Vacuum 73 (2004) 317326

Applications of plasma coatings in articial joints: an overview

Hong Liang
a,
*, Bing Shi
a
, Aaron Fairchild
a
, Timothy Cale
b
a
Department of Mechanical Engineering, University of Alaska, Fairbanks, AK 99775-5905, USA
b
Rensselaer Polytechnic Institute, Troy, NY 12180-3590, USA
Abstract
Current surgical implants such as articial hip and knee joints undergo degradation after 1015 years of use. Joint
implant failure is common enough that attempts at improvement have been made. Plasma coating technologies have
proven to be effective in improving the performance of articial joints. Plasma coating can enhance the fatigue strength,
the corrosion and wear resistance as well as the load-bearing capacity. In this work, we review the common failures in
articial joints and the role of plasma coating in biomedical applications.
r 2004 Elsevier Ltd. All rights reserved.
Keywords: Articial joints; Plasma coatings; Biomaterials; Biotribology
1. Introduction
As advances have been made in medical
sciences, the aging population has grown signi-
cantly. More organs, joints, and other critical
body parts will wear out and must be replaced to
maintain a good quality of life for elderly people.
There are implants that play a major role in
replacing or improving the function of every major
body system (skeletal, circulatory, nervous, etc.).
Materials we use in these replacements are by
denition biomaterials. Some common implants
include orthopedic devices such as total knee, hip,
shoulder, and ankle joint replacements, spinal
implants, and bone xators; cardiac implants such
as articial heart valves and pacemakers; soft
tissue implants such as breast implants and
injectable collagen for soft tissue augmentation;
and dental implants to replace teeth/root systems
and bony tissue in the oral cavity. In this review,
we will focus on joint replacements.
Joint replacement surgery is most commonly
performed for hips, knees, and shoulders as shown
in Fig. 1, although toes, ngers, and elbows have
been successfully replaced [1]. Most articial joint
replacements are designed to remove diseased
areas of the joint and replace them with implants
designed specically to restore that joints function
and stability. For biomedical applications, materi-
als engineers must consider the physiologic loads
to be placed on the implants. Material choices also
must take into account immune system biocom-
patability, the environment, corrosion issues,
friction and wear of the articulating surfaces, and
implant xation either through osseointegration
(the degree to which bone will grow next to or
integrate into the implant) or bone cement. One
of the major problems plaguing these devices is
purely materials-related: wear of the polymer
cup in total joint replacements. A summary of
ARTICLE IN PRESS
*Corresponding author. Tel.: +1-907-474-6135; fax: +1-
907-474-6141.
E-mail address: ffhl@uaf.edu (H. Liang).
0042-207X/$ - see front matter r 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.vacuum.2003.12.160
tribo-biomaterials is list in Table 1 [26]. These
conventional materials t into the specic needs of
bio-applications.
2. Problems in articial joints
Despite the success of surgical implants such as
articial hip and knee joints, materials used in
these procedures still do not satisfy the demands of
a durable functioning joint. Current synthetic
materials, such as stainless steel, titanium alloy,
polymers, and ceramic composites, undergo de-
gradation after 1015 years of use [7]. There are
several common failure types. Studies have sug-
gested that the macrophage response to phagocy-
tosis of particulate wear debris, occurring in
interaction between the cement and bone, is an
important causative factor in osteolysis, leading to
eventual loosening of joint surfaces [8]. Due to
ARTICLE IN PRESS
Fig. 1. Joints of hips, knees, shoulders, and articial ankle and foot (left to right).
Table 1
Summary of common biomaterials
Materials Applications Major properties description
Metals: brass, stainless steel, nickel plated, nickel
plated steel, zinc plated steel
Inserts
Alloys: titanium alloys [6], titanium aluminum
vanadium alloy [2], cobalt chromium alloy [3], cobalt
chromium molybdenum alloy [4,5]
Total joint replacement Wear and corrosion resistance
Inorganic: diamond-like carbon Biocompatible coatings, Reduced friction and increased wear
resistance
Ceramics [6]: Al
2
O
3
, ZrO
2
, Si
3
N
4
, SiC, B
4
C, quartz,
bioglass(Na
2
OCaOSiO
2
P
2
O
5
), sintered
hydroxyapatite (Ca
10
(PO
4
)
6
(OH)
2
)
Bone joint coating Wear and corrosion resistance
Polymers: Ultra-high molecular weight polyethylene
(UHMWPE), Polytetraouroethylene (PTFE)
Joint socket Wear, abrasion and corrosion resistance
Interpositional implant
temporomandibular joint(Jaw)
Low coefcient of friction
Polyglycolic acid Joint bone Elastic with less wear
Leaet heart valve Highly biocompatible, high strength,
and dynamic ranges of breathability
Polyurethane
Composites: Specialized silicone polymers Bone joint Wear, corrosion, and fatigue resistance
H. Liang et al. / Vacuum 73 (2004) 317326 318
signicant localized contact stresses at the ball/
socket interface, small regions of implant materi-
als, such as ultra-high molecular weight polyethy-
lene (UHMWPE) tend to adhere to the metal
or ceramic ball [9]. During the reciprocating
motion of normal joint use, brils will be drawn
from the adherent regions on the polymer surface,
and these break off to form submicrometer-sized
wear debris. This adhesive wear mechanism,
coupled with fatigue-related delamination of the
UHMWPE (most prevalent in knee joints), results
in billions of tiny polymer particles being shed into
the surrounding synovial uid and tissues. Biolo-
gical interaction with these small particles in
the body then becomes critical [10,11]. The bodys
immune system attempts, unsuccessfully, to digest
the wear particles (as it would a bacterium or
virus). Enzymes are released that eventually result
in the death of adjacent bone cells, or osteolysis.
Over time, sufcient bone is resorbed around
the implant to cause mechanical loosening which
necessitates an implant replacement or revision,
costly and painful options [12]. The parti-
culate debris has emerged as a major factor in
the long-term performance of joint replacement
prostheses [13]. When present in sufcient
amounts, particulates generated by wear, fretting,
or fragmentation induce formation of an inam-
matory, foreign-body granulation tissue that
has the ability to invade the boneimplant inter-
face [1422]. This may result in progressive
periprosthetic loss of bone, a loss that threatens
the xation of prostheses inserted with or with-
out cement [15,23,24]. Since the loosening is not
caused by an associated infection, it is termed
aseptic. When present in sufcient amounts,
particulates generated by wear, fretting, or
fragmentation induce formation of inammatory,
foreign-body granulation tissue that has the
ability to invade the boneimplant interface.
Corrosive attack is often found in the taper
crevice of modular implants made of similar
metals or mixed-metal combinations [2529]. The
corrosive attack results in metal release and
mechanical failure of the joint component [30].
Due to the cyclic loading, corrosive fatigue,
wear, fretting, and fragmentation are all expected
[3141].
The following is the summary of common
failures:
*
Deciencies in design (size and shape) of the
device for a particular patient (e.g., an under-
sized noncemented stem)
*
Surgical problems (e.g., problematic orientation
or problems in wound healing)
*
Host abnormalities or diseases (e.g., osteope-
nia)
*
Infection
*
Material fracture, wear, and corrosion.
2.1. Fracture and wear
Fractures occur often in both orthropedic
implants and bone where load-bearing ability is
important. Once fractured, however, biomaterials
do not regenerate like bone. Fracture eventually
leads to catastrophic failure of implants [42,43].
Bioenvironments are mostly wet. Wear is
increased for wet sliding wear compared with dry
sliding wear for unlled polymers [44]. The wear
volume also increases in carbon ber and glass-
reinforced composites compared with unlled
polymers, thus enhancing the cutting/lowing/
cracking mechanism of abrasive particles against
the polymer or polymer composite material [44]. In
a physiological environment, metallic, ceramic, or
polymeric wear particles may be trapped between
two moving surfaces, causing three-body wear,
which generally causes a signicantly higher wear
rate than two-body wear. Other mechanisms for
increased in vivo wear include environmental
stress cracking, polymer degradation, microstruc-
tural imperfections, and creep [45]. This wear may
cause loosening of the prostheses by the resulting
poor mechanical t between the ball and socket of
the hip. Generation of wear debris is an important
factor both because of the potential for wear
debris to migrate to distant organs, particularly
the lymph nodes where accumulation of particle-
containing macrophages causes enlargement and
chronic lymphadenitis [46] and because of local
physiological responses such as inammatory,
cytotoxic, and osteolytic reactions.
A major cause of late failures of articial hips
has been loosening between the hip stem and the
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H. Liang et al. / Vacuum 73 (2004) 317326 319
partially resorbed surrounding bone, causing pain
and requiring hip replacement. Sometimes femoral
bone weakened by osteolysis can fracture under
high loading conditions and require replacement.
It was thought that this condition was the result of
osteolysis of the bone caused by bone cement
particles released by wear and fatigue microfrac-
tures [47], and it was occasionally called bone
cement disease.
Research has shown that polyethylene [48],
titanium, and ceramic wear debris can cause the
same osteolytic problem associated with bone
cement debris. Both micro-sized particulates seen
in earlier histological slides, as well as submicron
particulates now found using digestion and scan-
ning electron microscopic techniques, have been
implicated in osteolytic destruction of the bone
implant interface. Assuming a million steps per
year and 0.03 to 0.08 mm per year wear into
polyethylene acetabular cups, one recent calcula-
tion estimates that on an average as many as
470,000 polyethylene particles of 0.5-mm size could
be released to the surrounding tissues at each step
[49]. Other examples of nonspecic osteolysis
presumed to be caused by wear debris of devices
include bone resorbtion around failed elastomeric
nger, tow, and wrist prostheses and around failed
poly(tetrauoroethylene)-carbon ber temporo-
mandibular joint (jaw) prostheses. Therefore, an
important in the selection of materials for use in
medical implants is the quantity, size, shape, and
composition of wear debris that may be released
in vivo.
The wear problem that occurs with an articial
joint implant component (socket) constructed of
UHMWPE is illustrated in Fig. 2 [50]. At left is
unworn UHMWPE. The sample at right has
undergone a friction and wear test versus cobalt
chromium (articial joint ball material). The
brillation and small particles are characteristic
of an adhesive wear mechanism, which can result
in surrounding bone loss and the need for implant
replacement [50].
2.2. Corrosion and corrosive fatigue
The second type of wear is sub-surface fatigue.
High contact stresses in the articial joints will
cause a crack in the biological materials that will
propagate beneath the surface. Fig. 3 shows a
typical knee crack [51].
Corrosive attack in the taper crevice of modular
implants made of similar metals or mixed-metals
combinations [17,5254]. The corrosive attack
results in metal release and mechanical failure of
the component [55].
Corrosive fatigue is expected due to cyclic
loading and the corrosive environment of
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Fig. 2. SEM micrographs of socket of UHMWPE [50]. Left: no
wear. Right: with wear (20,000X).
Fig. 3. A typical knee crack [51].
H. Liang et al. / Vacuum 73 (2004) 317326 320
the human body. The fractures occurred at
grain boundaries of the microstructure and ap-
peared to be the result of three factors: porosity
at the grain boundaries; intergranular corrosive
attack initiated both at the head-neck taper and
at free surface; and cyclic fatigue-loading of
stem [56].
2.3. Plasma technology
Plasma coatings have been used for surface
hardening of materials in order to improve wear,
corrosion, and fatigue performances in biomedical
applications. This technique uses the plasma of a
current intensive glow discharge to cause the mass
transfer of doping element from generally a low-
pressure atmosphere to the material undergoing
treatment. Plasma coating can enhance the fatigue
strength and wear resistance as well as the load-
bearing capacity. In this work, we review the
common failure in articial joints and the role of
plasma coating in biomedical applications.
Surface modication techniques can functiona-
lize device surfaces through attachment of bioac-
tive molecules, among other methods. This is seen
in polymers and metals where surface modication
enhances their biocompatability. Surface modi-
cation has also been used widely to improve
properties of the outmost layers of material
surfaces. Surface modication can reduce the wear
and improve frictional behavior of surface regions
while maintaining desirable bulk properties of the
underlying substrate. Surface modication can
improve service life of components and devices
signicantly. Common surface coating methods
are:
*
Chemical reaction
*
Immobilization of biomolecules
*
Metalization
*
Micro-contact printing
*
Ozonolysis
*
Photoreaction
*
Plasma treatment and deposition
*
Ion etching
*
Ion implantation
*
Radiation grafting
*
Self assembly
*
Solvent case lms
*
Surface active modiers (low/high MW)
Plasma coating technology has been used in
manufacturing for more than two decades. It has
been used to improve the performance of auto-
mobiles and cutting tools [57]. Plasma coating
technique introduces elements onto surface able to
form structures that are favorable for mechanical,
chemical, and biological performance.
2.3.1. High-performance plasma coatings
High-performance plasma coatings aim at in-
creasing wear and corrosion resistance of materi-
als.
Nitrogen implanted plasma coating has been
widely used in manufacturing. This method can
improve tribological behavior, i.e., good lubrica-
tion and low wear, by obtaining improved
composition and microstructure of materials
surfaces [58,59]. High dose, high temperature
nitrogen implantation of Ti6Al4V produced
surfaces which exhibited lower friction and high
wear resistance than untreated Ti alloy. The best
performance for this specic implantation treat-
ment is due to the deep nitrogen penetration
depth, formation of TiN and Ti
2
N compounds,
and incorporation of oxygen in the near-surface
layer. It has also been reported that ion implanta-
tion and plasma treatment is effective for alumi-
num based alloys. The technique of ion nitriding
and electron cyclotron resonance (ECR) plasma
nitriding forms AlN and AlON layers [60]. These
layers lead to high strength and high wear
resistance.
Plasma immersion ion implantation (PIII) was
developed a decade ago. This technique increases
the hardness, wear resistance, and corrosion
resistance on metal alloys such as stainless steels,
nickel, aluminium, and titanium alloys including
those used in implants [6163]. The reason for
improvement is an improved microstructure. In
the case of steels, excellent tribological properties
were achieved at a treatment temperature of over
500

C due to the formation of a CrN precipitation

and the expanded austenite transferring to mar-
tensite. The good corrosion resistance was pre-
served up to 400

C with only a small decrease due

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H. Liang et al. / Vacuum 73 (2004) 317326 321
to nitrogen remaining in solid solution without
CrN-precipitation [63].
Parameters for PIII are, such as implantation
dose, ion density, pulse repetition rate, and sample
temperature. Using an improved vacuum-arc
plasma source can improve coating properties
effectively. It was reported that when titanium
and tantalum ions were implanted followed by
nitrogen PIII, it yields a modied surface layer
with superior wear resistance [64]. The wear
resistance of the samples implanted with (Ti+N)
and (Ta+N) was better than that of samples
undergoing nitrogen PIII alone due to the presence
of nitride phases in the implanted layer. For
aluminum implanted Ti-6Al4V, surface harden-
ing of the aluminum ion implantation resulted in
improvement of wear resistance of Ti alloy by a
factor of 2. It also appeared that surface precipita-
tion hardening could improve the mechanical and
surface properties without necessarily altering the
wear mechanism of Ti alloy. Wear tests simulating
joints showed the good wear resistance of
UHMWPE against Ti6Al4V bearing surface ion
implanted with oxygen and chromium or coated
with ZrN by PVD [65]. In particular, ion
implantation on Ti6Al4V reduced friction between
the titanium alloy and the UHMWPE. This effect
was not totally justied by the surface hardening
caused by lattice disorder, interstitial elements or
dispersed compounds. The chemical composition
of the surface is probably responsible for the
improvements of the wear resistance.
2.3.2. Plasma coating processessingle and duplex
coatings
Single plasma coating process is seen often in
metals resulting improved wear resistance and
surface hardness [66,67]. The duplex coating
method can improve further of the tribological
properties and load-bearing capacity of materials
beyond metals. This method combines plasma
coating with other coating technologies, such as
PVD and CVD [68,69].
A duplex plasma surface-engineering pro-
cess can be achieved by plasma nitriding the
low alloy steel rst so as to produce a thick, strong
substrate and then depositing a thin, hard and
wear resistant TiN coating on the nitrided
substrate by ion plating [70]. The TiN coating-
nitrided steel composite has enhanced wear
resistance, higher load-bearing capacity, intense
shearprevented surface, and preventability of
subsurface shear deformation during the wear
process as well as the material loss from the
coating caused by the micropolishing action of the
slider (alumina ball, for example). Duplex treat-
ment of plasma nitriding and PACVD allowed
tailoring of the surface properties such as wear and
corrosion resistance and is especially suitable for
complex loading [70,71].
2.3.3. Plasma-sprayed hydroxyapatite (HA)
coatings
In orthopaedic technology development, biome-
dical coatings are often used on total joint
replacement components. These coatings usually
comprise a group of novel (glass) ceramics. The
widely studied is a calcium-phosphate-based ma-
terialHA [72]. HA is a bioactive material. Its
formula is Ca
10
(PO
4
)
6
(OH)
2
. HA is one of the
most attractive materials for human hard tissue
implants because of its close resemblance to
chemical composition (Ca/P ratio) of teeth and
bones [73,74]. A HA coating can accelerate the
process of bony growth in the vicinity of the
prosthesis [7580]. HA has been clinically applied
as a dense, sintered material and as a coating on
bioinert metallic implants [81].
HA has good biocompatibility and bioactivity
for skeletal and dental Ti implants. This might due
to the OH and O concentrations decrease with the
distance from the surface of HA coatings, reaching
the minimum at the interface between HA and Ti
alloys [82]. Typically, the plasma sprayed HA/Ti
6Al4V composite material was a dense-layer [83],
containing HA, nely divided Ti6Al4V, and
amorphous calcium phosphate. A heat treatment
process after spraying determines composition,
structure, and properties of HA coatings [83].
Plasma-sprayed HA coatings on a Ti6Al4V
substrate are found to increase both resistance to
elastic and plastic deformation. However, such
coatings have no effects on strain hardening
behavior. The coating could reduce the resistance
to coating/substrate separation [84]. The residual
stress and bonding strength and fracture of
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H. Liang et al. / Vacuum 73 (2004) 317326 322
plasma-sprayed HA coatings are associated [85].
The fracture toughness of HA is about 1 MPam
1/2
.
This material is low in fatigue resistance [86,87]. In
order to achieve the mechanical characteristics
needed for biomedical applications, blending with
a tough phase is essential. Titanium metal, Ti
6Al4V alloy, ytrria-stabilized zirconia (YSZ),
Ni
3
Al, and Al
2
O
3
ceramics have been considered
good candidates as the reinforcing phases [8894].
HA coatings can be applied by a wide range of
surface deposition techniques, such as plasma
spraying, high-velocity oxy-fuel spraying (HVOF),
pulsed laser ablation, ion-beam sputtering, elec-
trophoretic deposition, radio frequency (RF)
magnetron sputtering, sol-gel and conventional
ceramic processes that involve pressing and
sintering [95106]. Plasma spraying is an efcient
method of depositing HA coating onto the surface
of the implant. The temperature of the plasma
ame is up to 10,000 K. Therefore, crystallization,
phase transformation, and dehydroxylation are
considered for optimizing coatings. Typical con-
ditions are listed in Table 2. According to the
table, pure crystalline HA powder used has a
spherical shape with an average diameter. The
plasma spray process is performed using a coating
system with a certain type of arc gas, generally
nitrogen. The arc current and voltage are typically
360400 A and 6070 V, respectively. The thick-
ness of a HA coating can be controlled between 40
and 400 mm [106].
Thermally sprayed coatings are layers made of
individual powder splats oriented parallel to the
substrate surface. These splats produce high level
of anisotropy for the coating [107]. There are
many parameters chosen in control of the thermal
spray technique, e.g. powder particle size and
morphology, plasma gas mixture, working dis-
tance, substrate cooling, etc. [108111]. Different
phases in HA are known to have different
solubilities and dissolution behaviors. Amorphous
HA has been shown to be more soluble in aqueous
solutions when compared to crystalline HA [112
115]. Fig. 4 is an example of HA coating layer
[116].
Ceramic coatings are particularly weak in
fatigue resistance. All joints in the human body
are constantly subjected to fatigue loading during
the simple actions of everyday living. There are
increased surface microcracks and bulk porosity
found in plasma sprayed HA coatings [117]. To
eliminate the delamination problem of HA from
their substrate [118,119], a bond coating, dical-
cium silicate, is applied using the plasma coating
technique. The plasma sprayed dicalcium silicate,
Ca
2
SiO
4
, is a bond coat for improving the bonding
of HA coatings on Ti alloys substrates [120].
Overall, HA coatings can improve the adhesion
and xation of an implant device. A mechanical
interlocking of implant with bone can eliminate
problems associated with micromotion, i.e. loosen-
ing. Consequently coated implants can be recom-
mended for applications involving younger or
more active patients.
2.3.4. Ammonia plasma treatment
Polymeric materials have been used in joint
implants since early 1060 s. Common ones are
UHMWPE, PTFE, and urethane for knee, hip,
jaw, or heart valves (refer to Table 1). Similar to
issues involved to metal and ceramic implants,
adhesion is one of the major focuses for develop-
ment.
The ammonia plasma treatment technique was
developed from the plasma polymerization meth-
od in early 1990s [121125]. Plasma polymeriza-
tion modies the surface by polymerization of
oxygen and nitrogen containing volatile chemicals
such as methanol, amine, and amide compounds.
Ammonia plasma modication generates surface
chemistry on a treated surface incorporating
amine and amide groups. These groups play an
important role in endothelial cells adhesion and
growth on a modied surface.
In this technique, a RF plasma generator
was capacitatively coupled to a plasma reactor.
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Table 2
Typical conditions for plasma-sprayed HA coatings
Arc gas N
2
Ha powder Micron size
Arc current 360400 A
Arc voltage 6070 V
Resulting thickness 40400 mm
H. Liang et al. / Vacuum 73 (2004) 317326 323
Samples were placed in the plasma reactor 7.5 cm
downstream from the ammonia gas inlet. The
plasma reactor was evacuated using a rotary
vacuum pump. Plasma treatment of substrates
was carried out at 400 Millitorr since incorpora-
tion of amino groups and amide groups to
substrate materials was found to be optimal at
this pressure [126]. This pressure was maintained
by a constant in-ow of ammonia into the reactor.
A pulsed RF power of 30 W was applied to the
plasma reactor for 30 min. The substrates were
evacuated for an additional 30 min to remove any
unreacted species.
Other plasma sprayed coatings are available
such as wollastonite/TiO
2
composite coatings on
titanium alloys [127]. Composite coatings exhibit
lamellar structure with alternating wollastonite
and TiO
2
coating. Dicalcium silicate (Ca
2
SiO
4
)
coatings on titanium alloys substrate were also
reported [127]. This coating was reported as
having excellent bioactivity.
3. Summary
Plasma sprayed coatings can improve corrosion
and wear resistance as well as load-bearing
strength of articial joints. These coatings can
also improve signicantly the adhesion between
bones, tissues, and implants. The improvement of
adhesion and xation of an implant device will
enable the mechanical interlocking of implant with
bone. This eliminates problems associated with
micromotion, i.e. loosening. Consequently coated
implants can be recommended for applications
involving younger or more active patients.
Acknowledgements
This work was nancially sponsored by UAFs
President Special Project Fund, and partially
supported by grants of NSF CAREER - CMS
0239136 and NSF DMI 0300574. Assistance
provided by Dr. G. Helen Xu during preparation
of this manuscript was greatly appreciated.
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