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Biotribology
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A R T I C LE I N FO A B S T R A C T
Keywords: A new test was developed to measure friction and wear of hip implant materials under reciprocating sliding
Synovial fluid conditions. The method requires a very small amount of lubricant (< 3 ml) which allows testing of human
CoCrMo synovial fluid. Friction and wear of Cobalt Chromium Molybdenum (CoCrMo) material pairs were measured for
Friction a range of model and human synovial fluid samples. The initial development of the test assessed the effect of
Wear
fluid volume and bovine calf serum (BCS) concentration on friction and wear. In a second series of tests human
Artificial hip joints
synovial fluid (HSF) was used. The wear scar size (depth and volume) on the disc was dependent on protein
content and reduced significantly for increasing BCS concentration. The results showed that fluid volumes
of < 1.5 ml were affected by evaporative loss effectively increasing the protein concentration resulting in
anomalously lower wear. At the end of the test thick deposits were observed in and around the wear scars on the
disc and ball; these were analysed by Infrared Reflection-Absorption Spectroscopy. The deposits were composed
primarily of denatured proteins and similar IR spectra were obtained from the BCS and HSF tests. The analysis
confirmed the importance of SF proteins in determining wear of CoCrMo couples.
1. Synovial Fluid Lubrication and Wear of Prosthetic Joints from Cobalt-Chromium-Molybdenum (CoCrMo) Alloys [3]. Although
the volumetric wear of the joint was reduced there was an increase in
In 2015 there were over 180,000 [1] primary hip and knee re- the number of wear particles causing metallosis damaging the peri-
placements recorded in the United Kingdom. These devices relieve pain articular bone and soft tissue eventually requiring implant revision
and restore function in articular joints affected by destructive arthro- [4,5]. High failure rates meant MoM joint implantation had reduced
pathy resulting from disease, trauma or infection. Prosthetic joints are to < 0.1% of all primary hip procedures by 2014 [1] although this
tribological devices with bearing surfaces articulating under load, and combination (1–2%) is still used in resurfacing hip replacement [1].
thus are susceptible to high friction, wear, corrosion and fatigue. These The wear of implant materials are usually evaluated in bench top
issues can contribute to early failure necessitating implant revision and and joint simulator tests [6–18]. Bench-top tests [6–12] focus upon
in 2015 nearly 10% of hip replacements required revision [1]. Pros- material response to rubbing rather than the joint design factors. The
theses are increasingly being implanted into younger patients in- tests have a simple geometric configuration, usually pin-on-disc [6–8],
creasing the performance demands on joint due to higher activity levels pin-on-plate [9, 10] or pin/flat-on-sphere [11,12] which simulates in
and longer operational life. To achieve this, new implant materials and vivo contact pressures. The loading (usually constant) and kinematics
joint designs have been developed [2]. (unidirectional/bidirectional sliding) are chosen to provide a simple
The first generation hip joint was the Metal-on-Polymer (MoP) simulation of implant contact conditions. Wear of the pin or ball after a
however they gave poor longevity due to polyethylene wear and par- certain sliding distance and specific number of cycles [7–11] is usually
ticle debris resulting in osteolysis [3]. Implant lifespans of only evaluated by simple weight loss [7–11].
12–15 years made the implant suitable solely for older patients. Designs Hip and knee joint simulators replicate the complex loading and
switched to the MoM prosthesis where both bearing surfaces are made kinematics experienced in a physiological gait cycle [19] and are used
⁎
Corresponding author.
E-mail address: harriet.stevenson10@imperial.ac.uk (H. Stevenson).
1
Now at UK AWE.
https://doi.org/10.1016/j.biotri.2018.04.001
Received 23 November 2017; Received in revised form 29 March 2018; Accepted 6 April 2018
Available online 11 April 2018
2352-5738/ © 2018 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/BY/4.0/).
H. Stevenson et al. Biotribology 14 (2018) 1–10
to evaluate the effect of implant design or material combinations. The performed. The protein concentration of PP (~30 mg/ml) was found to
test usually achieves millions of cycles before the cumulative wear is be significantly higher than that of bovine SF and dilution of BCS to
measured [14–18,20]. The measurement of wear on either the head or 40% would give similar total protein concentrations.
cup components is based on small changes in mass. This measurement The foregoing review has identified significant deficiencies in our
can also be affected by the environmental conditions over the lifetime understanding of synovial fluid lubrication of prosthetic joints. It raises
of the test [14–18,20] and so often has poor repeatability [20]. The two important questions:
joint specimens are usually submerged in Bovine Calf Serum (BCS)
which is changed regularly during the test, typically every 5 × 105 1. What is the effect of HSF composition on implant wear? Are some
cycles [17]. Thus completing a 5 million-cycle test requires very large patients/diseases/implant material combinations at a higher risk of
amounts (~ 5 l) of fluid [15,18]. implant failure as a result?
The focus of the majority of implant tribology testing is the effect of 2. Is 25 wt% BCS a suitable model lubricant to replace human synovial
implant design and material wear. The effect of synovial fluid chemistry fluid? If not can we define a better one?
on implant wear is rarely studied. Synovial fluid is the natural lubricant
found in articular joints. It is rarely available and only attainable in The overall aim of the study was to investigate how the friction and
small quantities, certainly less than the large volumes required for si- wear of implant materials are affected by SF chemistry including HSF.
mulator tests. Therefore, the lubricant model most communally used is The focus of this initial work was on the protein content as these are the
BCS diluted concentration of 25% w/w. It has been shown to have a most abundant molecular species in SF.
similar total protein content (18–21 mg/ml) when compared to healthy One of the practical problems is the very small volumes (< 5 ml) of
synovial fluid (HeSF) [21–23]. However, the overall chemical compo- HSF available from clinical procedures, typically joint effusion. The first
sition is different [21–23]. In addition diseased joints show large in- requirement therefore was to develop a test procedure which used very
creases in total protein content not mirrored by the model [23–27]. small volumes of fluid (< 3 ml) which would allow for some repeat
The chemical composition and physical properties of human syno- testing of samples from a single patient. We decided to concentrate
vial fluid varies between patients and healthy or diseased fluids initially on CoCrMo material pairs to understand if the fluid chemistry
[23–27]. The most abundant components of SF reported in the litera- might be a contributing factor to why this MoM produced such high
ture [22–26,28] are summarised in Table 1. The primary proteins are levels of wear for some patients but works very well for others. The
identified as albumin and γ-globulin and their relative and total con- MHRA [26] recently recommended routine monitoring of asympto-
centration can vary widely depending on the fluid pathology matic patients, highlighting a significant concern about implant life-
[23,24,26]. span and patient health. Thus a long term aim of the research is to
The influence of model SF composition upon implant wear (parti- develop a SF screening test identifying patients at risk of excess wear
cularly MoM), in both simulation tests and in vivo is unclear. This is problems with MoM and other implants.
driven, in part, by the idea [4,5] that some MoM hip designs operate The aims of the research program was as follows:
predominately in the fluid film (i-EHL) regime, this would reduce wear
rates to avoid clinical wear problems. In this regime lubricant film 1. Develop of simple bench test to measure friction and wear of im-
formation will not be affected by the biochemical properties of SF, such plant materials under simulated physiological conditions with small
as protein content. The lubricant film thickness is predicted to scale fluid volumes (~1–3 ml) as HSF volumes were restricted.
with the high-shear rate viscosity of the fluid [4,5] and the viscosity is 2. Investigate the effect of fluid volume, protein concentration and
fairly constant over the protein concentration range [29]. Therefore oxygen content on friction and wear using model SF.
protein concentration will have little effect on predicted i-EHL film 3. Investigate the use of HSF in the small volume wear test to examine
thickness and thus, by implication, wear. In contrast MoP hips are the validity of model SF for use in wear testing.
considered to operate in the boundary lubrication regime where the 4. Identify and characterise organic deposits in and around the wear
changing protein content and thus the boundary lubrication behaviour scar using an optical microscope and Micro InfraRed Reflection
might have an effect on wear [23]. Proteins (albumin and globulin) are
thought to adsorb at the implant surfaces and act as boundary additives Table 1
[6,30,31]. Thus most studies of the effect of SF chemistry on implant Comparison of model and human synovial fluid protein concentration and pH
friction and wear have been for UHMWPE components [6,31–35]. [21–26].
The vast majority of implant tribology testing uses BCS as the model
Albumin (mg/ Globulin (mg/ Approx. total pH
SF lubricant: There are very few instances of human synovial fluid ml) ml) protein (mg/ml)
(HSF) being used. Yao et al. [36] published one of the few papers to
report friction tests with HSF using a pin-on-disk tribometer. They HeSF 7–18 0.5–2.4 7–20 7.3–7.4
PP 20–39 4.6–15.4 43 25–55 7.5–8.5
compared friction measurements for different polymer pin materials
OA 17.8–18.5 12.9–13.4 30–34 7.4–8.1
rubbing against a CoCrMo disc with an array of lubricants: DI water, RA 18.6–28.0 4.8–23.5 22–52 6.6–7.6
varying concentrations of BCS diluted with DI water, bovine SF and 100 wt% 35.00 22.00 57 7.0–8.1
periprosthetic (PP) HSF. The PP HSF gave the lowest friction coefficient BCS
for all material combinations however no wear measurements were 25 wt% BCS 8.75 5.5 14 7.0–8.1
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H. Stevenson et al. Biotribology 14 (2018) 1–10
Absorption Spectroscopy (Micro IRRAS). and end of the test. This method was chosen as it only requires a very
small amount of fluid and there are no cleaning/decontamination issues
2. Materials and Methods when using HSF.
2.1. Friction and Wear Tests 2.2. Optical and Micro IRRAS Examination of Wear Scar Deposits
A High Frequency Reciprocating Rig (HFRR) (PCS Instruments At the end of the test low power microscope images were taken from
London) was used to measure friction and wear of CoCrMo specimens the disc before cleaning with detergent in order to carry out the wear
with BCS and HSF. The HFRR has been used extensively to study fric- measurement. The ball was carefully rinsed with water and then air
tion and wear of boundary lubricants [37]. The test parameters can be dried. An example of the disc wear scar is shown in Fig. 2.
adjusted to provide a slow speed reciprocating contact where hydro- The ball was retained for further analysis by Micro-IRRAS. This
dynamic effects are minimised. A similar test configuration has been technique provides information on the organic composition of films
used in earlier studies [13]. deposited on metal surfaces [43] and is used extensively to study the
A schematic diagram and photograph of the experimental set up is conformation and structure of proteins [44–47].
shown in Fig. 1. The upper specimen consists of a CoCrMo ball oscil- The sampling method is shown in Fig. 3. A Perkin Elmer Multiscope
lating against a stationary lower specimen (CoCrMo disc) using an Infrared Microscope coupled to a Spectrum One FTIR was used to take
electromagnetic vibrator. The upper specimen is attached to a pivoted Micro-IRRAS spectra from a small area of organic deposits in and
ridged shaft and loaded via a dead weight and a test fluid is injected around the wear scar on the ball. The sample diameter was 100 μm, 100
into the lower specimen holder to lubricate the contact. The fluid bath scans were taken and the resulting spectrum was baseline corrected,
was made of nylon rather than stainless steel to prevent contamination smoothed (11 point) and normalised (to absorbance 0.1 at 1650 cm−1)
of the test fluid by metal ions. A temperature-controlled plate beneath using the standard Perkin Elmer software. Before spectra were taken the
the lower specimen was used to heat the lubricant bath to 37 °C which ball was lightly rinsed with deionised water and allowed to dry, this
was monitored by a thermocouple immersed in the fluid. The test removed excess test fluid but left the tightly bound deposits.
conditions are summarised in Table 2. Ball and disc CoCrMo test spe-
cimens (19.05 mm diameter ball, 10 mm diameter disc) were polished 2.3. Wear Scar Analysis
to a mirror finish (as obtained from PCS Instruments, UK) with ar-
ithmetic average surface roughness 39.6 ± 1.5 nm and 8.8 ± 0.8 nm A White Light Interferometer (Wyko NT9100) was used to measure
respectively. the volume and depth of the wear scar formed on the disc during
Before testing the metal specimens were cleaned in 1% detergent rubbing tests. Images were obtained using a 20× magnification ob-
solution and rinsed (3 times) in distilled water. The specimens were jective (at 0.55 FOV). On each disc multiple images were taken and
then stored under isopropanol. Just before testing they were air-dried stitched together to enable examination of the full length of the wear
and cleaned in an oxygen plasma (Diener) which removes organic scar. An example of the final image is shown in Fig. 4. The wear volume
contamination and leaves a hydrophilic surface [38]. was obtained from the negative volume computed by the Wyko analysis
The CoCrMo ball was loaded and reciprocated against the disc to software. In addition wear depth readings at 30%, 50% and 70% along
simulate joint articulation. A frequency of 20 Hz and stroke length of the length of the scar were taken and averaged. The section and loca-
1 mm were used. The sliding speed varied from 0 (at the end of the tions of these are also shown in Fig. 4. Before scans were performed any
stroke) to approximately 42 mm/s at the mid stroke which covers the surface deposits on the discs were removed by soaking in 2% detergent
normal speed range of the hip gait cycle [39]. A load of 1 N was used, solution followed by rinsing with water (3×) and isopropanol and air
giving a mean Hertzian pressure of 216 MPa, this is high for a walking
gait cycle (MoM ~ 99.8 MPa max). However it has been calculated that
during running a maximum load of 10.3BW [40] (MoM ~ 141 MPa
max) can be experienced in the hip joint. Whilst the initial test contact
pressure is high this will rapidly decrease as the contact area increases
due to wear. The test was run for 72,000 cycles (1 h). Tests with the BCS
fluids were repeated at least twice, this was not possible for all the HSF
tests (due to the limited volumes of human samples) but repeats were
run where feasible.
The contact was immersed in a small volume (1–2 ml) of SF. The
depth of fluid above the sample was approximately ~5 mm for the 2 ml
volume. A lightweight cover placed over the fluid bath was used to
reduce evaporation during the test. The test device was housed in a
plastic box which ensured a stable temperature environment as one of
the practical challenges was to establish an equilibrium temperature
without significant loss of the fluid through evaporation. The ball and
disc were assembled and the fluid bath heated to the desired tem-
perature. Once this was reached the test fluid was introduced. The box
was then purged with N2 for 20 min to reduce the atmospheric oxygen
content to physiological levels (24 mmHg, GOX 100T Greisinger)
[41,42] The disadvantage of this method was it extended the total test
time and the continued flow of gas also contributed to increased eva-
poration. In later work the effect of this was investigated by running
tests without the purge but heating for the 20 min and omitting the
20 min delay but running the test once the fluid was introduced.
Friction was recorded throughout the test. At the end of the test the
samples were drained of excess fluid. The fluid pH was measured by Fig. 1. Schematic diagram of HFRR device and photograph of the loaded ball
narrow range litmus paper (pH 6.5–10 VWR MColorHast) at the start and fluid bath.
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H. Stevenson et al. Biotribology 14 (2018) 1–10
Table 2 was used as the reference test fluid. On receipt the 500 ml sample was
HFRR test conditions. divided into 7 ml aliquots and then refrozen and stored at −40 °C. An
Test conditions aliquot was removed the day before testing, defrosted overnight in a
Max Hertzian pressure 200 MPa refrigerator and then diluted (deionised water) to the required con-
Frequency 20 Hz centration before testing.
Stroke length 1 mm HSF samples were collected by MJ and his team during surgical
Temperature 37 °C
Duration 72,000 cycles
procedures. Sample SF from patients with joint effusions were not in-
Test specimens cluded. Immediately after collection the sample is centrifuged for
Material CoCrMo 15 min at 10000G to remove large debris and cellular material. Samples
Ball 19.05 mm diameter Ra are divided into ~1 ml aliquots and frozen (−80 °C) until required for
Disc 10 mm diameter Ra
testing. Ethical approval was obtained and subjects gave informed
consent for all human sample collection and testing. Results are shown
for SF samples from four patients, sample data is shown in Table 3.
3.1. Validation of Tribology Test Method: Effect of Fluid Volume for BCS
Reference Fluids
One of the aims of the work was to develop a wear test which only
required a small volume of fluid. To validate the test method a series of
initial tests were run and these included the effect of fluid volume on
wear. Fig. 5 shows example friction traces for BCS 25 wt% for different
fluid volumes (1 and 2 ml). The BCS fluids give low, stable friction
traces over the test period, typically COF was in the range
μ = 0.22–0.26. However sample volume appeared to affect friction as
CoF1ml < CoF2ml. For volumes of < 1.5 ml friction coefficient was
Fig. 2. Low power microscope image of wear scar on the disc specimen for
found to decrease compared to tests of > 1.5 ml, for example with BCS
25 wt% BCS after cleaning.
25 wt% the CoF averages for 1 and 2 ml tests are 0.223 ( ± 0.005) and
0.248 ( ± 0.007) respectively.
drying. WLI images of typical wear scars on the disc are shown in Fig. 6.
Results are shown for 25 wt% 1 and 2 ml. The wear scar is wider and
2.4. Test Fluids deeper for the 2 ml samples compared to the 1 ml sample. A series of
BCS 25 wt% tests were run for a range of fluid volumes between 1 and
Bovine calf serum (Sigma Aldrich Poole, UK12133C sterile-filtered) 2 ml and the wear results are shown in Fig. 7. We surmise this is due to
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H. Stevenson et al. Biotribology 14 (2018) 1–10
Fig. 5. Friction traces for BCS 25 wt% for different fluid volumes. 3.2. Friction and Wear Results: Human Synovial Fluid
In a second series of tests the friction and wear using HSF samples
evaporation effectively changing the protein concentration in the low
were investigated using the final configuration of 2 ml sample without
volume/low BCS concentration tests. Evaporation occurs preferentially
N2 purge. The average friction coefficient was similar for all tests and
from the upper surface of the fluid thus creating locally higher con-
was in the range μ = 0.24–0.27. Average wear depth results are shown
centrations of proteins close to the rubbing contact, which resulted in
in Fig. 10, error bars are shown were possible for repeat tests. The HSF
lower wear volumes for the 1 ml samples but had a negligible effect on
wear (both average depth and volume) was > 25 wt% BCS for all
the 2 ml tests. To further investigate the effect of protein concentration
samples.
a series of tests for 1 and 2 ml fluid volumes were run for a range of BCS
concentrations (10, 25, 50, 100 wt%).
Average CoF results are summarised in Fig. 8 for different BCS 3.3. Examination of Organic Deposits in and around the Wear Scar
concentrations. For low BCS concentrations (10, 25 wt%)
CoF1ml < CoF2ml but for the higher concentrations (50 and 100 wt%) Microscope images from the ball are shown in Fig. 11 for 25 wt%
CoF was similar for both volumes. Wear depth and wear volume are BCS and HSF77 samples. Surface deposits were clearly visible around
plotted against BCS concentration for different fluid volumes in Fig. 9a. the wear scar on the ball, these were generally seen as smooth, co-
The wear results are similar for the high concentrations tests (50, loured, “halo” films. The optical interference colours indicated film
100 wt%) but diverge significantly at low concentrations (10, 25 wt%). thickness to be in the range 100–400 nm. Chromatic optical inter-
This result is in line with the CoF values shown in Fig. 8 assuming these ferometry has been used extensively to measure EHL films in lubricated
can be used as an indicator of wear, in this case higher average friction contacts [42] The HSF “halo” films appeared to be thinner and less
equates to higher wear. Generally CoF cannot be used as an ersatz wear extensive than the BCS films. Beyond the “halo” films more extensive
measurement, particularly for very different chemical systems, however black, particulate deposits were observed. These images were taken
for these BCS results there does appear to be a CoF/wear correlation. after light rinsing to remove excess fluid. The wear scar is clearly seen
Error margins shown are the standard deviation of reported results. in the centre of the photograph. At either end of the wear scar smooth
Indications are given on the wear depth graph for approximate range of “halo” films are observed, this can be seen more clearly in the right
protein concentration for healthy and diseased SF. hand side image in Fig. 11.
Micro-IRRAS spectra were taken from the surface deposits, both the
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H. Stevenson et al. Biotribology 14 (2018) 1–10
Fig. 6. WLI images of wear scars on discs: 25% BCS 1 and 2 ml.
“halo” and black particulate films, on the ball after rinsing. Similar absorbing frequencies in the range of 1510–1580 cm−1 [44,45,48].
spectra were obtained from both these regions however the black par- Amide I and II vibrations are less affected by the nature of the side chain
ticulate films were generally too thick to give good results. The “halo” however they are influenced by the secondary structure of the backbone
deposit spectra were compared to FTIR spectra from the untested fluids. [44–46,48]. Therefore it follows that Amide I and II vibrational bands
These were sampled as dried films on a clean CoCrMo surface and ex- are used for secondary structure analysis, although interpretation of the
amples are shown in Fig. 12a for the HSF and BCS 25 wt% fluids. The Amide II band information is less straightforward than Amide I [44].
spectral range is limited to the Amide I and II peak region Generally HSF Amide I bands were above 1655 cm−1 and for BCS below
(1850–1450 cm−1). In this region the infrared absorption spectrum of 1645 cm−1, seen in Fig. 12, which is line with the greater γ-globulin
proteins is dominated by bonds on the polypeptide backbone of the content in BCS compared to HSF.
amino acid structure (44). Spectra from fresh fluid and deposited “halo” films are compared in
The Amide I peak is the most prominent absorbing at frequencies in Fig. 13a for BCS 25 wt% and Fig. 13b for HSF041. In all the BCS tests
the range of 1600–1700 cm−1 and arises mainly due to the C]O the Amide I main peak position decreases from ~1640 cm−1 for the
(~80%) stretching vibration [45] with contributions from the out of fresh sample to ~ 1630 cm−1 for the wear scar deposits. The Amide II
phase CN stretching vibration [44]. The Amide II peak is a combination band also broadens and the maximum peak position shifts to a lower
of the NH bending (~60%) and CN stretching vibration (~40%) wavenumber (1542 to 1530 cm−1). IR spectra for HS041 films also
Fig. 7. Average wear depth plotted against fluid volume for BCS 25 wt%.
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H. Stevenson et al. Biotribology 14 (2018) 1–10
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H. Stevenson et al. Biotribology 14 (2018) 1–10
Fig. 10. Average wear depth results for human synovial fluid and 25 wt% BCS (no N2 purge).
to post-test deposits and important differences were observed. Different role in the lubrication process? These aspects will be studied further in
protein profiles were observed for the fresh HSF fluids and BCS; this is a future papers.
fairly trivial observation but still needs to be emphasised, even from the The author's recognise that there are several limitations in the
simplest analysis these fluids have very different protein chemistries. present study. First of all HSF contains many components not only
BCS is characterised by broad Amide I and II bands at 1644 cm−1 and proteins. Therefore to better simulate in vivo conditions the effect of
1543 cm−1 respectively. The HSF samples gave different spectra both in phospholipids and hyaluronic acid on friction and wear should be in-
the position and shape of the Amide I and II bands; this can be seen in vestigated and will be included in future work. Secondly at present
Fig. 12. This difference in protein chemistries may change the ability of exact protein concentration and composition values are not available
the fluid to from a protective lubricant film explaining why higher wear for the HSF fluids. This is important for direct comparisons to model
was seen for HSF despite the higher protein content. The long-term goal fluids. Thirdly a full interpretation of FTIR spectra for both HSF and
is to link HSF chemistry to implant wear and thus risk of failure and BCS. Many studies [58–60] have suggested that FTIR spectra can be
FTIR spectroscopy would provide a convenient and rapid clinical ana- used to diagnose different pathologies and in future work deconvolu-
lysis tool. tion and curve fitting techniques will be used to provide a more detailed
IRRAS analysis also showed that there were significant differences interpretation of the spectra. Finally it should be noted that although
when compared post-test deposits and dried untested fluids. The most only MoM material combinations are currently reported the test pro-
obvious change was a shift in the Amide I band position to lower wa- cedure can be extended to include ceramic bearings allowing the study
venumber. Typically this was from 1641 to 1630 cm−1 for 25 wt% BCS of CoC material combinations.
and is associated with the formation of β-sheet structures (44–46). In
nature β-sheet proteins are associated with animal “glues” for example
barnacles sticking to metal surfaces [56] where this material is typically 4. Conclusions
very strong high viscosity, insoluble and adherent [57]. The formation
of this material in a sliding contact raises a number of questions: is this A bench test was developed to measure implant material wear
behaviour representative of in vivo MoM implant lubrication? What is which uses small volumes of fluid which allowed HSF to be tested. Our
the mechanism of formation? And does this material play a significant findings are summarised below:
Fig. 11. Microscope optical images from ball wear scar (scale marker 0.2 mm) showing different amounts of protein deposits: HSF77 (LHS), BCS 25 wt% (RHS).
8
H. Stevenson et al. Biotribology 14 (2018) 1–10
Fig. 12. Micro IRRAS spectra from untested human synovial fluid samples and BCS.
3. Significantly higher wear was recorded for the HSF samples com-
pared to 25 wt% BCS fluid. All the HSF samples tested would be
expected to have higher protein concentrations and thus give lower
wear.
4. IRRAS analysis of deposits formed during the wear test indicated
they were predominately composed of proteins. Significant differ-
ences were observed between fresh films (untested) and post-test SF
deposits indicating denaturing of the proteins.
5. The protein deposits had a higher β-sheet content and appeared to
be adherent and solid when dried. It is suggested proteins denatured
during rubbing and contributed to reduced wear of the disc.
Acknowledgements
Conflict of Interest
The work was carried out under human ethics REC reference 15/
LO/0388 and patient consent was obtained for all human sample
testing.
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