Applied Surface Science 258 (2012) 9437–9442

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Laser surface modification of PEEK

A. Riveiro a,b,∗ , R. Soto a , R. Comesaña a , M. Boutinguiza a , J. del Val a , F. Quintero a , F. Lusquiños a , J. Pou a
a
Applied Physics Department, University of Vigo ETSII, Lagoas-Marcosende, 9, Vigo 36310, Spain
b
Centro Universitario de la Defensa, Escuela Naval Militar, Plaza de España 2, 36920 Marín, Spain

a r t i c l e i n f o a b s t r a c t

Article history: Polyether-ether-ketone (PEEK) is a synthetic thermoplastic polymer with excellent mechanical and
Available online 27 February 2012 chemical properties, which make it attractive for the field of reconstructive surgery. Nevertheless, this
material has a poor interfacial biocompatibility due to its large chemical stability which induces poor
Keywords: adhesive bonding properties. The possibilities of enhancing the PEEK adhesive properties by laser treat-
Laser ments have been explored in the past. This paper presents a systematic approach to discern the role of
Surface modification
laser irradiation wavelength on the surface modification of PEEK under three laser wavelengths ( = 1064,
PEEK
532, and 355 nm) with the aim to determine the most adequate processing conditions to increase the
Design of experiments (DOE)
roughness and wettability, the main parameters affecting cell adhesion characteristics of implants. Over-
all results show that the ultraviolet ( = 355 nm) laser radiation is the most suitable one to enhance surface
wettability of PEEK.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction
Polyether-ether-ketone (PEEK) is a kind of polyaryletherketones
(PAEKs) with very interesting properties for biomedical applica-
tions, namely, high strength and good wear resistance, excellent
chemical resistance, does not need additives for its processing and
radiolucency [1,2]. All these properties make it very suitable as
biomaterial, for example in orthopedic applications such as inter-
vertebral spacer, spinal cage, and cervical disc prosthesis [2,3].
However, this material has a poor interfacial biocompatibility due
to its large chemical stability; then, its inferior bioactivity may lead
to poor bone-implant interactions [4].
As it is well known, surface properties of an implant control
the amount and quality of cells adhered to it. In this sense, surface
chemistry and topography are the most determining properties for
cell adhesion. Surface chemistry, which controls the implant wet-
tability, can become a deciding factor for the protein adsorption
and therefore for the cell adhesion [5,6]. Some studies show the
existence of a range of optimal wettability which improves cell
growth, biocompatibility and cell adhesion [7]. On the other hand,
regarding the surface topography, it was reported that, engineered
surfaces with roughness values around 1 ␮m or above, improve
bone bonding to the implant surface [8].
In order to tailor the surface characteristics of PEEK, laser treat-
ments are a promising alternative due to their high resolution, high
∗ Corresponding author at: Applied Physics Department, University of Vigo ETSII,
Lagoas-Marcosende, 9, Vigo 36310, Spain. Tel.: +34 986812216; fax: +34 986812201.
E-mail address: ariveiro@uvigo.es (A. Riveiro).
operating speed, low cost and keeping unaltered the bulk prop-
erties [9,10]. These treatments can modify the surface chemistry
of PEEK, as demonstrated using excimer laser radiation [11,12].
However, it was not found in the literature any work exploring the
influence of other laser wavelengths and processing parameters to
modify and predict the surface topography and wettability of this
material. Therefore, we have conducted a comprehensive survey at
three different laser wavelengths:  = 1064, 532 and 355 nm with
the aim of correlating and predicting, by means of statistical meth-
ods, the required processing values to tailor the surface roughness
and wettability of PEEK for biomedical applications.
2. Experimental setup
2.1. Material
The base material used in this study was PEEK (Tecapeek from
ENSINGER; melting point of 343 ◦ C and glass transition tempera-
ture of 143 ◦ C). Plates of 80 mm × 50 mm × 8 mm were used after a
surface cleaning by ultra sonic treatment in ethanol.
2.2. Experimental conditions
The laser treatment was performed using a diode end-pumped
Nd:YVO4 (Rofin-Sinar PowerLine E) emitting a TEM00 pulsed laser
beam at 1064, 532 and 355 nm wavelengths. The pulse duration
was 10 ns at 20 kHz. The laser beam was focused using lenses with
different focal length: 211, 365, and 235 mm, respectively. In order
to treat large surfaces, galvanometric mirrors were used to scan the

0169-4332/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2012.01.154
9438 A. Riveiro et al. / Applied Surface Science 258 (2012) 9437–9442
Table 1
Factors and levels for the 25 full factorial design. Remaining processing parameters
were kept constant.
Factor
− +
xA − P = laser power (W) 5 39
xB − f = pulse frequency (Hz) 15,200
xC − v = scanning speed (mm/s) 200
xD − w = spot diameter (mm) 0.1
xE − Sup = spot overlapping (%) −50
polymer under the laser beam. Treatments were performed in air
at atmospheric pressure.
A 25 full factorial design (FFD) approach was performed to
screen out the key variables, usually called effects (laser power,
pulse frequency, scanning speed, spot diameter and overlapping
between pulses in this work) which significantly affects on the
response variables (in this work, the evaluated parameters were
the average roughness of samples and the contact angle, to deter-
mine the wettability of samples) during the processing under each
laser wavelength. The processing parameters for the full factorial
design were selected based on previous tests performed at the
laboratory (not included here). Two levels for each of the three pro-
cessing parameters were investigated, as summarized in Table 1.
Only factors with p < 0.08 are considered significant. In a full fac-
torial experiment, responses are measured at all combinations
(i.e. conditions at which the responses will be measured) of the
experimental factor levels. Using an ANOVA technique, the factors
having a significant effect on the response variables are detected,
while a regression model is used to estimate the response val-
ues as a function of the effects. This strategy allows the study
of a reduced number of different laser parameter combinations
without decreasing the accuracy of the results. Please, refer to Ref.
[13] for more details about the mathematical details.
2.3. Sample characterization
Selected samples were inspected in frontal view to the laser
treated area by means of an optical stereoscopic microscope (Nikon
SMZ-10A) with a photographic system in order to record and store
images. Furthermore, scanning electron microscopy (SEM) obser-
vations of treated areas were carried out using a XL-30 (Phillips)
after surface metallization with gold.
a b
5000
4000
3000
v (mm/s)
2000
1000
1 3
5 10 15
Fig. 1. Contour plot of average roughness Ra (␮m) versus laser power and scanning speed during the processing by means of (a) 1064 nm and (b) 532 nm laser radiation.
Roughness was measured by means of a Veeco Dektak
3ST surface profiler in several locations of the treated areas.
Then, an average value for the average roughness (Ra ) was
Level extracted from obtained data in order to characterize the sur-
face finishing. Measurements were made in accordance with
the recommendations specified in the International Standard ISO
50,000 4288:1996.
5000 Finally, measurements of the contact angle () using bidistilled
1 water were performed using the sessile drop technique in order to
50 determine the wettability of the treated areas. A liquid drop was
placed on the surface by means of a carefully rinsed syringe. Then,
the contact angle was measured using a Goniometer measuring
system (FIBRO System). At least ten measurements were performed
on each sample to evaluate the contact angle.
3. Results and discussion
3.1. Selection of laser treatment parameters
3.1.1. Roughness analysis
The analysis of the 25 full factorial design does not indicate any
factor as statistically significant during the processing under the
1064 nm laser radiation; however, laser power, scanning speed and
its combination slightly affects the average roughness (see Fig. 1a).
On the other hand, these factors arise as statistically significant dur-
ing the processing under the 532 nm laser radiation (see Fig. 1b).
As noted in Fig. 1a and b maximization of average roughness of
samples, will be obtained under high laser powers and low scan-
ning speeds. Roughness values Ra ≥ 1 ␮m are obtained for 1064 and
532 nm laser radiations. These values are adequate for promoting
cell adhesion because this is the optimum range to promote cell
adhesion (see Ref. [14]).
Using UV laser radiation (355 nm) does not substantially modify
the roughness as compared to the other wavelengths. In this case,
the statistically significant factor is the interaction of laser power,
pulse frequency, scanning speed and spot diameter (see Fig. 2). In
order to maximize the average roughness using UV laser radiation,
utilization of a high laser power, low pulse frequency, low scan-
ning speed and large spot diameter is required. Despite large spot
diameters reduce the energy density, the tested processing condi-
tions ensure enough energy density on the surface of the sample
to induce changes in the morphology of the material. Furthermore,
an increment in the spot diameter allows the treatment of larger
areas which is the reason of the increment in the average roughness.
5000
1,2
2 4000
3000 2,4
v (mm/s)
4 0,6
2000
3,6
6 1000
1,8 3,0 4,2
5
20 25 30 35 5 10 15 20 25 30 35
P (W) P (W)
 A. Riveiro et al. / Applied Surface Science 258 (2012) 9437–9442 9439

a 50000 b 1,0 0,56

0,48
0,390 0,415 0,9
45000
0,8 0,60
40000 0,7

w (mm)
0,465 0,6
35000 0,440 0,52 0,40

f (Hz)
0,5
30000 0,4
0,515
25000 0,3
0,2 0,44
0,490
20000 0,36
0,1
0,565
0,540
0 00 0 00 0 00 0 00 0 00 0
0 0 00 0
0
5 10 15 20 25 30 35 20 25 30 35 40 45 5
P (W) f (Hz)

c 5000
0,475 0,425

4000

3000 0,525
v (mm/s)

2000

1000
0,550 0,500 0,450 0,400

0 0 0 0 0 0 0
00 500 000 500 000 500 000
20 2 3 3 4 4 5
f (Hz)

Fig. 2. Contour plot of average roughness Ra (␮m) versus (a) laser power and pulse frequency, (b) pulse frequency and spot diameter and (c) pulse frequency and scanning
speed during the processing by means 355 nm laser radiation.

In this case, average roughness is below 1 ␮m; however, process-
ing map depicted in Fig. 2 indicates the way to achieve proper
values.
3.1.2. Contact angle analysis
Regarding the contact angle tests, the statistically significant
factor during the processing using the 1064 nm laser radiation
is the combination of pulse frequency, scanning speed, spot
diameter, and pulse overlapping. In order to minimize the con-
tact angle and improve the wettability, the utilization of high pulse
frequency, low scanning speed, low overlapping, and small spot
diameter is required (see Fig. 3). On the other hand, the most influ-
encing factors, using the 532 nm laser radiation, are the scanning
speed, spot diameter, and its interaction. Results depicted in Fig.
4 indicate that the contact angle is reduced when the scanning
speed is low and the spot diameter large. Finally, processing by
means of UV laser radiation (355 nm) is mainly affected by the
pulse frequency, scanning speed, and spot diameter (see Fig. 5).
The contact angle is minimized using low pulse frequencies and
scanning speeds, but large spot diameters. It can be observed that
these requirements also promote a higher average roughness of the
samples.
As depicted in Figs. 3–5, surface treatment at 1064 and 355 nm
induces a lower contact angle, more appropriated for promoting
cell adhesion, than in the case of the processing with 532 nm laser
radiation.

a 50 b 1,0
73,6 72,8 72,0 73,6 75,2 76,0
0,9
72,4
25 0,8
0,7
Sup (%)

w (mm)

0 74,4 0,6
0,5
-25 0,4
74,4
0,3
74,8 74,0 73,2
-50 0,2
72,8
0 0 0 0 0 0 0
00 00 00 00 00 00 00 0,1
20 25 30 35 4 0 45 50 1000 2000 3000 4000 5000
f (Hz) v (mm/s)

Fig. 3. Contour plot of the contact angle  (◦ ) versus (a) pulse frequency and overlapping and (b) scanning speed and spot diameter during the processing by means of the
1064 nm laser radiation.
9440 A. Riveiro et al. / Applied Surface Science 258 (2012) 9437–9442

1,0 the material. In this case, small grooves, with a typical width of
77,466 100 ␮m, were produced. The width of the affected zone is larger
0,9 than in the processing assisted by means of the 1064 nm laser
0,8 radiation and under the same processing conditions. Presence of
debris around the machined grooves, with a poor adhesion, makes
0,7 85,301 these wavelengths not adequate for biomedical applications. On
the other hand, samples treated with UV laser radiation (355 nm)
w (mm)

0,6
show a slight thermal affection. The micrographs depicted in Figs.
0,5 6 and 7 reveal a slight melting of the material as compared to
the burning observed when processing with longer wavelengths.
0,4
UV laser radiation may melt the material as suggested by the
0,3 93,137 disappearance of the scratches in the treated surface as com-
pared to the untreated surface (see Fig. 7). This thermal affection
0,2
81,384 89,219 probably induces the transformation of the material from semi
0,1 crystalline to amorphous, as reported in Ref. [15] during CO2 laser
1000 2000 3000 4000 5000 treatment.
The different effects of the studied wavelengths on the sam-
v (mm/s)
ples can be related to differences in the optical response of the
Fig. 4. Contour plot of the contact angle  (◦ ) versus scanning speed and spot diam- material. Despite, values of absorption coefficients for PEEK, cor-
eter during the processing by means of the 532 nm laser radiation. responding to the studied wavelengths, were not found in the
literature, absorption characteristics can be qualitatively extrap-
olated from etch rates found in the literature. As noted in Ref.
[16], optical absorption is larger for 532 nm laser radiation, then
3.2. Surface characterization for 1064 nm and lower for 355 nm. This different response to
studied wavelengths can explain the ablation of the material for
The comparison of the micrographs depicted in Fig. 6 reveals 532 nm, the burning for 1064 and only a slight thermal affection
a different surface topography for the samples processed with the for 355 nm.
three studied laser wavelengths. The utilization of 1064 nm radi- From the wettability point of view, it was observed, as a
ation produces the burning of the treated surface. On the other general rule, that the contact angle in samples treated with
hand, the 532 nm laser radiation is able to produce the ablation of 1064 nm and 355 nm is similar but lower than in samples treated

a 5000
75,5 b 1,0
72,8 73,6 74,4
0,9
4000 74,5
0,8
73,2
0,7
w (mm)

3000 0,6
v (mm/s)

75,0
74,0
0,5
2000 0,4
73,5
0,3 74,8
1000 75,2
0,2
73,0 74,0 0,1
0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 50 0 0 00 5 0 0 0 00 50 0 00 0
0 00 500 000 500 000 500 000 20 2 3 3 4 4 5
2 2 3 3 4 4 5
f (Hz)
f (Hz)
c 1,0
72,0 74,0
73,0 75,0
0,9
0,8 72,5

0,7
0,6
w (mm)

73,5
0,5
0,4
0,3 74,5

0,2
0,1
1000 2000 3000 4000 5000
v (mm/s)
Fig. 5. Contour plot of the contact angle  (◦ ) versus (a) pulse frequency and scanning speed, (b) pulse frequency and spot diameter, and (c) scanning speed and spot diameter
during the processing by means of the 355 nm laser radiation.
 A. Riveiro et al. / Applied Surface Science 258 (2012) 9437–9442 9441

Fig. 6. SEM micrographs of laser treated surfaces under identical processing conditions by means of the three studied laser wavelengths.

with 532 nm radiation (see Fig. 8). Furthermore, the surface
becomes highly hydrophobic in this case; the contact angle reaches
values around 110◦ because only in this case the ablation of
the material and the formation of grooves is produced. The
hydrophobic nature of the treated areas can be a consequence
of the groove size and spacing as observed during the process-
ing of other materials [17]. This property is not beneficial for
cell adhesion.
The large wettability of samples treated with the UV can be
probably explained as a result of the formation of polar groups
such as hydroxyl, carboxyl and peroxide groups (see Ref. [11]).
Nevertheless, further chemical analysis is required to confirm this
point. This treatment seems to be more adequate for biomedical
applications as compared to the processing by means of 1064 nm
laser radiation because surface of treated samples is depleted from
debris. Moreover, better wettability of samples treated by means
of this laser radiation will promote cell adhesion [18]. Obviously,
these results need to be corroborated “in vitro” and “in vivo” prior
to any tentative to treat the surface of PEEK implants for clinical
applications.

Fig. 7. SEM micrographs of laser treated surfaces by means of 1064 nm and 355 nm laser radiation.
9442 A. Riveiro et al. / Applied Surface Science 258 (2012) 9437–9442
Fig. 8. Optical images of water drops on laser treated areas with 1064, 532, and 355 nm laser radiation and in the base material.
4. Conclusions
Investigations of the influence of the processing parameters on
the roughness and wettability of PEEK samples, treated with 1064,
532 and 355 laser radiation, were carried out by means of statisti-
cally planned experimentation. Results indicated the influence of
the laser wavelength on the characteristics of the treated surfaces.
To increase the surface wettability for improving the adhesive sur-
face properties, which can be beneficial to promote cell adhesion “in
vivo”, the UV (355 nm) laser radiation arises as the most adequate
one.
Acknowledgments
The authors wish to thank the technical staff from CACTI
(University of Vigo) for their help with sample characterization.
This work was partially supported by the EU research project
IBEROMARE (0330 IBEROMARE 1 P), and by Xunta de Galicia
(PGIDIT05TMT30302PR, PR405A2002/11-0, INCITE081R303002ES
and INCITE08PXIB303225PR).
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