Carbon 143 (2019) 890e896

Contents lists available at ScienceDirect

Carbon
journal homepage: www.elsevier.com/locate/carbon

Nanodiamonds for improving lubrication of titanium surfaces in

simulated body fluid
Asghar Shirani a, Nicholas Nunn b, Olga Shenderova b, Eiji Osawa c, Diana Berman a, *
a
Materials Science and Engineering, University of North Texas, Denton, TX, 76203, USA
b
mas Nanotechnologies, Inc., Raleigh, NC, 27617, USA
Ada
c
NanoCarbon Research Institute, Asama Research Extension Centre, Shinshu University, Ueda, Nagano, 386-8567, Japan

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

Article history: Hip implants are often made from titanium or titanium-based alloys. However, wear during the oper-
Received 11 October 2018 ation inside the human body is a key source of implant failure and adverse health effects. We propose
Received in revised form new insight on the lubrication of titanium components. Addition of small amounts (less than 0.2 wt%) of
18 November 2018
nanodiamonds (NDs) to simulated body fluid promotes a substantial improvement in friction (3 times
Accepted 1 December 2018
Available online 3 December 2018
reduction) and wear (up to 2 orders of magnitude wear reduction) behavior of the titanium surfaces.
Interestingly, the amount of NDs needed for improvement of friction and wear characteristics is critically
dependent on the applied loads. With higher contact loads, larger concentrations of NDs are needed for
better friction and wear reduction. Analysis of the wear track formed during sliding indicates the for-
mation of a carbon-rich tribolayer which improves tribological properties of the contacting surfaces. Our
results suggest that the carbon layer is formed from the nanodiamonds embedding in the top layer of
titanium.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction high-molecular-weight polyethylene (UHMWPE) was used in

Premature natural joint degeneration is a common problem in
the population over the age of 40 as a result of excessive loading
conditions as well as failure of normal repair processes [1]. Artificial
joints made from metal, ceramic, or plastic materials have become
the only long-term solution for relief from pain, mobility, or other
adverse health effects related to joint degradation and failure [2]. In
recent years, the number of orthopaedic surgeries substantially
increased, though reliability and lifetime of the artificial joints
remain a major issue.
During operation, artificial joints are exposed to a complex
environment and subjected to mechanical degradation [3,4].
Additionally, biocompatibility of the materials, or their ability not
to cause an inflammatory or toxic response, is an important aspect
to consider [5].
The search for biocompatible, tribologically efficient materials
led to the exploration of different ceramic and metal alloy com-
ponents [6]. Ideally, the joint replacement material should exhibit
an identical performance to the bone when in operation [7]. Ultra-
* Corresponding author.
E-mail address: Diana.Berman@unt.edu (D. Berman).
earlier years [8], but raised concerns with regard to adverse tissue
reactions [9]. UHMWPE was replaced with stainless steel and then
with Co-Cr-Mo and alumina [10], which demonstrated good wear
resistance but lead to inflammation and pain in long-term. So far,
titanium remains the most favorable materials for artificial joints.
This has led to extensive research on titanium-based alloys for
biomedical applications, such as Ti-Nb-Ta-Zr or TNZT [11], Ti-6Al-
7Nb [12], Ti-6Al-4V [13], and Ti-5Al-2.5Fe [14], among others. Ti-
tanium and titanium-based alloys are the preferred materials used
for hip cup shells due to their high corrosion resistance and
biocompatibility over other materials, such as conventional stain-
less steels and cobalt-based alloys [15]. However, high wear of the
titanium components during exposure to normal and shear stresses
is a major cause for their failure [16]. As a result, degradation of the
metal implants during movement of the joints limits their lifetime
[17].
An alternative to modification of the alloy composition is to
modify the lubrication media with biocompatible additives
[18e21]. Nanodiamonds have proven to be excellent friction and
wear modifiers in various sliding systems [22e25]. Specifically,
adding small amounts of nanodiamonds to oils [26] or water [27,28]
resulted in substantial decrease in friction and wear of sliding metal

https://doi.org/10.1016/j.carbon.2018.12.005
0008-6223/© 2018 Elsevier Ltd. All rights reserved.
 A. Shirani et al. / Carbon 143 (2019) 890e896
surfaces [24] or silicon\sapphire surfaces [28]. Based on encour-
aging results of improved lubricity of aqueous ND suspensions, it
was hypothesized that NDs can potentially provide lubrication for
artificial joints [28]. In terms of biocompatibility, different forms of
carbon were already considered in various in-vivo and in-vitro
studies [29]. Previous studies demonstrated biocompatibility of
nanodiamonds [30,31]. Naturally occurring graphitic layers have
been detected in metal-on-metal hip replacements [32]. Therefore,
nanodiamonds could be an ideal solution for improving the
longevity of titanium components in the body.
In this paper, we propose the use of nanodiamonds for friction
and wear reduction in titanium-based components of hip implants.
Addition of small amounts of nanodiamonds to simulated body
fluid (SBF), we demonstrate a substantial reduction in friction and
wear of the surfaces.
2. Experimental procedure
To reproduce the joint environment in the body, tribological
testing was performed in a simulated body fluid. The SBF was
prepared using a standard protocol [33]. Sodium chloride, sodium
bicarbonate, potassium chloride, potassium phosphate dibasic tri-
hydrate, magnesium chloride hexahydrate, calcium chloride dihy-
drate, and sodium sulfate, purchased from Sigma Aldrich, were
dissolved in the right proportion in distilled water and held in an
incubator at a constant temperature of 37
C. The solutions were
used within a week to avoid any agglomeration and degradation of
the mixture. The fresh solution was prepared for replicate tests.
Grade 5 purity (99.999% titanium) titanium balls (diameter
6 mm) and titanium flats (RMS roughness measured with Veeco
Dektak 150 Surface Profiler Rq ¼ 50e60 nm) purchased from
American Elements were used during testing. The hardness of the
balls and flats measured with a Shimadzu Microhardness Tester
were 4900 MPa and 3300 MPa, correspondingly. Tests were per-
formed using the Anton Paar pin-on-disk macroscale tribometer in
reciprocating mode. The length of the wear track was kept at 5 mm
with reciprocal motion at 1 Hz. The samples were immersed in SBF
during the tests and the temperature was kept at 37
C to
approximate conditions inside the body a closely as possible. Dur-
ing the tests, the applied load was varied from 0.25 N up to 1 N
(maximum Hertzian contact pressure of 0.28e0.45 GPa). The con-
tact pressures experienced by the surfaces during sliding were
selected based on the previously reported contact pressure values
for hip replacement contacts [34].
Small amounts of carboxylated detonation nanodiamonds with
5 nm average volumetric size (see supplementary information,
Fig. S1) and zeta potential of 35 mV dispersed in DI water at
10 mg/mL concentration (NDH2O5N, Ad
amas Nanotechnologies)
were introduced directly to the SBF and the resulting solution was
sonicated for at least 30 min. Previous studies indicate good
colloidal stability of nanodiamonds with negative surface potential
[35] as was confirmed in the present study for a period of one
month. The added amounts of 1, 5, 10, 15, and 20 vol% of the
nanodiamond solution (NDS) correspond to 0.01, 0.05, 0.1, 0.15, and
0.2 wt% concentrations of nanodiamonds in SBF, correspondingly.
To confirm reproducibility of the results, at least three replicate
tribotests were performed for each concentration of nanodiamonds
in SBF.
After tests, the SBF was removed and the samples were rinsed
using DI water and the wear tracks were further analyzed. Optical
images of the wear tracks were acquired using a Zeiss Optical Mi-
croscope. Raman analysis was performed Nicolet Almega XR
Dispersive Raman spectrometer with 532 nm green laser. The
samples were further characterized using an FEI Quanta 200
Scanning Electron Microscope (SEM) with energy dispersion x-ray
891
analysis (EDX) to analyze the surface modification changes in the
wear track.
To estimate the wear rate after the tests, we calculated the wear
volume of the ball side as follows:
ph 3d2
V ¼ð Þð þ h2 Þ (1)
6 4
where d is the wear scar diameter, r is the radius of the ball, and h is
the wear scar depth:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
d2
h ¼ r  r2  (2)
4
3. Results and discussion
In the first test, we monitored changes in the coefficient of
friction (COF) and wear values of the titanium surfaces during
sliding under 0.25 N applied load. Our results demonstrate that in
contrast to pure SBF, the addition of 0.05 wt% of the nanodiamond
leads to a two times reduction of the COF value. As demonstrated in
Fig. 1, 0.01 wt% shows almost negligible changes. Therefore, further
analyses focused on 0.05, 0.1, and 0.15 wt% concentrations.
Increasing the applied load necessitates an increase in the
amount of nanodiamond for enhanced performance. As demon-
strated in Fig. 2, 0.1 wt% works better at 0.5 N applied load, while
0.15 wt% is optimal for 1 N applied load. This behavior is attributed
to higher contact loads requiring a more uniform ND tribolayer,
which may be achieved with higher ND content.
Analysis of the wear tracks further supports the benefits of
different ND concentrations for each specific applied load (Fig. 3).
Nevertheless, on average, the presence of NDs in SBF resulted in
lower wear than for the SBF alone, and the resulting wear of the
titanium surfaces depends on both parameters: ND concentration
and applied load. In Fig. 3, we highlight the wear scar measure-
ments for the optimal concentrations of NDs at each load.
Further understanding of the mechanism of lubrication
improvement in the presence of NDs is possible through detailed
characterization of the wear tracks corresponding to the tests in
pure SBF and in SBF with an optimal concentration of NDs. For these
analyses, we focused on the 0.5 N applied load.
Analysis of the tracks formed during the sliding in pure SBF
(Fig. 4) and SBF with 0.1 wt% NDs at 0.5 N load (Fig. 5) was per-
formed by acquiring energy dispersive x-ray spectroscopy (EDS)
spectra from multiple points inside and outside of the wear tracks.
Our tests indicate that for the pure SBF, titanium oxide is dominant
within the wear track. In the case of pure SBF, the titanium surfaces
are exposed to sliding contact and their wear increases oxidation of
the wear track region. When NDs are introduced to the SBF, the
wear track oxidation is substantially lower. Interestingly, the EDS
spectra inside the wear track clearly indicate the presence of car-
bon. Therefore, formation of the carbon rich layer in the wear track
provides better tribological performance of the sliding system and
protects the underlying titanium substrate from extensive wear.
Similar wear and corrosion protection characteristics of carbon
films were observed in case of graphitic layers [36,37]. As a result
less titanium surface is exposed to the oxidation in SBF environ-
ment rich of corrosion promoting ions.
Further evaluation of the uniformity of the carbon coverage
inside the wear track formed during sliding in the SBFþ0.1 wt% NDs
is shown in Fig. 6. A detailed EDS map of the SBFþ0.1 wt% NDs wear
track (Fig. 6d) indicates uniformity of the carbon presence inside
the wear track. Higher concentrations of oxygen (Fig. 6e) correlates
892 A. Shirani et al. / Carbon 143 (2019) 890e896

Fig. 1. (a) Coefficient of friction values and (b) corresponding wear tracks formed during sliding at 0.25 N load in different concentrations of ND solution in SBF. (A colour version of
this figure can be viewed online.)

Fig. 2. The coefficient of friction values during sliding in different concentration of ND in SBF under different applied load. (A colour version of this figure can be viewed online.)

with regions of lower carbon presence. Thus, the presence of car-
bon plays a critical role in reducing oxidation and minimizing wear
of the sliding surfaces.
The nature of the carbon-based tribolayer formed inside the
wear track was evaluated using Raman spectroscopy (Fig. 7). Our
results indicate that carbon shows a typical nanodiamond signa-
ture, suppressing formation of the titanium oxide inside the wear
track. In contrast, analysis of the wear track formed during sliding
in pure SBF (Fig. 7d) demonstrates the presence of representative
titanium oxide peaks at ~416 and ~650 cm1 [38]. Previous studies
demonstrated a tendency for graphitic carbon formation in artifi-
cial joints during sliding [32]. Here, in contrast, the formed tribo-
layer demonstrates a high-intensity carbon D peak (at ~1370 cm1),
suggesting that nanodiamonds are not completely graphitized
 A. Shirani et al. / Carbon 143 (2019) 890e896 893

Fig. 3. (a) Wear of the titanium surfaces during the tests at different loads. At 0.25 N load (Hertzian contact pressure ~ 0.28 GPa), the minimum wear is observed for 0.05 wt% of NDs;
at 0.5 N load (Hertzian contact pressure ~ 0.35 GPa), the minimum wear is for 0.1 wt% NDs; and at 1 N load (Hertzian contact pressure ~ 0.45 GPa), the minimum wear is for 0.15 wt%
NDs. (b) Optical images of the ball wear scar for the pure SBF and SBF with optimal concentrations of NDs. (A colour version of this figure can be viewed online.)

Fig. 4. SEM-EDS analysis of the wear track formed during the tests in SBF at 0.5 N load (Hertzian contact pressure ~ 0.35 GPa). Analysis indicates a high concentration of oxygen
inside the wear track. The Na, F, and Cl peaks originate from the residue of the SBF on the surface and are intentionally excluded from the further analysis of the oxidation amount.
(A colour version of this figure can be viewed online.)
894 A. Shirani et al. / Carbon 143 (2019) 890e896

Fig. 5. SEM-EDS analysis of the wear track formed during the tests in SBFþ0.1 wt% NDs at 0.5 N load (Hertzian contact pressure ~ 0.35 GPa). Inside the wear track, the presence of
carbon is observed. The Na, F, and Cl peaks originate from the residue of the SBF on the surface and are intentionally excluded from the further analysis of the oxidation amount. (A
colour version of this figure can be viewed online.)

Fig. 6. SEM-EDS map of the wear track formed during the test in SBFþ0.1 wt% NDs at 0.5 N load (Hertzian contact pressure ~ 0.35 GPa). (a) The area of the wear track with (b) higher
magnification image is highlighted. (c) Overlay map and detailed (d) carbon, (e) oxygen and (f) titanium map demonstrate uniformity of the titanium and oxygen concentration
inside and outside wear track while carbon is found inside the wear track only. (A colour version of this figure can be viewed online.)

during the sliding, enabling support of higher normal and shear as was observed earlier for carbon-based tribological films [39e42].
stresses. An additional peak at ~1560 cm1 is indicative of the sp2 Raman results confirm the formation of a carbon-rich tribolayer
bonded carbon peak, typical for graphitic carbon [32]. Presence of capable of minimizing friction and wear of sliding surfaces. Com-
the carbon layer results in substantial friction and wear reduction parison of the Raman spectra of dry NDs before the test (see
 A. Shirani et al. / Carbon 143 (2019) 890e896
Fig. 7. Raman 2D map of the sp3 bonded carbon peak (at ~1330 cm1) of the wear track formed during the test with SBFþ0.1 wt% NDs at 0.5 N load (Hertzian contact
pressure ~ 0.35 GPa). (a) Overview of the wear track selected for the Raman 2D map analysis. (b) Raman spectra inside and outside the wear track for the tests performed in (c)
SBFþ0.1 wt% NDs and (d) pure SBF. (A colour version of this figure can be viewed online.)
supplementary information, Fig. S2) and of the formed tribofilm
suggests that NDs experience high degree of amorphization during
sliding and embedding into the titanium substrate.
Based on these observations, we conclude that the mechanism
of the wear and friction reduction in presence of the NDs is as
follows: nanodiamonds embed inside a soft titanium surface layer
and minimize wear of the titanium surface. With an increase in
contact load, a larger amount of nanodiamonds is needed to form a
supportive tribolayer. At lower loads, an excess of nanodiamonds
instigates continuous wear of the protective tribolayer and tita-
nium surfaces via polishing. Therefore, the optimal concentration
of nanodiamonds adjusts correspondingly to the applied load.
However, the addition of NDs into SBF demonstrates reduced wear
and friction as compared to pristine SBF.
The trend observed for optimal concentration can be related to
the thickness of the tribofilm needed to supply the necessary
support under load. Since the higher applied load results in higher
contact pressure deformation and leads to higher friction force
experienced by the sliding surfaces, formation of a thicker protec-
tive film is critically important. The availability of NDs enables
formation of a thicker and more uniform tribofilm. Additionally, the
optimal concentration of NDs replenishes the tribofilm damaged
during wear. However, with further concentration increase, excess
of NDs may result in large material build up, eventually delami-
nating from the titanium substrate and instigating abrasion during
sliding [43]. Though the optimal concentration of the nano-
diamonds changes, our results clearly indicate improvement in
friction and wear characteristics of titanium surfaces in the pres-
ence of very small amounts of nanodiamonds in contrast to SBF
only. Subsequent experiments will focus on evaluation of nano-
diamond performance in actual synovial joint fluid providing
lubrication in the hip joints.
4. Conclusions
We demonstrated a new mechanism responsible for friction and
895
wear reduction in titanium tribopairs in the presence of nano-
diamond additives. Specifically, we show that adding nano-
diamonds into simulated body fluid, closely reproducing usual
operating environment for hip implants, results in a more than
two-times decrease in friction and leads to 3e4 orders of magni-
tude reduction in wear of titanium surfaces. Notably, the optimal
concentration of nanodiamonds is largely dependent on the
applied load. While at the applied loads of 0.25 N, only ~0.05 wt% of
nanodiamonds are needed to observe improvements. Increasing
the contact load to 1 N requires the concentration of nanodiamonds
to be increased up to ~0.15 wt% to achieve a similar benefit. We
attribute such an observation to the uniformity of the diamond-
based tribofilm formation necessary for supporting contact pres-
sure and shear loads.
The presented results suggest the potential for nanodiamonds to
serve as effective biocompatible nanoadditives in joint re-
placements. By injecting small concentrations in the regions of high
load and shear stresses, the lifetime of the artificial joints can be
substantially increased.
Acknowledgments
This work was performed in part at the University of North
Texas' Materials Research Facility. Support from Advanced Mate-
rials and Manufacturing Processes Institute (AMMPI) at the Uni-
versity of North Texas is acknowledged.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.carbon.2018.12.005.
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