Sadiq Ameen Hakim

Republic of Iraq
Ministry of Higher Education and Scientific Research

Middle Technical University
Collage of Health and Medical Technology / Baghdad
Effect of Surface Treatment on Adhesion of CAD\CAM

Pekkton to Veneering Composite Resin
A THESIS SUBMITTED
TO THE COLLEGE COUNCIL OF HEALTH AND
MEDICAL TECHNOLOGY AS A PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF MASTER
OF TECHNOLOGY IN DENTAL PROSTHETIC
By
Sadiq Ameen Hakim
B.Sc. Dental Prosthetic Technology/2016
Supervised by
Amaal kadhim Mohammad
Assistant professor
2021 A.D 1443 A.H

‫صــدَق هللا ال َعظيـــم‬
‫َ‬
‫سورة التوبة ‪ -‬اآلية ‪105‬‬
Dedication
This thesis is wholeheartedly dedicated to:
My beloved wife “Ola”

Thanks for your endless support and encouragement and for always being
there for me when I needed you the most
My son “Jaffer”
Thank you for bringing happiness and joy into my life
Acknowledgments
First and foremost, I want to thank Allah for always being there for me and for
gracing my life with His blessings.
Second, I would like to thank my supervisor Assistant Professor Dr. Amaal Kadhim
Mohammed for her valuable suggestions, encouragement, assistance, and support
during the course of my Master postgraduate duration. The completion of this thesis
would not have been feasible without her instruction and patience.
I Would like to express my gratitude to my employer, College of
Dentistry/University of Kufa, for giving me the chance to complete my postgraduate
studies.
Furthermore, thanks go to Dr. Adam, Ms. Thamer blash and Ms. Ali Mohamed for
technical support and assistance in lab procedures.
I also appreciate the assistance of Mrs. Bushra Ali for her assistance to prepare
Piranha solution and her safety instruction .
Finally, I extend my sincere thanks to my family for their love and support
throughout my life. Thank you for giving me the strength to reach for the stars and
follow my goals. I could not have done this study without all of them.
I
Summary
Background: Polyetherketoneketone (PEKK) has been recently

introduced for dental uses and is recognized for superior mechanical and
physical characteristics, good wear resistance, good dimensional stability
at high temperature, and high biocompatibility. Due to the low
translucency and garish color of PEKK material, making veneering
material is essential to produce esthetic restoration, but it has low surface
energy and high resistance to surface modifications. As a result, various
surface modifications, such as acid etching and plasma, should be utilized
to achieve an acceptable bond with veneering material. So, the aim of this
study is to evaluate the effect of different surface treatments on the shear
bond strength between Pekkton® ivory with veneering composite resin.
Materials and methods: Thirty-five PEKK specimens were designed and

milled by CAD/CAM with a dimension of (7 x 7 x 2 mm). The samples
were placed in auto-polymerizing acrylic resin such that just one surface
measuring 7x7 mm was exposed. The samples were arranged randomly
into five groups (n = 7). The groups were (1) Control group (Sandblasting),
(2) Piranha acid etching group, (3) Sandblasting + Piranha acid etching
group (4) Air plasma treatment group and (5) Sandblasting + Air plasma
treatment group. After surface modification, surface topography was
evaluated with scanning electron microscopy. Veneering composite was
applied with the help of a bonding jig and light cured before being
submitted to shear bond strength (SBS) test. After the SBS test, fracture
patterns were categorized. Statistical analysis was performed with One-
way ANOVA followed by post-hoc LSD test.
Results: All groups showed SBS over 5 MPa, which means that they are
suitable for the clinical application, according to ISO 10477. Sandblasting
II
+ Piranha acid etching group showed the highest SBS among all groups (p
< 0.001), while the air plasma treatment group showed the lowest SBS
among all Groups.
Conclusions: To improve bonding with veneering composite resin, acid

treatment of the PEKK surface with piranha solution may be an excellent
alternative to sandblasting. While, air plasma surface treatment of PEKK
is not required.
III
List of contents
Page
Subject
No.
Acknowledgments I
Summery II
List of Contents IV
List of Tables VII
List of Figures VIII
List of Abbreviations X
Chapter One: Introduction
Introduction 1
Aim of the Study 3
Chapter two: Review of Literature
2.1 Polymers 4
2.2 High Performance Polymers (HPPs) 5
2.3 PAEKs polymers in dentistry 6
2.3.1 PEKK Polymer 8
2.3.1.1 Properties of PEKK 10
2.3.1.2 Processing Techniques of PEKK 13
2.3.1.3 Applications of PEKK 14
2.4 Polymer Surface Modifications in Prosthodontic 17
2.4.1 Mechanical Surface Treatment 18
2.4.2 Chemical Surface Treatment 18
2.4.3 Physical Surface Treatment 20
2.5 Scanning electron microscopy (SEM) 21
2.6 Resin-based Composites in Dentistry 21
2.6.1 Composite Resins for Veneering Substructures 22
2.7 Bond Strength 23
2.7.1 Shear Bond Strength 24
2.7.2 Bond Strength of PAEKs to Resin-based Materials after 25
Various Surface Treatments.
IV
Chapter Three: Materials and Methods
3.1 Materials and Equipments 29

3.1.1 Materials 29
3.1.2 Equipments and Machines 31
3.2 Methods 36
3.2.1 Pilot Study 36
3.2.2 Specimen Preparations 37
3.2.2.1 Specimen Design 37
3.2.2.2 Milling of the Specimens 37
3.2.3 Specimen Holder Fabrication 39
3.2.4 Specimens Polishing 41
3.2.5 Specimen Surface Cleaning 42
3.2.6 Surface Treatment 42
3.2.7 Scanning Electron Microscopy (SEM) 46
3.2.8 Bonding Procedure of Specimens with Veneering 47
Composites
3.2.8.1 Application of Adhesive Primer 48
3.2.8.2 Application of Composite Resin 49
3.2.9 Shear bond Strength Test 50
3.2.10 Analyses the Types of Failure 52
3.2.11 Statistical Analysis 53
Chapter Four: Results of the study
4.1 SEM Observations 54

4.1.1 Control Group 54
4.1.2 Piranha Etching Group 54
4.1.3 Sandblasting + Piranha Etching Group 55
4.1.4 Air plasma Group 56
4.1.5 Sandblasting + air plasma group 56
4.2 Results of Shear Bond Strength (SBS) Test 57
4.3 Fracture Mode Analysis 60
Chapter Five: Discussion, conclusions and recommendations
5.1 Discussion 62
V
5.1.1 Piranha Etching Groups 63
5.1.2 Air Plasma Treatment Groups 65
5.1.3 Comparison Between All Groups 66
5.2 Conclusions 68
5.3 Recommendations 69
70
References
VI
List of Tables
Table Page
Title
No. No.
(2.1) Elastic Modulus of Framework Materials and Natural 12
Bone Adapted from (Han et al., 2016)
)2.2( Mechanical properties of PEKK based restorative 13
material (Pekkton® ivory) from the company’s website
and other restorative materials adapted from (Alqurashi
et al., 2020).
)3.1( materials used in the Study and their Manufacturers. 29
)3.2( Equipments and Machines used in this Study and their 31
Manufacturers.
)3.3( Programs and Software used in this Study and their 32
Manufacturers.
(3.4) Mean Value of SBS Test of Pilot Study for Control, 36
Piranha and Air plasma Groups.
(4.1) Descriptive Statistics and ANOVA Test for Different 57
Surface Treatment Groups.
(4.2) Multiple Pairwise Comparisons using Post hoc (LSD) 59
Tests According to Surface Treatments of PEKK.
VII
List of Figures
Figure Page
Title
No. No.
(2.1) Schematic Structure of PEKK, and PEEK Polymers. 7
)2.2( Synthesis of PEKK. 9
Performance and Structure of PAEK (PEEK and 10
)2.3(
PEKK).
)2.4( Pressable Ingots of Pekkton®ivory. 14
)2.5( CAD/CAM Blank of Pekkton®ivory. 14
)3.1( Some of the materials Applied in this Study. 30
)3.2( Aluminum Oxide Particles (110μm) 30
)3.3( Some of the Equipments used in this Study. 33
)3.4( Roland Milling Machine. 33
)3.5( Sandblasting Machine. 34
)3.6( Ultrasonic Cleaner. 34
(3.7) Incubator. 34
)3.8( Light-curing Device. 35
(3.9) 3D Printer. 35
)3.10( Computer Controlled Electronic Universal Testing 35
Machine.
)3.11( Designing of PEKK Sample by ExoCAD. 37
(3.12) Nesting Procedure of the Specimens. 38
(3.13) Milling of Specimens. 38
(3.14) A. Pekkton®ivory Blank after Milling, B. Specimens 39
after Separation.
)3.15 A. Wax block ,B. Wax block Embedded into Silicon. 40
(3.16) A. Specimen in the Center of the Mold, B. Auto- 40
Polymerizing Acrylic Resin Pouring into the Mold, C.
Removal of the Holder with the Specimen, D. Thirty-
Five Pekkton Specimens with Holder.
(3.17) Different Grits of Abrasive Silicon Carbide Paper. 41
(3.18) Specimens into Ultrasonic Cleaner Device. 42
(3.19) Diagram Shows the Distribution of the Specimens. 43
(3.20) Sandblasting Procedure using Custom made Holder. 44
(3.21) Application of Piranha Etching Solution. 45
VIII
(3.22) RF.Magnetron Plasma Device. 45
(3.23) SEM Device. 46
(3.24) A. Bonding Jig (3d view), B. Designed Bonding Jig. 47
(3.25) Bonding Jig after 3D Printing. 48
(3.26) Application of Visio.link Primer. 49
(3.27) Light-curing of the Specimen after Visio.link Primer 49
Application.
(3.28) A. Positioning of Bonding Jig, B. Bonding Jig Filled 50
with Composite Resin.
(3.29) A. Removal of Bonding Jig, B. Light-curing of 50
Composite Resin
(3.30) Specimens Inside the Incubator 51
(3.31) Specimen During Shear Bond Strength Test 52
(3.32) Specimen under the Microscope 52
(4.1) SEM Image of the PEKK Surface after Sandblasting 54
(4.2) SEM Image of the PEKK Surface after Piranha etching 55
(4.3) SEM Image of the PEKK Surface after Sandblasting + 55
Piranha Etching
(4.4) SEM Image of the PEKK Surface after Air plasma 56
(4.5) SEM Image of the PEKK Surface after Sandblasting + 56
Air plasma
(4.6) Bar chart Represents the Mean Value of SBS of the 58
Studied Groups.
(4.7) Fracture Mode of Control Group, A. Adhesive, B. 60
Mixed
(4.8) Fracture Mode of Piranha Etching Group, A. Adhesive, 60
B. Mixed
(4.9) Fracture Mode of Sandblasting + Piranha Etching 61
Group, A. Adhesive, B. Mixed
(4.10) Adhesive Fracture Mode of Air plasma Group 61
(4.11) Fracture Mode of Sandblasting + Air Plasma Group, A. 61
Adhesive, B. Mixed
IX
List of Abbreviations
Abbreviation Description
AlCl3 Aluminum Trichloride
ANOVA Analysis of Variance
Bis-GMA Bisphenol A-glycidyl Dimethacrylate
C2H4O3S Vinylsulfonic Acids
CA Contact Angle
CAD/CAM Computer Aided Design/Computer Aided Manufacture
Co-Cr Cobalt-Chromium
DMA Dimethacrylate
FTIR Fourier Transform Infrared Spectroscopy
GPa Gigapascal
HPP High Performance Polymer
ISO International Organization for Standardization
LSD Least Significant Difference
MMA Methylmethacrylate
MPa Megapascal
Mbar Millibar
N Newton
Ni-Cr Nickel-Chromium
OPM Oxford Performance Materials
PA Polyamide
PAEK Polyaryletherketones
PAI Polyamideimide
PC Polycarbonates
PEEK Polyetheretherketone
PEI Polyethylenimine
PEK Polyetherketone
PEKEKK Polyetherketoneetherketoneketone
PEKK Polyetherketoneketone
PEMA Polyethylmethacrylate
PES Polyethersulfone
PMMA Polymethylmethacrylate
POM Polyoxymethylene
PPS Polyphenylene Sulfide
Ra Surface Roughness
RPD Removable Partial Denture
SBS Shear Bond Strength
X
SD Standard Deviation
SE Standard Error
SEM Scanning Electron Microscope
STL Stereolithography
SiC Silicon Carbide
TBS Tensile Bond Strength
TEGDMA Triethyleneglycol dimethacrylate
UDMA Urethane Dimethacrylate
VHN Vickers Hardness Number
eV Electron Volts
kHz Kilohertz
keV Kiloelectron Volts
Max. Maximum
Min. Minimum
rpm Revolution per Minute
μm Micrometer
XI
Chapter One Introduction & Aim of the Study
Introduction
Producing an optimal restorative material that will mimic the natural

tooth’s appearance, longevity, and durability is always the goal of dental
professionals (Alsadon, 2017). Studies currently concentrate on materials
with high esthetics, good biocompatibility, and good mechanical and
chemical properties (Stawarczyk et al., 2017, Hong et al., 2020). Polymer
is one of the most important materials in dentistry since it is used to
fabricate a variety of restorations, removable appliances, and denture base
materials . (Xu et al., 2017). Polyaryletherketones (PAEKs) are a family
of high-performance thermoplastic polymers that have been studied for
their superior chemical and mechanical characteristics also they have a
good resistance to abrasion when compared to Polymethylmethacrylate
(PMMA)(Hong et al., 2020). PAEKs have been used in medicine for many
years in spinal implants, femoral stems, and trauma implants. Due to their
reasonable fracture resistance, shock-absorbing abilities and superior stress
distribution, high-performance polymers are being considered as a
substitute dental material to glass ceramics and metals in dentistry (Lee et
al., 2017a, Prechtel et al., 2020). The most well-known members of the
PAEK family are poly etheretherketone (PEEK) and poly
etherketoneketone (PEKK) (Alqurashi et al., 2020). PEKK, which was
recently released to the market for dental applications, has 80% better
compressive strength and better long-term fatigue properties than the
PEEK (Dawson et al., 2018, Fokas et al., 2019). PEKK can be utilized in
the fabrication of crowns, fixed and removable dental prostheses (Choi et
al., 2017, Ozyilmaz et al., 2021). It is also useful in the fabrication of
implant frameworks because it is light in weight and compatible with
different veneering materials (Han et al., 2016). It is gaining popularity
because of its manufacturing versatility (Dawson et al., 2018). Although
-1-
PEKK has attractive mechanical properties and biocompatibility, the low

translucency and white/grayish color limit its use as a monolithic dental
restoration material (Lee et al., 2017a). Therefore, additional veneering
with an aesthetic material is required (Sakihara et al., 2019). appropriate
surface treatment can achieve high bond strengths between PEKK and
other dental materials. (Stawarczyk et al., 2017, Hong et al., 2020).
However, the interfacial bonding strength between PEKK and veneering
materials remains the main issue, and this is due to the low surface energy,
chemical inertness, and resistance to surface modification of PEKK
material that stood as an obstacle for establishing a durable and strong bond
with veneering composite materials, which influences the success rates and
long-term survival of dental treatment (Fokas et al., 2019, Jun et al., 2020,
Gama et al., 2020). Therefore, a variety of surface treatments have been
suggested to overcome the mentioned limitations such as mechanical
modification (sandblasting and paper abrasion), chemical modification
including (chemical etching and decreasing solvent) and physical
modification like (plasma and laser treatments) (Jun et al., 2020). Only a
few studies have investigated the effect of surface treatment on the PEKK
surface, and the majority of previous in vitro studies for bonding composite
resin to high-performance polymers have focused on PEEK materials.
Thus, this study will focus on bond strength between veneering composite
and PEKK material.
-2-
Aim of the Study

This study aimed to:
1. Evaluate the effect of different surface treatments such as

(Sandblasting, Piranha etching solution, Sandblasting with Piranha
etching solution, Air plasma, and Sandblasting with Air plasma) on the
shear bond strength between Pekkton® ivory (PEKK-based high
performance polymer) with veneering composite resin.
2. Compare of SBS among studied groups and identify the optimum
surface treatment method for treating PEKK surface.
-3-
Chapter Two Literature Review
Literature Review
2.1 Polymers
A polymer is a long-chain macromolecule composed of “monomers,”
which are repeating subunits. In polymers, covalent bonds link the
monomers together. The name "polymer" comes from the Greek terms poly
and meres, meaning respectively "many" and "part" (Narayan, 2018).
Polymers are utilized widely in the dental field for various applications,
from impression materials to base materials for dentures and direct
composite restorative materials. Plastic materials have been used to replace
teeth for many years, but they have rarely fulfilled the optimum properties
for fixed prostheses, particularly in terms of rigidity and color instability.
Vulcanized rubber was the primary polymer used in dentistry before the
introduction of acrylic polymers in the mid-1930s. The first acrylic
polymer form was available under the name vernonite, also known as
polymethyl methacrylate (PMMA) (Alsadon, 2017, Samantaray et al.,
2020, Ali et al., 2020).
PMMA and its copolymers remain the most common nonmetallic

materials. Its benefits were low cost, simple processing, consistent colours,
optical characteristics, appropriate strength, and other physical features
that made them excellent materials for use, free of toxicity, and easily
coloured. The application of acrylic resin has improved significantly such
that by 1940, PMMA was used to make fixed dental prostheses and inlays
in 1946, PMMA was the predominant material for denture fabrication
(Khindria et al., 2009, Zafar, 2020, Shen et al., 2021). Typically, the
polymers are supplied as a powder and a liquid. The powder's main
component is PMMA beads, which may be mixed with the liquid (mostly
methylmethacrylate monomer) (Narayan, 2018). The heat was used to
-4-
polymerize acrylic resins at first. However, in 1947, chemical accelerators

were utilized in acrylic resin for polymerization (self-cure or auto
polymerization resins) (Khindria et al., 2009).
Based on thermal behaviour, polymers can be classified into

thermosetting and thermoplastic. When thermosetting polymers are heated
in the manufacturing process, chemical changes occur, converting them to
an infusible mass. The curing or setting process causes chain molecules to
increase and cross-link, resulting in gigantic molecules. Thermosetting
polymers cannot be remelted after they have been manufactured.
Thermoplastics are resins that can be softened and shaped repeatedly under
pressure and heat without undergoing any chemical changes (Manappallil,
2015, Narayan, 2018).
2.2 High Performance Polymers (HPPs)

Polyaryletherketones (PAEKs) are a family of high-performance
thermoplastic polymers and have been studied due to their excellent
chemical and mechanical properties, resistance to abrasion, and
biocompatibility compared to PMMA (Hong et al., 2020). Since the 1980s,
PAEK polymers have been utilized in the industrial applications, such as
automobile and aircraft industry, as well as medical products (Fuhrmann
et al., 2014, Kurtz, 2019). Due to their characteristics, PAEK has
gradually become the top polymer material used in the medical field for
orthopedic applications and trauma (Ates et al., 2018, Hu et al., 2021).
PAEKs are processed in two main synthetic routes: nucleophilic and

electrophilic routes. The chemical structure of PAEKs consists of a chain
of aromatic backbones linked with functional ketone and ether groups.
According to the proportion of keto and ether groups, different PAEK
polymers can be formed such as PEK (polyetherketone), PEEK
-5-
(Polyetheretherketone), PEKK (Polyetherketoneketone) and PEKEKK

(Polyetherketoneetherketoneketone). The higher the ratio of ketone groups
in comparison to ether groups, the higher the strength of PAEK material as
well as the glass transition and melting temperatures are increasing
(Fuhrmann et al., 2014, Kewekordes et al., 2018, Kurtz, 2019, Gama et
al., 2020).
The performance of such polymers is influenced by a few key aspects

(Alsadon, 2017, Kurtz, 2019):
I. Crystallinity, in which more crystalline content led to higher density,

elastic modulus, and dimensional stability but reducing thermal expansion,
impact strength, and creep propensity.
II. Ketone percentage, the greater ketone concentration enhances the

stiffness of the polymer chain, e.g. the ketone percentage in the
ketone/ether linkage ratio in PEEK is 33% and 67% in PEKK, therefore
corresponds to the thermal and mechanical difference between PEEK and
PEKK.
III. The strength, quantity, shape, and adherence of the filler to the polymer
matrix all have a part in defining the mechanical characteristics of the final
product.
2.3 PAEKs Polymers
In dentistry, PAEK became promising dental material to replace metal

and glass ceramics due to its ability of shock-absorbing, superior stress
distribution, good fracture resistance and radiolucency (Choi et al., 2017;
Yuan et al., 2018).
-6-
PEKK and PEEK are the dominant members used in the dental field
and both materials exhibit great strength above the minimum strength
criteria for dental plastic restorative material of 65 MPa, with PEEK
exhibiting flexural strength of 165 MPa and PEKK of 200 MPa. PEKK is
the oldest PAEK member, which was introduced by Bonner in 1962 which
differs from PEEK that was first prepared by Rose and Staniland in 1982
by the slightly different chemical structure of two ketone functional groups
between chains as in figure (2.1) ( Alsadon, 2017, Sakihara et al., 2019,
Younis, 2019).
PEKK
PEEK
Fig. (2.1): Schematic structure of PEKK, and PEEK polymers (Younis,

2019).
PEEK has good biocompatibility with excellent mechanical, physical

and aesthetic properties ,that can be used in a various of orthopedic and
dental applications (Benakatti et al., 2019, Amornvit et al., 2019).
PEEK can be used for dental implants fabrication (Najeeb et al., 2016),
removable dental prosthesis (Tannous et al., 2012), fixed prosthesis
(Stawarczyk et al., 2015a), and finger prosthesis (Amornvit et al., 2019).
-7-
PEEK has recently become the material of choice when it comes to

high-performance polymers. Nevertheless, PEEK might not be the ideal
option for dental applications in which esthetic and long-term structural
properties are of prime concern. PEEK's performance is limited due to its
crystalline form, and the complexity of its manufacturing process requires
high accuracy. Unlike PEEK, PEKK polymer offers a significant
advantage in long-term dental applications when polyaryl matrices are
exposed to a wet environment and repeated stress. Also, PEKK can be
customized to meet the various structural and processing needs (Shetty,
2018, Salah, 2019).
2.3.1 PEKK Polymer
PEKK overtop all the other PAEK materials due to its superior
properties. Because of the two ketone functional groups between aryl ring,
PEKK has an up to 80% higher compressive strength and broader
processing methods than PEEK (Shetty, 2018, Dawson et al., 2018,
Roland et al., 2021).
PEKK can be synthesized by condensing diphenyl ether with iso- and

terephthaloyl chlorides in nitrobenzene solvent using an aluminum
trichloride catalyst (AlCl3) by an electrophilic substitution as in figure (2.2)
( Díez-Pascual et al., 2012, Alqurashi et al., 2020).
-8-
Fig. (2.2): Synthesis of PEKK (Silla, 2018).
Physical properties of PEKK are comparable in certain respects to the

dentin and bone, while mechanical properties such as wear-resistance and
hardness as well as the color of PEKK polymer can be improved by the
addition of Titanium dioxide (TiO2) ( Alsadon, 2017, Shetty, 2018,
Kewekordes et al., 2018).
PEKK polymer made by Oxford Performance Materials (OPM), both

industrial and medical grades trade under OXPEKK. In 2000, PEKK was
used in the implant market for the first time. In 2011, the company
Cendres+Métaux produced Pekkton®ivory as a definitive dental prosthesis
in which the mechanical properties are optimized by the addition of TiO 2
filler particles ( Silla et al., 2016, Kurtz, 2019).
PEKK is at the top of the thermoplastics quality pyramid and displays

crystalline and amorphous material properties, allowing for a wider range
of products to be offered (figure 2.3). PEKK, which is based on a
crystalline structure, is characterized by high stiffness and strength values.
-9-
Whereas PEKK, which is based on an amorphous structure, has increased

flexibility (Shetty, 2018). According to the manufacturer's information
(Cendres+Métaux), Pekkton® ivory has a semicrystalline structure which
gives it excellent mechanical properties with high flexibility.
Fig. (2.3): Performance and structure of PAEK (PEEK and PEKK).

Nomenclature: PAEK: Polyaryletherketone, PEEK: Polyetheretherketone, PEKK:
Polyetherketoneketone, PPS: Polyphenylene sulfide, PAI: Polyamideimide, PES:
Polyethersulfone, PEI: Polyethylenimine, POM: Polyoxymethylene, PC:
Polycarbonates, PA: polyamide, PMMA: Polymethyl methacrylate.
2.3.1.1 Properties of PEKK
PEKK has superior mechanical and physical properties, such as

melting temperature and strength, compared to other dental materials
(Alqurashi et al., 2020).
- 10 -
a. Biological Properties
PEKK is an inert material and presents high biocompatibility. It

doesn't produce any side effect to the living tissues such as mutagenic or
cytotoxic activities and also doesn’t degrade within human tissue (Younis,
2019).
Regarding antibacterial properties, Wang et al. (2017) claimed that
PEKK polymer showed less bacteria growth and adhesion of on its surface
than PEEK (Wang et al., 2017).
b. Physical Properties
PEKK has an opaque white\grayish color. The radiolucency of PEKK

makes restoration complications easily detected during diagnostic imaging
like X-ray and magnetic resonance imaging. Due to these properties,
PEKK is considered a substitute material for metal and ceramic
restorations (Han et al., 2016, Fokas et al., 2019, Gama et al., 2020).
According to the manufacturer company (Cendres+Métaux),

Pekkton®ivory has a high glass transition temperature (157°C) and
melting temperature (363°C), and due to its good resistance to hydrolysis,
it is compatible with all current sterilization methods, including gamma
and steam-sterilization without any visible changes in physical or
mechanical properties ( Fuhrmann et al., 2014, Shetty, 2018).
c. Mechanical Properties
According to a study done by PEKK manufacturing company, they

claimed that Pekkton®ivory material transfers 3x less force to bone tissue
compared to zirconium dioxide and due to the shock-absorbing property,
acceptable fracture resistance and dispersion of stress of PEKK polymer,
it is possible to substitute metals and ceramics (Song et al., 2018).
- 11 -
PEKK also has low elasticity modulus which is comparable to the

elasticity modulus of bone and tooth that can easily create a passive fit with
a wide framework providing the benefits of distribution of stress and shock
absorption. It is also lighter in weight in comparison to other dental
material, this lead to use it in bone resorption and overload cases (Han et
al., 2016).
Table (2.1): Elastic Modulus of Framework Materials and Natural Bone

Adapted from (Han et al., 2016)
Cancellous PEKK Cortical

Material Titanium Zirconia
bone (Pekkton) bone
Elastic modulus
1.37 5.1 13.7 110 269
in GPa
Alsadon et al. (2020) assessed the fatigue behaviour of PEKK, zirconia

and nickel-chromium (Ni-Cr) crowns veneered with resin-based
composite. The fatigue limit value was 790.4 ± 29.2 N for PEKK bilayered
crown, which is the highest compared to zirconia (442.8 ± 42.1 N) and Ni-
Cr ( 608.7 ± 7.6 N) (Alsadon et al., 2020).
Also, Katzenbach et al. (2021) analyzed the fatigue behaviour of PEKK
made crowns on three different artificial prepared teeth: PMMA artificial
teeth, cobalt-chromium (Co-Cr) artificial teeth and human extracted teeth.
They concluded that PEKK crowns had a high fatigue limit of 720 N,
indicating that PEKK crown might give a good, anticipated performance
in clinical applications (Katzenbach et al., 2021).
Mechanical properties of Pekkton®ivory restorative material and other
restorative materials can be seen summarized in Table (2.2).
- 12 -
Table (2.2): Mechanical properties of Pekkton® ivory (PEKK based

restorative material) from the website of the manufacturer and other
restorative materials adapted from (Alqurashi et al., 2020).
Properties PEEK Pekkton Titanium PMMA
Tensile strength (MPa) 100.69 115 240 - 890 48 - 62
Elastic modulus (GPa) 3.5 5.1 103 - 114 3.8 x 103
Flexural strength (MPa) 163.88 200 65 107 - 117
Compressive strength (MPa) 118 - 169 246 130 - 170 76
Melting temperature (°C) 334 - 350 363 - 386 1650 - 1670 160
Hardness 26 - 29 VHN 252 MPa 90 VHN 89 - 95 MPa
Water absorption (mg/mm3) 0.1 - 0.5 8.7 0.04 0.1 - 0.3
Density (g/cm3) 1.3 FEFF1.3 4.4 - 4.5 1.16 - 1.18
2.3.1.2 Processing Techniques of PEKK

Pekkton®ivory can be constructed in two methods, providing
versatility in the fabrication of various prosthetic substructures. The first
method is injection molding, which uses a vacuum pressing machine with
a preheated muffle and a pressing plunger and PEKK delivered as a
pressable ingot (figure 2.4). The second method involves utilizing
computer-aided design and manufacturing technologies (CAD/CAM) to
mill pre-pressed blanks (figure 2.5) (Younis, 2019).
- 13 -
Fig. (2.4): Pressable Ingots of Pekkton®ivory (Pekkton®ivory

company)
Fig. (2.5): CAD/CAM Blank of Pekkton®ivory (Pekkton®ivory

company)
2.3.1.3 Applications of PEKK

I. Medical Applications
Due to superior mechanical properties, antibacterial properties,
biocompatibility and compatibility with imaging techniques, PEKK has
been used as an alternative to titanium in medical field for orthopedic
implant applications such as trauma and spinal implant. Moreover, PEKK
implant can be easily modified during surgery to fit patient bone structure
(Kemmish, 2010, Tannous et al., 2012, Yuan et al., 2020, Prechtel et
al., 2020).
- 14 -
The most common uses of PEKK in medicine are bone pins, bone
screws, bone plates, and in replacement of joints. In craniofacial fields,
PEKK implants can be easily designed by CAD/CAM technology
according to structural information from the patient to completely fit the
defect area (Kemmish, 2010, Younis, 2019, Cheng et al., 2020).
II. Dental Applications
due to the excellent properties of PEKK such as shock-absorbing,

fracture resistance, stress distribution, lightweight, biocompatibility, and
radiolucency, it can be used in widely in dental applications as prosthetic
and biomaterial implant and considered successful substitutional to
ceramic and metal (Alqurashi et al., 2020).
1. Dental Implant
PEKK processability, adjustable stiffness, thermal conductivity and the
ability of it to be sculptured by the dentist to fit the patient makes PEKK
an interesting material to be used in dental applications, also allergic
reactions caused to the tissues by metal ions make PEKK a substitute
material for titanium (Kemmish, 2010). It can be used as a dental implant,
transitional abutment, healing abutment, healing caps and as a framework
or crown material over the implant ( Shetty, 2018, Gama et al., 2020,
Alqurashi et al., 2020).
A case studied by Jun et al. (2020) described the treatment of

edentulous maxilla with an implant-supported prosthesis using PEKK
framework material. The authors suggest that PEKK is a promising
alternative that can replace traditional prosthetic framework materials due
to its various advantages (Jun et al., 2020).
Another study by Han et al. (2016) showed that reasonable functional

and esthetic outcomes could be achieved when using pekkton as a
- 15 -
framework in implant and tooth support fixed restoration for completely

edentulous maxilla and partly edentulous mandible (Han et al., 2016).
2. Fixed Prosthesis
Due to the wide processing parameters of PEKK, it can be used as a
restorative material for fixed dental prostheses such as a single crown or
framework. However, the whitish or grayish color and the opacity of
PEKK limit its usage as a monolithic restoration. Thus, additional
veneering with an aesthetic material is needed to achieve adequate
aesthetic results (Alsadon, 2017, Labriaga et al., 2018).
The long-term success of the prosthesis depends mainly on the fitness
of the restoration. When the internal and marginal fit is poor, recurrent
caries, plaque deposition and restoration failure can ensue (Bae et al.,
2017, Alqurashi et al., 2020).
Bae et al. (2017) analyzed and compared the internal and marginal fit of
PEKK and zirconia copings by the three-dimensional analysis. They found
that PEKK copings demonstrated better fitness than the zirconia copings
(Bae et al., 2017).
3. Removable Prosthesis
In removable partial dental restoration (RPD), PEKK can be used as a
frameworks and clasps to overcome the problems associated with metal
clasps that can cause allergic reactions in addition to the non-esthetic
appearance of metals in the patient's mouth (Fokas et al., 2019, Alqurashi
et al., 2020).
Tannous et al. (2012) evaluated the clasps retentive force made from
Co-Cr and three thermoplastic polymers (PEKK, PEEK, and
polyoxymethylene (POM). They found that the resin clasp provides a
longer duration of retention than the Co-Cr clasp with less retention and
adequately crafted resin clasps have retentive force that could give
- 16 -
acceptable clinical outcomes. However, PEKK clasp can give longer

duration retention (Tannous et al., 2012).
Choi et al. (2018) compared the retention of two attachments (nylon
insert and PEKK insert) on implant overdenture. The attachment system
with PEKK insert displayed less damage and fewer changes in retention
compared to the attachment with nylon insert. Thus PEKK insert is
considered as an alternative to nylon insert (Choi et al., 2018).
4. Maxillofacial Prosthesis
Custom-made PEKK implants can be milled by CAD/CAM or 3D
printed and modified during surgery to suit various maxillofacial defects,
particularly large and complicated one (Younis, 2019).
For the rehabilitation of intraorally defects, a case report by Oh et al.
(2018) showed that the treatment of mandibulectomy patient with implant-
supported fixed prosthesis using a framework made with PEKK polymer
produced functional and esthetic improvements (Oh et al., 2018).
Another study by Sun et al. (2020) described the rehabilitation of a
patient with squamous cell carcinoma in the soft palate and undergone
surgery by removable speech bulb prosthesis made with PEKK framework.
The study showed adequate performance clinically with good stability and
retention of the prosthesis (Sun et al., 2020).
2.4 Polymer Surface Modifications in Prosthodontics

Surface modification or treatment for adhesion is a method used to
modify a material's surface to obtain the desired properties, such as
enhanced wettability and increased surface energy to which adhesive
material is applied for bonding purposes. Various surface treatments have
- 17 -
been proposed to the enhance PEKK surface, making it more suitable for
prosthodontic uses ( Ebnesajjad and Ebnesajjad, 2013, Younis, 2019).
Methods surface modification can be categorized into three mean
groups. Mechanical such as (sandblasting and paper abrasion), chemical
including (chemical etching and decreasing solvent) and physical like
(plasma and laser treatments) (Ourahmoune et al., 2011).
2.4.1 Mechanical Surface Treatment

Sandblasting or air abrasion is the most common process for preparing
metal, ceramic, and polymer surfaces before applying adhesives. It is the
process of directing a stream of abrasive particles against a surface at high
velocity in order to remove contaminants on the surface and roughen a
smooth surface ( Ourahmoune et al., 2011, Younis, 2019). Peaks and
valleys created on the abraded surface provide micromechanical
interlocking between the adhesive and the substrate (Ourahmoune et al.,
2011, Lümkemann et al., 2018).
Sandblasting is a commonly used technique for surface treatment
because it is simple, rapid, and inexpensive (Kurtz, 2019). In dentistry, the
most common used abrasive particles is aluminum oxide (Al2O3) which is
supplied in three particle sizes 50 μm, 110 μm, and 250 μm (Younis,
2019).
2.4.2 Chemical Surface Treatment
Chemical treatments, also known as wet treatments, modify the

chemical structure of surfaces by causing a direct chemical reaction in the
presence of a solution which is either strong acids or alkalis. Therefore, it
can be then classified according to the solvent used as oxidizing and
reducing treatments (Kurtz, 2019). Most types of chemical surface
- 18 -
treatment include wet treatments under which the polymer is

sprayed/coated or dipped with a chemical in order to improve surface
properties and eliminate debris from the surface (Nemani et al., 2018).
The etching effect of these treatments influences the chemical
characteristics of the surface of polymers and physical changes to the
surface structure take place such as surface roughness (Kurtz, 2019).
Chemical etching aids in increasing surface energy by providing
oxidized functional groups on polymer surface to which adhesive
components can bond. The deep penetration of the acidic solution into the
pores of the polymer matrix allows for large-scale polymer treatment at a
considerably low cost (Nemani et al., 2018, Fokas et al., 2019). The
etching results depend largely on the type of acid, acid’s concentration, and
etching duration (Younis, 2019). Due to PAEK’s surface chemistry which
is highly resistant to etching, strong acids are required for successful
etching. The most widely used acids for etching PAEK’s are Sulfuric acid
and piranha solution (Younis et al., 2020).
Piranha solution, which is also known as piranha etch, is a combination
of highly concentrated sulfuric acid (H2SO4) and hydrogen peroxide
(H2O2). In light of its strong oxidizing ability, it is used to remove organic
residues from the substrate surface ( Hallmann et al., 2012, Silthampitag
et al., 2016). The chemical reaction of concentrated sulfuric acid and
hydrogen peroxide produces highly reactive atomic oxygen species (Pan
and Yapici, 2016), as shown in the equation below:
H2SO4 + H2O2 H3O+ + HSO4- + O
This highly reactive oxygen species allows piranha solution to dissolve

elemental carbon. Carbon allotropes normally resist the attack due to the
- 19 -
strong hybridized bonds but piranha solution for surface treatment can
disturb the stable carbon–carbon bonds (Pan and Yapici, 2016).
2.4.3 Physical Surface Treatment

Plasma surface treatment is environmentally friendly, relatively safe
and can treat complex-shaped surface structures without changing the bulk
properties of the material being treated (Wang et al., 2020, Fu et al.,
2021). Plasma is a partially ionized gas and is considered “the fourth state”
of matter. It consists of ions, electrons and neutral particles like Atoms,
molecules and radicals ( Chen et al., 2013, Li et al., 2020).
Plasmas are often classified into two types: thermal (hot) plasma with
temperatures ranging from 100 electron volts (eV) to 30 kilo electron volts
(keV) and non-thermal (cold) plasma with temperatures less than 100 eV.
( Younis, 2019, Pinson and Thiry, 2020). Hot plasma is characterized by
a thermal equilibrium condition between electrons, ions, and neutrals
inside the plasma. It cannot be used to process polymers due to the high
plasma temperatures which lead to polymer melting (Younis, 2019,
Pinson and Thiry, 2020, Borges et al., 2021).
Unlike heat plasmas, cold plasma discharges have no absolute
equilibrium state. Because it requires minimal equipment and the reaction
temperature is near to room temperature, cold plasma is easily created and
commonly utilized in the field of material modifications. Also, due to the
low energy of cold plasma, the change will happen only on the sample
surface, with no change in the material's inherent properties or structure.
The chemical functionalities introduced by plasma discharge are strongly
dependent on the chemical composition of the biocompatible material and
the processing gas ( Slepička et al., 2013, Liu et al., 2021).
- 20 -
2.5 Scanning electron microscopy (SEM)

In general, two types of microscopy are available: optical microscopy
(OM) and scanning electron microscopy (SEM). The former is the oldest
one, which has been used since the last two centuries in the form of simple
device with limited capabilities. It is also called light microscopy. the main
principle of work in OM is the light unlike SEM, which depend upon
electron emission (Mohammed and Abdullah, 2018). The main
advantage of electron microscopy is the high image resolution compared
to light microscopy. Also, electron microscopes offer a very high
magnification range, typically in the range 10 - 500,000 times. This enables
characterization of microstructures at many different length scales, from
micro- to nanoscale, within an imaging session (Inkson, 2016).
2.6 Resin-based Composites in Dentistry

Resin-based composites for dental restorations have been developed in
dentistry due to the increasing demand for tooth-colored, aesthetic
restorations. It can be used as a direct restorative material that can be
employed by the dentist for fillings and as indirect restoration produced in
the laboratory for making extraoral restorations (inlays and onlays) as well
as a veneering material for substructures (Alsadon, 2017, Khalesi et al.,
2020, Stawarczyk et al., 2021).
The mechanical and physical properties of resin composites depend on
their chemical composition. They consist of an organic resin matrix,
inorganic fillers, coupling agent and an initiator/accelerator system
(Sakaguchi et al., 2019). The organic matrix is a cross-linked matrix
represented by dimethacrylate monomers, mostly bisphenol A-glycidyl
dimethacrylate (Bis-GMA), urethane dimethacrylate (UDMA) and
triethyleneglycol dimethacrylate (TEGDMA). Various filler particles (e.g.
- 21 -
silica) are coated with a coupling agent to create the bond between the
inorganic filler particles and the organic matrix. The initiator/accelerator
system's aim is to harden the system by polymerizing and cross-linking it
either by light activation, chemical activation (self-curing), or dual curing
(light and chemical curing) (Antoniac, 2016, Mayinger et al., 2021).
The dental veneering material includes porcelain, composite resin and
PMMA. Resin-based composites have a high mechanical properties, low
thermal coefficient of expansion, low dimensional changes on the setting,
and high wear resistance, which improve clinical performance. Therefore,
the composite resin veneering material was used as an acceptable
alternative to PMMA veneer to overcome the drawbacks such as shrinkage
after curing and limited wear resistance. It is also become a suitable
substitutional to porcelain veneer to aid in the dissipation of impact forces,
reduction of restoration weight, and reduction treatment costs (Alsadon,
2017, Sakaguchi et al., 2019, Zeighami et al., 2020).
2.6.1 Composite Resins for Veneering Substructures

To be able to guarantee the success of restoration, there should be a
stable and durable bond between the framework and veneering material
(Stawarczyk et al., 2017). Without using an adhesive system, minimal
bond strength can be achieved between the polymers. Therefore, the use of
adhesives was found to be adequate following surface pre-treatment
(Gama et al., 2020, Çulhaoğlu et al., 2020).
Regardless of the surface treatment used to achieve the necessary
micromechanical roughness and improve surface wettability, the adhesives
chemical composition plays a key role in the formation of a strong bond
between PEKK and veneering composite ( Stawarczyk et al., 2014,
Younis et al., 2020). Methylmethacrylate (MMA)-containing adhesives in
- 22 -
conjunction with additional dimethacrylate (DMA) allow adequate

bonding to resin composites (Uhrenbacher et al., 2014, Stawarczyk et
al., 2017). Different adhesive systems were evaluated and Visio.link
proved to be the most suitable adhesive system used for bonding PAEK
materials and veneering composites under various testing conditions
(Younis et al., 2020).
2.7 Bond Strength

The longevity of the restoration is estimated to some degree by its
adhesive ability, which can be assessed by bond strength tests. An ideal
bond-strength test should be fast, accurate and simple (low technique-
sensitive). Bond strength test can be evaluated by laboratory tests and
clinical trials. Due to the effect of many pressures on the restorations inside
the oral cavity, Clinical trials are unable to identify the exact cause of
failure. Laboratory tests collect data on a certain parameter or property
instantly and easily. One parameter can be measured when all other
variables remain constant. In one study, different experimental groups can
be examined simultaneously. Clinicians and dental technologists have
focused on laboratory tests to select the adhesion technique in their daily
clinical practice for many years. Therefore, the main goal of a laboratory
test should be to collect data in order to predict the eventual clinical result
(Van Meerbeek et al., 2010, Sirisha et al., 2014b, Jin et al., 2016).
Laboratory bond strength tests can be categorized into static or
dynamic tests. In dynamic tests, samples are actively moving while being
tested, whereas, in static tests, the samples remain stationary during load
application (Younis, 2019).
Various methodologies are available today that can be utilized for
measuring interfacial bond strength. Depending on the bonding size, static
- 23 -
tests are categorized into micro tests (when the bonding area is 3 mm 2 or
less) and macro tests (when the bonding area is more than 3 mm 2). Static
tests are categorized as shear, tensile and out-push tests according to the
loading technique at the bonding region interface. (Sakaguchi et al., 2019,
Younis, 2019).
2.7.1 Shear Bond Strength

The shear strength is the highest stress a material can withstand in a
shear mode prior to failure. It is especially important for studying two-
material interfaces (Sakaguchi et al., 2019). Unlike the tensile bond
strength test, the shear bond strength test does not require additional sample
preparation after the bonding procedure. Therefore, it is widely used in
laboratory tests (Sirisha et al., 2014b, Jin et al., 2016).
In the shear bond strength test, usually a composite cylinder is
connected to a substrate by using adhesives. After a specified storage time,
the sample is placed in the universal testing machine and force application
can be made with a variety of tools (e.g., knife-edge chisel, a flat-end rod,
metal tape or wire loop) ( Van Meerbeek et al., 2010, Sakaguchi et al.,
2019). Crosshead speeds ranging from 0.5 mm/min to 5.0 mm/min can be
utilized; however, in many circumstances, the most frequently employed
speed is 1.0 mm/min. A load transducer mounted to the crosshead will
measure the force. The counterforce of the crosshead would increase
steadily while in contact with the sample, starting at 0 N and increasing to
a nominal value until the fracture of the sample occurs (Jin et al., 2016,
Younis, 2019).
Owing to the low risk of critical size errors, small test specimens are
stronger than large ones. in contrast to micro-bond strength tests, the
macro-bond strength tests failures are cohesive rather than adhesive and
- 24 -
the bond strengths are overestimated. As a result, micro tests were

developed to minimize the flaws, allowing for higher visible "strength" to
be tested with more interface failures (Sirisha et al., 2014a).
2.7.2 Bond Strength of PAEKs to Resin-based Materials after

Various Surface Treatments.
Patcharawan et al. (2016) investigated the impact of surface pre-
treatment on the bonding of veneering resin to polyetheretherketone
(PEEK). PEEK was subjected to 4 different types of surface conditions: no
modification, etched with 98 % H2SO4, etched with piranha solution, and
air abrasion with 50 um Al2O3 particles. Twenty pretreated samples of each
group were divided into two groups with and without adhesive. After each
modification, surface roughness (Ra) was examined as well as scanning of
the surface by scanning electron microscopy (SEM) and Fourier Transform
Infrared Spectroscopy (FTIR). The findings confirmed that the 98% H2SO4
pretreatment with adhesive group had the greatest bonding strength
measures when compared to the other studied groups.
Lee et al. (2017) tested the bonding strength of composites to PEKK using
various of surface modification techniques and adhesive materials. Three
surface modifications were designed 95 % sulfuric acid, 50 μm Al2O3, and
110 m silica-coating alumina airborne abrasion. Each group subdivision
into five groups according to adhesive material that used (Luxatemp Glaze
and Bond, Single-Bond Universal, Visio-link, Monabond Plus with
Heliabond, and All-Bond Universal). Surface topography was examined
using SEM after surface modification, and Ra and Contact Angle (CA)
were analyzed. According to the results, mechanical surface modification
groups had significantly higher shear bonding strength than chemical
surface modification groups. However, regardless of surface modification
- 25 -
technique, Single-Bond Universal can be an effective adhesive material to

Pekkton®ivory.
Schwitalla et al. (2017) probed the impact of cold argon/oxygen plasma

on the adhesive strength of PEEK to composite resin. 3 types of PEEK
materials were used (unfilled, ceramic filled and pigment powder filled).
Forty rectangular samples for each type of PEEK material were divided
into four groups (no treatment, Plasma treatment, Sandblasting with 110um
Al2O3 particles, and Sandblasting + plasma treatment). After each
modification, Ra and CA were recorded. Then the samples were placed in
deionized water for 1 day before being tested. The results showed that the
CA was significantly reduced after plasma modification, while
sandblasting modification caused significantly high CA measurements. In
comparison to the control group, plasma decreased Ra while sandblasting
increased it. The highest SBS was achieved in the group of combination
pretreatments (sandblasting + plasma).
Stawarczyk et al. (2017) assessed the effectiveness of several surface

conditions and adhesive products on the TBS of Pekkton®ivory to resin-
based materials. All 1200 samples of PEKK were sandblasted with Al 3O2
and then subdivided into 8 groups: 1-Visio.Link, 2-Visio.Link + opaquer,
3-Pekkbond, 4-Pekkbond + opaquer, 5-plasma, 6-plasma + opaquer, 7-
plasma followed by Visio.Link then opaquer, and 8-plasma followed by
Pekkbond and opaquer. Following pretreatment, the samples were bonded
to 3 various types of resins: 1-PMMA, 2-packable composite, and 3-
flowable composite. Besides, 20 specimens from each subgroup were
thermocycled 10k cycles between 5 - 55 ° C. According to the results, when
opaquer was added, it increased Ra and TBS. Visio.link's bond strength
was higher than Pekkbond. The highest TBS was recorded in
- 26 -
plasma+Viso.link while only Plasma group couldn’t establish acceptable

TBS.PMMA resin has higher TBS than other studied resins.
Sakihara et al. (2018) investigated the SBS between indirect veneering

resin and Pekkton®ivory after etching with two strong acids: sulfuric acid
(H2SO4) and vinylsulfonic acids (C2H4O3S). They prepared two unetched
control groups (with adhesive and without adhesive). The sulfuric acid
groups were prepared with 3 concentrations (80, 90, and 98%) and 3
durations (5, 30, and 60 s), while vinyl sulfonic acids groups were prepared
with 2 concentrations (90 and 95%) and also 3 durations (5, 30, and 60 s).
After each treatment, SEM was used to examine the etched surfaces.
Following that, an adhesive bond (Metal Primer Z) was applied and light-
cured, and an indirect veneering composite was applied (Gc Gradia
Opaque then Gc Gradia Body). The samples were placed in deionized
water for 1 day and after that subjected to 20K thermocycles between 4-60
˚c. According to the findings, the maximum SBS values were achieved
only after etching with 90% H2SO4 for five seconds or 95% C2H4O3S for
thirty seconds.
Hong et al. (2020) compared the shear bond strength of three types of resin
to Pekkton®ivory depending on using adhesive. Sixty samples made from
PEKK were divided into two main groups (with and without Visio. link
adhesive). Each group was subdivided into three groups
according to the resin that bonded to PEKK: polymethylmethacrylate,
polyethylmethacrylate, and bis-acryl compostie resin. After that, all
samples were kept at 37 °C for 24 hours in deionized water. The findings
of this study show, there was no significant difference in SBS between the
PMMA and PEMA groups based on whether Visio.link was used or not.
Furthermore, SBS was significantly higher in the bis-acryl compositie resin
- 27 -
group with Visio.link than in the bis-acryl compositie resin group without
Visio.link.
Younis et al. (2020) examined the SBS between PEKK and composite
veneer after plasma treatment. Various gases were tested in the study
including: argon, acetylene, nitrogen, oxygen and air plasma. Firstly, 80
specimens of PEKK were modified with the argon plasma and both SBS
and TBS were examined to identify which bonding test type can be
employed. Afterwards, 160 PEKK samples were subdivision into 8 groups
according to the type of surface modification (untreated surface,
sandblasting, adhesive, Argon, oxygen, acetylene, air and nitrogen). All
veneered samples were thermocycle by following ISO 10477. In addition
to SBS, Ra and SEM examinations were also carried out. According to the
results, the sandblast group had the highest SBS, followed by the acetylene
plasma group. While oxygen plasma may have no influence on the PEKK's
adhesion to the veneering composites.
Gouveia et al. (2021) propped the impact of sandblasting and

manufacturing method on adherent strength of veneering resin to PEKK
and PEEK. Two main groups were either treated with 110um Al2O3 or no
surface treatment was used. Each group was subdivided into three groups
according to manufacturing method (pressed PEKK, milled PEKK and
milled PEEK). All samples bonded to veneering composite (Gradia
Revolution 2) with Visio.link primer. This study concluded, surfaces of
PEEK and PEKK treated with Al2O3 particle abrasion had a greater shear
bond strength to resin composites and when PEKK was subjected to the
same bonding procedure, the manufacturing method (milled or pressed)
had no effect on the bond strength.
- 28 -
Chapter Three Materials and Methods
Materials and Methods

3.1. Materials and Equipments
3.1.1. Materials
The materials applied in this study are listed in the following table:
Table (3-1): Materials used in the Study and their Manufacturers.
N. Materials Manufacture and Origin
1 Adhesive primer (Visio.link) Bredent, Germany
Shera Werkstoff Technologie,

2 Aluminum oxide particles (110μm)
Germany
Composite resin (GRADIA PLUS
3 GC corporation, Japan
GUM Heavy Body)
4 Distilled water) Iraq
5 Filament polylactic acid Creality, China
6 Hydrogen peroxide (H2O2) 30% BDH, England
7 Modelling wax) Cavex, Holland
8 Pekkton® ivory blank Cendres+Metaux, Switzerland
9 Rubber silicon Iraqi rubber silicon, Iraq
10 Sulfuric acid (H2SO4) BDH, England
Silicon carbide paper (p180-p320-

11 Struers, Denmark
p600-p1200
Self-curing denture base acrylic Spofa Dental Product, Czech
12
resin (Duracryl®plus Republic
13 Vaseline Unilever, British
- 29 -
Fig. (3.1): Some of the Materials Applied in this Study.
Fig. (3.2): Aluminum Oxide Particles (110μm).
- 30 -
3.1.2. Equipments and Machines

The equipments, machines and programs used in this study are listed in
the following Tables (3.2) – (3.3):
Table (3-2): Equipments and Machines used in this Study and their
Manufacturers.
N Equipments and Machines Manufacture and Origin

Computer controlled electronic
Laryee technology co. LTD,
1 universal testing machine
China
Custom made holder for Specimen Iraq
2
fixation in sandblasting machine
Roland DGA Corporation,
3 DWX-51D Dental Milling Machine
Japan
4 Eye protection glasses China
5 Fissure bur and mandrel bur Im3, Australia
6 Gloves Romed CO., Holland
7 Incubator KKTECT, China
Light-curing device (Labolight

8 GC corporation, Japan
DUO)
9 Microscope OXION, China
10 Micropipette China
Prosthetic hand piece (K-Control

11 Kavo, Germany
TLC))
12 RF. magnetron plasma Iraq
13 Sandblasting machine (Basic eco) Renfert, Germany
Scanning Electron Microscope

14 FEI, USA
(Inspect S50
- 31 -
15 Ultrasonic cleaner (Ultra 3) TECNO-GAZ, Italy
Wax knife, lacron carver, sharp

16 China
knife, micro-brush and dental flask
17 yrex Eppendorf AG, Germany
18 3D printer (ender 3 pro.) Creality, China
Table (3-3): Programs and Software used in this Study and their
Manufacturers.
N Programs and Software Manufacturer
1 Exocad DentalCAD exocad GmbH, Germany
2 EndNote X9 software Thomson Reuters, USA
Roland DGA Corporation,

3 Millbox
Japan
4 SPSS 24 IBM Corp, USA
Dassault Systèmes
5 SolidWorks Premium 2014
SolidWorks Corp, France
- 32 -
Fig. (3.3): Some of the Equipments used in this Study.
Fig. (3.4): Roland Milling Machine.
- 33 -
Fig. (3.5): Sandblasting Machine.
Fig. (3.6): Ultrasonic Cleaner. Fig. (3.7): Incubator
- 34 -
Fig. (3.8): light-curing Device Fig. (3.9): 3D Printer
Fig. (3.10): Computer Controlled Electronic Universal Testing Machine
- 35 -
3.2. Methods
3.2.1 Pilot Study

A pilot study was conducted to select the best treatment time for
Piranha acid etching and Air plasma by testing SBS of PEKK to veneering
composite (3 samples were selected for each group). The times selected
were 30 seconds and 60 seconds for piranha acid etching (Hallmann et al.,
2012, Stawarczyk et al., 2014) while in Air plasma 5 minutes and 10
minutes (Labriaga et al., 2018, Younis et al., 2020). The results achieved
are documented in Table (3-4).
Table (3-4): Mean Value of SBS Test of Pilot Study for Control, Piranha
and Air plasma Groups.
Pilot study Control Piranha Acid Etching Air Plasma
Groups
30 sec 60 sec 5 min 10 min
Sample 1 15.50 16.90 18.35 7.70 9.90
Sample 2 14.80 15.50 17.25 8.40 10.05
Sample 3 14.90 15.85 18.70 6.55 8.45
SBS Mean 15.06 16.08 18.1 7.55 9.46
- 36 -
3.2.2 Specimens Preparation
3.2.2.1 Specimens Design
The PEKK specimens were designed by CAD software (ExoCAD

GmbH) with a dimension of 7 × 7 × 2 mm (length, width and thickness
respectively) and the design was exported as STL formatted file and sent
to the milling machine as shown in Figure (3.11) (Lee et al., 2017b,
Jahandideh et al., 2020)
Fig. (3.11): Designing of PEKK Sample by ExoCAD
3.2.2.2. Milling the Specimens
Firstly, MillBox software was used to locate thirty-five square shaped

Pekkton®ivory virtual specimens in a virtual blank and connected with 1.5
mm connector as shown in figure (3.12).
- 37 -
Fig. (3.12): Nesting Procedure of the Specimens
Then Pekkton®ivory blank was fixed in the blank holder inside DWX-
51D Dental Milling Machine. Milling burs with dimension 1mm and speed
not excessing 17’000 rpm was used to prevent the specimens from
warping, according to manufacturer instructions then milling procedure
started with a 5-axis milling under cooled air as shown in figure (3.13).
Fig. (3.13): Milling of Specimens.

- 38 -
After finishing the milling process, the blank is removed from the
holder and the specimens separated from the blank by hand piece using
fissure bur as shown in figure (3.14).
A B
Fig. (3.14): A. Pekkton®ivory blank after Milling, B. Specimens after
Separation
3.2.3. Specimens Holder Fabrication
A square shape was carved from wax with a dimension of 15×15×5mm

(length, width, and thickness respectively) to make a holder for the
specimens that can fit into the universal testing machine jaws. Rubber
silicon was used to fabrication the silicon mold and mixed according to the
manufacturer's instruction then the wax block was embedded into the
silicon mold and left to set for 24 hours, Figure (3.15).
Following complete solidification of the silicon mold, the wax block

was removed. Subsequently, each specimen was placed in the center of the
mold and according to the instruction of the manufacturer, auto-
polymerizing acrylic resin was mixed and used in the dough stage to fill
the mold in such a way that only the surface of the specimen measuring
7×7 mm remain exposed. The holder with the specimen was removed from
the silicon mold after polymerization completed as in figure (3.16)
(Jahandideh et al., 2020).
- 39 -
A B
Fig. (3.15): A. Wax Block, B. Wax Block Embedded into Silicon
A B
C D
Fig. (3.16): A. Specimen in the Center of the Mold, B. Auto-polymerizing
Acrylic Resin Pouring into the Mold, C. Removal of the Holder with the
Specimen, D. Thirty-five Pekkton Specimens with Holders.
- 40 -
3.2.4 Specimens polishing

Each specimen polished with four abrasive silicon carbide paper (SIC)
with Prosthetic hand piece for surface standardization. The polishing
procedure starts with P180 then P320 then P600 and finally P1200 for 60
seconds at 150 rpm under constant water cooling (Younis, 2019, Hong et
al., 2020).
Fig. (3.17): Different Grits of Abrasive Silicon Carbide Paper.
- 41 -
3.2.5 Specimen Surface Cleaning

After polishing, the surface of the specimens was ultrasonically
cleaned for 10 minutes in ultrasonic cleaner containing deionized water and
then allowed to dry in the air before surface treatment, figure (3.18) (Hong
et al., 2020).
Fig. (3.18): Specimens into Ultrasonic Cleaner Device.
3.2.6 Surface Treatment

The specimens were randomly numbered and assigned to five group
according to used surface treatment, each group consisted of 7 specimens.
The groups were (1) Control group (Sandblasting with 110 μm Al2O3), (2)
Piranha acid etching group (H2SO4 + H2O2), (3) Sandblasting (110 μm
Al2O3) + Piranha acid etching group (4) Air plasma treatment group and
(5) Sandblasting (110 μm Al2O3) + Air plasma treatment group. Figure
(3.19) shows grouping of the specimens.
- 42 -
PEKK Specimens
(N=35)
Five Surface Treatments
Control Piranha acid Sandblasting Air plasma Sandblasting

(sandblasting etching (110 μm treatment (110 μm
with 110 μm (H2SO4 + Al2O3) + Al2O3) + air
Al2O3) H2O2) Piranha acid plasma
etching treatment
)N=7) ) N=7) )N=7) )N=7) )N=7)
Fig. (3.19): Diagram Shows the Distribution of the Specimens.
A. Control Group (Sandblasting with 110 μm Al2O3)

Sandblasting was carried out using 110 μm aluminum oxide particles
with 2 bar pressure and 10 mm distance from the nozzle to the specimen
for 10 seconds as recommended by Pekkton company. A custom-made
holder was used to fix the nozzle perpendicular to the surface of the
specimen and allow constant distance during the procedure of sandblasting,
figure (3.20) (Hong et al., 2020).
After that, the specimens were cleaned to remove contaminants and
residual particles for 10 minutes in an ultrasonic cleaner with deionized
water (Labriaga et al., 2018).
- 43 -
Fig. (3.20): Sandblasting Procedure Using Custom Made Holder
B. Piranha Acid Etching Group (H2SO4 + H2O2).
Piranha solution was prepared by adding 15ml sulfuric acid (98%) in

pyrex glass with slowly adding 5 ml of hydrogen peroxide (30%) to
achieve 3:1 ratio and the mixture was immediately applied to the specimens
surface using micro-pipette for 60 second and then rinsed with water spray
for five second in an even motion to prevent the surface topography from
any further directional changes and then air-dried as shown in figure (3.21)
(Stawarczyk et al., 2014, Stawarczyk et al., 2015b ,Sakihara et al.,
2019).
- 44 -
Fig. (3.21): Application of Piranha Etching Solution.
C. Sandblasting (110 μm Al2O3) + Piranha Acid Etching Group

The specimens of this group were first Sandblasted with 110 μm Al2O3
similar to group (A) and then cleaned for 10 minutes with deionized water
in an ultrasonic cleaner, then treated with Piranha etching solution like
group (B).
D. Air plasma Treatment Group

Specimens were placed inside low-pressure non-thermal air plasma
(RF.Magnetron plasma) as shown in figure (3.22). The surface treatment
settings were: 10 minutes period of treatment with 0.3 mbar pressure, 40
kHz frequency and under 100 watts power (Younis, 2019).
Fig. (3.22): RF.Magnetron Plasma Device

- 45 -
E. Sandblasting (110 μm Al2O3) + Air Plasma Treatment Group
The specimens of this group were first Sandblasted with 110 μm Al2O3
similar to group (A) and cleaned for 10 minutes with deionized water in an
ultrasonic cleaner, then treated with Air plasma like group (D).
3.2.7 Scanning Electron Microscopy (SEM)

Surface topography for one of PEKK specimens from each surface
treatment visually displayed by an SEM device (Inspect S50), figure
(3.23). The specimens were placed into the SEM device with an 8.5 mm
working distance and an operational voltage of 10 kV with ×10,000
magnification (Keul et al., 2014).
Fig. (3.23): SEM Device
- 46 -
3.2.8 Bonding Procedure of Specimens with Veneering

Composites
Before bonding, square bonding jig was designed using CAD
software; SolidWorks premium 2014. The dimensions were 7×7×2 mm
(length, width, and thickness respectively) in which bonding steps were
performed in the center through a hole with a dimeter of 3 mm as in figure
(3.24) and then exported as an STL file after design (Lee et al., 2017b).
Fig. (3.24): A. Bonding Jig (3d view), B. Designed Bonding Jig
A B
The bonding jig has been printed using the 3D printer which is based
on fused filament fabrication technology (ender 3 pro) and the printing
material (filament polylactic acid) from the same company.
- 47 -
Fig. (3.25): Bonding Jig after 3D Printing
Directly before beginning of bonding procedures, the inside wall of

the bonding jig hole was coated with a separating medium (Vaseline) for
easier removal of the jig from the composite resin before the curing
process. In the control group, bonding steps start after ultrasonic cleaning
of the specimens while in the other groups (piranha, sandblasting +
piranha, plasma, and sandblasting + plasma), the bonding steps start
immediately after surface treatment (Younis, 2019).
3.2.8.1 Application of Adhesive Primer

A thin film of adhesive primer (Visio.link) was applied to the surface
of the specimens with a single brush action, then, instantly light-cured for
90 seconds using dental laboratory light-curing device (Labolight DUO) as
recommended by Visio.link manufacturer.
- 48 -
Fig. (3.26): Application of Visio.link Primer.
Fig. (3.27): Light-curing of the Specimen after Visio.link Primer

Application
3.2.8.2 Application of Composite Resin

After curing of adhesive primer, the bonding jig was positioned on the
specimen as in figure (3.28:A) and filled with composite resin (GRADIA
PLUS GUM Heavy Body) as shown in figure (3.28:B), after that the
bonding jigs was immediately removed and the bonding area was checked
and light-cured for 180 seconds using dental laboratory light-curing device
as recommended by GC Gradia company (figure 3.29:A and B).
- 49 -
A B
Fig. (3.28): A. Positioning of Bonding Jig, B. Bonding Jig Filled with
Composite Resin
A B
Fig. (3.29): A. Removal of Bonding Jig, B. Light-curing of Composite
Resin
3.2.9 Shear Bond Strength Test

Before the bond strength test, all bonded specimens were placed in
distilled water at 37 ° C for 24 hours by an incubator device (kktect) as
shown in figure (3.30) (Schwitalla et al., 2017).
- 50 -
Fig. (3.30): Specimens Inside the Incubator.
Afterwards, the specimens were subjected to shear bond strength test

in a universal testing machine. the specimens are fixed and secured in the
testing machine tightly in a way that knife-edge shaped perpendicular to
the interface area between PEKK and composite (figure 3.31). The load of
piston was applied with 1 mm/min crosshead speed. The specimens were
then stressed until composite resin separated from the pekkton surface. The
force when failure occur was recorded in Newton (N) which has been
divided by the surface bonding area in square millimeters to achieve the
shear bond strength calculated in Megapascals (MPa) (Lee et al., 2017b).
SBS = F/SA = MPa SBS = shear bond strength

F = force (N)
SA = bonded surface area (mm2)
The bonded surface area was calculated as follows:
SA= R2 × 22/7 = mm2 (R2=square radius)
SA= (1.5)2 ×22/7
SA= 2.25×22/7 = 7.07 mm2
- 51 -
Fig. (3.31): Specimen During Shear Bond Strength Test.
3.2.10 Analyses the Types of Failure

After shear bond testing, the types of failure of each specimen were
evaluated under the microscope at a × 25 magnification (Fokas et al.,
2019).
Fig. (3.32): Specimen under the Microscope

- 52 -
There are three kinds of failure which have been described and
determined as follows: (A) Adhesive failure, where no composite remnants
were left on the PEKK surface. (B) Cohesive failure, where the failure
occurs in the composite's bulk layer. (C) Mixed, where composite traces
are partly left on PEKK and the surface of PEKK exposed (Lee et al.,
2017b).
3.2.11 Statistical Analysis

The following statistical methods were used to examine and evaluate
the results:
I - Descriptive Statistics
1- Statistical table includes mean, standard deviation (SD), standard
error (SE), minimum and maximum values of the SBS test.
2- Bar chart for mean values of SBS and failure mode.
II- Inferential Statistics
1- One-way ANOVA (analysis of variances test)
2- Least significant difference (LSD) for multiple comparisons
Between groups.
- 53 -
Chapter Four Results
Results
4.1 SEM Observations

The characterization of the PEKK surface after different surface
modifications was demonstrated by SEM at 10.000× magnification.
4.1.1 Control Group
Sandblast treated PEKK specimens show irregular surface topography

with flaws and streaks distributed along the surface (figure 4.1).
Fig. (4.1): SEM Image of the PEKK Surface after Sandblasting at

10.000× magnification
4.1.2 Piranha Etching Group
The surfaces were covered with small pits and filler particles after the
treatment of PEKK specimens with piranha etching (figure 4.2).
- 54 -
Fig. (4.2): SEM Image of the PEKK Surface after Piranha Etching at
10.000× magnification
4.1.3 Sandblasting + Piranha Etching Group
A more irregular surface pattern with microporosity was observed

when compared to the control group (figure 4.3).
Fig. (4.3): SEM Image of the PEKK Surface after Sandblasting + Piranha
Etching at 10.000× magnification
- 55 -
4.1.4 Air Plasma Group
Following air plasma treatment, plain and homogeneous surface

topography was seen compared to the control group (figure 4.4).
Fig. (4.4): SEM Image of the PEKK Surface after Air Plasma at 10.000×
magnification
4.1.5 Sandblasting + Air Plasma Group
The surface topography was similar to the control group, the structure
remained unchanged (figure 4.5).
Fig. (4.5): SEM Image of the PEKK Surface after Sandblasting + Air
Plasma at 10.000× magnification
- 56 -
4.2 Results of Shear Bond Strength (SBS) Test
The SBS of each sample was calculated in Megapascals (MPa) by

dividing the force (N) when the failure occurs to the surface bonding area
(mm2). Table (4.1) shows the descriptive statistics that include (mean,
standard deviation (SD), standard error (SE), minimum and maximum
values of the SBS test. The results showed that the highest mean value of
SBS was obtained in the sandblasting + piranha etching group (23.635 ±
1.405), while the lowest mean value was in the air plasma group (9.692 ±
1.333) as represented in figure (4.6). Furthermore, one-way ANOVA
between all studied groups shows a significant difference (P<0.01) among
them.
Table (4.1): Descriptive Statistics and ANOVA Test for Different Surface
Treatment Groups.
ANOVA
Studied Groups No. Mean SD SE Min. Max.
Test
Control 7 15.048 1.398 .528 13.43 17.68
Piranha 7 17.070 1.350 .510 14.85 18.80 000.
Sandblasting + 7 23.635 1.405 .531 21.21 25.45 significant
piranha (P<0.01)
Air Plasma 7 9.692 1.333 .503 8.48 12.02
Sandblasting + 7 15.881 1.210 .457 14.14 17.68
air plasma
Total 35
- 57 -
Fig. (4.6): Bar Chart Represents the Mean Value of SBS of the Studied
Groups.
Table (4.2) shows multiple pairwise comparisons between all studied

groups by using Least Significant Difference (LSD). The first section of
the table shows a significant difference at (P<0.01) between the control
group and all studied groups except Sandblasting + air plasma group that
shows a non-significant difference at (P>0.05). The second section of the
table also shows a significant difference at (P<0.01) between the Piranha
etching group and all studied groups except the Sandblasting + air plasma
group that shows a non-significant difference at (P>0.05). While the results
in the third section of the table that comparting Sandblasting + piranha
etching group to all studied groups show a significant difference at
(P<0.01) between them. And also, a significant difference at (P<0.01)
between Air Plasma group and all studied groups as presented in the fourth
section of the table.
- 58 -
Table (4.2): Multiple Pairwise comparisons using Post Hoc (LSD) Tests
according to Surface Treatments of PEKK
Mean
section (I) Groups (J) Groups P-value Sig.
Difference (I-J)
1 Control Piranha -2.021* .008 S
Sandblasting + piranha -8.587* .000 S
Air Plasma 5.355* .000 S
Sandblasting + air plasma -.8328 .255 NS
2 Piranha Control 2.021* .008 S
Sandblasting + air plasma 1.188 .108 NS
3 Sandblasting + Control 8.587* .000 S

piranha
Piranha 6.565* .000 S
Sandblasting + air plasma 7.754* .000 S
4 Air Plasma Control -5.355* .000 S
Piranha -7.377* .000 S
Sandblasting + air plasma -6.188* .000 S
5 Sandblasting + Control .8328 .255 NS

air plasma
Piranha -1.188 .108 NS
- 59 -
4.3 Fracture Mode Analysis
In the present study, the fracture mode analysis showed only adhesive
and mixed failures, while cohesive failure was not found in all groups. The
fracture mode distribution of debonded samples after SBS is shown in
figure (4.7). In the control group, the fracture mode was 57.1 % for
adhesive fracture and 42.9 % for mixed fracture. In Piranha etching group,
the facture mode was 57.1 % for mixed fracture and 42.9 % for adhesive
fracture. In Sandblasting + Piranha etching group, the fracture mode was
85.7 % mixed fracture and 14.3 % adhesive fracture. While Air plasma
group showed 100 % adhesive fracture and the last group, Sandblasting +
Air plasma group showed 57.1 % mixed fracture and 42.9 % adhesive
fracture.
A B
Fig. (4.7): Fracture Mode of Control Group, A. Adhesive, B. Mixed
A B
Fig. (4.8): Fracture Mode of Piranha Etching Group, A. Adhesive, B.

Mixed
- 60 -
A B
Fig. (4.9): Fracture Mode of Sandblasting + Piranha Etching Group, A.

Adhesive, B. Mixed
Fig. (4.10): Adhesive Fracture Mode of Air Plasma Group
A B
Fig. (4.11): Fracture Mode of Sandblasting + Air Plasma Group, A.

Adhesive, B. Mixed
- 61 -
Chapter Five Discussion
5.1 Discussion
The outstanding physical and mechanical properties, as well as the

excellent biocompatibility, made the PAEK family a widely used material
in the medical and dental fields (Song et al., 2018). PEKK, one of the best-
performing polymers among the PAEK members, is a promising
restorative material in dentistry. Since the general trend is toward metal-
free restorations, its bonding properties with other polymer-based materials
are of concern (Stawarczyk et al., 2017). In the literature, various surface
treatments are proposed to improve the bond strength between PEKK and
veneering composite.
Sandblasting increases the roughness of the surface removes organic

contaminants and creates an active, fresh surface layer. It also helps in
promoting micromechanical interlocking with the bonding agent, resulting
in increased bonding capacity (Gama et al., 2020). According to recent
studies by the Pekkton manufacturer, it recommends using MMA-based
primer after roughening the surface by sandblasting with 110 μm alumina
particles. Previous studies have demonstrated that Visio.link, a primer
containing MMA monomers, can achieve high bond strength between
PEKK and composite resin (Lee et al., 2017a, Stawarczyk et al., 2017,
Hong et al., 2020). Also, the sandblasting treatment with Visio.link primer
was the best combination to promote adhesion to PEKK (Stawarczyk et
al., 2017, Gouveia et al., 2021). Therefore, this study set the surface
treatment parameters of the control group in accordance to the instruction
by the PEKK manufacturer.
- 62 -
5.1.1 Piranha Etching Groups
PEKK possesses a hydrophobic inert surface, which makes it highly

insoluble in almost all organic and inorganic solvents at room temperature
with the exception of strong acids that is highly concentrated such as
sulfuric acid and piranha solution (Younis et al., 2020).
Recent studies have shown that the modification of PEEK surface with
acid etching has led to a chemical change in the surface which in turn led
to an increase in the number of functional groups available for bonding to
the adhesive components (Stawarczyk et al., 2014, Fokas et al., 2019,
Çulhaoğlu et al., 2020). However, the available researches regarding the
use of chemical etching as a surface treatment to improve the bond strength
of veneering composite to high-performance polymers are limited to PEEK
polymer. But since PEKK polymer has similar chemical surface properties
to PEEK, a comparable chemical treatment method is expected to obtain
adequate bonding. To the best of our knowledge, the influence of piranha
solution as a chemical surface treatment on the bond strength of PEKK to
veneering composite has not yet been investigated .
Piranha solution, which is chemically termed peroxymonosulfuric acid,

is a strong oxidizing and corrosive agent. It is a mixture of highly
concentrated sulfuric acid and hydrogen peroxide (Silthampitag et al.,
2016). According to previous studies, when PEEK's surface was solely
treated with sulfuric acid, only the functional ether bonds (C-O-C) and
carbonyl bonds (C=O) between the benzene rings were attacked by sulfuric
acid (Çulhaoğlu et al., 2020). While in piranha solution, the reaction of
sulfuric acid (H2SO4) with hydrogen peroxide (H2O2) has led to the release
of atomic oxygen, which reacts with and breaks the benzene ring. This
results in PEEK polymer oxidation, increase of surface polarity, opening
- 63 -
of the aromatic ring and emerging of carbon-oxygen compounds.

Therefore, more functional groups are available to bond to the components
of the adhesive systems. The developed cross-linking enhances the
diffusion of adhesive into the PEEK polymer, thereby enhancing bond
strength (Stawarczyk et al., 2014, Keul et al., 2014, Uhrenbacher et al.,
2014).
The above-mentioned advantages can explain the substantial

improvement in bond strength following piranha etching treatment with a
significant increase in the mean SBS value (17.070 ± 1.350 MPa)
compared to the control group (15.048 ± 1.398 MPa). Also, the SEM image
(figure 4.2) of piranha etched PEKK specimens confirmed these data by
displaying an irregular surface with pits and filler particles distributed on
the surface which, seems to agree with Silthampitag et al. (2016) and
Hallmann et al. (2012),who also found that piranha etching can cause
small pits on PEEK surface.
However, piranha etching after sandblasting showed a highly

significant improvement in the SBS (23.635 ± 1.405 MPa) compared to the
piranha etching alone. The main reasons for this improvement are that in
addition to the established cross-linking between the two polymers by the
increased rate of functional groups caused by piranha etching, the
roughened surface created by sandblasting allows the penetration of
adhesive material inside the polymer, which improved the micro-
mechanical retention between polymer-based materials and thus resulting
in increased bonding capacity. Also, SEM evaluation (figure 4.3) agrees
with Hallmann et al. (2012), who also stated that piranha etching after
sandblasting showed a more defined micro-roughness on PEEK surface
which contributes to a broader contact surface area available for
mechanical interlocking with adhesive material.
- 64 -
5.1.2 Air plasma Treatment Groups
Plasma treatment is considered to be a well-accepted treatment method

for improving bond strength. It offers an effective and clean treatment that
improves the surface properties while maintaining the bulk properties of
the polymer surface ( Chen et al., 2013, Liu et al., 2020). One of the
problems with the adhesive bonding of polymers is their low surface
energy. Low-temperature plasma treatment increases the surface energy,
thus leads to a better wettability of the material through the generation of
functional groups which in turn useful for the functioning of bonding agent
( Stawarczyk et al., 2014, Gama et al., 2020). Several studies assessed
the effectiveness of plasma treatment on PEKK surfaces (Stawarczyk et
al., 2017, Labriaga et al., 2018, Younis et al., 2020).
Younis et al. (2020) found that large numbers of oxygen‐ and nitrogen‐
containing functional groups were observed on the PEKK surface after air
plasma treatment. That was because the reactive oxygen and nitrogen
species were simultaneously present in air plasma. These functional groups
are responsible for increasing surface polarity with high surface energy and
hydrophilicity of polymer surfaces. However, the present study shows a
mean SBS value of (9.692 ± 1.33 MPa) which is comparable to the results
obtained by Younis et al. (2020), who reported a mean SBS value of (7.09
± 1.99 MPa) after air plasma treatment. Their study showed a significant
increase in SBS in contrast to the present study, which showed a
statistically decrease in it. This difference was explained by the fact that
the authors compared the results with untreated PEKK surface while the
present study compared the results with sandblasted PEKK surface.
Regarding the etching effect, air plasma demonstrated a plain surface with
no impact on surface topography as supported by SEM image (figure 4.4).
- 65 -
Moreover, studies concerning the use of air plasma in combination with

sandblasting for the surface treatment of PEKK are very limited. As a
result, there haven’t been enough studies to compare the present results to
their results. The only study is by Labriaga et al. (2018), who evaluated
the SBS between PEKK and resin cement, they found that air plasma
combined with sandblasting achieved a significantly higher SBS value
(17.7 ± 1.1 MPa) among the other tested groups. The current result does
not confirm their results since no statistically significant improvement in
SBS was achieved after using air plasma in combination with sandblasting
compared to the control group (15.881 vs. 15.048 MPa, respectively).
These differences may be attributed to the different plasma treatment
parameters used also they evaluated resin cement bonding to PEKK while
the present study evaluated veneering composite. As well as, SEM image
(figure 4.5) showed that air plasma has no impact on sandblasted PEKK
surface.
5.1.3 Comparison between all Groups
According to the guidelines of ISO 10477, the minimum acceptable

SBS value is 5 MPa between resin-based materials and substrate. However,
it has been reported that the minimum SBS value should be 10 to 12 MPa
to provide a clinically acceptable bond strength under oral conditions (ISO,
2004). In this study, all the studied groups displayed SBS value greater
than 5 MPa, but the clinically acceptable SBS value was not reached in Air
plasma group.
Also, the adhesion strength between the veneering resin and PEKK
substrate is indicated by the amount of fracture between them (Fokas et
al., 2019). Adhesive and mixed failures were the predominant types of
- 66 -
failure with no cohesive failure. However, when the bond strength is not
sufficiently high, adhesive failure can take place which is seen in air plasma
group. On the other hand, mixed failure was due to the irregular
distribution of forces at the interface which is seen mostly in Sandblasting
+ piranha etching group. Therefore, generally the groups with higher bond
strength values will exhibit a higher percentage of mixed failures and the
groups with lower bond strength will exhibit a higher percentage of
adhesive failures. The failure patterns support the results of this study, as
the bond strength increases, the failure pattern tendeds to shift from
adhesive to mixed failure which agrees with Ates et al. (2018).
In regard to the achieved results, piranha etching and piranha etching

combined with sandblasting can be considered valuable surface treatment
modalities for PEKK material.
- 67 -
Chapter five conclusions
5.2 Conclusions
Within the limitations of this in-vitro study, it could be concluded that:
1- Acid treatment of PEKK surface with piranha solution can be a

competitive method to sandblasting for providing good bonding with
veneering composite resin.
2- Sandblasting combined with piranha acid etching achieved the highest
SBS between PEKK and veneering composite resin.
3- Air plasma surface treatment of PEKK is not required as it showed
lower SBS values compared to the control group (sandblasting).
4- The number of mixed failures increased when SBS increased.
- 68 -
Chapter five Recommendations
5.3 Recommendations
1- Assess the piranha solution effect on the SBS of PEKK to other types
of composite resins and evaluation of surface roughness (Ra) and
contact angle (CA)
2- Determine the optimal etching time of piranha acid treatment on SBS
of PEKK to veneering composite.
3- Comparison of SBS between PEEK and PEKK to veneering resin after
deferent surface treatment.
4- Evaluation of SBS between veneering composite and PEKK by
utilizing various forms of surface treatment, such as Er:YAG and
Nd:YAG lasers.
5- Assess the impact of piranha acid treatment of PEKK surface on the
bonding strength to resin-based composites under different situations,
such as cyclic loading and aging.
- 69 -
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Control
Group
N F SBS Mode of Failure
1 110 15.55 mixed
2 100 14.14 mixed
3 110 15.55 adhesive
5 95 13.43 adhesive
7 105 14.85 mixed
Piranha
Group
1 130 18.38 Adhesive
2 133 18.80 Mixed
3 120 16.97 Mixed
6 125 17.68 Mixed
7 117 16.55 Mixed

Sandblasting+Piranha
Group
1 160 22.63 Mixed
2 165 23.33 Mixed
4 180 25.45 Mixed
5 170 24.04 Mixed
6 150 21.21 Mixed
7 170 24.04 Mixed
Air Plasma
Group
1 60 8.48 Adhesive
2 73 10.31 Adhesive
3 75 10.60 Adhesive
4 60 8.48 Adhesive
5 65 9.19 Adhesive
6 62 8.77 Adhesive
7 85 12.02 Adhesive
Sandblasting+Air
Plasma Group
2 110 15.55 Mixed
4 115 16.26 Mixed
5 112 15.72 Mixed
7 120 16.97 Mixed
Mode of Failure (N)

Type of Surface Treatment
(Groups) Adhesive Cohesive Mixed
Control
4 0 3
(sandblasting with 110 μm Al2O3)
(A)
Air plasma treatment
7 0 0
(B)
Piranha acid etching (H2SO4 + H2O2 (C) 3 0 4
Sandblasting (110 μm Al2O3) + air plasma

treatment 3 0 4
(D)
Sandblasting (110 μm Al2O3) + Piranha
1 0 6
acid etching
(E)
‫تأثير معالجة االسطح على قوة التصاق مادة البيكتون (بولي ايثر كيتون كيتون)‬
‫مع قشرة الراتنج المركب باستخدام نظام التصميم والتصنيع الرقمي‬
‫رسالة مقدمة الى مجلس‬

‫كلية التقنيات الصحية والطبية وهي جزء من متطلبات نيل درجة الماجستير التقني‬
‫في اختصاص صناعة األسنان‬
‫من قبل‬
‫صادق امين حاكم‬
‫بكالوريوس تقنيات صناعة أالسنان‪٢٠١٦ /‬‬
‫بأشراف‬
‫أ‪.‬م‪ .‬امال كاظم محمد‬
‫أستاذ مساعد‬
‫‪۱٤٤۲‬هـ‬ ‫‪ ۲٠۲۱‬م‬
‫الخالصة‬
‫مؤخرا ألستخدامات طب األسنان وهو معروف‬

‫ً‬ ‫الخلفية‪ :‬تم إدخال بولي ايثر كيتون كيتون (بيكتون)‬
‫بخصائصه الميكانيكية والفيزيائية الفائقة ‪ ،‬ومقاومة التآكل الجيدة ‪ ،‬وثبات األبعاد الجيد في درجات‬
‫الحرارة العالية ‪ ،‬والتوافق الحيوي العالي ‪ .‬بسبب الشفافية المنخفضة واللون المتوهج لـ بيكتون‬
‫تجعل مادة القشرة ضرورية إلنتاج الترميم الجمالي ولكن لها طاقة سطحية منخفضة ومقاومة عالية‬
‫لتعديالت السطح‪ .‬نتيجة لذلك ‪ ،‬يجب استخدام تعديالت سطحية مختلفة ‪ ،‬مثل النقش الحمضي‬
‫والبالزما ‪ ،‬لتحقيق ارتباط مقبول مع مادة القشرة‪.‬‬
‫المواد والطرق‪ :‬تم اعداد خمسة وثالثون عينة بيكتون باستخدام نظام التصميم والتصنيع الرقمي‬
‫بأبعاد (‪ ٢ × ٧ × ٧‬مم)‪ .‬تم وضع العينات في راتنجات أكريليك ذاتية البلمرة بحيث تم تعريض‬
‫سطح واحد فقط بقياس ‪ ٧ × ٧‬مم‪ .‬تم ترتيب العينات بشكل عشوائي إلى خمس مجموعات (ن =‬
‫‪ .)٧‬كانت المجموعات (‪ )١‬مجموعة التحكم (السفع الرملي ‪١١٠‬ميكرومتر من أكسيد األلومنيوم)‬
‫‪ )٢( ،‬مجموعة الحفر بحمض البيرانا ‪ )٣( ،‬مجموعة السفع الرملي ‪ +‬التنميش بحمض البيرانا‬
‫(‪ )٤‬مجموعة معالجة بالزما الهواء و (‪ )٥‬السفع الرملي ‪ +‬المعالجة بالبالزما الهوائية‪ .‬بعد معالجه‬
‫السطح ‪ ،‬تم تقييم تضاريس السطح بالمجهر اإللكتروني الماسح‪ .‬تم تطبيق مركب القشرة بمساعدة‬
‫ادة مثبة وتعريضها لضوء المعالج قبل تقديمه الختبار قوة رابطة االنزالقيه‪ .‬بعد اختبار القوه‬
‫الرابطه االنزالقية ‪ ،‬تم تصنيف أنماط الكسرباستخدام مكبر‪.‬‬
‫النتائج‪ :‬أظهرت جميع المجموعات قوة ترابط انزالقي أكثر من ‪ ٥‬ميجا باسكال ‪ ،‬مما يعني أنها‬
‫مناسبة للتطبيق السريري ‪ ،‬وفقًا لمنظمة الدولية للمعايير رقم ‪ .١٠٤٧٧‬أظهرت مجموعة السفع‬
‫الرملي ‪ +‬التنميش بحمض البيرانا أعلى قوة ترابط انزالقي بين جميع المجموعات‪ .‬بينما أظهرت‬
‫مجموعة معالجة بالزما الهواء أقل قوة ترابط انزالقي بين جميع المجموعات‪.‬‬
‫االستنتاجات‪ :‬لتحسين الترابط مع راتنج القشرة المركب ‪ ،‬قد تكون المعالجة الحمضية لسطح‬
‫بيكتون بمحلول البيرانا بديالً جيدًا للسفع الرملي‪ .‬أي ً‬
‫ضا ‪ ،‬معالجة سطح البيكتون بالزما الهواء غير‬
‫مطلوبة‪.‬‬

Sadiq Ameen Hakim

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Sadiq Ameen Hakim

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Republic of Iraq

Ministry of Higher Education and Scientific Research

Effect of Surface Treatment on Adhesion of CAD\CAM

2021 A.D 1443 A.H

This thesis is wholeheartedly dedicated to:

My beloved wife “Ola”

Background: Polyetherketoneketone (PEKK) has been recently

Materials and methods: Thirty-five PEKK specimens were designed and

Conclusions: To improve bonding with veneering composite resin, acid

3.1 Materials and Equipments 29

4.1 SEM Observations 54

Producing an optimal restorative material that will mimic the natural

PEKK has attractive mechanical properties and biocompatibility, the low

Aim of the Study

1. Evaluate the effect of different surface treatments such as

PMMA and its copolymers remain the most common nonmetallic

polymerize acrylic resins at first. However, in 1947, chemical accelerators

Based on thermal behaviour, polymers can be classified into

2.2 High Performance Polymers (HPPs)

PAEKs are processed in two main synthetic routes: nucleophilic and

(Polyetheretherketone), PEKK (Polyetherketoneketone) and PEKEKK

The performance of such polymers is influenced by a few key aspects

I. Crystallinity, in which more crystalline content led to higher density,

II. Ketone percentage, the greater ketone concentration enhances the

2.3 PAEKs Polymers

In dentistry, PAEK became promising dental material to replace metal

Fig. (2.1): Schematic structure of PEKK, and PEEK polymers (Younis,

PEEK has good biocompatibility with excellent mechanical, physical

PEEK has recently become the material of choice when it comes to

2.3.1 PEKK Polymer

PEKK can be synthesized by condensing diphenyl ether with iso- and

Fig. (2.2): Synthesis of PEKK (Silla, 2018).

Physical properties of PEKK are comparable in certain respects to the

PEKK polymer made by Oxford Performance Materials (OPM), both

PEKK is at the top of the thermoplastics quality pyramid and displays

Whereas PEKK, which is based on an amorphous structure, has increased

Fig. (2.3): Performance and structure of PAEK (PEEK and PEKK).

2.3.1.1 Properties of PEKK

PEKK has superior mechanical and physical properties, such as

PEKK is an inert material and presents high biocompatibility. It

PEKK has an opaque white\grayish color. The radiolucency of PEKK

According to the manufacturer company (Cendres+Métaux),

According to a study done by PEKK manufacturing company, they

PEKK also has low elasticity modulus which is comparable to the

Table (2.1): Elastic Modulus of Framework Materials and Natural Bone

Cancellous PEKK Cortical

Alsadon et al. (2020) assessed the fatigue behaviour of PEKK, zirconia

Table (2.2): Mechanical properties of Pekkton® ivory (PEKK based

Properties PEEK Pekkton Titanium PMMA

Tensile strength (MPa) 100.69 115 240 - 890 48 - 62

Elastic modulus (GPa) 3.5 5.1 103 - 114 3.8 x 103

Flexural strength (MPa) 163.88 200 65 107 - 117

Compressive strength (MPa) 118 - 169 246 130 - 170 76

Hardness 26 - 29 VHN 252 MPa 90 VHN 89 - 95 MPa

Water absorption (mg/mm3) 0.1 - 0.5 8.7 0.04 0.1 - 0.3

Density (g/cm3) 1.3 FEFF1.3 4.4 - 4.5 1.16 - 1.18

2.3.1.2 Processing Techniques of PEKK

Fig. (2.4): Pressable Ingots of Pekkton®ivory (Pekkton®ivory

Fig. (2.5): CAD/CAM Blank of Pekkton®ivory (Pekkton®ivory

2.3.1.3 Applications of PEKK

II. Dental Applications

due to the excellent properties of PEKK such as shock-absorbing,

A case studied by Jun et al. (2020) described the treatment of