Materials Science and Engineering C 62 (2016) 643–655

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Materials Science and Engineering C

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

Tribological characterization of zirconia coatings deposited on Ti6Al4V

components for orthopedic applications
M. Berni a,⁎, N. Lopomo b,c, G. Marchiori a, A. Gambardella a, M. Boi a, M. Bianchi a, A. Visani b, P. Pavan d,
A. Russo a, M. Marcacci a,b
a
Laboratorio di NanoBiotecnologie — NaBi, Istituto Ortopedico Rizzoli, via di Barbiano 1/10, Bologna, Italy
b
Laboratorio di Biomeccanica ed Innovazione Tecnologica, Istituto Ortopedico Rizzoli, via di Barbiano 1/10, Bologna, Italy
c
Dipartimento di Ingegneria dell'Informazione, Università degli Studi di Brescia, via Branze 38, Brescia, Italy
d
Dipartimento di Ingegneria Industriale, Centro Interdipartimentale di Ricerca di Meccanica dei Materiali Biologici — CMMB, Università di Padova, Via F. Marzolo 9, Padova 35131, Italy

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

Article history: One of the most important issues leading to the failure of total joint arthroplasty is related to the wear of the plas-
Received 4 November 2015 tic components, which are generally made of ultra high molecular weight polyethylene (UHMWPE). Therefore,
Received in revised form 15 January 2016 the reduction of joint wear represents one of the main challenges the research in orthopedics is called to address
Accepted 3 February 2016
nowadays. Surface treatments and coatings have been recognized as innovative methods to improve tribological
properties, also in the orthopedic field.
Keywords:
Pulsed plasma deposition
This work investigated the possibility to realize hard ceramic coatings on the metal component of a prosthesis, by
Ceramic coating means of Pulsed Plasma Deposition, in order to reduce friction and wear in the standard coupling against
Titanium alloy UHMWPE.
Ultra-high molecular weight polyethylene Ti6Al4V substrates were coated with a 2 μm thick yttria-stabilized zirconia (YSZ) layer. The mechanical proper-
Ball-on-disk ties of the YSZ coatings were assessed by nanoindentation tests performed on flat Ti6Al4V substrates. Tribological
Wear performance was evaluated using a ball-on-disk tribometer in dry and lubricated (i.e. with fetal bovine serum)
Friction coefficient highly-stressing conditions, up to an overall distance of 10 km. Tribology was characterized in terms of coefficient
of friction (CoF) and wear rate of the UHMWPE disk. After testing, specimens were analyzed through optical mi-
croscopy and SEM images, in order to check the wear degradation mechanisms. Progressive loading scratch tests
were also performed in dry and wet conditions to determine the effects of the environment on the adhesion of
the coating.
Our results supported the beneficial effect of YSZ coating on metal components. In particular, the proposed solu-
tion significantly reduced UHMWPE wear rate and friction. At 10 km of sliding distance, a wear rate reduction of
about 18% in dry configuration and of 4% in presence of serum, was obtained by the coated group compared to the
uncoated group. As far as friction in dry condition is concerned, the coating allowed to maintain low CoF values
until the end of the tests, with an overall difference of about 40% compared to the uncoated balls. In wet condi-
tions, the friction values were found to be comparable between coated and uncoated materials, mainly due to a
premature delamination of the coating. Scratch tests in wet showed in fact a reduction of the critical load required
to a complete delamination due to a formation of blister, although no change or damage occurred at the coating
during the soaking period.
Although conditions of high values of contact pressure were considered, further analyses are however required to
fully understand the behavior of YSZ coatings in wet environment and additional research on the deposition pro-
cess will be mandatory in order to improve the coating tribological performance at long distances addressing or-
thopedic applications.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
Total joint arthroplasty (TJA) is reported to be one of the most fre-
quent approaches used to surgically treat inoperative and aching joints
that are severely damaged by traumas or end-stage degenerative
⁎ Corresponding author.
E-mail address: m.berni@biomec.ior.it (M. Berni).
diseases [1]. In this perspective, TJA has been both clinically and techno-
logically designed to restore joint functionality and relieve pain [2].
Among TJAs, the most common type of prosthetic joint involves the
use of ultra-high molecular weight polyethylene (UHMWPE) sliding
against metal alloys (e.g. Co–Cr–Mo, stainless steel and titanium alloys).
These couplings were reported to have low friction coefficients but, in
general, a relatively high wear rate [3]. High wear rate broadly means
both loss of the dimensional stability, due to irreversible deformations,

http://dx.doi.org/10.1016/j.msec.2016.02.014
0928-4931/© 2016 Elsevier B.V. All rights reserved.
644 M. Berni et al. / Materials Science and Engineering C 62 (2016) 643–655
and release of plastic debris within the joint environment, with possible
development of osteolysis [4]. Further, because of wear, metallic ions
could be released at a local level, leading to tissue inflammatory re-
sponses [5] and corresponding bone resorption [6]. All these factors
have been identified as critical for the long-term stability of the prosthe-
sis and they could lead to the aseptic loosening of the implant itself [7].
Several approaches have been proposed to reduce wear rate and
thus improving the lifetime of the prosthetic implant. In general, the
most common approach involved the introduction of harder materials.
This choice led to ceramic-on-ceramic, metal-on-metal or hybrid cou-
pling approaches [8]. At present, the bulk ceramic-based components
coupled with UHMWPE represent the optimal solution in terms of com-
promise between costs, clinical reliability and wear performance [9]. On
the other hand, in their monolithic form, ceramics present high brittle-
ness, which can lead to in vivo catastrophic failures of the implant [10].
So far, Co–Cr–Mo components remain the standard de facto for metal-
on-UHMWPE coupling, because of their higher abrasion resistance com-
pared to both titanium alloy and stainless steel [11], as well as their
overall long-term clinical outcomes. However, titanium alloys have
been widely used in biomedical applications because of their biocom-
patibility, optimal mechanical properties (i.e. elastic modulus compara-
ble with human bone), good corrosion and fatigue resistance and high
mechanical strength [12]. Titanium was reported as one of the
privileged material used in the hip prosthesis stem for its biocompatibil-
ity [13]. Unfortunately, in a prosthetic coupling, several concerns have
been raised over titanium hardness, tribological properties and overall
wear performance, which is mainly affected by the presence of hard
third bodies [14]. For these reasons, in general, Co–Cr–Mo alloys or ce-
ramics have been identified as privileged materials in coupling, support-
ed by a modular approach in designing the prosthesis. However, even
this solution reported several drawbacks mainly related to fretting
and corrosion at the interface between the modular components, due
to high local loads and to non-practical substitution [13]. In order to
minimize wear issues, different studies focused on chemo/physical en-
gineering of the metal part [15], the plastic inlay [16] or both coupling
components [17]. Among these approaches, literature reported the pos-
sibility of modifying the surface of the actual components in order to en-
hance hardness and reduce the overall friction coefficient, without
losing the bulk mechanical advantages [18]. In particular, untreated tita-
nium alloys were reported to have issues related to excessive wear,
especially in hip prosthesis, therefore coatings was discussed as a possi-
bility to enhance their surface properties [19]. Literature reported, for
instance, the use of diamond-like carbon (DLC) [20], Si-DLC [21], TiN
[22] and Ti–C–N [23], each with its own advantages and disadvantages.
In this perspective, several deposition techniques have also been pro-
posed, including chemical vapor deposition (MOCVD) [24], electron
beam physical vapor deposition (EBPVD) [25], arc ion plating [26],
pulsed laser deposition (PLD) [27] and magnetron sputtering [28]. In
the past few years, Pulsed Plasma Deposition (PPD) technique emerged
as a powerful technique for the stoichiometric deposition of ceramic
coatings even at room temperature and on plastic substrates [29–30].
The main advantages of PPD, compared to CVD and EB-PVD, are the
lower operating temperature [31], the higher rate of deposition [32],
the absence of volatile precursors [32] and the highly energetic deposi-
tion process, which allows to reliably maintain the composition of the
target material while ensuring optimal adherent coatings [33]. Recently,
PPD demonstrated its feasibility in realizing ceramic coatings also on
metal substrates [34–35]. Chemical, microstructural and phase analysis
have shown that the coatings obtained by PPD are composed by a crys-
talline structure and characterized by cubic phase, with impurities
lower than 1%. Morphological analysis showed a columnar growth
and a high density of grain, revealing a rather homogeneous deposition
[36,37]. However, to our knowledge, an extended tribological character-
ization of titanium alloy components coated by PPD and coupled with
UHMWPE, thus addressing biomedical applications, is still lacking.
Therefore, the main goal of this work was to assess the potential
mechanical and tribological benefits in realizing yttria-stabilized zirco-
nia (YSZ) coating onto titanium alloy components. The coatings, specif-
ically realized by means of PPD technique, were characterized by
thickness, hardness, Young's modulus and adhesion studies.
The overall tribological performance of the coated titanium alloy
samples was tested against the UHMWPE component by using a ball-
on-disk tribometer and considering both dry and wet conditions. The
worn surfaces of both metal (coated and uncoated) and polymeric spec-
imens were analyzed after the tests in order to check the wear degrada-
tion mechanisms.
2. Experimental
2.1. Materials
YSZ coatings were deposited by ablating a tetragonal zirconia
(zirconium dioxide) target, stabilized with 3 mol% Y2O3. Cylindrical
targets (Ø ~ 3 cm, thickness ~ 0.7 cm) were produced starting from
pure 3Y-TZP powder (Tosoh, Tokyo, Japan), by cold isostatic pressing
(30 MPa, 60 s) and sintering at 1500 °C for 1 h (process performed by
ISTEC-CNR, Faenza, Italy). YSZ coatings were deposited on titanium
alloy balls (Ø = 6.00 ± 0.03 mm, Hi = 0.9 ÷ 1.3 GPa, Ei = 103 GPa,
Ra = 0.1 μm, International Standard R56400, Grade 100, R.G.P. Inter-
national S.r.l, Milan, Italy) for tribological tests. Titanium alloy flat
samples (29 × 29 mm, thickness ~ 6 mm, Ra = 1.92 ± 0.06 μm,
CITIEFFE Srl, Bologna, Italy) were used as a substrate for the deposi-
tion addressing nanoindentation and scratch tests. UHMWPE disk
samples (radius ~ 28.5 mm, thickness ~ 11.3 mm, International Stan-
dard ASTM F-648, ISO-5834-1/2, CITIEFFE srl, Bologna, Italy) were
realized for the tribological analysis. Prior to deposition and tests,
all samples were ultrasonically cleaned in serial baths of water,
isopropanol and acetone (10 min each) and dried under N2 flux.
2.2. Coating deposition
The technique used to realize YSZ coatings was a physical vapor de-
position process based on a commercial Pulsed Plasma Deposition gun
(Gen III Advance Electron Gun, Organic Spintronics Srl, Bologna, Italy).
The deposition was achieved through the ablation of the target material
by a fast pulse (100 ns) of high energy (10 J*cm−2) and high density
(108 W*cm−2) electrons. The ablated material was then directed to-
ward the substrate located at a suitable distance from the target [36].
The substrate was mounted on a rotating sample holder specifically po-
sitioned at a distance of 65 mm from the rotating target surface. The dis-
tance between the surface of the target and the tip of the quartz tube
(length ~ 10.5 cm, inner diameter ~ 3 mm, external diameter ~ 6 mm)
was kept at ~ 1 mm. The function of the quartz tube is mainly related
to its role in the ablation of the target. The quartz tube is specifically
necessary for the channeling and the addressing of the high density
electron beam. The working pressure of the vacuum chamber was
6 × 10− 3 mbar, controlled by a flow of oxygen (purity level =
99.99%). The working voltage, current and frequency were set at
17 kV, 3 mA and 5 Hz respectively. The deposition was performed with-
out heating the substrate. The deposition parameters were adjusted in
order to obtain an uninterrupted plasma plume and a suitable deposi-
tion rate (250 nm*h−1). On the flat samples, a thickness of ~2 μm and
a roughness of 75.6 ± 8.9 nm were evaluated by stand-alone atomic
force microscopy (AFM, NT-MDT, Moscow, Russia) operating in semi-
contact mode at ambient conditions.
2.3. Nanoindentation tests
Nanoindentation tests were performed with an instrumented in-
denter (Nanoindentation Tester NHT2, CSM Instruments — Anton Paar
S.r.l, Peseux, Switzerland) in order to determine the indentation hard-
ness (HIT) and the Young's modulus (EIT) of the deposited YSZ coatings
 M. Berni et al. / Materials Science and Engineering C 62 (2016) 643–655
according to the Oliver–Pharr method [38]. In order to estimate the me-
chanical properties, along the coating thickness, the Continuous
Multicycle Method (CMC) was used [39]. Ten CMC indentations were
performed on different areas of the coated samples according to the fol-
lowing protocol: the first loading–unloading cycle was constituted by a
loading ramp up to 1 mN followed by an unloading down to 5% of the
maximum load, 14 more cycles were then executed, using a quadratic
load increment, up to the final load of 100 mN. The loading and
unloading time was set to 10 s with a pause of 2 s between loading
and unloading. In addition, a pause of 5 s was set between two subse-
quent cycles. Ten additional single indentations were performed to
allow the determination of the correct coating HIT and EIT values,
avoiding the hardening phenomenon [40]. In this case the following
procedure was adopted: loading to the maximum load in 10 s, holding
time of 2 s and unloading in 10 s.
The choice of the maximum load value in single indentation was
consequent to the depth at which the peak of hardness and elastic mod-
ulus were obtained by using CMC analysis, corresponding to a value of
about 3 mN. All tests were performed in air and at (25 ± 2) °C using a
Berkovich diamond tip after a preliminary calibration on a standard
fused-silica sample.
2.4. Tribological tests
The tribological analysis was carried out by using a standard pin-on-
ball tribometer (TRB, CSM Instruments — Anton Paar S.r.l, Peseux,
Switzerland). A lower rotating UHMWPE disk sample was coupled
against an upper stationary coated or uncoated titanium ball (Ø =
6.00 ± 0.03 mm). Tests were performed under the following operation-
al conditions: reciprocating mode, normal load 1 N, acquisition rate
10 Hz, linear max speed 70 mm/s, and at (25 ± 2) °C. The length of
the wear track was 10 mm to account for the roughness of the
UHMWPE disk. The chosen load produced an approximate Hertzian
contact pressure of 21 MPa between the disk and the sphere. This pres-
sure corresponds to the contact pressure peak generated in physiologi-
cal conditions, considering – for instance — the contact between an
UHMWPE cup and a 36 mm titanium head in a hip prosthesis under a
body weight of 80 kg during stair climbing or a body weight of 100 kg
during slow walking [41–42]. The sliding distance for all experiments
was set to 10 km, corresponding to a path of ~300,000 cycles obtained
in 6 months of in vivo activity [43]. Friction and wear recordings were
collected at 25, 50, 100, and 500 m and 1, 5, and 10 km. The friction co-
efficient was assessed in real-time by using the tribometer load cell. A
contact profilometer (Surtronic 25 Profilometer, Taylor Hobson —
Ametek Inc., Berwyn, PA, USA) equipped with a 2 μm round diamond
stylus (Small Bore Pick-up 112/1504) was instead used to estimate
the UHMWPE wear rate at each interval by performing five measure-
ments of wear area on each track. The correlation between wear rate
and volume loss is given by the following equation:
V
k¼
SF
where k is the wear rate (mm3/Nm), V is the volume loss (mm3), S is the
sliding distance (m) and F is the load (N). Wear rate represents the
slope of the curve obtained by plotting volume loss against sliding dis-
tance; therefore, a constant value during a phase of the test means
that the wear tends to a steady-state condition. For each coupling,
tests were carried out in dry environment – to amplify wear related
phenomena – and in the presence of fetal bovine serum solution, cur-
rently indicated by ASTM as standard for in vitro tests, although it was
demonstrated to be more aggressive in terms of corrosion rate com-
pared to the in vivo conditions [44]. The solution (75 ml) was composed
by 25% (v/v) fetal bovine serum and by 75% (v/v) deionized water. The
volume was monitored to ensure the complete immersion of the con-
tact surfaces. At each measurement step, the lubricant was replaced to
645
avoid the presence of impurities and worn material generated during
the test. Before each wear rate measurement the sample was rinsed
with deionized water and dried under N2 flux. Three tests were
performed for each coupling, both in dry and lubricated conditions.
Scanning Electron Microscope (Field Emission Scanning Electron Micro-
scope S-4000, Hitachi, Tokyo, Japan) and optical microscope (CSM In-
struments — Anton Paar S.r.l., equipped with objectives Olympus M
Plan N from 5× to 100×) were used to qualitatively assess the samples
after the tests.
2.5. Scratch tests
To evaluate coating adhesion, scratch tests were performed using a
Micro-Scratch Tester (MST, CSM Instruments — Anton Paar S.r.l, Peseux,
Switzerland), following the specifications of ASTM C 1624-05 for deter-
mination of mechanical failure modes of ceramic coatings [45]. A conical
Rockwell C stylus with spherical apex indenter tip (angle 120° and
sphere radius 100 μm) subjected to a progressive normal load from
1 N to 10 N moved across the surface of the coated titanium sample
with a scan speed of 10 mm/min and a loading rate of 10 N/min. To as-
sess the effect of lubricant on the coating adhesion, tests were conduct-
ed in dry condition and in wet condition after soaking the sample for a
time equal to the mean duration of the tribological test (using the
same solution described in Section 2.4).
In order to balance any possible deposition inhomogeneity and sub-
strate/coating surface defects, tracks performed in dry and in serum
were spatially alternated (Fig. 1).
According to ASTM, a minimum of five scratches was made on the
sample for each condition. The worn tracks were investigated with an
optical microscope (zooms 20 × and 50 ×) – mounted on the micro-
scratch platform – in order to determine the failure modes of the coating
and associate them with the load at which they occurred. It is worth
underlining that in a scratch track, a number of consecutive coating-
failure events may be generated at increasing normal force values. In
general, a series of failure modes can be observed and used to study
the mechanical behavior of the coated surface, where the onset of the
n-th failure mode defines the critical normal force Lcn.
2.6. Statistical analysis of the data
Coating indentation hardness and Young's modulus were evaluated
on the whole set of performed measurements and reported as mean ±
standard deviation. Friction coefficients were determined on the whole
distance for each test and reported as mean ± standard deviation. For
repeated tests, the mean values were averaged on the whole set. For
each reported distance, wear rates were averaged on five measure-
ments equally-spaced over the entire wear track. Again, for repeated
tests, the mean values were averaged on the whole set. A generalized
ð1Þ
Fig. 1. Micrograph of the initial phase of the scratch tests which shows the alternating
tracks in dry (D) and wet (W) conditions.
646 M. Berni et al. / Materials Science and Engineering C 62 (2016) 643–655

Linear Model based on Gamma distribution and post hoc pairwise anal-
ysis with Sidak test were used to compare friction and wear rate be-
tween uncoated and coated configuration, both in dry and lubricated
conditions, with a level of statistical significance α = 0.05. The use of
this type of test is due to the distribution of the data, which is not a
Gaussian distribution but a Gamma distribution, according to the results
of Kolmogorov–Smirnov test. The values of the normal force at which
every failure mode occurs, in both dry and lubricated conditions, were
reported as mean ± standard deviation.

3. Results and discussion

3.1. Nanoindentation testing
The CMC method allowed to obtain a profile of indentation hardness
and Young's Modulus as function of the reached penetration depth
(Fig. 2). The trend of both HIT and EIT curves was characterized by an ini-
tial steep increase, mainly due to a combination of effects correlated to
tip size and geometry, contact-point determination and surface rough-
ness [36].
Considering an overall coating thickness of ~2 μm and the “10% rule
of thumb” [46], the behavior of the coating prevailed within an indenta-
tion depth ranging between 100 and 150 nm. Within this range, a peak
in both Young's modulus and hardness could indeed be identified. At
this range, the obtained measurements were mainly related to the coat-
ing characteristics, whereas – by increasing the depth – they became
more and more affected by the presence of the softer metallic substrate.
Nanoindentation test reported superior mechanical properties of the
coating (HIT = 11.1 ± 1.1 GPa, EIT = 195.8 ± 27.8 GPa) compared to
the underlining metal sample (Hi = 5.48 ± 0.411 GPa, Ei = 133 ±
10 GPa). These values were comparable to the results reported in liter-
ature, considering several deposition techniques [47–49].
The indentation depth of 100 ÷ 150 nm corresponded to a load of
~ 3 mN applied during CMC tests. For this reason, this load value was
also chosen as the maximum value for the single indentation measure-
ments on the uncoated and coated titanium samples (Fig. 3). According
to these findings, the tests reported a value of 11.8 ± 2.2 GPa and
192.3 ± 18.7 GPa for indentation hardness and Young's modulus, re-
spectively, thus confirming CMC results.
Fig. 3. Load-depth curve of titanium alloy (i.e. uncoated) and YSZ-titanium alloy (i.e.
coated), considering a maximum load of 3 mN.
condition. In this state, we can suppose that the action of the hardest
smooth surface – regardless of its composition – was able to steadily
abrade the polymeric counterpart. In fact, the volume loss continuously
increased with the distance, but according to Eq. 1 a decrease in the
wear rate indicated the gradual achievement of this steady-state condi-
tion. Concerning dry testing (Fig.4), the presence of the coating reduced
the wear rate at each considered distance, showing an average decrease
of about 9%. Statistical differences between coated and uncoated sam-
ples in wear rate are steadily present from 500 m to 10 km and not in
the previous steps.
This finding was probably due to the higher variability observed in
the measures obtained during the “running-in” phase and it could be as-
sociated to the initial roughness of the samples surface [52–53]. In this
perspective, by analyzing the behavior of the coating in dry conditions,
we could assume that the “running-in” phase lasted less than 500 m. At
further distances, the higher hardness of the coating and its reduced
roughness lead indeed to a minor abrasion of the polymeric counter-
part, compared to the result obtained considering the uncoated samples
[54]. Finally, the values of wear rate at 10 km were 1.29 × 10–5 ±
3.55 × 10–7 mm3/(Nm) and 1.06 × 10–5 ± 4.71 × 10–7 mm3/(Nm) for

3.2. Wear rate

Considering both dry/lubricated conditions and coated/uncoated

samples, the wear rate associated with UHMWPE disk (Figs. 4 and 5)
showed an initial “running-in” phase [50–51]. The mean value of wear
rate specifically presented a steep increase mainly due to the gradual
removal of the surface asperities on both sides of the reciprocating
surfaces.
At increasing testing distances, this phenomenon resulted to be
more and more attenuated until the coupling reached a steady-state

Fig. 4. (a) Wear rate of UHMWPE disk for uncoated and coated configurations in dry
Fig. 2. Hardness and Young's Modulus profile as a function of indentation depth reached condition. (b) Particular of the wear rate at 5 and 10 km in the same conditions. *
for the zirconia coating realized by PPD. indicates a statistically significant difference (pvalue b 0.05).
 M. Berni et al. / Materials Science and Engineering C 62 (2016) 643–655
Fig. 5. (a) Wear rate of UHMWPE disk for uncoated and coated configuration in lubricated
conditions. (b) Particular of the wear rate at 5 and 10 km in the same conditions. *
indicates a statistically significant difference (pvalue b 0.05).
uncoated and coated samples, respectively. This difference
corresponded to a final reduction in wear rate of about 18%, when con-
sidering the coated sample (Fig. 4b). Relating the presence of the coat-
ing to what happens on bulk ceramics, the values of wear rate
obtained at 10 km were very similar to the findings reported by Gutiér-
rez et al. [55] and by Ge et al. [56]. The former study was specifically con-
ducted by using a pin-on-disk apparatus and a UHMWPE plate sliding at
the velocity of 60 mm/s against an Al2O3 pin under a load of 30 N; at
10 km and considering a contact pressure of 2.5 MPa the authors report-
ed a wear rate value of 1.05 × 10−5 mm3/(Nm). In the latter study, tri-
bological tests were performed by considering a ZrO2 ball (ø ~ 3 mm)
sliding at the velocity of 190 mm/s against an UHMWPE disk under a
load of 5 N; at 75.2 km and estimating a contact pressure of about
57 MPa, these authors also reported a similar wear rate value of
1 × 10−5 mm3/(Nm). The wear rate values reported in those specific
cases, compared to the findings presented here, would be worth
discussing. First of all, in spite of different testing conditions, but consid-
ering values normalized on loads, both studies reported wear rate
values extremely close to those observed in the present work. These re-
sults, obtained in dry conditions, specifically suggested us to consider
the proposed solution as a “clean” ceramic-polymer coupling, at least
until the coating was present. Secondarily, the wear rate should be con-
sidered, in this perspective, as a property associated to a specific testing
distance and a corresponding coupling condition. Although not report-
ed, we supposed that in the abovementioned studies, the authors calcu-
lated the wear-rate when the coupling reached a steady-state
condition; for this reason, we thought it was reasonable to compare
those values to the results we obtained at 10 km (Fig. 4).
Concerning the tests conducted in bovine serum (Fig. 5), a reduction
of wear rates was obtained considering the coated samples compared to
the uncoated ones, specifically reaching an average reduction of about
11%. At each considered distance, wear rate was indeed lower in pres-
ence of the ceramic coating. In particular, we could highlight an oppo-
site trend in wear rate compared to the dry conditions; specifically
data reported a statistically significant difference between coated and
uncoated samples at each considered distance, which however
647
decreased approaching 10 km. At this distance, wear rates were
9.06 × 10− 6 ± 7.68 × 10− 8 mm3/(Nm) and 8.69 × 10− 6 ±
3.11 × 10−7 mm3/(Nm) for uncoated and coated samples, respectively,
which corresponded to a reduction rate of only 4%. This finding was
probably due to both a partial removal of the coating – that led to an
UHMWPE wear rate very similar to the one obtained in the uncoated
configuration – and to the evidence of increased measurement
variability.
It is worth focusing on the values assumed by wear rate compared to
dry testing. Considering the presence of lubricant, for both coated and
uncoated sample and at each considered distances, the wear rate re-
ported lower values compared to the ones obtained in dry conditions,
For uncoated samples and steady-state condition (i.e. at and after
10 km of sliding distance), the obtained wear rate was of the same
order of magnitude of the one found by Jiang et al. [57], Xiong et al.
[58] and Dong et al. [59] analyzing the tribological properties of a
Ti6Al4V-UHMWPE coupling in serum. Instead for the coated samples
in the same condition, the reduction of wear rate compared the uncoat-
ed samples was much lower than the one obtained in dry conditions; in
particular, wear rate values were one order of magnitude greater than
what reported by Ge et al. [56] and Xiong et al. [60], who tested
UHMWPE specimens against ZrO2 ball and Al2O3 pin, respectively.
This finding is probably due to the occurrence of a partial delamination
of the coating, related to the presence of the lubricant, which - in this
case - seemed to amplify the wear phenomenon rather than reducing
it. Imperfections generated during the deposition process, such as
micro-droplets, pinholes, or other point defects, could in fact be consid-
ered as corrosion initiation sites, resulting in wear or delamination of
the coating [61]. In addition, the presence of biological species in solu-
tion such as proteins could also encourage corrosion of the adhesion-
promoting interlayer; the most common corrosion mechanisms found
in coatings when in contact to body fluids have been indeed reported
to be pitting and stress-induced corrosion, which were related to slow
crack advancement or interlayer dissolution, thus resulting in a delam-
ination [62].
Furthermore, as Section 3.4 will report, the realized coating present-
ed also a more hydrophobic behavior compared to the underlying sub-
strate; for this reason the serum was not able to properly work as
lubricant as for the uncoated samples, leading to reduced performances
of the coated samples when compared to dry conditions. In dry condi-
tions, the UHMWPE wear was strongly reduced by the coating, which
seemed to exhibit a self-lubricating behavior typical of several ceramic
materials. Nanocomposite structure of YSZ coatings, consisting in a
combination of amorphous and crystalline phases, was reported to be
able to provide a chameleon-like surface adaptation, in which different
phases turn into lubricants in response to different test environments,
contact loads, sliding speeds and temperature [63–64]. Moreover, prop-
er sizing of nanocrystalline grains [65] can reduce crack sizes and create
large volumes of grain boundaries, increasing overall toughness and
contact load bearing capabilities [66].
3.3. Wear mechanisms
The hypothesis of coating delamination in lubricant was qualitative-
ly supported by optical microscopy and SEM analysis. Under dry testing
(Fig. 6), the overall amount of contact area of the metal component in
the presence of the coating (Fig. 6a, c) was lower with respect to uncoat-
ed samples (Fig. 6b, d). Further, even at the maximum sliding distance,
the presence of the coating was still perceptible, with the only presence
of small areas of metal substrate exposed (Fig. 6c). According to Dong
et al. [59], in the absence of coating and in dry conditions (Fig. 6a), the
surface of the bare metal component was characterized by deep and
wide grooves, an indication of severe abrasive and adhesive wear. As
found by Xiong et al. [60], SEM image of the uncoated sample in dry
(Fig. 6c) showed both the presence of debris (10–20 μm) and flakes of
UHMWPE transferred on Ti6Al4V counterface.
648 M. Berni et al. / Materials Science and Engineering C 62 (2016) 643–655
Fig. 6. Images of the contact zone of the ball affected by tribological tests. Optical images of the (a) uncoated and (b) coated specimens (scale 25 μm). SEM images of the uncoated (c) and
coated (d) samples (scale 150 μm). Arrows in (c) indicate debris and flakes of UHMWPE. Arrows in (d) indicate flakes of polymer. The images refer to dry testing after 10 km.
Optical image of the coated specimen showed a lower presence of
grooves compared to the uncoated one, indicating that the use of ce-
ramic film significantly changed the mechanical properties of Ti6Al4V
alloy. Differently from what is seen for the uncoated samples, SEM
image showed the only presence of few flakes of UHMWPE transferred
on the counterpart but not debris.
Regarding the behavior of the coating in serum, the amount of con-
tact area appeared to be lower (Fig. 7b) compared to uncoated samples
(Fig. 7a). Grooves on the uncoated specimens were still present
(Fig. 7a). Optical (Fig. 7b) and SEM images (Fig. 7c, d) of the coated sam-
ple in wet condition showed that a large amount of the surface indeed
presented coating delamination. This finding could support the similar
values of wear rate and friction obtained in serum at 10 km. Neverthe-
less only surface grooves are present on the substrate (Fig. 7d), showing
that only the final portion of the test interested the underlying metal,
proving that the detachment of the coating took place in the final stages
of the sliding.
The worn surfaces of the polymeric specimens were also exam-
ined by SEM (Fig. 8). The tracks on UHMWPE obtained by sliding in
dry condition against uncoated metal counterface presented ripples
perpendicular to the sliding direction (Fig. 8a). As found by Ge
et al. [67] these topographies were formed due to plastic deforma-
tion in sliding contact area. Because the ripples on UHMWPE are
more easily broke off when they subject cross-directional shearing,
more wear particles are removed and higher wear mass loss of
UHMWPE is induced. The rougher topography of the worn surface
included fibrous piling, shredding and white plows, which suggested
that the wear mechanism was a combination of abrasive and
adhesion wear.
The UHMWPE surface tested against coated metal component in dry
showed lower amount of ripples (Fig. 8b). This may suggest a reduction
of plastic deformation in the sliding contact area. Some evidence of fi-
brous piling was still present at the edge of the track but no plastic tear-
ing was recognized in the central part. This behavior was consistent to
the low wear rate of UHMWPE in the presence of coating in dry
condition.
As regards the tests conducted in serum, both in the absence
(Fig. 9a) and in the presence of coating (Fig. 9b), only some traces of rip-
ple and fibrous pilling were detected, highlighting a decrease in plastic
deformation and adhesion wear mechanism (Fig. 9). Nevertheless, no
significant difference was highlighted by the analysis of the wear tracks
obtained with and without the coating on the metal counterface.
3.4. Friction
During dry testing, at any sliding distance the coefficient of friction
(CoF) (Fig. 10) showed lower values in presence of the coating com-
pared to the uncoated samples. Furthermore, along with the progress
of the test, the uncoated configuration presented a large CoF increase
whereas the coated samples approximately maintained the same CoF
value. CoF trends reported for uncoated and coated samples against
UHMWPE could be identified as representative and typical for titanium
alloy against polymer [68–69] and ceramic against polymer [55,60], re-
spectively. In spite of the marked CoF reduction induced by the coating,
 M. Berni et al. / Materials Science and Engineering C 62 (2016) 643–655 649

Fig. 7. Images of the contact zone of the ball affected by tribological tests. Optical images of the (a) uncoated and (b) coated specimens (scale 25 μm). SEM images of the coated (c, d)
samples (scale 150 μm). The images refer to wet testing after 10 km.

a statistically significant difference was confirmed only for the sliding
distances of 1, 5 and 10 km. This finding was mainly due to the great
variability shown by the CoF in the uncoated configuration, especially
up to 500 m. At 10 km, CoF specifically reported a value of 0.22 ± 0.01
and 0.13 ± 0.02 in the absence and presence of the coating, respectively.
Friction, differently from the wear rate, was explicitly indicated as a fac-
tor depending on test parameters, among which the applied load and
the sliding speed [70]. Moreover, as previously reported, depending
on the proportion of the crystalline phase, the coatings can present
higher or lower hardness, wear resistance and friction coefficient [71].

Fig. 8. SEM images of the tracks resulted by sliding against (a) uncoated and (b) coated metal specimens (scale 75 μm). Arrows in both images indicate ripples and fibrous pilling due to
plastic deformation. The images refer to dry testing after 10 km.
650 M. Berni et al. / Materials Science and Engineering C 62 (2016) 643–655
Fig. 9. SEM images of the tracks resulted by sliding against (a) uncoated and (b) coated metal specimens (scale 15 μm). Arrows in both images indicate ripples. The images referred to wet
testing after 10 km.
Nevertheless, in a comparative perspective, it is noteworthy to men-
tion the CoF values reported by several studies, which worked on simi-
lar tribological couplings. Xiong et al. [60], for instance, found a steady-
state CoF value of about 0.14 considering an UHMWPE pin sliding
against an Al2O3 disk; this value is very close to the findings reported
in the present study. Regarding bare Ti6Al4V against UHMWPE samples,
Loinaz et al. [72] reported similar value of CoF in steady-state condition
by testing the same materials. Furthermore, the trend of the CoF curve
we reported was similar to what was found by Wang et al. [69]. Specif-
ically, a low CoF value of about 0.14 was identified at the initial stage,
followed by an increasing trend, which did not reach a steady-state con-
dition within the investigated distance. This finding could be explained
by the initial presence of a thin passive natural oxide layer (TiO2)
formed in air on the uncoated metal surface (~ 10–15 nm thick [73,
74]), which enhanced the tribological behavior of the Ti6Al4V/
UHMWPE coupling and lead to a low friction coefficient at the begin-
ning of the tests. Then, due to the progressive abrasion of this thin
oxide layer, friction and wear progressively increased [59, 69]. The pres-
ence of an oxide layer could also justify the absence of a statistically sig-
nificant difference between coated and uncoated samples during the
first steps of the tests.
For the tests conducted in serum (Fig. 11), an initial greater CoF
value was found with the coating, followed by a progressive increase,
which characterized both coated and uncoated samples. In particular,
a higher slope was recognizable for the uncoated samples, which led
to a higher increment of the initial CoF value of about 40%, compared
to about 35% for the coated samples.
Nevertheless, the CoF values became comparable between the
two configurations with the progress of the test, reaching, at
Fig. 10. CoF as a function of sliding distance in dry condition tests for uncoated and coated
configuration. * indicates a statistically significant difference (pvalue b 0.05).
10 km, the steady-state values of 0.194 ± 0.018 and 0.194 ± 0.004,
in the absence and presence of the coating, respectively. With the
due caution in comparing CoF values, as previously mentioned, we
could report several comparisons with the literature. The steady-
state CoF value obtained in the absence of the coating was, in partic-
ular, comparable to the value of 0.2 reported for similar conditions by
Wang et al. [68]; specifically, a final value of about 0.220 ÷ 0.224 was
obtained after an initial growing phase and a second phase in which
the curve tends to a steady-state condition. Trend and steady-state
values were also very close to the results found by Wilches et al.
[75], who tested an identical coupling in the presence of bovine
serum, reaching a final value of about 0.195. Analyzing CoFs for the
coated samples, the mean value reached at 10 km was much higher
compared to the results obtained by Xiong et al. [60] and Ge et al.
[56], who considered UHMWPE samples against Al 2O 3 and ZrO 2
specimens, respectively, reporting a steady-state CoF of about
0.04 ÷ 0.06. In this study, the friction reached at 10 km in the pres-
ence of lubricant for the coated samples seemed to be more similar
to the classical metal–polymer coupling.
This specific behavior could be partially explainable by analyzing the
wettability of the coating surface. By using the Contact Angle DigiDrop
(GBX, Bourg de Peage, France), the static contact angle of bare titanium
alloy was found to be (72 ± 2)° in the presence of bovine serum [58,68,
76], quite lower than (83 ± 5)°, obtained for the ceramic coatings. The
coated samples resulted indeed to be hydrophobic compared to both
the simple titanium surface and the bulk ceramic materials, especially
zirconia [76]. This behavior of the coating could be ascribable to its
nanostructured surface, but further analyses are required. Nevertheless,
this finding, associated to the presence of coating delamination, could
Fig. 11. CoF as a function of sliding distance in serum lubrication tests for uncoated and
coated configuration.
 M. Berni et al. / Materials Science and Engineering C 62 (2016) 643–655 651

explain the comparable values of CoF. Moreover, a hydrophobic coating 0.86) N. The last critical load, Lc3, is referred to a complete delamination
could reduce the beneficial effect of the lubricant [68], avoiding the for- of the coating, corresponding to a value of (8.89 ± 0.76) N. In one of
mation of the tribo-film which has been reported to be a usual conse- these tests, no signs of delamination were found even at the maximum
quence of the sliding contact in serum medium, especially in the load of 10 N, but only buckle and wedging spallation occurred.
presence of ceramic [77]. Surely, even if the hydrophobic coating Before starting tests in wet, the surface of the coated sample was
avoided the formation of the tribo-film, wear rate was modified by its evaluated by optical microscope. No sign of defect or damage of the
presence. Wear rate was in fact more affected by the increase in surface coating was found. The same above-mentioned sequence of failure
hardness, which reduced the contact area and the possibility of adhesive modes was generally obtained also for the tests conducted in serum.
interaction and abrasion of the UHMWPE sample [54]. Even in this case, chevron cracks were the first events appearing at
the coating, after which arc tensile cracks occurred at an average load
3.5. Adhesion test of (1.52 ± 0.35) N, which is approximately the same value found in
dry conditions. Recovery spallation was then found, but in lesser extent.
To better understand the lubricant effect on the coating perfor- Unlike from the dry situation, a new adhesive failure mode, buckling
mance, scratch tests were conducted. During dry and lubricated test- (Fig. 12d), was found. It refers to adhesion as for buckle and wedging
ings, both cohesive and adhesive failure modes were identified by spallation and in particular occurs ahead of the moving indenter, with
using optical microscope, as the ASMT standard recommends. By visual spallation being enhanced by the pile-up of the softer substrate material
analysis it was possible to associate each event to the corresponding [82]. In wet conditions, usually buckling or buckle spallation occurred
load that caused it. The isolated failures were ignored and critical load first and wedging spallation was present only in two tracks. The load
values generally refer to the normal load measured when the position value associated with adhesive failure in the presence of serum was
of the stylus was at the beginning of each cluster event [78]. Despite (3.28 ± 1.15) N. In addition, peculiar of the wet situation was the ap-
many articles cite only the critical load value at which a complete de- pearance of many partial delamination areas before increasing the in-
lamination of the coating occurs [79], hereinafter all the main failure denter penetration; Complete delamination (Fig. 13) happened at
modes encountered during the test were reported (Table 1). (7.43 ± 1.85) N, about 16% less than in dry tests.
Concerning dry tests, at the beginning of the loading were generally The revealed failure modes, both in dry and wet, are ductile failure
detectable chevron tensile cracks at the borders of the track, followed by modes and are related to the case of a hard coating on a softer substrate
arc tensile cracks at (1.53 ± 0.35) N. These failure modes are usually indi- [82]. No adhesion studies with related failure modes on ceramic coat-
cated as through-thickness cracking and may extend into the substrate if ings performed in wet conditions were found in the literature.
it is sufficiently brittle but they are stopped at the interface in presence of Concerning dry testing, a reduced number of studies for ceramic coat-
a hard coating [80]. The first critical normal force Lc1 is associated with the ings on metal substrates are present in the literature but using different
onset of arc tensile cracks (Fig. 12a), indicating a cohesive failure mecha- test conditions [78,81,83,84].
nism in the coating. After these earlier failures, the analysis identified re- What emerged is that adhesive and critical failure modes occurred at
covery spallations, which are associated with the elastic recovery that a lower load in wet conditions compared to dry testing. This revealed a
occurs behind the stylus as it travels over the coated surface; this phe- negative effect of the wet environment on the ceramic coating adhesion
nomenon depends on the plastic deformation within the substrate and to the metal substrate. Due to slow crack advancement, fluids can pen-
on through-thickness cracking in the coating [81]. Recovery spallation is etrate through the film and act as a corrosive electrolyte, forming coat-
generally not observed for a ductile failure, although it has been observed ing blisters: if the blister exceeds a certain dimension, local
in cases where ductile substrates fail in a brittle manner [82]. delamination can occur [62]. This confirms what hypothesized about
As previously reported, the failure modes mentioned up to now do not wearing during the harsher tribological test.
refer to a reduction of coating adhesion. The adhesion related failures -
which represent the basis of the scratch adhesion test for hard coatings 4. Conclusions
- are buckle and wedging types [80] (Fig. 12b, c), followed by a complete
delamination [78]. Because both buckle and wedging refers to a loss of ad- The main novelty of the present work is related to the use of the
hesion, it was decided to consider the one of them which occurred first as innovative PPD technique to realize ceramic coatings on metal com-
Lc2; it was generally buckle spallation for dry tests, occurring at (4.82 ± ponents. PPD already demonstrated its optimal performance in real-
izing ceramic coatings on both plastic [29,30,33] and metal
substrates [31,32]. This study systematically analyzed the wear per-
formance of YSZ coating realized by means of PPD technique on tita-
Table 1 nium alloy substrates under the hypothesis that this solution was
Failure mode results for the progressive load scratch tests. Lc1 refers to arc tensile crack,
able to improve the mechanical and tribological properties, includ-
sign of cohesive failure, Lc2 to buckle spallation, sign of adhesive failure, and Lc3 to a com-
plete delamination of the coating. ing friction and wear rate, when coupled with UHMWPE counter-
part. Tribological tests were specifically carried out at a load of 1 N
Environment Scratch no. Failure mode (N)
and a sliding speed of 7 mm/s using a ball-on-disk tribometer and
Lc1 Lc2 Lc3 considering two different configurations, i.e. dry and with fetal bo-
Dry 1 1.34 4.92 9.49 vine serum. Optical and SEM images of the worn surfaces were pro-
2 1.17 4.90 9.32 vided to check the wear degradation phenomena. Progressive load
3 1.81 5.24 8.95 scratches (following ASTM C 1624-05) were performed in dry and
4 1.35 5.66 7.81
a wet to determine the effects of the environment on the coating adhe-
5 2.00 3.38
Mean 1.53 4.82 8.89 sion. Summarizing and concluding the study:
SD 0.35 0.86 0.76
Serum 1 1.09 2.67 8.52 1. Nano-mechanical characterization of the coating confirmed that its
2 1.78 3.56 6.99
presence improves hardness and Young's modulus of the underling
3 1.97 2.37 7.94
4 1.40 2.63 4.46 metal component surface, with an increase of about 54% and 31%, re-
5 1.38 5.17 9.22 spectively. This improvement allows the reduction the contact area
Mean 1.52 3.28 7.43 between UHMWPE sample and metal counterpart.
SD 0.35 1.15 1.85 2. YSZ coatings deposited on titanium components, sliding against
a
Indicate that no delamination occurred even at the maximum load. UHMWPE inserts, showed good tribological properties. In particular,
652 M. Berni et al. / Materials Science and Engineering C 62 (2016) 643–655
Fig. 12. Particulars of the failure modes of the coating tests. (a) Arc Tensile crack, (b) Buckle spallation, (c) Wedging spallation and (d) Buckling as highlighted in wet condition. Arrow in
(a) indicates the start of arct tensile phenomenon. Arrows in (b) indicate buckle spallation. Arrow in (d) indicates buckling. The scale is 25 μm for each image.
the overall wear rate considering the coated samples was consider-
ably lower compared to the uncoated ones, leading to a reduction of
about 17% and 4% in dry and lubricated conditions, respectively. Fur-
thermore, in dry conditions, the coefficient of friction between coat-
ed samples and UHMWPE presented constant values along the
conduction of the whole test, underling the possibility of realizing
a “clean” ceramic-plastic coupling.
Conversely, in wet conditions, CoF values were reported to be
comparable between coated and uncoated sample, mainly due to
the hydrophobic behavior of the coating and its partial delamination
related to the presence of the serum.
3. Optical and SEM images of the worn surfaces showed a lower degra-
dation and damage of the coated metal counterface compared to the
Fig. 13. Particulars of complete delamination of the coating The scale is 25 μm.
uncoated one. The main wear mechanism for UHMWPE specimen
are adhesion and abrasive, which in dry are reduced by the presence
of coating. Nevertheless, no differences in the degradation mecha-
nisms are shown in the tracks during wet testing. As previously re-
ported, this result was mainly due to the negative effect of the
lubricant on the adhesion of the coating.
4. The static presence of serum reported no negative effect on the coat-
ing, which was not degraded after the soaking period. However,
scratch tests showed that in dynamic conditions the lubricant re-
duced the critical load necessary to completely detach it from the
substrate, causing its premature delamination.
The present work represented indeed the first complete investiga-
tion on a very preliminary study addressing the possibility of realizing
hard coatings on metallic substrates by means of PPD and concerning
its tribological performance. Addressing industrial application, the coat-
ing process was deliberately realized by depositing target ceramic mate-
rial directly on the metal substrates, without introducing interlayers or
surface treatments. In dry condition, and thence not considering a phys-
iological environment, tests reported improved tribological characteris-
tics, whereas in fluid, findings showed a reduction of the beneficial
effects of the coating. Concerning in particular wear rate, although re-
sults underlined a statistically significant difference between coated
and uncoated samples, this enhanced behavior decreased approaching
10 km. Even if this study highlighted the detrimental effect of the lubri-
cant on the tribological performance of the realized ceramic coatings,
this issue presented a multifactorial cause. The coating was in fact affect-
ed to both the presence of the fluid itself and by the high values of con-
tact pressure considered during the testing, which indeed represented
one of the most critical condition. Therefore, further analyses are strictly
required to fully understand the tribological behavior of PPD-realized
YSZ coating, above all, in presence of synovial fluid. Moreover,
 M. Berni et al. / Materials Science and Engineering C 62 (2016) 643–655
additional research on the deposition process is mandatory to improve
coating adhesion, its resistance to lubricant effect and its tribological be-
havior at long distances. The introduction of an interlayer [85–87] or a
set of layers with different mechanical properties [88] could, for in-
stance, increase the overall performances of the coating. Furthermore,
the coating behavior in wet conditions could be improved by working
also on its inherent nanostructure, addressing the optimization of PPD
parameters [89], the use of a more hydrophilic compound as target ma-
terial or the possibility of heating the coating after the deposition, thus
to reduce crack formation and fluid penetration.
Acknowledgments
The study was supported by the project “Nanostructured Coatings
Enhancing Material Performances in Joint Arthroplasty” (project code:
GR-2010-2312686), co-funded by the Italian Ministry of Health. This
study was also partially supported by the “5 × 1000” (2012) funding,
provided by Istituto Ortopedico Rizzoli, Bologna (Italy). The authors
would like to particularly thank Emil Ferretti for his remarkable contri-
bution in laboratory IT management and Carmelo Carcasio for his sup-
port in mechanical manufacturing and Dr. Simone Sprio (ISTEC-CNR of
Faenza, Italy) for providing the zirconia target.
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Matteo Berni
Position: Researcher
Institution: Laboratory of NanoBiotechnologies (NABI),
Rizzoli Institute of Orthopedics
Biography: Ing. Matteo Berni obtained a Biomedical Engi-
neering degree at the Engineering Faculty of the University
of Padua in 2015 (101/110), with a thesis on mechanical
characterization of ceramic films for biomedical applications
obtained by Pulsed Plasma Deposition. From July 2015 to
March 2015 he is a researcher at Rizzoli Institute of Orthope-
dics, where he deals with tribological and nanoindentation
test of materials.
Nicola Lopomo
Position: Associate Professor
Institutions: Dipartimento di Ingegneria dell'Informazione,
Università degli Studi di Brescia; Laboratorio di Biomeccanica
e Innovazione Tecnologica, Istituto Ortopedico Rizzoli.
Biography: in 2003, Prof. Lopomo graduated in Biomedical
Engineering at the University “Politecnico di Milano” in
Milano (Italy) and there, in 2008, he got also his PhD in
Bioengineering defending with merits a thesis on comput-
er-assisted surgery. Since 2004 he has been a research fellow
at the “Laboratorio di Biomeccanica e Innovazione
Tecnologica” and “Laboratorio di NanoBiotecnologie” (NaBi)
of “Istituto Ortopedico Rizzoli” in Bologna (Italy), where he
dealt with musculoskeletal biomechanics and deposition/
characterization of ceramic coatings for orthopedic applications, respectively. Since 2015
he has been an associate professor in Bioengineering at the “Dipartimento di Ingegneria
dell'Informazione” of “Università degli Studi di Brescia” in Brescia (Italy).
 M. Berni et al. / Materials Science and Engineering C 62 (2016) 643–655
Gregorio Marchiori
Position: Researcher
Institution: Laboratorio di NanoBiotecnologie (NABI), Istituto
Ortopedico Rizzoli
Biography: Ing. Marchiori graduated in Biomedical Engineer-
ing in 2012 (107/110) at the University of Padua and he took
part at the Training Program “Multidisciplinary specialist in
new materials for orthopedics” in 2013. From 2014 he is a re-
searcher at the Istituto Ortopedico Rizzoli, where he deals
with the finite element modeling of prosthetic components
and anatomical structures.
Alessandro Gambardella
Position: Researcher
Institution: Laboratorio di NanoBiotecnologie (NABI), Istituto
Ortopedico Rizzoli
Awards: Best Oral Presentation at IMC 2011 (Urbino, Italy)
Biography: Dr. Gambardella graduated in Physics at the Uni-
versity “Federico II” of Naples and got his PhD in Physics at
University of Modena and Reggio Emilia. His field of interest
is the application of Scanning Probe Microscopes, and espe-
cially Scanning Tunneling and Atomic Force Microscopy to
Materials Science. After a six year-long research activity at
ISMN institute of CNR in Bologna, working on semiconduct-
ing and organic materials of interest in innovative devices,
he is currently a researcher at the Istituto Ortopedico Rizzoli
where he deals with spectroscopic and microscopic characterization of bioactive materials
for prosthetic joint implants.
Marco Boi
Position: Researcher
Institution: Laboratorio di NanoBiotecnologie (NABI), Istituto
Ortopedico Rizzoli
Biography: Dott. Marco Boi grew up in Italy and received his
laurea in Photochemistry and Chemistry of Materials (108/
110) from the University “Alma Mater Studiorum” of Bolo-
gna in 2011. From 2012, he is a researcher at the Istituto
Ortopedico Rizzoli (Bologna, Italy) where he is involved in
research about the mechanical behavior of biological mate-
rials and biomaterials for prosthetic joint implants.
Michele Bianchi
Position: Researcher
Institution: Laboratorio di NanoBiotecnologie (NABI), Istituto
Ortopedico Rizzoli
Awards: Springer Thesis Prize 2011 recognizing outstanding
Ph.D. Research across the physical sciences.
Biography: Dr. Bianchi graduated in Photochemistry and
Chemistry of Materials in 2007 (110/110) at the University
“Alma Mater Studiorum” of Bologna and he got his PhD in
Chemical Sciences in 2011 working at the ISMN-CNR of Bolo-
gna on micro- and nano-patterning for tissue regeneration.
From 2011 he is a researcher at the Istituto Ortopedico
Rizzoli, where he deals with the deposition of low-wear
and bioactive materials for prosthetic joint implants.
Andrea Visani
Position: Medical Director, Specialist in Orthopedic Surgery
Institution: Laboratorio di Biomeccanica ed Innovazione
Tecnologica, Istituto Ortopedico Rizzoli
Biography: Dr. Visani graduated in Medicine and Surgery in
1987 at the University “Alma Mater Studiorum” of Bologna
where he became a specialist in orthopedic surgery in
1992. Currently he Is medical Director at the Istituto
Ortopedico Rizzoli where he Has Management of Several Re-
search Projects. His interests are focused on sport medicine
in the orthopedic/traumatology field.
655
Piero Pavan
Position: Associate Professor of Industrial Bioengineering
Institution: Department of Industrial Engineering of the Uni-
versity of Padova
Biography: Piero G. Pavan obtained a Structural Engineering
at Engineering Faculty of the University of Padova, Italy. He
had a PhD degree in Structures Mechanics. From 1998 he
works in the field of biomechanics, with particular regard
to mechanics and constitutive modeling of tissues. He is cur-
rently an Associate Professor of Industrial Bioengineering at
the Department of Industrial Engineering of the University
of Padova. He is a member of the Centre of Mechanics of Bio-
logical Materials of the University of Padova. The present ac-
tivity is focused on the mechanical characterization of tissues
and biomaterials by means of combined experimental and computational methods.
Alessandro Russo
Position: Medical Specialist, Specialist in Orthopedic Surgery
Institution: Laboratorio di NanoBiotecnologie (NABI), Istituto
Ortopedico Rizzoli
Biography: Dr. Alessandro Russo is a permanent staff mem-
ber at the II Clinic of Orthopedics and Traumatology Depart-
ment and at the NABI laboratory at the Istituto Ortopedico
Rizzoli. He conducts research at the Istituto Ortopedico
Rizzoli and at the University of Bologna as part of the Nano-
technology for bone and osteochondral regeneration and
for the development of wear-resistant prosthetic materials.
He′s a member of the leading European scientific society,
and has participated as a speaker at numerous international
conferences. He′s the author of 36 publications in interna-
tional print journals.
Maurilio Marcacci
Position: Full Professor
Institutions: Laboratorio di NanoBiotecnologie (NABI),
Laboratorio di Biomeccanica e Innovazione Tecnologica,
Istituto Ortopedico Rizzoli
Biography: Prof. Maurilio Marcacci serves as Member of Clin-
ical Advisory Board at Ivy Sports Medicine LLC. Prof. Marcacci
served as the President of SIGASCOT. He leads the Orthope-
dics and Trauma Clinic at the Istituto Ortopedico Rizzoli in
Bologna Italy where he is also a full professor of musculoskel-
etal disorders at the University's School of Medicine. He is the
author of five patents, 13 book chapters, and over 300 peer-
reviewed publications, including several long-term studies
of ISM's collagen meniscus implant. He is a member of
EFORT's executive and educational committees and ISAKOS' educational and strategic
planning committees. He serves on the Editorial Board of the Journals of Sport
Traumatology, Technique Knee Surgery, and European Orthopedics and Traumatology.
Prof. Marcacci received his M.D. with Honors from Pisa University.