steel. Additionally, at the extreme condition of multi-pass
scratch, the thickest boride coating exhibited a normalized volume loss per load of
4 × 10–4 mm3 N−1 , in contrast to 11.8 × 10–4 mm3 N−1 of the untreated AISI H13
steel.
3 High-Temperature Wear of Boride Coatings
Wear is a material loss occurring from frictional forces between two contacting
surfaces moving relative to one another. It is a system property, meaning that there
are numerous factors that can influence the wear behavior (Fig. 5). Hardness and
Young’s modulus are generally two key factors controlling wear. Hardness is used
as a parameter in Archard’s equation for estimating the wear rate [73–75], and a
high hardness translates to the high resistance of the surface asperities against plastic
deformation and cutting. A low Young’s modulus enables the surface asperities to
“accommodate” the applied pressure by elastic deformation. As a result, the ratio
of hardness to Young’s modulus (H/E) is a measure of a material’s resistance to
wear [76–78]. However, the wear environment, the formation of lubricative and/or
protective oxide layers on the sliding surfaces, and the potential material transfer to
and from the counter-body should never be disregarded [79, 80]. Such factors can
markedly influence wear and friction, especially at high temperatures [81–83].
The temperature associated with the sliding surfaces can greatly influence wear;
the surface temperatures can be increased significantly by increasing the normal load,
the sliding velocity, or by external heating. In metallic materials, the wear process
can be further complicated by oxidation. In some cases, the increase in temperature
can provide a positive outcome: if the oxide has sufficient adhesion and strength
combined with a low friction coefficient, it may provide a beneficial lubricating
Fig. 5 Factors affecting the wear resistance of a coating-substrate system

effect. If not, it may fracture, and loose hard oxide particles can cause three-body
abrasion between the sliding surfaces [84–88]. At high temperatures, oxide particles
can develop into a smooth, densely packed tribofilm (sometimes referred to as a
“glaze layer”), allowing for a more favorable wear response.
In this context, boriding is one of the easiest ways to improve the room and/or
high-temperature wear resistance of metallic materials, obtaining promising results.
Furthermore, the wear resistance of boride coating is influenced by the hardness,
fracture toughness, and the state of residual stresses along the depth of the coating-
substrate system.
Moreover, in most of the cases, the high-temperature wear resistance of boride
coatings (up to 750 °C) on various metallic materials appears to be caused by the
substantial increase in hardness, which usually surpasses the hardness of the substrate
material by a significant margin. Besides, oxidation plays an essential role in the
wear process, especially at high temperatures: forming a low-melting point oxide
layer can seal surface pores and, in some cases, act as a lubricant. For example,
the presence of boric acid (resulting from the chemical reaction between the boron
oxides and ambient humidity) is considered as a self-lubricating mechanism that
reduces the friction on the borided surface [21, 31, 89, 90]. The temperature at
which oxidation results in beneficial properties is currently unknown, and the present
literature suggests that the transition may depend on the wear test variables (including
normal load, sliding velocity, counter-body material, and wear atmosphere) as well
as the substrate material.
At room temperature, the effective wear mechanism of the borided steels involved
microcracking; at higher temperatures, surface fatigue-induced microcracking,
plastic deformation, oxidation, spalling, and plowing were dominant [91].
Some of the surface features and mechanisms that are commonly observed in the
high-temperature wear of borided metallic materials are summarized in Fig. 6.
3.1 High-Temperature Wear Resistance of Borided Steels
Low carbon and low alloy steels have widespread use in the industry due to their
availability and low cost. These steel grades are used in many fields such as agriculture
and construction, marine environment, oil, and natural gas applications [92, 93].
Their only major drawback is their somewhat low wear performance, which can be
overcome by boriding [94].
Mindivan [93] evaluated the wear resistance of a Fe2 B coating on an AISI 1020
steel. Reciprocating dry wear tests at room temperature, 200 °C, 400 °C, and 600 °C
revealed that the boride coating exhibited 95.6%, 19.8%, 17.6%, and 55.4% wear
loss, respectively, compared to the untreated AISI 1020 steel. At higher temperatures,
the untreated AISI 1020 steel exhibited extensive surface plastic deformation, while
the borided AISI 1020 steel revealed greater friction attributed to three-body abrasion
caused by oxides spalling during wear.
Fig. 6 Typical high-temperature wear failures on borided surfaces
The influence of the boride coating’s microstructure on the high-temperature wear

of AISI 4140 steel was investigated by Cimenoglu et al. [5]. Ball-on-disk dry tests
were performed at room temperature, 300 °C and 500 °C. The Fe2 B coating and
FeB + Fe2 B coating on an AISI 4140 steel exhibited similar tribological behavior at
room temperature, but marked changes were observed at elevated temperatures. At
high-temperature wear (300 °C and 500 °C), the friction coefficient and mass loss
increased for both boride coating microstructures due to the presence of cracking
on the borided surfaces. This failure mechanism resulted from the accumulation of
combined mechanical and thermal stresses in the boride coatings and a “stick-slip”
mechanism during wear. The superior wear resistance at high temperatures of the
FeB + Fe2 B coating compared to the Fe2 B coating was attributed to the reduction
of thermal stresses (due to the incorporation of FeB) in the coating.
Taktak [95] investigated the wear response of borided AISI 52100 steel at room
temperature, 300 °C, 450 °C, and 600 °C, and the results were compared with that
of the untreated AISI 52100 steel. The borided steel exhibited better wear resistance
than the untreated steel for all circumstances, attributed to the boride coating’s high
hardness and low friction characteristics. Also, borided AISI 52100 steel’s wear rates
gradually increased up to 450 °C and remained constant at 600 °C associated with
oxidation wear. The oxidation of FeB and Fe2 B at temperatures above 300 °C and
400 °C resulted in the formation of B2 O3 and Fe2 O3 at the borided surface [96],
developing a three-body abrasion mechanism that accelerated the material loss.
The high-temperature wear behavior of borided high-alloy steels (cold tool steels,
hot work tool steels, stainless steels, speed steels, etc.) was highly studied. This way,
the wear behavior at room temperature and 500 °C of the borided 31CrMoV9 and
borided X40CrMoV5-1 steels were investigated [97]. At room temperature, the wear
responses for borided steels were similar; at 500 °C the borided 31CrMoV9 steel and
the borided X40CrMoV5-1 steel revealed superior wear resistance almost 143 and 12
times, respectively, compared to the untreated steels. The superior wear resistance
of the borided X40CrMoV5-1 was attributed to the boride coating’s high-volume
fraction of FeB (47%). The volumetric ratio of FeB and Fe2 B in the boride coating
( VVFeFeBB ) has a direct impact on wear resistance: for a high VVFeFeBB ratio, compressive
2 2
stresses are developed within the boride coating that reduces cracking during wear;
a low VVFeFeBB ratio has an opposite effect, originating tensile stresses in the coating,
2
leading to flaking and three-body abrasion.
Moreover, some studies showed that the wear behavior of borided AISI H13
steel at 1000 °C can be improved by shot-peening before boriding [98]. The shot-
peening modified the steel’s surface, developing a nanostructured surface layer,
which enhanced the growth kinetics of a Fe2 B coating. The presence of compressive
residual stresses and refined grain structure in the coating impeded fatigue crack
propagation, which helped reduce wear; the worn surfaces of the borided AISI H13
steel appeared smoother and exhibited less cracking compared to the untreated steel.
On the other hand, the addition of rare earth elements (2.5%, 5%, and 10% CeCl3 )
in the boriding powder mixture revealed a great influence on the high-temperature
wear behavior (700 °C) of the boride coating on an AISI H13 steel [99]. The addition
of 2.5% and 5% CeCl3 in the boriding powder mixture increased the thickness,
microhardness, and density of the boride coatings, however, a drop in microhardness
and density was observed for the boriding powder mixture contained 10% CeCl3 . The
improved high-temperature wear resistance of borided AISI H13 steel was closely
linked to the hardness and thickness of the boride coating.
3.2 High-Temperature Wear Performance of Borided

Ni-Base Superalloys
Ni-base superalloys exhibit excellent mechanical stability and high resistance to

fatigue, corrosion, and oxidation at temperatures up to 1000 °C. These properties
make them highly suitable for modern aircraft engines, gas turbines, nuclear reactors,
and many other high-temperature applications [100–102]. The Ni-base superalloys
have also been borided to increase the wear resistance at high temperatures.
The boride coating microstructure on a Nimonic 80 alloy mainly consists of Ni2 B
with minor quantities of CrB, Cr2 B, and Cr5 B3 [103]. The presence of chromium
borides increased the hardness and Young’s modulus of the boride coating as a
function of the boriding temperature and exposure time. The wear performance of
the borided Nimonic 80 alloy at 500 °C was associated with an increase in surface
hardness and the lubrication provided by the generated oxide layers.
Similarly, Gheisari and Polycarpou [104] established the wear behavior of borided
Ni-base alloy at room temperature and 450 °C. The boride coating on the mate-
rial’s surface improved the wear performance (at room temperature and 450 °C)
and reduced the friction coefficients compared to the untreated Ni-base alloy. The
possible friction-reducing mechanism, especially at higher temperatures, was related
to the formation of a lubricative and/or protective oxide layer (H2 BO3 ) and the oxide
layer’s capability to generate stable material transfer.
Similar results about the dry wear performance at 400 °C and 750 °C of borided
Inconel 718 alloy were obtained by Gunen [105]. The thicknesses of the boride
coatings were between 21 μm and 130 μm, depending on the different powder-pack
boriding conditions. For both temperatures, the presence of a protective oxide layer
on the surfaces and the influence of the boride coating thicknesses decreased the
wear rates by approximately 1.7 times (coating thickness of 21 μm) and 5.5 times
(coating thickness of 130 μm) compared to the untreated Inconel 718 alloy. The
wear mechanism of the untreated Inconel 718 alloy was two-body abrasive wear,
dominated by cutting and plowing at 400 °C and 750 °C, respectively. The primary
wear mechanism of the borided Inconel 718 alloy was oxidative wear assisted by
microcracking and spalling.
3.2.1 Multi-component Coatings for High-Temperature Wear
Many of the studies show that boride coatings can be used for improving the wear
resistance of metallic materials used for high-temperature applications. On the other
hand, economic considerations can often dictate the use of low-cost substrates for
specific applications. In such cases, coating the surface of a low-cost substrate with a
more inert metallic coating is an option. For high-temperature applications, combined
treatments involving the application of protective metal coatings and boriding are
currently being considered.
Kayali et al. [106] deposited Inconel 718 alloy coating on the surface of AISI
H13 steel using electro-spark deposition (ESD), and then exposed it to boriding.
The untreated AISI H13 steel, the Inconel 718 coating on the hot-work steel, and the
Inconel 718 coating + boride coating on the steel’s surface were subjected to abrasion
wear testing at 650 °C. In the wear tests, the boride coating showed a lower and more
stable friction coefficient than that of untreated AISI H13 steel and the Inconel 718
coating; the boride coating reduced the volume losses around of 55% and 41%
compared to untreated AISI H13 steel and Inconel 718 coating, respectively. The
wear behavior at high temperatures of Inconel 718 coating + boride coating on AISI
H13 steel was attributed to the reduction of voids, oxide islands, and microcracks in
the coatings.
High entropy alloys (HEAs) are gaining popularity because of their extraordinary
properties at elevated temperatures. Few studies explore the effects of boriding on
the high-temperature wear performance of HEAs. The study of Gunen et al. [107]
investigated the effects of different boriding media on microstructure, mechanical
properties, and high-temperature wear resistance (650 °C) of as-clad AlCrFeCoNi
coating + boride coating on an AISI 316L steel. The AlCrFeCoNi coating was
deposited on the material’s surface, then exposed to pack-boriding at 1000 °C for
4 h in air, argon, and vacuum environments. The cross-sectional view of as-clad
AlCrFeCoNi coating + boride coating on an AISI 316 steel is shown in Fig. 7.
Although (CoFe)B2 , (CrFe)B2 , and Cr2 Ni3 B6 phases were detected in all circum-
stances, the boride coatings’ thicknesses, the superficial hardness, and borided
surface roughness varied significantly. The presence of boride coating on the outer
zone of the surface reduced the friction coefficient and improved the wear resistance
by approximately 4 – 5 times (depending on the boriding environment) compared
to the as-clad AlCrFeCoNi coating. The study showed that the borided AlCrFeCoNi
coating has the potential for use in high-temperature wear applications.
Fig. 7 Cross-sectional view

of a multicomponent coating
on an AISI 316 steel. The
AlCoCrFeNi layer was
performed with a Trumpf
high-speed laser cladding
system, while the boride
coating was obtained by the
powder-pack technique at
1000 °C for 4 h
4 Oxidation and Corrosion Resistance of Boride Coatings

in Aggressive Environments
Although boriding primarily aims to improve wear performance, many studies have
shown that borided metallic materials exhibit good corrosion resistance in various
aggressive media [3, 108–110]. Notably, corrosion resistance becomes important for
materials exposed to high temperatures, acidic environments, or neutral solutions
containing oxidized species. In the subsections that follow, the corrosion of borided
metallic materials is reviewed with a focus on the type of environment to which they
are exposed.
4.1 Oxidation Behavior of Borided Metallic Materials
At high temperatures under ambient atmospheric conditions, metal borides tend to

oxidize, forming a complex oxide layer consisting of metal oxides and boron trioxide
(B2 O3 ). This behavior (generally referred to as scaling) usually occurs under two
distinct temperature regimes: the low-temperature regime, where the oxide provides
some protection against further oxidation, and the high-temperature regime, where
the oxide layer is unprotective. The low-temperature regime is referred to as passive
oxidation and involves parabolic oxidation kinetics. In this regime, B2 O3 serves as a
liquid barrier (above 510 °C) against the O diffusion. The high-temperature regime,
termed active oxidation, results in linear oxidation kinetics. This regime is associated
with the evaporation of B2 O3 (which takes place above 1800 °C) and often results
in the breakdown of the oxide layer. On the other hand, intermediate temperatures
are often characterized by para-linear oxidation kinetics [111, 112], i.e., parabolic
oxidation is followed by linear oxidation. Diborides of Zr, Hf, and Ti have good
high-temperature oxidation resistance and they are considered good candidates for
ultra-high temperature (above 2000 °C) structural applications.
One of the earliest studies on the oxidation resistance of borided steels was studied
by Tsipas et al. [113]. The borided AISI 1020 steel was exposed to naphthenic acid
and subjected to high-temperature oxidation. The FeB–Fe2 B coating was extremely
resistant to the naphthenic acid-containing media in both liquid and gaseous form.
During high-temperature oxidation in air at 650 °C, a 10 μm protective scale on the
borided surface acted as a barrier to O and/or Fe diffusion, while the microstruc-
ture of the FeB–Fe2 B coating changed to solely Fe2 B homogeneous coating for
prolonged exposure at 170 h. Furthermore, from thermogravimetric analysis, the
borided AISI 1018 steel revealed significant changes in the coating depending on the
testing oxidation temperatures [114]. Fe2 B4 O7 , FeB2 O4 , and FeBO3 were formed
at around 550 °C, while at temperatures above 800 °C, only FeBO3 was revealed,
dissociating to produce B2 O3 (in liquid form) and Fe2 O3 . The complete deterioration
of the boride coating was observed at 900 °C.
Caillet et al. [115] performed oxidation experiments between a range of 700 °C –

1000 °C on borided commercial-purity Ni. The borided alloy’s oxidation was charac-
terized by four consecutive stages: (i) the mass gain of the borided pure Ni increased
parabolically, (ii) the mass decreased linearly in relation to the first stage, (iii) the
mass of the borided pure Ni remained constant, and (iv) the mass gain increased very
slowly. The authors stated that the second stage corresponded to the period during
which B2 O3 was formed and evaporated; after that, a protective scale of Ni3 B2 O6
appeared and prevented the formation of NiO.
In the same way, a boride coating mixture consisting of NiB, Ni2 B, Ni3 B, and
Ni4 B3 on the Inconel 600 alloy was subjected to oxidation tests at 1000 °C for 24 h.
The results confirmed strong oxidation on the borided surface, regarding the presence
of Cr2 O3 , Cr3 O4 , NiO, B2 O3 , and Fe3 O4 [116].
The oxidation resistance of a borided Zr2 (AlSi)4 C5 /SiC composite in flowing air
at 900 °C – 1300 °C, and in static air at 1800 °C was investigated by Lu et al. [117]. A
homogeneous mixture of ZrB2 and Al2 O3 was detected on the surface of the borided
composite. When oxidation tests were carried out in the range of 900 °C – 1100 °C, a
protective liquid B2 O3 containing scale formed on the surface served as a continuous
barrier to O diffusion and resulted in the parabolic oxidation kinetics of ZrB2 . Above
1100 °C, evaporation of B2 O3 took place, but the formation of borosilicates continued
to hinder the O diffusion. The SiC reinforcement positively affected the oxidation
resistance at 1300 °C due to the formation of protective Si-containing phases, such
as SiO2 and mullite, filling the cracks formed within the scale. After additional tests
conducted in static air at 1800 °C, the boriding was found to be highly beneficial
for improving the oxidation resistance of the Zr2 (AlSi)4 C5 /SiC composite within the
temperature range of 1000 °C – 1800 °C.
Studies indicate that intermetallics’ corrosion resistance may also be improved
with boriding. Intending to hinder the “pest oxidation” of MoSi2 alloy, which is a
form of accelerated oxidation at low temperatures, Yokota et al. [118] investigated
the oxidation resistance of borided MoSi2 alloy using cyclic oxidation tests. Molyb-
denum boride, Mo2 B5 , was formed on the surface of MoSi2 . After 100 h of cyclic
oxidation at 773 K, the “pest oxidation” in the borided MoSi2 alloy was not observed;
the mass gain of the borided MoSi2 alloy was lower compared to the mass gain of
the as-cast (untreated) MoSi2 control.
In a later study, Yokota and Suzuki [119] reported that the high-temperature oxida-
tion resistance of TiAl alloy could be improved by liquid boriding using boride- and
chloride-containing molten salt baths. Boriding generated TiB2 and Al3 Ti coatings
on the surface combined with a compact and protective Al2 O3 film. The contin-
uous and cyclic oxidation tests at 900 °C and 950 °C revealed parabolic oxidation
kinetics, and throughout the entire duration of the oxidation tests, Al2 O3 spalling
was not observed.
Thermochemical diffusion treatments involving siliciding and boriding are
becoming increasingly popular. The formed scale after high-temperature oxidation
is usually expected to have a greater thickness than siliciding or boriding treatments
alone. The silicates, borates, and borosilicates scales served as a glassy, continuous
protective film during high-temperature oxidation.
Qiao et al. [120] produced composite coatings on the Nb-Ti-Si base alloy surface
using siliciding and boriding to improve its oxidation resistance. The two treatments
developed a dense (Nb, X)B2 outer coating, an (Nb, X)Si2 intermediate coating and
a (Ti, Nb)5 Si4 transition coating. During the boriding process, the (Nb, X)B2 coating
was formed by an exchange reaction between the active B atoms and (Nb, X)Si2 .
mg
The coatings provided excellent oxidation resistance with a mass gain of ~1.35 cm 2
at 850 °C for 100 h of oxidation. A compact scale, consisting mainly of TiO2 , SiO2 ,
and B2 O3 , was able to protect the substrate without spalling up to 1250 °C.
Swadzba [121] applied boriding and subsequent siliconizing on a C103 Nb-base
alloy using pack cementation treatments. The treatments resulted in the formation
of NbSi2 and NbB2 coating microstructure on the alloy’s surface; the outer zone of
the coating revealed NbSi2 with very small precipitates of the NbB2 phase (~100 nm
in diameter). The high-temperature oxidation tests were carried out at 1100 °C for
1000 h, and the results showed that the coating provided good protection against high-
temperature oxidation of the base metallic material. The reaction between NbSi2 and
NbB2 resulted in the formation of Nb5 Si3 and Nb5 (Si, B)3 phases, while the oxidation
resistance of the alloy was significantly improved by the formation of a mixed oxide
scale consisting of Nb2 O5 , NbO2 and borosilicate glass.
Cyclic oxidation studies of borided alloys are rare, but at least two studies indi-
cate that boriding can significantly improve cyclic oxidation resistance. Mu and
Shen [122] carried out cyclic oxidation tests on borided CoCrMo alloys in static air
at 950 °C. They reported that the borided CoCrMo alloy displayed superior oxida-
tion resistance compared to untreated alloy, attributed to the formation of a B2 O3
protective layer on the borided surface.
Moreover, Dokumaci et al. [123] established the cyclic oxidation behavior at
800 °C in static air of the borided AISI 304 steel with different boride coating
thicknesses. The mass gain of borided AISI 304 steel was lesser in comparison with
the untreated AISI 304 steel; the thicker boride coating on the steel exhibited the
smallest mass gain during oxidation. The formation of FeBO3 and liquid B2 O3 scale
over the borided surface showed a parabolic growth.
On the other hand, the scale formed on borided S235JRG1 low carbon steel
exposed in flowing synthetic air at 600 °C – 900 °C was composed of Fe2 O3 and
Fe3 BO6 ; their presence had a protective effect against oxidation at temperatures
below 900 °C. In contrast, the Fe2 O3 scale on the S235JRG1 untreated steel was
non-protective with a high spalling tendency. During the scale growth at 900 °C, the
local chemical equilibrium between Fe2 O3 and Fe3 BO6 increased the growth rate
of the Fe2 O3 , resulting in the gradual decomposition of Fe3 BO6 . This phenomenon
caused two successive parabolic stages in the mass gain, and the breakaway oxidation
behavior of the boride coating [124].
4.2 Corrosion Resistance of Boride Coatings to Neutral

and Acidic Solutions
To simulate the highly corrosive environments in oil wells, Medvedovski et al.

[125] subjected borided low-carbon steel, borided AISI 310 stainless steel, and
borided Inconel 718 alloy to water steam with the presence of hydrocarbons, CO
+ CO2 , H2 S, and chloride salts (NaCl, CaCl2 ). The boride coatings displayed no
sign of microstructural degradation (no phase transformations, no cracking, spalling
or delamination) after 7 – 10 days of exposure.
In addition, the corrosion resistance of borided materials in molten baths is rarely
studied, but other works show boriding can obtain certain benefits [18, 126]. For
example, DC04, C45, CK60, and C105U steels (with C contents ranging from 0.08%
to 1.1%) used in wettable selective soldering tools were borided and then exposed to
a SAC309 lead-free solder bath consisting of >96 wt.% Sn. The presence of a FeB–
Fe2 B coating on the steel surfaces increased the corrosion resistance after 40 days of
continuous immersion testing, with no change in the microstructure or the thickness
of the boride coating and inhibiting the formation of reaction products on the borided
surfaces.
Similar corrosion behaviors of the borided Inconel 718 alloy and borided Hastelloy
C276 alloy were obtained when immersed at 800 °C in a molten KCl–MgCl2 –NaCl
salt. The formation of a uniform and compact boride coating on both alloys revealed
a superior corrosion resistance compared to their untreated counterparts. Particularly,
the boride coating microstructures consisted of an outermost silicide’s coating and
metal borides, an intermediate metal borides’ “compound” coating, and beneath the
coating, a diffusion zone intermixed with metal borides.
Medvedovski [6] tested the high-temperature corrosion of borided low-carbon
steels (J55 and A36/44 both with C contents ranging between 0.2% and 0.3%) and
compared them to untreated AISI 304 and AISI 316L stainless steels immersed in two
acidic solutions: one consisting of 15% HCl and the other consisting of 70% H2 SO4 ,
both held at 100 °C, with a total test duration of 168 h. The corrosion behavior of the
stainless steels in the acids was complicated: in HCl, the corrosion of both steels was
intensive in the first 24 h – 36 h, after which the corrosion rate decreased significantly;
in H2 SO4 , corrosion was very intensive during the first 72 h – 96 h during which
the protective chromium oxide scale was dissolved entirely, increasing the corrosion
rate significantly. The untreated stainless steels lost between 6.5% and 23.5% of their
masses after 168 h. However, the borided low carbon steels lost less than 1% of their
masses within the entire duration of the corrosion test. The boride coating did not
show evidence of delamination, pitting, bubble formation, or cracking.
Petrova et al. [114] showed similar corrosion results in seven borided metallic
materials exposed to H2 SO4 solution: AISI 1018 steel, AISI 4340 steel, AISI 304
steel, Inconel 625 alloy, Inconel 718 alloy, and Ti–6Al–4V alloy. In all the circum-
stances, the presence of boride coatings on metallic materials improved corrosion
performance compared to untreated materials.
Moreover, the effects of selective boriding (i.e., where only part of the material’s
surface is subjected to boriding) and full boriding in the corrosion performance
of Nimonic 80A alloy were evaluated by Makuch et al. [127]. For the immersion
corrosion tests conducted at 145 °C in H2 O, H2 SO4 , and Fe2 (SO4 )3 solutions, the
mm
untreated Nimonic 80A alloy depicted the lowest corrosion rate (~0.555 year ), and
mm
the fully borided Nimonic 80A alloy revealed a corrosion rate around 1.352 year . The
mm
highest corrosion rate (~515.92 year ) measured for the selectively borided Nimonic
80A alloy was associated with the significant differences in electrochemical potential
between the coated (borided) and uncoated regions, which in turn aggravated the
corrosion of the base material.
The results of the abovementioned studies demonstrate the potential of boriding in
improving the corrosion resistance of various alloys, intermetallics, and composites.
In general, the boride coating produced on the surfaces appears to be highly resistant
to a variety of corrosive environments, especially in acidic and oxidative (high-
temperature oxidation) environments.
However, the surface of the borided X12CrNiMoV12-3 stainless steel becomes
more susceptible to corrosive attack when it is immersed in a NaCl + Na2 SO4
solution. The solution simulates the corrosive environment created by the combustion
reaction of Na, S, and O when the X12CrNiMoV12-3 stainless steel is used as turbine
blades. As turbine blades operate, Na and S might be present as fuel impurities,
whereas NaCl and sulfates might enter the air needed for combustion, reacting with
S in the fuel to become Na2 SO4 (an alkaline metal sulfate layer is formed at the
surface of gas turbine blades). The latter causes hot corrosion, reducing load-carrying
capacity, and might lead to a catastrophic failure of the component.
Mejía-Caballero et al. [128] performed potentiodynamic polarization tests at room
temperature on the borided X12CrNiMoV12-3 steel and the untreated stainless steel
immersed for 5 days in a 0.1 M NaCl + 0.04 M Na2 SO4 solution. After 5 days of
immersion in the neutral solution, the polarization resistance of the borided stainless
steel was around 8 kΩ cm2 compared to the value of ~579 kΩ cm2 obtained in the
untreated stainless steel. The corrosion performance of the borided X12CrNiMoV12-
3 steel was explained by the presence of {020}//ND, {021}//ND texture components
of the FeB coating; the corrosion process started in the grains associated with the
texture components, as they were the more susceptible sites. In addition, the polar-
ization resistance was affected by the formation of corrosion products (Fe2 O3 and
B2 S3 ) in a crystal cluster form over the borided surface (Fig. 8), resulting from the
interaction of the chloride-sulfate solution and the FeB–Fe2 B coating.
5 Tribocorrosion of Borided Metallic Materials
Tribocorrosion is a form of surface degradation that leads to the progressive

removal of material resulting from the simultaneous interaction of tribological effects
caused by the relative movement between two or more surfaces in contact and the
Fig. 8 a SEM image on the borided X12CrNiMoV12-3 surface after 5 days of immersion in a
NaCl + Na2 SO4 solution. b Crystal clusters on the borided surface after the 5th day of immersion
in a NaCl + Na2 SO4 solution. c, d High resolution XPS spectra of B1s and O1s over the borided
X12CrNiMoV12-3 surface after 5 days of immersion in a NaCl + Na2 SO4 solution. Courtesy of
Grupo Ingeniería de Superficies, Instituto Politécnico Nacional
electrochemical action due to the exposition with a corrosive environment. This

phenomenon, also called wear-corrosion synergism, where a worn surface interacts
with a corrosive medium, can occur in various engineering systems such as in power
generation, marine devices, chemical pumps and pipelines, biomedical implants, etc.
[129–131].
The synergy between wear and corrosion causes a significant increase in mate-
rial loss than the damage generated by each effect acting separately. Therefore, the
material loss due to tribocorrosion can be greater than the sum of the individual
contributions and is expressed as follows:
[ ]
mm3
T = W +C +S (1)
mm2 year
T is the total material loss, W is the material loss due to wear, C is the material loss
due to corrosion, and S is the synergy between wear and corrosion. From Fig. 9, the
synergy between wear and corrosion (S) occurs as follows: the physical interaction of
the surfaces in relative motion (which generates phenomena of adhesion, abrasion,
erosion, etc.) can provide particle and passive film detachment due to wear loss
material. The active material surface (zone I) is exposed to the corrosive environment,
through electrochemical dissolution causing an “accelerated wear corrosion” until

the passive film is formed again (repassivation process). The corrosion products,
in combination with wear debris, can act as abrasive particles, generating a “wear
accelerated corrosion”. The combined effects of wear and corrosion can significantly
increase the material’s degradation exposed to tribocorrosion [129, 130, 132].
Conventionally, the parameters recorded in a tribocorrosion test are the friction
coefficient, the material loss rate, the electrochemical potential of the contact surfaces
exposed to a corrosive medium during sliding, and/or the corrosion current. The
sliding or relative movement between the contacting surfaces may be continuous,
discontinuous, unidirectional, or reciprocating [130, 131].
Some metallic materials are used in high-temperature applications (up to 370 °C)
in fossil-fired power-generating plants, aircraft power plants, chemical processing
plants, petroleum-processing plants, and aircraft components such as critical rotating
parts, airfoils, supporting structures, and pressure vessels. Under these conditions, the
degradation by high-temperature oxidation (hot-corrosion) is a typical components’
failure mode in hot sections, reducing the load-carrying capacity and might lead to
a catastrophic failure [133–136]. Furthermore, the metallic materials are exposed to
aggressive corrosive environments and oxidizing atmospheres. In different environ-
ments, the inherent corrosion resistance of a material usually depends on its ability to
form a thin protective, and stable oxide film on the material’s surface, i.e., stainless
steels, Ni-base alloys, Co-base alloys, and Ti-base alloys [129, 137–139].
However, the erosion-corrosion phenomenon occurs in applications subjected to
multiphase flow conditions. In this way, the behavior of a material under erosion-
corrosion conditions (e.g., the exposition to the continuous impingement of hard
particles or detached debris from the passive film) is related to the materials’ passi-
vation rate and the impact resistance of the passive film. When the metallic materials
Fig. 9 Schematic representation of tribological contact involving simultaneous mechanical and

chemical effects
are exposed to specific mechanical effects, the passive film can break down, and the
material enters a transpassive state, accelerating the material loss [102, 138, 140].
Tribocorrosion studies have been conducted on different borided metallic mate-
rials exposed to various environments, including saltwater, acidic solutions (HCl,
H2 SO4 , HNO3 , etc.), and biological fluids, among others. For all the circumstances,
the boride coatings showed a superior tribocorrosion resistance that can enhance the
metallic material’s performance and service life for high-temperature applications.
Low-carbon steels are employed in petroleum production applications. The
contact of low-carbon steels with corrosive petroleum products causes severe damage
to machine parts. In this sense, Medvedovski et al. [141] applied thermal diffusion
based on the CVD process on A36/44W low-carbon steel. The tribocorrosion tests
were performed using the rod-on-flat reciprocating sliding on the borided A36/44W
steel and the untreated A36/44W steel immersed in water and oil solution (SAE30)
combined with 0.02 M NaCl and 0.001 M H2 SO4 . In addition, another set of tribo-
abrasive-corrosion experiments was performed by adding 5% of silica sand (diameter
size of 38 μm – 53 μm) to simulate the abrasive effect. In both types of tests, the
boride coating exhibited significantly lower wear-corrosion losses without delami-
nation and fragmentation failures. For the tribocorrosion tests, the borided A36/44W
reduced the wear-corrosion effect roughly by 76 times compared to the untreated
steel, while for the tribo-abrasive-corrosion, the wear rate was decreased by around
194 times. The superior tribocorrosion performance of borided A36/44W was related
to the boride coating’s high hardness and chemical inertness.
Therefore, Medvedovski and Antonov [142] evaluated the erosion-corrosion resis-
tance of a FeB–Fe2 B coating (total coating thickness of ~200 μm) on J55 carbon
steel. The slurry erosion-corrosion tests were conducted in a mixture of 10% SiC and
3% NaCl with a centrifugal erosion device at 20 m s−1 impact velocity. The erosion-
corrosion performance of the boride coating showed a 25% – 57% reduction of the
volume loss than that of the untreated steel, attributed to its high hardness, chemical
inertness, coating thickness, and coating adhesion to the substrate. The latter reduced
the microcrack propagation at erosion impacts. The untreated steel exhibited plastic
deformation and plowing erosion mechanisms, while the boride coating revealed
microcracking, commonly observed for many advanced ceramics.
Similarly, da Costa Aichholz et al. [26] evaluated the influence of the boriding
process on the tribocorrosion behavior of an AISI 4140 steel. This steel is commonly
used in petroleum and natural gas applications. The borided AISI 4140 steel (with
a Fe2 B coating) was subjected to dry sliding and wet (3.5% NaCl solution) sliding
conditions, respectively. The boride coating depicted lower wear rates in both dry
and wet conditions as compared to the untreated AISI 4140 steel. During the dry
condition, the boride coating exhibited higher friction coefficient values than the
untreated steel; an opposite behavior was observed for the wet sliding conditions.
Notably, the low friction coefficient of the boride coating (in wet conditions) was
attributed to the surface formation of an H3 BO3 thin film due to the exposition of
the NaCl solution. Before the wet sliding tests, the open circuit potential (OCP) was
measured in both borided and untreated steels immersed in the NaCl solution. The
untreated AISI 4140 steel showed more positive OCP values regarding the borided
steel. In contrast, during sliding, the borided AISI 4140 revealed the most positive
OCP values, associated with the protective H3 BO3 film developed on the surface,
decreasing the influence of the wear effect and enhancing the corrosion resistance
than that of untreated AISI 4140 steel.
In another study, Panda et al. [143] established the tribocorrosion behavior of a
boride coating + BN-based layer on A36/44W low-carbon steel, and the results were
compared with the untreated AISI 316 L and A36/44W steels. The boride coating
+ BN-based layer was evaluated under ball-on-flat technique in dry conditions and
exposed to a 0.5 M NaCl solution. The multi-component coating had a lower friction
coefficient, wear rate, and surface damage as compared to the untreated A36/44W and
316L steels in both dry and NaCl environments. The better performance of the borided
low-carbon steel was regarded as the higher hardness and chemical inertness of the
FeB–Fe2 B coating. In addition, the top BN-based layer reduced the boride coating
susceptibility to crack propagation and decreased the friction coefficient because of
its high lubricating property. Moreover, the accumulation of soft debris (from the
top BN-based layer) on the boride coating achieved reduced material detachment,
while the plowing effect on the untreated steels promoted debris accumulation on
the worn surface. This accelerated the wear rate (at least 10 times), enhancing the
friction coefficient (between 2 and 6 times) by three body abrasion wear.
For all the circumstances, an adverse effect of the wear-corrosion synergy on the
material surfaces was observed, increasing the wear rates in the NaCl environment.
For the boride coating + BN-based layer, a tribofilm based on the partial oxidation
of BN was developed on the borided surface. The tribofilm reduced the probability
of the micro-crack formation, limiting the penetration of abraded microparticles and
corrosive liquid through the coating microdefects compared to the common boride
coating’s wear and corrosion mechanisms at least until the total detachment of the
top BN-based layer.
The tribocorrosion behavior of the borided AISI 321 steel, borided AISI 431 steel,
and borided 30NiCrMo16 (FDMA) steel was evaluated by Chilali et al. [144]. The
borided steels were exposed to 3.5 wt.% NaCl solution and reciprocating sliding
wear. Under tribocorrosion conditions, the borided steels showed lower corrosion
resistance than the untreated steels due to the porosity and microcracks within the
boride coatings and the chemical reaction between the boron species and the corrosive
environment. Although the borided steels showed lower corrosion resistance, the
synergistic effect between wear and corrosion resulted in a decreased material loss
(17% – 27%) with respect untreated steels. The latter was regarded as the boride
coating’s high hardness.
On the other hand, turbine blades are one of the significant applications for Ni-
based superalloys, which are exposed to a corrosive environment produced by the
combustion reaction of Na, S, and O. By simulating these demanding conditions in
accordance with ASTM G119-09 procedure (Standard Guide for Determining Syner-
gism between Wear and Corrosion), Morón et al. [145] exposed the borided Inconel
718 alloy to a sodium sulfate (0.04 M Na2 SO4 ) and sodium chloride (0.1 M NaCl)
solution to evaluate the tribocorrosion behavior under ball-on-flat wear test. The
boride coating (~50 μm thicker) consisted of a Ni4 B3 –Ni2 B–Ni3 B microstructure
with a high superficial hardness around of 25 GPa. The results revealed a wear-
dominant regime for the untreated alloy affected by the passive film removal and
high contact pressure at the tribopair, increasing the total material loss rate by wear.
The nickel boride layer on the Inconel 718 superalloy displayed a wear-corrosion
regime due to boride layer debris that increased the corroded area. The contribution
of wear-corrosion synergism to the total material loss (T) was around 73% for the
untreated alloy and about 64% for the borided Inconel 718 alloy. Under these exper-
imental conditions, the presence of the nickel boride layer on the Inconel 718 alloy
improved tribocorrosion resistance by approximately three times.
Figure 10 shows the wear tracks developed during tribocorrosion on the surface of
borided Inconel 718 alloy and untreated alloy, both immersed in a Na2 SO4 + NaCl
solution.
Gunen et al. [146] proposed using Fe-based superalloys instead of high-cost Ni-
based superalloys in tribocorrosion applications. However, the strength and hardness
of the Fe-based superalloys limit their use in tribological applications. For this reason,
the A-286 superalloy was subjected to different boriding conditions (temperature and
exposure times) to develop a FeB, Fe2 B, NiB, Ni3 B4 , and CrB coating microstructure
and then exposed to sliding wear in a 3.5% NaCl solution. The results of the borided
A-286 superalloy showed lower friction coefficients (around 18% – 67%) and higher
wear resistance (6 – 35 times) compared with the untreated material. These values
were attributed to both high hardness and Young’s modulus of the boride coatings. On
the other hand, the wear resistance results were not proportional to the boride coating
thicknesses (20 μm – 130 μm), regarding factors such as porosity, residual stresses,
fracture toughness, and the Kirkendall effect. In the worn surface of untreated A-
286 superalloy, the presence of grooving-type micro-scratching wear was observed,
while the worn borided surface displayed a fracture-type wear mechanism assisted
by oxidative effect.
Currently, two studies are related to the tribocorrosion behavior of a boride coating
on High Entropy Alloys (HEAs). In both studies, the boride coatings demonstrated
the potential for expanding the use of HEAs in tribocorrosion applications.
The boriding process was applied to Co1.19 Cr1.86 Fe1.30 Mn1.39 Ni1.05 Al0.17 B0.04
HEA at different temperatures, obtaining a boride coating microstructure of
Cr2 Ni3 B6 , Fe0.4 Mn0.6 B, Cr0.4 Mn0.6 B and CrFeB2 [147]. The tribocorrosion resis-
tance of borided HEA and untreated HEA was evaluated by ball-on disk wear tests
immersed in a 5% HCl solution. The friction coefficient values and the wear losses
on the borided HEA were reduced (6 – 30 times) compared to the untreated HEA.
Fig. 10 Worn surfaces after tribocorrosion tests: a Borided Inconel 718 alloy and b Inconel 718
alloy. The counterpart was Al2 O3 ball that applied 20 N for a sliding distance of 100 m. The solution
was Na2 SO4 + NaCl. Courtesy of Grupo Ingeniería de Superficies, Instituto Politécnico Nacional
The tribocorrosion effect was more pronounced for a thicker boride coating, as deter-
mined by increased hardness and Young’s modulus on the borided surface. The wear
mechanism on the borided HEA was abrasive, accompanied by oxidation and pitting,
while abrasive combined with pitting was observed on the untreated HEA surface.
Similar tribocorrosion results were obtained on the borided
Al0.07 Co1.2 6Cr1.80 Fe1.42 Mn1.35 Ni1.10 HEA [148]. The boriding process was
conducted at diverse conditions (temperature and exposure time) to obtain
different boride coating thicknesses with a (Cr0.4 Mn0.6 )B, (CoFe)B2, and Cr2 Ni3 B6
microstructure. The borided and untreated HEA were evaluated under sliding
conditions and exposed to 3.5% NaCl and 5% H2 SO4 solutions, respectively. The
boride coating on the HEA reduced the material loss (up to 30 times) and the friction
coefficients in both corrosive environments more effectively than on untreated
HEA, associated with the high hardness on the surface and the influence of the
coating’s thickness. However, for all the circumstances, the H2 SO4 solution was
more aggressive in relation to the NaCl solution, causing an increase in wear loss.
Finally, during the exposition of the NaCl solution, the worn borided surface was
smoothened by a polishing mechanism. Meanwhile polishing and flaking wear
mechanisms were observed on the borided surface exposed to H2 SO4 solution.
Acknowledgements The authors gratefully acknowledge the members of the Grupo Ingeniería
de Superficies (Instituto Politécnico Nacional) A. D. Contla-Pacheco, L. E. Castillo-Vela, K.
D. Chaparro-Pérez, M. Olivares Luna, J. L. Rosales-López, and J. Escobar-Hernández for
their important contribution to this Chapter. A. D. Delgado-Brito thanks Consejo Nacional de
Humanidades Ciencia y Tecnologia (CONAHCyT) in Mexico. I. E. Campos-Silva would like to
thank Tammy Williams Abram for her valuable assistance in the chapter revision.
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Tribological Characterization
of Electroless Nickel Coatings at High
Temperatures
Arkadeb Mukhopadhyay, Tapan Kumar Barman, and Prasanta Sahoo
Abstract Electroless nickel (EN) coatings are widely applicable in industries.

Current trends also present enhanced high-temperature performance of EN-based
coatings. The high-temperature tribological behaviour is guided by phase trans-
formations and formation of tribo-oxide layers. The present chapter reports high-
temperature tribological characterization of EN coatings. The electroless coatings
present a globular morphology. The wear surface at high temperatures consists of
oxide glaze. At 100 °C, tribological behaviour is controlled by formation of strain-
hardened wear debris. Nickel phosphides and nickel borides are formed due to heat
accumulation and high flash temperature at the interface. Further, the future scope
and possibilities of improvement of wear resistance of the coatings have also been
discussed.
Keywords Electroless nickel · Wear rate · COF · High temperature · Oxide layer
1 Introduction
Surface coatings are applied on a substrate to modify surface properties rather than
bulk properties. A thin layer of coating is applied to improve surface performance,
which includes low coefficient of friction (COF), hardness, wear, etc. Degradation of
any mechanical component initiates at the surface when exposed to harsh conditions.
Surface engineering or surface coatings are an effective way to mitigate such damage.
There are various methods of surface engineering or application of surface coat-
ings on a surface. This includes laser surface modification [1, 2], physical vapour
deposition [3, 4], chemical vapour deposition [5, 6], thermal spray [7, 8], using an
aqueous bath [9, 10], friction surface processing [11, 12], etc. Each method has their
A. Mukhopadhyay
Department of Mechanical Engineering, Birla Institute of Technology, Mesra, Ranchi 835215,
India
T. K. Barman · P. Sahoo (B)
Department of Mechanical Engineering, Jadavpur University, Kolkata 700032, India
e-mail: psjume@gmail.com; prasanta.sahoo@jadavpuruniversity.in
262 A. Mukhopadhyay et al.
own set of advantages and disadvantages [13]. An aqueous bath may be utilized for
electroless or electrodeposition. Various functional coatings with desired properties
may be deposited by both methods [14, 15]. Electroless method is a novel coating
deposition technique, which does not utilize electricity for coating deposition and
is an autocatalytic process [16]. As the coatings’ initial layer is deposited, process
continues and hence is termed autocatalytic [17]. The advantage of electroless method
includes the deposit uniformity wherein a sharp edge, blunt hole or intricate parts
can be coated with ease [18–20]. Other functional advantages include smooth surface
appearance, corrosion and wear resistance, conductivity, etc. [21, 22].
Various metals may be deposited by electroless process like copper, gold, silver,
nickel, cobalt, etc. [23–25]. But the electroless nickel (EN) coatings were primarily
utilized for tribological applications [26]. The applicability of EN coatings is summa-
rized in Fig. 1. The electroless nickel coatings require reducing agents, which include
either sodium hypophosphite or sodium borohydride. Ni–P or electroless Ni–B
(ENB) coatings are formed consequently [27–30]. Better corrosion resistance was
seen for Ni–P coatings whereas ENB coatings are associated with high wear resis-
tance and hardness [31–34]. Though pure nickel may be deposited by electroless
process, they are not in use due to hazards related to hydrazine in the coating bath
[17, 18].
With rising demand from industries and growing challenges/harsh environments,
there was a need for the expansion of the EN family. Apart from the pure nickel or
binary alloys, further metallic additions may be also carried out to form ternary and
quaternary coatings [35–38]. The coating matrix may be dispersion strengthened by
forming composite coating by addition of ceramic particles or self-lubricating parti-
cles or both [39–45]. EN classification is depicted in Fig. 2. The coating properties
Fig. 1 Applications of electroless nickel coatings

Tribological Characterization of Electroless Nickel Coatings at High … 263
Fig. 2 Classification of EN coatings
may be further enhanced through aid of different heat treatments. The coatings may
be heat treated in a furnace in the presence of air, vacuum and nitride [46–50]. Precip-
itation of hard crystalline phases takes place consequently [46–50]. This improves
microhardness and wear resistance. Though, higher heat treatment temperature leads
to an increase in grain size and degradation in mechanical properties [46–50].
The EN bath comprises of several chemicals such as nickel, reducing agent, buffer,
complexing agent, surfactants, nano/micro-particles, etc. [17, 18]. These chemical
composition and deposition conditions may be tailored to produce coatings with
varying microstructures, which in turn influences mechanical properties, tribological
behaviour and corrosion resistance [17, 18, 22]. The aid of experimental designs,
optimization and machine learning has been successfully utilized to optimize the
coatings for harsh conditions [27–29, 34]. Recent studies have also found out the
usefulness of EN coatings at high temperature. Thus, the present chapter discusses
deposition of EN coatings and their high-temperature tribological behaviour along
with the recent progress and future prospects.
2 Deposition of EN Coatings
The Ni–P coatings can be deposited from alkaline or acidic baths. The acidic bath Ni–
P coatings were better than those obtained from alkaline bath. Sodium hypophosphite
is a reducing agent and pH lies between 5–6 and 8–9 for the acidic and alkaline
baths, respectively. The bath composition of Ni–P-based binary and ternary coatings
is represented in Table 1. The Ni–P coatings from acidic baths can be considered
as high P (10–14% P), medium P (6–9% P) and low P (3–5% P) [17]. The medium
phosphorus coatings are the most popular variants for corrosion and wear protection.
The Ni–P coatings obtained from alkaline bath on the other hand have lower adhesion
to steel and are difficult to process on substrates such as aluminium.
On the other hand, ENB coatings may be also obtained from acidic and alkaline
baths. The ENB coatings from acidic bath may be obtained from dimethyl amino
borane (DMAB) as reducing agent with a lower bath temperature of 50–60 °C.
The coating deposition rate is fairly high and produces coatings with high melting
point [16–18]. The alkaline bath ENB coatings are normally found from sodium
borohydride as reducing agent. Similar to Ni–P coatings, ENB coatings obtained
from alkaline baths may be also categorized as low, mid and high B coatings [51–55].
Different poly-alloys may be also deposited from alkaline baths and the compositions
are depicted in Table 2.
Therefore, the EN coatings may be deposited from both alkaline and acidic baths.
The Ni–P coatings obtained from acidic baths are more popular whereas ENB coat-
ings obtained from alkaline baths are more popular. The ENB coatings obtained from
both acidic as well as alkaline baths have high as-deposited hardness with respect to
Ni–P coatings and are more suitable for tribological applications [16–18].
3 Coating Characteristics
The EN coatings may be characterized in terms of their surface appearance,

constituents and structure. A globular morphology is detected for both Ni–P and
ENB coatings. Figure 3 shows Ni–P coatings after deposition. The coatings appear
greyish and free of porosities. In some cases, bright particles and overgrowths of
Ni were seen for EN coating with W [51, 55]. The EN coatings with Cu appear as
aggregates and clusters of nodules [51, 55].
The surface of ENB based coatings resemble a typical cauliflower [53]. On
observing their cross-sections, it was seen that there are columnar growths, which
act as lubricant retainers in adhesive wear situations [54]. Furthermore, inherent self-
lubricating capability of ENB-based coatings was attributed to these cauliflower-like
growths [53]. Furthermore, the columnar growths decrease actual area of contact.
Interestingly, for EN coatings, the nodular sizes tend to increase on heat treatment
as a sign of occurrence of crystallization. The ENB-based coatings are depicted in
Fig. 4 similar to morphology resembles a typical cauliflower especially for ENB-Mo
coatings.
The coating structure is an important aspect in determining its mechanical prop-
erties and tribological behaviour. Generally, the crystal structure is determined from
X-ray diffraction (XRD). Immediately after deposition and without any treatment,
a broad peak is observed indicating amorphous phase. For Ni–P coatings, low P
coatings are a combination of amorphous and nano-crystalline. High P coatings are
amorphous [51, 55]. Similarly, the crystallinity of ENB coatings in as-deposited
is dependent on B content [53]. The high B coatings are entirely amorphous and
the crystallinity increases with a decrease in B content [52]. This is due to the fact
Table 1 Bath composition of Ni–P coatings obtained from alkaline and acidic baths
Coating bath formulation (Composition in g/l)
Coatings Nickel sulphate Nickel Sodium Sodium Sodium citrate Ammonium Lactic acid Sodium Copper
chloride hypophosphite succinate sulphate tungstate sulphate
Ni–P 30 30 10 12 × × × × ×
Ni–P–W 20 × 20 × 35 30 5 2.5 ×
Ni–P–Cu 30 × 15 × 15 × × × 0.5
Coating deposition parameter
Coatings pH Bath temperature ( °C) Coating time Bath volume
Ni–P 4.5 80 ± 2 3h 200 ml
Ni–P–W 7–8 90 ± 2
Ni–P–Cu 9.5 85 ± 2
Tribological Characterization of Electroless Nickel Coatings at High …
265
Table 2 Bath composition of

Composition Values (g/L)
ENB-based coatings obtained
from alkaline baths Ni–B Ni–B–W Ni–B–Mo
Nickel chloride 20 20 20
Sodium borohydride 0.8 0.8 0.8
Ethylenediamine 59 59 59
Lead nitrate 0.0145 0.0145 0.0145
Sodium hydroxide 40 40 40
Sodium tungstate × 25 ×
Sodium molybdate × × 25
Coating deposition conditions
Deposition condition Values
pH 12.5
Temperature 90 ± 2 °C
Time of coating 4 h (2 + 2 double bath)
Bath volume 200 ml
Fig. 3 Surface morphology of as-deposited. a Ni–P, b Ni–W–P and c Ni–Cu–P coatings [55]
that higher B content prevents nucleation of Ni. Thus, higher B content leads to
ENB coatings exhibiting amorphous nature. Furthermore, the phase transformation
temperatures are also dependent on P or B content in EN coatings. For example, high
B coatings crystallize at a higher temperature compared to low or mid B coatings
Fig. 4 Morphological images of ENB-based coatings [53]
[52]. Furthermore, the crystallization temperature is also raised on addition of W

or Mo in the EN coatings [53]. A typical XRD of Ni–P-based coatings is depicted
in Fig. 5. The Ni–P or Ni–P–Cu coatings are amorphous whereas for the Ni–P–W
coatings, they are seen to be mixed amorphous and nano-crystalline [55].
The as-deposited ENB coatings’ structure is represented in Fig. 6. They are amor-
phous. This is manifested as a broad dome in the XRD peak representing disorder
in crystal arrangement [53]. The coating structure of ENB coatings is dependent on
B segregation as well as the content of the third element such as W or Mo [53].
EN coatings show crystalline structure post-thermal treatments. Crystalline Ni and
its phosphides were seen when Ni–P coatings were heat treated while borides were
precipitated on heat treatment of ENB coatings. This in turn increased hardness and
improved the tribological behaviour.
Fig. 5 Structure of as-deposited. a Ni–P, b Ni–P–W and c Ni–P–Cu coatings [55]
4 High-Temperature Tribological Behaviour of EN

Coatings
Recent studies have shown promising tribological behaviour of EN coatings at high

temperature. High-temperature tribological behaviour is dominated by various mech-
anisms such as abrasive wear, adhesive wear, fracture, oxidation, formation of oxide
glazes etc. The tribological behaviour of EN coatings is discussed subsequently.
4.1 Performance of Ni–P Coatings at High Temperatures
The Ni-10% P coatings were deposited, and heat treatment was carried out at 600 °C
[56]. The as-deposited coatings were found to show improved tribological behaviour
at high temperature (550 °C) while heat-treated ones at room temperature (RT). The
as-deposited coatings underwent phase transitions due to in-situ heat treatment. The
heat-treated coatings’ poor tribological performance was attributed to grain coars-
ening at the high temperature and crack propagation by Orowan mechanism. The as-
deposited coatings showed adhesive wear at RT sliding wear tests with torn patches.
Fig. 6 Coating structure of ENB coatings in as-deposited state [53]
On other hand, heat-treated coatings showed abrasive wear at room temperature.

While at high temperature, as-deposited coatings hardness increased post wear test.
It was finally concluded that an optimal grain size exists for Ni–P coatings, which
allows enough plastic deformation slowing down the crack growth and relax stress
concentration. The already crystalline and heat-treated coatings undergo further grain
growth and grain coarsening due to high-temperature sliding conditions.
The effect of variation of P content with 4, 5, 9 and 12% P on the tribological
behaviour at 250 °C was investigated by Ghaderi et al. [57]. All the coatings were
heat-treated 400 °C under argon gas for 1 h. The heat-treated coatings were crystalline
and also had enhanced hardness compared to as-deposited ones. With rise in P,
the wear mass loss declined and highest wear resistance was concluded for 12% P
coatings. Formation of oxide layers was also observed using energy dispersive X-ray
spectroscopy (EDS). The coating microhardness post wear test for 9% P coatings
increased by ~10 Vicker’s hardness due to further crystallization of the coatings. But
for low P coatings, a significant variation in microhardness was not detected.
The Ni–P coatings with high P were investigated at 100–500 °C [58]. The load
and velocity were also varied. Both as-deposited and heat-treated coatings (400 °C
for 1 h) were investigated. The COF and wear rate rise with rise in load. This trend
was followed at all the test temperatures investigated. On the other hand, wear rate
and COF decreased with rise in velocity as shown in Fig. 7. At high temperatures,
Fig. 7 COF variation at high temperature for Ni–P in as-deposited state with a load and b speed
[58]
especially near phase transformation temperature of Ni–P coatings, the as-deposited

variants exhibited enhanced tribological behaviour. This was due to in-situ heat treat-
ment of the coatings and undergoing crystallization. Wear mode was dominated by
mixed adhesion and abrasion as well as tribo-oxidation.
The Ni–P–B coatings’ tribological behaviour was investigated at room tempera-
ture to 500 °C [59]. The Ni–P–B coatings were also heat treated at 400 °C for 1 h.
The hardness of as-deposited and heat-treated coatings were larger than Ni–P or
ENB coatings. Comparison of wear rate of as-deposited and heat-treated coatings
with Ni–P deposits shows enhanced wear resistance of the former than the latter
in Fig. 8. Furthermore, here again wear rate was lower at 300 °C with respect to
100 or 500 °C, which was attributed to the sliding of coatings nearer to their phase
transformation temperature. The phase transition investigation using X-ray diffrac-
tion (XRD) post-wear tests also revealed precipitation of hard phosphide phases and
borides.
Electroless Ni–P–W coatings with high as-deposited hardness were obtained by
Kundu et al. [60]. Heat treatment at 400 °C for 1 h was done. Addition of W enhances
thermal stability and crystallinity of coatings. Both as-deposited and heat-treated
coatings were exposed to RT and high-temperature tests (100, 300 and 500 °C).
The heat-treated coatings show lower wear rate than as-deposited ones at all test
temperatures as shown in Fig. 9. This was attributed to creation of oxide layers and
coating crystallization during high-temperature tests. Interestingly, a 46% rise in
(compared to as-deposited films) microhardness of the coatings was observed after
sliding wear tests at 500 °C. Similarly, there was a 12.8% rise in microhardness after
the coatings underwent sliding at 300 °C. The rise in hardness of heat-treated coatings
was marginal post-sliding wear at all temperatures with respect to as-deposited Ni–
P–W coatings.
Fig. 8 The wear rate of Ni–P and Ni–P–B coatings at different temperatures in a as-deposited and
b heat-treated state [59]
Fig. 9 The wear rate of Ni–P–W coatings at different temperatures in a as-deposited and b heat-
treated state [60]
Composite coatings with Ni–P matrix can also be a suitable alternative at high
temperature. The composite coatings enhance mechanical and tribological behaviour
by dispersion strengthening of coating matrix. The Ni–P–BN (h) coatings were
deposited on 310L stainless steel [61]. The tribo-behaviour was studied at 25–400 °C.
The wear rate and COF rise with rise in temperature. The coatings were categorized
by gross plastic deformation at high temperature. Adhesion and fracture were domi-
nant at high-temperature sliding and coating material transfer to the ball. Finally, it
was concluded that the high-temperature tribological response was dependent upon
the Ni matrix and not on BN (h) particles.
Fig. 10 Wear rate of

as-deposited and heat-treated
Ni–P–BN(h) at a RT and
b 300 °C [62]
In another study, Ni–P–BN(h) heat treated at 400 °C was investigated at RT-

300 °C [62]. Due to high hardness and less adhesive wear, heat-treated coatings
exhibited enhanced wear resistance at RT as represented in Fig. 10. The hardness of
as-deposited coatings increased by 40% post-sliding wear at 300 °C. Furthermore,
wear resistance changed negligibly post-heat treatment at 300 °C test temperature.
Incorporation of Al2 O3 leads to an overall enhancement in hardness and high-
temperature wear resistance of Ni–P coatings [63]. High-temperature wear was char-
acterized by microstructural changes and improvements associated with formation
of oxide layers at 500 °C.
The Ni–P–SiC coatings were deposited on AISI 1020 steel and tribological
behaviour was investigated at RT and high temperature of 100 °C and 300 °C [64].
Heat treatment caused an increase in wear resistance by 135% (with respect to as-
deposited coatings) at RT. The higher particle size to coating thickness ratio aggra-
vated the wear rate at high temperature. At 100 and 300 °C, wear rate increased by 23
and 116 times, respectively, with respect to RT tests. Franco et al. [65] investigated
composite Ni–P–SiC coatings at elevated test temperature of 200 °C. As-deposited
and 400 °C heat treated coatings were evaluated. The reinforcing SiC particles were
varied from 0 to 42%. The specific wear rate decreases as the reinforcing particles
increase as shown in Fig. 11. Heat treatment also enhances the wear resistance. Inves-
tigation of sub-surface of coatings after wear test was also carried out. It was seen
that micro-cracks were developed in the particle-free coating. While the inclusion of
SiC reduced the probability of lengthening of the cracks.
Addition of self-lubricating particles in Ni–P coatings may enhance wear resis-
tance and decrease COF at high temperatures. The Ni–P–Ag coatings were developed
on medium carbon steel specimens [66]. The as-deposited and heat-treated hardness
of Ni–P–Ag coatings were lesser than Ni–P coating. High-temperature tribological
tests at 500 °C revealed that heat treated Ni–P–Ag coatings had lesser wear rate
than Ni–P coating. At RT, the COF of Ni–P–Ag coating was found to be 0.32 and
0.37 at 500 °C. This was lower compared to Ni–P coating. The enhanced tribo-
logical behaviour at high temperature was attributed to entrapment of Ag particles
Fig. 11 Specific wear rate

of Ni–P–SiC coatings (A =
0%, B = 14%, C = 24% and
F = 42% SiC) [65]
and their nucleation at the surface acting as self-lubricants. The Ag particles also
decrease the fluctuations in COF at high temperature. Addition of alumina also leads
to enhanced tribological behaviour of Ni–P–Ag coating and there was a ‘chameleon’
like behaviour due to creation of self-lubricating film [67]. The hybrid Ni–P–Ag–
Al2 O3 coating provided an optimum combination of enhanced high-temperature
tribological behaviour and hardness.
Self-lubricating MoS2 particles were incorporated in Ni–P coatings and deposited
on AISI 1045 specimens [68]. The coated specimens were heat treated at 300 °C for
2 h. Tribological investigation was done by rising temperature from RT to 600 °C
by progressively increasing temperature by 100 °C. The COF was high at RT (0.78)
and decreased as the test temperature increased with lowest value of 0.27 at 500 °C.
The wear rate firstly increased with a rise in temperature up to 200 °C then started
falling with the lowest at 400 °C and then again started increasing up to 600 °C as
shown in Fig. 12. A dense and continuous oxide film decreased the COF or wear rate
at elevated temperature. The wear mechanism was mild scuffing.
Fig. 12 Variation of wear

rate of Ni–P–MoS2 coatings
at high temperatures [68]
The Ni–P coatings with inclusion of MoS2 and CaF2 were deposited and heat
treated at 300 °C for 2 h [69]. High-temperature tribological tests were carried out
at RT to 570 °C. The friction and wear behaviour are depicted in Fig. 13. The COF
declines with a rise in temperature. The wear rate displays a similar trend but increases
570 °C. At 200 °C, the surface was characterized by discontinuous oxide films and
micro-scuffing. At 390 °C, the surface was smoother and with a compact film. This
consequences in a decrease in COF and wear rate. At 570 °C, surface was fully
covered by a compact film along with micro-ploughing and micro-scuffing. The wear
rate rises due to a decrease in strength of coating matrix. The coatings also exhibited a
stable COF during entire sliding period at RT and high-temperature tribological tests.
The self-lubrication at high temperature was due to synergistic effects of the oxides
of Ni and Mo, MoS2 , CaF2 , sulphates, phosphates and CaMoO4 , which provides a
lubricating effect due to formation of a low shear film at the interface of sliding.
Fig. 13 Variation of a COF

and b wear rate of
Ni–P–MoS2 –CaF2 coatings
at high temperatures [69]
4.2 Performance of ENB Coatings at High Temperatures
Recent studies have also shown potential of ENB-based coatings at high tempera-
tures. As-deposited ENB coatings in mid-B range were deposited on AISI 1040 steel,
and the tribological behaviour was investigated at RT, 100, 300 and 500 °C [70]. The
wear rate rises from RT to 100 °C (Fig. 14). Then, wear rate decreased at 300 °C. This
was attributed to the existence of phase transition during high-temperature sliding.
The phenomenon was supported by XRD results of the coatings post-wear test. At
high temperature of 500 °C, there was depletion of B at the surface and possibility
of occurrence of the inter-diffusion phenomenon (diffusion of B from the surface
towards the substrate at high temperature) was also noted. The COF also decreased
at 500 °C. An important phenomenon observed for the coatings was the effect of
bi-layered coatings as shown in Fig. 15. The upper layer was deformed and an oxide
layer was formed. This oxide layer was supported by a toughened bottom layer. This
led to an enhanced tribological behaviour at high temperature.
A comparative study of as-deposited ENB binary and ternary alloy coatings at high
temperature was done by Mukhopadhyay et al. [71]. The Ni–B–W coatings showed
the highest wear resistance as shown in Fig. 16. Ni–B–Mo coatings offered lowered
COF. At 100 °C, coatings undergo severe grinding by strain-hardened debris. The
debris cut the coating matrix and produce deep grooves. This results in a rise in COF
or wear rate at 100 °C. Phase transformation at 500 °C with boride precipitation was
detected for all three coating variants in XRD results of worn surface. The coatings
Fig. 14 Wear rates of as-deposited ENB coating at different temperatures [70]

Fig. 15 The bi-layered ENB

as-deposited coating
undergoing wear test at
300 °C [70]
were amorphous before the sliding wear test. While after wear test at 500 °C, XRD
of the worn surface revealed coating crystallization with precipitation of Ni, Ni2 B
and Ni3 B.
The effect of heat treatment on tribological behaviour of ENB-based coatings was
also investigated [72–74]. The heat treatment was carried out at 350, 400 and 450 °C
for 1 h. It was concluded for the coatings that high heat treatment temperature and
high sliding temperature result in grain coarsening and rise in wear rate. Optimal
tribological behaviour at high temperature was concluded for ENB and Ni–B–W
coatings for a heat treatment temperature of 350 °C for 1 h while for Ni–B–Mo
coatings, optimal heat treatment temperature was 450 °C for 1 h. The variation of
wear rate can be seen for Ni–B–W coatings in Fig. 17. The wear rate clearly rises
with rise in heat treatment at 100 °C. While heat treatment did not cause a noticeable
effect at 300 or 500 °C operating temperature. This also reflected the enhanced
thermal stability of coatings on addition of W. A similar behaviour was also seen
for Ni–B–Mo coatings [74]. A significant change in COF or the wear rate was not
detected with rise in heat treatment temperature.
Pal et al. [75] investigated the tribological behaviour of ENB coatings for various
heat treatment conditions. Completely crystalline ENB coatings were obtained by
heat treatment at 385 °C for 4 h. They were investigated at high-temperature tribolog-
ical tests as shown in Fig. 18. At both 1 N and 5 N loads, COF or wear rate increased
with test temperature. Though there was no significant effect on COF, wear rate was
affected profoundly. The worn surface was characterized by breakage of oxide film
at high temperatures with a dominating effect of plastic ratcheting. The flash temper-
ature was found to increase to almost 1010 at 450 °C test temperature. The inert
counterface was supposedly the reason for such high flash temperature occurring at
the sliding interface.
The effect of load, speed and temperature was also investigated for crystalline
ENB, Ni–B–W and Ni–B–Mo coatings by Mukhopadhyay et al. [76–79]. Within
10–50 N, the load was varied. Whereas speed range was 0.25–0.42 m/s. The test
Fig. 16 ENB coatings

undergoing wear at a RT and
b elevated temperatures [71]
temperature was varied between ambient temperature and 500 C. At 10 N load

and ambient temperature, the mass loss was almost steady with an increase in sliding
speed [79]. Whereas as the load was increased to 50 N, the mass loss of ENB coatings
showed a steep rise. The COF also showed a similar nature. At 100 °C, the wear rate
and COF both increased with an increase in load and speed for all the three coating
variants. This was attributed to grinding action of strain-hardened wear particles. On
the other hand, at 300 °C, there was a curvature in the variation of wear rate and
COF with an increase in sliding speed at all loads. Formation of oxide glazes was
reported at 500 °C leading to a lowering of wear rate. At all temperatures and load,
Ni–B–W coatings show higher wear resistance. At 100 and 300 °C, ENB coatings
exhibit an overall lower COF at the aforesaid constraints, i.e., load and sliding speed.
At 100 °C, overall COF of Ni–B–Mo coatings was lower [79].
Fig. 17 Effect of heat

treatment on wear behaviour
of Ni–B–W coatings at high
temperatures [73]
Recent developments in ENB coatings include the elimination of heavy metal-

based stabilizers from coating bath. In this regard, ENB coatings obtained from a
stabilizer-free bath were investigated at high temperatures [80]. The results were
quite similar to lead stabilized Ni–B variants. At 100 °C, wear rate was higher with
respect to 300 °C. The initiation of phase transformation was also reported. But one
of the interesting findings was the formation of a mechanically mixed oxide layer
with Fe, which results in an enhanced tribological behaviour comparable to that of
lead-stabilized coatings. It was concluded that the coating adhesion was poor for
the lead-free coatings, thereby the coatings were delaminated and got mechanically
mixed with Fe from substrate.
5 Conclusions and Future Directions
With progress of time, industrial demands have become stringent and mechanical
components are subjected to harsh environment. There are several coatings methods
for surface engineering of such components. But EN coating is a novel technique that
can be used to coat complex geometry substrates. Recently, in the last 5 years, a signif-
icant progress has been made where the high-temperature tribological behaviour has
been reported. The Ni–P coatings perform well at elevated temperature. There exists
a critical grain size which arrests cracks and its propagation. Apart from the binary
alloy, ternary coatings were also investigated. A significant finding of all studies was
improved tribological behaviour of EN coatings near to their phase transformation
temperature. This result is also applicable to the Ni–B-based binary and poly-alloys.
The high-test temperature and frictional heating may result in the flash tempera-
ture rising to almost 1010 °C. This essentially causes microstructural changes and
Fig. 18 The a COF and b wear rate of completely crystalline ENB coatings at high temperatures
[75]
phase transformations. Therefore, it becomes quite critical to select coating depo-

sition parameters, which would result in coating with appropriate P and B content,
which finally would result in achieving optimal grain size during sliding at harsh
conditions. This is a challenge and may be addressed in future research works. On
the other hand, composite coatings were also investigated. The composite coatings
also improve mechanical properties by dispersion strengthening. But at high temper-
atures, the sustainability essentially depends on the strength of the coating matrix.
Furthermore, in a recent development, mechanically mixed layers of coating and
substrate and formation of the oxide layer resulted in a significant improvement in
wear resistance. Hence, this aspect may be also further investigated with in-depth
studies of sub-surface layers of wear track and the oxide layers.
Acknowledgements The authors gratefully acknowledge the support of DST-PURSE, PHASE II

program of Jadavpur University. The first author also acknowledges the funding of DST-SERB Core
Research Grant (File Number: CRG/2022/001441).
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672X/aca784
Heat Resistant Coatings
Thin Chromium-Based Coatings
for Internal Combustion Automobile
Engine Valve Protection
Zbigniew Grzesik and Grzegorz Smoła
Abstract The chapter presents the latest findings concerning the impact of various
liquid fuel types on the course of internal combustion engine valve high temperature
corrosion, as well as a method to increase the heat-resistance of these elements by
applying innovative chromium-based metallic coatings that are only a few microm-
eters thick. It also presents experimental results confirming the beneficial effect of
adding nickel as an alloying element on the functionality of the thin chromium coat-
ings along with an active element—yttrium. The latter significantly improves the
heat-resistance of valve steels covered with the aforementioned protective coatings
under thermal shock conditions. Finally, examples of potential application areas for
chromium-based thin metal coatings outside the automotive industry are indicated.
Keywords Valve steels · Thin coatings · Biofuels · High temperature corrosion ·

Kinetics · Isothermal conditions · Thermal shocks
1 Introduction
Nowadays, high temperature corrosion of metallic materials is a cause of significant

difficulties in various branches of modern industry [1, 2]. Due to the high rank of
this problem, several methods have been elaborated to protect constructive materials
against degradation at high temperatures. One of them is the application of protective
coatings [1, 3–7]. Thermal barrier coatings (TBCs) are treated as some of the most
promising because they exhibit extraordinary protective properties in high tempera-
ture aggressive environments [8–14]. However, the relatively high thickness (usually
100 μm–2 mm) of such TBC coatings limits their use in the protection of movable
machine parts, due to the danger of their destruction during work. Deposition of TBC
coatings on movable well-matched parts requires their redesigning in order to give
them smaller dimensions. Unfortunately, it is a rather expensive and time-consuming
Z. Grzesik (B) · G. Smoła

Faculty of Materials Science and Ceramics, AGH University of Science and Technology, Al.
Mickiewicza 30, 30-059 Krakow, Poland
e-mail: grzesik@agh.edu.pl
288 Z. Grzesik and G. Smoła
process that involves changing the manufacturing method of the parts mentioned
above. Consequently, many operating elements are entirely unprotected by coatings
against the attack of aggressive gasses at high temperatures. Such a situation occurs,
e.g., in the case of engine valves applied in lower and middle-class automobiles,
in spite of the fact that car engine valves operate in very aggressive environments
containing corrosive exhaust gases at high temperatures reaching 1173 K.
The solution to the presented problem may be to elaborate a new generation of
thin, cost efficient coatings based on chromium, which would ensure an acceptable
high level of anti-corrosion protection for movable elements without the requirement
of changing their dimensions. The results of the first systematic research to develop
such coatings were presented in 2015 [15]. It should be emphasized that no previous
attempts were made to test the effectiveness of the protection provided by coatings
with a thickness of the order of one micrometer. Indeed, attention was drawn to the fact
that these coatings were too thin to provide a sufficient chromium reservoir over a long
period of time. Taking into account the high corrosion rates at high temperatures, it
was expected that the chromium contained in such a thin coating would be completely
consumed in a short period of time, about a dozen or so hours. Such a short service life
of the coating would make their use of no practical value. Nevertheless, the results of
preliminary tests on the oxidation rate of one micrometer thick chromium coated steel
[15] showed that the effectiveness of the proposed thin coating is much longer than
the life-time of the coating itself. This chapter demonstrates that a one micrometer
thick chromium layer deposited on valve steels enhances the growth of corrosion
products containing chromium-rich oxides (Cr2 O3 , CrMn2 O4 , Cr1.5 Mn1.5 O4 ) that
exhibit excellent protective properties and increase the heat-resistance of the steel
substrates. This unexpected phenomenon can be explained by the fact that the thin
chromium layer only begins the growth of the previously mentioned oxides, after
which this layer rapidly disappears and the scale continues to form as a result of
outward chromium diffusion from the metallic core. Subsequently, steels protected
by thin coatings demonstrate higher oxidation resistance under isothermal conditions
in comparison to particular unmodified steels for a considerably longer duration than
the lifetime of the deposited coatings.
In the following years, the previously mentioned hypothesis was experi-
mentally verified using selected valve steels currently utilized to manufacture
engine valves (X33CrNiMn23-8, X50CrMnNiNbN21-9, X53CrMnNiN20-8 and
X55CrMnNiN20-8) coated with thin chromium-based coatings. This chapter
presents the results of these tests with comparison to analogous data received for
the same types of unmodified steels.
Thin Chromium-Based Coatings for Internal Combustion Automobile … 289
2 Operating Conditions of the Internal Combustion

Automobile Engine Valves
Engine valves operate in particularly aggressive conditions, i.e. relatively high

temperatures (up to around 1173 K) and rapid temperature changes, which are called
thermal shocks in literature. It is common knowledge that during such shocks, high
thermal stresses appear at the scale/substrate interface, being the result of different
thermal expansion coefficients of these two materials [2, 16]. Thus, during the start
and finish of the automobile engine operation, the scale can crack and spall off,
consequently significantly lowering the valve steel’s corrosion resistance [2, 16–18].
Under such a situation, the problem of adhesion between the substrate surface and
scale is very important and its solution is very significant to considerably increase
the corrosion resistance of discussed steels.
In recent years, corrosion problems of engine valves became more severe due
to an increase in the maximum operation temperature of automobile engines (from
about 973 to 1173 K), as well as application of biofuels. Biofuels in automobile
applications are standard petroleum or fuel oil with the addition of bio-components.
Fatty Acid Methyl Ester (FAME) additions constitute bio-components for fuel oil and
on European Union territory ethanol is added to petroleum. Nowadays, the FAME
concentration or ethanol content utilized as a bio-component addition to fuel oil and
petrol, respectively, in European Union countries is equal to about 5 wt.%. However,
it is expected that in the following decade, this content will increase up to 10 wt.%
[19]. It should be noted that biofuels seem to be particularly useful in automotive
transport, because they can become alternatives to petroleum and fuel oil [19–22].
It should be noted that rapid exhaustion of crude oil is a reason for the continuous
increase of its price. Furthermore, the application of conventional fossil fuels leads
to major environmental damages, like global climate changes, ozone layer loss and
acid rains [23]. Moreover, the widespread use of biofuels may become a significant
renewable energy resource, reducing the concentration of carbon dioxide (CO2 ) and
other greenhouse gases in Earth’s atmosphere [19, 21, 24, 25]. They have also great
economical promise, assuming a future increase in fossil fuel prices. This aspect is
particularly relevant today. Unfortunately, in addition to important benefits, biofuels
also exhibit several disadvantages, which currently limit their large scale use in
the automotive industry [26–31]. From a purely technical point of view, the main
reason for these limitations is due to accelerated corrosion of those car engine parts
that operate at the highest temperatures and in environments of aggressive exhaust
gasses, which are the products of biofuel combustion, i.e., exhaust engine valves.
The problem of engine valves corrosion during their exploitation has not yet been
solved, due to its high complexity.
3 Methods for Testing the Oxidation Resistance

of Materials Used in the Manufacture of Engine Valves
Tests performed on individual components of internal combustion engines—

including engine valves—are primarily carried out as a result of automotive concerns.
Basically, they use two test methods. The first method consists of placing the complete
engine on the engine test house and specifying its operation under the given load
conditions. In the second method, the engine is placed in the car, which then is oper-
ated under strictly defined field conditions for a given period of time. In both cases,
after the tests are completed, the engine is disassembled and the wear of individual
parts of the engine is analyzed. Unfortunately, such tests are extremely expensive and
do not easily lead to conclusions on the kinetics and corrosion mechanism of engine
valves. In addition, little can be said concerning the details of individual research
results, as these results are usually treated by automotive companies as confidential,
which means that their dissemination is limited.
Being active in the high temperature corrosion field, studying metallic materials
degradation for years, in our laboratory, we undertook systematic corrosion tests
of valve steels, both surface-modified and covered with protective coatings, which
were performed in both isothermal conditions and thermal shocks. Corrosion rate
studies at a constant temperature were conducted using the gravimetric method. This
method consists of measuring changes in the mass of the tested sample, suspended
in the reaction zone of the microthermogravimetric setup, filled with reaction gases
heated to the desired temperature, as a function of time. On the basis of this type of
experiment, conclusions can be drawn regarding not only the corrosion rate, but also
the kinetics law, according to which the oxidation process takes place. In general, the
smaller the mass increments of the test sample, the greater its resistance to oxidation.
Since the rate at which valve steels oxidize is low, mass change measurements of
the tested samples must be carried out with high precision. This requires the use
of an electronic microbalance that records these changes with a high sensitivity of
10–7 g. This equipment should create conditions in which, on the one hand, a strictly
defined composition of the atmosphere flowing through the reaction space is ensured,
and on the other hand, the space of the electronic microbalance must be protected
against aggressive exposure to a corrosive atmosphere with a protective noble gas
(helium or argon). Finally, this device must ensure a constant temperature inside the
reaction chamber with ±1 °C precision during long-term measurements carried out
for hundreds of hours.
Corrosion rate tests under thermal shock conditions are performed by heating a
given sample starting from room temperature up to the required temperature with high
speed. Next, the sample is maintained at this temperature for a specific duration of
time (in the case of our investigations: two hours). Subsequently, the sample is rapidly
cooled down to room temperature. The approximated heating time in our experiments
was 1 min, whereas the cooling (quenching) time was about two minutes. Next, the
subsequent heating cycle is started. After a specific amount of such thermal cycles,
the mass of a given sample relative to its surface area is measured and recorded as a
function of thermal cycles. The discussed tests are interpreted in the following way.
When the oxidized sample systematically loses its mass during consecutive thermal
cycles, this effect results in the scale cracking and spalling off from the sample
surface, because of thermal stresses. From these experiments, it can be concluded
that if the mass losses as a function of thermal shocks number of the investigated
material are higher, then the scale adherence is worse and thereby, so are the scale
protective properties. Conversely, when the sample mass is virtually constant as the
shock number progresses, it denotes that despite thermal stresses present between the
scale and metallic core, cracking and spalling of the scale from the substrate surface
is not observed. In this case, scale adherence is very good and thus, it satisfactorily
provides protection against high temperature corrosion.
The corrosion rate tests, the results of which are presented in this chapter, were
performed in real combustion gases and air. Tests performed in air do not reflect
the conditions prevailing in the atmosphere of real exhaust gases, however, they
allow for preliminary identification of the degree of heat-resistance the materials
intended for the production of engine valves have. It turned out that valve steels
with higher resistance against oxidation are also characterized by higher corrosion
resistance in atmospheres of real exhaust gases. This thesis is fully confirmed by the
results presented in the next part of this work. In addition, oxidation studies in air are
many times less expensive than the tests carried out in real exhaust gas atmosphere.
However, a large part of the corrosion studies under thermal shocks was performed in
an atmosphere of real combustion gases, obtained from engines placed in an engine
test house. A schematic representation of the equipment used in such conditions is
illustrated in Fig. 1. It should be noted that, although the apparatuses for testing
the oxidation kinetics in isothermal conditions, as well as under thermal shocks are
standard and commonly used in many laboratories around the world, such a unique
setup has never been used before in corrosion studies of valve steels. More details
on the course of measurements both in isothermal and thermal shock conditions can
be found in the literature [32–34].
Fig. 1 Schematic representation of the equipment used for thermal shock experiments conducted
in an atmosphere of real combustion gases
4 Corrosion Behavior of Popular Automobile Engine Valve

Steels at High Temperatures
In the automobile industry, four chromium-nickel steels (X33CrNiMn23-8,

X50CrMnNiNbN21-9, X53CrMnNiN20-8 and X55CrMnNiN20-8) are currently
being utilized in the production of valves intended for automobile engines in low
and medium class cars. Valves from these steels constitute about 90% of the total
primary market of engine valves in Europe. The nominal chemical compositions of
these steels are presented in Table 1.
The test specimens presented for the purpose of the discussed investigations were
prepared using a standard metallographic procedure. They were obtained from rods
of a given valve steel with a ~20 mm diameter by cutting them into flat disks with
around 1 mm thickness. In order to obtain mirror-like surfaces of the samples, they
were ground with different SiC papers and finally polished using diamond pastes.
4.1 Oxidation in Air Atmosphere
The oxidation behavior of the above-mentioned valve steels was studied both in
isothermal [35, 36], as well as thermal shock conditions [33]. The tests conducted
under isothermal conditions showed that oxidation kinetics of all investigated valve
steels at temperatures lower than 1173 K can be described as in accordance with the
parabolic oxidation rate law. Only oxidation courses obtained at 1173 and 1273 K
for X33CrNiMn23-8 steel firmly follow parabolic kinetics from the initial time of
the reaction, indicating that the process is controlled by diffusion. In the case of the
three other remaining steels with lower chromium content, the oxidation process is
more complex. After a certain incubation period, during which the oxidation rate
is relatively low, sample mass increases with reaction time but in agreement with
the parabolic oxidation rate law. Figure 2 presents exemplary kinetics obtained at
1173 K (Fig. 2).
As illustrated in Fig. 2, X33CrNiMn23-8 steel demonstrates the best oxidation
resistance. It should be emphasized that this steel exhibits the best behavior compared
to the remaining steels at all temperatures, at which oxidation tests were performed
[36]. The difference between the oxidation kinetic rates of studied steels, represented
by parabolic rate constants (k p ), increases along with temperature and at 1273 K
is more than one hundred times higher. Such results are not unexpected. In accor-
dance with earlier expectations, the chromium concentration in the X33CrNiMn23-8
steel is high enough for its selective oxidation and the growth of a highly protec-
tive chromia scale. In addition, the relatively high concentration of nickel in this
steel, exceeding 7 wt.% (Table 1), increases selective oxidation of chromium by
accelerating outward chromium diffusion in the metallic substrate to the metal-scale
interface [37]. The chromium and manganese concentrations in the three remaining
Table 1 The nominal concentrations of elements (wt.%) in X33CrNiMn23-8, X50CrMnNiNbN21-9, X53CrMnNiN20-8 and X55CrMnNiN20-8 valve steels
Grade of steel C Mn Si Cr Ni N W Nb S P Mo Fe
X33CrNiMn23-8 0.28 1.50 0.50 22.00 7.00 0.25 Max. – 0.030 0.045 Max. Bal.
– – – – – – 0.50 0.50
0.38 3.50 1.00 24.00 9.00 0.35
X50CrMnNiNbN21-9 0.45 8.00 Max. 20.00 3.50 0.40 0.80 1.80 0.030 0.045 – Bal.
– – 0.45 – – – – –
0.50 10.00 22.00 5.50 0.60 1.50 2.50
X53CrMnNiN20-8 0.48 8.00 Max. 20.00 3.25 0.35 – – 0.030 0.045 – Bal.
– – 0.25 – – –
0.58 10.00 22.00 4.50 0.50
X55CrMnNiN20-8 0.50 7.00 Max. 19.50 1.50 0.20 – – 0.030 0.045 – Bal.
– – 0.25 – – –
0.60 10.00 21.50 2.75 0.40
Thin Chromium-Based Coatings for Internal Combustion Automobile …
293
Fig. 2 Exemplary oxidation

kinetics of discussed valve
steels obtained at 1173 K and
stable level of oxygen
pressure, equal to 2.1 ×
104 Pa (∆m/S—mass
changes of the oxidized
samples per unit surface
area)
Fig. 3 Schematic
representation of
multilayered scale formation
on valve steels
steels are practically the same, but greater differences can be seen in nickel concen-
trations (1.5–5.5 wt.%). Literature data clearly indicates that the nickel existence
in chromium-containing steels has a beneficial effect on their oxidation resistance
[37]. Manganese, in turn, has the opposite influence [2]. The concentration of nickel
and manganese is the lowest in X55CrMnNiN20-8 steel and therefore, it may then
be expected that the higher oxidation rate of the X55CrMnNiN20-8 steel compared
to those of X50CrMnNiNbN21-9 and X53CrMnNiN20-8 steels is the result of a
compromise between manganese and nickel contents in these materials.
It can be also highlighted that the oxidation processes of four different valve steels
do not depend on the oxygen pressure [36]. Such a situation is rather common in
the case of oxidation of a number of commercial chromium-containing steels and
alloys. This fact is the result of parabolic rate growth of multilayered scales, the
external layer of which is thinner than the thickness of the entire scale, Fig. 3. As a
consequence, the change in oxygen pressure in the given reactive atmosphere only
affects the formation kinetics of the most external layer of the scale, while the majority
Fig. 4 Comparison of the

results obtained during
oxidation of investigated
steels under thermal shocks
(298–1173 K)
of the scale forms at a constant oxygen pressure, being equal to the decomposition
pressure of this external oxide.
A summary of the valve steels oxidation kinetics investigated under thermal
shocks in air atmosphere is presented in Fig. 4. From this diagram it follows that
all of the studied materials demonstrate rather good oxidation resistance, but the
X33CrNiMn23-8 steel containing the highest chromium concentration, as in the
case of the isothermal experiments, exhibits the best oxidation resistance in high
temperature conditions. This denotes that the chromia scale cracks and spalls off only
fragmentarily and thereby the oxidation products provide relatively good protection
for this valve material. The scale growing on the X33CrNiMn23-8 steel, formed
after 500 shocks, is mainly built of chromium oxide (Cr2 O3 ), along with islands of
iron oxides (Fe3 O4 and Fe2 O3 ) on its surface. On the contrary, the scale grown on
the steel with lowest chromium concentration is complex and only consists of iron
oxides (Fe3 O4 and Fe2 O3 ).
4.2 Oxidation in Combustion Gasses of Fuels Containing

Bio-Additions
Corrosion of four valve steel types at high temperature in combustion gasses of

bio-additive containing fuels was investigated only under thermal shocks. Results
concerning the application of 5 different types of fuels are described in this subsec-
tion. In the fuel oil case, 5 and 10 wt.% FAME concentrations were used (fuel oil
B5 and B10) as bio-additions [38], while for petrol 5, 10 and 50 wt.% of ethanol
concentrations were added (petrol containing 5 wt.% ethanol is designated as 95Al,
10 wt.% ethanol petrol as 90Al and 50 wt.% ethanol petrol as 50Al) [34]. The fuel
oil and petrol properties, consisting of different bio-component concentrations are
listed in Tables 2 and 3, respectively.
Table 2 Properties of diesel fuels [38]

Property Fuel oil B5 Fuel oil B10 EN standard Specification limit
Density at 15 °C, kg/m3 832.0 838.0 EN ISO 12185 820–845
Ignition temperature, °C 61.0 69.5 EN ISO 2719 >55
Cetane no. 55.0 51.4 EN ISO 5165 >51
Water content, mg/kg 26 150 EN ISO 12937 <200
Sulfur content, mg/kg 4.9 8.1 EN ISO 20846 <10
Solid impurities, mg/kg 6.0 9.0 EN ISO 12637 <24
Residue after incineration, 0.001 <0.001 EN ISO 6245 <0.01
mg/kg
CCFP, °C −24 −29 EN 116 <−20
Fractional composition
up to 250 °C, % 36.7 32.2 EN ISO 3405 <65
up to 350 °C, % 95.4 95.8 >85
Temperature, at which 95 348.5 347.0 <360
vol. % of fuel distillates,
°C
FAME content, % 4.9 9.5 EN 14078 5 ± 0.5/10 ± 1
The corrosion kinetics of the discussed valve steels in environments containing

petrol and fuel oil combustion gases with different bio-additions is presented in
Fig. 5. First of all, it can be seen that the degradation of steels in combustion gas
atmospheres is faster compared to that in air. Secondly, petrol combustion gases with
bio-components are less aggressive than those of fuel oil with the same concentration
of bio-additions. Third, the higher the bio-addition concentration, the higher the
degradation rates of the tested steels. It should be also noted that the degree of scale
degradation in all investigated conditions is very low in the case of X33CrNiMn23-8
steel, which is the richest in chromium content. In fact, only in the case of fuel oil
combustion gases exhibiting 5 and 10 wt.% of FAME is the material degradation
slightly higher than in pure air atmosphere. On the other hand, the corrosion rate
of all the remaining steels with lower chromium concentration (X55CrMnNiN20-8,
X53CrMnNiN20-8 and X50CrMnNiNbN21-9) is much faster in FAME-containing
fuel oil combustion gases compared to when the materials are exposed to combustion
gases of ethanol-containing petrol. From this comparison, it seems that combustion
gases of ethanol-containing petrol have a much less harmful influence on engine
valves than fuel oils with FAME as a bio-component. Reported differences in the
tested steel corrosion rates in combustion gas environments again are related to
oxidation products present in growing scales on the surfaces of these steels [34, 38].
During oxidation in air, the chromium concentration in X33CrNiMn23-8 steel is
sufficiently high for selective oxidation of this metal to take place, as well as for a
highly protective chromia scale, well-adherent to the metallic core, to form. However,
Table 3 Properties of petrol fuels [34]

Property Petrol 95Al Petrol 90Al Petrol 50Al EN standard
Density at 15 °C, kg/m3 753.6 742.2 772.4 EN ISO 12185
Motor octane no 86.7 81.4 88.1 EN ISO 5163
Research octane no 95.5 90.2 103.2 EN ISO 5164
Lead content, mg/l <2.5 <2.5 <4.0 EN 237
Benzene content, vol. % 0.76 0.73 0.38 EN 238
Sulphur content, mg/kg 5.6 3.8 5.2 EN ISO 20846
Existent gums, mg/100 ml 1.0 1.0 <1.0 EN ISO 6246
DVPE, kPa 60.0 82.2 51.4 EN 13016-1
Fugacity index VLI 848 862 714 EN 228
Fractional composition
Up to 70 °C, vol. % 36.6 39.7 28.6 EN ISO 3405
Up to 100 °C, vol. % 58.2 60.0 85.3
Up to 100 °C, vol. % 92.9 92.4 90.2
Finish of distillation FBP, °C 191 192 191.7
Residue, vol. % 1.0 1.0 1.0
Content of organic oxygen compounds, vol. %
MEOH 0.0 0.0 0.0 ASTM D 4815-09
ETOH 5.0 9.2 49.76
IPA 0.0 0.0 0.0
TPA 0.0 0.0 0.0
IBA 0.0 0.0 0.0
Ethers (containing 5 or more 5.8 5.2 1.4
C atoms)
this chromium concentration in combustion gases is not enough for the growth of an
entirely compact chromia scale.
Consequently, this material is less resistant to corrosion in combustion gas envi-
ronments than in an atmosphere, where only oxidation occurs, yet much more
resistant compared to the three remaining steels with lower chromium concentra-
tions, insufficient to inhibit the corrosion process, which leads to the formation of
heterogeneous scales, mainly composed of unprotective iron oxides.
It should be mentioned that in previous studies it was not possible to unambigu-
ously identify a single component of the complex atmosphere of combustion gases
responsible for such a rapid increase in corrosion rate compared to that observed in
air. In that regard, the influence of water vapor presence [39] and acetic acid (created
during ethanol combustion) [40] was tested, but in each case, the corrosion rate was
never as high as that in combustion gases. Probably, it is not a single component that
is responsible for the higher valve steel corrosion rate in combustion gases, but a
synergy effect of several different components.
Fig. 5 Comparison between oxidation kinetics of discussed valve steels under thermal shocks,
investigated in petrol and fuel oil combustion gases with different additions of bio-components, and
those obtained in pure air [34]
In practice, a comparison of the kinetics results presented in Fig. 5 allows for

the conclusion that engine valves should in the future be manufactured only from
X33CrNiMn23-8 steel. It is important in the case of a further increase in bio-additives
and, in particular, FAME to fuel oil. Otherwise, the possibility of using protective
coatings to reduce the corrosion rate of engine valves should be considered. An
additional argument in favor of using coatings to protect engine valves is the fact
that the valves achieve a maximum operating temperature that is about 30 K higher
when using diesel oil with 10% FAME addition [41]. This measurable increase in
temperature further increases the degradation rate of the valves, regardless of how
aggressive the exhaust gases are. The second practical remark resulting from the data
illustrated in Fig. 5 relies on the observation that, in order to reduce the huge costs
of testing using exhaust gases in an engine test house, preliminary results can be
obtained by examining the oxidation rate of individually coated steels in air. As a
result of the research carried out so far, it turns out that if a given material behaves
well in the air, it will also be more resistant in the atmosphere of exhaust gases than
other steels.
4.3 Oxidation in Combustion Gasses of LPG Fuel
Since the beginning of the 1990s, there has been a steady increase in the number of
passenger cars equipped with gas installations that enable LPG (liquid petrol gas)
fueling. For economic reasons, i.e. much lower prices of LPG than gasoline, as well as
relatively low costs of gas supply installations, this trend is visible in many countries
around the world. Unfortunately, the use of LPG to power car engines is the cause of
their higher failure rate, which can be usually visible after driving 50–100 thousand
kilometers [42].
As engine valve corrosion in the atmosphere of LPG exhaust gases has not been
the subject of systematic research, the first studies carried out using the thermal
shock method in the apparatus schematically presented in Fig. 1 were published
relatively recently [43]. These studies were carried out in the atmosphere of real
LPG exhaust gases, obtained from the combustion engine working in the engine test
house of the “BOSMAL” Automotive Research and Development Institute (Bielsko-
Biala, Poland). Comparison of the results obtained from the discussed tests with the
data obtained in the atmosphere of real exhaust gases of petrol with 5% ethanol
content shows that the corrosion rate of the tested materials in both types of aggres-
sive atmospheres is comparable. This means that, contrary to popular opinion, the
“aggressiveness” of the exhaust gases obtained during the combustion of LPG is
not greater than the “aggressiveness” of the exhaust gases of currently used fuel in
gasoline engines. This conclusion is confirmed by both morphological observations
of the tested samples surface and by phase composition analysis of scales formed on
particular steels in both atmospheres.
Conversely, the short-lived service of valves and other components of internal
combustion engines adapted to LPG combustion—repeatedly reported by users in
the mass media—should be associated with the gas combustion conditions of LPG
in the engine, and above all with a higher combustion temperature compared to that
of the same engine powered by traditional fuel. Application of LPG fuel increases
the temperature near the engine valves by 30–50 K, which significantly reduces the
heat-resistance of steel [34, 38]. It should be added that the temperature increase in an
engine that is not adapted to this also negatively impacts the mechanical properties of
the valves. Both of these factors should therefore be held responsible for the increased
wear of LPG-powered engines. From a practical point of view, it is recommended to
consider using only steel with the highest chromium content, i.e. X33CrNiMn23-8
steel, for manufacturing valves if LPG fuel is used. Another more costly solution
to the problem of increased corrosion of the internal combustion engine elements
would be a design that enables the dissipation of a significant amount of heat from
the engine head and the valves. In that light, a better alternative seems to be the
development of appropriate protective coatings.
5 Thin Chromium-Based Coating Protective Properties

Against High Temperature Oxidation of Valve Steels
In the last two decades, the issue of automobile engine valve corrosion resistance has
become increasingly more important. As presented in the previous subsection, this
situation results from, on one hand, the application of alternative fuels in automobile
industry, such as biofuels, the combustion gases of which are very aggressive and, on
the other hand, an increase in operating temperature of modern internal combustion
engines. One of the solutions to this issue is to apply protective coatings on engine
valve surfaces. As already mentioned, preliminary results on the protective properties
of thin chromium coatings [15] appear to be very encouraging for more systematic
studies. In all these investigations thin chromium-based coatings were deposited on
sample surfaces of the discussed four valve steels as a layer around one micrometer
thick, using the magnetron sputtering method. Details on the sputtering process
are given elsewhere [15]. Coated valve steel samples obtained in such a manner
were the subject of corrosion tests under isothermal and thermal shock conditions
[44]. In the conducted research, the effect of chromium coating thickness on steel
oxidation resistance was also investigated. In addition, the effect of small yttrium
addition was tested [44], due to the well-known fact that small percentages of reactive
element (RE) additions enhance the adherence of the oxide scale grown on iron- and
nickel–chromium alloys [1, 2, 6, 45–50]. Studies of the effectiveness of coatings also
included testing the resistance to oxidation of nickel-chrome coatings with different
nickel contents [51]. The most important experimental results are presented in the
subsequent subsections.
5.1 Chromium Coatings
Comparing the oxidation rate at a constant 1173 K temperature of the discussed four
valve steel with a chromium layer either one or two micrometers thick, where the
one micrometer thick chromium coating contains yttrium, with that of the respec-
tive uncovered steels (Fig. 2) leads to the conclusion that thin chromium coat-
ings, in general, improve oxidation resistance, Fig. 6, wherein the thicker coat-
ings the lower the oxidation rate. The best effect of coating application is visible
in the case of X33CrNiMn23-8, while the worse oxidation resistant shows coated
X55CrMnNiN20-8 steel. It is interesting that during the initial stages of oxidation,
up to about 10 h, all coated steels are oxidized approximately with the same rate.
Yttrium addition present in coatings plays a very positive role, limiting oxidation rate
even of X55CrMnNiN20-8 steel during 50 h. In practice, it is extremely important
that the positive chromium influence on the investigated steel oxidation resistance
can be seen for a much longer duration than the chromium coating lifetime itself.
The chromium layer can be observed up to around 15 h for each coated steel, after
which the coating disappears. However, despite a metallic chromium layer no longer
being present on the surface of investigated steels, the oxidation resistances of the
studied steels remained on the same level, with the exception of X55CrMnNiN20-8
steel covered by a one micrometer thick coating. This statement is supported by the
virtually unchanged character of the kinetic curves illustrated in Fig. 6. The visible
differences in the investigated materials can be interpreted in terms of different phase
compositions of the scale growing on surfaces of individual steels. Chromium present
in the coating favors formation in the initial stage of oxidation of highly protective
Cr2 O3 oxide, instead of Fe3 O4 and Fe2 O3 (Fig. 7).
The obtained results denote the possibility of developing novel innovative thin
coatings that provide protection for valve steels against oxidation at high tempera-
tures. The chromium coating’s beneficial influence on the steel’s oxidation resistance
may be additionally increased by the application of yttrium. It has been shown that
yttrium addition, electrochemically deposited on the coating in the amount of 2 ×
10–6 kg/m2 (1023 Y3+ ions/m2 ) has a positive effect on the heat-resistance of all
studied steels.
It is very important that chromium coatings increase the investigated steel’s heat-
resistance not only under isothermal conditions, but also thermal shocks, Fig. 8.
In this case, the beneficial effect of yttrium on the valve steel’s scaling-resistant
properties can also be observed, even though its impact is not as great as in the case
of studies performed at constant temperatures.
It is worth emphasizing that thin chromium coatings behave very well not only
in purely oxidizing conditions but also in the atmosphere of real combustion gases.
In these conditions, even after a 100 h test performed in an engine test house, the
remains of the chrome coating are clearly visible, in spite of the partial oxidation
and diffusion, Fig. 9. This distinctly suggests that it is possible to use a thin coating,
which can remain present even after a relatively long period of oxidation time.
5.2 Chromium–Nickel Coatings
Although thin chrome coatings, as described in the previous subsection, signifi-

cantly increase high temperature oxidation resistance of valve steels, the funda-
mental question remains whether this is the optimal solution or whether it is possible
to choose a different, perhaps better strategy of conduct. The strategy of enriching
the chromium coating with additional elements that would synergistically improve
oxidation resistance could potentially be more beneficial than the use of pure
chromium coatings.
Analysis of the literature data leads to the conclusion that nickel could be such
an additional element. It is known, namely, that chromium-containing valve steels
with higher nickel content demonstrate improved heat-resistance due to their outward
chromium diffusion becoming enhanced leading to the formation of a highly protec-
tive chromium oxide scale [37]. Such an effect was also indirectly confirmed in
studies described in the work [36]. Thus, it is very interesting to see whether the same
phenomenon can be determined in the case of both chromium and nickel-containing
Fig. 6 Oxidation kinetics

comparison for four valve
steels with different types of
coatings, obtained at 1173 K
in air
Fig. 7 X-ray diffraction

patterns for the Cr-coated
and unmodified
X50CrMnNiNbN21-9 steel
oxidized for 100 h in air
atmosphere at 1173 K
thin coatings. To verify this working hypothesis, chromium-nickel coatings with a

nickel content of 10 and 50 wt.% were deposited on valve steel samples, which were
then subjected to oxidation tests under isothermal conditions and thermal shocks
[51]. The results of the oxidation rate tests performed at a constant temperature of
1173 K in air are shown in Fig. 10. The kinetics results shown in this figure demon-
strate that the use of chromium-nickel coatings results in lower oxidation rates for
the investigated valve steels. This is especially evident in the case of the Cr–50%Ni
coating, which provides better corrosion resistance compared to pure chromium for
X33CrNiMn23-8 steel throughout the entire duration of the test. In the case of other
steels, this enhanced corrosion resistance is only seen after a certain initial period that
lasts around 20–60 h. Conversely, the Cr–10%Ni coating guarantees generally lower
heat-resistance compared to that provided by a chromium layer with the exception
of X55CrMnNiN20-8 steel, for which such oxidation courses are comparable.
In turn, after an initial oxidation period of about 50 h, X53CrMnNiN20-8 steel
with Cr-10%Ni coating experiences faster oxidation than the same uncoated steel. It
can be added that the positive influence of all the coatings on each steel can be clearly
seen and is visible for a longer duration than required for oxidizing a one micrometer
layer of pure chromium or nickel. Results presented in Fig. 10 strongly confirm the
benefits of nickel addition to chromium coatings, however, it is necessary to find
the optimal nickel content in the coatings, which may be different for various steel
grades. At this point, it should be noted that yttrium’s influence on the heat-resistant
properties of chromium-nickel coatings has never been investigated. However, based
on previous experience in this field, it can be expected that it will additionally reduce
the oxidation rate.
While the results of oxidation kinetics studies in isothermal conditions on steels
covered with chromium-nickel coatings can be considered extremely promising and
may suggest the potential possibility of using these coatings in practice, the results
of tests under thermal shock conditions are not as exciting. As shown in Fig. 11,
Fig. 8 Oxidation of
chromium and Cr-Y coated
valve steels under thermal
shock conditions performed
at 298–1173 K in air
Fig. 9 SEM cross-section microphotograph of the scale formed on a valve surface coated with a
1 μm layer obtained after an engine test
Fig. 10 Influence of nickel present in chromium coatings on the oxidation rate of four types of
valve steels at 1173 K in air [51]
Fig. 11 Oxidation kinetics under thermal shocks (298–1173 K) performed on four valve steels
both covered with different types of coatings and unmodified [51]
only X53CrMnNiN20-8 steel coated by Cr–50%Ni features a degradation rate that

is clearly lower than those observed for the same steel with chromium coating. This
result suggests that, for the above-mentioned steel, the Cr coating enriched with 50
wt.% Ni is more appropriate than other tested compositions. On the other hand, the
nickel content in the coating was probably not chosen optimally in the case of other
studied steels. It is therefore reasonable to expect that a much better resistance against
oxidation provided by Cr-Ni coatings with a properly selected composition can be
obtained. However, this requires further intensive corrosion tests.
6 Summary
All the results presented in this work clearly indicate the unnoticed up to now potential
of thin chromium-based coatings, which enables their utilization for high temperature
corrosion protection of engine valves. However, these coatings can potentially be
used not only in automotive industry, but in several branches of modern industry and
are not just limited to valve steels but can work equally as well in conjunction with
other alloys, including different grades of austenitic and ferritic steels. Particularly, in
devices or complex mechanisms containing moving parts, made with the tolerance
of the order of micrometers. In this context, it is worth mentioning that there are
attempts to use thin chromium coatings with a thickness of only a few micrometers
to protect materials in nuclear power plants [52–55].
Finally, it should be added that metallic coatings are not the only type of coat-
ings that could potentially be used to protect engine valves against high temperature
corrosion. Recently, thin ceramic coatings based on SiC [56] and SiCO [57], with
a thickness of about one micrometer, have been developed, which to an unexpect-
edly high degree protect steels against oxidation at high temperatures. Therefore, all
available literature data allows us to conclude that a new period of intensive research
has begun, aimed at using thin protective coatings in high temperature applications.
Potentially, these studies may in the future lead to the massive usage of such kind
of coatings in a number of industries where currently used materials are unprotected
by means of high temperature corrosion.
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Protective Coatings
for High-Temperature Thermoelectric
Materials
S. Nanthini, Pandiyarasan Veluswamy, and H. Shankar
Abstract Thermoelectric materials (TEM) are one of the renewable energy sources
which convert heat directly into electricity without the emission of any harmful
gases and can fulfill the present energy demand. TEM seems important because it
is lightweight, has low synthetic cost and better environmental stability, is highly
durable, and can be integrated into many forms. A good thermoelectric material
should have a maximum power factor and minimum thermal conductivity. According
to the operating temperature, thermoelectric materials are classified into three ranges,
low (up to 450 K), medium (up to 850 K), and high temperature (up to 1300 K).
Low- and medium-temperature materials are generally used for power generation and
cooling applications, and high-temperature TEM is used in industrial applications
like high-heat piping, power stations, aircraft parts, energy sectors, and many metal
protection systems. TEM is prone to oxygen corrosion and sublimation when used
in a high-temperature environment. It lacks long-term stability, performance degra-
dation, and repeatability loss in heating–cooling cycles and will further decrease its
properties. This chapter summarizes various types of protective coatings and their
properties, and the importance of careful selection and design to achieve effective
protection for high-temperature thermoelectric materials is highlighted.
Keywords Thermoelectric materials · High temperature · Protective coatings ·

Corrosion · Sublimation
S. Nanthini · H. Shankar (B)

Department of Physics, KPR Institute of Engineering and Technology, Arasur, Coimbatore,
Tamilnadu 641407, India
e-mail: shankarnh@gmail.com
S. Nanthini · P. Veluswamy (B)
SMart and Innovative Laboratory for Energy Devices (SMILE), Indian Institute of Information
Technology Design and Manufacturing (IIITDM), Kancheepuram, Chennai 600127, India
e-mail: pandiyarasan@yahoo.co.in
P. Veluswamy
Department of Electronics and Communication Engineering, Indian Institute of Information
Technology Design and Manufacturing (IIITDM), Kancheepuram, Chennai 600127, India
312 S. Nanthini et al.
1 Thermoelectric Materials—Introduction
Thermoelectric materials are a class of materials that can convert thermal energy
into electrical energy and vice versa. Typically, these materials are composed of
intermetallics or semiconductors that incorporate elements such as Sb, In, Ge, Bi,
Te, Pb, Mg, Mn, Si, or Co [1]. Researchers have made significant efforts to develop
thermoelectric materials (TEM) with high figures of merit. Several techniques have
been employed, such as doping with elements or composites, band convergence,
quantum confinement, nano-structuring, and meso-structuring. These techniques are
used to adjust the electrical properties and improve the power factor (PF = S 2 σ )
(Wm−1 K−2 ) of TEM [2]. It works on the principle of the Seebeck effect, i.e., when
the temperature difference is applied between two sides of different materials, a
voltage is created. There are three main components of a thermoelectric device: a
p-type leg, an n-type leg, and an electrode. When selecting a thermoelectric material,
one needs to look into a term called Figure of Merit. It can be written as
S2 σ T
ZT = (1)
κ
where ZT—Figure of merit, σ —Electrical conductivity (Sm−1 ), S—Seebeck coef-

ficient (VK−1 ), T—Temperature, and K—Thermal conductivity (Wm−1 K −1 ) of the
material. Therefore, a good thermoelectric material should have greater values of σ
and S, ZT and lower value of K. Thermal conductivity is a material property that
describes a substance’s ability to transfer heat either by the electron or through the
vibrations of the lattice (phonons) as
K = KE + KL (2)
where K E is the thermal conductivity of electron and K L is the thermal conductivity

of phonons [2]. Research on TEM, for decades, has focused on discovering new
materials with a higher figure of merit. Some of the earlier materials found were
Bi2 Te3 and PbTe [3], and now recent research has focused on growing new materials,
and only very few of them turned into excellent TEMs that is, it shows an increased
figure of merit greater than 1. This chapter is intended to provide a comprehensive
introduction to thermoelectric materials and the field’s current state. It will be helpful
for those interested in learning about the fundamentals of thermoelectric, as well as
for researchers and engineers working in the field.
Classification of TEM Based on Operating Temperature
The classification of thermoelectric materials based on temperature is shown in Fig. 1
[3–6].
1. Low-temperature thermoelectric materials (up to 450 K) Bismuth Telluride

(Bi2 Te3 ), alloys of Bi with (Sb, Se), Sb2 Te3 , etc.
Protective Coatings for High-Temperature Thermoelectric Materials 313
Fig. 1 Classification of
thermoelectric materials
based on temperature
2. Medium-temperature thermoelectric materials (up to 850 K) Chalcogenides

(e.g., Cu2 Sb, AgSbTe2 ), intermetallics (e.g., Ni2 MnGa, MnCoGe), oxides (e.g.,
Ca3 Co4 O9 , BaTiO3 ), Heusler alloys (e.g., CoSb3 , NiMnSb), etc.
3. High-temperature thermoelectric materials (up to 1300 K) SiGe, skutteru-
dites (CoSb3 ), clathrates (Ba8 Au13 Ge40 ), (CeFe4 Sb12 ), etc.
From the above materials, bismuth telluride [2] is the most studied material at
low temperatures (Operating Temperature (OP)—320 K) since it has a high figure
of merit and good thermal stability. The limitation of this material is its scarcity and
highly toxic nature. This temperature range suits air compressors, internal combus-
tion engines, and furnace doors. The highest figure of merit reported so far is around
2.5 at a temperature of around 600 K (327 °C). This value was obtained using a
combination of doping and nano-structuring techniques to improve the material’s
thermoelectric properties.
The figure of merit (ZT) value of a thermoelectric material is dependent on the
temperature, and the value of 1.6 at 800 K for the compound Ca3 Co4 O9 [7] is
considered to be one of the highest values achieved for medium-temperature ther-
moelectrics. The search for new and more efficient thermoelectric materials is an
active area of research, and new materials with even higher ZT values are expected
to be discovered in future. This temperature range applies to steam boiler exhaust,
heat-treating furnaces, etc.
At higher temperatures, the figure of merit is achieved more than 1, and the highest
figure of merit (ZT) value reported is around 2.5 at a temperature of around 1273 K
(about 1000 °C) for skutterudites. Skutterudites [4] are a class of compounds with
the general formula AM3 X 4 , where A is a metal, M is a transition metal, and X is
a chalcogenide. This value was obtained using a combination of doping and nano-
structuring techniques to improve the material’s thermoelectric properties. It’s worth
mentioning that this value is still not high enough for practical use, and research is
ongoing to increase the ZT of high-temperature thermoelectrics. Other than skut-
terudites, SiGe alloys: OP—1173 K, also have significant importance in high TEM
with the only limitation of material scarcity. New thermoelectric materials called
Phonon-Liquid Electron Crystal (PLEC) [4] possess low thermal conductivities and
a figure of merit of around 1.5. These materials are applied in marine, aircraft, and
turbine blades as protective coatings. The upcoming topics will discuss a detailed
view of high-temperature materials and their application as protective coatings.
Way to Protect High-Temperature TEM
Thermoelectric materials have one major limitation: short lifespan. When these mate-
rials undergo to high temperatures, they result in sublimation, corrosion, and also
oxidation [8]. To prevent this degradation at elevated temperatures, high-temperature
TEM are coated with different coating materials like glass coating [9], hybrid coat-
ings [10], silane-based coatings [11], amorphous coatings [12], MoSi2 coatings [13],
and so on. In order for a protective coating on thermoelectric materials to be effective,
it should meet three crucial requirements.
1. Thermoelectric—Should have poor electric conductivity to prevent short-
circuiting and thermal conductivity to prevent parasitic heat loss.
2. Chemical—Should have good adhesion and stability and be inert to the substrate
(TEM).
3. Thermomechanical—Should have high tensile strength for durability [12].
Glass is often considered the ideal material for coatings owing to its high stability,
excellent electrical and thermal insulation, and ease of application. The key factors
determining the suitability of glass coatings are the coating temperature and thermal
expansion properties. Ideally, the coating temperature should be within the range of
the glass transition temperature T g and the softening temperature T s . Beyond T g , the
thermal expansion of the coating tends to increase.
Therefore, coatings are necessary to decrease oxidation, enhance emittance, and
decrease the ability for recombination of dissociated hot-gas species for the specific
materials in question. They also provide environmental protection and thermal
control. A detailed view of the coating and its history with different fabrication
methods are described below.
2 Coatings
Coating involves applying a material layer to the surface of a substrate to improve

its properties, protect it from wear and tear, corrosion, and oxidation, and ultimately
give the product a radiant appearance. The coating is the last stage of production,
where it can be applied to almost all products with the thickness ranging from a
few microns to millimeters, and it has diverse applications like machinery, all types
of equipment, construction, sports, and also in high-temperature applications like
turbines blades, combustion chamber, etc. The characteristics of coating materials
should have high impact resistance, chemical resistance, and abrasion so that it
doesn’t disturb the substrate material’s properties. Coatings have to be in the form
of continuous thin films, and if any imperfection occurs, it may be the root cause to
get corrode and breaking the structure. It should withstand all exposures, climatic
conditions, and different types of resistance like physical, chemical, water, and high
temperatures. Different coatings are done by considering epoxy, acrylics, silicones,
and polymer resins, organic and inorganic materials as bases and can also be applied
to their particular applications accordingly. In the upcoming topics, we will detail the
history of coating technology, the mechanism behind and different coating processes.
2.1 Background of Coating Techniques
In ancient times, coatings were majorly used for decorative purposes, which vibrated
their mind and also conveyed many interesting stories behind them. Later, people
also used coatings as a protective tool that shows resistance to oxidation, corrosion,
etc.; generally, coatings are done for two main purposes [14].
1. Decoration
2. Protection.
Decorative Coatings
Coatings have been utilized as a form of communication throughout history. Early
on, people used various materials to draw, paint, and create signs on various surfaces,
including walls [15], stones, and caves [16, 17]. These works of art conveyed a range
of messages, from indicating hunting records and migrating patterns of animals
expressing religious ceremonies, etc. Renaissance people first started coatings for
decorative purposes, mainly for communication. Next to it, Altamira’s paintings
convey directions or some information by embossing a picture of animals on rocks.
Three different techniques were used by Lascaux chalk, a swab, and an innovative
technique [14]. These paintings are expected to be drawn in (15,000–13,000 BCE).
Mostly their drawings were bull and bison, which were engraved—scratching the
outer layer of rock, which creates differences in colors. They also used spray paintings
to paint different parts of the bison’s body.
Thousands of years ago, people were making art with stones; as their name indi-
cates, “Stone Age Artists” made simple stone tools to cover their artworks in caves.
Historically, they are classified into three distinct eras: Paleolithic (from 2,500,000
to 10,000 BCE), Mesolithic (from 10,000 to 4,000 BCE), and Neolithic (from 4,000
to 2,000 BCE) [18].In each period, the usage of tools became a little different and
stronger than before. Their paintings were of clay ochres, iron oxide, manganese
oxide, and charcoal for producing different colors like red, yellow, and black. They
also used natural polymers and colloids for their artworks. Aborigines [19] are the
creators of rock art that was created over a period of 43,000 years. They used earth
pigments as their source for paintings.
Oceanians [20] were religious and cultural, and their artworks are complex to
predict. These people will almost do Petroglyphs, Tattooing, wood carving, etc.
Their works are mostly related to temples and monuments. Asians [14] started their
paintings with different sources like beeswax, gelatine, and egg white, and their
works are more related to natural pigments which add up different colors for their
artworks. In the Zhou dynasty (1111–255 BCE) [14], they used lacquer to make food
utensils, decorate carriages, bows, arrows, musical instruments, and even decorate
buildings. Hence, in ancient days, different people used many different types of
coating techniques for decorative purposes, as shown in Fig. 2, History of Decorative
Coatings.
Protective Coatings
As shown in Fig. 3, Egyptian artists [21] used both local and imported materials
for their artworks using a wide range of material collections. They used limestone,
sandstone, quartz, calcite, sedimentary diorite, basalt, metamorphic quartzite, etc., for
making statues, temples, and sculptures. Two different kinds of stones are available
hard and soft stones (based on the Mohs scale), where hard can be directly used, and
soft layered materials are coated. Stones with a variety of colors indicate different
relationships; black stone [22] indicates the life-giving silt of the Nile, whereas green
stone [22] indicates living things, and red indicates [22] sun gods. Plasters are filled
upon these stones to increase their lifetime as coatings. Lake pigments were used
Fig. 2 History of decorative coatings

Fig. 3 History of protective coatings
to avoid fading in the presence of sunlight. They use a binding medium [23] that
consists of various materials like resins, gums, egg tempera, etc., Various types of
coatings and layers were applied on those sculptures, and this is why those very old
monuments withstand all types of climatic conditions.
During the Medieval Age (500–1400), artists utilized a painting technique called
egg tempera, where the pigments were blended with water and egg before being
applied. The dried protein serves as a binder and evaporates, leaving the pigment
to adhere to the surface. These forms of paintings give perfect finishing with thin
layers, hence medieval paintings look perfect and keen. In the fourteenth century,
coatings were oleo resinous type, which means materials consisted of spices, such
as cardamom, celery seed, cinnamon bark, clove bud, basil, capsicum, fenugreek,
and flax seeds. Oil extracted from flax seeds is called linseed oil [14], mostly used
in making paints and coating materials. The seventeenth century emerges with the
large-scale production of coatings, where recoating became frequent because of using
naturally and oxidizable available vegetable oils. At present, coating techniques have
become computer-based and operated with high technologies with various forms of
ingredients, colors, and pigment contents. Synthetic resins also play a major role in
making of these coatings solutions with emulsions, water-born polymers, and latexes.
2.2 Components of Coating Materials and Its Importance
Coating technology is an interdisciplinary topic where it deals with all the fields of
experts together to solve specific purposes like
. Microbiologist/Medical Expert—to have resistance to fungal, bacterial, and

hygienic properties.
. Material Scientists—to prevent corrosion (including anticorrosive pigments),
oxidation, and abrasion resistance.
. Designers/Artists—in terms of decorative purposes, whereas color coding also
gives improved working conditions, enhanced safety, and related physiological
effects.
. Environmentalist—by energy saving, increasing lifespan, and reducing toxicity
percentage.
The most important part of the coating is protecting the surface of the material
[24], which should withstand both physical and chemical effects by means of varying
climatic conditions like very high and very low temperatures. Liquid coating mate-
rials typically consist of various ingredients such as binders, plasticizers, additives,
solvents, pigments, and extenders, as shown in Fig. 4.
Binders
In coatings, binders refer to the non-pigment and non-extender components that
remain after the coating has dried or cured. They consist of film-forming agents and
additives of non-volatile components. The film-forming agent plays a critical role
in coating materials as it solidifies through either chemical or physical processes.
Typically, oligomers or polymeric organic materials are utilized as film-forming
agents owing to their capacity to stick on the substrate, offer mechanical robustness
with flexibility, and endure environmental degradation. These agents can be derived
from natural materials that have undergone chemical modification or are produced
through industrial synthesis [24]. Depending on their origin, filmformers can be
categorized as
. Natural substances
. Modified natural substances
. Synthetic substances.
Examples include [25]:
Fig. 4 Various ingredients of coating materials

Acrylics: Acrylic polymers and copolymers are widely used as film-forming

agents in water- and solvent-based coatings. They offer good weather ability,
adhesion, and UV resistance.
Polyurethanes: Polyurethane resins are commonly used as film-forming agents
in coatings for their excellent adhesion, flexibility, and durability.
Epoxies: Epoxy resins are used as film-forming agents in coatings for their high
adhesion, chemical resistance, and durability.
Vinyls: Vinyl polymers and copolymers, including PVC (polyvinyl chloride), are
commonly used as film-forming agents in coatings. They offer good flexibility,
adhesion, and weather resistance.
Cellulose Derivatives: Cellulose derivatives such as methylcellulose and hydrox-
ypropyl methylcellulose are used as film-forming agents in coatings and paints.
They provide good film-forming properties and can provide controlled release of
active ingredients.
Alkyds: Alkyd resins are commonly used as film-forming agents in solvent-based
coatings for their good adhesion, gloss, and durability.
Silicones: Silicone resins and polymers are used as film-forming agents in coatings
for their excellent heat resistance, weather ability, and gloss.
Polyesters: Polyester resins are used as film-forming agents in coatings for their
good weather ability, chemical resistance, and adhesion.
Inorganic materials can also be used as film-forming agents. Some examples are
metal oxides, silicates, and clays used in various applications, including coatings,
paints, and cosmetics. Metal oxides, such as titanium dioxide and zinc oxide, are
commonly used as film-forming agents in sunscreens and other cosmetic products due
to their ability to create a protective barrier on the skin. Silicates, such as magnesium
silicate and aluminum silicate, are often used as film-forming agents in cosmetics,
pharmaceuticals, and food products. Clays, such as kaolin and bentonite, are also
used as film-forming agents in cosmetics and personal care products [25].
The film-forming agent’s properties and their suitability for different applications
are determined by the shapes, sizes, and functional groups of the molecules. Linear
molecules exhibit different characteristics compared to branched ones. Dendrimers
are polymers with a tree-like structure that have a large number of chain ends,
enabling a higher level of functionality despite their relatively lower molecular
weight. This structure results in a high crosslink density, which can significantly
impact the processing properties and final quality of the product. Additionally, the
size and size distribution of dendrimer molecules can have a substantial effect on
these properties [24].
Plasticizers
Coatings can be made more flexible [26] by adding plasticizers, which lower the
film-forming temperature. Plasticizers work by impeding the formation of bonds
between film-forming agents, which can be accomplished by introducing elasticizing
segments or monomers during production. These substances are largely chemically
inert and do not affect the resistance of the coatings to various substances such as
gasoline, oils, and soaps. They are also resistant to UV light and considered safe
for human use. Classic plasticizers are liquid or solid, organic substances with low
vapor pressure, typically of an ester-like nature, and they do not chemically react with
the polymer but interact with them by swelling properties and form a homogeneous
mixture. They have polar and nonpolar molecular particles, enabling them to interact
with polar groups of the film-forming agents and prevent intermolecular interaction
between resin molecules by steric hindrance, promoting their mobility.
Additives
Additives are used to improve the properties of paint during production and appli-
cation. They can prevent pigments from settling, improve flow and smoothness, and
enhance the paint’s resistance to UV radiation and damage from bacteria or mildew.
They are typically added in small quantities but have a significant impact on the final
product. It is important to use the correct amount of the correct additive, as too little
or too much can have the opposite effect. Additives can be used to modify various
properties of paint, and are often multifunctional, serving multiple purposes at the
same time. They are used to form and stabilize the film properties of the paint [27].
Additives play a crucial role in the final coating film’s production, processing,
and formation as they are added in small amounts to raw materials or coating mate-
rials. These substances have multiple functions that can impact various properties of
paints and finished coatings, including improving resistance to aging. Tenside-based
substances are often utilized as wetting agents and materials for pigment dispersion,
and they can also serve as defoamers or anti-settling agents.
When formulating coatings, the assumption is often made that the desired proper-
ties can be attained by utilizing appropriate film-forming agents or superior-quality
pigments. However, if this strategy proves unsuccessful, additives may be incorpo-
rated to enhance the coating’s characteristics. Care must be taken when determining
the appropriate dosage of additives as they are typically used in small quantities and
can have a significant impact on the final properties of the coating. If the dosage is
incorrect, the desired effect may not be achieved or the coating may be negatively
affected. Additives [28] can be classified based on their intended use and are often
multifunctional, affecting multiple properties of the coating at once. For example,
substances with a tenside structure can be used for dispersing pigments, reducing
foam, preventing floating, and modifying the processing properties of water-based
paints. Additives are used to improve the film properties and stability of coatings.
Solvents
In order to achieve successful processing and film formation, it is essential to carefully
select and combine the appropriate materials. The selection of suitable combinations
of solvents must be based on the type of resin used. Selecting the right solvent
combinations with suitable evaporation properties is crucial to maintain a balance
between the flow and stability of paint applied to vertical surfaces. While water is
a common solvent used in environmentally friendly paints, its purpose differs from
other solvents.
Solvents [29] are liquids that are used to dissolve film-forming agents in coating
materials, and they evaporate quickly and completely once the coating is applied.
Unlike reactive thinners, plasticizers, and additives, solvents do not chemically react
with the resin and do not remain in the film. Their main function is to make the
coating material easier to process and apply by reducing its viscosity and improving
its sprayability, coatability, rollability, or dippability. The strength of the solvation
depends on the interactions between the molecules of solvents and film-forming
agents. Solvents are used with the aim of achieving a homogeneous liquid phase of
all constituents present in the coating material.
Pigments
Pigments [28] play a crucial role in coatings, providing the desired color intensity and
hiding power and dependent on their chemical physical properties such as crystalline
structure and the crystal shape and size. They also enhance the protective proper-
ties of the coating, such as resistance to corrosion, UV radiation, light scattering,
and selective absorption. When combined with film-forming agents, solvents, and
additives, pigments create opaque coating materials. Clearcoats, on the other hand,
are transparent and are used to seal wood, plastics, and metallic coatings. In order
to create color, hiding power, and special optical effects, fine, insoluble particles
known as pigments are added to coating mixtures, which are resistant to weather,
heat, and chemicals. Additionally, color pigments can offer functional properties
such as sandability and hardness [24]. The general term “colorant” encompasses all
types of additives used for coloring, including pigments and soluble dyes. There are
several types of pigments used in coatings, including [24]:
Inorganic Pigments: These are pigments made from inorganic compounds such
as metal oxides, sulfides, and carbonates. Examples of inorganic pigments include
titanium dioxide (white pigment), iron oxide (red, yellow, and brown pigments),
and chromium oxide (green pigment).
Organic Pigments: These are pigments made from organic compounds such as azo
dyes, phthalocyanine, and quinacridone. Examples of organic pigments include
phthalocyanine blue and green, quinacridone red, and azo yellow.
Metallic Pigments: These are pigments made from metallic flakes such as
aluminum, bronze, and copper. Metallic pigments provide a metallic or reflec-
tive appearance and are commonly used in automotive coatings and decorative
coatings.
Pearlescent Pigments: These are pigments made from mica coated with metal
oxide. Pearlescent pigments provide a pearl-like or iridescent effect and are
commonly used in automotive coatings, cosmetics, and decorative coatings.
Fluorescent Pigments: These are pigments that absorb light at one wavelength
and emit it at a longer wavelength, producing a fluorescent effect. Fluorescent
pigments are commonly used in safety coatings and inks.
Phosphorescent Pigments: These are pigments that absorb and store light
energy and release it slowly over time, producing a glow-in-the-dark effect.
Phosphorescent pigments are commonly used in safety coatings and signs.
Interference Pigments: These are pigments that produce a color-shift effect

depending on the angle of viewing. Interference pigments are commonly used
in automotive coatings, cosmetics, and decorative coatings.
The properties to be considered while choosing the pigments are crystal structure,
particle size, shape, hardness, surface area, oil absorption, the quantity of pigment,
paint type, and formulation and also depending on applications [30]. The detailed
study of pigments can be referred from [31].
Extenders
Extenders [32], which are inorganic substances with varying chemical compositions
and physical properties, are added to coating materials to increase the solid content
and improve the mechanical properties of the coating. They do not have a significant
impact on the optical properties, such as scattering and hiding power, as they have
a refractive index of less than 1.7. When formulating coatings, extenders should be
considered along with pigments in order to calculate the pigment volume concentra-
tion, which is a key factor in determining the mechanical and technological properties
of the coating.
Extenders [28] are used to fill coatings and affect the mechanical properties of the
paint film. They do not have a significant effect on hiding power or light scattering but
are taken into account when calculating the pigment volume concentration (PVC).
The use of extenders can impact the impact strength, swelling power, and water
vapor permeability of the coating, and this effect can extend to the coating interface.
Extenders are primarily used in primers, fillers, primer surfacers, and dispersion
paints, but are used minimally in solvent-borne topcoats. They can enhance appli-
cation properties, such as sandability and hardness, and increase the non-volatile
content of the coating material. Their primary purpose is to improve the mechanical
and technological properties of the coating, rather than the optical performance.
2.3 Different Stages to Coat Materials
The process of coating technology is to make paints using the above-mentioned

components and transform into a functional coating. There are mainly 3 different
stages for coating a material or a substrate as shown in Fig. 5.
Stage 1: Selecting an appropriate substrate and pre-treating it.
Stage 2: Coating the substrate according to the specific application.
Stage 3: Drying and Curing using different techniques.
Stage 1: Substrate and Pre-treatment Methods

Selection of substrate [33] is an important factor, so the substrate should be thermally
stable, and it is the base where the coatings (paint and adhesives) are to be deposited
or coated. The nature of substrates can be rigid like metals, stones, and concrete and
Fig. 5 Different stages for coating material
they can also be flexible (paper, leather, rubber, and elastomers). Classification of
those substrates are listed in Table 1.
The pre-treatment process, which is crucial before applying a coating, varies
depending on the type of substrate being coated. This step is used to remove any
unwanted impurities from the surface of the substrate, and the method used will
depend on the specific material being coated.
Before applying coatings, it is important to properly prepare the substrate by
removing any unwanted impurities. The method of pre-treatment will vary depending
on the type of substrate, such as wood, metal, plastic, concrete, or rubber. For example,
on wood, the pre-treatment process may include brushing, cleaning, and sanding. On
metal, the pre-treatment process may include mechanical cleaning methods such as
brushing or sandblasting. On plastics, pre-treatment may include removing residues
from release agents. On concrete, pre-treatment may include surface treatment to
remove release agent residues. On rubber, impurities can be removed by washing
with solvents or detergents.
Stage 2: Coating Methods
Different coating techniques are used depending on the intended application. Tech-
niques for applying coatings at low and medium temperatures include methods
commonly used in the automotive industry, such as coating cars and vehicles.
Dip Coating
Dip coating [34] is a method of painting industrial goods that is easy to automate,
has a higher material yield, and has low capital costs. In the painting process, the
object to be coated is dipped in low-viscosity paint, then removed and conveyed to an
oven through a draining section. Adequate time is required for the solvents to drain
and evaporate, which helps to prevent surface defects such as blisters, pinholes, or
Table 1 Different substrates used for coating [24]

Substrates for coating process
Natural materials Synthetic materials
Organic Wood, rubber, leather, cardboard, Organic Thermoplastic materials,
paper elastomeric materials
Inorganic Stones, concrete Inorganic Glasses, alloys, iron, zinc
Fig. 6 Dip coating process
runs. For water-based dip paints, a lengthy blow-drying zone is typically necessary,
which is usually heated. However, it may be challenging to achieve a consistent film
thickness across all parts of the object (Fig. 6).
Additionally, paint tends to run, especially around edges, when using conventional
dip coating with water-based paints. Painting complex objects with cavities [24] can
exacerbate the aforementioned limitations. The process of evaporation and heating
in the oven can create a saturated vapor atmosphere within the cavities, hindering the
flow of air. Consequently, fresh paint film may be washed off due to condensation
resulting from the slower heating of cooler portions of the object. This can lead to
unpredictable weakening of cavity protection, which is difficult to monitor.
Disadvantages
It has several drawbacks such as a lack of uniformity in film thickness, defects like
runs and blisters, and the need for special precautions when using solvent-based
paints. The use of water-based dip coats is now prevalent due to concerns about fire
and explosion risks. However, even water-based dip coats have their own issues,
particularly when applied to complex objects with cavities. The process can result
in an uneven distribution of paint, and the build-up of vapor in cavities can cause the
paint to be washed off, leading to weakened protection of those areas.
Electro Coating
Coating complex objects in a more uniform manner without the risk of paint washing
out of cavities can be accomplished by using electrochemical deposition on electri-
cally conductive substrates. Applying a direct voltage between two electrodes causes
charged paint micelles or dispersion particles to move toward the electrode with the
opposite charge [35, 36] via a diffusion-controlled interface. This movement occurs
because of the change in pH value resulting from the electrolytic decomposition of
water [37]. If the surface charge of the dispersion particles is positive, they deposit
at the cathode, while if it is negative, they deposit at the anode.
One advantage of electrocoating [38] is its environmental compatibility due to low
emissions, and a high material efficiency of 99% or more can be achieved through the
use of ultrafiltration. Additionally, this method allows for a uniform coating of even
complex components [35–37], both inside and out, with a high level of reliability. In
2006, the global market for electrocoat paints was estimated at 1,000 kt, with about
300 kt being used by automotive manufacturers.
Roller Coating
There are two commonly used methods for applying coatings. The first method
is the direct application, which involves techniques such as brushing, manual and
mechanical rollers [39], and curtain or flood coating, and achieves high material
efficiency by directly transferring the coating material to the object. The second
method is indirect, which requires breaking down the material into small particles
before transporting it to the object. This method results in varying material yields
depending on the method of atomization used. Some methods such as electrostatic
spray coating can achieve yields of up to 98%, while other methods like pneumatic
atomization can have yields as low as 40%.
The oldest methods of applying paint, such as brushing and manual roller
coating, are primarily used for house painting. These methods are versatile and can
be used on complex shapes, they provide good and uniform paint distribution and
have a high material yield of nearly 100%. However, they have the disadvantages
of being slow, requiring skilled and experienced operators to produce smooth and
uniform coatings, and not being suitable for industrial-scale applications [24].
Coating methods such as mechanical roller, flood, and curtain involve the use
of a rotating dispensing roll (pick-up roll) and a transfer roll to transfer the coating
material from a storage tray to the object being painted. A smoothing roll (doctor roll)
may be placed between the pick-up roller and transfer roll to ensure a smooth film.
Each roll can be driven and controlled independently, allowing for a wide range of
film thicknesses to be achieved. These methods can produce texture-free films with
a uniform thickness profile and a high material yield of up to 100% using viscosities
of up to 600 mPa s. Reverse-operation machines can apply thicker films of up to 100
µm, while the synchronous system is limited to applying coatings of only 10–15 µm
with adequate surface smoothness [24].
The direct method of applying paint to objects, known as curtain coating, involves
pouring the paint onto the objects as they move on conveyor belts. From a storage
reservoir that contains a slit, the paint is transformed into a flowing curtain using a
pouring head. The film thickness is determined by the width of the slit and the feed
rate of the object. In case the width of the curtain exceeds that of the object or there is
no object present, any excess material is collected and filtered prior to being returned
to the pouring head. The coating process is maintained by allowing air bubbles to
escape in a settling chamber and by being able to open the pouring head for cleaning.
Flood coating involves applying paint to objects through nozzles as they pass by,
with excess paint being collected and filtered before being fed back to the nozzle.
This method is limited in its use due to the uneven film thickness and formation
of runs, leading to unattractive surfaces. It is mainly used for coating large items
such as engine blocks and radiators and is being replaced by other processes like
electrodeposition. Due to the high solvent evaporation in open systems, water-based
paints are mainly used in flood coating.
Direct coating methods such as drum coating, doctor coating (Fig. 7), and filling
are also used for applying paint to small components. In drum coating, the parts are
placed in a drum or cage with the paint and rotated or shaken. The excess paint is
then drained off and the film is dried or cured by heat. Doctor coating involves using
a coating knife or scraper to press highly viscous paint onto a paper or textile web,
resulting in uniform film thickness. This process is commonly used in the textile
and paper industries. Filling, on the other hand, is used for the manual application
of non-free-flowing coating materials. It is not as widely used as other industrial
methods.
Spray Coating
Indirect paint application methods, such as spraying, are widely used in industrial
paint processing despite their environmental drawbacks. These methods are used
to achieve a uniform coating on complexly shaped parts and are especially useful
when a wide range of colors and pronounced effects are required. To form a smooth
film on the object being painted, the process typically involves generating droplets
of paint, which can be achieved using various methods such as electrical forces,
centrifugal forces, accelerated air, or the energy of the paint itself. The droplets are
then transported to the object using shaping air [24].
Spray painting [40] is a popular method for industrial coating due to its ability to
produce uniform and attractive coatings on complex-shaped parts. Although spray
painting is a popular technique, it raises environmental concerns such as the formation
of overspray and the high emissions and paint waste generated by spray booths. A
specific droplet spectrum is necessary to obtain optimal results, with droplets that are
too small leading to increased material spill and solvent evaporation and droplets that
Fig. 7 Roller-supported
doctor blade method
are too large resulting in poor surface properties. Typically, a compromise is reached
with droplets that have an average size of 30–35 µm. To use this technique, a spray
booth in addition to the spray head is required, and the booth must have appropriate
systems for air intake, extraction, and paint supply.
Spin Coating
Spin coating [41] is a commonly used technique for depositing thin films onto a
substrate. It involves the application of a small amount of solution or dispersion onto
a substrate, which is then rapidly spun at high speed to spread the liquid into a thin
and uniform film. This process is repeated iteratively until the desired thickness is
attained. The spin coating process typically consists of the following steps, as shown
in Fig. 8:
Step 1: Preparation of the substrate: The substrate is typically cleaned and prepared
to ensure a uniform surface. The substrate is usually placed on a spin-coater chuck,
which is designed to hold the substrate securely during the spin-coating process.
Step 2: Application of the solution: A small amount of solution or dispersion is
applied onto the substrate, usually at the center of the substrate. The volume of
the solution is chosen based on the size of the substrate, the desired thickness of
the film, and the properties of the solution.
Step 3: Spinning: The substrate is then spun at high speed, typically in the range
of 1,000–8,000 revolutions per minute (RPM), for a specific time. The speed
and time of the spinning process can be adjusted to control the thickness and
uniformity of the resulting film.
Step 4: Evaporation: As the substrate spins, the centrifugal force spreads the liquid
into a thin film. The solvent or carrier liquid in the solution begins to evaporate,
leaving behind a thin layer of the desired material on the substrate.
Step 5: Drying: Once the spinning process is complete, the substrate is allowed to
dry completely to remove any remaining solvent or carrier liquid from the film.
Spin coating is a relatively simple and cost-effective technique for depositing thin
films with precise control over thickness and uniformity. Protective coatings applied
using spin coating can provide excellent barrier properties, corrosion protection, wear
resistance, and other protective functionalities. Spin coating is especially useful in
protective coating applications where a thin, uniform coating is required and high
throughput is desired. For example, spin coating can be used to apply a protective
coating of alumina to aluminum surfaces, which improves the corrosion resistance of
the metal. The spin coating can be used to apply a thin and uniform layer of protective
material onto the surface of the component [42], which provides protection against
moisture, scratches, and other environmental factors.
Atomic Layer Deposition (ALD)
Atomic Layer Deposition [43] is a vacuum deposition technique used to produce thin
films with precise thickness and composition. ALD coatings can provide high-quality,
uniform, and conformal films with precise thickness control, making them ideal for
a wide range of coating applications. One potential application of ALD coatings is
Fig. 8 Spin coating process
in the development of protective coatings for various substrates, including metals,

ceramics, and polymers. ALD coatings can provide excellent barrier properties and
can help to prevent corrosion, oxidation, and wear. For example, ALD coatings of
aluminum oxide, titanium dioxide, or zinc oxide have been used to protect surfaces
from corrosion and wear. ALD is a self-limiting process that involves the sequen-
tial exposure of a substrate to alternating pulses of reactive precursor gases. These
precursor gases react with the substrate surface to deposit a single atomic layer at a
time. The ALD process consists of the following steps (Fig. 9):
Step 1: Preparation of the substrate: Before the ALD process begins, the substrate
must be cleaned and prepared to ensure a uniform surface. The substrate
is typically placed in a vacuum chamber and heated to remove any surface
contaminants.
Step 2: Exposure to precursor gas: The substrate is exposed to a pulse of the first
precursor gas, which reacts with the substrate surface to form a monolayer of the
desired material. The pulse is then stopped, and the chamber is purged with an
inert gas to remove any excess precursor gas.
Step 3: Exposure to a second precursor gas: The substrate is then exposed to a
pulse of the second precursor gas, which reacts with the first monolayer to form
a second monolayer of the desired material. The pulse is then stopped, and the
chamber is purged with an inert gas to remove any excess precursor gas.
Step 4: Repeat process: Steps 2 and 3 are repeated until the desired film thickness
is achieved. The number of cycles required depends on the desired film thickness
and the specific ALD process.
The ALD process is highly controlled and allows for the deposition of uniform,
conformal films with precise thickness and composition. The self-limiting nature of
the process ensures that the film thickness is determined by the number of cycles
and is not dependent on the deposition time. ALD coatings of materials such as
Fig. 9 The atomic layer deposition process
silicon dioxide [44], aluminum oxide, and titanium dioxide can be used to improve
the performance of electronic devices by providing insulation, passivation, or antire-
flective properties. ALD coatings of materials such as zinc oxide, tin oxide, and
indium tin oxide can be used to provide transparent conductive coatings for solar
cells, displays, and other applications.
Plasma Electrolytic Oxidation (PEO)
PEO stands for Plasma Electrolytic Oxidation [45, 46] also known as Micro Arc
Oxidation (MAO), which is a surface treatment process that is used to produce
ceramic coatings on metals. The process involves immersing a metal component in
an electrolyte bath and then applying a high-voltage electrical pulse to the component,
causing a micro-arc discharge to occur. This micro-arc discharge generates a plasma
that interacts with the electrolyte and the metal surface, leading to the formation of
a ceramic oxide layer on the metal. The ceramic oxide layer produced by PEO is
typically very dense and adherent, with a thickness ranging from a few microns to
several hundred microns. This layer is highly uniform and can be engineered to have
specific properties such as high hardness, wear resistance, corrosion resistance, and
biocompatibility. PEO coatings can be produced on a variety of metals, including
aluminum, magnesium, titanium [47], and their alloys. The specific properties of the
ceramic oxide layer can be controlled by adjusting the composition of the electrolyte
and the processing parameters such as voltage, current, and pulse duration.
One of the key advantages of PEO over other surface treatment processes is its
ability to produce a highly porous coating [45]. The porosity of the ceramic oxide
layer can be used to incorporate functional materials such as lubricants or biologi-
cally active agents, allowing for the creation of multi-functional surfaces. PEO has
a wide range of applications, including in the aerospace, automotive, biomedical,
and electronics industries. In aerospace and automotive applications, PEO is used

to improve the corrosion and wear resistance of engine components. In the biomed-
ical industry, PEO is used to improve the biocompatibility and Osseointegration of
implant materials. In the electronics industry, PEO is used to improve the adhesion
and electrical properties of metal substrates.
Stage 3: Drying and Curing using Different Techniques
The process of forming a film involves the release of solvents and chemical reactions,
which can be accelerated by applying heat. In the case of liquid paints with organic
solvents or water that need to be cured [39], it is crucial to remove as many of the
volatile components as possible and speed up the chemical reaction through thermal
initiation. Heat transfer can be achieved by using convection drying with heated
air or by exposing the surface to infrared radiation. However, for paints that cure
through polymerization reactions, heat transfer is not necessary, and short-wave UV
or electron-beam radiation is used to initiate the chemical crosslinking reaction. Using
heat treatment in these cases could lead to the emission of volatile polymerizable
reactants, resulting in a different coating [24]. Systems that use thermal energy, such
as IR radiation, heat conduction, or convection heat, for curing and physical drying
at the same time are called ovens. Systems that use heat or short-wave radiation
without releasing solvents, like radiation curing, are referred to as curing systems.
In thermal curing [48], heat and mass transfer are crucial variables that influence the
final coating properties. In radiation curing, the formation of free radicals by high-
energy radiation initiates the double bonds in the film-forming agents or reactive
thinners.
2.4 Coatings for High Temperature
High-temperature structural coatings are used to enhance the performance of compo-

nents that operate at high temperatures, increase their durability, and allow the use of
different types of fuels in engines for land and marine applications. These coatings
are also utilized in various industries, including manufacturing, energy, transporta-
tion, waste management, nuclear, and space. Three common methods for applying
high-temperature coatings include
1. Physical Vapor Deposition (PVD)
2. Chemical Vapor Deposition (CVD)
3. Thermal spray techniques.
Diffusion coatings are strongly bonded to the substrate and form a continuous
composition with the substrate through diffusion. They rely heavily on the substrates’
chemistry.
Overlay coatings are more expensive and provide more compositional flexibility.
They are also well-bonded to the substrate. Thermal Barrier Coatings (TBC) fall
under the category of overlay coatings and can be applied to various substrates.
Physical Vapor Deposition
PVD [49] is a method of depositing a coating by vaporizing the material and then
depositing it onto the surface of the substrate. As shown in Fig. 8, it is an atomistic
process that involves two steps:
1. Vaporization
2. Deposition.
PVD, a method of atomistic deposition, involves vaporizing a coating material and
depositing it onto a substrate. This process can deposit various materials including
metals, alloys, and ceramics in different shapes. The most commonly used method
of PVD is an electron-beam gun (EB-PVD) because it deposits with high energy
densities. This method can also deposit mixed oxide coatings like Yttria-stabilized
zirconia TBSs by controlling the plasma and ions to achieve the desired coating.
Sputtering is another example of PVD and is notable for its ability to deposit a wide
range of materials including alloys, intermetallics, and oxide solutions.
Chemical Vapor Deposition
As shown in Fig. 9, [49] is a method of depositing coating materials by intro-
ducing gaseous source materials to a substrate and causing them to dissociate
under high temperatures. Various techniques can be used such as plasma-enhanced
CVD, atmospheric-pressure CVD, low-pressure CVD, ultrahigh vacuum CVD, and
metalorganic CVD, to deposit different materials on the substrate.
Thermal Spray Techniques
Thermal spraying [49] is a technique that involves injecting a powder form of a
material into a hot carrier gas and spraying it onto a target substrate using a gun.
This enables the rapid deposition of a wide variety of coatings. As shown in Fig. 10,
this method is widely used in gas turbine applications for overlay coatings. The key
parameters that need to be considered for uniform and perfect coating include the
plasma powder, pressure, flow rate, plasma gas composition, carrier gas flow, and
distance between the target and substrate. This technique has the advantage of being
able to coat almost all materials that do not decompose when melted, without heating
the substrate. Additionally, the substrate can be recoated using this technique and the
process can be made more reliable by controlling the carrier gas and power, using
feedback, and closely monitoring key steps (Fig. 11).
Fig. 10 Physical vapor deposition
Fig. 11 Chemical vapor deposition
2.5 Challenges in High-Temperature (HT) Coatings
Developing a coating that can withstand environmental conditions while remaining

securely attached to the substrate can be difficult as certain temperatures can cause
degradation of bulk or structural materials through phenomena such as oxidation,
corrosion, sulfidation, erosion, and carburization (Fig. 12).
The use of coatings goes beyond just protecting the substrate, it also helps to
increase the longevity of components and improves the overall reliability of the
assembly. Some common issues that need to be addressed include:
HT Oxidation
When exposed to high temperatures in air [50], the surface of metals or alloys under-
goes oxidation, a process in which metal atoms are converted into metal oxides. This
Fig. 12 Thermal spraying

techniques
can cause thinning of the material and eventual failure. The rate of oxidation increases
significantly with increasing temperature. For example, above 840–870 °C, Chromia
(Cr2 O3 ) offers less protection than alumina because it tends to turn into CrO3 at these
temperatures.
Hot Corrosion
When exposed to high temperatures, metals, and alloys can degrade through oxida-
tion, where the surface atoms are converted into metal oxide, resulting in thinning
of the material and ultimately, failure. The rate of oxidation increases with temper-
ature. To combat this, coatings such as Chromia (Cr2 O3 ) can be used, but they are
less effective at temperatures above 840–870 °C as they tend to sublimate to CrO3 .
Additionally, the presence of molten salts such as sulfur and potassium in air and
fuels can cause corrosion [50]. To protect against this, coatings are designed based
on the type of environmental attacks, such as high-temperature oxidation, Type I
hot corrosion (occurring at temperatures between 800 and 950 °C), and Type II hot
corrosion (occurring at temperatures between 670 and 750 °C) [51, 52]. Type I hot
corrosion is typically seen in thermal power plants and gas turbine engines operating
at high temperatures, while Type II corrosion is more common in thermal plants
operating at lower temperatures. In order to prevent hot corrosion, it is crucial to
preserve the protective layer and keep the hot-corrosion process in its incubation
period, as the coating can quickly degrade if the protective layer is lost or breached.
Sulfidation
When exposed to an atmosphere containing sulfur, materials may experience a sulfi-
dation attack as a result of the formation of SO2 and SO3 gases [51]. This can lead
to the formation of polysulfides, aliphatic sulfides, disulfides, thiophenes, or other
sulfur compounds on the surface of the material, which can degrade its properties
over time.
Erosion
Erosion [51] occurs when solid particles in working gases impact and wear away at
a surface, and the extent of erosion is determined by the density of particulates and
the angle of impact. In thermal power plants and boilers, there are various types of
erosion, with fly ash erosion being the most significant, caused by the presence of
quartz in coal.
Solid-State Diffusion
Another significant degradation mode is the loss of aluminum due to diffusion, which
can result in a decrease in the concentration of aluminum in the coating, making it
unable to form a protective oxide layer after spallation, once the concentration drops
below a certain level [52].
Spallation
The absence of the protective layer at the coating-substrate interface can be especially
harmful as it necessitates the creation of a new protective layer. Studies have shown
that this process, known as spallation, can be intensified by the presence of sulfur in
the material. Spallation of thermal barrier coatings (TBCs) can quickly degrade the
insulation properties of the coating and accelerate damage to the underlying metal
substrate [51, 52].
2.6 Different Types of Coatings
There are currently three types of high-temperature coatings: aluminide, chromite,

and MCrAlY. MCrAlY [52] is a type of metallic coating that is composed of different
elements such as M (cobalt, nickel, or a combination of both), Cr (chromium),
Al (aluminum), and Y (yttrium). Different materials are used in these coatings
to prevent corrosion, oxidation, and high-temperature damage to the base mate-
rial. These coatings include aluminide, chromide, and MCrAlY. The composition of
different diffusion coating materials is listed in Table 2.
Oxidation and Corrosion Resistance Coatings
Since the 1950s, coatings [53] have been applied to gas turbines to protect against
corrosion and oxidation. These coatings are typically made of aluminum or contain a
high level of chromium to combat the effects of sulfur. Future developments in coat-
ings will likely involve improving the chemistry of diffusion or overlay systems and
controlling undesirable elements in both the substrate alloys and coatings. Alternative
Table 2 Composition of different diffusion coating materials [24]

Diffusion coatings Composition (weight %) Coating temperature range (°C)
Al/Cr/Si NH4 Cl Al2 O3
Aluminide 1–15 1–3 Remaining 750–1050
Chromize 48 4 Remaining 750–1050
Silicide 5 3 Remaining 750–1050
Table 3 Thickness range of

Layer Coating materials Thickness range (µm)
each layer of TBCs [24]
1 Ceramic 125–1000
2 Bond coat 50–125
3 TGO 0.5–10
materials such as ceramics, intermetallics, and refractory metals are also used in high-
temperature applications, but they come with their own challenges. Therefore, more
research is needed on developing superalloys that can withstand high-temperature
environments.
Thermal Barrier Coatings (TBC)
Thermal barrier coatings (TBCs) [50] are designed to protect components and
substrates from high temperatures and corrosion. They consist of four main elements:
a superalloy substrate, a metallic bond coat on the substrate, a thermally grown oxide
(TGO) layer, and a ceramic topcoat. The ceramic topcoat is typically made of a low
thermal conductivity material such as ZrO2 and is applied to an oxidation-resistant
bond coat, such as MCrAlY or aluminide. The bond coat serves as an insulating layer
and TGO forms on its surface, binding the ceramic layer to the bond coat. The final
layer is typically a metallic coating, such as aluminide, platinum, or NiCoCrAlY
[53], which is chosen based on the substrate alloy composition. TBCs can be applied
using a variety of methods and are intended to reduce the temperature of the compo-
nent and increase its lifespan. The thickness range of each layer is listed below in
Table 3.
Thermal Barrier Coatings (TBCs) are used to protect high-temperature compo-
nents in gas turbines and diesel engines. These coatings consist of several layers,
including a superalloy substrate, a metallic bond coat, a Thermally Grown Oxide
(TGO), and a ceramic topcoat. The main goal of TBCs is to reduce the temperature
of the substrate and increase its lifespan. In the future, research should focus on
understanding the mechanisms of energy transport in TBCs, improving reliability,
and increasing turbine efficiency.
Non-destructive Inspection (NDI) of Coatings
This method aims to reduce the presence of defects in coatings through the use of
statistical process control and quality control techniques. There are two types of
inspection techniques:
1. Destructive Coatings
2. Non-destructive Coatings [53].
Destructive coatings are very expensive compared to non-destructive, particularly
in the gas turbine hardware since it is high in cost. Hence non-destructive inspection
coating is very attractive and is in the stage of development. This method is divided
into two sections, one that utilizes external stimulation such as ultrasonic pulses, and
the other that relies on radiography alone, without the need for external stimulus.
The ultrasonic Non-Destructive Inspection (NDI) technique is used to detect

defects in a wide range of materials, including metals, non-metals, dielectrics,
magnets, and non-magnets. It can also be used to measure the thickness and elastic
properties of ceramic and metallic coatings. On the other hand, Radiographic Testing
(RT) is a non-destructive method that uses X-rays or gamma rays to examine the
internal structure of manufactured parts and identify any defects or flaws.
3 Applications
Coatings were first applied on gas turbines in the early 1950s to protect against
high-temperature oxidation and corrosion. These coatings are now used in various
applications, including transportation, mechanical driving, and power generation.
Maximizing the service life and reliability of gas turbine engines is crucial and can
be achieved through proper coating selection and application.
3.1 Coatings for Gas Turbines
Gas turbine engines [54] are commonly used in various applications such as trans-
portation, mechanical drive, and power generation. However, these engines operate
in harsh environments where the temperature can reach near the melting point of
the materials, leading to defects in the components. To combat this, various coat-
ings are applied to different parts of the engine such as erosion resistance coat-
ings, anti-fretting coatings, abradable coatings, and diameter adjustment coatings
for compressor blades and vanes. Thermal barrier coatings (TBCs) [55, 56] are
commonly used in high-temperature environments of aircraft and industrial gas
turbine engines. TBCs consist of metal and ceramic multilayer insulation that protects
the turbine and combustor from the hot gas stream, improving the durability and
energy efficiency of the engine. Modern gas turbines with TBCs can operate at
temperatures of around 1300 °C, allowing for thousands of takeoffs and landings in
commercial jet engines and up to 30,000 h of operating time.
Yttria-stabilized zirconia (YSZ) [57] is a popular choice for thermal barrier coating
materials due to its stability at high temperatures and low thermal conductivity.
Intermetallic compounds such as aluminides (Nia Al, FeAl, TiAl, etc.) are also
commonly used in TBCs but can suffer from the formation of Kirkendall porosi-
ties at high temperatures due to internal diffusion of Al from the coating to the
substrate. However, the addition of Cr can prevent the formation of Kirkendall porosi-
ties, making YSZ coatings a more reliable option. Additionally, YSZ coatings can
be applied using e-beam Physical Vapor Deposition (PVD) techniques [58], which
further improves their performance.
3.2 Coatings for Solar Thermal Power
One way to harness solar energy and reduce reliance on fossil fuels is through the
use of solar thermal conversion methods, such as concentrating solar power (CSP).
CSP has the potential to produce a significant portion of global electricity by 2050. A
key area of focus in this technology is the development of solar selective absorbing
coatings, which capture solar energy as heat. These coatings can be divided into
different types based on the materials used, such as double cermet, transition metal
nitride, or transition metal oxide layers, each with unique properties and advantages.
These coatings can help increase the efficiency and cost-effectiveness of solar
thermal power [59].
Absorber coatings can be classified into two types: non-selective and selective.
Non-selective coatings have the same optical properties regardless of the wavelength
of light. Examples of non-selective coatings include black paint and urethane paint
with high absorptivity (97–98%) but also high emissivity (89–90%). As a result, the
efficiency of non-selective coatings is low. Selective coatings are designed to absorb
specific wavelengths of light, usually in the range of 0.25–2.5 µm. Beyond 2.5 µm,
black body radiation starts to occur, which is undesirable as it increases emissivity.
For optimal performance [59], absorber coatings should have high absorptivity
(α > 0.9), low emissivity (ε < 0.2), and maintain their optical properties at high
operating temperatures (100–500 °C) and in various environmental conditions. They
should also be stable and not react with the environment and should be protected from
erosion by abrasive particles. Additionally, they should have a consistent long-term
performance at high temperatures.
When designing absorber coatings, it is crucial to ensure maximum absorption of
solar radiation and minimize heat loss through emission from the substrate held at
high temperatures. An absorber coating typically has a sandwich structure, with a top
layer of anti-reflection coating, typically a transparent oxide that enhances absorption
by absorbing the solar radiation and not reflecting it back. The second layer is a cermet
coating, a metal-oxide composite structure that absorbs solar radiation and transfers
heat to the substrate. The third layer is an IR reflecting coating that reduces substrate
emittance, placed above the substrate and below the cermet coating.
Zhang and colleagues have successfully demonstrated the use of Mo–Al2 O3 [60]
cermet selective surfaces produced through vacuum co-evaporation. These surfaces
showed an absorbance of 0.96 and near-normal emittance of 0.08 at 350 °C when
deposited on a copper infrared reflector. Other cermet coatings that have been
explored include those made with Al2 O3 , AlN, SiO2 , YSZ, and AlSiOx [61] as
matrix materials, with metal particles like Ni, W, Mo, and Ag. Researchers have also
adjusted the optical properties of cermet coatings through annealing at high temper-
atures. For example, Antonia adjusted the optical properties of the WeAl2 O3 cermet
layer by annealing at 580 °C under vacuum for 2 days. The coatings exhibited an
absorptance of 94% and emittance of 13% at 550 °C. In another study, when a silicon
substrate was replaced with a stainless steel substrate, the double WeAl2 O3 cermet
layer still showed excellent thermal stability at 400 °C in the air for 2500 h and at
580 °C in a vacuum for 850 h. In addition, Nuru sputtered Pt–Al2 O3 [62] multilayer
coating, which was stable up to 800 °C for 24 h with an absorptance of 93.8% and
thermal emittance of 10% at 82 °C. However, the selectivity decreased sharply to
0.892/0.13 at 1000 °C due to inter-diffusion and formation of the h-Fe3 Mo3 C phase.
3.3 Coatings for Space Applications
The use of coatings in space has been found to have limitations due to their tendency
to absorb moisture in the atmosphere, leading to changes in performance over time.
One solution to this problem is using plasma electrolytic oxidation (PEO) coating,
which was used in the Soviet MIR space station project and could protect compo-
nents for 15 years in the harsh conditions of space [63]. Scientists at Keronite have
also developed a ceramic plasma electrolytic oxide coating that can withstand high
temperatures, UV light, and thermal shocks without yellowing. Optical coatings
have been used for many years to regulate the temperature of electronic and optical
equipment in spacecraft by utilizing certain materials’ reflective and heat-resistant
properties. These coatings, known as thermal control coatings, are typically made
up of a reflective layer applied to the back surface of a glass or fused silica substrate
to maintain a consistent internal temperature during sunlit and dark periods.
Coatings that resist harsh space environments are typically made of hard oxide
materials deposited using high-energy processes such as magnetron sputtering, IAD
E-beam, or IBS. These materials include a combination of SiO2 , Ta2 O5 [64], HfO2 ,
ZrO2 , and others. To ensure the suitability of coatings for space applications, several
factors must be considered, including resistance to atomic oxygen attack, flexibility
and abrasion resistance, freedom from defects, high surface conductivity, lightweight
and thin design, and tolerance to vacuum ultraviolet radiation.
Coatings that provide resistance consist of hard oxide materials deposited by
high-energy processes such as magnetron sputtering, IAD E-beam, or IBS. Mate-
rials include SiO2 combined with Ta2 O5 [64], HfO2 , ZrO2 and others. Protective
coatings have been investigated for their resistance to atomic oxygen concentration
and Vacuum UV radiation. For space applications, several factors must be consid-
ered, such as resistance to atomic oxygen attack, flexibility, abrasion resistance,
free of defects, high surface conductivity, lightweight, thin, and VUV tolerant. It is
important to note that the presence of coating defects can lead to strong erosion and
undercutting of the substrate. The glow discharge process is much explored. Thin Si
or Si compounds like P-SiO2 , P-SiN, and PP-HMDSO deposited by plasma-assisted
chemical vapor deposition using micro-wave discharge show promise as protective
coatings for spacecraft materials. Further developments are needed in polymers that
can withstand high temperatures.
3.4 Coatings for Marine Applications
Offshore oil and gas platforms, as well as other marine [65] assets, are continu-
ously at risk of corrosion that can lead to significant economic consequences. To
address this issue, designers utilize a combination of barrier coatings and cathodic
protection (CP) methods, which provide cost-effective and long-lasting protection
against corrosion. Different types of available marine coatings include amine–epoxy
systems, polyamide–epoxy systems, siloxane–epoxy systems, and coal tar–epoxy
systems. These coatings are especially formulated to withstand the harsh conditions
of saltwater and salt in ambient air. Table 4, Lists the different marine-based coating
systems with advantages and disadvantages.
Research teams have developed nanoparticle coatings for advanced offshore [66]
and marine applications. These coatings, designed for use by the Navy on ships
and submarines, are made from tiny particles of alumina, titania crystals, and other
ceramics. These nano-size particles provide a long service life, exceptional adhesive
properties, abrasion resistance, mechanical toughness, impact strength, and fatigue
protection. These nanoparticle structures of titania–alumina coating are used for
coating moving components of pumps and drives in naval ships. The coatings are
applied using a plasma spray method.
Researchers are developing new coatings using nanoparticles for advanced
offshore and marine applications. These coatings, composed of alumina, titania,
and other ceramic particles, are highly durable and have exceptional adhesive prop-
erties, abrasion resistance, and mechanical toughness. They are used to protect the
moving components of pumps and drives on naval ships. A plasma spray method is
used to apply the coatings. Additionally, new epoxy coatings [67] that can withstand
high temperatures are being developed for use in crude oil tanks at 80 °C (176°F)
and all-season primers for extreme temperatures. New biocide-free antifouling prod-
ucts are also being tested to meet regulatory requirements for eco-friendly coatings.
Low-friction antifouling products and hull protection products are also being devel-
oped. New eco-friendly coatings are also being developed for the smooth surfaces
of rudders to minimize cavitation damage while ensuring fuel-saving through higher
speeds.
4 Existing Materials for Protective Coatings
There are a variety of materials that can be used for protective coatings, each
with unique properties and advantages. Some common materials used for high-
temperature thermoelectric materials include.
Table 4 Lists the different marine based coating systems with advantages and disadvantages [66]
Different coating system Advantages Disadvantages
Chlorinated rubber coatings • Superior intercoat adhesion, • Poor heat resistance and a
as well as the ability to dry tendency to discolour in
well even in extremely cold sunlight
temperatures
• They also have excellent
resistance to both water and
chemicals
Amine-epoxy system • Resistant to alkali and • Mild toxicity of amine
solvents epoxies
• High water and acid resistance • Limited recoat duration or
• High durability, strength and lifespan
abrasion resistance • Slow drying of the film
• Long-term protection against
corrosion
• Effective barrier against
moisture and chemicals
Polyamide epoxy system • Good resistance to water and • Viscosity is higher compared
alkali to other epoxies
• Adequate resistance to acid • Coating strength varies with
• Easy to apply and cure, with temperature changes
good adhesion and flexibility
• Has moderate ability to
withstand weathering
Siloxane epoxy systems • High resistance to • Limited ability to withstand
environmental factors heat and limited resistance to
• Good resistance to wear and solvents
tear
• Excellent resistance to acid
• Retains a shiny appearance
well
Coal-tar-epoxy system • Excellent resistance to • Not suitable for use in
saltwater and freshwater drinking water; subject to
• Strong film strength certain regulatory limitations
• Good protection against • Unsuitable for certain
cathodic disbondment applications due to its dark
• Reasonably priced color
• Prolonged recoating and
repair time required
4.1 Superalloys
Nickel-base and cobalt-base superalloys are explored more in high-temperature envi-

ronments. Both served over 50 years in coating industries in gas turbine applications.
Nickel-based superalloys [52] are a class of materials studied for use as protective
coatings in high-temperature thermoelectric materials. They are known for their
excellent mechanical properties, corrosion resistance, and thermal stability, which
make them well-suited for high-temperature applications. One of the most common
nickel-based super alloys used in protective coatings is Inconel. It is a family of nickel
chromium-based superalloys with excellent resistance to high-temperature corrosion
and oxidation. Their high strength and excellent resistance to corrosion make them
suitable for use in high-temperature environments, such as aerospace, automotive,
and power generation, where they can maintain their properties at temperatures up
to 1800°F (980 °C).
Another nickel-based superalloy used in protective coatings is Haynes 282. It is
a cobalt–chromium–nickel–tungsten superalloy that has excellent mechanical prop-
erties and thermal stability. It can maintain its strength and corrosion resistance at
temperatures up to 2100°F (1150 °C) and it has been used in the aerospace industry
as a protective coating for high-temperature thermoelectric materials.
Cobalt-based superalloys [52] are a class of materials studied for use as protec-
tive coatings in high-temperature thermoelectric materials. These alloys are known
for their excellent mechanical properties, corrosion resistance, and thermal stability,
which make them well-suited for high-temperature applications. One of the most
common cobalt-based superalloys used in protective coatings is Stellite. It is a
family of cobalt–chromium-based alloys with excellent wear resistance, erosion,
and corrosion resistance. They can maintain their strength and corrosion resistance at
temperatures up to 1000 °C (1832°F), making them ideal for use in high-temperature
environments such as aerospace, automotive, and power generation.
Another cobalt-based superalloy used in protective coatings is Haynes 230 [68].
It is a cobalt–chromium–tungsten superalloy that has excellent mechanical prop-
erties and thermal stability. It can maintain its strength and corrosion resistance at
temperatures up to 1204 °C (2200°F) and it has been used in the aerospace industry
as a protective coating for high-temperature thermoelectric materials. Cobalt-based
superalloys have also been used as a coating via the electroplating method [69].
CoCrW alloys [70] are known to have good corrosion resistance, thermal stability,
and a high melting point, making them suitable for high-temperature applications.
It’s worth noting that their use could be limited due to their high cost and limited
availability compared to other alloys.
4.2 Ceramics
They possess excellent mechanical properties, high-temperature stability, and corro-

sion resistance, which make them well-suited for high-temperature applications. One
of the most common ceramics used in protective coatings is alumina (Al2 O3 ) [52].
Alumina has excellent thermal stability and can maintain its strength and corrosion
resistance at temperatures up to 1700 °C (3100°F). It has good chemical stability,
and it’s a good electrical insulator. It has been used in high-temperature applications
such as aerospace and power generation.
Another ceramic [71] used in protective coatings is silicon carbide (SiC). Silicon
carbide has excellent mechanical properties and thermal stability. It can maintain
strength and corrosion resistance at temperatures up to 2000 °C (3632°F). It’s also

an excellent electrical and thermal conductor. It has been used in high-temperature
aerospace, automotive, and power generation applications. Ceramics can also be
coated via CVD [72] or PVD. These methods allow for the precise control of the
thickness and composition of the ceramic coating. It’s worth noting that the use of
ceramics as protective coatings may be limited by their brittle nature and the difficulty
in applying them to complex geometries.
4.3 Intermetallics
They have the possibility of achieving both higher temperatures and higher specific
strength than superalloys. Most studies focus on nickel, aluminum, and titanium
aluminides. Other compounds like nickel, titanium, cobalt, and iron are also used
in coating industries. Alloys with higher aluminum content (NiAl, TiAl, and TiAl3 )
have a good inherent resistance to oxidation. One of the most common intermetallics
used in protective coatings is NiAl (nickel–aluminum). NiAl [52] is an intermetallic
compound that has excellent thermal stability and can maintain its strength and
corrosion resistance at temperatures up to 1100 °C (2012°F). It has good chem-
ical stability, and it’s an excellent electrical conductor. It has been used in high-
temperature applications such as aerospace, power generation, and thermoelectric
materials.
Another intermetallic used in protective coatings is Ni3 Al (nickel–aluminum).
Ni3 Al [73] is an intermetallic compound with excellent mechanical properties and
thermal stability. It can maintain its strength and corrosion resistance at tempera-
tures up to 1204 °C (2200°F). It’s also a good thermal conductor. It has been used in
high-temperature aerospace, automotive, and power generation applications. Other
intermetallics under elevated temperatures include MoSi2 [74], FeAl [75], and CoAl
[76]. Intermetallic [77] can also be used as a coating via the Chemical Vapor Depo-
sition (CVD) or Physical Vapor Deposition (PVD) method. These methods allow for
the precise control of the thickness and composition of the intermetallic coating.
4.4 Refractory Materials
Refractory materials have an attractive combination of high melting points [78]

higher than ceramic materials. Most research focuses on niobium [79], molybdenum,
tantalum [79], and tungsten in case of low cost compared to other refractory metals.
Niobium has a density slightly lower than nickel while still melting temperature
approximately 1000 °C higher than nickel. Niobium alloys have also been used in
many unmanned aircraft.
One of the most common refractory materials used in protective coatings is silicon
nitride (Si3 N4 ) [80]. Silicon nitride has excellent thermal stability and can maintain
its strength and corrosion resistance at temperatures up to 1600 °C (2912°F). It has

good chemical stability, and it’s an excellent electrical insulator. It has been used in
high-temperature applications such as aerospace and power generation.
Another refractory material used in protective coatings is alumina–silica
(Al2 O3 SiO2 ). Alumina–silica [81] has excellent mechanical properties and thermal
stability. It can maintain strength and corrosion resistance at temperatures up to
1700 °C (3100°F). It’s also an excellent electrical insulator. It has been used in high-
temperature aerospace, automotive, and power generation applications. It’s worth
noting that their use could be limited due to their high cost and limited availability
compared to other materials.
5 Explored High-Temperature Protective Coatings

for TEM
As discussed in the above topics, TEM is those materials that convert thermal gradient
into electricity or vice versa. Since TEM are used at high temperatures in aerospace,
military, and national defense applications, they are prone to oxidation and corro-
sion, which will deteriorate the properties and require protection. Recent research on
protective coatings for thermoelectric materials (TEMs) has focused on developing
new materials and methods to improve the thermal stability and corrosion resistance
of TEMs and their thermoelectric performance. Considering the same, protective
coatings like amorphous coatings, glass coatings, polymer coatings, and hybrid coat-
ings are developed with materials such as Si–O–C coatings, enamel, Si3 N4 , SiO2 ,
HTP, and PbO–SiO2 and also by solvent and water-based resins.
S. Battiston et al. used radio frequency magnetron sputtering to synthesize multi-
layered molybdenum silicide-based coatings for protection against oxidation at
middle to high temperatures of Mg2 Si thermoelectric materials [13]. Due to its high
melting point (2030 °C), MoSi2 is appropriate for corrosion protection at high temper-
atures. The researchers found that a MoSi2 thin film barrier with a thickness of 2.5 µm
had good thermo-mechanical compatibility with the sintered Mg2 Si pellet substrate
and effectively protected it up to 600 °C.
Another work on Mg2 Si TEM [11] was carried out by P. Nieroda, et al. by
coating amorphous silicon oxycarbide (SiOC) on Mg2 Si that was prepared by self-
propagating high-temperature synthesis (SHS) and hot–pressing method. The sample
shows good adhesion till 450 °C and starts cracking at higher temperatures. Hence,
they concluded that amorphous Si–O–C coatings are best-suited candidates for
thermoelectric materials against oxidation.
Nesbitt from NASA Glenn Research Center has revealed an alternative material for
Si–Ge to be used as a Radioisotope Thermoelectric Generator (RTG). The compound
Yb11 MnSb11 [82] is a TEM which can be an alternative to Si–Ge, which suffers from
high sublimation at elevated temperatures (up to 1000 °C). In order to prevent this
material from sublimation, rare oxides, rare earth silicates, and ZrO2 + 7Y2 O3 (YSZ)
are used since they are chemically compatible with the substrates. From this Y2 O3
is considered very stable because of its very low free energy. The main limitation of
Y2 O3 is debonding; it can be avoided by developing a coating with cohesive solid
strength.
Juliusz et al. coated Si–O–C on In0 .4 Co4 Sb12 skutterudite [12] using the sol-gel
method by hydrolysis of a mixture of organosilicon compounds. It was concluded that
black glass coating decreased the oxidation rate, and single-dip coating is preferable
to have much uniformity. When the thicker layer is coated and annealed, cracking is
observed. So further developments in Si–O–C coating are needed to eliminate cracks
and improve protective properties.
Glass coatings have been proposed by Yatir et al. to solve both the sublimation
and oxidation of TEM. The PbO–SiO2 glass was doped B2 O3 and Na2 O [83] and
produced by melting and quenching. This lead silicate coatings can be coated with
TEMs: Mg2 Si, PbTe, GeTe, and CoSb3 upon 1%
Park et al.’s work has demonstrated enamel coatings for p-type
(Ce0.9 Co0.5 Fe3.5 Sb12 ) and n-type (Ba0.05 Yb0.025 CoSb3 ) and tested at 600 °C in
the air continuously for 8 days [84]. This was the first report demonstrating the
efficacy of enamel coatings’ efficacy in suppressing oxidation in p-SKD containing
oxygen-sensitive elements such as Ce, La, Fe, and Sb. Since oxidation of p-type is
considerably more challenging than n-type SKD, this work has been done.
Zawadzka et al. designed glass coating to protect CoSb3 TEM [9] against degra-
dation in the air at elevated temperatures. This coating was made of borosilicate glass
high content titania (TiO2 ) and coated in a simple dipping technique at 700–740 °C.
These coatings appeared to adhere well and effectively protect the thermoelectric
substrate against antimony loss and oxidation up to 600 °C.
Gucci et.al taken two commercially available resins (CP4040-S1)—solvent-
based for (Mg2.1 Si0.487 Sn0.5 Sb0.13 ) Mg-Silicide and (CP4040)—water-based for and
(Cu11.5 Zn0.5 Sb4S13 ) tetrahedrite and was concluded that solvent-based resin signifi-
cantly reduced the oxidation rate of Mg–Silicide and the water-based hybrid coating
was adequate to provide barrier coatings [10].
Another avenue of research is focused on using nanocomposite coatings, which
offer unique properties such as high thermal stability, corrosion resistance, and low
thermal conductivity.
Hence, the development of protective coatings for thermoelectric materials
(TEMs) is a highly active area of research, with new materials and methods being
developed to improve the thermal stability and corrosion resistance of TEMs and
their thermoelectric performance. Amorphous alloys, refractory materials, multi-
layer coatings, and nanocomposites have all been explored as potential protective
coatings [85] for TEMs, and have shown promise in increasing the high-temperature
stability and corrosion resistance of TEMs. However, more research is needed to
optimize these coatings’ properties fully and evaluate their long-term performance
in high-temperature environments. Despite this, the research on protective coatings
for TEMs has excellent potential to improve the performance and reliability of TEMs,
making them more suitable for high-temperature applications.
6 Future Outlook
The future perspective of protective coatings for high-temperature thermoelectric

materials (TEMs) [86] is very promising. The development of new materials and
methods for protective coatings is ongoing. It is expected to continue improving
the thermal stability and corrosion resistance of TEMs and their thermoelectric
performance. In-depth research should be conducted on designing and fabricating
high-temperature protective coatings for TEM with superior corrosion resistance,
oxidation, and sublimation.
One area of research that is gaining attention is using advanced nanocomposite
coatings that can be engineered to have unique properties such as high thermal
stability, corrosion resistance, and low thermal conductivity. These coatings could
potentially offer superior performance in high-temperature environments.
To improve high-temperature performance in thermoelectric materials,
researchers are exploring advanced substrate materials such as monolithic ceramics
and ceramic composites. These materials are resistant to rapid oxidation at high
temperatures. However, to achieve the desired performance levels, it is necessary
to use advanced substrate materials, implement cooling systems that have minimal
impact on performance, and develop highly dependable thermal barrier coatings or
other insulation technologies.
Research on stability issues is a high priority, and working on engineering systems
at high temperatures also needs the reliability of extended service life.
Another area of research that is expected to grow is the development of coatings
that can be applied to TEMs using non-vacuum processes. These processes, such as
Chemical Vapor Deposition (CVD) and Atomic Layer Deposition (ALD), are more
cost-effective and environmentally friendly than vacuum-based processes and could
make it easier to scale up the production of TEMs with protective coatings.
Additionally, using simulation and modeling tools to optimize the properties of
protective coatings is expected to become more prevalent. These tools will enable
researchers to predict the performance of coatings under various conditions and to
optimize the properties of coatings for specific applications.
The future of protective coatings for high-temperature thermoelectric materials
is very promising. New materials and methods are being developed to improve the
thermal stability, corrosion resistance, and thermoelectric performance of TEMs.
Advanced nanocomposite coatings, non-vacuum processes, and simulation and
modeling tools are expected to play a significant role in developing protective
coatings for TEMs in future.
7 Summary
The development of protective coatings for thermoelectric materials (TEMs) is a

highly active area of research, with new materials and methods being developed to
improve the thermal stability and corrosion resistance of TEMs and their thermoelec-
tric performance. Amorphous alloys, refractory materials, multilayer coatings, and
nanocomposites have all been explored as potential protective coatings for TEMs,
and have shown promise in increasing the high-temperature stability and corrosion
resistance of TEMs. However, more research is needed to optimize these coatings’
properties fully and evaluate their long-term performance in high-temperature envi-
ronments. Despite this, the research on protective coatings for TEMs has great poten-
tial to improve the performance and reliability of TEMs, making them more suitable
for high-temperature applications.
Acknowledgements Ms. Nanthini S. would like to acknowledge the KPR Institute of Engineering
and Technology, Coimbatore, India, for the grant of Ph.D. fellowship. We would like to thank
the Innovation in Science Pursuit for Inspired Research INSPIRE Faculty Program through the
Department of Science and Technology (DST) funded by the Ministry of Science and Technology.
(DST/INSPIRE/04/2017/002629), Indian Institute of Information Technology, Design, and Manu-
facturing, (IIITDM Kancheepuram) for funding and their valuable support. The authors would also
like to acknowledge the Centre of Excellence for Advanced Materials Characterization, CFRD,
KPR Institute of Engineering and Technology, Coimbatore, India, for their support of the research
facilities.
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Electrically Insulating
Corrosion-Resistant Tritium Permeation
Barrier Coatings for High Temperature
Liquid Metal Breeders of Nuclear Fusion
Reactors
Abhishek Saraswat, Chandrasekhar Sasmal, Ashokkumar Prajapati,

Rajendraprasad Bhattacharyay, Paritosh Chaudhuri, and Sateesh Gedupudi
Abstract Requirement of coatings to provide functionalities including high elec-

trical resistivity, corrosion inhibition, thermal stability, chemical compatibility and
anti-permeation characteristics has been well identified and accepted as one of the
focus areas of research in the worldwide fusion community. To fully exploit the
advantages offered by liquid metal breeders, candidate coatings are being studied to
mitigate the design issues arising from exorbitantly large magneto-hydrodynamics
pressure drops, corrosion of structural materials and radiological hazards owing to
tritium permeation. Such functional coatings additionally enable the development of
advanced diagnostics to study and characterize two-phase flow, a phenomenon which
could lead to critical issues such as a reduced tritium breeding ratio for the lithium-
based breeders of fusion reactors, compromised structural integrity of breeding blan-
kets and an improper neutron shielding. A candidate coating, therefore, shall be thor-
oughly validated in the relevant environment(s), up to the extent possible, to demon-
strate the required performance and suitability before its actual application in a fusion
reactor. This chapter primarily focusses on detailed experimental investigations on
AlPO4 -bonded Al2 O3 coating to assess the deposition feasibility, electrical insulation
integrity and thermal/chemical stability in static molten lead–lithium (PbLi) alloy,
which is a material of interest owing to its potential utilization as a tritium breeder, a
neutron multiplier and a coolant in various breeding blanket concepts of fusion reac-
tors. Results from the elaborate metallurgical analyses and characterizations (SEM,
EDX and XRD) of PbLi exposed coated samples are presented and discussed. Further,
A. Saraswat (B) · C. Sasmal · A. Prajapati · R. Bhattacharyay · P. Chaudhuri

Institute for Plasma Research, Gandhinagar 382428, India
e-mail: asaraswat@ipr.res.in
R. Bhattacharyay · P. Chaudhuri
Homi Bhabha National Institute, Training School Complex, Anushaktinagar, Mumbai 400094,
India
S. Gedupudi
Heat Transfer and Thermal Power Laboratory, Department of Mechanical Engineering, Indian
Institute of Technology Madras, Chennai 600036, India
352 A. Saraswat et al.
on the application fronts, the chapter provides the first experimental results from
a PbLi-gas two-phase detection probe developed using the Al2 O3 coating, perfor-
mance assessments of complex geometry Flow Channel Inserts (FCIs) containing
Al2 O3 insulating layers and preliminary observations from ongoing coating trials on
non-planar substrates for future applications in molten Pb/PbLi circuits.
Keywords Alumina · Coating · Liquid metal · Electrical insulation · MHD ·

Lead–lithium · Two-phase flow · Flow channel insert
Abbreviations
SEM Scanning Electron Microscopy

EDX Energy Dispersive X-ray
XRD X-Ray Diffraction
MHD Magneto-Hydro Dynamics
LM Liquid Metal
DCLL Dual-Coolant Lithium Lead
HCLL Helium-Cooled Lithium Lead
LLCB Lead-Lithium Ceramic Breeder
WCLL Water-Cooled Lithium Lead
TBR Tritium Breeding Ratio
TPB Tritium Permeation Barrier
CTE Coefficient of Thermal Expansion
IR Insulation Resistance
LOCA Loss of Coolant Accident
LFR Lead-cooled Fast Reactor
MSR Molten Salt Reactor
RT Room Temperature
UHP Ultra-High Purity
USB Universal Serial Bus
DC Direct Current
ICDD International Centre for Diffraction Data
TBM Test Blanket Module
RELAP Reactor Excursion and Leak Analysis Program
FCI Flow Channel Insert
TIG Tungsten Inert Gas
RIC Radiation-Induced Conductivity
RIED Radiation-Induced Electrical Degradation
PRF Permeation Reduction Factor
PLD Pulse Laser Deposition
MOD Metal Organic Decomposition
Electrically Insulating Corrosion-Resistant Tritium Permeation Barrier … 353
1 Introduction
Lead–lithium Liquid Metal (LM) based breeding blanket concepts like Dual-Coolant
Lithium Lead (DCLL), Helium-cooled Lithium Lead (HCLL), Lead–Lithium
Ceramic Breeder (LLCB) and Water-cooled Lithium Lead (WCLL) provide several
key design advantages including neutron multiplication, high Tritium Breeding Ratio
(TBR), neutron moderation, low vapor pressure, high thermal conductivity and
stability under radiation environments typical for a fusion reactor. However, a plasma
confining transverse magnetic field significantly modifies the flow geometry of elec-
trically conducting LMs due to the retarding Lorentz force, putting high demands
on the pumping power to compensate the ensuing Magneto-Hydrodynamic (MHD)
pressure drops. Successful utilization of such LM based ancillary systems in a fusion
power plant indispensably requires optimization of process parameters including
MHD pressure drop reduction, which mandates an electrical isolation between the
LM and structural material [1–24]. By virtue of its non-porosity towards LM ingress,
a properly selected electrical insulation material could also function as a corrosion
inhibitor and a Tritium Permeation Barrier (TPB) [4, 8–11, 14, 20, 25–37]. In addi-
tion, the above functionalities could be selectively exploited towards the development
and lifetime enhancement of specific diagnostic tools aimed towards applications in
corrosive LM systems [38–42]. Oxides are well known to exhibit good electrical
insulation properties. However, specific efforts have been made to study the tritium
permeation barrier performance of such oxides with experimental assessments of
permeation for hydrogen/deuterium as surrogates. For instance, the study in [4]
reports the performance of a Pulse Laser Deposition (PLD) technique based alumina
coating achieving a Permeation Reduction Factor (PRF) of 105 for operating temper-
ature upto 650 °C while [12] provides an account of Er2 O3 Metal Organic Decom-
position (MOD) based coatings with a PRF over 100. In an advanced methodology
utilizing aluminum electroplating to generate aluminide coatings [26], the deuterium
PRF could be enhanced by two orders of magnitude for operating temperature in the
range of 600–727 °C. Similarly, an Al2 O3 /Cr2 O3 composite coating prepared using
a combination of pack cementation and sol-gel techniques [28] enhanced the PRF
by a factor of 63 as compared to the bare substrate and almost by a factor of 30 as
compared to Cr2 O3 coating. A more significant and practical investigation on the
effect of microstructure and deuterium PRF due to thermal cycles at 550 °C [29]
corroborated good phase stability and thermal stability for Al2 O3 coatings for up to
100 cycles. In this case, the permeation flux was observed to increase in conjunc-
tion with exfoliation with an increase in the number of thermal cycles due to cracks
generation.
Numerous experimental and simulation studies are being carried out worldwide
towards the qualification of promising functional materials with a specific focus on
ceramic coatings such as Al2 O3 , Er2 O3 , ZrO2 , SiC etc. To achieve the desired objec-
tives, these investigations incorporate the candidate materials either in the form of
thin coatings or thick insulation layers called FCIs [9, 10, 13, 43, 44]. However, such
small-scale attempts are yet in their nascent stages to be of practical significance
towards a fruitful full-scale implementation in fusion reactors. As such, scarcity of

relevant experimental data can be observed towards quantitative performance assess-
ment of coatings to provide an appreciable electrical insulation integrity over long
duration PbLi exposure at relevant operational temperatures. In this view, for further
advancements in the domain of PbLi breeder technologies, initially, an experimental
investigation is performed on AlPO4 bonded calcined Al2 O3 coating to address the
crucial requirements of electrical insulation. Al2 O3 is preferentially chosen as the
coating material of interest for its thermodynamic and chemical stability, while the
selection of substrate materials such as SS-304/SS-316 is largely dominated by the
commercial availability, inexpensiveness and proven usage as structural material and
wetted parts of diagnostics in PbLi R&D facilities. Although ceramics are of immense
interest for critical applications in high temperature corrosive environments, one of
the major challenges in the application of ceramic coatings over metallic substrates
is the wide difference between Coefficients of Thermal Expansions (CTEs) of the
two materials over the temperature range of interest [45]. In the first phase of the
study, an attempt is made towards experimental optimization of heat cure parame-
ters to develop Al2 O3 coated SS-316L electrodes. Coated samples are validated for
their electrical insulation integrity in static molten PbLi for continuous durations of
over 1300 h, including thermal cycling, at operational temperature in the range of
300–400 °C. Estimations of in-situ volumetric electrical resistivity and temperature
derating factors are performed using high voltage Insulation Resistance (IR) measure-
ments while chemical stability in terms of LM ingress and coating characterization
is ascertained through detailed metallurgical analyses.
In the second phase of the study, the rigorously validated high purity Al2 O3 coating
is employed as an electrical insulation and corrosion inhibitor to design, fabricate and
validate an electrical conductivity based compact multivariable two-phase detection
probe to characterize PbLi-argon two-phase vertical columns covering a wide range
of flow regimes from bubbly flow up to in-box Loss of Coolant Accident (LOCA).
Along with time-averaged void fractions, the developed probe is simultaneously
utilized to estimate two-phase bulk temperature trends, bubble frequency and average
bubble residence time. The probe is shown to provide high reliability and good
temporal resolution towards individual bubble detections.
The third experimental phase concentrates on the application of thick Al2 O3 layers
as electrical insulators inside the LM flow ducts to alleviate the MHD pressure drops.
In this part, two different cross-sectional prototype configurations, namely circular
and square, of steel-alumina-steel sandwich FCIs are fabricated. An elaborate char-
acterization of the electrical insulation is performed over an operating temperature
range of 100–600 °C to validate the electrical and mechanical integrity of the assem-
blies over the typical fusion reactor operational temperature regime. Detailed aspects
of the fabrication along with estimations of electrical resistivities are presented in
this chapter.
At the end of this chapter, recently initiated investigations related to alternative
spray coating methodology are discussed from an implementation feasibility as a
corrosion inhibitor for advanced nuclear reactor concepts such as Lead-cooled Fast
Reactors (LFRs) and Molten Salt Reactors (MSRs).
2 Experimental Methods and Materials
Many studies have well demonstrated a successful Al2 O3 layer growth exhibiting
an excellent corrosion resistance against static and flowing PbLi [4, 27, 33, 46–
48]. A few attempts have also been made towards an in-situ validation of solid
high purity Al2 O3 pieces as electrical insulation in PbLi environment [2]. However,
no reported study has provided a relevant long duration IR performance database
for Al2 O3 coated substrates to address the critical issues related to MHD pressure
drops and development of diagnostics, in the absence of which a satisfactory real-
ization of LM circuits is quite challenging. Additionally, during the initial phases
of this study, plasma-assisted tempering and thermal tempering [46, 49] of hot dip
aluminized SS-316L substrates are repeatedly observed to result in an electrically
conductive surface layer suggesting an incomplete transformation from aluminum
to Al2 O3 . This methodology is also found to result in undesirable substrate deforma-
tions owing to high temperature exposure requirements for the growth of an aluminide
layer. It may therefore be concluded that such coating application methods demand
independent sophisticated optimization of parameters for different substrate mate-
rials. In the present study, with an aim to homogenize the coating application method
towards various substrate materials, a refractory coating suspension of AlPO4 bonded
calcined Al2 O3 with 99.8% purity (containing ~75% solids by weight) is investigated
on 1.6 mm thick solid electrodes of SS-316L. Pre-coating preparation of the substrate
includes surface roughening using grit #80 emery paper followed by acetone cleaning
for removal of dust, grease and foreign particles to allow for a better coating adhe-
sion. The coating is then applied in two steps: (i) dip coating for 30 s and (ii) manual
brush coating on the surface of the electrode. To ensure the experimental objective
of in-situ IR measurements in electrically conducting PbLi, the tip of the electrode is
provided with an additional dip cycle resulting in a blob shaped coating deposition.
Thereafter, coated samples are provided an air-set for ~24 h in a vertical orientation
(with coated probe tip at the top). A gradual retraction of the coating material under
gravity allows the suspension to fill any remnant voids and undulations intentionally
induced by surface roughening. This air-set period, acting as a necessary drying and
pre-bonding stage, is followed by high temperature heat cure in a muffle furnace
with the coated electrode(s) arranged in a horizontal orientation. High temperature
heat cure involves the following stages:
(a) Ramp-up time of 2 h from Room Temperature (RT) to 93 °C followed by 2 h
heat cure at 93 °C. This step is intended towards gradual coating dehydration.
(b) Ramp-up time of 2.5/10/12 h from 93 to 427 °C followed by 2 h heat cure at
427 °C. This step is intended towards achieving a good bond between Al2 O3
and SS substrate.
(c) A natural cool down from 427 °C to RT.
Post heat treatments, absence of any voids and cracks is ensured through visual
inspections, which are followed by high voltage IR measurements at RT. A represen-
tative image of the fabricated probes and the novel in-situ IR measurement scheme
Fig. 1 a Fabricated sample probes; b a novel in-situ IR measurement test facility
for PbLi environment are depicted in Fig. 1a, b. To the best of the authors’ knowledge,
this is the first time in-situ high voltage IR measurements are employed for Al2 O3
coated substrates immersed in PbLi environment over long durations. The novel test
set-up consists of a PbLi tank provided with surface mount electrical heaters oper-
ating in temperature feedback control loops and ports for vacuuming, gas feeding/
purging and venting. Three coated probes, namely P1, P2 and P3, are fabricated as
per the procedure described above. However, for P2 & P3, fully heat cured layers are
further deposited with an additional brush coated layer to allow gradual heat curing
through system operations over a long duration. P2 is installed as such in the tank
while P3 is first dehydrated at 93 °C for 2 h (step (a)) prior to its installation. A bare
SS-316L electrode (A) acts as the reference conducting electrode for proposed IR
measurements.
PbLi in the tank is melted and heated up to a temperature of 300 °C in an Ultra-High
Purity (UHP) grade argon inert environment with repeated gas purging and a positive
cover gas pressure maintained over the complete test duration. After liquefaction
of PbLi (at ~235–236 °C), coated probes and the bare SS-316L electrode (A) are
immersed in PbLi (at t = 0). A good electrical contact between the electrode A and the
test facility structure is ensured through electrical resistance measurements (<1 Ω)
while the high electrical conductivity of PbLi [50, 51] is utilized to measure IR of the
coating being equal to the measured resistance between accessible conducting parts of
the coated probes (Px, x = 1, 2, 3) and the electrode A. High voltage insulation tests are
performed at regular intervals over complete test durations including thermal cycles.
Temperature derating factors, signifying the ratio of IR at any given temperature to
the IR value at base temperature, are evaluated during the last thermal cycle for every
10 °C rise in temperature from the base temperature and investigations are concluded
to observe the cumulative degradation effect on the IR due to thermal aging, corrosion
and thermal cycling. Afterwards, samples of ~8 mm length are cut across the cross-
section using a diamond wire-cutter (Make: Gatan, wire diameter: 200 μm) followed
by gold sputter coating of the samples for Scanning Electron Microscopy (SEM)
and Energy Dispersive X-Ray (SEM-EDX) analyses. Metallurgical analyses on the
prepared samples are carried out for coating thickness estimations, microstructure
evaluations and LM ingress detection. Particle size measurements are performed
using SEM-image analysis software and open source ImageJ software tool.
3 Results and Discussions
3.1 Coating Observations
The adopted dip coating method is observed to yield a 150–200 μm thin wet-film
over the substrate. A short ramp-up time (2.5 h) for the heat treatment (step (b) of
Sect. 2) results in visible cracks along the coated length with the formation of surface
blisters as shown in Fig. 2a. These observations could be attributed to a sudden larger
differential thermal expansion and coating dehydration, respectively.
Although a longer ramp-up time (~10–12 h) greatly minimized the cracks and
blisters during first heat cure, elimination of very fine cracks could not be achieved.
Hence, additional coating cycles are deemed necessary until no visible cracks are
identified. The IR at RT for one of the probes, prepared with a single dip coat cycle
followed by full heat curing, is found exceptionally high providing an insulation
leakage current <1 nA. In view of the highly brittle nature of Al2 O3 , preliminary
non-destructive investigations are carried out using a calibrated portable USB micro-
scope to estimate the coating thicknesses using average diametrical measurements
as shown in Fig. 2b. Detailed average coating thickness estimations across the cross-
section (destructive examinations) using SEM for the tested probes are presented
under metallographic investigations (Sect. 4). Details for the as-fabricated probes
are summarized in Table 1. All the weight measurements are performed using a cali-
brated precision weighing balance (Sartorius make, CPA225D) with a resolution of
10 μg.
Fig. 2 a Surface blisters along with full length crack due to short ramp-up time; b successfully
Al2 O3 coated SS electrodes (coating thickness ~155 μm)
Table 1 Details of as-fabricated probes tested under different test campaigns

Test campaign Probe identification Coated length (mm) Weight (g)
1 P1 85 8.57521 ± 0.00001
P2 65 7.45867 ± 0.00001
2 P3 60 7.66220 ± 0.00001
3.2 Electrical Insulation Performance in High Temperature

Molten PbLi Environment
3.2.1 Test Campaign-1
A plot depicting temperature variations with time duration details for the first
campaign is provided in Fig. 3 where the red markers (circle) represent instances
of in-situ high voltage IR measurements. Table 2 provides the measured IR values
against elapsed duration and test temperature. In accordance to the industrial norms,
all the IR measurements are performed 60 s after the test voltage application to
minimize the effects of capacitive charging current and dielectric absorption current
[52].
A decrease in the IR is observed for both P1 and P2 probes with an increase
in PbLi temperature from 300 to 350 °C, an expected temperature based derating
phenomenon in insulators. However, for P2, during 260 h in static PbLi at 300 °C,
an increase in the IR value is observed which could be accounted for gradual heat
curing of the uppermost untreated coat layer over long operational durations. The
immediate observable advantages of the coating methodology, as derived from the
Fig. 3 Temperature and time duration details for test campaign-1

Table 2 IR measurements for P1 and P2 in PbLi environment during test campaign-1

Time (h) (since t Temperature (°C) DC test voltage IR for probe P1 IR for probe P2
= 0) (V) (×109 Ω) (×108 Ω)
72 300 100 >6 >1
260 300 100 >6 >3
380 350 100 >1 >1
525 350 100 >1 >0.9
measured performance data, include feasibility of selective coating/masking on diffi-

cult substrate geometries including the internals of pipe-sections and complex mani-
folds, an easy application without exposure of substrate to very high temperatures
as required in the previous works [11, 14, 24–29, 35, 37, 46, 48, 49] and a highly
dense compact coating with complete surface coverage conforming to the electrical
insulation requirements in harsh LM environment of interest.
After exposure of over 520 h in PbLi, thermal cycling within PbLi environment is
performed to examine the insulation integrity towards possible temperature gradients
in an operational LM circuit. Considering the normal operational regimes for PbLi
facilities, 300 °C is taken as the base temperature for test campaign-1 and the IR
value at the start of the last thermal cycle is taken as the base IR value. A gain in
measurement accuracy is achieved using a digital IR tester (Make: Fluke, Model:
1550C) with ±5% uncertainty. The corresponding IR values measured are reported in
Table 3 while the IR derating trends are shown in Fig. 4. In addition to the temperature
effect, observed IR derating is also affected owing to the rising PbLi level surrounding
the probes. However, for the current set-up, the overall level rise per 10 °C change
is estimated less than 1 mm. Therefore, in view of the marginal increase in the PbLi
level and in consideration to the chemical stability of Al2 O3 , temperature parameter
is assumed to be the prominent derating factor for a conservative estimation of IR
derating.
Table 3 Temperature derating factors for IR during last thermal cycle of test campaign-1
Temperature DC test IR for Probe Temperature IR for Probe Temperature
(°C) voltage (V) P1 (×109 Ω) derating for P2 (×108 Ω) derating for
P1 P2
300 (base) 275 6.18 1.00 3.15 1.00
310 275 3.75 0.61 2.09 0.66
320 275 2.42 0.39 1.60 0.51
330 275 1.73 0.28 1.35 0.43
340 275 1.20 0.19 1.08 0.34
350 275 0.822 0.13 0.835 0.27
300 275 6.08 0.98 2.39 0.76
The above assumption is supported by the rising trend of IR values towards the
base IR value as mentioned in the last row of Table 3, taken just after achieving 300 °C
at the surface of the tank, corroborating the thermal and chemical stability of Al2 O3
insulation in high temperature PbLi environment. The observed decrease in the IR
value while returning to the base temperature of 300 °C could be explained by consid-
ering the phenomenon of dielectric relaxation in the absence of an external electric
field, where the dipoles within the dielectric tend to arrange in a random orientation.
However, in the presence of an external electric field, the dipoles align preferentially
within the bulk to counter the effect of this external field. An agitated dipole state
at a high temperature could not be brought to the low energy state instantaneously
with a sudden temperature drop, leading to a delay in effective dielectric polariza-
tion (dipole alignment). Existence of this non-zero dielectric absorption current leads
to the measurement of a reduced IR [52]. It should also be noted that the derating
factors are estimated post-exposure of the insulation to high temperature corrosive
PbLi environment for over 690 h. In view of the similarity of the fabricated probes
with commercial electrical cables, the observed temperature based IR derating is
much better [52].
After removal from the PbLi tank, P1 and P2 probes are chemically cleaned in a
1:1:1 (volume ratio) solution of CH3 COOH, H2 O2 and C2 H5 OH. However, only a
partial cleaning with a blackish appearance left behind, as shown in Fig. 5, suggests
partial ingress of PbLi in the coated layer over longer exposure durations. Such a
discoloration is not observed during a separate short duration experimental study,
where a complete cleaning could be achieved for one of the sample probes exposed
to PbLi at 300 °C for continuous 250 h. After chemical cleaning, no weight loss is
observed for P1, while a normalized weight loss of ~1.56 mg/cm2 over the coated
surface area is observed for P2. This weight loss could be primarily accounted for
dehydration of the topmost untreated coat layer of P2 during facility heating and could
also include partial thinning of the coating section immersed in PbLi. However, in
view of no variation in the order of magnitude for IR (within uncertainty limits) at
relevant temperatures (refer Tables 2 and 3), dehydration could be ascribed as the
prominent cause for the observed weight loss.
3.2.2 Test Campaign-2
The electrical insulation performance achieved for probe P2 (test campaign-1)

through gradual heat curing of the uppermost layer during system operations provides
a promising methodology to achieve coating on substrates with sharp bends, multiple/
parallel internal flow sections, complex geometries etc. To establish the repeatability
and reliability of this coating technique, a rigorous test campaign-2 is conducted
using probe P3 as per the details provided in Fig. 6, while the measured IR values
with time and temperature are reported in Table 4.
The variation in IR follows a pattern similar to that observed during test campaign-
1, accounting for the gradual heat curing of the uppermost untreated coat layer.
After continuous high temperature PbLi exposure of over 1340 h, temperature based
Fig. 4 Temperature dependent IR derating trends for P1 and P2 (post-exposure to PbLi for ~690 h)
Fig. 5 a After continuous PbLi exposure of over 700 h; b after chemical cleaning
Fig. 6 Temperature and time duration details for test campaign-2

Table 4 IR measurements for P3 in PbLi environment during test campaign-2

Time (h) (since t = 0) Temperature (°C) DC test voltage (V) IR for Probe P3 (×108 Ω)
72 300 275 2.90
261 300 275 4.57
338 350 275 1.30
526 350 275 2.18
766 350 275 2.99
838 350 275 2.89
917 400 275 0.583
1106 400 275 0.767
1109 350 275 2.99
derating is estimated using a base temperature of 350 °C as reported in Table 5 and

Fig. 7. For the insulation health estimations and to address the dielectric relaxation
observations made under test campaign-1, IR readings are taken at 60 and 120 s, after
the application of high voltage, for all the cases. As observed from Table 5, at any
given temperature, a rising value of IR from 60 to 120 s substantiates the insulation
health. A comparison of data between Tables 4 and 5, along with consideration to
the fact that capacitive charging current normally decays within initial 30 s while the
conduction current remains constant throughout the test, suggests a larger amount of
time taken by the dielectric to polarize, a phenomenon indicative of insulation health
[52]. This observation further corroborates the prominent effect of delayed dielectric
polarization discussed in Sect. 3.2.1. However, considering the retention of the order
of magnitude for IR readings taken at 60 and 120 s, this effect is not of any significant
practical implication towards achieving a satisfactory electrical insulation in a LM
environment.
Table 5 Temperature derating factors for IR during last thermal cycle of test campaign-2
Temperature DC test IR for P3 after Temperature IR for P3 after Temperature
(°C) voltage (V) 60 s (×108 Ω) derating for 120 s (×108 Ω) derating for
P3 (as per IR P3 (as per IR
data at 60 s) data at 120 s)
350 (base) 275 0.945 1.00 1.29 1.00
360 275 1.06 1.12 1.39 1.08
370 275 1.26 1.33 1.22 0.95
380 275 0.804 0.85 0.98 0.76
390 275 0.735 0.78 0.821 0.64
400 275 0.638 0.68 0.768 0.60
350 275 2.28 2.41 2.37 1.84
Fig. 7 Temperature dependent IR derating trends for P3 (post-exposure to PbLi for ~1340 h)
Figure 7 also affirms that the temperature deratings estimated using IR at 120 s
are higher than the corresponding deratings using IR data at 60 s. However, degra-
dation in the IR over a temperature gradient of 50 °C is relatively low compared
to both the cases under test campaign-1. Additionally, the IR value essentially does
not deteriorate between 350 and 370 °C in contrast to the observations from the test
campaign-1. These improvements could all be ascribed to a long duration exposure
near the required curing temperature of 427 °C. After a cool down to the base temper-
ature, the IR is observed ~83% higher than the corresponding value at the start of
the cycle, seemingly the result of an effective dielectric polarization due to repetitive
high voltage tests leading to the polarization current component to zero.
This assumption is in coherence to the nearly identical IR values observed at 60
and 120 s after a few IR measurements (refer Table 5). However, this further needs
to be experimentally investigated with similar tests. The IR at the base temperature
of 350 °C measured at the end of last thermal cycle (1350 h of PbLi exposure)
tends towards the measured IR at same temperature between 500 h and 800 h of
exposure. Similarly, the measured IR values at 300 °C (1367 h of PbLi exposure)
are 1.89 × 108 Ω and 3.32 × 108 Ω after 60 s and 120 s, respectively. All these
observations corroborate the high integrity and good health of electrical insulation
over the complete test duration.
After removal from the PbLi tank followed by chemical cleaning, the PbLi exposed
coated section appeared blackish, which is in close agreement to the experimental
findings reported under [53]. Spontaneous chipping of a few coat sections is noticed
during chemical cleaning, while major visible cracks over the complete PbLi exposed
section are observed afterwards, as shown in Fig. 8.
Delamination of almost complete coating is observed during subsequent drying
of the cleaned probe. Therefore, weight measurements for P3 post-exposure could
Fig. 8 a After continuous PbLi exposure of over 1360 h; b after chemical cleaning
not be performed. A similar observation with an AlN-BN sample immersed in Li has

been reported [21], where the Li covered surface broke into pieces during subsequent
cleaning in water, accounting for the induced stresses owing to a reaction between
the water and Li content. However, in the present study, Li activity is negligible
owing to a low weight percentage of Li (0.62–0.68%) in PbLi eutectic. Addition-
ally, neither such observations have been reported for alumina coated samples in
previous PbLi corrosion studies nor observed during the test campaign-1 for probe
P2, which had a similar fabrication method and PbLi immersion process as that of
P3. Thermal cycling could be attributed as one of the possible factors for crack gener-
ation/initiation considering the large difference in CTEs. However, the top section
of the coating (~20 mm), which is not exposed to molten PbLi but is expected to
experience similar thermal gradients within the tank, remains well adhered to the
substrate exhibiting no cracks or indication of brittleness. In addition, a crack gener-
ation in the coating within the LM bulk would have led to a sharp decline in the
measured IR, which is not observed over the complete duration of 1360 h. There-
fore, in view of the IR integrity observed from Tables 4 to 5, it is inferred that the
through-crack generation occurred post-removal of the probe from the PbLi tank.
One of the possibilities could be the cracking due to compressive stresses generated
over the LM exposed portion of the coated substrate due to temperature depen-
dent volumetric contraction of the surface adhered PbLi during cool down period.
The Al2 O3 crystal structure is known to contain a predominant ionic bonding [54]
with essentially non-existent slip planes. Due to large repulsive forces, this type
of arrangement does not allow the movement of one row of atoms over another,
under the influence of an external stress. Consequently, it is likely that the generated
compressive stresses could not be relieved through a re-arrangement of the atoms,
leading to a coat fracture. However, the solidified PbLi layer, adhered to the surface,
held the coat together until it was removed through chemical cleaning, after which
the coating seemed to spontaneously chip-off from the substrate. Under the present
experimental constraints, such compressive stresses are inevitable. In contrast, during
the flowing PbLi condition in a coolant/breeder system of a fusion reactor, LM will
be surrounded by the ceramic insulating coatings, leading to an absence of such
compressive stresses. However, as the coating cracks are not observed during test
campaign-1, the contribution of PbLi exposure duration and temperature is of interest
for further compatibility studies. In view of the similarity of the fabricated probes with
electrical cables, the volumetric electrical resistivity is estimated for the enveloping
cases using the IR relation for an electrical cable. It should be emphasized that in
the present study, a conservative estimation of volumetric electrical resistivity is
performed by taking the tip portion (blob) as a perfect electrical insulation owing
to its relative higher thickness compared to the coating thickness along the length.
Thus, whole of the insulation leakage current is assumed to flow only through the
thickness of the coating along the probe length, leading to an underestimation of
calculated volumetric electrical resistivity under reported operating conditions. The
estimated volumetric electrical resistivity remained of the order of 107 –109 Ω m
within the investigated temperature range of 300–400 °C. The coating resistance, a
product of volumetric electrical resistivity and insulation thickness, remained of the
order of 104 –106 Ω m2 , orders of magnitude higher than required for the successful
operation of LM based coolant circuits with an acceptable MHD pressure drop [2,
24, 55]. Calculations for volumetric electrical resistivity and coating resistance are
provided under Appendix A. These experimental observations further substantiate
the applicability of Al2 O3 coatings for high temperature PbLi coolant/breeder circuits
in fusion power plants. It is observed that the volumetric electrical resistivity for the
fully treated probe P1 is one order higher than that of P2 at the same temperature,
an effect that can be attributed to a higher degree of compaction achieved with full
heat curing. However, the sufficient volumetric electrical resistivity achieved and the
ease of coat formations using gradual heat curing through system operations make
the second method more promising and attractive.
4 Metallographic Investigations
Dip coating technique usually results in an uneven coating thickness along the length.
Additionally, heat cure of the coated probes in a horizontal orientation, as mentioned
under Sect. 2, is also expected to contribute to the coating thickness variations under
the influence of gravity. In this view, cross-sectional samples are cut across the PbLi
exposed portions for probes P1 and P2, using a diamond wire-cutter, to examine the
coating thicknesses and PbLi ingress depth. A representative SEM-image for one of
the cross-sectional samples from P1, as shown in Fig. 9a, confirms a compact coating
free from cracks (cracks/damages appearing on the surface are due to wire-cutting).
The average coating thickness is estimated from the coating thickness measurements
performed at various points of the cut samples from a given probe. For illustration
purposes, coating estimations for one of the samples cut from the probe P2 are
depicted in Fig. 9b. As per the method described above, average coating thicknesses
of ~495 μm and ~212 μm are estimated for the PbLi immersed portions of probe P1
and P2, respectively.
Estimations of PbLi coating ingress depth are perfomed using EDX point-
analysis at different locations across the cross-sections. Illustration presented through
Fig. 10a, b indicates the methodology adopted for the selection of the analysis points
Fig. 9 a SEM view of a wire-cut sample from P1 showing Al2 O3 layer well adhered to the substrate;
b cross-sectional view of a sample from P2 for estimation of average coating thickness
(P1 –P3 , such that the point P1 lies at the coating surface exposed to PbLi) moving radi-
ally inwards towards the substrate region. The technical details for probes P1 and P2
along with the respective analysis points are mentioned in Table 6. The corresponding
EDX elemental analyses are presented in Fig. 11 for probes P1 and P2. In view of
the primary objective of validating electrically insulating coating towards application
in PbLi eutectic alloy, the ingress depth of Pb (~99.32–99.38% by weight in PbLi
eutectic) is considered representative in consistency with the previously reported
coating qualification studies [27, 33, 36, 46, 48]. Repeated analyses at various points
corroborate Pb ingress limited to 20 μm depth for both the probes tested under test
campaign-1.
The limited penetration depth of Pb validates Al2 O3 coating functionality as an
electrical insulator as well as a corrosion barrier for high temperature PbLi applica-
tions. The restricted ingress also substantiates the assumption of temperature being
the prominent factor in IR derating, as discussed under Sect. 3.2.1.
As shown in Fig. 12a, the coating thickness for probe P3, as estimated from the
chipped-off coat sections and averaged over 04 data points, is ~429 μm. A repre-
sentative image for one of the samples with observed cracks across the thickness is
Fig. 10 EDX point-analysis for Pb ingress depth estimations for a Probe P1; b Probe P2
Table 6 Ingress profile of Pb for probes P1 and P2

Probe identification Point number (marked in yellow) Pb % as per EDX analysis
Probe P1 P1 (at surface) 13.08
P2 (~20 μm from P1 ) 0.00
P3 (~40 μm from P1 ) 0.00
Probe P2 P1 (at surface) 2.92
P2 (~10 μm from P1 ) 0.69
P3 (~20 μm from P1 ) 0.00
Fig. 11 EDX elemental analysis for probes P1 and P2
shown in Fig. 12b. The PbLi ingress depth estimations for P3 are rendered inconclu-
sive owing to Pb detection over complete coating thickness, in stark contrast to the
observed IR values reported in Tables 4 and 5. This could be explained in view of
the major visible cracks after chemical cleaning (refer Fig. 8b), which seems to have
Fig. 12 SEM analysis for P3. a Coating thickness estimations; b cracks across coating thickness
allowed ingress of Pb from the cleaning solution itself across the complete coating
thickness. All the analyzed samples from P3 are observed to indicate similar results.
Surface microstructure of the PbLi exposed coating portion for P1 is presented in
Fig. 13a, suggesting a dominating presence of flaked/whisker-type structures (marked
as A) along with agglomerates less than 1 μm in size (marked as B), where B
is mostly covered with A on the surface. The typical flake/whisker-type pattern
is in close agreement to the reporting of α-Al2 O3 in [56, 57], while the globular
pattern is generally associated with θ-phase of Al2 O3 [57]. Powder X-ray Diffraction
(XRD) analysis of the sample, shown in Fig. 13b, depicts the presence of only α-
phase of Al2 O3 (ICDD card no: 02-002-1227). A prominent presence of the α-phase
is attributed to the calcined Al2 O3 powder utilized as a raw ingredient in coating
suspension, which is separately verified through XRD analysis of dried powdered
sample having no exposure to PbLi.
As reported under various studies, α-Al2 O3 is the thermodynamically stable phase
formed through irreversible phase transformations from other transition aluminas
when heated at a temperature in excess of 1000 °C, resulting in the crystal shapes
varying with the nature of precursor until heated above 1500 °C [57]. Therefore,
Fig. 13 a Surface morphology of PbLi exposed coated section for P1; b XRD pattern
the α-Al2 O3 agglomerates can be concluded to have been converted from θ-Al2 O3
particles during the calcination of raw powder used for the suspension preparation.
The aluminium monophosphate (AlPO4 ) detected in powder XRD (ICDD card no:
00-048-0652) is the binding agent, while the presence of lead oxides (PbO and PbO2 )
is primarily accounted for the oxidation of Pb content adhered to the probe coated
surface and pre-existing oxides in used PbLi melt.
A critical observation is the formation of LiAlO2 (ICDD card no: 00-001-1306),
instead of generally observed Li2 O for PbLi melt systems. This is in agreement to
the observations in the reported interaction and compatibility studies between Al2 O3
and PbLi [36, 46, 58]. The lithium content reacts with the trace amount of oxygen
present in the argon cover gas to produce Li2 O, which further undergoes a reaction
with Al2 O3 over time to produce LiAlO2 as per the followng reactions:
4Li + O2 (trace amount from argon) → 2Li2 O(s)

Li2 O(s) + Al2 O3 (s) → 2LiAlO2 (s)
The regular argon filling/purging cycles to maintain an inert atmosphere above the
LM act as a constant supply source for oxygen in the present experimental study. The
surface particle morphology of PbLi exposed section and the corresponding powder
XRD analysis for probe P3, as shown in Fig. 14a, b respectively, also confirm the
presence of α-Al2 O3 with a nearly spherical and uniform particle size <100 nm.
An important establishment from the XRD results for all the three probes is the
prominent presence of α-Al2 O3 and AlPO4 , both of which are promising candi-
dates for TPB with high permeation reduction factors and exhibit high mechanical
and chemical stability at relevant operating temperatures [59–65]. This observa-
tion along with successful coating trials performed on different substrate materials,
including P-91 sheets and internals of SS-316L pipe-sections, paves the way towards
an exhaustive qualification of the studied coating material and the coating technique
for nuclear fusion applications.
Fig. 14 a Detailed particle morphology of PbLi exposed coated section for P3; b XRD pattern
5 Applications and Outlook
5.1 Development of a Two-Phase Detection Probe for High

Temperature Liquid Metal Systems
Nuclear fusion breeding blanket concepts employ attractive solid and liquid candi-
date breeder materials in the form of lithium/lithium-containing compounds like Li,
Pb–16Li, Li2 O, LiAlO2 , Li4 SiO4 , Li2 SiO3 , Li2 TiO3 and Li2 ZrO3 [24, 66] with the
primary objectives of an efficient heat extraction and tritium breeding to achieve
self-sufficiency. Out of these candidate materials, PbLi has gained immense focus
for its various advantages as discussed in Sect. 1. Success of a breeder concept is
primarily governed by the TBR and its heat extraction performance, both of which
can be well achieved using PbLi in a self-cooled concept. However, as reported under
various studies, Li interaction with fusion neutrons to breed tritium also leads to the
generation of helium gas, a by-product, having relatively low solubility in PbLi and a
tendency to precipitate in the form of bubbles affecting the overall system design and
safety [67–69]. This entrapped gas volume within a breeder/coolant LM circuit tends
to cause local hot-spots, an improper nuclear shielding and a reduction in TBR, due to
the displaced LM volume. As reported under [67], for PbLi flow rates up to 1000 kg/s,
this gas phase generation is quite significant and independent of the system pressure.
Various concepts like HCLL, WCLL, DCLL and LLCB, therefore, would be prone
to such a gas precipitation phenomenon requiring detailed design considerations. In
some of the concepts like HCLL and LLCB, an in-box Test Blanket Module (TBM)
LOCA may lead to the ingress of high-pressure helium gas inside the PbLi circuit
resulting in a liquid–gas two-phase flow with a high density ratio between the two
phases. Additionally, preliminary experimental runs, at Institute for Plasma Research
(IPR), with water as a test fluid flowing in complex configurations similar to LLCB
TBM have corroborated the presence of trapped gas pockets at sharp 90° bends inside
TBM-like geometry along with entrained gas bubbles in re-circulation zones. Like-
wise, two-phase flow and trapped gas pockets are also expected in lab-scale PbLi
R&D facilities due to the charging in the presence of an inert cover gas.
To model such occurrences of high relevance towards the design and operation
of ancillary breeder/coolant circuits of fusion reactors, an extensive experimental
database needs to be generated for two-phase flow regimes in high density LMs,
mandating the development of proper diagnostic tools compatible with high temper-
ature corrosive PbLi environment. Numerous two-phase flow studies have been
conducted for room temperature LMs utilizing commercially available non-contact
techniques such as particle image velocimetry, laser, γ-ray, X-ray, neutron emission
etc. [39, 70–77]. However, the opaque nature, extreme operating environments and
installation constraints specifically encountered in high temperature LM facilities
make these techniques less attractive towards practical implementation in a fusion
reactor environment with stray magnetic and radiation fields. Specifically, localized
detection of trapped gases within a confined zone mandates the miniaturization of
the measurement technique/probe. In this view, electrical impedance based detection
techniques enable a better route in consideration to the installation ease, adaptation

feasibility and sensitivity due to a large difference between the electrical conductivi-
ties of LM and gas [38]. A relevant and detailed two-phase study, utilizing electrical
conductivity probes, has been performed on PbBi eutectic up to a temperature of
200 °C with the application of epoxy-resin insulation [78]. However, adaptation of
the technique to PbLi exerts severe demands on the electrical insulation performance
in terms of the chemical compatibility with highly corrosive PbLi at an operational
temperature up to 400 °C. As per a recent study [79] and to the best knowledge of
authors, no experimental data exist at present relevant to two-phase flow detection
and characterizations with PbLi as one of the constituent phase. Therefore, numer-
ical techniques like RELAP/SCDAPSIM/MOD4.0 codes are being applied to study
different flow regimes.
In the present study, a multivariable sensor probe is fabricated from a duplex
configuration K-type thermocouple with both sensing junctions located at 1.5 mm
from the sheath tip having an outer sheath diameter of 1.5 mm covered with an
insulation layer of Al2 O3 coating. An ungrounded configuration allows the utilization
of a single probe for simultaneous electrical conductivity based measurements and
bulk two-phase temperature measurements. The dimensional schematic (not to scale)
of the multivariable probe and an image of the as-fabricated probe are shown in
Fig. 15a, b, respectively. A recrystallized alumina tube of 200 mm in length with a
2 mm bore and 1 mm wall thickness provides necessary protection and ruggedness
to the probe in a heavy LM environment against impacts from the argon bubbles
rising in the two-phase column. Developed PbLi-argon two-phase test facility and
the probe installation scheme within the facility are presented in Fig. 16a, b.
Working principle for the probe is similar to that mentioned in [38, 80] except
that the second electrode is replaced by another K-type thermocouple, which also
measures bulk PbLi temperature in the test facility before argon gas injection. Fabri-
cated probe provides thermal trends for the two-phase flow in addition to discrete
voltage dips corresponding to the bubble interactions with the exposed metallic tip of
the sheath. Installation of the probe is facilitated using compression fittings providing
a gas tight seal to maintain an inert cover gas environment and to minimize probe
movement during bubble impaction.
Fig. 15 a Dimensional schematic for the multivariable probe; b image of as-fabricated probe
Fig. 16 a Schematic for the two-phase test facility; b facility with installed multivariable probe
Probe calibration is performed in static liquid PbLi at a bulk temperature of 290 °C

by manual dipping and retrieval giving rise to an almost pulsed shaped voltage output,
across a 250 Ω sensing resistor, nearly equal to the excitation voltage of 5 VDC due
to the high electrical conductivity of PbLi [50, 51]. Data-processing for the temper-
ature trends also involves smoothening using a moving average function of last 100
samples. A representative data logged at 0.2 kHz sampling frequency is shown in
Fig. 17. The similarity in the temperature variation trends for both the junctions
of duplex thermocouple validates the accuracy of measurements. The calibration
data highlights an excellent response of the electrical conductivity based measure-
ments, but a sluggish response of the two-phase bulk temperature trends providing
a qualitative insight related to the existing two-phase flow regime.
The multivariable probe is exposed to two-phase flow regimes in PbLi-Ar vertical
column with a bulk PbLi temperature of 390 °C and varying time-averaged void frac-
tions (hereafter denoted as α). Obtained voltage pulses from electrical conductivity
based measurements are normalized in binary, where the data points with a voltage
magnitude ≥80% of the maximum voltage output are assigned logic HIGH (1) and
remaining data points are assigned a logic LOW (0). The ratio of the number of data
points with logic LOW to the total number of data points defines α for the time-
interval under consideration. Relevant extracted data from the enveloping validation
tests are presented under Fig. 18a–c to demonstrate the performance of fabricated
probe over a wide range of α, representing single phase LM flow (α = 0), well-
dispersed bubbly column regime (α = 0.02) and localized annular flow regime (α =
0.95).
Variation in the experimentally measured two-phase bulk temperature using the
multivariable probe is observed to be inversely dependent on α. The obtained voltage
data in agreement with the bulk temperature trends establishes a reliable detection of
Fig. 17 Calibration tests for the multivariable probe in static molten PbLi environment
two-phase using the fabricated multivariable probe. For all the cases, the measured
two-phase bulk temperature is lower than the bulk PbLi temperature (390–400 °C)
owing to the coupled effect of forced convection by the injected RT argon gas and a
resultant simultaneous decrease in the effective thermal conductivity of the two-phase
mixture, leading to a reduced heat extraction from the resistively heated test facility
tank walls. The multivariable probe also enables the detection of average bubble
frequency and average bubble residence time [81]. A continuous probe exposure in
high α (>0.9) PbLi–Ar two-phase environment for over 2 h followed by high voltage
tests generating an insulation leakage current of <1 nA corroborates the integrity of
applied Al2 O3 coatings in a dynamic LM environment. During the tests, the probe
is exposed to temperature gradients of up to 300 °C within a few seconds (during
immersion) and pressure gradients up to 3 bar(g) during the sparger tests. No adverse
effects of such rigorous tests are observed.
Fig. 18 Probe validation tests in a Single phase flow; b well-dispersed bubbly flow; c localized
annular flow (similar to a LOCA) with bulk PbLi at 400 °C
In the present study, up to 8 bubble/s could be resolved successfully at α ~ 0.58

using the developed probe. Further, it is experimentally observed that for α ≤ 0.6, the
bubble frequency tends to increase with an increase in α, while for α > 0.6, the bubble
frequency shows a decreasing trend with an increased gas phase fraction leading to
an increased bubble residence time. This phenomenon could be primarily attributed
to the coalescence of smaller bubble pockets. Although an unavailability of fully
developed two-phase flow regime in the present facility limits the identification of
clear transitions between different flow regimes, the primary aim of validating the
developed probe as a tool towards experimental detection of PbLi–Ar two-phase
flows at relevant operating temperature has been successful considering the satisfac-
tory functioning of probe covering all the operational ranges of time-averaged void
fraction.
The developed probe is expected to be an indispensable tool enabling future exper-
imental studies on two-phase flow at high temperature, providing substantiation for
software models being developed for advanced LM based breeding blanket concepts.
5.2 Development of Electrically Decoupled Liquid Metal

Flow Channels
Although the LM breeders exhibit several attractive key advantages, the rewards
are to some extent shadowed by their inherently high electrical conductivity, which
results in humongous MHD pressure drops in the presence of a transverse magnetic
field as discussed under Sect. 1. The position is further worsened as this pressure
drop varies in a square fashion to the magnitude of transverse magnetic field and
in proportionality to both the LM channel wall thickness and LM flow velocity as
follows [82]:
P = L · B 2 · V · σw · (tw /a) (1)
where, L is the length of the flow channel, B is the transverse magnetic field strength,
v is the mean velocity of flowing LM, σw and t w are the electrical conductivity and
thickness of the wall material, respectively, and a is the half-width of the channel in
the direction of B. Therefore, for a given field strength, utilization of high throughput
circulation pumps to counter the MHD pressure drops may only partly improve the
situation due to the requirements of thicker pipe walls to sustain the internal pressures.
Likewise, reduction of the LM velocity requires thoughtful considerations towards
the design aspects and material compatibility in view of the resulting temperature
rise at the LM-structure interface, corrosion criteria and the ensuing inefficiency of
heat extraction.
Ideally, a complete electrical decoupling of the pipe wall from the flowing LM
can be achieved by employing a thermally and chemically compatible electrically
insulating coating. In addition to providing a high electrical resistivity and thermal
stability, a promising functional material shall also be resistant to exfoliation/cracking
during thermal cycles over the expected blanket lifetime. Therefore, innovative tech-
nological developments yielding a dense, compact and non-porous layer could pave
a path to resolve some of these critical issues. Such developments are also addition-
ally being sought for possible implementations in the advanced LFRs and MSRs.
In this direction, and in view of the promising electrical insulation characteristics
observed for the AlPO4 -bonded Al2 O3 coating in static PbLi environment (Sect. 3.2),
the coating methodology through atomization/spray coating technique is being addi-
tionally explored to obtain a thinner coating with a uniform thickness. Some of
the successfully fabricated planar and non-planar geometries, with coating thick-
ness less than 100 μm, are depicted in Fig. 19a. However, scalability of the spray
coating methodology for non-planar pipe ducts is still under development stage and
compatibility tests are being planned in a dynamic Pb/PbLi LM environment.
Another practical way to alleviate the MHD pressure drop, without exerting addi-
tional stresses on the structural materials, is to use steel-insulator-steel sandwich
configuration FCIs where the inner steel liner in contact with the LM is relatively
thinner (0.5–1 mm) and helps avoid the LM ingress into the electrically insulating
porous ceramic layers [83–86]. Such a configuration, in compliance to Eq. (1) enables
Fig. 19 a Spray coated planar and non-planar samples; b dimensional schematics for circular
cross-section and square cross-section FCI prototypes
significant reductions in the MHD pressure drop. For instance, for a given duct diam-
eter, a 1 mm thin liner in contact with the LM is expected to generate ~75% less MHD
pressure drop per unit length as compared to a nominal duct of 40 schedule (~3.91 mm
thickness). This configuration also benefits from the absence of constraints including
peeling resistance, damage due to mismatch of CTEs and chemical compatibility
requirements on the LM exposed coating, making this one of the highly sought-after
solutions in the fusion community [2, 87, 88]. However, the functional performance
of an FCI is also guided by the lower limit on the inner liner thickness consid-
ering the corrosion allowance and the mechanical integrity aspects. In this view, a
range of relevant FCI prototype geometries (including square cross-section, circular
cross-section, 90° bend etc.) are being fabricated at IPR to assess the electrical and
mechanical performances at fusion blanket relevant temperature/pressure regimes.
Figure 19b presents the dimensional schematic for the fabricated FCI prototype
geometries containing a thicker insulation layer created from the same refractory
coating suspension. These prototypes are being tested for scalability and mechanical
integrity through Tungsten Inert Gas (TIG) welding, pressure tests up to ~10 bar(g)
followed by minor machining operations. Initial results on the estimated electrical
insulation performances, evaluated over several runs, for the prototype FCIs are
presented in Fig. 20a, b. It shall be noted that the adopted methodology in this work
provides homogeneity and necessary flexibility towards the fabrication of difficult
FCI geometries and critical sections, including expanders and reducers, transition
joints, etc.
The repeatability of the data observed from Fig. 20 suggests a good stabiliza-
tion and representativeness of the electrical resistivity values over the investigated
temperature range. Over the relevant temperature range, the order of magnitude for
the estimated electrical resistivities for thicker FCI ceramic layers also agrees well to
the resistivity estimations of thin coats exposed to PbLi environment (refer Appendix
A) and to the recent works on oxides in the representative temperature range [89, 90].
This further corroborates the thermal and chemical stability of the α-Al2 O3 /AlPO4
Fig. 20 Electrical resistivity estimations: a Circular cross-section FCI; b square cross-section FCI
based insulation. The electrical resistivity remains higher than 105 Ω m over the
investigating temperature regime (100–600 °C), affirming the applicability of FCI
assemblies fabricated through this methodology [90].
6 Conclusions
• An α-Al2 O3 /AlPO4 based coating-bonding pair is studied as a candidate func-

tional material to address the electrical insulation requirements in molten PbLi
breeder applications. The optimized heat cure parameters enable coating deposi-
tion at a relatively low temperature and the coating demonstrates good adherence,
compactness, non-porosity and high insulation resistance at room temperature.
• The coated metallic substrates exposed to static molten PbLi for ~1360 h at 300–
400 °C demonstrate good chemical compatibility, thermal stability and electrical
insulation characteristics with an estimated coating resistance of the order of
104 –106 Ω m2 , orders of magnitude higher than required towards practical appli-
cations in MHD pressure drop reductions in PbLi liquid metal based breeders,
leaving ample margins for insulation degradation through Radiation-Induced
Conductivity (RIC)/ Radiation-Induced Electrical Degradation (RIED).
• EDX analysis affirms Pb ingress limited to 20 μm of coating thickness for ~700 h
duration exposure to PbLi at temperature up to 350 °C.
• Considering the application ease, the adopted coating methodology provides
promising solutions to coat difficult and irregular substrate geometries typical of
breeder blankets. The prominent presence of thermodynamically stable α-Al2 O3
further advocates the coating utility towards TPB applications addressing the
concerns related to radiological hazards.
• A multivariable two-phase detection probe fabricated using high purity α-Al2 O3 /
AlPO4 electrically insulating coating enabled the first two-phase detection exper-
imental studies in molten PbLi for temperature up to 400 °C under a wide range of
two-phase flow regimes i.e., single phase flow, dispersed bubbly flow and local-
ized annular flows with α varying from 0 to 0.95. The developed probe provides a
highly reliable means to quantitatively characterize gas bubbles with estimations
of bubble frequency, average bubble residence time along with bulk two-phase
temperature. Further, experimental observations suggest that for α ≤ 0.6, the
bubble frequency tends to increase with an increase in α while for α > 0.6, the
bubble frequency decreases suggesting the possible phenomena of bubble coales-
cence. The developed probe is expected to be an indispensable tool enabling exper-
imental studies at high temperature providing substantiation for software models
being developed for advanced liquid metal based breeding blanket concepts.
• The α-Al2 O3 /AlPO4 coating suspension is exploited in a systematic attempt to
assess the fabrication feasibility of complex FCI geometries for intended imple-
mentations in liquid metal breeders and coolant circuits of fusion power plants.
The exhibited insulation performance at 600 °C is orders of magnitude higher
than required for achieving satisfactory FCI performance. Further, the cracks and
damages arising within the insulation layer are of no significant concern owing
to a relatively higher insulation thickness providing a complete electrical isola-
tion between the two electrically conducting liners. These technological solu-
tions can enable extended fusion blanket operations with negligible repairing/
replacement requirements. The predominant presence of α-Al2 O3 /AlPO4 ceramic
network widens the utilization towards tritium permeation barrier as well.
Considering the initial applications in lab-scale PbLi R&D facilities, the prelim-
inary investigations on thin coatings are conducted over a moderate temperature
limited up to 400 °C only. However, further investigations are planned for extended
durations at higher temperature in flowing PbLi. A complete corroboration towards
application suitability in fusion grade blankets, however, requires further rigorous
validations under flowing PbLi conditions at representative temperature and radiation
environment to assess the extent of radiation-induced conductivity.
Acknowledgements Part of this book chapter has been reprinted from Abhishek Saraswat, Chan-
drasekhar Sasmal, Ashokkumar Prajapati, Rajendraprasad Bhattacharyay, Paritosh Chaudhuri,
Sateesh Gedupudi. Experimental investigations on electrical-insulation performance of Al2 O3 coat-
ings for high temperature PbLi liquid metal applications. Annals of Nuclear Energy, Volume 167,
(2022), 108856, https://doi.org/10.1016/j.anucene.2021.108856, with permission from Elsevier,
under the license number: 5406831492670, dated Oct 12, 2022.
Part of this book chapter has been reprinted from Abhishek Saraswat, Ashokkumar Prajapati,
Rajendraprasad Bhattacharyay, Paritosh Chaudhuri & Sateesh Gedupudi. Development of a
Compact Multivariable Sensor Probe for Two-Phase Detection in High Temperature PbLi–argon
Vertical Columns. Instruments and Experimental Techniques, Volume 65, 179–189 (2022) https://
doi.org/10.1134/S0020441222010109, with permission from Springer Nature, under the license
number: 5406860014286, dated Oct 13, 2022.
Appendix A: Estimation of Volumetric Electrical Resistivity

and Coating Resistance
Insulation resistance of an electrical cable is given by the following relation:

R
Ri = ln (2)
2πl r
where, Ri = Insulation resistance of the cable (Ω), = Volumetric electrical resistivity
of the insulation material (Ω m), l = Length of the insulation over the cable (m), R =
Outer radius of the cable with insulation (m) and r = Outer radius of the conductor
(m).
Using data from Tables 1, 2, 3, 4 and 5 and taking the enveloping IR values at
each temperature:
Test Probe Insulation Average Coated Temperature Resistivity Coating

campaign resistance coating length (°C) (Ω m) resistance
(Ω) thickness (m) (Ω m2 )
(mm)
1 P1 6 × 109 0.495 0.085 300 6.65 × 109 3.29 ×
106
6.18 × 109 0.495 0.085 300 6.85 × 109 3.39 ×
106
0.822 × 0.495 0.085 350 9.12 × 108 4.51 ×
109 105
1 × 109 0.495 0.085 350 1.11 × 109 5.49 ×
105
P2 1 × 108 0.212 0.065 300 1.74 × 108 3.68 ×
104
3.15 × 108 0.212 0.065 300 5.47 × 108 1.16 ×
105
0.835 × 0.212 0.065 350 1.45 × 108 3.08 ×
108 104
1 × 108 0.212 0.065 350 1.74 × 108 3.68 ×
104
2 P3 2.90 × 108 0.429 0.060 300 2.55 × 108 1.09 ×
105
4.57 × 108 0.429 0.060 300 4.01 × 108 1.72 ×
105
1.29 × 108 0.429 0.060 350 1.13 × 108 4.86 ×
104
2.99 × 108 0.429 0.060 350 2.63 × 108 1.13 ×
105
0.583 × 0.429 0.060 400 5.12 × 107 2.20 ×
108 104
(continued)
(continued)
Test Probe Insulation Average Coated Temperature Resistivity Coating
campaign resistance coating length (°C) (Ω m) resistance
(Ω) thickness (m) (Ω m2 )
(mm)
0.768 × 0.429 0.060 400 6.74 × 107 2.89 ×
108 104
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Silicone-Based Coatings
for High-Temperature Applications
T. Dharini, Anand Krishnamoorthy, and P. Kuppusami
Abstract This chapter explores the use of silicone-based coatings for high-
temperature applications. These coatings have unique properties that make them ideal
for use in environments that experience extreme temperatures, such as aerospace,
automotive, and industrial applications. This chapter also discusses the benefits of
using these coatings, including their excellent thermal stability, resistance to oxida-
tion and corrosion, and ability to maintain their properties over a wide temperature
range. This chapter also looks at some of the key factors that influence the perfor-
mance of silicone coatings, including temperature, stress, exposure, and curing time.
In addition to the benefits mentioned above, silicone-based coatings offer other
advantages such as flexibility, adhesion to various substrates, and chemical resis-
tance. These properties make them suitable for use in harsh environments when
exposed to chemicals, abrasion, and weathering. Finally, the chapter highlights the
importance of curing conditions on the coating performance. In conclusion, silicone
coatings play a vital role in many industries, and understanding their properties is
essential for achieving optimal performance and durability.
Keywords Silicone coatings · Silanes · Polydimethylsiloxane · Silicone

polyethers · Silicone elastomers · Silicone resins
Abbreviations
BTSE Bis-[Triethoxysilyl] Ethane

PDMS Polydimethylsiloxane
EO Ethylene Oxide
BO Butylene Oxide
T. Dharini · P. Kuppusami
Centre for Nanoscience and Nanotechnology, Centre of Excellence for Energy Research,
Sathyabama Institute of Science and Technology, Chennai 600 119, India
A. Krishnamoorthy (B)
Adi Shankara Institute of Engineering and Technology, Kalady, Ernakulam 683 574, Kerala, India
e-mail: anandkrishnamoorthy20@gmail.com
386 T. Dharini et al.
HCR Heat Cured Rubber

LSR Liquid Silicone Rubber
RTV Room Temperature Vulcanization
TGA Thermogravimetric Analysis
DSC Differential Scanning Calorimetry
DMA Dynamic Mechanical Analysis
DVS Dynamic Vapour Sorption
1 Introduction
Silicone coatings are a novel class of high-temperature coating materials due to

their unique and distinct properties which make them suitable for various industrial
applications [1]. Silicone resin found its first commercial application during Second
World War, when they were used as damping fluids in engines of aircraft to minimize
corona discharge at elevated altitudes. Adherent silicones synthesized from trifunc-
tional organosilicone intermediates were employed as insulation in electric motors
in conjunction with glass films. Then, in 1945, Dow Corning and General Electric
both announced the creation of silicone rubber, which could be used at temperatures
both hot and cold [2]. The majority of silicone were methyl and phenyl crosslinked
silanol polysiloxanes weighs approximately from low molecular weight to average
molecular weight of 2,000–50,000.
The factors that influence the properties of silicone resins are the degree of
crosslinking, phenyl to methyl ratio, molecular weight, and the concentration of
silanol. Silicone resins are in the form of emulsions, solids, and organic solvent
solutions. The advancement of silicone resins enabled the creation of hundreds
of high-temperature-resistant coating compositions. The use of silicone resins as
additives, reactive intermediates, and carriers has evolved a new market. The high-
temperature service of silicone chemistry and formulation leads to high corrosion
resistance, weathering resistance, and colour retention improvement in a wide variety
of silicones operating from medium to high-temperature applications.
During the early 1950s, these silicone formulations were applied to stove parts,
boilers, engines, mufflers, heat exchangers, exhaust stacks, and aircraft components
to give protection at temperatures up to 816 °C [3]. During the 1950s, pigments for a
wide range of colours became accessible, enhancing the utility of silicone coatings for
applications requiring specific colour requirements, such as olive drab space heaters
and military truck exhaust pipes. Formulators at the time began to modify silicones
with organic polymers, or organic polymers with silicones, in order to dramatically
reduce product costs while maintaining quality performance. Alkyd resins are still
the most often used. Silicone advancements, like many other technologies, were
propelled by the space programme and eventually applied to other sectors. A 100%
silicone coating (with a thermal resistance of 1371 °C) used to protect the space
shuttle’s orbiter’s tiles during re-entry into the Earth’s atmosphere1 has since found
Silicone-Based Coatings for High-Temperature Applications 387
use in the nuclear manufacturing sector. Later, in the chemical processing sector, a
patented procedure using this coating was developed to prevent fused-glass structures
against crystal formation at temperatures of 982 °C during the manufacturing of
titanium dioxide.
It is predominantly used in aerospace, automotive, and construction industries
because of its ability to withstand higher temperatures, corrosion resistance, and high
thermal stability over a longer period. Substrate materials like ceramics, polymers,
and metals that operate at a temperature ranging from 200 to 600 °C must be coated
with silicone coatings to protect from corrosion, heat, and abrasion without losing
their physical properties. Since silicone coatings have low thermal conductivity (i.e.)
the heat transfer rate is less from the substrate where it is coated to the environment,
it acts as an insulator inside the combustion chamber, exhaust systems, and furnace
linings. It also continues to play a vital role in innovation and advancing technology.
Another advantage of using these coatings in high-temperature environment is their
better adhesive strength to different types of substrates [4]. It is even enhanced by
mixing with polymers to increase the bond strength between coating and substrate.
These coatings are also used in harsh environments where lots of chemical reactions
occur. It is resistant to various organic solvents, acids, and bases. It also offers elec-
trical insulation where the coating prevents the ingress of moisture between substrate
and environment and finds its application in the electronics industry also. Silicone
coatings are known for their UV resistance and hence it is coated in solar panels
without undergoing degradation. With the continuous advancements in technology,
applications of silicone coatings are further driving innovations in various industries
[5, 6].
2 Silicone Materials and Their Unique Properties
Silicone materials are a family of synthetic polymers composed of silicon, oxygen,

carbon, and hydrogen. They have a wide range of chemical and physical proper-
ties that suit various applications [7]. They are resistant to many chemicals, UV
radiations, sunlight, water, and ozone which makes them ideal for outdoor appli-
cations when exposed to weather conditions. It is also biocompatible making them
suitable for use in medical and pharmaceutical industries. Another distinct property
of silicone material is their formulation to be rigid and flexible and can be used as
flexible and soft seals, gaskets, and hard encapsulations. This unique combination
of properties such as high thermal and chemical resistance, and better flexibility
makes them an ideal choice for high-temperature applications in the form of coat-
ings. The components and structures that exist in high-temperature environments
are protected by silicone coatings against corrosion and wear. These coatings play a
vital role in automotive, aerospace, and industrial equipment. In aviation industries,
particularly the heat engines that operate at high temperature can resist thermal shock
by providing a layer of insulation due to the application of silicone coatings. It can
reduce the effect of thermal cycling, material degradation, and failure. Therefore,
the reliability and fuel efficiency of turbine blades, combustors, and exhaust systems
have increased and reduced emissions. Silicone coatings are also coated in industrial
equipment such as furnaces, reactors, and boilers and used in pipelines and other
components in the oil and gas industries to protect them from corrosion. It is also
used in metal working and glass manufacturing industries because of its operation
in high-temperature environments such as melting, shaping, and casting. Further-
more, silicone coatings are biocompatible and have low toxicity. Hence, it is used to
protect medical devices and pharmaceutical products. Overall, these coatings have
been used in various industries and have led to increase the efficiency, reliability,
and safety thereby reducing the maintenance cost [8]. Further research and develop-
ment in silicone-based coatings may lead to even more significant advancements in
high-temperature applications. Table 1 lists the key properties of silicone material.
Silicone materials are synthetic polymers that have a unique combination of phys-
ical and chemical properties which makes them useful in many applications. The most
important property is thermal stability up to 200–250 °C due to the presence of Si–O–
Si bonds in the backbone of silicone that are highly stable even at high temperatures.
They remain flexible at low temperatures, down to as low as −100 °C. Because of
the high molecular weight and flexibility of the silicone chains, they can move and
rearrange themselves even at low temperatures. It is also used for electrical insulation
due to its high dielectric strength, where the ability of strong Si–O bonds to polarize
in an electric field. Because of this property, it can resist high voltage and electrical
arcing in cables, seals, and connectors. Silicone materials show a hydrophobic nature
which repel water and are resistant to many chemicals. They are non-reactive and do
not support microbiological growth. Hence, it is used for food and beverage appli-
cations. They are commonly used in adhesive applications, due to the ability of the
polymer to form strong bond with many substrates. Overall, the unique combina-
tion of physical and chemical properties of silicone materials makes them a versatile
and valuable coating material for a wide range of industries and applications [9].
Table 1 Key properties of silicone

Thermal conductivity Low thermal conductive
Chemical reactivity Naturally non-reactive
Water repellency Highly repellent to water
Toxicity Nontoxic
Resistance to UV light and oxygen Highly resistant to degradation by both radiation and
oxidation
Sealing ability Extremely adhesive to smooth surfaces
Gas permeability Highly permeable to gas molecules
Electrical conductivity Naturally, insulator but adding fillers can make them
conductive
Organic solvent resistance Resistive to most chemicals
Thermal stability Thermally stable over a wide temperature range
Fig. 1 Components of silicone coating agents and their applications
Figure 1 shows the various components of silicone coating agents with their major
applications.
3 Types of Silicone Coatings and Its Performance at High

Temperature
3.1 Silanes
A group of biocompatible materials, based on organic and inorganic silicon, are

known as silanes. Silanes quickly hydrolyze in an aqueous solution and generate
silanol groups (SiOH), which allow them to connect to any hydrated metal surface
(metal–OH) through the creation of metal linkages of silicon and oxygen [10] (Fig. 2).
It forms a protective layer on the surface of metal substrates by siloxane bonds
that formed due to the self-cross linkage of silanol groups. The corrosion resistance
of Mg alloy after being coated with silane coating has been investigated by many
researchers. In 0.005 M NaCl solution, the development of a silane layer on a WE54
Mg alloy raised its impedance by two orders of magnitude, and the impedance values
persisted in the 1 MU cm2 range for several hours. However, after 3 days of immer-
sion, the impedance value reduced to 0.2 MU cm2 and became comparable to that
of the untreated Mg alloy after 1 week of immersion [11]. For AZ31 Mg alloy, a
Fig. 2 Chemical structure of

silane SiH4
stable impedance value was observed after coated with silane coating by immersing
it into Hank’s solution for a duration of 48 h. When the duration exceeds, a large
defect formed at the silane coating leading to a sudden decrease in impedance value.
Therefore, it can be concluded that silane-coated Mg alloys are protected against
corrosion in the short term due to the accumulation of corrosion products. As the
immersion duration increases, corrosion of Mg alloy takes place by the penetration
of a corrosive medium through the silane layer. This prolonged alkalization leads
to spallation of coating with increased defects and delamination occurs due to the
accumulation of corrosion products. As a result, enhancing the bond strength and
hydrolytic stability of silane coatings becomes crucial in corrosion resistance for Mg
alloys [12].
Another approach was tried by Xue et al. [13] by modifying the surface of Mg-
4Y alloy with epoxy resin and bis-[triethoxysilyl] ethane (BTSE). The resistivity
of the epoxy-modified BTSE silane coating was successfully increased. But it fails
to provide long-term corrosion resistance in 0.9 wt.% NaCl. Crack initiation and
propagation are developed by the high-temperature exposure (100 °C) and short
curing time during the curing process of epoxy-modified BTSE silane coating. The
silane coatings functioned as a physical barrier, improving the corrosion resistance of
the AZ31 Mg alloy. Heparin functionalization of the silane-coated AZ31 Mg alloy
decreased the level of corrosion protection provided by the silane coating while
dramatically lowering platelet adhesion. It is advantageous for silane coatings to
provide a good base for imparting bifunctional characteristics. However, the bond
strength and hydrolytic stability must be enhanced before they can be accepted as a
surface modification strategy for Mg alloys in the creation of Mg-based degradable
biomaterials.
3.2 Polydimethylsiloxane (PDMS)
PDMS is a silicon elastomer polymer composed of inorganic chains with high surface
energy linked to silicates, methyl groups, inorganics, and low surface energy. These
methyl groups are abundant in the chemical structure of PDMS and are critical in
providing PDMS’s hydrophobic properties, with a surface tension of roughly 20.4
mN/m [14]. PDMS is commonly synthesized through hydrolysis and the condensa-
tion process of dichlorosilanes, yielding cyclic and linear polymers. The polymers
obtained through this synthesis method have low molecular weights that cannot be
employed in most practical applications. As a result, to increase molecular parameter,
the prior synthesis method was gradually replaced by ring-opening polymerization of
cyclic siloxanes. It should be emphasized that the anionic polymerization of hexam-
ethylcyclotrisiloxane monomer provides the basis for the kinetically controlled poly-
merization of PDMS. Based on a chain reaction in which a specific catalyst reacts
with hexamethylcyclotrisiloxane to generate short silanolate-ended chains capable of
attacking other hexamethylcyclotrisiloxane molecules, this synthesis method allows
the formulation of almost monodisperse PDMS with customized structures. The
Fig. 3 Chemical structure of

polydimethylsiloxane
CH3 [Si(CH3 )2 O]n Si(CH3 )3
molecular structure consists of a (Si–O) backbone and repeating (Si(CH3 )2 O) units,

which may be written as CH3 [Si(CH3 )2 O]n Si(CH3 )3 , where n represents the number
of repetitive units. These repeats define a material’s molecular weight, which in turn
specifies qualities such as viscoelasticity. Furthermore, (CH3 ) indicates the methyl
group, and (Si–O) represents the strength of the siloxane linkages that keep this
material chemically and thermally stable. The crosslinking reaction with groups like
phenyl and vinyl can produce significant property changes for a variety of appli-
cations and significant property modifications for a variety of applications [15–17]
(Fig. 3).
Because this elastomer is commonly utilized in the biomedical field, it has great
biocompatibility and biostability. These names refer to materials that have no negative
effects when they come into contact with biological tissues. Although the process for
biocompatibility is still not completely understood, it is known that interactions with
water in proteins are essential factors that are connected to physicochemical prop-
erties such as surface free energy, stiffness, surface charge, and wettability. Another
key component of biomaterials is structural biocompatibility. This is connected to
mechanical interactions between an implanted device and the surrounding tissues.
3.3 Silicone Polyethers
Silicone (or siloxane) polyether copolymers are typically made up of a silicone

polymer component chemically coupled with one or more organic polyether compo-
nents. Polar organic groups such as polyoxyalkylene, quaternary ammonium ions,
and betaines have been chemically bonded to the polysiloxane backbone to generate
siloxane surfactants [18]. The chemical reaction between a polysiloxane and a
polyether can result in the creation of hydrolytically stable silicon-carbon bonds
(Si–C) or hydrolytically unstable silicon–oxygen–carbon bonds (Si–O–C). These
types of linkages is desired in the silicone polyether copolymer which determines
the chemicals required for the chemical coupling reaction as well as the physical
qualities of the final copolymer. The hydrosilylation of a silicon hydride functional
polysiloxane with an allyloxy polyether results in the production of a Si–C bond.
The most frequent structures are rake or pendant type silicone polyethers, which are
given by the formula Me3 SiO (Me2 SiO)x (RMeSiO)y SiMe3 , where Me represents
a methyl group and R denotes the polyether functionality. The levels of x and y,
as well as the x/y ratio, can vary greatly and influence the physical, chemical, and
surface properties of the resultant copolymer. R’s shape might also vary greatly. It
is denoted by the notation (EO)m (PO)n (BO)o , where EO stands for ethylene oxide
(CH2 CH2 O), PO stands for propylene oxide (CH2 CHCH3 O), and BO stands for buty-
lene oxide (CH2 CH(CH2 CH3 )O). Structures ranging from high molecular weight
siloxane polymers with large x to those with no dimethylsiloxane units are feasible.
A large range of items can be generated because of the nearly limitless possibility
of change. These range from very efficient super-spreaders to emulsifiers with high
molecular weight. Silicone polyethers, which are manufactured from ethylene oxide
and propylene oxide-based combinations, are widely employed in a wide range of
applications, including lubricants, water in oil emulsions, textile additives, leather
additives, paints and coatings, agro chemicals, release agents, personal care, etc.
3.4 Silicone Resins
Silicone resins are polymers with a three-dimensional branching chain structure

that have a low molecular weight. Their various qualities, including great thermal
stability, make them ideal for use as binders in paints, varnishes, and impregnating
materials. Silicone resins, like oils, are composed of an alternating chain of silicon
and oxygen atoms in the shape of a 3D network [1]. It might be in the form of a
liquid, powder, or dissolved in an aromatic solvent. Silicone resins are branched,
cage-like oligosiloxanes with the general formula Rn SiXm Oy , where R is a non-
reactive substituent, typically Methyl (Me) or Phenyl (Ph), and X is a functional group
Hydrogen (H), Hydroxyl group (OH), Chlorine (Cl), or Alkoxy group (OR). In many
applications, these groups are further condensed to produce strongly crosslinked,
insoluble polysiloxane networks. When R is methyl, the four functional siloxane
monomeric units are “M” representing Me3 SiO, “D” for Me2 SiO2 , “T” for MeSiO3 ,
and “Q” for SiO4 . It is worth noting that a network consisting solely of Q groups trans-
forms into fused quartz. The most common silicone resins are made of D and T units
(DT resins) or M and Q units (MQ resins), although many additional combinations
(MDT, MTQ, QDT) are utilized in the industry as well. Silicone resins are used in
a wide variety of items. Pressure-sensitive adhesives, silicone rubbers, coatings, and
additives benefit greatly from materials with molecular weights ranging from 1000
to 10,000. To make thermoset polymer matrix composites, coatings, and adhesives,
polysiloxane polymers with reactive side group functionality, such as vinyl, acry-
late, epoxy, mercaptan, or amine, are employed. Hydrolytic condensation of several
silicone precursors produces silicone resins. Sodium silicate and other chlorosi-
lanes were employed as starting ingredients in early silicone resin manufacturing
procedures.
Silicone rubber is frequently used in applications where it operates at high temper-
atures when other elastomers are ineffective [19]. It is non-toxic, making it suitable
for food contact, implants, and so on. It has a good electrical resistance, can tolerate
steam sterilization, and can be coloured easily. It has low mechanical strength and
abrasion resistance. To increase its application in specific goods, the material is
mixed with various fillers and chemical additives. Carbon black can be used to boost
conductivity in cable connectors, keypads, and other applications. The material’s
hardness can range from soft gels for use in shoe insoles to moderately hard rubber,
which is comparable to several thermosets and thermoplastics. Additives can also
improve thermal conductivity, flame resistance, and adhesiveness. Because of its
biocompatibility, silicone rubber is suitable for various devices that come into touch
with the body, such as face masks, mouthpieces, catheters, baby nurseries, pacifiers,
and so on. The material is increasingly being utilized in cookware, such as muffin
pans, where its heat resistance and innate slipperiness provide a flexible alternative to
PTFE-coated bakeware. It has no taste or odour and has no effect on food. Its excel-
lent compression-set properties make it an excellent material for various gaskets
and O-rings. Because of its limited abrasion resistance, it is typically used in static,
non-running seals. Silicone resins are also employed in lubricants, releasing agents,
speciality films, dielectric greases, and other similar applications.
3.5 Silicone Elastomers
Silicone elastomers are made by combining reactive, straight chained molecules with
a crosslinking agent and reinforcing to provide good mechanical properties (elas-
ticity, absorption, tear strength). Silicone elastomers are formed from a combination
of linear polymers, reinforcing agents, a crosslinker, and a catalyst. The viscosity and
kind of basic straight-chain molecule, as well as the processing temperature, influence
the type of elastomer produced: Heat Cured Rubber (HCR), Liquid Silicone Rubber
(LSR), and Room Temperature Vulcanization (RTV). Mineral fillers such as silica,
alumina, calcium carbonate, silicone resins, and so on can be used to reinforce these
elastomers. Depending on the technology chosen to suit exact processing require-
ments, radical, condensation, or addition crosslinking processes may be utilized. To
assure certain properties (colour, rheology, pot life, etc.) or performance standards
(electrical insulation or conduction, heat transfer, fire retardancy, chemical adhesion,
mould release, etc.), a wide range of additives can be added to the elastomer in its
final composition.
Silicone elastomers are employed in high-performance applications, particularly
in hostile situations where conventional polymers might fail. Parts constructed of
silicone elastomer rubber offer extended durability and reliability, especially when
exposed to extreme outside conditions (humidity, UV, Ozone) [20]. Their dielec-
tric qualities and thermal resistance make them ideal for insulating and protecting
electronic equipment, particularly high voltage lines. These items will retain their
elastomeric features, such as very high elongation before breaking point and/or
great ripping resistance (important in moulds, modelling and replication, kitchen-
ware). Silicone elastomers are also non-toxic to the human body and resistant to the
Table 2 Key properties and applications of various silicone coatings

Type of silicone coating Properties at high Applications
temperature
Silanes Hydrophobic, thermal Automotive primer coats, protective
stability, chemical and architectural coatings
abrasion resistance
Polydimethylsiloxane Good water repellence, Water repellent coatings for fabrics,
wetting, foam control, protective automotive coatings, and
abrasion resistance and anti-fouling coatings for marine
anti-slip properties applications
Silicone polyethers Abrasion and slip resistance Decorative, agricultural, industrial,
and fabric coatings
Silicone resins Water repellence, thermal Heat resistant coatings for kitchen
stability, chemical appliances, moisture proofing, and
resistance, electrical insulating coatings for building and
insulation, and hardness construction materials
Silicone elastomers Extremely durable with high Electrical applications such as
resistance against powerline insulators
temperature, moisture, and
UV radiation
high temperatures used in sterilization processes, making them perfect for medical
applications (skin contact, medical equipment, long-term implants) (Table 2).
4 High-Temperature Coating Applications of Silicone

Materials
4.1 Aerospace and Aviation
Due to its high-temperature weatherability, thermal stability, corrosion, and chem-

ical resistance, silicone coatings are widely used in aerospace and aviation indus-
tries. Aerospace components like re-entry vehicles and rocket engines are protected
by silicone-based thermal systems from extreme heat during high-speed flights. The
design of silicone coating plays a major role to withstand temperatures up to 1500 °C
with low thermal conductivity. The efficiency and performance of turbine engine can
be improved by silicone coatings. These coatings showed excellent anti-corrosion
and anti-wear properties in a simulated gas turbine environment. The aircraft struc-
tures such as fuselage and wings are protected by silicone-based coatings from harsh
environmental conditions. The use of these coatings improves the aircraft’s aero-
dynamics and reduces the fuel consumption. It also shows excellent weatherability
and adhesion to aluminium alloy substrates. According to a study by Ullah et al.
[21], in a simulated heat exchanger environment, silicone-based coatings are used
to improve thermal stability and corrosion resistance [21]. To prevent ice buildup on
aircraft surfaces, silicone coatings are used as an anti-icing coating. It also shows
good adhesion to the underlying substrates according to Laroche et al. [22].
4.2 Automotive Industry
Silicone coating has showed better corrosion resistance and high-temperature

stability in a simulated exhaust gas environment. It is also used for thermal manage-
ment in automotive components such as engines and batteries. It can reduce thermal
stress and heat dissipation and prevent overloading according to a study by Chen et al.
[23]. It can also be used as an anti-fouling coating which can prevent the buildup
of debris, dirt, and other contaminants. It is also used to improve the durability,
wear resistance, and performance of braking components, such as rotors and brake
callipers. According to a study by Izmitli et al. [24], the weatherability and scratch
resistance of paints can be improved by adding silicone-based additives to the paints
[24].
4.3 Oil and Gas Industries
Silicone high-temperature coatings are used to protect oil and gas pipelines from
environmental hazards and thermal shocks. It can enhance the mechanical strength
of pipelines at temperature up to 800 °C. It can also protect metal surfaces and it is
corrosion resistant against harsh chemicals in a simulated acidic environment. It is
used as an anti-fouling coating on various parts of gas and oil pipelines in a simulated
seawater environment [25]. Silicone-based coatings are also used as a thermal barrier
to protect metal surfaces from extreme heat and erosion [26]. It can protect downhole
tools from wear and corrosion as studied by Li et al. [27].
5 Factors Affecting the Performance of Silicone Coatings

in High-Temperature Environments
Even though the silicone coatings have unique properties to use them in high-
temperature environments, there are some key points to consider that affect their
performance in such conditions [28]. It can form oxide, which results in a loss
of thermal stability and degradation. The rate of oxidation and thermal degrada-
tion depends on the time of exposure, temperature, and the presence of oxygen,
ozone, and other chemicals. FTIR and thermogravimetric analysis (TGA) are the
analysis techniques to measure the rate of oxidation. The degree of degradation can
be measured by differential scanning calorimetry (DSC) and dynamic mechanical

analysis (DMA). Silicone coatings can also crosslink when exposed to high temper-
ature which results in loss of flexibility. The degree of crosslinking is dependent on
the presence of reactive species such as free radicals or moisture. It can be measured
by DMA and swelling tests. The degree of moisture absorption can be measured by
the dynamic vapour sorption (DVS) test. The coating can be filled with fillers content
such as silica and alumina to improve the mechanical property and thermal stability.
However, the type and amount of filler can affect other properties also. The filler
content can be optimized by various analytical techniques such as TGA and DMA.
Overall, a deep understanding of how these properties affects various properties
need to be understood to develop high-performance silicone coatings and adhesives.
Several analytical techniques can be used to study the effect of these factors and
optimizing the formulation can lead to improved performance in high-temperature
applications [29].
The remarkable disadvantage of silicone coatings is their cost of production and
application over other types of high-temperature coatings. They may not adhere well
to certain substrates, which can lead to delamination or peeling of the coating. Surface
pretreatment is necessary in this case to make them more adhesive to underlying metal
substrates. On considering the curing time of silicone coatings, it takes longer when
compared to other types of coating which leads to longer processing time. According
to the study, it can be reduced by using photoinitiators [30]. The hardness of silicone
coatings can be further increased by adding inorganic fillers.
6 Performance of Silicone-Based Coatings

in High-Temperature Applications
6.1 Effects of Temperature, Stress, and Exposure Time

on the Performance of Silicone-Based Coatings
Temperature is a critical factor that influences the stability and durability of silicone
coatings. It has been reported that silicone coatings show excellent thermal stability
up to 400 °C and they can withstand temperature as high as 600 °C for a short
period of time. However, the mechanical and physical properties of the coatings can
deteriorate at high temperatures, resulting in cracking, delamination, and oxidation.
For instance, a study investigated the thermal stability of silicone-based coatings for
steel substrates and found that the coatings remained stable up to 300 °C, but above
this temperature, the coatings start to degrade, resulting in a significant reduction in
their anti-corrosion performance.
The performance of silicone coatings can also be affected by the stress and strain
they experience. When exposed to high temperatures, there will be a development
of internal stress within the coating because of its low thermal expansion coefficient.
Again, this can reduce the adhesion strength and lead to cracking and delamination of
the coating from the substrate. Sampaio et al. [31] studied the thermal cycling effect
on adhesion strength of silicone coatings coated on steel substrates and concluded
that the coating shows a decrease in adhesion strength with an increasing number of
thermal cycles.
Another critical parameter that describes the performance of silicone coating
is its exposure time. Exposing the coating to a higher temperature for longer hours
significantly reduces the corrosion resistance of the coatings. The prolonged exposure
of silicone coatings coated on carbon steel substrates gradually reduces the anti-
corrosion property of silicone coatings. Therefore, understanding the effects of these
factors on the coatings can help to optimize their design and improve the durability
and thermal stability of the coatings at higher temperatures [32].
6.2 Comparison of the Performance of Silicone-Based

Coatings with Other High-Temperature Coating
Materials
Because of its unique properties such as low surface energy, good adhesion, high-
temperature stability, and resistance to chemicals and weatherability, it is used in
many applications. However, there are other materials that are also used for high-
temperature coatings, including ceramic coatings, metallic coatings, and organic
coatings. Zirconia and alumina ceramic coatings are known for their thermal barrier
properties and high-temperature stability, but they tend to be brittle and not as
durable as silicone coatings [33]. Nickel and chrome metallic coatings are also used
for high-temperature applications, but they tend to oxidize and corrode at elevated
temperatures. Organic coatings such as epoxy and polyurethane are not suitable for
high-temperature applications because they have poor thermal stability.
Several studies compared the performance of silicone-based coatings with other
high-temperature coating materials. Another study by Barroso et al. [34] compared
the thermal stability of silicone and ceramic coatings on carbon/carbon composites
exposed to high temperature. The study found that both coatings were able to with-
stand high temperatures, but the silicone coating had a lower thermal conductivity
and better adhesion to the substrate. Overall, while there are other materials that can
be used for high-temperature coatings, silicone-based coatings have demonstrated
excellent performance in a variety of applications and have become the material of
choice for many industries.
7 Future Directions and Conclusions
Silicone-based coatings have significant potential for use in high-temperature appli-

cations due to their excellent thermal stability, durability, and resistance to corrosion
and oxidation. Scientific studies have shown that silicone-based coatings can with-
stand temperatures ranging from 200 to over 1000 °C, making them suitable for a
range of high-temperature environments.
In addition to their thermal stability, silicone-based coatings offer several other
advantages for high-temperature applications, including excellent adhesion to a range
of substrates, including metals, ceramics, and plastics. High chemical resistance to
acids, bases, solvents, and low toxicity in environmental impact [35, 36]. Despite
these advantages, there are still some challenges associated with using silicone-based
coatings in high-temperature applications, such as their high material and labour
costs and the need for specialized equipment and surface preparation. However,
ongoing research into the development of new formulations, additives, and appli-
cation methods is helping to overcome these challenges and make silicone-based
coatings more accessible and affordable for industrial applications.
Overall, silicone-based coatings have significant potential for use in high-
temperature applications, and ongoing research is likely to lead to further improve-
ments in their properties and performance.
7.1 Future Research Directions on the Development

of Advanced Formulations and Manufacturing Processes
The development of advanced formulations and manufacturing processes is a crucial

area of research for silicone-based coatings in high-temperature applications. Some
potential future research directions in this area include:
• Use of nanotechnology: Incorporating nanomaterials into silicone-based coatings
can help enhance their thermal stability, mechanical strength, and other properties.
For example, adding carbon nanotubes to silicone coatings improved their thermal
stability and mechanical properties.
• Development of multifunctional coatings: Multifunctional coatings can provide
both high-temperature resistance and other functional properties, such as self-
cleaning, anti-corrosion, or anti-fouling. Multifunctional coating based on sili-
cone and zirconium oxide nanoparticles that exhibited excellent high-temperature
stability and self-cleaning properties.
• Use of sustainable materials: The development of silicone-based coatings using
sustainable and renewable raw materials can reduce their environmental impact
and increase their potential for widespread use. A study discussed the use of
sustainable raw materials for coatings, including silicone-based coatings [32].
• Development of new manufacturing processes: Innovative manufacturing
processes, such as 3D printing, can help produce silicone-based coatings with
complex geometries and improved properties and the use of 3D printing to produce
silicone-based coatings with tailored properties.
7.2 Conclusion and Recommendations for Future Work

in the Field of Silicone-Based Coatings
for High-Temperature Applications
Silicone-based coatings have been widely used in high-temperature applications

due to their excellent thermal stability and oxidative resistance. However, to further
enhance the performance of silicone coatings in high-temperature environments,
there is a need for further research in the field. Based on current research, the following
conclusions and recommendations can be made for future work in the field of silicone-
based coatings for high-temperature applications.
Conclusions
• The properties of silicone coatings, such as thermal stability, oxidative resis-
tance, and adhesion, can be significantly improved by the addition of appropriate
additives, such as fillers, pigments, and crosslinkers.
• Hybrid coatings that combine silicone with other materials, such as ceramics or
organic resins, have shown promising results in improving the performance of
silicone coatings in high-temperature environments.
• The selection of appropriate curing conditions, such as temperature and curing
time, is critical for achieving optimal performance of silicone coatings in high-
temperature applications.
Recommendations for Future Work
• Investigations on the effect of different types and amounts of additives on the
properties of silicone coatings in high-temperature environments. For example,
the effect of adding nanoscale fillers, such as carbon nanotubes or metal oxides,
could be studied.
• Further exploration of hybrid coatings that combine silicone with other materials,
such as inorganic or organic materials, to achieve enhanced high-temperature
performance.
• Study of the effect of environmental factors, such as humidity and oxidation, on
the properties of silicone coatings in high-temperature applications.
• Development of advanced testing methods for evaluating the performance of sili-
cone coatings in high-temperature environments. For example, the use of in-situ
monitoring techniques, such as infrared thermography, could provide valuable
insights into the behaviour of silicone coatings under high-temperature conditions.
• Investigation of the potential for sustainable silicone coatings, using bio-based
or renewable materials as precursors, to replace conventional silicone coatings in
high-temperature applications.
In conclusion, future research in the field of silicone-based coatings for high-

temperature applications should focus on the development of new additives and
hybrid coatings, understanding the effect of environmental factors, developing
advanced testing methods, and exploring the potential for sustainable silicone
coatings.
Acknowledgements The authors acknowledge the Chancellor, President, Vice Presidents, and Vice
Chancellor of Sathyabama Institute of Science and Technology, Chennai-600119 for providing the
necessary facilities to carry out the research work.
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Heat Resistant Coatings—An Overview
A. Anitha , A. Hemalatha, and P. Udhayakumar
Abstract Many industries (viz., aeronautical, aerospace, automobile, and advanced

power generation) utilize materials that can withstand heavy load, pressure, and
vibration, and endure hot air flow and high-temperature combustion products. In
order to increase the lifetime of such materials, we are in dire need of heat resistant
coatings. Heat resistant coating not only increases the durability of the engines but
also reduces the surface temperature of the underlying components. Heat resistant
coatings when used with super alloys increase the efficiency and performance even
at the operating temperatures higher than the melting temperature of the super alloys.
Heat resistant coatings must withstand high temperature, large temperature gradient,
complex stress condition, and corrosive atmosphere. The complexity and severity
of operating conditions will lead to premature failure of heat resistant coatings. In
automobiles, the coated surface may be exposed to hot gases with temperatures in
excess of 3000°F. Heat resistant coatings are generally a combination of multiple
layers of coatings with each layer having a specific function and requirement. The
topmost layer provides thermal insulation and consists of a ceramic, with low thermal
conductivity followed by a bond coat layer above the substrate to hold the ceramic
coat on the substrate and a thermally grown oxide layer to provide adhesion between
the ceramic coat and the bond coat. A complex heat resistant coating structure is
to be developed to satisfy multifunctional requirements. Research has been focused
on developing the coating system to achieve long-term effectiveness in oxidative
and corrosive environments at high temperatures. Heat resistant coating is the key
in the field of automobile and aeronautical industries. In view of this, fundamental
investigations into heat resistant materials, properties, preparation, and assessment
of performance and failure mechanisms have been systematically presented. The aim
is not only to provide a clear and thorough presentation of fundamental principles
and applications of heat resistant coatings but also to prepare the way for future heat
resistant coating systems by understanding previous achievements.
A. Anitha (B)
Department of Chemistry, V.V. Vanniaperumal College for Women, Virudhunagar 626 001, India
e-mail: anithaa@vvvcollege.org
A. Hemalatha · P. Udhayakumar
Department of Mechanical Engineering, K.L.N. College of Engineering, Pottapalayam,
Madurai 630612, India
404 A. Anitha et al.
Keywords Heat resistant coatings · Ceramic coating · Oxidation · Corrosion ·

Failure mechanism
Abbreviations
APS Air Plasma Spraying

CeSZ Zirconia doped with CeO2
CVD Chemical Vapor Deposition method
EB-PVD Electron Beam-Physical Vapor Deposition
HRC Heat Resistant Coatings
LPPS Low-Pressure Plasma Spray
MGC Metal–glass Composite
TGO Thermally grown oxide
MSZ MgO stabilized with Zirconia
REE Reactive Element Effect’
SPC Small Punch Creep
SPPS Solution Precursor Plasma Spraying
TEC Coefficient of thermal expansion
YSZ Yttria Stabilized Zirconia
1 Introduction
The physical and chemical characteristics of the material surface are continuously
changing when the materials are frequently exposed to different environments such
as high temperature, large temperature gradient, and corrosiveness. Nowadays,
improved material properties and surface coating techniques are the buzz words
in many industrial sectors. A coating is defined as a material that is applied to cover
the surface of an object to achieve the desired inert behavior while exposed to a
degrading environment. The coating is an effective method to protect the substrate
from the harmful effects of the environment.
The field of coating technology has been developed over a few decades and opti-
mized continuously. As a result, a wide range of engineering coating materials on
different substrates are used for electrical, magnetic, optical, thermal, and medical
applications. High-temperature coatings are developed to achieve properties like
thermal barrier, hardness, anti-wear, and corrosion. Heat resistant coatings (HRC)
are designed to work in the temperature range from 150 to over 2000 °C to provide
protection against hot environments.
The heat resistant coatings have the ability to decrease the surface temperature
of the working components thereby improving the durability of the engines working
in high-temperature environment. Hence there is a great demand for the coatings in
Heat Resistant Coatings—An Overview 405
the field of automotive, aircrafts, industrial engines, and turbines. HRC increases the
performance of gas turbines and propulsive efficiency of aero engines when applied
over internally cooled superalloys. Heat resistant coated components can have better
performance in environmental conditions like large temperature gradient, dynamic
stress condition, and chemically reactive atmosphere. Hence, it finds its applications
in heat exchangers, oil and gas processing, power generation, energy management,
refining and petrochemical, gasification systems, semiconductor fabrication systems,
water, and wastewater management, and analytical or process monitoring systems.
A complex coating structure is required to fulfill the multifunctional requirements.
Intensive research is carried out since 1970 on the coating system. Long-term effec-
tiveness is achieved at higher temperatures by three-layered coating, overcoming
oxidation and corrosion. Heat resistant coating system consists of ceramic top coat,
bond coat and a thermally grown oxide layer. Ceramic top coat keeps the component
thermally insulated. Bond coat on the substrate fixes the ceramic coat. The thermally
grown oxide layer serves to bind the two coats namely the top coat and bond coat
by adhesion. Different ceramic, metallic, and nanomaterials are used in the prepa-
ration of heat resistant coatings. These coatings are either deposited by Electron
Beam-Physical Vapor Deposition (EB-PVD) or by Air Plasma Spraying (APS). The
durability of the heat resistant coatings is an important factor in aero engines. The
complexity of the working environment and coating system structure leads to prema-
ture failure of the coatings. Certain important factors causing premature failure of
the coatings are high-temperature oxidation and infiltration of detrimental factors
such as molten salts, which lead to spalling upon thermal cycling and formation of
thermally grown oxide (TGO).
In view of this, this chapter represents the need for heat resistant coatings, different
classification of coating materials, various methods of preparation of coatings, prop-
erties, and performance characteristics of heat resistant coating materials. Moreover,
the newer kinds of materials suitable for this type of coatings are also presented.
This chapter provides information about the fundamental principles behind HRC
and its possible applications. With a clear understanding of the above, it can lead us
to explore new HRC materials with improved performance.
2 Requirement for Heat Resistant Coating
Most of the critical components working under high-temperature environment are

made of super alloys, which excel in their mechanical properties. The limitation of
the super alloy is its readiness to corrode and oxidize. Hence, the structural material
of most critical components is at risk for degradation.
The material properties [1] required for manufacturing critical components are:
• Heat resistance
• Oxidation resistance
• Corrosion resistance.
Further, the requirement includes:

• Increasing engine power
• Reducing fuel consumption
• Improving thermal conductivity
• Increasing lifespan of parts.
Hence, a coating material with the following properties is required for thermal
protection to ensure both performance and durability.
• High melting point
• Low thermal conductivity
• Chemically inert
• Similar coefficient of thermal expansion (TEC).
Heat resistant coatings are coating applied to the surface of super alloy to improve
their lifetime. These coatings are made of ceramic which is harder and stronger than
metals. Ceramics are superior over metals as they resist corrosion and have better
oxidation. The high melting point of ceramics can insulate the super alloy from high
temperatures.
The exterior region of the heat resistant coating (i.e., top coat) is made of porous
oxide which possesses lesser thermal conductivity, thereby withstands the stresses
created due to the changes caused by thermal expansion. Moreover, it insulates the
alloy at elevated temperature.
The core region of the heat resistant coating (bond coat) spreads over the super
alloy offering oxidation resistance and barrier for diffusion. In order to avoid the
spalling of the coating, while working at various temperatures, the bond coat should
adhere well with the alloys and should possess a uniform coefficient of thermal
expansion.
3 Classification of Heat Resistant Coating Materials
Lower thermal conductivity of certain ceramics leads to the usage as heat resis-
tant coating materials in turbines. It increases the turbine inlet temperatures. In aero
engines, it reduces the surface temperature and increases the life of the hot sections,
thus increasing the engine efficiency. Selection of HRC is based on high melting
point, lower thermal conductivity, no phase transformation during operating condi-
tions, inert nature, thermal expansion and adherence to the substrate, etc., Based on
chemical composition, different materials are tested for its possible application as
HRC, which are given as follows.
3.1 Ceramic Heat Resistant Coating Materials
Intrinsic physical and chemical properties of pure zirconia (ZrO2 ), viz., high hard-
ness, wear resistance, low coefficient of friction, ionic conductivity, chemical inert-
ness, low thermal conductivity, and high melting point make it an excellent engi-
neering material. Continuous efforts have been made to improve the mechanical
behavior of ZrO2 . Stabilizing oxides like CaO, MgO, Y2 O3 , and CeO2 can be suitably
added with ZrO2 to make it heat resistant ceramic.
3.1.1 Yttria Stabilized Zirconia (YSZ)
The addition of stabilizer Y2 O3 (6–8 wt.%) with ZrO2 improves the thermal shock
resistance thus enhanced performance [2] when compared to pure ZrO2 [3, 4]. 7-
8YSZ is the most widely used HRC because of its superior properties such as
~2680 °C as the melting point, thermal conductivity as low as ~2.1 to −2.2 Wm−1 K−1
at 1000 °C in bulk material, ~11 × 10−6 K−1 TEC, ~6.4 g/cm3 density, ~40 GPa
elastic modulus, and ~14 GPa hardness. All these features provide excellent heat
resistance to the components with lesser weight and better erosion resistance. Due
to this, 7-8YSZ finds its application in turbine as well as in diesel engines [5, 6].
7-8YSZ coating is superior over the usage of other stabilizers like CaO or MgO as it
protects the substrate by preventing the corrosion caused by Na2 SO4 and V2 O5 . The
disadvantages of YSZ are limiting operating temperature (<1200 °C), sensitivity to
hot corrosion, and detrimental effect due to the presence of impurities. Despite this,
a high concentration of oxygen ion vacancies leads to the development of thermally
grown oxides over the bond coat surface which limits its usefulness.
3.1.2 Zirconia Doped with CaO
ZrO2 stabilized with CaO (3–5 wt.%) has lower thermal diffusivity at temperature
below 1027 °C [7]. This coating has a remarkable thermal insulation. The major
disadvantage of CaO–ZrO2 is the destabilization from c-ZrO2 to m-ZrO2 while
coated. However, it can be overcome by the addition of CeO2 , and excellent thermal
shock resistance is observed at temperatures between 1000° and 1200 °C [8].
3.1.3 MgO Stabilized with Zirconia (MSZ)
Zirconia stabilized with MgO (15–24 wt.%) can avoid the tetragonal to monoclinic
phase transition of ZrO2 , thereby the existence of cubic ZrO2 and MgO. ZrO2 with
24 wt.% of MgO possess excellent TEC value of 12.3 × 10−6 K−1 [9]. MSZ system
can be replaced for YSZ system in diesel engines which operate on non-quality fuels
and deposit liquid salt over the ceramic components, but sulphidation of the MgO
cannot be ruled out. It is observed from low-quality fuel tests that deterioration of
the MSZ coatings occurs due to the excess deposition of MgSO4 [10].
3.1.4 Zirconia Doped with CeO2 (CeSZ)
CeO2 (16–26 wt.%) can be employed to stabilize t-ZrO2 in CeSZ. CeSZ (25 wt.%)
shows better moisture stability over YSZ while performing in the parallel envi-
ronment [11, 12]. CeSZ (21 wt.%) has lesser fracture strength and higher fracture
toughness (∼17 MPa m1/2 ) than YSZ (∼10 MPa m1/2 ) [13].
3.1.5 Rare Earth Oxides
Dy2 O3 and Yb2 O3 , the rare earth oxide can be used as stabilizers. Thermal conduc-
tivity can be reduced by ∼40% with 12 mol.% DySZ [14]. Thermal cycling behavior
studies reveal that ZrO2 –Yb2 O3 coatings [15] have an increase of ∼30% in cycle
time. Granulating plasma-sprayed ZrO2 with Nd2 O3 , Er2 O3, or Sm2 O3 (4–6 mol.%)
prevents the phase transformation of ZrO2 (t → m) [16–18]. The ScSZ coating
(Sc2 O3 –ZrO2 ) possesses higher corrosion resistance than the vanadates and sulfates
[19]. GdSZ is preferred over 7YSZ due to its chemical stability at elevated tempera-
tures and lower thermal conductivity (∼30% lesser) [20]. ZrO2 –Y2 O3 –Ta2 O5 /Nb2 O5
can also be used as the heat resistant coating materials [21, 22]. Some oxide addi-
tives like Al2 O3 , CoO, Er2 O3, La2 O3 , Nd2 O3, Pr2 O3, and SrO are used to increase the
density, thereby transforming YSZ into compact powder. Significant density increase
is observed on adding Al2 O3 or CoO gives an increase in density [23, 24].
3.1.6 Yttria Stabilized Hafnia
HfO2 –Y2 O3 (19–38 mol.%) coatings prepared by EB–PVD can be another coating
material, [25] and the thermal conductivity of 1.1 W/mK is achieved for HfO2 –Y2 O3
(25 mol.%). It exhibits high sintering resistance over 8YSZ and as a result, it acquires
lesser thermal conductivity at elevated temperature.
3.1.7 Alumina
Al2 O3 does not prove as a good coating material, but on combination with YSZ shows
improved hardness and bond strength without any significant changes in Young’s
modulus, toughness, and the resistance of the substrate toward oxidation [26–28].
8YSZ–Al2 O3 coating exhibits an enhanced thermal cycling lifetime when compared
to 8YSZ coating [29].
3.1.8 Mullite
Another preferred ceramic coating material is Mullite (3A12 O3 · 2SiO2 ) as it has low
density, high thermal stability, and chemical stability in high temperature, increased
strength, improved creep, and reduced thermal conductivity [30]. Mullite has a very
lower TEC, increased thermal conductivity, and oxygen resistance than YSZ.
3.2 Metallic Heat Resistant Coating Materials
When metals are exposed to high-temperature conditions, thermally grown oxides

(TGOs) form a scale over the surface safeguarding the underlying metals from envi-
ronmental corrosion. TGO scale on the metal surface provides good thermal stability,
compactness, and reduced growth rate with the desired degree of protectiveness and
provides effective adhesion to the base metal matrix. On the other hand, the formation
of non-protective scale over metal leads to rapid metal deterioration by oxidation,
damaging the desired mechanical properties and the service lifetime. Kinetic and
thermodynamic oxidation resistance at elevated temperature is provided by TGO
oxides such as chromia and alumina. Moreover, chromia scale is more suitable for
resistance of oxidation less than 1000 °C and hot corrosion between 700 and 800 °C
(Type II) (See Sect. 6.3). Alumina scale (α phase) prevents oxidation when the
working temperature is greater than 1000 °C and hot corrosion between 800 and
950 °C (Type I) (See Sect. 6.3).
Metallic heat resistant coating materials are of two types, namely, diffusion
coatings and overlay coatings, and are explained as follows.
3.2.1 Diffusion Coatings
Diffusion coatings are prepared by pack cementation, a variant form of chemical

vapor deposition. It consists of dissociation and chemical reactions of gaseous reac-
tants in a stimulant environment and the formation of a stable solid product. The
stimulant environment may be heat, light, or plasma. The process involves both
gas phase reactions (homogeneous) and on heated surface (chemical reactions) thus
producing powders or films, respectively [31].
Two types of extensively used diffusion coatings are:
1. Aluminized coatings
2. Chromized coatings.
Aluminized coatings
Aluminized coatings consist of pure metal/alloy (Al, FeAl), activator (halide salt),
and filler (alumina). These aluminized coatings extend the life of metals by growing a
protective scale of alumina in a hot environment. In these coatings, the alumina scale
which is thermally grown undergoes stresses created by thermal cycling and growth of
oxides [32]. This will cause the spalling of scale. Small addition of reactive elements
like Ce, Hf, La, and Y increases the adhesion of alumina scale on the underlying
metal and thus improves the alumina formers oxidation resistance. This effect is
termed as the “Reactive Element Effect” (REE) [33, 34].
Chromized coatings
Chromized coatings on steels are prepared by the pack cementation process [34]. Pack
cementation is a technique by which the components to be coated are immersed in
a powder mixture in a sealed retort. The entire apparatus is placed in a furnace and
heated in a protective atmosphere to high temperature for a sufficient period to form
a coating. Chromized coatings can also be prepared by Ni–CeO2 co-electroplating
followed by pack chroming on nickel-base metals for improving oxidation resis-
tance [35–37]. In thermal cyclic conditions, chromized ferritic steels deposit a layer
of carbide over the surface which prevents the required oxidation resistance. To
minimize the effect of carbon, electro deposition of reactive element oxides can be
employed.
M–Cr–Al diffusion coatings
The pack cementation method is employed for this type of diffusion coatings. In
this method, chroming and aluminizing take place simultaneously, or aluminizing
is followed by chroming and vice versa [38]. Few observations are made about the
oxidation of this type of coatings [39, 40].
3.2.2 M–Cr–Al (–Y) Overlay Coatings
Industrial turbine blades made of Ni- or Co-base structural super alloys require
M–Cr–Al–Y overlay coatings for developing oxidation resistance. These types of
coatings are prepared by the electron beam physical vapor deposition (EB–PVD)
process. These types of coatings have reduced thermal conductivity in the range of
1.5–1.9 and 0.8–1.1 Wm−1 K−1 [65]. M–Cr–Al–Y overlay coatings prepared by the
atmospheric plasma spray method reduce the residual thermal stresses and thermal
shock resistance is improved [70]. Porosity is increased in coatings prepared by both
methods. Co–Cr–Al–Y overlay coating is superior over Ni–Cr–Al–Y type, since
the former decreases oxidation resistance and improves resistance to hot corrosion.
Hence, NiCo-base is developed to improve both oxidation and hot corrosion perfor-
mance. Figure 1 provides information about the corrosion resistance and oxidation
resistance offered by various materials.
Fig. 1 Oxidation and

corrosion resistance offered
by different coating systems
3.2.3 Metallic Coatings as Bond Coats for Heat Resistance Coatings
Figure 2 shows a coating system [40, 41], with a bond coat as bottom layer, a ceramic
coat as top layer, and TGO (mostly Al2 O3 ) as an intermediate layer. Each layer is
designed with materials to perform unique function and exhibit improved properties.
The bond coat is usually 100–200 μm thick metallic layers. Bond coats (Ni–Cr–Al–Y
or Ni–Co–Cr–Al–Y) are prepared by plasma spray or EB–PVD.
Fig. 2 Cross section of heat

resistant coating
Pt-Modified aluminide bond coats

Deposits of Pt-modified aluminides are fabricated by a combination of Pt electro-
plating and pack aluminization or CVD. This type of bond coats is used in first-stage
turbine blades and recognized as useful bond coats [42].
M–Cr–Al–Y bond coats
Fabrication of bond coats such as Ni–Cr–Al–Y or Ni–Co–Cr–Al–Y is carried out
by Low-Pressure Plasma Spray (LPPS) or EB–PVD [43, 44]. Adhesion of TGO can
be improved by removing the sulfur segregants which causes the weakening of the
interface bond through the addition of yttrium [45].
3.3 Nanostructured Heat Resistant Coating Materials
Nanostructured zirconia HRC excels with its properties like reduced thermal conduc-
tivity, exalted TEC, and remarkable mechanical properties [46–51]. Variations made
in the structure result in enhanced thermal and mechanical properties [52–61]. Nanos-
tructured coatings are prepared by two methods namely plasma spray and spray
drying process.
Nanostructured air plasma-sprayed YSZ coatings possess lesser thermal conduc-
tivity and higher thermal stability at elevated temperature. Improvement in mechan-
ical and chemical properties of nanostructured YSZ is achieved when added with
Al2 O3 , HaO2, and La2 O3 .
4 Preparation of Heat Resistant Coating Materials
One of the major objectives of the automotive/turbine industry is to improve the

thermal efficiency of components at elevated temperatures [62, 63]. Super alloys
have increased the operational temperature by 100 °C. Heat resistant coatings act as
a protecting substrate to reduce temperature of the metal surface and increase the
components’ life.
There are two layers in HRC, namely, outer insulated top coat (made of ceramic)
and metallic bond coat. Top coat reduces the transmission of heat energy to the
bottom layer, and the bond coat is the actual thermal barrier affecting oxidation
resistance. Bond coat is applied directly on the metallic components followed by
top coat. While working at higher temperature, oxidation of bond coat leads to the
generation of thermally grown oxide between bond and top coat. Use of ceramic as
top coat protects the substrate by withstanding high temperature even more than the
substrate which increases the durability and efficiency of the components [64–67].
4.1 Electron Beam—Physical Vapor Deposition Method

(EB-PVD)
It is a vacuum coating method widely used for making thick coatings. A high energy
electron beam is used as a heat source. The factors influencing uniform coating are
the intensity of electron beam power, location, and size of beam spot which can
be controlled accurately to achieve. High energy electron beam rapidly melts and
evaporates both metal and ceramics. When the evaporation rate is high, the bond
between the substrate and coating becomes stronger. Moreover the crucible reacts at
elevated temperature. In order to reduce this type of reactions, the crucible is water
cooled. Optical prisms, filters, semiconductors, and thermal barrier coating devices
are some of the applications of this method. A brief description of this process, its
preparation conditions, and its parameters is noteworthy here.
4.1.1 Process in EB-PVD
• Electron beam is maintained under magnetic/electric field and it is focused over

the target. This electron beam heating leads to evaporation.
• By reducing pressure, the evaporated atoms get deposited over the substrate
surface as a thin film.
To improve the interfacial bonding between the coating and the substrate, the
substrate is heated while preparing for the coating process. The evaporated atoms
may completely deposit, diffuse on the substrate, and react with substrate elements,
or re-evaporate away the substrate. The different states of evaporated atoms depend
on various parameters such as substrate temperature, shape, structure, composition,
cleanliness, and electrical potential difference between the source of evaporation and
the substrate.
This type of coating method consists of a central vapor deposition chamber (one
main chamber) and pre-vacuum chambers (two for target storage). The pre-vacuum
chambers have 2 ∼ 6 electronic guns to heat and evaporate the materials. The main
chamber has water cooled copper crucibles which are heated by electron guns. The
target material is fed slowly by the transmission components. The substrate in the
central vapor deposition chamber can be simultaneously tilted or rotated as required
by the workpiece geometry and thickness of the coating. For continuous coating, the
valves are provided between the main chamber and pre-vacuum chamber. While a
workpiece is deposited, the other is preheated. Figure 3 represents the production
system of EB-PVD.
4.1.2 Factors Affecting EB-PVD Process
To achieve high quality HRC the followings factors are considered.

Fig. 3 Production system of EB-PVD
(i) Vacuum pressure,

(ii) Substrate temperature, and
(iii) Deposition rate.
(i) Vacuum pressure
Presence of O2 decreases the background vacuum pressure. The bond coat is not
effective at low background vacuum pressure, as inter-oxidation is induced by
oxygen. The vacuum pressure between 10–2 and 10–3 Pa is optimum for the bond
coat to be effective.
(ii) Substrate temperature
Substrate temperature decides the coating nature and crystal structure. On heating
substrate to a temperature less than 2/3 of the fusion point, the atomic vapor cloud
condenses immediately to solid. When the substrate temperature is above 2/3 of the
fusion point, the atomic vapor cloud liquefies, followed by crystallization to solid.
The substrate should be maintained in the range of 800 and 900 °C for desired crystal
structure.
(iii) Deposition rate
In EB–PVD process, the columnar crystals size and number of holes between the
grain boundaries are decided by the rate of deposition. Both these parameters increase
with the increase in deposition rate. The deposition rate depends on voltage and
current. The most preferred rate of deposition is 1 μm/min.
4.2 Plasma Spray Method
Plasma spray method is an economical and effective method for ceramic coatings
and reduces the surface temperature of hot components by 100–200 °C. This method
finds its application in jet engines and different turbines [68–71]. Plasma-sprayed
heat resistant coatings have three layers such as top coat, an overlay of bond coat, and
substrate. In this process, electrically generated plasma is used to heat and melt the
feedstock material. The powder is injected into the plasma jet which is maintained at
high temperature through feedstock. The metallic/nonmetallic materials are sprayed
Fig. 4 Atmospheric plasma spray process
in a molten/semi-molten state over the substrate (shown in Fig. 4). The Plasma zone
is maintained at a very high temperature of 10000 K where the feedstock material is
melted and propelled toward the substrate.
4.2.1 Various Components of Plasma Spray System
1. Spray torch—used for liquefying and increasing the velocity of the depositing
particles
2. Feeder—to provide the torch with powder or liquid
3. Media supply—gases to carry powder or to generate plasma jet
4. Robot—for manipulating the torch and the substrates to be coated
5. Power supply for torch
6. Control console(s).
The feed material either a powder or liquid from the feeder is melted or plasma
jet is produced and is made to deposit on the substrate. When the powder material
touches the substrate, it gets flattened and solidifies rapidly and the deposits/splats
are formed. If the process is carried out at atmospheric pressure, wavy interface will
be produced. To overcome this limitation, the following plasma spray methods are
employed
1. Low-Pressure Plasma Spraying (LPPS),
2. laser cladding plus plasma spraying, and
3. Solution Precursor Plasma Spraying (SPPS) methods.
4.2.2 Processing Parameters in Plasma Spray Method
The deposit properties depend on the particles interaction with the plasma jet and
substrate. The particle interaction is influenced by the following factors namely
• Nature of feedstock
• Composition of plasma gas
• rate of plasma gas flow
• amount of energy transferred

• offset distance of torch
• temperature of substrate.
4.3 Chemical Vapor Deposition Method (CVD)
Pack cementation, a variant form of CVD is employed for the preparation of diffusion
coatings of HRC. Metals, such as aluminum and chromium, are made to embed with
a mixture of pure metal and activators like halide salt and filler. The pack is heated
in the controlled environment of Ar and heated to the temperature when the metallic
powder starts to react with the activator salt and forms a volatile metal halide.
This process consists of four [31] steps as follows.
1. Thermodynamic equilibrium exists between the activator and the metal powder.
2. Gaseous metal halides get diffused into the alloy matrix.
3. Surface metal reacts with the vapor and deposition takes place.
4. Coating process takes place in the solid state.
In aluminized coatings, the mechanisms of coating growth are detailed below:
1. At low temperature normally below 950°, coating layer grows inward
2. At high temperature above 950°, the layer grows outward [38].
The limitations of this type of CVD method are contamination, difficult cleaning
process, and huge wastage of powder, and disposal of the waste incurs long time
[40].
5 Properties of Heat Resistant Coating Materials
5.1 Mechanical Properties
5.1.1 Hardness
Hardness is the ability of the coatings to withstand deformation. Microhardness

testing is typically used for thin films and plated surfaces. Microhardness of HRC is
measured considering the planar or cross-sectional surface of individual splats and the
area is measured on circles or ellipses. The planar hardness is measured for an indent
load of 1000 g and it is normalized with cross-sectional hardness values. Vickers and
Knoop microhardness is measured for a load of 1000 g on the cross-sectional area.
5.1.2 Elastic Modulus
The value of elastic modulus represents the material’s resistance toward elastic defor-
mation. Micro-cantilever bending technique is employed to measure fracture tough-
ness and elastic modulus and heat resistant coatings. The micro-cantilevers were
machined by a focused ion beam having central arms either parallel or normal
to the interface of the bond coat/topcoat. As a micro-scale measurement method,
the indentation technique has been employed to estimate the elastic modulus of
plasma-sprayed coatings.
5.2 Thermo Physical Properties
5.2.1 Coefficient of Thermal Expansion (CTE)
The coefficient of linear thermal expansion and a material property indicates the
expansion of the material when heated. Different substances have different CTEs.
This property plays a crucial in predicting the formation of cracks in layers. To
achieve crack-free coatings, heat resistant coating materials with a high coefficient
of thermal expansion are preferred. Optical interference techniques are used for
measuring the CTE of thin coating materials. The Digital image correlation technique
also measures CTE for heat resistant coatings. The difference in linear coefficient of
thermal expansion on different layers of coating leads to mechanical stress between
the layers, resulting in cracking or delamination of the coating. Therefore, the three-
layered coating is preferred as it has similar CTE.
5.2.2 Creep
Creep is the deformation of the material when a constant load is applied for a partic-
ular period of time at a specific temperature. Structural materials with low creep can
withstand heavy loads. At elevated temperatures, material with high creep value will
undergo permanent deformation at an earlier stage before reaching the yield point.
Hence, coating material with higher creep strength is chosen. Creep behavior of the
coatings can be determined by the small punch creep (SPC) test.
5.2.3 Thermal Conductivity
Thermal conductivity is the characteristic of a material that measures the amount

of heat, it allows in unit time with a temperature gradient through the unit area of
the sample. Thermal conductivity decides the life of the coating and its design and
is measured using the laser flash technique. This method measures the temperature
changes developed due to the laser input on the front surface. An infrared detector is
used at the back side of the sample to measure the changes in temperature. Ceramic
sintering enhances thermal conductivity which in turn reduces thermal insulation of
the coating and boosts the oxidation of bond coat/substrate. A coating material with
lesser thermal conductivity is preferred.
5.3 Failure Behavior
Heat resistant coatings experience different failures when they are functioning under
severe environmental conditions having synergetic effects offered by mechanical
loads, temperature gradient, hot corrosion, and oxidation.
According to the engine-operating conditions, the two predominant failures that
occur in EB–PVD coatings are as below.
1. Under low temperature, long cycle operating conditions, cracking occurs at the
TGO interfaces (Top Coating/TGO or TGO/Bond Coat) especially when the
thickness of TGO is above 5 μm.
2. Continuous damage in the interface leads to the failure and thus fragmentation of
the coating under high temperature and short cycle working conditions, termed
as “ratchet.”
Ratchet failure depends on the nature of the bond coat. Soft bond coat results in
less displacement and more cracks on top coat above TGO. Unstable conditions and
thus propagation of cracks occur in a cyclic process.
6 Performance of Heat Resistant Coating Materials
The performance of HRC materials is studied with the behavior of the coating in
the functioning environment. Coating undergoes oxidation, failure, and degradation
which are discussed as follows.
6.1 Oxidation
Oxidation is a process by which the conversion of metal to metal oxide occurs, when
exposed to an oxygen-rich and high-temperature environment [72]. Corrosion and
erosion of metals also occur, when they are exposed to CO2 , SO2 , and molten salts.
Moreover, hot corrosion deteriorates gas turbines, waste incinerators, IC engines, etc.,
and rapid material consumption occurs at high temperatures. The exposed material
should produce effective adherent surface scales to protect the underlying substrate
material. Al, Cr, and Si will produce excellent oxides and form protective scales
[73–76].
The metallic bond coat in heat resistant coatings serves the following:
• Provides bonding surface to topcoat.
• Prevents substrate corrosion.
• Prevents substrate oxidation.
Bond coat oxidation behavior is a key factor in deciding the life of the heat resistant
coatings. Hence, it is essential to resist the oxidation of bond coat by suitable selection
of substrate and bond coat material. Morphology of TGO, inter diffusivity, cracking,
and phase transition of coating also contribute to bond coat oxidation resistance.
6.2 Failure Mechanisms
Spallation is the peeling of top coat from bond coat. As it increases the temperature of
the surface, it destroys the substrate in a short span of time. Spallation of HRC starts
with a crack at TGO interfaces (Top Coating/TGO or TGO/Bond Coat) [77]. Spalla-
tion of the coating begins with the development of cracks and thus buckling. When
the planar interface changes to non-planar interface, cracks propagate by mechanical
forces. When the cyclic thermal process occurs, roughening of the interfaces (bond
coat/TGO/topcoat) takes place. This kind of roughening begins with the initial geom-
etry imperfection (as shown in Fig. 5) and lengthening of TGO during oxidation [78,
79]. TGO starts penetrating into the bond coat creating micro-cracks. Micro-cracks
can initiate and progress in different ways in HRC and the reasons are the type of
coating material, already consumed spallation life and thermal environment. This
leads to the ultimate failure of the coating [80].
TGO growth leads to volume expansion in constrained space results in compres-
sive growth stress sustaining at all temperatures. When the component is cooled, the
mismatch of coefficient of thermal expansion between TGO and bond coat leads to
high thermal compressive residual stresses.
Fig. 5 Tensile stresses in heat resistant coating due to surface imperfection

Fig. 6 Four failure mechanisms in heat resistant coatings by APS
For heat resistant coatings prepared by APS, there are four failure mechanisms
(as depicted in Fig. 6) [38, 81, 82] as follows:
• Mechanism I—Tensile stress hikes at the interface of bond coat/TGO followed
by cracking at crests of the interface.
• Mechanism II—Tensile stress occurs at the crest and compression stress occurs
at the trough. This out-of-plane stress is due to the undulating nature of the metal/
ceramic interface. This stress results in the fracture of TGO/top coat interface at
crests.
• Mechanism III—Top coat cracks near the crest since it is highly brittle.
• Mechanism IV—As TGO thickens, the thermal expansion coefficient of both the
top coat and the bond coat exceeds that of the composite bond coat/TGO. Hence,
compression force is converted to tension force which in turn creates cracks in
top coat in between the crests (valleys).
For heat resistant coatings prepared by EB–PVD, the two failure mechanisms (as
represented in Fig. 7) [74, 83, 84] are:
• Mechanism I—Separation of the bond coat/TGO interface (Similar to APS).
• Mechanism II—Separation of the TGO/top coat interface and penetration of the
TGO into the bond coat due to one or more of the following reasons:
– Progressive roughening of TGO due to bond coat cyclic creep.
– Increased growth of embedded oxides due to localized TGO cracking.
– Formation of the cavity in the bond coat.
For EB–PVD Coatings with relatively flat and defect-free interfaces, the compres-
sion in the TGO causes large-scale buckling.
Fig. 7 Failure mechanisms in heat resistant coatings by EB-PVD
6.3 Degradation Mechanisms
Heat resistant coatings experience corrosion due to the presence of deposited salts.
“Type I hot corrosion” occurs if the temperature (T ) exceeds the fusion point (T f )
of the deposited salt, whereas “Type II hot corrosion” occurs if T < T f , whereas the
corrosion at lower temperature range is called (as portrayed in Fig. 8). The extent of
hot corrosion reflects the amount of metal loss at varying temperature.
In hot corrosion, the deposited salts corrode both coating and protective oxide
scale over super alloys. If the protective scale is destroyed by the salts, then the
substrate/coating is deteriorated by oxidation and sulphidation [85–89].
Two stages of hot corrosion
Stage I—Initial step involves breaking down of protective scale.
Fig. 8 Effect of temperature on severity of corrosion

Stage II—Propagation stage involves the rapid propagation of corrosion on the

unprotected substrate/coating.
Degradation due to deposits leads to severe damage as it deteriorates both ceramic
top and bond coat either chemically or mechanically. Molten salt reacts with a metallic
bond coat by diffusion through pores and cracks in the ceramic top coat.
7 Newer Materials for Heat Resistant Coating
Growing demand for advanced engines in automotive, aerospace, and power

plant sectors leads to an exploration of new materials and innovative manufac-
turing technologies for HRC. Ceramic materials possessing high-temperature resis-
tance, superior thermo physical, and sustaining mechanical properties are under
investigation.
7.1 Chemically Modified Yttria Stabilized Zirconia (YSZ)
Element with low thermal conductivity (κ) excels as ceramic top coats, as its lattice
vacancy serves as source for scattered phonons of low κ. Addition of an appropriate
dopant creates more vacancies because of the varying valences of the host atoms.
Introduction of yttria as dopant to zirconia emerges as coating material with low
thermal conductivity.
7.2 Pyrochlore Oxides (A2 B2 O7 )
Pyrochlore oxides (A2 B2 O7 ) evolved as excellent heat resistant coating as the thermal
conductivities of many zirconate pyrochlores are lower than that of YSZ [90].
Pyrochlores have six BO6 octahedra (corner-shared) and A ions can fill the octa-
hedral holes. Large vacancies are available at the A, B, and O sites without phase
transformation. Both A and B sites can be substituted by other elements with similar
ionic radii when the electrical neutrality is satisfied, so that the thermal properties
can be modified and lower thermal conductivity is achieved.
7.3 Lanthanum Cerium Oxide (La2 Ce2 O7 )
Lanthanum cerium oxide (La2 Ce2 O7 ), a solid solution of La2 O3 in CeO2 is preferable
as heat resistant coating over YSZ as it has a higher thermal expansion coefficient and
lower thermal conductivity. It has 1/8 O sites as vacancies with fluorite structure. The
thermal expansion coefficient of La2 Ce2 O7 (∼12.3 × 10−6 K−1 , at the temperature
range of 300–1200 °C) makes it a suitable material [91, 92].
7.4 Silicates
Zircon (ZrSiO4 ), natural zircon sand, and wollastonite (CaSiO3 ) can be used as heat
resistant coating material. Zircon owns low TEC (4.99 × 10−6 K−1 , at the temperature
range of 25–1400 °C), high thermal conductivity (3.46 Wm−1 K−1 , at the temperature
range of 90–1500 °C), and low temperature chemical stability [93, 94].
7.5 Rare Earth Oxides
Oxides of rare earth elements (La2 O3 , CeO2 , Pr2 O3, and Nb2 O5 ) are advantageous
coating materials as it has high fusion points above 2200 °C, lower thermal diffusiv-
ities, and higher TECs [95]. Mostly all the rare earth oxides have similar chemical,
physical, and mechanical properties except Ce, Pr, Eu, and Tb.
7.6 Y3 Al5 O12
Y3 Al5 O12 (YAG) is a promising material for high-temperature coatings [9] because
of the following reasons:
1. low oxygen diffusion.
2. low thermal conductivity (3.2 Wm−1 K−1 , 1000 °C) at high temperatures.
3. less creep rate.
4. reduced electrical conductivity.
5. thermal stability up to the temperature of 1970 °C.
7.7 Lanthanum Aluminates
LnMAl11 O19 , where Ln = La to Gd; M = Mg, Mn–Zn, can be used as HRC since
it has high fusion points, less thermal conductivities, and higher values of thermal
expansion [96, 97].
7.8 LaPO4
Lanthanum phosphate (LaPO4 ) retains low thermal conductivity (∼1.8 Wm−1 K−1
at 700 °C), high TEC (9–10 × 10−6 K−1 ), low Young’s modulus (133 GPa), and
stability at elevated fusion point (∼2070 °C). All these superior thermo physical
properties advocate it as usefulness as heat resistant coating [98].
7.9 Metal–Glass Composite (MGC)
In MGC, (mixture of metal and glass), the metal–glass ratio affects TEC ranging
from 9.5 to 12.3 × 10−6 K−1 . This coating prevents bond coat oxidation and thereby
improved life is achieved. High TEC of the coatings provides better bond coat
adhesion without any open pores [99–102].
8 Conclusion
Heat resistant coatings are employed in hot corrosive environment as it offers thermal
insulation to metals and resist oxidation of metals. Thus heat resistant coating finds
application in power generation engines, aircraft, and marine propulsion. HRC mate-
rials are selected based on the properties such as high melting point, no phase transfor-
mation between room temperature and operating temperature, low thermal conduc-
tivity, chemical inertness, thermal expansion matching with the metallic substrate,
good adherence to the metallic substrate, and low sintering rate of the porous
microstructure. Various classifications of the HRC materials are elaborated. Methods
of preparation of HRC, viz., EB-PVD and plasma spray method are described.
Mechanical and thermal physical properties of HRC materials are discussed. The
performance characteristics like oxidation, failure, and degradation mechanisms are
exhibited and the future trends in the coating materials are also discussed. Thus all
aspects regarding HRC are presented in a flawless and organized manner.
All the materials used for HRC have their own merits and demerits and no material
is ideal in all aspects. As the need for HRC has never been depleted, investigation
toward novel HRC materials will also be flourishing. Moreover, cost-effective HRC
materials which are easily available and stable under extreme temperature ranges
are the need of the hour. In this aspect, a single material possessing all the required
qualities (with no limitation) is reserved for future research.
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Engineering Materials

ISSN 1612-1317 ISSN 1868-1212 (electronic)

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Organization of the Chapter

Corrosion-resistant materials are becoming increasingly in demand. The fundamental

Chapter “Thin Chromium-Based Coatings for Internal Combustion Automobile

Trenčín, Slovakia Amirhossein Pakseresht

Trenčín, Slovakia Amirhossein Pakseresht

Corrosion Resistant Coatings for High Temperature Environment

High Temperature Wear Resistance Coatings

Research on Anti-Oxidation and Wear-Resistance

Heat Resistant Coatings

I-Tseng Liu, Yi-Chen Weng, and Ying-Chih Liao

Keywords Corrosion under insulation (CUI) · Non-destructive testing ·

I-T. Liu · Y.-C. Weng · Y.-C. Liao (B)

© The Author(s), under exclusive license to Springer Nature Switzerland AG 2024 3

Scheme 1 Corrosion types

Table 1 Temperature range

2 Case Studies of Corrosion Under Insulation (CUI)

occurring temperature. However, the reactor maintenance required a catalyst regen-

3 Fundamental Concepts of Corrosion and CUI

Corrosion is an electrochemical oxidation–reduction reaction. The reaction is

3.1 Environmental Factors

Moisture can interact with metals through the following reaction:

M(s) + H2 O(g) → MO(s) + H2(g) (2)

If oxygen is present in the environment, hydrogen would be oxidized to water

Fig. 4 Ellingham diagram for several common metal oxides [29]

FeO(s) + H2 O(g) → Fe(OH)2(g) (3)

2Fe2 O3(s) + 4H2 O(g) → 4Fe(OH)2(g) + O2(g) (4)

3.1.3 Ion Effect

The presence of ions can accelerate corrosion reactions. Particularly, chloride-

Fe → Fe2+ + 2e− (5)

Fe2+ + 2Cl− → FeCl2 (6)

FeCl2 + 2H2 O → Fe(OH)2 + 2H+ + 2Cl− (7)

A Pourbaix diagram, or a potential-pH diagram, is useful for determining the stability

3.2 Other Factors

Fig. 5 Pourbaix diagram for iron at 25 °C [31]

3.2.1 Insulation Materials

3.2.2 Human Factors

3.3 On-Site Non-destructive Testing (NDT) Methods for CUI

CUI is difficult, or even impossible, to manage by only visual inspections. At

4 Concepts and Methods for CUI Protection

4.1 Recognized and Generally Accepted Good Engineering

4.2 Modified Thermal Insulation Structures

4.2.1 Insulation Cladding

Waterproof Enhancement of Insulation Materials

To diminish water uptake, insulations can be modified by water repellent agents,

Non-contact Insulation System

Fig. 7 Non-contact (or

of polytetrafluoroethylene (PTFE) spacers and perforated aluminum plates as shown

4.2.2 Thermal Insulation Coatings

Because of the water impermeability (or relatively low permeability), thermal

4.3 Anti-CUI Coatings

Fig. 8 Strategies for CUI protection

5 Materials of Anti-CUI Coatings

Corrosion at high-temperature conditions involves the participation of moisture.

5.1 Polymer Coatings

5.1.2 Phenolic/Novolac Epoxy