J O U R N A L O F T H E M E C H A N I C A L B E H AV I O R O F B I O M E D I C A L M AT E R I A L S 6 (2012) 128–138

Available online at www.sciencedirect.com

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

Research paper

Using scratch testing to measure the adhesion strength of

calcium phosphate coatings applied to
poly(carbonate urethane) substrates

Dunstan Barnes a,∗ , Scott Johnson b , Robert Snell b , Serena Best a

a Cambridge Centre for Medical Materials, Department of Materials Science & Metallurgy, University of Cambridge, UK
b Ranier Technology Limited, Cambridge, UK

A R T I C L E I N F O A B S T R A C T

Article history: Bioactive coatings are applied to components of modern orthopædic implants to improve
Received 15 June 2011 the host tissue response to the implants. Such coatings cannot be applied to polymeric
Received in revised form implants by high-temperature techniques, because the use of high temperatures may
30 September 2011 critically degrade the polymer substrate. Regardless of the coating technique that is used,
Accepted 1 October 2011 the coating must be sufficiently well adhered to the underlying substrate to provide any
Published online 17 November 2011 practical benefit.
This paper investigates the use of scratch testing to measure the adhesion strength of
Keywords: calcium phosphate (CaP) coatings that were applied to a poly(carbonate urethane) (PCU)
Scratch testing substrate by an aqueous process at temperatures of 19, 28, 37, and 50 ◦ C. This work
Adhesion strength represents the first time that scratch testing analysis has been used to study CaP coatings
Thin coatings deposited by an aqueous, low-temperature process on to a polymer substrate.
Compliant substrate Scratch testing was shown to be a useful technique for obtaining comparative, rather
Calcium phosphate than absolute, values of adhesion strength for hard coatings formed on a compliant
CaP substrate. Generally, the coating temperature was not found to influence the CaP–PCU
Poly(carbonate urethane) adhesion strength. Although CaP coatings formed at 19 ◦ C exhibited considerably lower
PCU adhesion strengths than CaP coatings formed at 28, 37, and 50 ◦ C, this finding was
attributable to the inconsistency of CaP coatings formed on the PCU substrates at 19 ◦ C.
The coating–substrate adhesion strength was measured for CaP coatings of four
different coating ages (0, 1, 2, and 3 years). CaP coatings that were aged for 0, 1, or 2
years exhibited similar coating–substrate adhesion strengths to each other. In contrast,
CaP coatings that were aged for 3 years demonstrated considerably lower coating–substrate
adhesion strengths. The observed reduction in adhesion strength with age was thought to
be attributable to suspected “drying out” of the CaP coatings.
⃝c 2011 Elsevier Ltd. All rights reserved.

∗ Corresponding author. Tel.: +1 312 909 5361.

E-mail addresses: dunstan.barnes@cantab.net (D. Barnes), scott.johnson@ranier.co.uk (S. Johnson), robert.snell@ranier.co.uk
(R. Snell), smb51@cam.ac.uk (S. Best).

c 2011 Elsevier Ltd. All rights reserved.

1751-6161/$ - see front matter ⃝
doi:10.1016/j.jmbbm.2011.10.010
 J O U R N A L O F T H E M E C H A N I C A L B E H AV I O R O F B I O M E D I C A L M AT E R I A L S
1. Introduction
Previous research into the adhesion strength of thin
calcium phosphate (CaP) coatings applied to a polymeric
substrate by aqueous, low-temperature processes has utilised
inappropriate measurement techniques. For example, pull-
off testing was used to test the adhesion strength of
such coatings (Tanahashi et al., 1995), even though such
a technique is appropriate only for coatings thicker than
0.38 mm, due in part to possible penetration of the epoxy
bonding agents into the coating (ASTM, 2008). Tape peel
testing has also been used (Miyazaki et al., 2003), and
although this technique is useful as an initial test of adhesion
strength, it does not provide quantitative data and may not
be reproducible (Chalker et al., 1991). There is thus a genuine
need for an accurate, reproducible, quantitative adhesion
strength testing technique that can be used to test thin
coatings on compliant substrates, where “compliant” means
that the substrate material is significantly less stiff than the
applied coating material.
1.1. Calcium phosphate coatings
Modern orthopædic implants are often coated with a
bioactive material to improve the host tissue response to
the implant. “Bioactive” materials are materials that elicit a
chemical reaction between the surrounding host tissue and
the material to form an interfacial chemical bond (Hench
et al., 1993). Several materials in the CaP family are known
to exhibit bioactivity when implanted in vivo. Indeed, the
formation of a bone-like carbonate-containing apatite (a
calcium phosphate) layer on the surface of a material has
been hypothesised to be an essential requirement for a
biomaterial to bond to living bone (Nakamura et al., 1985;
Ducheyne, 1987; Woesz and Best, 2008). Previous research
has reported that bone bonds to hydroxyapatite (i.e. a
calcium phosphate) through both a chemical bond and a
mechanical interlock (Geesink et al., 1987; Cook et al., 1988).
Transmission electron microscopy studies by Porter et al. have
suggested that collagen fibrils perpendicular to the surface
of hydroxyapatite play a major role in bone apposition by
forming a mechanical interlock between the host tissue and
the implant (Porter et al., 2002, 2004).
1.2. Poly(carbonate urethane)
Polyurethanes have been used in a range of biomedical
applications, including intra-aortic balloons, catheters, and
pacemaker leads (Lelah and Cooper, 1986; Gogolewski, 1991;
Zhao et al., 1991; Stokes et al., 1995; Bergeron et al., 2001).
Although polyurethanes have exhibited excellent material
properties for implantable medical devices, including high
tensile strength, lubricity, abrasion resistance, and formabil-
ity (Pinchuk, 1994; Christenson et al., 2004; Wiggins et al.,
2004), the use of polyurethane implants has been somewhat
limited by their long-term instability in certain biological en-
vironments (Szycher, 1988; Tang et al., 2001).
The long-term stability of poly(carbonate urethanes) tends
to be much greater than that of both poly(ether urethanes)
and poly(ester urethanes) (Pinchuk, 1994; Tanzi et al., 1997),
6 (2012) 128–138 129
which are prone to degradation in oxidative environments
(Pande, 1983; Szycher and McArthur, 1985). There is evidence
that poly(carbonate urethanes) have better biocompatibility
than poly(ether urethanes), based on in vitro tests (Hsu et al.,
2004).
The particular poly(carbonate urethane) (PCU) used in this
study was produced by Ranier Technology for use as endplate
material in an orthopædic implant for the spine. The PCU
endplate material contains carboxylic acid groups (-COOH)
that are designed to enhance the bonding of metal ions to
the surface and thus improve the nucleation and growth of
calcium phosphate layers on the PCU surface.
1.3. Applying a CaP coating to a PCU substrate
There are numerous techniques for applying CaP coatings
to substrates. Most commercially available hydroxyapatite
coatings are produced by plasma spraying (León, 2009).
However, plasma spraying is a high-temperature technique.
Plasma spraying is unsuitable for applying coatings to PCU
substrates, because temperatures above approximately 150 ◦ C
may degrade the PCU substrate (Eceiza et al., 2008), which
would severely compromise the PCU’s mechanical properties
and render it useless as a load-bearing implant. Therefore,
coatings must be applied to PCU substrates at temperatures
below 150 ◦ C.
Low-temperature aqueous deposition techniques have
gathered interest in recent years (Ohtsuki et al., 1995; Barrere
et al., 2000; Habibovic et al., 2002; Oyane et al., 2003;
Takadama et al., 2004; Tas and Bhaduri, 2004; Kim et al.,
2006; Lu et al., 2007; Kokubo et al., 2009). Many of these
techniques involve forming a CaP coating by immersing
the substrate material in a concentrated ionic solution. The
method used to apply a coating can be a major factor in
the coating–substrate adhesion strength. For hydroxyapatite
coatings, different coating methods have been shown to
result in significant differences in adhesion strength (Yang
and Chang, 2001; Zhang et al., 2006; Pichugin et al., 2008).
1.4. Adhesion strength testing
Coatings must exhibit sufficient adhesion to the underlying
substrate to provide any practical benefits. A weakly adhered
coating on a medical implant may delaminate after implan-
tation, which could severely limit the effectiveness of the im-
plant (Lacefield, 1993).
No single adhesion strength testing technique is univer-
sally accepted or applicable in all coating–substrate situ-
ations. An ideal adhesion strength testing method would
measure only the coating adhesion; however, all known test-
ing methods are affected by other properties of the coating
and substrate system (Valli, 1986). The most appropriate test
is usually one that most closely simulates usage stress condi-
tions (Mittal, 1995).
Pull-off testing is a quick, inexpensive method for mea-
suring coating–substrate adhesion strength that has become
widely used because it provides absolute numbers of adhe-
sion strength, which allows for direct comparison of adhe-
sion strengths (García-Sanz et al., 1997). In pull-off testing, a
cylinder of substrate material is coated on its top face and
adhesively bonded to an uncoated cylinder, using glue or
130 J O U R N A L O F T H E M E C H A N I C A L B E H AV I O R O F B I O M E D I C A L M AT E R I A L S
epoxy resin (Valli, 1986; Chalker et al., 1991). A normal tensile
force is applied to pull the cylinders apart, and the adhesion
strength is defined as the applied stress at which failure of
the coating–substrate bond occurs (Chalker et al., 1991).
Despite its widespread use, pull-off testing has several
disadvantages. The pull-off test described in ASTM Standard
C633-01 is only appropriate for plasma-sprayed calcium
phosphate coatings thicker than 0.38 mm, due to penetration
of the epoxy bonding agents or the development of additional
stresses in the coating layer (ASTM, 2008). Tsui et al.
(1998) performed pull-off testing in accordance with ASTM
C633, on coatings of thicknesses below 380 µm, and found
that misleadingly high strengths were obtained when the
adhesive penetrated the coating (Tsui et al., 1998).
Further, to avoid uneven peeling of the coating, uniform
tensile stress must be produced throughout the test area
during pull-off testing; however, in practice, uneven peeling
occurs because it is difficult to apply uniform loading to
the entire test area (Steinmann and Hintermann, 1989).
And for orthopædic implants that are primarily loaded in
compression, pull-off testing does not effectively simulate
stress loading conditions during use, and therefore it is not,
under Mittal’s criterion, the most effective measurement of
adhesion strength (Mittal, 1995).
Scratch testing is a simple, semi-quantitative technique
that can be used to measure the adhesion strength of
a variety of coating–substrate systems. The advantages of
scratch testing include (1) that it simulates the usage stress
conditions of orthopædic implants more closely than tensile
adhesion strength testing techniques and (2) that it can
be used to measure the adhesion strength of thin coatings
without the risk of bonding agents penetrating the coating.
Scratch testing involves applying a normal load to the surface
of a sample through a stylus while the stylus is displaced
relative to the sample at a constant speed (Valli et al., 1985).
The critical load is the normal force at which the coating fails,
and it can be used as a comparative measure of adhesion
strength (Valli et al., 1985).
One of the main difficulties with scratch testing is the
determination of critical load (Ollivier and Matthews, 1995).
During scratch testing, complete detachment of the coating is
not always observed when the coating fails (Perry, 1981), and
coatings fail in a number of different ways, including spalling,
buckling, chipping, conformal cracking, and tensile cracking
(Feddes et al., 2009).
There are several techniques that are used to detect
the critical load, Lc , of which microscopic examination is
believed to provide the most information (Sekler et al.,
1988). Due to the numerous variable parameters involved in
scratch testing, it remains a more valuable test as a relative
comparison between similar film–substrate combinations
rather than an absolute measurement of adhesion strength.
Despite potential drawbacks, scratch testing is one of the few
adhesion strength testing techniques that relates practical
levels of adhesion to the performance of real components in
service (Chalker et al., 1991).
The expected failure mode for a brittle coating (e.g. CaP)
on a ductile substrate (e.g. PCU) under compressive loading
is by buckling (Bull, 1991). If the coating–substrate adhesion
is good, the buckling should propagate through the coating;
if the adhesion is poor, the buckling should propagate at the
coating–substrate interface (Bull, 1991).
6 (2012) 128–138
1.5. Research aims
Although scratch testing has been used to measure the
adhesion strength of thin CaP coatings applied to titanium
substrates (Wang et al., 2004; Forsgren et al., 2007), it has not
been used to measure the adhesion strength of CaP coatings
applied to compliant substrates.
The aims of the present research are (1) to examine
whether scratch testing can provide a suitable method for
measuring the adhesion strength of thin calcium phosphate
coatings applied to a compliant substrate, and, if it is a
suitable method, (2) to use scratch testing to analyse changes
in adhesion strength as a function of deposition temperature
and coating age.
2. Materials and methods
2.1. Samples
Square PCU samples of height and width 20.0 mm and
thickness 1.1 mm were formed by injection moulding.
The particular poly(carbonate urethane) used in the study
contained carboxyl (-COOH) groups, which were incorporated
in the PCU to enhance the formation of CaP coatings on the
PCU surface, similar to previous research that used polyamide
substrates (Miyazaki et al., 2003). The PCU squares were
coated with CaP by immersing them in a concentrated coating
solution for five hours at a temperature of 19, 28, 37, or
50 ◦ C. The concentrated coating solution was adapted from
Kokubo’s Simulated Body Fluid (SBF) (Kokubo et al., 1990),
but contained calcium and phosphate ionic concentrations
approximately equal to ten times their typical concentration
in SBF, similar to previous research (Tas and Bhaduri, 2004).
In the present research, these enhanced ionic concentrations
were used to significantly increase the rate of CaP coating
deposition. After the coating process, the samples were
carefully washed three times in deionised water.
2.2. Calcium phosphate coating characterisation
Scanning electron microscopy (SEM), Fourier transform infra-
red-attenuated total reflectance (FTIR-ATR), X-ray diffraction
(XRD), and white light interferometry (WLI) analysis tech-
niques were used to characterise the PCU substrate and CaP
coatings.
SEM was used to examine the surface microstructure and
morphology of the PCU substrate and CaP coatings as well as
the thickness of the CaP coatings. A JEOL 5800-LV microscope
equipped with INCA software was used to collect micrographs
at an accelerating voltage of 10–15 kV. Samples were sputter
coated with a thin layer of palladium (Pd) for 90 s at 30–40 mA
prior to SEM analysis.
A Perkin Elmer Spectrum One FTIR Spectrometer was
used in direct contact mode to analyse the chemical bonds
present near the surface of uncoated and CaP-coated PCU
squares. The transmittance of infra-red waves was measured
for wavenumbers between 4000 and 510 cm−1 at a resolution
of 4 cm−1 . Sample and background scanning frequencies of
eight scans were used. At least three points on the surface
 J O U R N A L O F T H E M E C H A N I C A L B E H AV I O R O F B I O M E D I C A L M AT E R I A L S
were analysed for each sample, and at least two samples were
analysed per sample group.
XRD was used to characterise the crystallographic
structure of the CaP coatings on the PCU substrate. A Philips
Gen1 X’Pert X-ray generator (operated with Cu Kα radiation at
40 kV and 40 mA) was used for XRD analysis. A divergence
slit of 12 ◦ , anti-scatter slit of 12 ◦ , and receiving slit of 0.2 mm
were used to scan each coated sample from 20◦ to 45◦ 2θ with
a step size of 0.1◦ 2θ and dwell time of 15 s. X’Pert HighScore
Plus software was used to analyse the XRD spectra.
A Wyko RST-Plus white light interferometer (Wyko
Corporation) in vertical scanning interferometry (VSI) mode
was used to assess the surface roughness. White light
interferometry (also known as optical profilometry) provides
a measure of the surface roughness by reflecting a beam of
white light off of the surface of a sample and comparing
the path difference with a beam of white light reflected off
a reference material. At least three points on the surface of
at least two samples were analysed for each sample group,
to generate average values of Ra and Rq . The average surface
roughness, Ra , is the arithmetic mean deviation of all points
from a plane fit to the test surface. Rq , also known as RMS,
is the root-mean-square average of the measured height
deviations taken within the evaluation area and measured
from the mean linear surface. Rq represents the standard
deviation of profile heights.
2.3. Scratch testing
A micro-scratch testing device (known as the CUED scratch
tester), developed and built by the Cambridge University
Engineering Department (CUED), was used to perform scratch
testing. The CUED scratch tester works by lowering an
indenter connected to a solid spring onto a coated sample in
order to simulate a single asperity contact.
Prior to scratch testing, square CaP-coated PCU samples
were fixed to an aluminium sample holder before being
loaded into the CUED scratch tester. Samples were fixed in
place with a drop of Loctite⃝ R
Super Glue and compressed by
applying pressure to opposite edges of the sample for 30 s
until the Super Glue had set. To prevent contamination, nitrile
gloves were worn when handling samples.
A 500 µm radius stainless steel spherical ball indenter
was used as a stylus. The ball indenter was wiped between
scratches with a clean cloth to remove any debris, and
wiped with ethanol between different samples. Load was
applied to the sample via the ball indenter attached to a
solid spring, and lowered onto the sample. The sample stage
was connected to a precision motor that provided horizontal
motion to generate a scratch across the surface of a sample.
Strain gauges in a Wheatstone Bridge arrangement were used
to measure the deflections normal and tangential to the
surface of the sample. The measured normal strain arose
from the normal load applied via the ball indenter, while the
measured tangential strain was generated by the tangential
frictional force created as the ball indenter moved across
the sample surface. Calibration factors were calculated by
applying a series of known loads to the load cell, and they
were used to convert the measured strains to be converted
into forces.
6 (2012) 128–138 131
The temperature inside the room containing the CUED
scratch tester was maintained at 21 ◦ C. Since the strain
gauges are sensitive to temperature, the load cell was
switched on one hour prior to testing to allow the strain
gauges to warm up. Prior to each scratch, the Wheatstone
Bridge was balanced to overcome any changes in measured
strain resulting from thermal drift.
The critical normal loads for initial delamination, Lc1 , and
total delamination, Lc2 , of the coating were recorded. Lc1 was
defined as the load at which the coating layer began to fail,
as indicated by severe cracking or detachment of segments of
the CaP coating. Lc2 was the load associated with failure of the
CaP coating across the whole scratch width. Lc1 and Lc2 were
assessed using SEM analysis subsequent to scratch testing.
Two critical loads were used to provide a better understanding
of the coating behaviour, similar to previous research (Wang
et al., 2004).
The coating–substrate adhesion strength was measured in
relation to two variables: coating temperature and coating
age. Scratch testing was performed on batches of PCU squares
that had recently been coated at temperatures of 19, 28, 37,
and 50 ◦ C and on batches of PCU coated at 28 ◦ C 0, 1, 2,
and 3 years prior to scratch testing. Three samples from each
coating batch were used. Each sample was scratch tested
in two series of scratches. Within each scratch series, each
scratch was spatially separate from each other scratch, and
the normal load was increased between each scratch. The
reported critical loads were determined by averaging the data.
After scratching, the samples were removed from the
sample holder and mounted on SEM stubs to allow for
microscopic analysis of the scratches. Samples were sputter
coated with palladium prior to SEM and energy-dispersive X-
ray spectroscopy (EDX) analysis. Palladium was selected to
avoid peak interference during the EDX analysis.
2.4. Mean contact pressure and reduced Young’s modulus
According to Hertz’s theory, the pressure distribution in the
contact area beneath a spherical indenter follows a semi-
elliptical distribution, with a mean contact pressure, pm ,
given by Johnson (1985)
 1
2 6LN E∗2 3
pm = , (1)
3 π3 R2
where LN is the applied normal force, R is the radius of the ball
indenter, and E∗ is the reduced Young’s modulus. The reduced
Young’s modulus was calculated using the relation (Oliver and
Pharr, 1992)
1 (1 − ν2s ) (1 − ν2i )
= + , (2)
E∗ Es Ei
where νs and νi are the Poisson ratios of the sample and
indenter, respectively, and Es and Ei are the Young’s moduli
of the substrate and indenter, respectively.
Microindentation tests demonstrated that the mechan-
ical properties of CaP-coated PCU substrates were domi-
nated by the mechanical properties of the PCU substrate
(results not shown). With similar mechanical properties,
Es(uncoated−PCU) ∼ = Es(CaP−coated−PCU) . The properties used to
calculate the reduced Young’s modulus are shown in Table 1.
132 J O U R N A L O F T H E M E C H A N I C A L B E H AV I O R O F B I O M E D I C A L M AT E R I A L S
Fig. 1 – SEM micrographs from the surface of PCU samples that were (a) uncoated; (b) CaP coated at 19 ◦ C; (c) CaP coated at
28 ◦ C; (d) CaP coated at 37 ◦ C; and (e) CaP coated at 50 ◦ C.
2.5. Post-scratch analysis
Secondary electron imaging (SEI) in a scanning electron
microscope was used to examine the damage that scratch
testing caused to the CaP coatings applied to PCU substrate
material. A JEOL 5800-LV microscope equipped with INCA
software was used to collect micrographs. An accelerating
voltage of 10–15 kV was used during analysis. Energy-
dispersive X-ray spectroscopy (EDX) within the JEOL 5800-LV
microscope provided a semi-quantitative assessment of the
elemental surface composition of each sample.
3. Results and discussion
3.1. Calcium phosphate coating characterisation
3.1.1. Scanning electron microscopy (SEM)
The surface of an uncoated PCU sample is shown in Fig. 1(a).
PCU samples that were coated with CaP at different tempera-
tures are shown in Fig. 1(b)–(e).
SEM micrographs can be used to qualitatively identify
CaP phases based upon their morphology. Apatite coatings
deposited by an aqueous low-temperature method typically
have a fine-scale microstructure containing submicron-sized
apatite crystals, which are observable in results reported
by Liu and Hunziker (2009); Kokubo and Takadama (2006).
Brushite (DCPD) crystals tend to be plate like and micron
sized, with crystal lengths and widths much greater than
their thicknesses (Arifuzzaman and Rohani, 2004). Monetite
6 (2012) 128–138
Table 1 – Material properties used to calculate the
reduced Young’s modulus. Steel values are from (Boyer
and Gall, 1984); the Poisson ratio of PCU was assumed to
be 0.5, as in previous research on poly(carbonate
urethanes) (Christenson et al., 2004); and the Young’s
modulus of PCU was measured by compression testing
(results not shown).
Material Poisson ratio Young’s
modulus (MPa)
Steel (ball indenter) 0.29 200,000
PCU (substrate) 0.50 109
Calculated reduced Young’s modulus 145
(DCPA) crystals tend to have a more block-like than plate-
like morphology when compared to brushite crystals (Asaoka,
1996; Prado da Silva et al., 2001). The typical morphologies
of DCPD and DCPA crystals are distinct from the typical
morphology of apatite crystals (Asaoka, 1996; Barrere et al.,
2002; Müller and Müller, 2006).
Based on the SEM micrographs, CaP coatings formed on
PCU at 19 ◦ C consisted primarily of monetite, but did not form
a fully contiguous layer across the PCU surfaces. A contiguous
coating layer consisting of both monetite and apatite was
formed during CaP deposition at 28 ◦ C. CaP coatings formed
at 37 and 50 ◦ C were contiguous and composed primarily of
apatite.
Fig. 2 shows SEM micrographs of cross-sections of CaP
coatings formed on PCU at 28, 37, and 50 ◦ C. The measured
coating thickness was 2.0–4.0 µm for samples from each of
these groups. No cross-sectional images were possible for
coatings formed at 19 ◦ C because a contiguous coating layer
did not form.
 J O U R N A L O F T H E M E C H A N I C A L B E H AV I O R O F B I O M E D I C A L M AT E R I A L S
Fig. 2 – SEM micrographs of CaP coating cross-sections for CaP coatings formed on PCU at (a) 28, (b) 37, and (c) 50 ◦ C.
Fig. 3 – Representative FTIR-ATR spectrum from (a) the
surface of uncoated PCU, and (b) from PCU samples coated
with CaP at different temperatures.
3.1.2. Fourier transform infra-red-attenuated total reflectance
(FTIR-ATR)
Fig. 3(a) shows a typical FTIR-ATR spectrum from the surface
of an uncoated PCU disc sample, with vibration bands that
are consistent with poly(carbonate urethane) (Socrates, 1994;
Feddes et al., 2009). When the PCU substrate was coated
with CaP, the bands associated with PCU were “suppressed”
(“masked”) by the CaP coating, and bands associable with
phosphate bonds appeared. As shown in Fig. 3(b), the CaP
coating formed at 19 ◦ C exhibited FTIR-ATR bands associable
with both PCU and CaP, reinforcing the idea that, although
CaP was present on the surface, the coating layer was not fully
contiguous. The FTIR-ATR spectra were similar for the PCU
coated with CaP at 28, 37, and 50 ◦ C; as shown in Fig. 3(b),
each of these samples exhibited FTIR-ATR bands associable
with CaP and no bands associable with PCU.
6 (2012) 128–138 133
Fig. 4 – XRD spectra from PCU disc samples coated at 19,
28, 37, and 50 ◦ C. A XRD spectrum of uncoated PCU161
substrate is shown for comparison.
3.1.3. X-ray diffraction (XRD)
Representative XRD spectra collected from the surface of PCU
samples coated at different temperatures are shown in Fig. 4.
Uncoated PCU exhibited an amorphous halo between 12◦ and
25◦ 2θ.
The XRD spectra of CaP-coated PCU contained three peaks:
a peak close to 13.3◦ 2θ, an intense, sharp peak at 26.6◦ 2θ, and
a small, sharp peak close to 40.3◦ 2θ. The peaks at 13.3◦ , 26.6◦ ,
and 40.3◦ 2θ were likely attributable to the (0 0 1), (0 0 2) and
(0 0 3) diffraction lines for monetite (DCPA), respectively
(Elliott, 1994). The fact that each of these diffraction lines
was along the c-axis, and that the other major peaks for
monetite were not visible, suggested an extremely high
degree of preferred crystal growth orientation. The preferred
c-axis orientation observed for these coatings concurred with
previous research into the preferred growth orientation of
apatites deposited by an aqueous, low-temperature technique
(Müller et al., 2007).
No XRD peaks attributable to apatite were observed,
despite evidence of apatite in the SEM micrographs of the CaP
coatings, which suggested that the apatite had an amorphous
structure. This implication was reinforced by the observed
broadening of the amorphous halo between 12◦ and 25◦ 2θ
after CaP coatings were applied to the PCU substrate.
134 J O U R N A L O F T H E M E C H A N I C A L B E H AV I O R O F B I O M E D I C A L M AT E R I A L S 6 (2012) 128–138

Table 2 – Surface roughness parameters of PCU coated

with CaP at different temperatures.

Coating Ra (µm) Rq (µm)

temperature (◦ C)
PCU 1.5 ± 0.3 1.9 ± 0.3
19 2.1 ± 0.3 2.5 ± 0.3
28 2.0 ± 0.6 1.8 ± 0.5
37 1.7 ± 0.2 1.8 ± 0.3
50 1.5 ± 0.2 1.9 ± 0.2

Table 3 – Critical mean pressures as tested by scratch

Fig. 5 – Adhesion strengths of CaP coatings formed on PCU
testing and calculated using Eq. (1). pm,c1 and pm,c2 are
the critical mean pressures for initial and total at different temperatures. Lc1 = initial delamination;
delamination, respectively. Lc2 = total delamination.

pm,c1 (MPa) pm,c2 (MPa)

Comparison:
PCU at applied normal loads above the critical load. The CaP
Coating temperature coatings may have been forced into the surface of the PCU
CT19 7.9 11.3 substrate because the substrate was relatively compliant.
CT28 15.7 23.1 Fig. 6 shows SEM micrographs of scratch tests on CaP
CT37 16.9 24.7 coatings applied to PCU at 19, 28, 37, and 50 ◦ C. CaP coatings
CT50 17.5 23.3 formed at 19 ◦ C were not fully contiguous and were pushed
Comparison: aside by the spherical indenter at normal loads of 0.3 N. CaP
Age of coating coatings formed at 28, 37, and 50 ◦ C exhibited signs of initial
New 15.7 23.1 delamination at a normal load of 2.4 N.
1 year 12.6 22.6
2 years 11.9 24.4
3 years 7.0 11.1
3.2.2. Adhesion strength as a function of coating age
Fig. 7 shows the critical loads required during scratch testing
for delamination of differently aged CaP coatings applied to
3.1.4. White light interferometry (WLI)
PCU samples. The CaP coatings were formed at 28 ◦ C on
Table 2 shows the quantitative variation in surface roughness different dates, approximately 1 year apart from each other.
with coating temperature. None of the samples exhibited a The age of the CaP coatings was found to affect the mea-
significant variation in mean surface roughness compared sured adhesion strength. The average required critical pres-
to PCU. The PCU samples coated at 19 ◦ C demonstrated the sure for initial delamination was greatest for CaP coatings of
greatest change in surface roughness relative to uncoated age 0 years at 15.7 MPa, was slightly lower at 12.6 and 11.9 MPa
PCU, which was thought to be attributable to the lack of for coatings aged 1 and 2 years, respectively, and was low-
a fully contiguous CaP coating. A minor decrease in Ra est for samples aged 3 years at 7.0 MPa. The CaP coatings of
with increasing coating temperature was observed, perhaps ages 0, 1, and 2 years experienced total delamination during
attributable to the greater CaP coating homogeneity with scratch testing at a critical pressure of between 22.6 and 24.4
increasing coating temperature, as observed by SEM. MPa. For CaP coatings aged for 3 years, the critical pressure for
total delamination was considerably lower at 11.1 MPa, which
3.2. Scratch testing results suggested that the CaP coatings were degrading after more
than two years in storage. Coatings of age 3 years exhibited a
Table 3 shows a summary of the results in terms of critical higher density of surface cracking. It was hypothesised that
mean pressures for initial, pm,c1 , and total, pm,c2 , delamina- the coatings were becoming increasingly dehydrated over
tion for each of the sample groups studied. time, so that, after a certain threshold of dehydration, the ad-
hesion strength of the calcium phosphate coatings dropped.
3.2.1. Adhesion strength as a function of coating temperature Fig. 8 shows SEM micrographs of scratch tests on coatings
CaP coatings formed on PCU at 19 ◦ C required lower critical of different ages. Tangential (frictional) force profiles are
pressures for initial and total delamination than CaP coatings shown for informational purposes. Scratches on CaP coated
formed at 28, 37, and 50 ◦ C (see Fig. 5). In fact, the CaP samples aged 0, 1, and 2 years exhibited minor damage
coatings formed at 19 ◦ C had fully delaminated before initial at normal loads close to the onset of initial delamination.
delamination was observed for the CaP coatings deposited at The damage occurred within the coating, which suggested
higher temperatures, which was attributed to the lack of a that the coatings were well adhered. Several CaP coatings
fully contiguous CaP coating forming on PCU at 19 ◦ C. CaP that were 3 years old delaminated at much lower values of
coatings formed on PCU at 28, 37, and 50 ◦ C required similar applied load. SEM micrographs showed that microcracking
critical pressures to each other for both initial and total was extremely prevalent in several of the CaP coatings aged
delamination. CaP coating failure on these samples occurred 3 years, and that the failure occurred between the substrate
through buckling of the CaP coating. Portions of the buckled and the coating on these samples, which also suggested that
CaP coatings were observed to be embedded in the surface of the coatings were not well adhered to the substrate.
 J O U R N A L O F T H E M E C H A N I C A L B E H AV I O R O F B I O M E D I C A L M AT E R I A L S
Fig. 6 – SEM micrographs of scratch tests on CaP-coated PCU samples. The coatings were formed at (a) 19 ◦ C, (b) 28 ◦ C, (c)
37 ◦ C, and (d) 50 ◦ C. The applied normal load was 0.3 N for the 19 ◦ C sample and 2.4 N for the 28, 37, and 50 ◦ C samples.
Fig. 7 – Adhesion strengths of CaP coatings applied to PCU
substrates from sample batches coated on different dates.
Lc1 = initial delamination; Lc2 = total delamination.
EDX analysis was used to perform elemental area scans
across the area of a scratch in order to determine whether a
CaP layer remained. Fig. 9 shows EDX elemental area scans
taken from areas around scratches formed during scratch
testing. The CaP coating of age 0 years remained almost
entirely intact when the applied normal load was below
Lc2 , as shown in Fig. 9(a). In fact, the CaP coating of age
0 years remained on the PCU surface above Lc2 (Fig. 9(b)).
Because the PCU substrate is compliant relative to CaP, the
CaP coating likely became embedded in the PCU substrate due
to the normal force applied by the scratch testing indenter. In
contrast, for CaP coatings aged 3 years before scratch testing,
the EDX area scan demonstrated that the majority of the CaP
coating had been removed from the scratch area at applied
normal loads above Lc2 , with relatively little calcium or
6 (2012) 128–138 135
phosphate detected within the scratch area (Fig. 9(c)). Because
the CaP coating failed at a relatively low applied normal load,
it did not become embedded in the PCU substrate.
4. Conclusions
The present research demonstrated that scratch testing could
be used to measure the adhesion strength of thin calcium
phosphate coatings on a compliant poly(carbonate urethane)
substrate. Scratch testing has certain advantages over other
adhesion strength testing techniques, because it does not
use epoxy bonding agents and is thus not limited to thicker
coatings.
Based on the scratch testing results, the optimal CaP
coating–PCU substrate adhesion strengths were attained
when the coatings had been deposited at 28, 37, or 50 ◦ C,
and within the previous 2 years before testing. These opti-
mal critical contact pressures compared favourably with a re-
ported critical contact pressure of about 20.0 MPa measured
by scratch testing for CaP coatings of thickness 2.7 µm sput-
tered onto titanium substrates (Pichugin et al., 2008).
Acknowledgements
This work was generously supported by the Engineering
and Physical Sciences Research Council (EPSRC) and Ranier
Technology Ltd. The authors are also grateful to Ranier
Technology Ltd. for provision of poly(carbonate urethane)
136 J O U R N A L O F T H E M E C H A N I C A L B E H AV I O R O F B I O M E D I C A L M AT E R I A L S 6 (2012) 128–138

Fig. 8 – SEM micrographs of scratch tests on CaP coatings aged (a) 0 years, (b) 1 year, (c) 2 years, and (d) 3 years prior to
scratch testing. The CaP coatings were applied to PCU substrate material at 28 ◦ C. The applied normal load was 1.0 N for
each sample. The measured tangential (frictional) force for each scratch is shown above each SEM micrograph.

Fig. 9 – EDX elemental area scans around scratches formed during scratch testing of CaP-coated PCU samples. Green = Ca;
Red = P. The CaP coatings were deposited on PCU at 28 ◦ C for each of the samples shown. (a) shows a scratch made in a
coating of age 0 years at pm ∼ 15 MPa (below Lc2 ), (b) shows a scratch made in a coating of age 0 years at pm ∼ 25 MPa (above
Lc2 ), and (c) shows a scratch made in a coating of age 3 years at pm ∼ 25 MPa (above Lc2 ). (For interpretation of the references
to colour in this figure legend, the reader is referred to the web version of this article.)

substrate material, and to Dr. Hugh Shercliffe, Dr. Feiyang Liu,
and Mr. Mark Rainer of the Cambridge University Engineering
Department for assistance with scratch testing.
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