coatings
Article
High-Temperature Corrosion of Nickel-Based Coatings for
Biomass Boilers in Chlorine-Containing Atmosphere
Jan Hruska * , Jakub Mlnarik and Josef Cizner






Citation: Hruska, J.; Mlnarik, J.;
Cizner, J. High-Temperature
Corrosion of Nickel-Based Coatings
for Biomass Boilers in
Chlorine-Containing Atmosphere.
Coatings 2022, 12, 116. https://
doi.org/10.3390/coatings12020116
Academic Editor: Ludmila
B. Boinovich
Received: 26 November 2021
Accepted: 18 January 2022
Published: 20 January 2022
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Copyright: © 2022 by the authors.
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distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Coatings 2022, 12, 116. https://doi.org/10.3390/coatings12020116
Corrosion Laboratory, SVUM a.s., 250 88 Celakovice, Czech Republic; mlnarik@svum.cz (J.M.);
cizner@svum.cz (J.C.)
* Correspondence: hruska@svum.cz
Abstract: As there is a strong pressure in the EU to reduce CO2 emissions and overall fossil fuel
consumption in the energy sector, many boilers are burning biomass instead of traditional fuels (coal,
natural gas, oil, etc.). This is mainly due to the EU 2030 energy strategy, which commits Member
States to reduce fossil fuel emissions by at least 40% (compared to the 1990 level) and to use at
least 32% of renewable energy. The combustion of biomass containing aggressive elements such
as chlorine or sulfur causes serious damage to various boiler components, with negative impacts
such as reduced boiler lifetime, increased investments and maintenance costs, reduced availability,
and others. These problems occur mainly in plants/boilers designed to burn coal and redesigned
to burn biomass (straw, wood chips, wood pellets, etc.). In this paper, the corrosion resistance of
heat coatings determined in long-term laboratory tests in an environment specifically corresponding
to biomass flue gas is presented. These results can be used to design a suitable modification of
existing coal boilers using conventional materials. The aim was to compare three completely different
technologies currently available on local markets for the preparation of these coatings—thin wire
arc spray (TWAS), high-velocity oxygen fuel (HVOF), and water-stabilized plasma. These coatings
were compared with the base material of the boiler tubes—low alloyed steel 16Mo3 and high alloyed
austenitic stainless steel AISI 310 as a more expensive option for retrofit. After 5000 h of exposure in
an environment containing HCl and SO2 , no cracks or structural defects were observed in any of the
coatings, and the substrate material showed no signs of oxidation. All the tested coatings had higher
corrosion resistance than the 16Mo3 material, and some of them presented a corrosion behavior close
to that of the high alloy AISI 310 steel. Structurally and corrosion-wise, the thermally sprayed coating
prepared by HVOF technology was the best of all tested materials.
Keywords: coatings; biomass boiler; high-temperature corrosion; thermally sprayed coatings;
chlorine-induced corrosion; HVOF; plasma coatings
1. Introduction
As a part of European policy, the strategy for the energy sector 20-20-20, has been
introduced—targeted to the end of 2020. It has been stated that at least 20% of greenhouse
gas emission would be cut (compared to 1990), 20% of all energy produced in EU would
be from renewable sources, and energy efficiency would be improved by 20% [1]. One
of the ways to lower fossil fuel consumption is to produce electricity and energy from
renewable sources—in case of Czechia, mainly out of biomass. According to Eurostat data,
in 2018 nearly 60% of non-fossil fuel was in the form of biofuel [2]. Predictions indicate that
biomass will be the dominant form of renewable energy also in a near future, especially
because of the rapid increase of biomass harvest (mainly wood) in recent years compared
to the period 2011–2015. This increase is about 50% in total and is caused by growing wood
markets and, in some member states, by bark beetle outbreaks [3]. Therefore, more and
more biomass together with other alternative types of fuels (enhanced recycled fuel, waste,
etc.) is burned in boilers and, due to the presence of very reactive elements in this kind of
https://www.mdpi.com/journal/coatings
Coatings 2022, 12, 116 2 of 14

fuel (chlorine, sulfur), there is a higher risk of boiler corrosion compared to that linked to
coal combustion.
Several studies have investigated how firing and/or co-firing of biomass can enhance
the corrosive aggressivity of flue gas—especially due to a high content of sulfur and
chlorine in raw fuel. A high chlorine content in biomass can be devastating for heat-
exchanging surfaces in plants combusting straw, and conventional boiler tube materials
cannot be used in such case [4]. In the case of wooden chips, the flue gas is not corrosive
as that from straw or grass/hay but, still, the corrosion rate is much higher than that in
coal-fired powerplants using ferritic/pearlitic steels up to 550 ◦ C or austenitic steels in
supercritical boiler units. This can be particularly problematic for power/heating plants
with coal-fired boilers that are switching to wooden chips fuel without major investments
or enhancements in superheater materials. Generally, in in this case, it is better to use
austenitic or nickel-based alloys, but the investments cost is high. Another viable option
is to use alloyed claddings or thermally sprayed coatings, which can greatly improve the
corrosion resistance of conventional materials in chlorine-containing environments [5].
In this study here presented, various thermally sprayed coatings were tested in an
atmosphere containing chlorine/hydrogen chloride, simulating the biomass burner flue
gas, which usually contains Cl2 /HCl as the most corrosive species [6]. This laboratory at-
mosphere was prepared after determining the flue gas chemical composition in a particular
coal-fired fluidizing bed boiler (in The Czech Republic) that had been adapted to biomass
fuel and presented severe corrosion damages after several months of straw/woodchips
burning on the windward side of the superheater.

2. Materials and Methods

2.1. Substrate Materials
Five different metallic coatings and two steel materials, as a reference, were tested
in this work. One of them was ferritic/pearlitic steel 16Mo3, which is widely used as a
superheater material for coal-fired boilers up to 550 ◦ C. This steel is also used in waste
incineration plants or biomass boilers at lower temperatures but, often there are certain
corrosion problems as aggressive deposits are formed on tubes’ surfaces during the opera-
tional time [7]. The second reference material was austenitic high alloyed steel AISI 310,
which can be used as a replacement for boiler tubes that switched from coal to biomass
or waste fuel, as it has significantly higher thermal and corrosion resistance compared to
standard ferritic/pearlitic or martensitic boiler tubes, e.g., 16Mo3, P91, T23, and others [8].
The test temperatures for materials and coatings were 500 and 600 ◦ C. Data about the
chemical composition of tested coatings and base materials are shown in Table 1.

Table 1. Chemical composition of the coating precursors and base materials (wt.%).

Material Ni Cr Fe Mo Si Co Y Nb
16Mo3 <0.3 <0.03 bal. 0.25–0.35 <0.35 – – –
AISI 310 19–22 24–26 bal. – <1.5 – – –
K50-Plasma bal. 9.5 3.5 – 4.00 – – –
TWAS 45CT bal. 42–46 <0.5 – <0.2 – – –
HVOF Amperit 469 – 23–27 – – 0.6–0.9 bal. 0.6–0.9 –
TWAS Alloy 625 bal. 20–23 <5 8–10 <0.5 <0.5 – 3.15–4.15
TWAS Pseudo-alloy 1 bal. 20–23 <5 8–10 <0.5 <0.5 – 3.15–4.15
TWAS Pseudo-alloy 2 bal. 25–28 – 15–18 – – – 5.0
 Table 1. Chemical composition of the coating precursors and base materials (wt.%).
Material Ni Cr Fe Mo Si Co Y Nb
Coatings 2022, 12, 116 16Mo3 <0.3 <0.03 bal. 0.25–0.35 <0.35 – – 3– of 14
AISI 310 19–22 24–26 bal. – <1.5 – – –
K50‐Plasma bal. 9.5 3.5 – 4.00 – – –
TWAS 45CT bal. 42–46 <0.5 – <0.2 – – –
HVOF1.Amperit
Table Cont. 469 – 23–27 – – 0.6–0.9 bal. 0.6–0.9 –
TWAS Alloy 625 bal. 20–23 <5 8–10 <0.5 <0.5 – 3.15–4.15
Material TWAS
MnPseudo‐alloyAl
1 bal. Cu 20–23 Ti<5 8–10C <0.5 Ta <0.5 N – 3.15–4.15
B
TWAS Pseudo‐alloy 2 bal. 25–28 – 15–18 – – – 5.0
0.40–
Material Mn
16Mo3 – <0.3 Al –Cu Ti
0.12–0.20 C – Ta <0.012N B–
0.9016Mo3 0.40–0.90 – <0.3 – 0.12–0.20 – <0.012 –
AISI 310 <2AISI 310 – <2 – – –– <0.1
– <0.1 – – <0.11
<0.11 ––
K50-Plasma –
K50‐Plasma – – 0.3 – 0.3 <0.3 <0.3 – – – – 2.5
2.5
TWAS 45CT <0.2
TWAS 45CT – <0.2 <0.5 – 0.3-1
<0.5 0.01–0.1
0.3‐1 0.01–0.1 – – – – ––
HVOF Amperit 469 HVOF– Amperit6.5–8.5
469 – – 6.5–8.5 –– 0.6–0.9
– 6.9–9.5
0.6–0.9 6.9–9.5 – – ––
TWAS Alloy 625 <0.5 Alloy 625
TWAS <0.4 <0.5 – <0.4 <0.4– <0.1
<0.4 <0.1 – – – – ––
TWAS Pseudo-alloy 1 <0.5Pseudo‐alloy
TWAS <0.41 <0.5 – <0.4 <0.4– <0.1
<0.4 <0.1 – – – – ––
TWAS Pseudo-alloy 2 –
TWAS Pseudo‐alloy –2 – – – –– – – – – – – – 33
1 Firstwire
First wire(anode).
(anode). 2 Second wire (cathode).
2 Second wire (cathode).

2.2. Thermally Sprayed Coatings

Three different technologies of thermal spray—TWAS, HVOF, and and water-stabilized
water‐stabilized
plasma—were compared and tested in this work. Three coatings were prepared by the
standard TWAS TWAS (thin(thin wire
wirearcarcspray)
spray)method.
method.This technology
This technology is relatively easyeasy
is relatively and and
can
produce
can a high
produce amount
a high of coating
amount per hour
of coating (up to(up
per hour 80 to
kg/h). Other advantages
80 kg/h). Other advantagesare a rela‐
are
atively
relatively low price,
low price, mobility, mobility,
and easyandinstrumentation.
easy instrumentation.During TWAS,During theTWAS, thematerial
coating coating
material
is fed intoisthe
fedgun
intoin thethegun in the
form form
of two of two
wires. Anwires.
electricAnarc electric arc is generated
is generated between between
the ends
the ends
of the of the
wires, wires,
whose whoseisenergy
energy used toismelt
usedthe to melt the material.
material. The acceleration
The acceleration of the
of the particles
particles
towards thetowards the substrate
substrate is provided
is provided by compressed
by compressed air. The temperature
air. The temperature of the arcofisthe arc is
around
around 4000 ◦ C, but due to the cold carrier medium, it is reduced before the particles hit the
4000 °C, but due to the cold carrier medium, it is reduced before the particles hit the sub‐
substrate.
strate. TheThe particle
particle impact
impact velocity
velocity onon thethe substrateisis100
substrate 100toto130
130 m/s.
m/s.TwoTwoof of the
the three
TWAS
TWAS coatings
coatings were
were prepared
prepared from
from wires
wires of of the
the same
same alloys
alloys (the
(the anode
anode and cathode were
and cathode were
made
made ofof the
the same
same additive
additive material)—in
material)—in the the first
first case,
case, itit was
was Alloy
Alloy 625,
625, and
and in
in the
the second
second
case,
case, it
it was
was 45CT
45CT material. The third
material. The third one was made
one was made of of aa so‐called
so-called pseudo-alloy
pseudo‐alloy [9], [9], which
which
was prepared by feeding a spraying jet with two different wires
was prepared by feeding a spraying jet with two different wires which were simultane‐which were simultaneously
melted in an in
ously melted electric arc, forming
an electric a mixture
arc, forming of the
a mixture of two
the twoalloys—schemes
alloys—schemes areare
shownshownin
Figure
in Figure 1a. The anode was made of an alloy 625 wire, while the cathode consisted of aa
1a. The anode was made of an alloy 625 wire, while the cathode consisted of
NiCrMoB
NiCrMoB wire.wire. In addition, in
In addition, in this
this case,
case, aa base
base layer
layer consisting
consisting of pure nickel
of pure nickel was
was used
used to
to
ensure
ensure good
good adhesion
adhesion of of the
the coating
coating toto the
the base
base material.
material.

(a) (b)
Figure 1.
Figure 1. (a)
(a) Electric arc spraying
Electric arc spraying scheme;
scheme; (b)
(b) schematics
schematics of
of the
the plasma
plasma torch
torch with
with Gerdien
Gerdien arc.
arc.

The fourth tested coating consisted of K50 alloy (a nickel‐based

nickel-based material alloyed with
chromium, silicone, and boron) prepared by a hybrid water–gas DC Arc plasma torch. A
schematic image of the plasma torch with Gerdien arc is shown in Figure 1b. The chamber
is divided into several sections where water is injected tangentially, and a water vortex is
created. The inner diameter of the vortex is determined by the diameter of the holes in the
segments between the sections. Water is exhausted at two positions at the ends of the arc
chamber. A consumable cathode is created by a graphite rod, and the anode, consisting of
a copper disc with internal cooling, is located outside the arc chamber, downstream of the
exit nozzle. The anode disc rotates to reduce the electrode erosion in the plasma stream.
The coating material in this case was in the form of a fine powder (20–40 µm) that was
filled directly into the plasma arc [10].
 segments between the sections. Water is exhausted at two positions at the ends of the arc
chamber. A consumable cathode is created by a graphite rod, and the anode, consisting of
a copper disc with internal cooling, is located outside the arc chamber, downstream of the
Coatings 2022, 12, 116 4 of 14
exit nozzle. The anode disc rotates to reduce the electrode erosion in the plasma stream.
The coating material in this case was in the form of a fine powder (20–40 μm) that was
filled directly into the plasma arc [10].
Last,
Last, the fifth
fifth thermally
thermallysprayed
sprayedcoating
coatingwas was made
made using
using the the HP/HVOF
HP/HVOF (High-
(High‐Pres‐
Pressure/High-Velocity
sure/High‐Velocity Oxygen Oxygen Fuel)
Fuel) technologyusing
technology usingAmperit
Amperit469.088
469.088 (CoCrAlYTaCSi)
(CoCrAlYTaCSi)
with
withparticle
particlesize
sizedistribution
distributionfor
forHP/HVOF
HP/HVOF of of 20–53 μm. The
20–53 µm. The precursor
precursor powder
powder for
forthis
this
coating was fed directly into the flame stream at a temperature of about 5000 ◦ C with a flue
coating was fed directly into the flame stream at a temperature of about 5000 °C with a
gas
fluevelocity of 500–1200
gas velocity m/s.m/s.
of 500–1200 The The
burner usedused
burner purepure
oxygen andand
oxygen kerosene. TheThe
kerosene. chemical
chem‐
composition of the wires used for TWAS of a particular coating preparation
ical composition of the wires used for TWAS of a particular coating preparation as as well aswell
of theas
powders used forused
of the powders plasma and HVOF
for plasma andlayers
HVOF are shown
layers areinshown
Table 1.inOptical
Table 1.light micrographs
Optical light mi‐
of all thermally
crographs of allsprayed
thermallycoatings
sprayed before testing
coatings are shown
before testingin
areFigure
shown 2. in Figure 2.

Figure 2.
Figure 2. Optical
Optical light
lightmicrographs
micrographsofofthe thermally
the sprayed
thermally coatings
sprayed before
coatings testing:
before (a) HVOF
testing: Am‐
(a) HVOF
perit 469, (b) TWAS 45CT, (c) Plasma K50, (d) TWAS Alloy 625, and (e) TWAS pseudo‐alloy.
Amperit 469, (b) TWAS 45CT, (c) Plasma K50, (d) TWAS Alloy 625, and (e) TWAS pseudo-alloy.

2.3.
2.3. Testing
TestingSamples
Samples
The
Thehigh-temperature
high‐temperaturecorrosion
corrosionresistance
resistanceof ofthe
thetested
testedthermally
thermallyspray spraycoatings
coatingswas was
tested
tested in
inaagas-tight
gas‐tightfurnace;
furnace;each
eachspecimen
specimenwas wasin inits
itsown
ownalumina
aluminavessel.
vessel.All
Allcoatings
coatings
were
wereprepared
preparedusingusingtwo
twobase
basematerials—ferritic/pearlitic
materials—ferritic/pearlitic16Mo3 16Mo3steel steeland
andaustenitic
austeniticsteel
steel
AISI 310—in the form of 30 mm-long cylindrical coupons. Since
AISI 310—in the form of 30 mm‐long cylindrical coupons. Since it is extremely it is extremely complicated
compli‐
and
catedsometimes impossible
and sometimes to spraytoeach
impossible spraytesting
each sample
testing separately, it was necessary
sample separately, to make
it was necessary
atorod out aofrod
make individual samples, which
out of individual samples,waswhich
coated wasand then cut
coated andintothenpieces—Figure
cut into pieces— 3a.
Because of this procedure, the samples after cutting were left without
Figure 3a. Because of this procedure, the samples after cutting were left without coating coating on their
sides; thissides;
on their couldthis
cause severe
could causecorrosion during the
severe corrosion test and
during the spallation of sprayed
test and spallation of coating,
sprayed
especially in the case of the 16Mo3 substrate material. For this reason, individual
coating, especially in the case of the 16Mo3 substrate material. For this reason, individual specimens
(28 mm-long
specimens (28cylinders)
mm‐longwere provided
cylinders) were with Inconelwith
provided 625Inconel
tips (TIG 625welding)
tips (TIGand then were
welding) and
welded
then were welded together, forming whole rods of 10 samples. Subsequently, one spray
together, forming whole rods of 10 samples. Subsequently, one of the tested of the
coating
Coatings 2022, 12, x FOR PEER REVIEW methods
tested spray wasmethods
coating applied. was
After spraying,
applied. thespraying,
After bars were thecut again
bars wereright
cut in the5 spot
again of 14
right
welds, and the resulting sample was thus protected on all its sides (either
in the spot welds, and the resulting sample was thus protected on all its sides (either by by the coating
itself or by welded material on the sides).
the coating itself or by welded material on the sides).

(a) (b)
Figure 3.3. (a)
Figure (a) Scheme/picture
Scheme/picture of
of testing
testing aa rod
rod before
before cutting
cutting itit into
into individual
individual samples,
samples, with
with and
and
without coating; (b) testing facility scheme.
without coating; (b) testing facility scheme.

2.4. Exposure Tests

High‐temperature corrosion tests were carried out in a gas‐tight furnace with a cy‐
lindrical alumina muffle. All samples were placed into a small ceramic vessel and packed
together into a set that was exposed in a model biomass flue gas testing atmosphere which
had been controlled by a mass flow controller/regulator; the flow rate was set to 100
mL/min. The composition of the testing gas is shown in Table 2—selected as a compromise
Coatings 2022, 12, 116 5 of 14

2.4. Exposure Tests

High-temperature corrosion tests were carried out in a gas-tight furnace with a cylin-
drical alumina muffle. All samples were placed into a small ceramic vessel and packed
together into a set that was exposed in a model biomass flue gas testing atmosphere which
had been controlled by a mass flow controller/regulator; the flow rate was set to 100
mL/min. The composition of the testing gas is shown in Table 2—selected as a compro-
mise between real flue gas measurements and literature data [11,12]. Water was supplied
to the flue gas by a high-precision pump with a microinjection system—liquid water (1
mL/min) was added to the furnace, and evaporation occurred directly inside the ceramic
muffle—Figure 3b. The remaining atmosphere exiting the furnace was neutralized by a
potassium hydroxide solution.

Table 2. Testing atmosphere composition.

Compound HCl SO2 CO2 CO O2 N2

Content 200 ppm 30 ppm 12 vol% 50 ppm 3 vol% bal.

In total, five samples of each type of coating and base material were tested in the
model flue gas atmosphere at 500 and 600 ◦ C—the most temperature range for boilers in
the Czech Republic that are being considered for biomass burning. After 5000 h of exposure,
one of the tested specimens was removed for metallographic analysis. After the exposure
tests, the corrosion resistance of all sprayed coatings and substrate materials was evaluated
by gravimetry, light metallography, and other methods.

3. Results
The determination or comparison of the corrosion rate of the individual tested materi-
als was carried out by gravimetric analysis, measuring the weight changes of the samples
during exposure to the model atmosphere. In this case, the level of oxidation was de-
termined by measuring weight gains—it was impossible to determine weight losses, as
the oxidic layer on the surface of the sprayed coatings could not be selectively removed,
chemically or physically.

3.1. Gravimetric Results

The results of long-term exposure at 500 ◦ C in a model atmosphere containing hy-
drogen chloride are shown in Table 3. All gravimetric data were calculated in grams per
square meter (g/m2 ). In the right column of Table 3, a mini graph shows the trend of
weight growth of the tested materials/coatings. Most of the coated samples showed a
slow parabolical trend of corrosion; especially, after the first 200 h of exposure, weight
gains were substantially high. This essentially corresponds to a slow parabolic law, where
the oxidation rate is controlled by the diffusion rate, which is reduced by the growth of
oxides on the surface. However, in the case of thermally sprayed coatings, the initial rate
of oxidation was accelerated by the large surface area of the samples, which were usually
very coarse, and by their porosity [13,14].
However, these weight changes plummeted in time (after a rapid oxidation of the
coarse surface layer), and further corrosion changes were extremely limited. For example,
in the case of the K50 coating made using the plasma torch, the initial weight growth was
very large, but approximately after the first 500 h in model atmosphere at 500 ◦ C, it almost
stopped; afterwards, there were practically no weight changes.
 Coatings
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2022, 12,
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FOR
PEER
FOR PEER
PEER
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PEER REVIEW
REVIEW
REVIEW 6666 of
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14
14
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FOR PEER
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the
the surface.
surface.
the surface.
the However,
However,
surface. However,
However, inin
in the
the
in the case
case
the case of
of
case of thermally
thermally
of thermally sprayed
sprayed
thermally sprayed coatings,
coatings,
sprayed coatings, the
the
coatings, the initial
initial
the initial rate
rate
initial rate of
of
rate of oxida‐
oxida‐
of oxida‐
oxida‐
the
the surface.
the surface.
surface. However,
However,by
However, in
in the
inthe
the case
thelarge of
case of
case of thermally
thermally
thermally sprayed
sprayed
sprayed coatings, the
coatings,which
coatings, initial
the initial
the initial rate
rate
rate of oxida‐
of oxida‐
of oxida‐
Coatings 2022, 12, 116 tion
tion was
was
tion was
tion accelerated
accelerated
was accelerated by
accelerated by the
by the large
the large surface
surface
large surface area
area
surface area of
of
area of the
the
of the samples,
samples,
the samples, which
samples, which were
were
which were usually
usually
were usually very
very
usually very
6 of very
14
tion
tion was
was accelerated
accelerated by
by the
the large
large surface
surface area
area of
of the
the samples,
samples, which
which were
were usually
usually very
very
coarse,
coarse,
coarse,
coarse, and
and
and
and by
by
by
by their
their
their
their porosity
porosity
porosity
porosity [13,14].
[13,14].
[13,14].
[13,14].
coarse, and
coarse, and by
by their
their porosity
porosity [13,14].
[13,14].
Table
Table 3.
3. Gravimetric
Gravimetric results
results of
of coatings/materials
coatings/materials after
after exposure
exposure at
at 500
500 °C
°C in
in model
model atmosphere—
atmosphere—
Table
Table 3.
Table 3. Gravimetric
223.
Gravimetric results
Gravimetric results of
results of coatings/materials
of coatings/materials after
coatings/materials after exposure
after exposure at
exposure at 500
at 500 °C
500 °C in
°C in model
in model atmosphere—
model atmosphere—
atmosphere—
Table
in
Table
in g/m
Table3.
g/m 3.
3.. Gravimetric
Gravimetric
Gravimetric
2222..
results
results
results of of
of coatings/materials
coatings/materials
coatings/materials after
after
after exposure
exposure
exposure at at
at
500 500
◦
500
C °C
°C
in in
in model
model
model atmosphere—
atmosphere—
atmosphere—in
in
in
in g/m
g/m
g/m .
g/m22...
2
in2g/m
in
g/m .
Exposure
Exposure
Exposure Time
Exposure Time
Time
Time (h) (h)
(h)
(h)
Coating‐Substrate
Coating‐Substrate
Coating‐Substrate
Coating‐Substrate Exposure
Exposure
Exposure Time
Time (h)
Time (h)
(h) Trend
Trend
Trend
Trend
Coating‐Substrate
Coating‐Substrate
Coating-Substrate 200
200
200
200 500
500
500
500 1000
1000
1000
1000 2000
2000
2000
2000 5000
5000
5000
5000 Trend
Trend
Coating‐Substrate 200
200 500
500 1000
1000 2000
2000 5000
5000 Trend
Trend
TWAS Pseudo‐AISI 310 200
200
9.18 500
500
14.57 1000
1000
15.9 2000
16.072000 17.76 5000 5000
TWAS
TWAS Pseudo‐AISI
TWAS Pseudo‐AISI
Pseudo‐AISI 310 310
310 9.18
9.18
9.18 14.57
14.57
14.57 15.9
15.9 16.07
15.9 16.07
16.07 17.76 17.76
17.76
TWAS
TWAS Pseudo‐AISI
Pseudo‐AISI 310 9.18 14.57 15.9 16.07 17.76
TWAS
TWAS
TWAS
TWAS
TWAS Pseudo‐16Mo3
Pseudo-AISI
Pseudo‐16Mo3
Pseudo‐16Mo3
Pseudo‐16Mo3 310310 9.18
14.12
9.18
14.12
14.12
14.12
14.57
21.05
14.57
21.05
21.05
21.05
15.9
22.91
15.9
22.91
22.91
22.91
16.07
23.15
16.07 25.27
23.15
23.15
23.15
17.76
25.27
25.27
25.27 17.76
TWAS
TWAS
TWAS Pseudo‐16Mo3
Pseudo‐16Mo3
Pseudo‐16Mo3 14.12
14.12
14.12 21.05
21.05
21.05 22.91
22.91
22.91 23.15
23.15
23.15 25.27
25.27
25.27
TWAS
TWAS
TWAS 625‐AISI
Pseudo-16Mo3
625‐AISI
TWAS 625‐AISI
TWAS 625‐AISI 310 310
310
310 5.19
14.12
5.19
5.19
5.19 12.51
21.05
12.51
12.51 12.81
12.51 12.81
22.91
12.81
12.81 13.8 13.8
23.15
13.8
13.8 14.17
14.17
14.17
14.17 25.27
TWAS
TWAS
TWAS
TWAS 625‐AISI
625‐AISI
625‐AISI
625-AISI 310310 310
310 5.19
5.19
5.19
5.19 12.51
12.51
12.51
12.51 12.81
12.81
12.81
12.81 17.02 13.8
13.8
13.813.8 16.54 14.17
14.17
14.17 14.17
TWAS
TWAS 625‐16Mo3
625‐16Mo3
TWAS 625‐16Mo3
TWAS 625‐16Mo3 5.79
5.79
5.79
5.79 13.64
13.64
13.64 13.81
13.64 13.81
13.81
13.81 17.02 17.02
17.02 16.54 16.54
16.54
TWAS
TWAS
TWAS 625‐16Mo3
625‐16Mo3
625-16Mo3 5.79
5.79
5.79 13.64
13.64
13.64 13.81
13.81
13.81 17.02
17.02
17.02 16.54
16.54 16.54
TWAS
TWAS 45CT‐AISI
45CT‐AISI
TWAS45CT-AISI
TWAS 45CT‐AISI
45CT‐AISI 310
310
310
310 3.79
3.79
3.79
3.79 6.10
6.10
6.10
6.10 6.20
6.20
6.20
6.20 7.96
7.96
7.96
7.96 8.11
8.11
8.11
8.11
TWAS
TWAS
TWAS
TWAS 45CT‐AISI
45CT‐AISI
45CT‐AISI 310 310
310
310 3.79
3.79
3.79
3.79 6.10
6.10
6.10
6.10 6.20
6.20
6.20
6.20 7.96
7.96
7.96
7.96 8.11
8.11
8.11 8.11
TWAS
TWAS 45CT‐16Mo3
45CT‐16Mo3
TWAS45CT-16Mo3
TWAS 45CT‐16Mo3
45CT‐16Mo3 10.02
10.02
10.02
10.02 12.37
12.37
12.37 12.75
12.37 12.75
12.75
12.75 15.16
15.16
15.16
15.16 15.24
15.24
15.24
15.24
TWAS
TWAS
TWAS 45CT‐16Mo3
45CT‐16Mo3 10.02
10.02
10.02 12.37
12.37
12.37 12.75
12.75
12.75 28.22 15.16
15.16
15.16 15.24
15.24 15.24
K50
K50 Plasma‐AISI
Plasma‐AISI
K50Plasma-AISI
K50 Plasma‐AISI
Plasma‐AISI 310
310
310 16.63
16.63
16.63 27.36
27.36
27.36 27.48 27.48
27.48
27.48 28.22
28.22 27.6
27.6
27.6
K50
K50
K50 Plasma‐AISI
Plasma‐AISI 310310 310
310
16.63
16.63
16.63
16.63
27.36
27.36
27.36
27.36 27.48 28.22
27.48
27.48 28.22 27.6
28.22
28.22 27.6
27.6 27.6
K50
K50
K50
K50 Plasma‐16Mo3
Plasma‐16Mo3
Plasma‐16Mo3
Plasma‐16Mo3 19.88
19.88
19.88
19.88 32.43
32.43
32.43
32.43 32.49
32.49
32.49
32.49 32.8
32.8
32.8
32.8 32.31
32.31
32.31
32.31
K50
K50
K50
K50 Plasma‐16Mo3
Plasma-16Mo3
Plasma‐16Mo3
Plasma‐16Mo3 19.88
19.88
19.88
19.88 32.43
32.43
32.43
32.43 32.49
32.49
32.49
32.49 32.8
32.8
32.8
32.8 32.31
32.31
32.31
32.31
HVOF‐AISI
HVOF‐AISI
HVOF‐AISI
HVOF‐AISI 310
310
310
310 2.27
2.27
2.27
2.27 4.19
4.19
4.19
4.19 4.26
4.26
4.26
4.26 5.52
5.52
5.52
5.52 6.06
6.06
6.06
6.06
HVOF-AISI
HVOF‐AISI
HVOF‐AISI 310 310
310 2.27
2.27
2.27 4.19
4.19
4.19 4.26
4.26
4.26 5.52
5.52
5.52 6.06
6.06 6.06
HVOF‐16Mo3
HVOF‐16Mo3
HVOF‐16Mo3
HVOF‐16Mo3
HVOF-16Mo3
2.65
2.65
2.65
2.65
2.65
4.91
4.91
4.91
4.91
4.91
4.98
4.98
4.98
4.98
4.98
6.24
6.24
6.24
6.246.24
6.95
6.95
6.95
6.95 6.95
HVOF‐16Mo3
HVOF‐16Mo3
HVOF‐16Mo3 2.65
2.65
2.65 4.91
4.91
4.91 4.98
4.98
4.98 6.24
6.24
6.24 6.95
6.95
6.95
AISI
AISI
AISI
AISI
AISI 310
310310
310
310 1.40
1.40
1.40
1.40
1.40 2.45
2.45
2.45
2.45
2.45 2.86
2.86
2.86
2.86
2.86 4.03
4.03
4.03
4.03
4.03 4.55
4.55
4.55
4.55 4.55
AISI
AISI
AISI 310
310
310 1.40
1.40
1.40 2.45
2.45
2.45 2.86
2.86
2.86 4.03
4.03
4.03 4.55
4.55
4.55
16Mo3
16Mo3
16Mo3
16Mo3
16Mo3 9.05
9.05
9.05
9.05
9.05 18.09
18.09
18.09
18.09
18.09 23.65
23.65
23.65
23.65
23.65 26.86
26.86
26.86 27.05
26.86
26.86 27.05
27.05
27.05 27.05
16Mo3
16Mo3 9.05
9.05 18.09
18.09 23.65
23.65 26.86 26.86 27.05
27.05
However,
However,
However,the
However, these
these
these
these weight
weight
weight
weight changes
changes
changes
changes plummeted
plummeted
plummeted
plummeted in
in
in(in time
time
time (after
(after
(after aaa rapid
rapid
rapid
rapid oxidation
oxidation
oxidation of of
of the
the
of the
the
Technically,
However,
However, weight
these
these weight
weightgains after 5000
changes
changes h at 500 ◦in
plummeted
plummeted C
in
in
time
time
timeg/m (after
2 ) ina
(after
(after aathe
rapid
rapid
oxidation
high-temperature
oxidation
oxidation of the
of the
the
coarse
coarse
coarse However,
surface
surface
surface these
layer),
layer),
layer), weight
and
and
and changes
further
further
further corrosion
corrosion
corrosionplummetedchanges
changes
changes inwere
were
weretime (after
extremely
extremely
extremely a rapid
limited.
limited.
limited.oxidation
For
For
For of
example,
example,
example,
testcoarse
were surface
coarse
coarse higher
surface
surface
layer),
for any type
layer),
layer),
and
and
and
further
of coating
further
further
corrosion
than forchanges
corrosion
corrosion austenitic
changes
changes
were
were
were steelextremely
AISI 310.limited.
extremely
extremely The best
limited.
limited.
For
For
For
example,
behavior
example,
example,
coarse
in
in the
the
inshown
in surface
case
case
the case
the case of
of
of
of layer),
the
the
the
the K50
K50
K50treated
K50 and
coating
coating
coating
coatingfurthermade
made
made
made corrosion
using
using
using
using the
thechanges
the
the plasma
plasma
plasma
plasma weretorch,
torch,
torch,
torch, extremely
the
the
the
the initial
initial
initial
initial limited.
weight
weight
weight
weight For
growth
growthexample,
growth
growth was
was
was
was
wasin
in the
the case
caseby samples
of
of the
the K50
K50 coating
coating with
made
made HVOF using
using coating,
the
the which
plasma
plasma had
torch,
torch, anthe
theexceptionally
initial
initial weight
weight fine surface;
growth
growth was
was
very
very
very
very large,
large,
large,
large, but
but
but
but approximately
approximately
approximately
approximately after
after
after
after the
the
the
the first
first
first
first 500
500
500
500 h
h
h
h in
in
in
in model
model
model
model atmosphere
atmosphere
atmosphere
atmosphere at
at
at
at 500
500
500
500 °C,
°C,
°C,
°C, it
it
it
it almost
almost
almost
almost
their
very
very corrosion
large,
large, butrates equaled
but approximately
approximately that of
after
after thethe base
the first material.
first 500500 h
h in
in model However,
model atmosphere
atmosphere at since the surface
at 500
500 °C,
°C, it of the
it almost
almost
stopped;
stopped;
stopped;
stopped; afterwards,
afterwards,
afterwards,
afterwards, there
there
there
there were
were
werethere
were practically
practically
practically
practically no
no weight
weight
no weight
no weight changes.
changes.
changes.
changes.
coated
stopped;
stopped;sample was much
afterwards,
afterwards, there
there larger,
were
were will always
practically
practically no
no weight
weightbe rapid changes.
changes. oxidation and weight gain
stopped; afterwards,
Technically,
Technically,
Technically,
Technically, the
the there
weight
weight
theexposure.
weight were
gains
gains
gains practically
after
after
after 5000
5000
5000 noh weight
at
hhFigure
at 500
500
at 500
500 °C °C
°C
°C changes.
(in
(in g/m
(in g/mg/m
g/m
22) in the high‐temperature
)) inin
in the high‐temperature
the high‐temperature
high‐temperature
at the initial phase the
Technically,
Technically, of
the
theany
weight
weight
weight
gains
gains
gainsTheaftergraph
after
after
5000
5000
5000 inh h
h at
at
at
at 500 4°C
500 °C (in
°Cshows
(in
(in g/m
g/m
22222)
the 22))) inin
in
the
dependency
the of AISI
high‐temperature
the high‐temperature
high‐temperature
test
test
test Technically,
were
were higher
higher
were higher
higher the
for
for
for any weight
any
any type
type
type of gains
of
of after
coating
coating
of coating
coating 5000
than
than
than h
for
for 500
austenitic
austenitic
forcoated
austenitic (insteel
steelg/m
steel AISI AISI
AISI
AISI 310. the
310.
310.
310. The
The best
best
The best behavior
behavior
best behavior
behavior
310test
test
test
were
weight
were
were gains
higher
higher
for
and
for
for of
any
any
type
weight
type
type of
of gains
coating
coating ofthan
other
than
than
for
for
for
austenitic
austenitic
austenitic
steel
samples—the
steel
steel AISI
AISI 310.
310.
The
initial
The
The weight
best
best for
behavior
behavior
test
was
was
was were
shown
shown
was shown
shown higher
by
by for
samples
samples
by samples
by samples any type
treated
treated of
treated with
treated coating
with
with
with than
HVOF
HVOF
HVOF
HVOF for austenitic
coating,
coating,
coating, which
which
which steel
had
had
had InAISI an
an
anthis 310. The
exceptionally
exceptionally
exceptionally best behavior
fine
fine
fine sur‐
sur‐
sur‐
gravimetric
was shown analysis
by was considered
samples treated with thatHVOFaftercoating,
500 h ofwhich
coating, exposure.
which had
had an
an exceptionally
graph, thefine
exceptionally black
fine sur‐
was
face;
face; shown
their
their by samples
corrosion
corrosion rates
rates treated
equaled
equaled with that
that HVOF
of
of the
the coating,
base
base which had
material.
material. However,
However, an exceptionally
since
since the
the fine sur‐
surface
surface sur‐of
of
lineface;
face; their
their
indicates
face; their corrosion
corrosion
the
their corrosion weight
corrosion rates rates
ratesgainsequaled
equaled
rates equaled of that
that
austenitic
equaled that that of of
of the
the
of the steel
the base base
base AISImaterial.
material.
base material. 310. The
material. However, However,
However,
samples
However, since since
since the
the
situated
since the surface
surface
surface of
above
the surface of
of
face;
the
the coated
coated sample
sample was
was much
much larger,
larger, there
there will
will always
always be
be rapid
rapid oxidation
oxidation and
and weight
weight gain
gain of
the
the
this
the linecoated
coated
showed
coated sample
sample
samplehigher was
was
was much
much
corrosion
much larger,
larger,
rates
larger, there
there
than
there will
will
this
will always
always
steel.
always We be
be
be rapid
rapid
can
rapid see oxidation
oxidation
oxidationthat a goodand
and
and weight
weight
portion
weight gain
gain
of
gain
thethe
the coated
coated sample
sample was
was much larger,
much larger, there
there will
will always4 be
always be rapidthe
rapid oxidation
oxidation and weight
and weight gain
at
at
theat
at
the
attested
the
the
the
initial
initial
initial
materials
initial
initial
phase
phase
phaseshowed
phase
phase
of
of
of
of
exposure.
exposure.
of exposure.
exposure.
a similar
exposure.
The
The
Theor
The
The
graph
graph
graph
better
graph
graph
in
in
in
in
Figure
Figure
incorrosion
Figure
Figure
Figure
shows
4444 shows
shows
shows
behavior
shows
the
the
the
the in dependency
dependency
dependency
chlorine-containing
dependency
dependency
of
of AISIgain
AISI
AISI
of AISI
of
of AISI
310
310
310
310
310
at the
at the initial
weight initial
gains phase
phase
and of
◦ Cof of
of exposure.
exposure.
weight gains The
The of graph
graph
other in
in Figure
Figure
coated 44 shows
shows
samples—the the
the dependency
dependency
initial weight of
of AISI
AISI
for 310
310
gravi‐
weight
atmosphere
weight gains
weight gains
at 500
gains and and
and of weight
than
of weight high
weight gains gains
alloyed
gains of of other
austenitic
of other coated
other coated steel samples—the
AISI
coated samples—the 310.
samples—the initial Better initial weight
coatings
initial weight for
corrosion
weight for gravi‐
for gravi‐
gravi‐
weight
weight gains
gains and and of weight
weight gains
of considered gains of other
ofafter
other500 coated
coated samples—the
samples—the initial
initial weight
weight for
for gravi‐
gravi‐
metric
metric
resistance analysis
analysis
was observed
metric analysis
metric analysis was
was considered
was considered
was for samples
considered that
that
thatwith
that after
afterthe
after 500
500AISI
500 h
h of
hh of
of exposure.
exposure.
of310
exposure.substrate.
exposure. In
In
In this
In this
this
this graph,
graph,
Everygraph,
graph, the
the
sample black
black
the black
the of the
black line
line
line
line
metric analysis
metric analysis was
was gains considered
considered that after
that after 500
500 h
h ofof exposure.
exposure. In
In this this graph,
graph,above the black
the black line
line
indicates
indicates
tested coatings
indicates
indicates the
the
the
the weight
weight
showed
weight
weight gains
better
gains
gains of
of
of
of austenitic
austenitic
austenitic
austenitic steel
steel
corrosion/gravimetric
steel
steel AISI
AISI
AISI
AISI 310.
310.
310.
310. The
The
results
The
The samples
samples
than
samples
samples low situated
situated
alloyed
situated
situated above
boiler
above
above this
this
steel
this
this line
line
line
line
indicates the
indicates the weight
weight gains gains of of austenitic
austenitic steel steel AISIAISI 310.310. The The samples
samples situated situated above above this this line
line
Coatings 2022, 12, x FOR PEER REVIEW showed
showed
16Mo3—if
showed
showed higher
higher
we
higher
higherdo corrosion
corrosion
not consider
corrosion
corrosion rates
rates
ratesthe
rates than
than
initial
than
than this
this steel.
steel.
phase
this
this steel.
steel. of We
We
Werapid
We can
can
can
can see
see
oxidation
see
see that
that
that
that aaathat
a good
good
good
good portion
portion
occurred
portion
portion of
of
in
of
of the
the
7the
the
the tested
tested
offirst
14
tested
tested
showed
showed higher
showed higher
higher corrosion
corrosion
corrosion rates
rates
rates than
than
than this steel.
thiscorrosion
this steel. We
steel. We can
Webehavior
can see
can see that
see that
that aa goodgood
good portion portion
portion of of the
of the tested
theatmos‐
tested
materials
materials
200materials
or 500 h of
materials
materials
showed
showed
showed
showed
showed aaaaa similar
high-temperature similar
similar
similar
similar
or
or
or
or
better
better
oroxidation.
better
better
better
corrosion
corrosion
corrosion
corrosion
behavior
behavior
behavior
behavior in achlorine‐containing
in
in
in
in
chlorine‐containing
chlorine‐containing
chlorine‐containing
chlorine‐containing
tested
atmos‐
atmos‐
atmos‐
atmos‐
materials
materials showed
showed aa similar
similar or better
or better corrosion
corrosion behavior inBetter
chlorine‐containing atmos‐
phere
phere
phere at
phere
phere
at
at
at
500
500
at 500
500
500
°C
°C than
than
°C than
°C
°C than
than
high
high alloyed
alloyed
high alloyed
high
high alloyed
alloyed
austenitic
austenitic
austenitic
austenitic
austenitic steelbehavior
steel
steel
steel
steel
AISI
AISI
AISI 310.
AISI
AISI
310.
310.
310.
310.
in chlorine‐containing
Better
Better
Better
Better
coatings
coatings corrosion
corrosion
coatings corrosion
coatings
coatings corrosion
corrosion
atmos‐ re‐
re‐
re‐
re‐
re‐
phere
sistance
sistance at 500
was
was °C than
observed
observed high
for
for alloyed
samples
samples austenitic
with
with the
the AISI
AISIsteel310
310 AISI 310.
substrate.
substrate. Better
Every
Every coatings
sample
sample corrosion
of
of the
the tested
testedre‐
sistance was
sistance
sistance was observed
was observed for
observed for samples
for samples with
samples with the
with the AISI
the AISI 310
AISI 310 substrate.
310 substrate. Every
substrate. Every sample
Every sample of
sample of the
of the tested
the tested
tested
sistance was
coatings
coatings showed
showedobserved better
better for samples with the AISI 310
corrosion/gravimetric
corrosion/gravimetric substrate.
results
results than
than Everylow
low sample of
alloyed
alloyed the tested
boiler
boiler steel
steel
coatings showed
coatings
coatings showed better
showed better corrosion/gravimetric
better corrosion/gravimetric results
corrosion/gravimetric results than
results than low
than low alloyed
low alloyed boiler
alloyed boiler steel
boiler steel
steel
coatings
coatings
16Mo3—if showed
showed
we do not better
better
consider corrosion/gravimetric
corrosion/gravimetric
the initial phase of results
results
rapid than
than
oxidation low
low that alloyed
alloyed
occurred boiler
boiler
in the steel
steel
first
16Mo3—if
16Mo3—if
16Mo3—if we
we
we do
do
do not
not
not consider
consider
consider the
the
the initial
initial
initial phase
phase
phase of
of
of rapid
rapid
rapid oxidation
oxidation
oxidation that
that
that occurred
occurred
occurred in
in
in the
the
the first
first
first
16Mo3—if
16Mo3—if
16Mo3—if we
we
we do
do
do not consider
not consider
not consider the the initial
theoxidation. phase
initial phase
initial phase of of rapid
of rapid oxidation
rapid oxidation
oxidation that that occurred
that occurred
occurred in in
in thethe first
the first
first
200
200
200
200 or
or
or
or 500
500
500
500 hh of
hh of
of
of high‐temperature
high‐temperature
high‐temperature
high‐temperature oxidation.
oxidation.
oxidation.
200
200 or
200 or 500
or 500
500 h h of
h of high‐temperature
of high‐temperature
high‐temperature oxidation. oxidation.
oxidation.

Figure
Figure 4.
4. Comparison between the
Comparison between theweight
weightgains
gains(determined
(determinedafter
after
thethe first
first 500500
h ofh exposure)
of exposure) of
of AISI
AISI 310 and those of samples of various sprayed coatings after exposure at ◦500 °C.
310 and those of samples of various sprayed coatings after exposure at 500 C.

Table 4 presents the gravimetric data of all tested sprayed coatings and base materials
after exposure in model atmosphere containing chlorine at 600 °C. In this case, the meas‐
ured weight gains were generally higher compared to those measured in the experiments
carried out at 500 °C. Especially, low alloyed steel 16Mo3 showed an extremely high cor‐
 Figure 4.
Figure 4. Comparison
Comparison between
between the
the weight
weight gains
gains (determined
(determined after
after the
the first
first 500
500 hh of
of exposure)
exposure) of
of
Figure 4.
Figure
Figure 4. Comparison
4. Comparison between
Comparison between the
between the weight
weight gains
gains (determined
(determined after
after the
the first
first 500
500 hh of
of exposure)
exposure) of
of
Figure
AISI
Figure 4.and
AISI 310
310
4. Comparison
and those of
those
Comparison betweenofthe
betweenof
of samples
samples the weight
weight
various
various
the
gains
sprayed
sprayed
weight gains
(determined
gains coatings
coatings afterafter
(determined
after
(determined after the
the first
exposure
exposure
after the first 500
at 500
at
first500
500
hh of
500°C.
°C.
h of exposure)
of exposure) of
exposure) of
of
Coatings 2022, 12, 116 AISI 310
AISI
AISI 310 and
and those
those of
of samples
samples of
of various
various sprayed
sprayed coatings
coatings after
after exposure
exposure atat 500
500 °C.
°C. 7 of 14
AISI 310
AISI 310 and
310 and those
and those of
those of samples
of samples of
samples of various
of various sprayed
various sprayed coatings
sprayed coatings after
coatings after exposure
after exposure at
exposure at 500
at 500 °C.
500 °C.
°C.
Table 44 presents
Table presents thethe gravimetric
gravimetric data data of of all
all tested
tested sprayed
sprayed coatings
coatings and and base
base materials
materials
Table
Table
Table 444 presents
presents
presents the
the gravimetric
gravimetric data
gravimetric
theatmosphere data
data of
of all
of all tested
all tested
tested sprayed
sprayed
sprayed coatings
coatings
coatings and
and base
base
andcase, materials
basethematerials
materials
afterTable
after exposure
exposure 4 in model
presents
in model
the atmosphere
gravimetric containing
data of
containing all chlorine
tested
chlorine at 600
sprayed
at 600coatings
°C. In
°C. In this
this
and case,
base the meas‐
materials
meas‐
after
after
after exposure
exposure
exposure in
in
in model
model
model atmosphere
atmosphere
atmosphere containing
containing
containing chlorine
chlorine
chlorine at
at
at 600
600
600 °C.
°C.
°C. In
In
In this
this
this case,
case,
case, the
the
the meas‐
meas‐
meas‐
ured
after
ured Table
weight
exposure 4 presents
gains
in were
modelthe gravimetric
generally
atmosphere data
higher of
containing all
compared tested to
chlorine sprayed
those
at coatings
measured
600 °C. In in
thisand
the base materials
experiments
case, the meas‐
ured weight
ured weight gains gains were
were generally
generally higherhigher compared
compared to to those
those measured
measured in
in the
the experiments
experiments
afterweight
ured
ured weight
carriedexposure
out at
weight
carried out
gains
gains
500
500
were
were
in model
atgains °C.
were
°C.
generally
generallylow
atmosphere
Especially,
generally
Especially,
higher
higher
low
compared
compared
containing
alloyed
higher steel
compared
alloyed steel
to
to those
chlorine
16Mo3
to
16Mo3 those
at 600
those
measured
◦ C. In thisin
measured
showed
measured
showed
the
incase,
an extremely
an extremely
in the
experiments
the the
experiments
measured
high cor‐
experiments
high cor‐
carried
carried
carried out
out
out at
at
at 500
500
500 °C.
°C.
°C. Especially,
Especially,
Especially, low
low
low alloyed
alloyed
alloyed steel
steel
steel 16Mo3
16Mo3
16Mo3 showed
showed
showed an
an
an extremely
extremely
extremely high
high
high cor‐
cor‐
cor‐
weight
carried
rosion gains
rosion rate—which
rate—which were
out at 500 °C.was generally
was
wasEspecially,
also higher
also the
thelow compared
initial
alloyed
initial to
presumption,those
steel 16Mo3
presumption, measured
as these
as in the
these materials
showed materialsexperiments
an extremely are not
are nothigh carried
a good
good
cor‐
rosion
rosion
rosion rate—which
◦ C. Especially,
rate—which
rate—which
out at for
500application was
was also
lowthe
also
also the
the initial
initial presumption,
presumption,
initialthese
alloyed presumption,
steel 16Mo3 as
as
as
showed these
these
thesean materials
materials
materials
extremely are
are
are
highnot
not
not aaaa good
good
good
corrosion
choice
rosion
choice for application
rate—which wasin boilers
in boilers
also the under
initial
under these conditions
presumption,
conditions (biomass
as these
(biomass fuel) without
materials
fuel) without
are any
not
any a addi‐
good
addi‐
choice
choice
choice for
for application
for
rate—which application
application
was As in
in boilers
intheboilers
boilers
alsoobserved under
under
initialunder these
these
these
presumption, conditions
conditions
conditions
as these(biomass
(biomass
(biomass
materials fuel)
arewithout
fuel)
fuel) without
without
not any
any
any
a good addi‐
addi‐
addi‐
choice
tional
choice
tional protection.
for application
protection. As observed
in boilers before,
under
before, the vast
these
the vast majority
conditions
majority of the
(biomass
of the tested
tested
fuel) coatings
without
coatings suffered
any addi‐
suffered
tional
tional
for protection.
protection.
application
tional protection.(weightinAs
As observed
observed
boilers
As observed
observed under before,
before,
these
before, the
the vast
vast
conditions
the vast majority
majority
(biomass
majority of
of the
the
fuel)
of the
the tested
tested
without coatings
coatings
tested coatings any
coatings suffered
suffered
additional
suffered
rapid oxidation
tional
rapid
rapid oxidation
protection.
oxidation (weight
As
(weight gains) before,
gains)
gains) during the
during
during the first
the first 200
vast
first 200
200 h of
majority
hh of the
of the
of
the experiment.
tested
experiment.
experiment. After approxi‐
After
After approxi‐
suffered
approxi‐
rapid
rapid oxidation
protection.
oxidation As (weight
observed
(weight gains)
before,
gains) during
the
during the
the
vast
the first
majority
first 200
200 h
of
h of
the
of the experiment.
tested
the coatings
experiment. After approxi‐
suffered
After approxi‐rapid
mately
mately 500
rapid oxidation
500 h, h, these
h, these
these weight
(weight
weight changes
gains) during
changes rapidly
the first
rapidly declined
200 h as
declined as before.
of the
as before. The
experiment. corrosion
The corrosion rate
After rate
corrosion approxi‐
rate was
was
mately
mately
oxidation
mately 500
500
500 h,
h, these
(weight
these weight
weight
gains)
weight changes
changes
during
changes the rapidly
rapidly
first
rapidly 200 declined
declined
h of
declined the as before.
before.
experiment.
as before. The
The
The corrosion
After rate
approximately
corrosion rate was
was
was
certainly
mately
certainly 500 influenced by the
h, these weight
influenced by the coating
coating surface
changes surface profile:
rapidlyprofile:
declined
profile: the
the finest
asfinest
before. surface of HVOF
The corrosion
surface of HVOFrate coating
coatingwas
certainly
certainly
500 h, theseinfluenced
influenced
weight by
by the
by
changesthe coating
coating
rapidly surface
surface
declined profile:
asmaterialthe
the finest
the
before. finest
The surface
surface of
of HVOF
HVOF coating
coating
certainly
showed
certainly
showed influenced
better
influenced
better corrosion
corrosionby the
the coating
behavior
coating
behavior surface
than the base
surface
than the profile:
base
profile:
materialthe AISIcorrosion
finest
finest
AISI surface
310, while
surface
310, while
rate
of
of was
HVOF
the
HVOF
the K50certainly
K50 coating
Plasma
coating
Plasma
showed
showed
influenced
showed better
better
better corrosion
by thecorrosion
coating
corrosion behavior
behavior than
than the
than
surfacesuffered
behavior profile: the
the
the base
base material
finest
base surfaceAISI
material
material AISI
ofthe
AISI 310,
310,
HVOF
310, while
while
coating
while the
the
the K50
K50
showed
K50 Plasma
Plasma
better
Plasma
layer
showed
layer with
withbetter the
the coarsest
corrosion
coarsest surface
behavior
surface than
suffered rapid
the base
rapid oxidation
material
oxidation at
AISI
at beginning
the310, while
beginning theof
of the Plasma
K50
the experi‐
experi‐
layer
layer with
with
corrosion
layer with the the
the coarsest
coarsest
behavior
the coarsest than surface
surface
the
coarsest surface basesuffered
suffered
surface suffered material
suffered rapid rapid
rapid
AISI oxidation
oxidation
310,
rapid oxidation while
oxidation at at
at the
the
the
at the beginning
beginning
K50 Plasma
the beginning
beginning of of
of the
the
layer
of the experi‐
experi‐
with
the experi‐ the
experi‐
ment.with
layer
ment.
ment.
ment.
coarsest
ment. surface suffered rapid oxidation at the beginning of the experiment.
ment.
Table 4.
Table 4. Gravimetric
Gravimetric results
results of
of coatings
coatings and
and materials
materials after
after exposure
exposure at
at 600
600 °C
°C in
in model
model atmosphere,
atmosphere,
Table
Table
Table 4. 4. Gravimetric
Gravimetric results
Gravimetricresults of
resultsof coatings
ofcoatings and
coatingsand materials
andmaterials after
materialsafter exposure
afterexposure at
exposureat 600
at600 °C
600°C ininmodel
◦ Cin model atmosphere,
modelatmosphere,
in g/m4.
Table
Table
Table
in g/m 4. 24.
224.. . Gravimetric
Gravimetric
Gravimetric
results
results
results
of
of
of
coatings
coatings
coatings
and
and
and
materials
materials
materials
after
after
after
exposure
exposure
exposure
at
at
at
600
600
600
°C
°C
°C
in
in
in
model
model
model
atmosphere,
atmosphere,
atmosphere,
atmosphere,
in g/m
in
in g/m22222... 2
g/m
in g/m
ing/m
in g/m 2.. .
2
Exposure Time
Exposure Time (h)
(h)
Coating‐Substrate
Coating‐Substrate Exposure
Exposure
Exposure Time
Time
Time (h)
(h)
(h) Trend
Trend
Coating‐Substrate
Coating‐Substrate 200
200 500
500 Exposure
Exposure
1000
1000 Time
Time (h)
(h)
2000
2000 5000
5000 Trend
Trend
Coating‐Substrate
Coating‐Substrate
Coating-Substrate 200
200 500
500 1000
1000 2000
2000 5000
5000 Trend
Trend
Trend
TWAS Pseudo‐AISI
Pseudo‐AISI 310 310 200
20.08 500
200 200 22.74
22.74 1000
500 500 23.08
10001000 24.67
23.08 2000
2000
2000
24.67 5000
5000
5000
28.99
TWAS
TWAS Pseudo‐AISI 310 20.08
20.08 22.74 23.08 24.67 28.99
28.99
TWAS
TWAS Pseudo‐AISI
Pseudo‐AISI 310
310 20.08
20.08 22.74
22.74 23.08
23.08 24.67
24.67 28.99
28.99
TWAS
TWAS
TWAS
TWASPseudo‐AISI
Pseudo‐16Mo3
Pseudo‐16Mo3 310
Pseudo-AISI 310 20.08
25.49 22.74
25.4920.08 30.04 23.08
30.0422.74 30.69 24.67
30.6923.08 34.48
34.48
24.67 28.99
40.93
40.93
28.99
TWAS
TWAS
TWAS Pseudo‐16Mo3
Pseudo‐16Mo3
Pseudo‐16Mo3 25.49
25.49
25.49 30.04
30.04
30.04 30.69
30.69
30.69 34.48
34.48
34.48 40.93
40.93
40.93
TWAS
TWAS
TWAS
TWAS Pseudo‐16Mo3
625‐AISI 310
Pseudo-16Mo3
625‐AISI 310 25.49
20.72 30.04
20.7225.49 21.92 30.69
21.9230.04 21.82 34.48
21.8230.69 24.91
24.91
34.48 40.93
25.49
40.93
25.49
TWAS
TWAS
TWAS 625‐AISI
625‐AISI
625‐AISI 310
310
310 20.72
20.72
20.72 21.92
21.92
21.92 21.82
21.82
21.82 24.91
24.91
24.91 25.49
25.49
25.49
TWAS
TWAS
TWAS
TWAS 625‐AISI
625‐16Mo3
625-AISI
TWAS 625‐16Mo3
625‐16Mo3 310
310 20.72
23.94
23.94 21.92
23.9420.72 30.45
30.45 21.82
30.4521.92 30.94
30.94 24.91
30.9421.82 36.38
36.38
24.91
36.38 25.49
44.90
25.49
44.90
44.90
TWAS
TWAS 625‐16Mo3
625‐16Mo3 23.94
23.94 30.45
30.45 30.94
30.94 36.38
36.38 44.90
44.90
TWAS
TWAS
TWAS TWAS 625‐16Mo3
45CT‐AISI
625-16Mo3
45CT‐AISI 310
310 23.94
8.41 30.45
8.4123.94 10.54 30.94
10.5430.45 11.47 36.38
11.4730.94 13.37
13.37
36.38 44.90
14.52
44.90
14.52
TWAS
TWAS 45CT‐AISI
45CT‐AISI 310 8.41
8.418.41 10.54 11.47 13.37 14.52
TWAS
TWASTWAS
TWAS
TWAS 45CT-AISI310
45CT‐AISI
45CT‐AISI
45CT‐16Mo3
45CT‐16Mo3
310
310
310
8.41
8.41
16.23
16.23
10.54
10.54
10.54
18.91
11.47
11.47
18.9110.54 20.36
11.47
13.37
13.37
20.3611.47 23.91 13.37
13.37
23.91
14.52
14.52
14.52
14.52
25.17
25.17
TWAS
TWAS
TWASTWAS
45CT‐16Mo3
45CT‐16Mo3
45CT‐16Mo3
45CT-16Mo3
16.23
16.23
16.23 18.91
18.91
18.91 20.36
20.36
20.36 23.91
23.91
23.91 25.17
25.17
25.17
TWAS
K50 45CT‐16Mo3
Plasma‐AISI
K50 Plasma‐AISI
Plasma‐AISI 310 310
310 26.1516.23 34.92
16.23
26.15 34.9218.91 33.32
18.91 33.3220.36 39.71
20.36 23.91
23.91
39.71 25.17
25.17
47.21
47.21
K50
K50
K50 Plasma‐AISI
K50 Plasma-AISI310
Plasma‐AISI 310
310 26.15
26.15
26.15 34.92 33.32
26.15 34.9234.92 33.3233.32 39.71
34.92 33.32 39.71
39.71
39.71 47.21
47.21
47.21
47.21
K50
K50Plasma‐AISI
K50 Plasma‐16Mo3
Plasma‐16Mo3 310 26.15
34.10
34.10 34.92
44.85
44.85 33.32
44.06
44.06 39.71
52.43
52.43 47.21
63.50
63.50
K50
K50
K50 Plasma‐16Mo3
Plasma‐16Mo3
K50 Plasma-16Mo3
Plasma‐16Mo3 34.10
34.10
34.1034.1044.85
44.85
44.85 44.85 44.06
44.06
44.0644.06 52.43
52.43
52.43
52.43 63.50
63.50
63.50
63.50
K50 Plasma‐16Mo3
HVOF‐AISI
HVOF‐AISI 310
310 34.10
3.30
3.30 44.85
3.79
3.79 44.06
5.61
5.61 52.43
7.19
7.19 63.50
7.68
7.68
HVOF‐AISI
HVOF-AISI
HVOF‐AISI
HVOF‐AISI 310
310
310
310 3.30
3.30
3.30 3.30 3.79
3.79
3.79 3.79 5.61
5.61
5.61 5.61 7.19
7.197.19
7.19 7.68
7.68
7.68
7.68
HVOF‐AISI
HVOF‐16Mo3
HVOF‐16Mo3 310 3.30
3.57
3.57 3.79
6.00
6.00 5.61
7.45
7.45 7.19
9.47
9.47 7.68
8.73
8.73
HVOF‐16Mo3
HVOF-16Mo3
HVOF‐16Mo3
HVOF‐16Mo3 3.57
3.57
3.57 3.57 6.00
6.00
6.00 6.00 7.45
7.45
7.45 7.45 9.47
9.479.47
9.47 8.73
8.73
8.73
8.73
HVOF‐16Mo3
AISI
AISI
AISI 310
310310 3.57
3.64 6.00
3.643.64 6.10 7.45
6.10 6.10 6.16
6.16 6.16 9.47
7.76
7.767.76 8.73
10.76
10.76
10.76
AISI
AISI
AISI 310
310
310 3.64
3.64
3.64 6.10
6.10
6.10 6.16
6.16
6.16 7.76
7.76
7.76 10.76
10.76
10.76
AISI
16Mo3
16Mo3 310
16Mo3
16Mo3 3.64
146.04
146.04 6.10
174.85
146.04174.85
146.04 174.85 6.16
228.60
174.85228.60
228.60 7.76
276.99
228.60 276.99
276.99
276.99 10.76
369.31
369.31
369.31
369.31
16Mo3
16Mo3 146.04 174.85
146.04 174.85
174.85 228.60228.60
228.60 276.99
276.99 369.31
369.31
16Mo3 146.04 276.99 369.31

During the experiment at 600 ◦ C, all thermally sprayed coatings showed significantly
better corrosion resistance than 16Mo3 steel. Figure 5 shows a comparison between the
weight gains of the samples and of AISI 310 steel. As before, all materials under the black
line showed better gravimetric results than this austenitic steel, when not considering the
first 500 h of oxidation, and the gravimetry analysis started after 500 h of exposure. Overall,
all weight changes were similar, and except for 16Mo3 steel, no tested samples exhibited
severe corrosion damage.

3.2. Metallographic Results

Figure 6 shows light microscopy photos of the coating samples after exposure at
500 ◦ C in a model atmosphere containing hydrogen chloride (5000 h), in this case, samples
with a base material consisting of 16Mo3. Compared with the exposed coatings in the
initial condition, no significant corrosion problems occurred during the exposure, and the
structure of the individual coatings was virtually identical to the initial one. Of course, the
most compact surface with practically no oxidation was observed for the sample coated
by the HVOF technology. Even in the plasma spraying coating case (e in Figure 6), where
higher porosity or higher number of oxidized particles were expected in the initial state,
the structure was relatively compact in a cross section, and no defects or cracks in the
coating structure were observed. No delamination was observed in the experiment at
500 ◦ C, neither on AISI 310 austenitic steel substrate material nor on 16Mo3 ferritic steel
base material.
 During the experiment at 600 °C, all thermally sprayed coatings showed significantly
better corrosion resistance than 16Mo3 steel. Figure 5 shows a comparison between the
weight gains of the samples and of AISI 310 steel. As before, all materials under the black
line showed better gravimetric results than this austenitic steel, when not considering the
first 500 h of oxidation, and the gravimetry analysis started after 500 h of exposure. Over‐
Coatings 2022, 12, 116 8 of 14
all, all weight changes were similar, and except for 16Mo3 steel, no tested samples exhib‐
ited severe corrosion damage.

Coatings 2022, 12, x FOR PEER REVIEW

Figure 5. Comparison
Figure 5. Comparisonbetween
betweenthe
theweight
weightgains
gains (determined
(determined after
after thethe
firstfirst
500 500
h of hexposure)
of exposure) of
of AISI 9 of 1
AISI 310of
310 and and
theofsamples
the samples of various
of various sprayed
sprayed coatings
coatings after exposure
after exposure at 600at◦ C.
600 °C.

3.2. Metallographic Results

Figure 6 shows light microscopy photos of the coating samples after exposure at 500
°C in a model atmosphere containing hydrogen chloride (5000 h), in this case, samples
with a base material consisting of 16Mo3. Compared with the exposed coatings in the
initial condition, no significant corrosion problems occurred during the exposure, and the
structure of the individual coatings was virtually identical to the initial one. Of course, the
most compact surface with practically no oxidation was observed for the sample coated
by the HVOF technology. Even in the plasma spraying coating case (e in Figure 6), where
higher porosity or higher number of oxidized particles were expected in the initial state,
the structure was relatively compact in a cross section, and no defects or cracks in the
coating structure were observed. No delamination was observed in the experiment at 500
°C, neither on AISI 310 austenitic steel substrate material nor on 16Mo3 ferritic steel base
material.

Figure6.6.Optical
Figure Optical light
light micrographs
micrographs ofthermally
of the the thermally
sprayedsprayed coatings
coatings after
after 5000 500 ◦hC at
h at5000 in 500 °C in mode
model
atmosphere:(a)(a)
atmosphere: HVOFHVOF Amperit
Amperit 469,469, (b) TWAS
(b) TWAS 45CT,45CT, (c) TWAS
(c) TWAS Alloy
Alloy 625, (d)625,
TWAS(d)pseudo-alloy,
TWAS pseudo‐alloy
and(e)
and (e)Plasma
Plasma K50—16Mo3
K50—16Mo3 steelsteel
basebase material.
material.

Similar
Similar results were
results obtained
were after exposure
obtained of the coatings
after exposure of the at 600 ◦ C inatan600
coatings environment
°C in an environ
containing
ment containing hydrogen chloride, as shown in Figure 7, which presentsfor
hydrogen chloride, as shown in Figure 7, which presents the results thethe
results fo
hot-sprayed samples on 16Mo3 steel substrate—the samples with AISI 310 austenitic steel
the hot‐sprayed samples on 16Mo3 steel substrate—the samples with AISI 310 austeniti
were similar or better after exposure under the same conditions. Again, small pores
steel
in the were similar
structure or coatings
of the better after exposure
(especially, underwere
plasma) the same conditions.
observed, Again,
but so far small pore
without
in theofstructure
signs of the
penetration of coatings (especially,
the corrosive plasma)
atmosphere were
to the baseobserved, but so farwhich
material (16Mo3), without sign
would otherwise highly oxidize in the given environment, and its weight gains would be would
of penetration of the corrosive atmosphere to the base material (16Mo3), which
otherwise
much higherhighly oxidize
than those in the given
of samples environment,
of individual and
protective its weight
coatings. gains
In this would
respect, thebe much
best sample
higher thanwas again
those ofthe HVOF-prepared
samples coating,
of individual which was
protective virtuallyIn
coatings. free of oxidized
this respect, the bes
particles,
sample was and its overall
again thestructure was also free
HVOF‐prepared of signs
coating, of corrosion.
which was virtually free of oxidized par
ticles, and its overall structure was also free of signs of corrosion.
 in the structure of the coatings (especially, plasma) were observed, but so far without sign
of penetration of the corrosive atmosphere to the base material (16Mo3), which would
otherwise highly oxidize in the given environment, and its weight gains would be much
higher than those of samples of individual protective coatings. In this respect, the bes
Coatings 2022, 12, 116 9 of 14
sample was again the HVOF‐prepared coating, which was virtually free of oxidized par
ticles, and its overall structure was also free of signs of corrosion.

Figure7.7.Optical
Figure Optical light
light micrographs
micrographs ofthermally
of the the thermally
sprayedsprayed coatings
coatings after
after 5000 600 ◦hC at
h at5000 in 600 °C in mode
model
atmosphere:(a)(a)
atmosphere: HVOFHVOF Amperit
Amperit 469,469, (b) TWAS
(b) TWAS 45CT,45CT, (c) TWAS
(c) TWAS Alloy
Alloy 625, (d)625,
TWAS(d)pseudo-alloy,
TWAS pseudo‐alloy
and(e)
and (e)Plasma
Plasma K50—16Mo3
K50—16Mo3 steelsteel
basebase material.
material.

3.3. SEM/EDS and EMPA Results

3.3. SEM/EDS and EMPA Results
Figures 8–11 show the SEM/EDS analysis of the coating samples after laboratory
Figures 8–11 show the SEM/EDS analysis of the coating samples after laboratory ex
exposure for 5000 h at 600 ◦ C in an environment containing sulfur dioxide and hydrogen
posure for
chloride. 5000
In all h at
cases, 600coatings
these °C in anwere
environment
on a 16Mo3containing
substrate. Ansulfur dioxide
electron and hydrogen
microscope
chloride. In all cases, these coatings were on a 16Mo3 substrate. An electron
with an EDS analyzer was used for an overview analysis of the distribution of the individual microscop
with an in
elements EDSthe analyzer wasthe
coatings, and used for an maps
elemental overview analysis
for each tested of the distribution
coating of the indi
are shown next
to the microstructures
vidual elements in the (incoatings,
the case ofand
the the
TWAS method,maps
elemental only the
for pseudo-alloy and 45CT
each tested coating are shown
alloy coatings are shown). It can be seen from element mapping that the distribution
next to the microstructures (in the case of the TWAS method, only the pseudo‐alloy and of
the individual elements was homogeneous for all coatings except for the Pseudo-alloy
coating, which displayed an interlayer of pure nickel on the substrate surface. Even after
such a long exposure at 600 ◦ C, no changes in chemical composition were observed in
the cross section of the coatings, and no new phases were observed in the structure of
the individual samples. The left side of the SEM images shows the area (red line) from
which line element microanalysis EMPA (electron microprobe analyzer with a multiple
WDS detector) was performed from the injection direction inside the base material in order
to detect possible changes in the chemical composition of the coatings due to corrosion or
diffusion. The analyzed area/line was composed of individual points with a displacement
step of 20 µm—each measured point was the average of a total of 10 measurements. The
results of the chemical composition of the individual coatings can be seen in Figure 12a,b
and Figure 13a,b. From these plots of the chemical composition of the tested coatings, it can
be seen that no changes in the chemical composition were detected and the coatings were
undamaged and practically the same as in the initial state. Figure 12a shows the underlying
nickel layer in the case of the TWAS pseudo-alloy-coated sample, which was between the
substrate and the actual protective layer.
 diffusion.
step of 20 The analyzed
μm—each area/linepoint
measured was was
composed of individual
the average points
of a total of 10with a displacement
measurements. The
diffusion.
step of 20 The analyzed
μm—each area/line
measured was was
point composed
the of individual
average of a points
total of 10 with a displacement
measurements. The
results of
step of of the
20 the chemical
μm—each composition of
measured pointofwas the individual coatings
the averagecoatings can
of a total be
of be seen
10 seen in Figure
measurements. 12a,b
The
results
and Figure chemical
13a,b. Fromcomposition
these plots of the individual
the chemical composition can ofbethe in Figure
tested 12a,b
coatings, it
results
and of
Figure the chemical
13a,b. From composition
theseinplots of the individual
of the chemical coatings
compositioncan seen in
of the tested Figure 12a,b
coatings, it
can be
and be seen
Figure that no changes the chemical composition were detected and the coatings
can
were seen 13a,b.
that noFrom
undamaged and
theseinplots
changes
practically
of the chemical
the the
chemical as
composition
same composition were
in the initial
of the tested
detected
state. Figure and coatings,
12athe coatings
shows the
it
Coatings 2022, 12, 116 can
were be seen that
undamaged no changes in the
and practically chemical composition were detected and the coatings
10 of 14
underlying
were undamagednickel layer in the casethe
and practically the
same
of the
same
as inpseudo‐alloy‐coated
TWAS the initial state. Figure
as inpseudo‐alloy‐coated
12a which
sample,
the initial state. Figure
showswas
12a which
showswas
the
the
underlying
between nickel
thenickel layer
substrate in
and the case
the case
actualof the TWAS
protective layer. sample,
underlying layer in the of the TWAS
between the substrate and the actual protective layer. pseudo‐alloy‐coated sample, which was
between the substrate and the actual protective layer.

Figure 8.
Figure 8. SEM/EDX
SEM/EDXimage
imageof
ofthe
theTWAS
TWAS pseudo‐alloy
pseudo-alloy coating
coating after
after 5000
5000 hh at
at 600
600 °C.
◦ C.
Figure 8. SEM/EDX image of the TWAS pseudo‐alloy coating after 5000 h at 600 °C.
Figure 8. SEM/EDX image of the TWAS pseudo‐alloy coating after 5000 h at 600 °C.

Figure 9. SEM/EDX image of the HVOF coating after 5000 h at 600 °C.
Figure 9.
Figure 9. SEM/EDX
SEM/EDXimage
imageof
ofthe
theHVOF
HVOFcoating
coatingafter
after5000
5000hhat
at600
600°C.
◦ C.
Figure 9. SEM/EDX image of the HVOF coating after 5000 h at 600 °C.

Figure 10. SEM/EDX image of the Plasma coating after 5000 h at 600 °C.
Coatings 2022, 12, x FOR PEER REVIEW
Figure 10. SEM/EDX image of the Plasma coating after 5000 h at 600 °C. 11 of 14
Figure 10.
Figure 10. SEM/EDX
SEM/EDX image
imageof
ofthe
thePlasma
Plasmacoating
coatingafter
after 5000
5000 hh at
at 600
600 °C.
◦ C.

Figure 11. SEM/EDX image of the TWAS—45CT coating after 5000 h at 600 °C.
Figure 11. SEM/EDX image of the TWAS—45CT coating after 5000 h at 600 ◦ C.
Coatings 2022, 12, 116 11 of 14

Figure
Figure 11.
11. SEM/EDX
SEM/EDX image
image of
ofthe
the TWAS—45CT
TWAS—45CT coating
coating after
after 5000
5000 hh at
at600
600°C.
°C.

(a)
(a) (b)
(b)
Figure
Figure 12. Chemical
12. Chemical analysis
Chemicalanalysis of
analysisof the
ofthe coatings
thecoatings
coatings performed
performed byby
performed EMPA
EMPA
by with
with
EMPA 20 20
with 20 μm
µm steps
steps
μm (each
(each
steps point
point
(each isis
is the
point
the average
average of of
10 10 separate
separate measurements).
measurements). (a) (a) TWAS—pseudo‐alloy;
TWAS—pseudo-alloy; (b) (b) HVOF.
HVOF.
the average of 10 separate measurements). (a) TWAS—pseudo‐alloy; (b) HVOF.

(a)
(a) (b)
(b)
Figure
Figure 13.13.
13. (a) Chemical
(a)Chemical analysis
Chemicalanalysis of
analysisof the
ofthe coatings
thecoatings performed
coatingsperformed
performedbyby EMPA
byEMPA
EMPA with
with 20 μm steps (each point
Figure (a) with 2020
µmμm steps
steps (each
(each point
point is
isis the
the average
average of
of 10
10 separate
separate measurements).
measurements). (a)
(a) Plasma;
Plasma; (b)
(b) TWAS—45CT4.
TWAS—45CT4.
the average of 10 separate measurements). (a) Plasma; (b) TWAS—45CT4.
4.
4. Discussion
4. Discussion
Discussion
In this work, various hot metal spraying techniques were tested in the laboratory in
an environment simulating biomass combustion containing hydrogen chloride. In total,
five different coatings produced by three different technologies—TWAS (twin wire arc
spray), HVOF, and water-stabilized plasma—were tested. The laboratory tests were carried
out at 500 and 600 ◦ C with an exposure time of 5000 h, after which the mass changes
were evaluated, and the samples were subjected to metallographic analysis. All the model
coatings were deposited on two different substrates, one of which was 16Mo3 steel (a
commonly used material for superheater tubes in power units within the Czech Republic)
and the other was austenitic refractory steel AISI 310, which is used for supercritical
parameters or for environments with high flue gas aggressiveness [8]. Coatings based on
NiCr, Inconel Alloy 625, CoCrAlY, and NiCrMo were also compared for their corrosion
behavior with the underlying base materials in order to verify whether it is possible to
use these protective systems to increase the durability and reliability of heat exchangers in
boilers that stopped burning lignite and switched to biomass combustion.
Coatings 2022, 12, 116 12 of 14

From the gravimetric results, it was clear that the tested coatings were quite resistant
in the specified environment, and their corrosion behavior was mainly influenced by the
surface condition and overall porosity in the hot spray. From this perspective, it is clear
that the best results were obtained for the specimens produced by HVOF technology, using
an alloy that is more likely to be used for aerospace applications and that would clearly be
an unnecessarily expensive option for the protection of heat exchangers in power boilers.
This was done as a test of the technology itself—the CoCrAlY-based coating produced by
HVOF technology showed in all cases better corrosion behavior during the tests than the
steels used as base material and tested separately to find a suitable alternative to austenitic
steels for superheater construction (for biomass boilers). This type of coating showed
almost no porosity and, after exposure for 500 h in an environment containing hydrogen
chloride, there was no noticeable corrosion/oxidation layer on the surface; the sample was
bluish due to the formation of a thin layer containing cobalt oxides. This type of coating
showed perfect cohesion with both austenitic and ferritic–perlite substrate materials, and
no delamination was observed during the tests. Due to the almost zero porosity and
relatively smooth surface of the HVOF-prepared coatings, the dependence of the mass
gains on time was almost linear but at the level of measurement error in absolute values.
The NiCr- and NiCrMo-based thermally sprayed coatings, which were fabricated
by TWAS technology, exhibited gravimetric gains virtually identical to those of the base
material AISI 310 after exposure in a biomass flue gas model environment. Overall, these
values were in the low or low tens of g/m2 and, especially at 600 ◦ C, the weight gains were
orders of magnitude lower than for 16Mo3 steel, which was subject to massive oxidation.
Since these coatings are layered, there is a certain number of pores or oxidic particles in the
microstructure, so that oxidation is more rapid at the beginning of the high-temperature
exposure but stops after a while, and the layer corrodes only very slowly; all these samples
showed a parabolic character of mass changes. It was observed that after the first 500 h of
testing, there was a massive slowing down of oxidation. The cohesiveness of these types of
coatings was excellent, and no delamination was observed on either the austenitic or the
ferritic–perlite substrate.
The coating prepared by water-stabilized plasma technology based on NiCrSiB showed
the highest mass gains during the first 500 h of exposure at both test temperatures. This
was probably due to the higher overall thickness of the coating and also to the fact that,
when using this technology, increased oxidation of the alloy particles already occurs during
the actual protective coating process. However, with longer exposure times, there was a
dramatic decrease in the corrosion/oxidation rate, and after an initial high increase in mass,
further increases stopped; this was the most significant corrosion-resistant sample of all the
tested samples.

5. Conclusions
After 5000 h of exposure at 500 and 600 ◦ C in a model atmosphere containing hydro-
gen chloride, all the tested thermally sprayed specimens were virtually free of signs of
corrosion—no significant oxide layers were observed on the outer surface of the specimens
or on the sections. Most of the coating types tested exhibited similar or better behavior than
the highly alloyed austenitic steel AISI 310, and all the samples tested were significantly
more corrosion-resistant than the ferritic–pearlitic steel 16Mo3 commonly used for the heat
transfer surfaces of coal-fired boilers. The objective of this work was to laboratory test
the protection capabilities of the superheater tubes of a particular power plant boiler that
was converted from coal to 100% biomass combustion. On the basis of the results and the
complexity of the different technologies, a TWAS (at this stage, the simplest in terms of
applicability to the superheater of a real boiler) NiCrMo-based pseudo-alloy coating was
selected, which was further coated with ceramic sealing and applied to the outlet super-
heater of a fluidized bed boiler burning wood chips (see Figure 14)—during laboratory
tests it was shown that there was some difference between the corrosion behavior of the
different coatings or of coatings prepared with different technologies, but it was also found
 atory test the protection capabilities of the superheater tubes of a particular power plant
boiler that was converted from coal to 100% biomass combustion. On the basis of the re‐
sults and the complexity of the different technologies, a TWAS (at this stage, the simplest
in terms of applicability to the superheater of a real boiler) NiCrMo‐based pseudo‐alloy
coating was selected, which was further coated with ceramic sealing and applied to the
Coatings 2022, 12, 116 13 of 14
outlet superheater of a fluidized bed boiler burning wood chips (see Figure 14)—during
laboratory tests it was shown that there was some difference between the corrosion be‐
havior of the different coatings or of coatings prepared with different technologies, but it
that
wasafter
also an initial
found phase
that afterof
anaccelerated oxidation,
initial phase most ofoxidation,
of accelerated the testedmost
materials
of theunderwent
tested ma‐
aterials
rapid underwent
slowdown of oxidation. The results and corrosion behavior of this coating
a rapid slowdown of oxidation. The results and corrosion behavior after real
of
exposure
this coating after real exposure will be evaluated in the future months/years andfurther
will be evaluated in the future months/years and will be the subject of will be
investigations and studies.
the subject of further investigations and studies.

Figure14.
Figure 14. TWAS
TWAScoating
coating(NiCrMo-based)
(NiCrMo‐based)on onaareal
realsuperheater
superheaterin
inaabiomass
biomassfluid
fluidboiler:
boiler:(a)
(a)before
before
installation, (b) after installation in a boiler.
installation, (b) after installation in a boiler.

Author Contributions: Methodology, J.C.; Project administration, J.H.; Supervision, J.C.; Valida‐
Author Contributions:
tion, J.M.; Methodology,
Writing—original J.C.;
draft, J.H. AllProject
authorsadministration,
have read andJ.H.; Supervision,
agreed J.C.; Validation,
to the published version
J.M.;
of theWriting—original
manuscript. draft, J.H. All authors have read and agreed to the published version of the
manuscript.
Funding: This work was performed as a part of the project TK01030089 “Resistance and degradation
Funding:
of alloys inThis
highwork was performed
temperature gaseousasmedium”co‐funded
a part of the project by
TK01030089 “Resistance
the Technological and degradation
Agency of the Czech
of alloys in high temperature gaseous medium”co-funded by the Technological Agency of the Czech
Republic.
Republic.
Institutional Review Board Statement: Not applicable.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data sharing is not applicable to this article.
Data Availability Statement: Data sharing is not applicable to this article.
Acknowledgments: The authors would like to thank David Braha (CASTOLIN EUTECTIC, Castolin
Acknowledgments: Thepreparation
s.r.o.) for his help with authors would like to thank
of samples. David Braha
The authors would (CASTOLIN
also like toEUTECTIC,
thank Adam Castolin
Poloch
s.r.o.) for his help with preparation of samples. The authors would also like to thank
for making the metallographically analysis and Jiri Kadlec for analyzing the samples using EMPA. Adam Poloch
for making the metallographically analysis and Jiri Kadlec for analyzing the samples using EMPA.
Conflicts of Interest: All authors declare no conflict of interest. The co‐founding agency (TACR)
Conflicts
had no roleof Interest: All authors
and/or influence declare
on the studynoand/or
conflict
onofthe
interest.
resultsThe co-founding
of this paper. agency (TACR) had
no role and/or influence on the study and/or on the results of this paper.

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