d e n t a l m a t e r i a l s 3 0 ( 2 0 1 4 ) 570577

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Bioactive glass particulate ller composite: Effect of

coupling of llers and ller loading on some
physical properties
Onur Oral a, , Lippo V. Lassila a , Ovul Kumbuloglu b , Pekka K. Vallittu a
a

Department of Biomaterials Science & Turku Clinical Biomaterials CentreTCBC, Institute of Dentistry, University
of Turku, Lemminkisenkatu 2, FI-20014 Turku, Finland
b Department of Prosthodontics, Faculty of Dentistry, Ege University, Izmir, Turkey

a r t i c l e

i n f o

a b s t r a c t

Article history:

Objectives. The aim of this study was to investigate the effect of silanization of biostable

Received 16 April 2013

and bioactive glass llers in a polymer matrix on some of the physical properties of the

Accepted 20 February 2014

composite.
Methods. The water absorption, solubility, exural strength, exural modulus and toughness
of different particulate ller composite resins were studied in vitro. Five different speci-

Keywords:

men groups were analyzed: A glass-free control, a non-silanized bioactive glass, a silanized

Bioactive glass

bioactive glass, a non-silanized biostable glass and a silanized biostable glass groups. All

Biostable glass

of these ve groups were further divided into sub-groups of dry and water-stored materi-

Silanization

als, both of them containing groups with 3 wt%, 6 wt%, 9 wt% or 12 wt% of glass particles

Polymers

(n = 8 per group). The silanization of the glass particles was carried out with 2% of gamma-

Composite

3-methacryloxyproyltrimethoxysilane (MPS). For the water absorption and solubility tests,

Biopolymer

the test specimens were stored in water for 60 days, and the percentages of weight change
were statistically analyzed. Flexural strength, exural modulus and toughness values were
tested with a three-point bending test and statistically analyzed.
Results. Higher solubility values were observed in non-silanized glass in proportion to the
percentage of glass particles. Silanization, on the other hand, decreased the solubility values
of both types of glass particles and polymer. While 12 wt% non-silanized bioactive glass
specimens showed 0.98 wt% solubility, 12 wt% silanized biostable glass specimens were
observed to have only 0.34 wt% solubility.
The three-point bending results of the dry specimens showed that exural strength,
toughness and exural modulus decreased in proportion to the increase of glass llers.
The control group presented the highest results (106.6 MPa for exural strength, 335.7 kPA
for toughness, 3.23 GPa for exural modulus), whereas for exural strength and toughness,
12 wt% of non-silanized biostable glass ller groups presented the lowest (70.3 MPa for exural strength, 111.5 kPa for toughness). For exural modulus on the other hand, 12 wt% of
silanized biostable glass ller group gave the lowest results (2.57 GPa).

Corresponding author. Tel.: +90 553 2175103; fax: +90 232 2274053/2273420.
E-mail address: onuora@utu. (O. Oral).

http://dx.doi.org/10.1016/j.dental.2014.02.017
0109-5641/Crown Copyright 2014 Published by Elsevier Ltd on behalf of The Academy of Dental Materials. All rights reserved.

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d e n t a l m a t e r i a l s 3 0 ( 2 0 1 4 ) 570577

Signicance. The silanization of glass llers improved the properties of the glass as well as
the properties of the composite. Silanization of bioactive glass may protect the glass from
leaching at early stage of water storage.
Crown Copyright 2014 Published by Elsevier Ltd on behalf of The Academy of Dental
Materials. All rights reserved.

1.

Introduction

Synthetic hydroxyapatites, bioactive glass (BG) and glassceramics have been used in recent years to transform biostable
implants made of metals and polymer composites into bioactive materials [15]. After the introduction of the rst BG
system, Bioglass 45S5 by Prof. Hench, the system has been
modied by many researchers, and it has been introduced to
the eld of tissue engineering [6,7]. Modications to the composition of BG were undertaken by Andersson et al. [8,9], and
presently BG S53P4 is used in applications where bioactivity and antimicrobial properties are required [10]. The most
prominent feature of BGs is their bioactivity. Bioactivity occurs
through the union of calcium and phosphate groups and
the subsequent formation of a calcium phosphate (CaO-P2 O5 ,
CaP, in short) layer. CaP formation is a tissue-dependent
process, and in vitro bioactivity correlates with in vivo
bioactivity [10,11].
Both biodegradable and biostable polymers are used widely
as biomaterials in medicine and dentistry [1214]. Poly(methyl
methacrylate) (PMMA) is a commonly used biostable polymer used for example in bone cements and dentures [1518].
PMMA has been combined with BG llers to be used as
long bone segmental defect repair materials and in calvarial
implants [1921]. Adhesion between ller and polymer, however, is important in the transfer of load from the matrix to
the ller particles. The BG ller particles, as they are leached
out of the matrix over time, could cause considerable changes
to the properties of the composite under moist conditions.
Silanes as bi-functional compounds can bind the ller particles to the polymer matrix regardless whether the glass is
biostable or leachable. In the latter case, silanization may also
provide protection for leaching, and thus the mechanical properties of the composite may be retained for a longer period of
time. Gamma-3-methacryloxypropyltrimethoxysilane (MPS),
the silane used in this study, is a trialkoxysilane and one of
the most studied silane compounds [2225].
The aim of the study was to evaluate some of the physical characteristics composites containing both bioactive and
biostable glass with regard to the silanization and ller loading
of the glass.

2.

Materials and methods

The resin system for the matrix of the composites was based
on an autopolymerizing methyl methacrylate and ethylene
glycol dimethacrylate (95:5, w/w) monomer system with a
powder component of PMMA (Palapress , Heraeus-Kulzer,
Wehrheim, Germany). Bioactive (particulate size from 315 to
1000 m, Vivoxid LTD., Finland) and biostable glass particles

(granular size from 915 to 1000 m, Vivoxid LTD., Finland),

both silanized and non-silanized, were used as llers in the
composites (Table 1).
The BG and biostable glass particles were measured with
the aid of precision scale of 1 mg (Mettler PM100, Toledo, USA)
and added to the resin in PMMA powder to prepare 3 wt%,
6 wt%, 9 wt%, and 12 wt% composites. Silanization of glass
particles was done before adding them in to the resin as
follows: 2 wt% MPS-silane (98% MPS, lot.0182EH-497, Aldrich)
and for the hydrolysis of the MPS-silane, double the amount
of glass of toluene (99.5%, A.C.S reagent lot.03334ME-157,
SigmaAldrich) were mixed with the glass particles in a
decanter. The silanization decanter was left in a fume hood
for 24 h to evaporate the toluene, and the glass powder was
then dried in 90 C for 3 h.
The glass particle containing resin mixture was poured
into 65 mm 10 mm 3.5 mm stainless steel molds and the
polymerization was carried out according to manufacturers
instructions (10 mL powder/7 mL liquid; under 55 C, 200 kPa
pressure, 15 min curing time) (Ivomat, Typ IP 2, Ivoclar AG.,
Schaan, Liechtenstein). Polymerized specimens were ground
down by 180, 500, 1200-grit (FEPA) silicon carbide papers
(Struers A/S, Rodovre, Denmark) under water cooling with
300 rpm speed (LaboPol-21, Struers A/S, Rodovre, Denmark) to
a thickness of 3 0.1 mm. The specimens dimensions were
controlled by the means of an electronic caliper, and they were
then kept in excicator for 1 week before testing. Test specimens were classied as shown in Table 2. There were eight
test specimens (n = 8) in each of the groups.
The water absorption of the composite specimens was
measured by determining the initial weights of the specimens
before immersion (m1 ) to distilled water and comparing it with
the weight of the specimen after immersion (m2 ). Specimens
were removed from water on days of 1, 2, 3, 7, 14, 21, 30, 45, 60;
dried and weighed after 1 min by the aid of precision scale of
0.1 mg (0.0001 g) (Mettler Toledo AT261 DeltaRang, USA). Ten
values were obtained in this way from each specimen. Water
absorption percentages were determined using the formula
below:
Water absorption% =

m2 m1
100
m1

m1 : initial weight before absorption test (g); m2 : last measured

weight (g).
The mechanical properties of the specimens were measured by a three point bending test performed by universal
testing machine (Lloyd LRX Plus, United Kingdom). Samples
were placed on supports 50 mm apart, and the force applying
tip on the sample in the middle of the two supports. The speed
of the device was set at 5 1 mm/min till fracture occurred.
Flexural strength, exural modulus and toughness data were

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d e n t a l m a t e r i a l s 3 0 ( 2 0 1 4 ) 570577

Table 1 Compositions of glasses used in the study.

Product

Description

Manufacturer

Composition

BG particulates

S53P4 glass system, particulate size

3151000 m
Particulate size 9151000 m

Vivoxid Ltd., Turku, Finland

SiO2 53 wt%, Na2 O 23 wt%,

CaO 20 wt% and P2 O5 4 wt%
SiO2 70 wt%, Na2 O 17 wt%
and CaO 13 wt%

Biostable glass
particulates

Vivoxid Ltd., Turku, Finland

Table 2 Description of test groups used in this study (n = 8/group).

Group

Storage

Description

Control groups
C-d
C-w

Dry
In water, 60 days

Control, no llers
Control, no llers

Non-silanized biostable glass ller groups

BS3-ns-d
BS3-ns-w
BS6-ns-d
BS6-ns-w
BS9-ns-d
BS9-ns-w
BS12-ns-d
BS12-ns-w

Dry
In water, 60 days
Dry
In water, 60 days
Dry
In water, 60 days
Dry
In water, 60 days

Biostable glass, 3%-wt, not silanized

Biostable glass, 3%-wt, not silanized
Biostable glass, 6%-wt, not silanized
Biostable glass, 6%-wt, not silanized
Biostable glass, 9%-wt, not silanized
Biostable glass, 9%-wt, not silanized
Biostable glass, 12%-wt, not silanized
Biostable glass, 12%-wt, not silanized

Silanized biostable glass ller groups

BS3-s-d
BS3-s-w
BS6-s-d
BS6-s-w
BS9-s-d
BS9-s-w
BS12-s-d
BS12-s-w

Dry
In water, 60 days
Dry
In water, 60 days
Dry
In water, 60 days
Dry
In water, 60 days

Biostable glass, 3%-wt, silanized

Biostable glass, 3%-wt, silanized
Biostable glass, 6%-wt, silanized
Biostable glass, 6%-wt, silanized
Biostable glass, 9%-wt, silanized
Biostable glass, 9%-wt, silanized
Biostable glass, 12%-wt, silanized
Biostable glass, 12%-wt, silanized

Non-silanized bioactive glass ller groups

BG3-ns-d
BG3-ns-w
BG6-ns-d
BG6-ns-w
BG9-ns-d
BG9-ns-w
BG12-ns-d
BG12-ns-w

Dry
In water, 60 days
Dry
In water, 60 days
Dry
In water, 60 days
Dry
In water, 60 days

Bioactive glass, 3%-wt, not silanized

Bioactive glass, 3%-wt, not silanized
Bioactive glass, 6%-wt, not silanized
Bioactive glass, 6%-wt, not silanized
Bioactive glass, 9%-wt, not silanized
Bioactive glass, 9%-wt, not silanized
Bioactive glass, 12%-wt, not silanized
Bioactive glass, 12%-wt, not silanized

Silanized bioactive glass ller groups

BG3-s-d
BG3-s-w
BG6-s-d
BG6-s-w
BG9-s-d
BG9-s-w
BG12-s-d
BG12-s-w

Dry
In water, 60 days
Dry
In water, 60 days
Dry
In water, 60 days
Dry
In water, 60 days

Bioactive glass, 3%-wt, silanized

Bioactive glass, 3%-wt, silanized
Bioactive glass, 6%-wt, silanized
Bioactive glass, 6%-wt, silanized
Bioactive glass, 9%-wt, silanized
Bioactive glass, 9%-wt, silanized
Bioactive glass, 12%-wt, silanized
Bioactive glass, 12%-wt, silanized

determined as previously [13,14,2629]. Formulas for calculation of strength, modulus of elasticity and toughness were:

b: sample width (mm); h: sample thickness (mm); d: highest

bending value (mm).

3FL
T.S. =
2 b h2

Toughness =

T.S.: exural strength (N/mm2 = MPa); F: load at time of failure (N), l: distance between the supports (mm); b: sample width
(mm); h: sample thickness (mm).

Toughness (J/m3 , N/m2 , MN/m3 , MPa); : amount of strain; f :

amount of stress at time of failure; : amount of stress.
Solubility percentages were obtained by subtracting the
absorption percentages of the specimens from percentages of
mass loss after drying. The mass loss percentages of the composites were tested immediately after three-point bending test
by rst weighing the specimens wet (m3 ) and then drying them
for nine days at 80 C and weighing again (m4 ). The weights

Y.M. =

Stress
P l3
=
Strain
4 b h3 d

Y.M.: Flexural modulus (N/mm2 , MN/m2 , MPa, GPa); P: load

at time of failure (N); l: distance between the supports (mm);

d
0

d e n t a l m a t e r i a l s 3 0 ( 2 0 1 4 ) 570577

1.85
BS12-s-w
BS3-s-w

1.8

C-w
BG12-s-w

1.75

BS6-s-w
BG9-s-w

BS9-s-w
BS3-ns-w

1.7
BG3-ns-w

BS9-ns-w

wt-% Water absorpon by day

1.65

BG3-s-w
BS12-ns-w
BG6-s-w

1.6

BS6-ns-w

1.55

573

Solubility percentages were calculated using the following

formula:
(Solubility%) = (Mass loss%) (Water absorption%)
Statistical analysis was carried out with SPSS 15.0 for
Windows (SPSS Inc., Chicago, USA) package program. Water
absorption results were evaluated by Shapiro-Wilk test to
demonstrate normal distribution of the data. Differences
between groups were evaluated by one-way ANOVA and Dunnett T3 test (p < 0.05). Solubility, exural strength, exural
modulus, toughness results were evaluated by Shapiro-Wilk.
Differences between groups were evaluated by KruskalWallis
and MannWhitney tests (p < 0.05).

1.5

3.

1.45
1.4
1.35

BG6-ns-w

1.3
BG9-ns-w

1.25
BG12-ns-w

1.2
Day-14

Day-21

BS3-ns-w
BS3-s-w
BG3-ns-w
BG3-s-w
C-w

Day-30

BS6-ns-w
BS6-s-w
BG6-ns-w
BG6-s-w

Day-45

BS9-ns-w
BS9-s-w
BG9-ns-w
BG9-s-w

Day-60

BS12-ns-w
BS12-s-w
BG12-ns-w
BG12-s-w

Fig. 1 Weight gain of specimens in water by day.

of the specimens were monitored during this period to conrm they had dried completely. Mass loss percentages of the
samples were then calculated by the formula below:
Mass loss% =

m m 
4
3
m3

100

m3 : initial weight before solubility test (g); m4 : last measured

weight (g).

Results

The water absorption of composites is presented in

Figs. 1 and 2, and weight gain in relation to storage time in
water in Fig. 1. The highest and lowest values observed in the
water absorption test were in groups BS12-s-w (1.83 0.04%wt) and BG12-ns-w (1.21 0.07%-wt). In the non-silanized
glass ller groups, 3%-wt groups showed no signicant difference to the control group (p > 0.05). In silanized glass
ller groups, only BG3-s-w and BG6-s-w groups were the
only groups which showed signicant difference to the
control group (p < 0.05). All in all, water absorption values
had a tendency to decrease with increasing proportions of
non-silanized glass ller, and to increase with increasing proportions of silanized glass ller. These changes were found
statistically signicantly different (p < 0.05). Generally, the
weight of the specimens increased during the 60 days period
with exception of groups BG6-ns-w, BG9-ns-w, BG12-ns-w
which showed reduction in weight after being stored in water
for more than 30 days (Fig. 1), and thus, maximum absorption
values for BG6-ns-w and BG9-ns-w groups were observed on
day 30. The BG12-ns-w groups highest water absorption value
was observed on day 21. The BG3-s-w, BG6-s-w, BG9-s-w and
BS12-ns-w groups peak values were observed on day 45.
The solubilities of the different composites are given in
Fig. 3. The highest solubility value was observed in BG12ns-w (0.98 0.03%-wt) and the lowest value in BS12-s-w
(0.34 0.03%-wt). Solubility values of biostable glass ller

Fig. 2 Water absorption values of sub-groups on day 60.

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d e n t a l m a t e r i a l s 3 0 ( 2 0 1 4 ) 570577

Fig. 3 Solubility percentages of sub-groups on day 60.

groups except BS12-s-w showed no signicant difference in

comparison to the control group (p > 0.05). However, in the BG
ller groups, most sub-groups except BG3-ns-w and BG9-s-w
showed signicant differences compared to the control group
(p < 0.05). As a whole, solubility values decreased with increasing proportions of silanized glass and increased in proportion
to non-silanized BG glass, and these differences were found
signicantly different (p < 0.05).
Flexural strength was found to be highest in the control
group (Fig. 4), and dry specimens were found to show higher
strength than water stored specimens (p < 0.05). In dry specimens, increased quanties of glass llers lowered the exural
strength. However, only the 12 wt% glass ller sub-groups
showed signicant differences in wet specimens. Silanization
of the llers, on the other hand, was not found to confer a signicant difference to the exular strength of the composites
(p > 0.05) (Fig. 4).
Flexural modulus was signicantly decreased by the addition of glass llers in all specimens (p < 0.05). The ller
silanization was observed with lower results than nonsilanized groups (Fig. 5).
Toughness was reduced by glass llers in all dry specimen groups, whereas in wet specimens, only 12%-wt biostable
glass ller groups showed reduction. Other wet specimen subgroups were not signicantly different in comparison to the
control group (p > 0.05) (Fig. 6).

4.

Discussion

Materials that combine biologically and clinically important

properties, such as the capability to provide an osteoconductive or osteoinductive surface and long term retention of
strength, are desired in bone reconstructions. One group of
materials that could provide such properties may be composites of bioactive glass and PMMA. Therefore the present study
focused on the characterization of composites of bioactive
glass and PMMA.
The concept of hybrid materials utilizing favourable
features of different constituent materials proposes a reduction in unfavourable initial properties. However, integration
between the components of hybrid materials has to be
attained [3032]. For this purpose, organic and inorganic
components were bound reciprocally by coating glass ller
particles with silanol groups by hydrolysis of MPS-silane [33].

Special emphasis in the study was given to the behaviour of

bioactive glass particles in the composites, as they are subject
to dissolution in aqueous environments. In some composite
groups particles were coupled to the polymer matrix by silane
in order to slow down the leaching of the glass ller particles. Dissolution of bioactive glass in the polymer matrix of
composite is based on water absorption to the matrix. It is
known that in immersed solutions high polymer solubility has
a negative effect on the physical properties of the material
[3436]. It is also known that the hydrophobicity of a material
is related to its water absorption and solubility [37,38]. Water
absorption in a polymer matrix occurs by diffusion and it is
related to the amount of ller content, as ller reduces the
volume of the polymer matrix phase and creates potential
paths for water diffusion through the interphases between
the matrix and llers. Thus, water absorption and solubility
have to be studied in order to understand the properties of a
material [34,39]. Certain biopolymers and bioactive glasses are
vulnerable to water absorption and solubility. These materials
can take components from the immersed solution and leach
their components to the liquid. These leached components
can generate tissue reactions [17,40].
In the present study, water absorption testing was performed on cumulative days to receive an understanding of
weight stabilization. In the water absorption test, it was
observed that non-silanized glass ller groups had lower
absorption than silanized ller groups. Generally, ller loaded
materials showed lower water absorption than control materials without llers. In principle, the group with 12 wt% glass
ller should have had the lowest water absorption of the
tested materials, but this was found only in the case of nonsilanized bioactive glass llers. Higher water absorption with
biostable glass llers may reect the existence of minor gaps in
the structure of the composite, which increase water absorption. Comparison of silanized and non-silanized llers in
terms of water absorption demonstrated that water absorption was slightly higher in the groups with silanized glass
ller (Figs. 1 and 2). This may be due to polysiloxane networks
caused by silanization and the tendency of water to diffuse
into the polysiloxane network more readily than into the
PMMA polymer matrix.
In general, solubility results were opposite to water absorption results: where lower water absorption values were
measured, higher solubility values were observed, as for
example, in non-silanized glass ller groups. Increasing the
loading of silanized glass llers, both bioactive and biostable,
was found to decrease solubility. The decreasing solubility in
the silanized glass ller groups can be attributed to the protection of the glass structure by the silane based polysiloxane
network. In addition, the bioactive glass groups were observed
to have higher solubility than the biostable glass groups (Fig. 3).
This result can be associated with the difference of the composition and structure of the two types of glass. Biostable
glass has a tetrahedron structure resistant to reactions, while
bioactive glass has a structure more open to reactions with
cations. Cations in bioactive glass disrupt the continuity of
SiOSi links and this process results with formation of nonbridging oxygen ions. The amount of non-bridging oxygen
ions is directly related to the bioactivity of bioactive glass
[10,41,42].

d e n t a l m a t e r i a l s 3 0 ( 2 0 1 4 ) 570577

575

Fig. 4 Flexural strength values of sub-groups on day 60.

Discontinuity and stress transfer interruption in the main

matrix by ller particles was prevented by saturating the particles by viscous acrylate using silane coupling agents to provide
a stronger bond between the substrate and ller [36]. It has
been reported that the polymerization and structure of the
polymer is not affected by MPS-silane [43]. In fact, silane
reduces the amount of monomer required for the saturation
of the glass ller. Thus, the adverse effects of monomers can
be reduced [44].
The long-term function of a material depends on its physical properties, of which load-bearing capacity is clinically the
most important. Particulate llers in composites do not efciently reinforce a material against bending and tensile forces.
Fillers of higher aspect ratio, namely bers, have considerably
better reinforcing and toughening capabilities than particulate
llers [45]. From this perspective the decrease of transverse
strength and toughness and the increase of transverse modulus in dry specimen groups were what was to be expected due
to the features of glass llers. However, polymer properties
were found to have no change when immersed in an aqueous
environment (Figs. 46).

Test specimens were subjected to a three-point bending

test immediately after the conclusion of the absorption test.
According to ISO 1567:1999 standards, transversal strength
of polymers must be at least 65 MPa. In our study, samples containing glass as llers showed values between 70.3
and 104.8 MPa, which is sufcient for ISO standards (Fig. 4).
However, novel composite materials for clinical applications,
especially leachable llers, cannot necessarily be judged by
ISO standards. After the three-point bending test the specimens were placed back in their solutions for the solubility
test which was carried out the same day. Percentage changes
in weights due to material loss in the three-point bending test
were taken into consideration in the solubility calculations.
In the literature, there are various interpretations of the
implications of materials modied by glass llers. Researchers
agree on the course of the physical degradation of polylactids
and hybrid polylactid materials with BG ller in vitro [36,46,47];
on the other hand, in vivo physical properties were found to
be better due to bioactivity and enhanced bonding to living
tissues promoted by BGs [48]. Likewise, it has been stated
that polylactids containing BG coupledby MPS-silane confer

Fig. 5 Flexural modulus values of sub-groups on day 60.

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d e n t a l m a t e r i a l s 3 0 ( 2 0 1 4 ) 570577

Fig. 6 Toughness values of sub-groups on day 60.

improved strength, osteoblastic activation and osteoconductivity properties in vivo [49]. According to our ndings, hybrid
materials have to be applied carefully until bioactivity occurs,
and not be implanted on load-bearing areas if the hybrid material contains over 12%-wt of glass ller. One alternative to
increase the strength of the composite could be the utilization of ber reinforcements of high aspect ratio to reinforce
the particulate ller composite [10].
In this study, the modication of polymers by glass particles was investigated in vitro. Next, our ndings should be
compared to in vivo results and investigate more in detail how
silanes may alter bioactivity of the bioactive glass.

5.

Conclusion

The main ndings obtained in this study are as follows:

1. According to the results of the water absorption and solubility tests, the highest water absorption was observed
in non-silanized BG groups. Increasing the amount of
glass ller loading decreased water absorption while at the
same time increasing solubility. After silanization, however, solubility decreased with increasing proportions of
both bioactive and biostable glass.
2. Dry composite specimens showed lower physical values
with increasing glass ller loading, whereas the exural
properties of water-stored specimens did not alter with
increasing glass proportions.
3. The coupling of glass ller particles with silane improves
the resistance of the composite resin against weakening
caused water and may protect bioactive glass llers from
leaching.

Acknowledgements
This research was nancially supported by CIMO (Centre for
International Mobility) and it was carried out in Turku Clinical
Biomaterials Centre - TCBC, University of Turku, Finland. This
research is part of the BioCity Turku Biomaterials Research

Program (www.biomaterials.utu.). Minttu Vigren, Genevieve

Alfont and Hanna Mark are thanked for their help with tests in
TCBC. Professor Jukka Matinlinna (University of Hong Kong) is
thanked for sharing his silane studies with us. Timothy Wilson
is thanked for proofreading the manuscript.

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