RESEARCH AND EDUCATION

Effect of surface treatment and manufacturing process on the

shear bond strength of veneering composite resin to
polyetherketoneketone (PEKK) and polyetheretherketone
(PEEK)
Diogo do Nascimento Machado Gouveia, DDS, MS,a Michael E. Razzoog, DDS, MS, MPH,b
Marianella Sierraalta, DDS, MS,c and Maria Fernanda Alfaro, DDSd

The group of high- ABSTRACT

performance semicrystalline
thermoplastic resins,
polyaryletherketones (PAEKs),
is characterized by the ratio of
keto and ether groups in the
material.1 The rigidity of the
polymer chain and the glass,
as well as the melting tem-
perature, is increased with the
addition of a higher ratio and
sequence of keto groups.1
However, good dimensional
stability at high temperatures,
high mechanical and chemical
resistance, resistance to wear,
and high tensile, fatigue, and
flexural strengths are common
characteristics of different
PAEKs.1
The characteristics of
PAEKs make them attractive
for use in the automobile,
aircraft, and food industries, as
well as for medical products.2
Polyetheretherketone (PEEK)
Statement of problem. Polyaryletherketones (PAEKs) are high-performance polymer materials in
which polyetheretherketone (PEEK) and polyetherketoneketone (PEKK) are the most used.
Although mechanical and shear bonding strength tests have been performed on the 2 materials,
studies on the influence of processing on bonding are scarce.
Purpose. The purpose of this in vitro study was to determine the influence of the surface treatment
and the manufacturing process on the shear bond strength of veneering composite resin to PEKK
and PEEK.
Material and methods. Thirty pressed PEKK, 30 milled PEKK, and 30 milled PEEK specimens
were distributed in 6 groups (n=13) as per the manufacturing process and treatment
surface. The specimens were either treated with airborne-particle abrasion with 110-mm
aluminum oxide, or no surface treatment was applied. Moreover, the PEKK specimens were
grouped regarding their manufacturing process, as either milled or heat-pressed. The
specimens were all bonded by using a methyl methacrylateebased adhesive (visio.link),
and composite resin (Gradia Revolution 2) was bonded to the specimens. An Instron
universal machine was used to calculate the shear bond strength between the PEEK or
PEKK and the composite resin. Two specimens from each group had their topography
modification assessed with a scanning electron microscope. Statistical analysis was
performed by using a 3-way ANOVA for multiple comparisons (a=0.05)
Results. The groups that were surface treated with 110-mm aluminum oxide (Al2O3) before bonding
showed significantly higher shear bond strength (P=.001) than the other groups. However, no
statistically significant difference was observed among the groups, regardless of the
manufacturing process (milled or heat-pressed) (P=.607).
Conclusions. PEEK and PEKK surfaces treated with 110-mm aluminum oxide airborne-particle
abrasion displayed better shear bond strength to composite resin. The manufacturing process
(milled or heat-pressed) did not significantly affect the bond strength of PEKK when subjected to
the same bonding process. (J Prosthet Dent 2022;128:1061-6)

This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors.
a
Assistant Professor, Department of Restorative and Prosthetic Dentistry, The Ohio State University, Columbus, Ohio.
b
Professor, Department of Biological and Material Sciences, Division of Prosthodontics, University of Michigan, Ann Arbor, Mich.
c
Clinical Professor, Department of Biological and Material Sciences, Division of Prosthodontics, University of Michigan, Ann Arbor, Mich.
d
Graduate Prosthodontics Resident, Department of Biological and Material Sciences, Division of Prosthodontics, University of Michigan, Ann Arbor, Mich.

THE JOURNAL OF PROSTHETIC DENTISTRY 1061

1062 Volume 128 Issue 5

PEEK
Clinical Implications O

Airborne-particle abrasion with 110-mm aluminum O

oxide should be used to increase the bond strength
between composite resin and both PEEK and PEKK. O
Milled or heat-pressed PEKK has similar bond A
strength to that of veneering composite resin when
the surfaces are prepared similarly. PEKK
O
O

(Fig. 1), is commonly used as an alternative to titanium in O

orthopedic application.2-4 In dentistry, PAEKs have B
mainly been used as interim implant abutments, Figure 1. Molecular structures. PEEK, polyetheretherketone; PEKK,
removable partial dentures, and, most recently, frame- polyetherketoneketone.
works for fixed partial dentures and fixed complete
dentures.5,6 Table 1. Details of test groups
The mechanical properties of PEEK can be adjusted Manufacturing
by including bioactive compounds,7 such as carbon fiber, Test Groups Material Surface Treatment Process
which will increase the polymer’s modulus of elasticity up Polyetheretherketone PEEK No surface treatment Milled
untreated milled
to 18 GPa.7 Similarly, titanium and ceramic have been
Polyetheretherketone PEEK PEEK surface airborne- Milled
added to modulate the mechanical properties of the airborne-particle particle abraded with 110-
polymer.8 abraded milled mm aluminum oxide
particles (Korox; Bego
Polyetherketoneketone (PEKK) has an 80% increased Canada Inc) for 15 seconds
compressive strength over PEEK, as per the manufacturer at 0.2 MPa, at 5 mm and 45
degrees to treated surface.
(Cendres+Métaux),1 making it interesting especially for the Specimens cleaned with oil-
fabrication of fixed partial and complete dentures for free compressed air for 30
seconds.
definitive restorations but unsuitable for removable partial
Polyetherketoneketone PEKK No surface treatment Heat-pressed
dentures.9 While PEKK and PEEK have been used for a untreated heat-pressed
variety of dental applications,5,6,10 their grayish and pearl Polyetherketoneketone PEKK Same surface treatment as Heat-pressed
white color requires a veneering composite resin for clinical airborne-particle described for Group B.
abraded heat-pressed
application.11-13 PEKK polymers are currently fabricated by
Polyetherketoneketone PEKK No surface treatment Milled
heat pressing and computer-aided design and computer- untreated milled
aided manufacturing (CAD-CAM).14 However, the au- Polyetherketoneketone PEKK Same surface treatment as Milled
airborne-particle described for Group B.
thors are unaware of published standardizations or abraded milled
comparative testing regarding the influence of the
manufacturing process and the surface treatment of PEKK
polymers. Furthermore, a consensus with respect to the best Therefore, the purpose of this in vitro study was to
surface treatment required to increase bonding strength in investigate the influence of surface treatment and the
PEEK and PEKK is lacking. The available studies have tested manufacturing process of PEEK and PEKK on the shear
different protocols, including airborne-particle abrasion, bond strength to composite resin. The null hypothesis
sulfuric acid application, and plasma and laser surface was that the surface treatment and manufacturing pro-
modification.9,10,15-27 cess would not influence the shear bond strength of
Knowledge concerning a definitive treatment protocol veneering composite resin to PEEK or PEKK.
for both the dentist and the dental laboratory technician
working with PEEK and PEKK is lacking, especially for MATERIAL AND METHODS
PEKK polymers. Presently, the surface treatment has
been the same when using milled PEKK versus heat- Ninety 7×7×2-mm specimens were tested, 30 from a
pressed PEKK, under the assumption that the different PEKK milling blank (Pekkton Ivory; Cendres+Métaux),
processing will not affect the interface with the bonding 30 from PEKK ivory pressing ingots (Pekkton Ivory;
system. However, current research to substantiate that Cendres+Métaux), and 30 from a PEEK milling blank
assumption is lacking. (Vestakeep; Evonik). The sample size was determined

THE JOURNAL OF PROSTHETIC DENTISTRY Gouveia et al

November 2022
30
Shear Bond Strength (MPa)
20
10
0
Abrasion No-abrasion
Milled PEEK
Figure 2. Mean load at failure and 95% confidence.
from a sensitivity power analysis software program
(G*Power software, version 3.1.9.2; Heinrich-Heine-
Universitat) with fixed main effects and interaction.
With a power of 95% and a=0.05, a difference between
groups of 3.14 MPa or greater would be found significant.
The milled PEEK and PEKK specimens were provided by
the manufacturer. The heat-pressed PEKK specimens
were hot pressed from the Pekkton ivory ingots in a
pressing furnace (Programat EP 3010; Ivoclar AG) from
milled wax patterns.
The methods followed the International Organization
for Standardization (ISO) 2902228 through specimen
preparation to the test design. The PEEK and PEKK
specimens were embedded in an autopolymerizing
methacrylate resin (KoldMount; Nobillium International
Inc) by using a polycarbonate 15-hole specimen mold
(Part #1599; Ultradent Products, Inc) to produce
Ø25.4×25.4-mm cylindrical specimens. Clear adhesive
tape was applied to 1 side of the mold, centering the
PEKK or PEEK specimen in the tube. The methacrylate
resin (Koldmount; Nobilium International Inc) was
mixed to a fluid consistency by combining 1-part powder
to 3-parts liquid and then poured into the specimen
mold. This entire procedure was repeated to produce 60
specimens of PEKK and 30 specimens of PEEK
embedded in acrylic resin.
For surface standardization, the bonding surfaces of
the blocks in all specimens were polished with a series of
rotating silicon carbide abrasive paper (200 grit up to 600
grit). The surface was cleaned in an ultrasonic bath
Gouveia et al
1063
Abrasion No-abrasion Abrasion No-abrasion Surface treatment
Milled PEKK Pressed PEKK Manufacturing Process
containing distilled water for 10 minutes and air-dried
before surface treatment. The specimens were divided
into 6 groups (n=15) as per the surface treatment. The
details of each group are described in Table 1.
After the respective surface treatment, 2 representa-
tive specimens of each group were sputter-coated with
gold nanoparticles (thickness <10 nm) and analyzed with
a field emission scanning electron microscope (MIRA 3;
Tescan). Each of the 2 specimens was analyzed
at ×500, ×2000, and ×1 000 magnification.
After the surface treatment, all the specimens sub-
jected to shear bond strength were bonded by using a
uniform thin layer of methyl methacrylate and composite
resin primer (visio.link; bredent GmbH & Co KG) and
photopolymerized (wavelength range of 370 nm-400 nm)
for 90 seconds (Valo Grand; Ultradent Products, Inc).
The specimens were assigned a random number to
prevent bias during testing. The specimens subjected to
shear bond strength testing were then placed in a shear
bond testing device (Part # 34224; Ultradent Products,
Inc). Flowable composite resin (Gradia Revolution 2; Kerr
Corp) was injected into the Ø2.38×2-mm-high opening in
the testing device and photopolymerized for 60 seconds.
The specimens were then removed and stored for 24
hours in distilled water at 37  C before the shear bond test.
The specimens were secured into a mounting clamp
(Part # 34223; Ultradent Products, Inc) which was loaded
horizontally into a universal testing device (Instron Model
5566; Illinois Tool Works Inc.), and the notched-edge
shear blade was positioned so that the crosshead
THE JOURNAL OF PROSTHETIC DENTISTRY
1064
Table 2. Summary statistics of 3-way ANOVA
Degrees of Freedom
Source of Variation Num DF Den DF F Value
Manufacturing process (MP) 2 71 0.50
Surface treatment (ST) 1 71 16.93
MP × ST 2 71 0.85
assembly (Part # 34230; Ultradent Products, Inc) contacted
the bonded specimen at the interface between the PEKK
or PEEK and the flowable composite resin. The specimens
were then loaded until failure with a crosshead speed of
1.0 mm/min. Shear bond strengths were reported in
newtons (N) and converted to MPa by dividing the
maximum load at failure by the bonding surface area (2.38
mm2) as per the ISO 29022.28 All fractured specimens
were visually examined to determine the bond failure
mode and classified as follows: adhesive failure when no
resin remnants were left on the polymer’s surface; cohe-
sive failure when the failure was located in the bulk layer
of the composite resin; or mixed failure when resin rem-
nants were partially left on the polymer’s surface but also
when part of the bulk surface was exposed.
The statistical analysis was performed by using a
statistical software program (SAS v9.4; SAS Institute Inc).
The normality of data distribution was tested (all
P.091), and no lack of normality was found within the
subgroups. Descriptive statistics (mean, standard devia-
tion, and 95% confidence intervals) were calculated. A 3-
way ANOVA was used to determine multiple compari-
sons between and within the mean shear bond strength
of the tested groups.
RESULTS
All specimens showed 100% adhesive failures. Mean
values of shear bond strength and its standard deviations
are presented in Figure 2. During the testing of the group
PEEK with no surface treatment, 1 specimen inadver-
tently fractured. This specimen was excluded from the
statistical analysis.
The 3-way ANOVA indicated no significant differ-
ence between PEEK and PEKK (P=.600). In addition,
no difference was found between the heat-pressed and
milled PEKK (P=.430). However, a statistically signifi-
cant difference on the shear bond strength of com-
posite resin to both PEEK and PEKK (P<.001) was
found based on the prebonding surface treatment
(Table 2).
Craters and major surface modifications across the
entire specimen were a common trait for both the PEEK
and PEKK specimens airborne-particle abraded with
110-mm aluminum oxide (Fig. 3). The specimens not
subjected to surface treatment showed an overall regular
surface with the polishing grooves still present.
THE JOURNAL OF PROSTHETIC DENTISTRY
Volume 128 Issue 5
DISCUSSION
P
The research hypothesis that the surface treatment and
.607 the manufacturing process would not affect the shear
<.001 bond strength of veneering composite to PEEK and
.431 PEKK was partially rejected, as the surface treatment did
affect the bond strength of veneer composite to PEEK
and PEKK but the manufacturing process did not.
Airborne-particle abrasion with 110-mm aluminum oxide
has been reported to increase the tensile and shear bond
strength of PEEK and PEKK to different composite
resins.10,16,18,20,21 However, the authors are unaware of
studies that addressed the impact of the manufacturing
process on the shear bond strength of PEKK.
The sensitivity power analysis showed that a differ-
ence of 3.14 MPa would be statistically significant for the
sample size selected. The null hypothesis that the
manufacturing process would not affect the shear bond
strength was accepted. No statistical difference in the
shear bond strength was found between the pressed
PEKK and milled PEKK groups. Therefore, the surface of
milled and pressed PEKK can be treated with the same
surface treatment protocol, and similar bond strength can
be expected. Similar results were reported by Alsadon
et al,14 with no difference in the mechanical and optical
properties of milled and pressed PEKK. The manufac-
turer (Cendres+Métaux Medtech) instructs dental labo-
ratory technicians and dentists to treat the surface of both
milled and pressed material with the same protocol, and
the present study supports this recommendation.
Different PEEK surface treatments have been evalu-
ated, including glycine coupling agent, helium plasma
surface modification, and silane surface conditioning,20,22
without showing a significant improvement in bonding
to PEEK.20,22 However, etching with 90% to 98% sulfuric
acid has been reported to increase both tensile and shear
bond strength.13,16,17,23,24 However, these authors
cautioned that working with such a strong and
dangerous acid requires appropriate safeguards13,16,17
that are not typically available in dental offices or
dental laboratories. Therefore, this surface treatment
method was not included in the present study.
Methyl methacrylate and composite primer (visio.-
link) have been reported to provide a reliable bond
independently of the surface treatment.8,11,12,15-18 This is
consistent with the present study, as even the groups
without surface treatment showed a bond strength
greater than zero. The pentaerythritol triacrylate (PETIA)
in visio.link has been reported to play an important role
because it acts as a solvent and might explain its efficacy
when bonding to PAEK.12
The standardization of the specimens with 200-grit up
to 600-grit silicon carbide abrasive paper created stria-
tions and irregularities on the surface that can be seen in
the SEM images. The surface topography obtained is
Gouveia et al
November 2022 1065

Figure 3. Representative scanning electron microscope images A, Airborne-particle abraded milled polyetherketoneketone. B, Airborne-particle
abraded milled polyetheretherketone. C, Airborne-particle abraded heat-pressed polyetherketoneketone. D, Untreated milled polyetherketoneketone.
E, Untreated milled polyetheretherketone. F, Untreated heat-pressed polyetherketoneketone. Original magnification ×2000.

similar to that in other studies that followed the same
protocol for standardization before and after the surface
treatment.1,12,20,23,25,26 This finding could explain the
high bond strength values obtained in both PEEK and
PEKK even without surface treatment. However, Sta-
warczyk et al21 in a study in which all PEEK specimens
were standardized with silicon carbide abrasive paper up
to 2400 grit reported that the PEEK specimens condi-
tioned with a methyl methacrylate adhesive system
(visio.link) displayed the highest bonding strength
values, regardless of the surface treatment.21 Therefore,
the results obtained in the groups without surface

Gouveia et al THE JOURNAL OF PROSTHETIC DENTISTRY

1066
treatment seem to have been more influenced by the
bonding agent than by the surface itself.21
To assess the longevity of bonding strength, adequate
oral environmental conditions should be simulated with
the use of artificial aging methods. A limitation of this
study was that no thermocycling or artificial aging was
applied to the specimens before the shear bond strength
test. Future research should assess the influence of the
surface treatment and the manufacturing process after
such artificial aging approaches.
CONCLUSIONS
Based on the findings of this in vitro study, the following
conclusions were drawn:
1. Airborne-particle abrasion with 110-mm aluminum
oxide increased the shear bond strength between
veneering composite resin to PEEK and PEKK
polymers.
2. The PEKK manufacturing process, milled or heat-
pressed, did not affect the shear bond strength to
veneering composite resin when subjected to the
same surface treatment.
3. The shear bond strengths of PEEK and PEKK were
similar when subjected to the same surface
treatment.
REFERENCES
1. Fuhrmann G, Steiner M, Wolf-Freitag S, Kern M. Resin bonding to three
types of polyaryletherketones (PAEKs)-durability and influence of surface
conditioning. Dent Mater 2014;30:357-63.
2. Kurtz SM, Devine JN. PEEK biomaterials in trauma, orthopedic, and spinal
implants. Biomaterials 2007;28:4845-69.
3. Horak Z, Pokorny D, Fulin P, Slouf M, Jahoda D, Sosna A. Poly-
etheretherketone (PEEK). Part I: prospects for use in orthopaedics
and traumatology. Acta Chir Orthop Traumatol Cech 2010;77:463-9.
4. Toth JM, Wang M, Estes BT, Scifert JL, Seim HB 3rd, Turner AS. Poly-
etheretherketone as a biomaterial for spinal applications. Biomaterials
2006;27:324-34.
5. Zoidis P. The all-on-4 modified polyetheretherketone treatment approach: A
clinical report. J Prosthet Dent 2018;119:516-21.
6. Dawson JH, Hyde B, Hurst M, Harris BT, Lin W. Poly-
etherketoneketone (PEKK), a framework material for complete fixed
and removable dental prostheses: A clinical report. J Prosthet Dent
2018;119:867-72.
7. Schwitalla AD, Spintig T, Kallage I, Muller W. Flexural behavior
of PEEK materials for dental application. Dent Mater 2015;31:
1377-84.
8. Lumkemann N, Eichberger M, Stawarczyk B. Bonding to different PEEK
compositions: the impact of dental light curing units. Materials (Basel). MDPI
Materials 2017;10:1-10.
9. Heimer S, Schmidlin PR, Roos M, Stawarczyk B. Surface properties of pol-
yetheretherketone after different laboratory and chairside polishing pro-
tocols. J Prosthet Dent 2017;117:419-25.
10. Stawarczyk B, Beuer F, Wimmer T, Jahn D, Sener B, Roos M, et al. Poly-
etheretherketone-a suitable material for fixed dental prostheses? J Biomed
Mater Res B Appl Biomater 2013;101:1209-16.
THE JOURNAL OF PROSTHETIC DENTISTRY
Volume 128 Issue 5
11. Stawarczyk B, Jordan P, Schmidlin PR, Roos M, Eichberger M, Gernet W,
et al. PEEK surface treatment effects on tensile bond strength to veneering
resins. J Prosthet Dent 2014;112:1278-88.
12. Stawarczyk B, Silla M, Roos M, Eichberger M, Lumkermann N. Bonding
behaviour of polyetherketoneketone to methylmethacrylate- and
dimethacrylate-based polymers. J Adhes Dent 2017;19:331-8.
13. Silthampitag P, Chaijareenont P, Tattakorn K, Banjongprasert C,
Takahashi H, Arksornnukit M. Effect of surface pretreatments on resin
composite bonding to PEEK. Dent Mater J 2016;35:668-74.
14. Alsadon O, Wood D, Patrick D, Pollington S. Comparing the optical and
mechanical properties of PEKK polymer when CAD/CAM milled and
pressed using a ceramic pressing furnace. J Mech Behav Biomed Mater
2019;89:234-6.
15. Keul C, Liebermann A, Schmidlin PR, Roos M, Sener B, Stawarczyk B.
Influence of PEEK surface modification on surface properties and
bond strength to veneering resin composites. J Adhes Dent 2014;16:
383-92.
16. Schmidlin PR, Stawarczyk B, Wieland M, Attin T, Hammerle CHF, Fischer J.
Effect of different surface pre-treatments and luting materials on shear bond
strength to PEEK. Dent Mater 2010;26:553-9.
17. Sproesser O, Schmidlin PR, Uhrenbacher J, Roos M, Gernet W,
Stawarczyk B. Effect of sulfuric acid etching of polyetheretherketone
on the shear bond strength to resin cements. J Adhes Dent
2014;16:465-72.
18. Rosentritt M, Preis V, Behr M, Sereno N, Kolbeck C. Shear bond strength
between veneering composite and PEEK after different surface modifications.
Clin Oral Investig 2015;19:739-44.
19. Rikitoku S, Otake S, Nozaki K, Yoshida K, Miura H. Influence of SiO2
content of polyetheretherketone (PEEK) on flexural properties and tensile
bond strength to resin cement. Dent Mater J 2019;38:1-7.
20. Kern M, Lehmann F. Influence of surface conditioning on bonding to poly-
etheretherketone (PEEK). Dent Mater 2012;28:1280-3.
21. Stawarczyk B, Taufall S, Roos M, Schmidlin PR, Lumkermann N. Bonding of
composite resins to PEEK: the influence of adhesive systems and air-abrasion
parameters. Clin Oral Investig 2018;22:763-71.
22. Schmidlin PR, Eichberger M, Stawarczyk B. Glycine: A potential coupling
agent to bond to helium plasma treated PEEK? Dent Mater 2016;32:
305-10.
23. Sakihara M, Taira Y, Sawase T. Effects of sulfuric and vinyl sulfonic acid
etchants on bond strength of resin composite to polyetherketoneketone.
Odontology 2018;107:158-64.
24. Chaijareenont P, Prakhamsai S, Silthampitag P, Takahashi H,
Arksornnukit M. Effects of different sulfuric acid etching concentrations
on PEEK surface bonding to resin composite. Dent Mater J 2018:
37385-92.
25. Lee KS, Shin M, Lee J, Ryu J, Shin S. Shear bond strength of composite resin
to high performance polymer PEKK according to surface treatments and
bonding materials. J Adv Prosthodont 2017;9:350-7.
26. Zhou L, Qian Y, Zhu Y, Liu H, Gan K, Guo J. The effect of different surface
treatments on the bond strength of PEEK composite materials. Dent Mater
2014;30:209-15.
27. Fokas G, Guo CY, Tsoi JKH. The effects of surface treatments on tensile bond
strength of polyether-ketone-ketone (PEKK) to veneering resin. J Mech
Behav Biomed Mater 2019;93:1-8.
28. International Organization for Standardization. ISO 29022-1. Dentistry
Adhesion. Notched-edge shear bond strength test. Geneva: Interna-
tional Organization for Standardization; 2013. ISO store Order: (Date:5/
21/2013).
Corresponding author:
Dr Diogo do Nascimento Machado Gouveia
3005D Postle Hall 305 W. 12th Avenue
Columbus, OH 43210
Email: Gouveia.5@osu.edu
Acknowledgments
The authors thank Cendres+Métaux for the specimens provided for this study and
Dr Willliam M. Johnston for his assistance with the statistical analysis and pre-
paring the manuscript.
Copyright © 2021 by the Editorial Council for The Journal of Prosthetic Dentistry.
https://doi.org/10.1016/j.prosdent.2021.02.003
Gouveia et al