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Plasma-Enhanced Vacuum Deposition of Carbon-Based Coatings Offer

Hope for Cardiovascular Implantable Devices.

Article · January 2017

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Megha Agrawal Shyamasri Biswas

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Plasma-Enhanced Vacuum Deposition
of Carbon-Based Coatings
Offer Hope for
Cardiovascular Implantable Devices
V
acuum deposition processes are
increasingly being employed in
the biotechnology led medical
implants industry to coat implantable de-
vices to enhance their functionalities. Vac-
uum technologies offer hope for patients
who use many life-saving implantable de-
vices. Millions of people across the globe
undergo implant surgery every year for
the insertion of various medical implants
such as coronary stents, pacemakers,
heart valves hip and knees prostheses. Ac-
cording to an estimate, around 1 million
orthopedic implants in the United States
are employed annually in patients for
knee and hip replacements, which is ex-
pected to increase to around 3 million by
the year 2030 [1]. Vacuum based coating
technologies can be leveraged to devel-
op medical implants with a superior life
span that can resist corrosion and wear,
especially in load bearing and blood and/
or tissue contacting applications. Such
coatings can also help exogenous mate-
rials to make them more biocompatible.
For example, when inserted in the body,
exogenous materials triggers immune
responses in the areas surrounding the
implant that can result in compromising
the implant performance that may lead
to revision surgery for implant replace-
Vacuum Technology & Coating • January 2017
By Dr. Megha Agrawal, Dr. Shyamasri Biswas, Dr. Kim Van Vliet, Contributing Editors
ment or extraction [1]. Researchers have
demonstrated that surface modulation or
surface engineering of medical implant-
able devices could mediate interactions
between the implant and the host to pre-
vent adverse reactions would clearly ben-
efit the ever growing global multi-billion
dollars biomedical devices industry. It is
believed that vacuum coating processes
can modulate the surface properties such
as hemocompatibility, protein adsorption/
immobilization, differential attachment,
proliferation and differentiation of cells
that are highly desirable to develop supe-
rior medical devices [1].
Among other vacuum coating technol-
ogies, plasma-based coating technologies
have emerged promising for coatings of
cardiovascular implantable devices, in
particular. The potential of using plas-
ma-based tools as a universal coating
technology for implantable medical de-
vices, with particular focus on coronary
stents is vast [1]. In this column, we will
describe some key advances made in
plasma-assisted vacuum coating process
for applications in cardiovascular devices
such as coronary stents.
Coronary stents are now considered
the dominant vascular implant in per-
cutaneous coronary interventions with
www.vtcmag.com 
around 800,000 stents implanted annual-
ly in the United States alone [1]. Stents
are expandable cylindrical meshes used
to re-establish the normal blood flow in
blocked atherosclerotic coronary arter-
ies that resupply ischemic tissue. While
current stent platforms have been used
routinely in patients, they have low
sub-optimal biocompatibility resulting in
poor interactions with vascular cells that
eventually promotes blood clot forma-
tion. Hence, current cardiovascular stent
platforms have a number of biomedical
limitations, which do not allow effective
integration with the human vasculature.
As a result, current stent technology still
relies on drug therapy to avoid early fail-
ure due to blood clotting. It is believed
that a drug-free coating technology that
allows a full integration with an implant-
ed stent through a combination of hemo-
compatibility and differential regulation
of endothelial cells and smooth muscle
cells would be superior over current clin-
ical cardiovascular approaches [1]. In
this regard, plasma discharges have been
considered as a coating technology in a
wide range of applications. Researchers
have prepared carbon-based thin films
by different plasma deposition methods
that are usually regarded as biocompati-
1
ble materials as they are able to prevent
the adhesion and activation of platelets
and preferentially promote the adsorption
of albumin over fibrinogen [1]. Plasma
based science and technology in explor-
ing coronary stent devices is an interdisci-
plinary endeavor that requires combined
efforts of scientific communities in plas-
ma physics, materials engineering, biol-
ogy and medicine. Figure 1 summarizes
various opportunities that plasma-based
coating technologies offer to make supe-
rior coronary stents [1]. The researchers
identified a strategy that consists of com-
binations of plasma discharge simulation
tools, plasma diagnostics and coating
characterization techniques could be used
to identify the relevant window of plasma
parameters for a reproducible and stable
process for effective coating functional-
ization (Figure 1) [1].
Figure 1. A proposed methodology for the development of a controllable and stable process
for the production of biocompatible coatings for cardiovascular stents using plasma discharges
[Source: Biosurface and Biotribology, 1, 146 (2015)].
2 vtcmag@vtcmag.com 
Plasma-enhanced chemical vapor
deposition (PECVD) has been employed
to biofunctionalize medically compatible
coatings for coronary stents. The coatings
deposited by PECVD method, especially
when bias is used to increase the energy
of the depositing species can result in
superior adhesion to the substrates, high
cross-linking, improved biocompatibil-
ity and chemically active and functional
surfaces [1]. Figure 2 shows a schematic
illustration of plasma surface modifica-
tion for coronary stents. Nitrogen, argon
and acetylene plasma is introduced into a
chamber under a vacuum and ionized by
a power source such as an RF electrode.
The charged ions in the chamber impact
the substrate to modify the surface im-
mersed in the plasma [2].
Further, it was shown that car-
bon-based coatings with high concen-
trations of long-lived unpaired electrons
prepared by PECVD can be used for the
covalent attachment of various biomol-
ecules in their bioactive form. Such ad-
vances are considered as breakthroughs
that could establish a new era of truly
bio-functional and bio-compatible car-
diovascular implants [1].
As described earlier, blood compatibil-
ity is considered an essential component
for biocompatible cardiovascular stents. A
coating process that allows stable immo-
bilization of bioactive biomolecules on
the coating surface could bring significant
breakthrough in true biofunctionalization
of cardiovascular implants such as arte-
rial stents. In this regard, plasma-made
radical-rich coatings for stents can be
employed to immobilize the appropriate
biomolecule or biomolecule cocktails that
can impart appropriate local biological
responses to achieve full vascular integra-
tion of stents (Figure 3) [1].
In related works, researchers reported
that rf-PECVD carbon-containing plas-
ma polymers prepared with bias have
the ability to covalently immobilize pro-
teins in their bioactive form [1, 3, 4]. It is
also noted that organic precursor plasma
discharges can be used to deposit hy-
drophilic plasma activated radical-rich
a-C:H-like coatings (PAC) if sufficient
sample bias up to −1 kV, is provided [1,
5]. In this process, the ions formed in the
plasma are accelerated with increased
energy provided by the high voltage bias
towards the growing carbonized film
on the substrate [1]. The process of ion
impacting the surface is important as it
promotes the formation of regions of car-
bon extended states such as π conjugated
sp2 carbon bonds with a high degree of
cross-linking. These regions that contain
stable unpaired electrons can then move
and diffuse towards the coating surface.
Researchers found that the free-radical
content as measured by electron para-
magnetic resonance spectroscopy to be
proportional to the bias voltage and thick-
ness of the deposited film [1].
In another work, vascular stents with
submicrometer-scale surface patterning
was realized via titanium deep reactive
ion etching [5]. Researchers demon-
strated using titanium deep reactive ion
etching technique (Ti DRIE) to fabricate
January 2017 • Vacuum Technology & Coating
 coat cardiovascular implantable devices
to obtain superior functionalities. We an-
ticipate that advanced processes based
on plasma-enhanced medical coatings
would play vital roles in future to develop
life-saving medical implants that would
benefit millions of patients across the
globe. However, there is a need to develop
more cost-effective processes.

References for Further Reading

1. M. Santos, M.M.M. Bilek, S.G. Wise. Plas-
ma-synthesised carbon-based coatings for
cardiovascular applications, Biosurface and
Biotribology, 1, 146-160 (2015).
2. 
Thamarasee M. Jeewandara, Steven G.
Wise and Martin K. C. Ng. Biocompatibili-
ty of Coronary Stents, Materials, 7(2), 769-
786 (2014).
3. M.M.M. Bilek, D.V. Bax, A. Kondyurin,
Y. Yin, N.J. Nosworthy, K. Fisher, A. Wa-
terhouse, A.S. Weiss, C.G. dos Remedios,
D.R. McKenzie. Free radical functionaliza-
tion of surfaces to prevent adverse respons-
es to biomedical devices, Proc. Natl. Acad.
Sci., 108, 14405-14410 (2011).
4. 
Y. Yin, M.M.M. Bilek, D.R. McKenzie,
Figure 2. Vacuum plasma surface modification of coronary stents [Source: Materials, 7(2),
N.J. Nosworthy, A. Kondyurin, H. Youssef,
769 (2014)].
M.J. Byrom, W. Yang. Acetylene plasma
polymerized surfaces for covalent immo-
bilization of dense bioactive protein mono-
layers, Surf. Coat. Technol., 203:10-11,
1310-1316 (2009).
5. M.M.M. Bilek. Biofunctionalization of sur-
faces by energetic ion implantation: Review
of progress on applications in implantable
biomedical devices and antibody microar-
rays, Appl. Surf. Sci., 310, 3-10 (2014).
6. Shannon C Gott, Benjamin A Jabola and
Masaru P Rao. Vascular stents with submi-
crometer-scale surface patterning realized
via titanium deep reactive ion etching, Jour-
nal of Micromechanics and Microengineer-
ing, 25, 8 (2015).
Figure 3. Schematic illustrations of proactive biofunctionalization of coronary stents using plas-
ma discharges carried out in carbon-based atmospheres. The process involves immobilization
of biomolecules on the coating via radical bonding and they maintain a bioactive conformation
after immobilization. Following stent implantation, the immobilized biomolecules induce fa-
vorable local cellular responses promoting endothelial cell migration, adhesion and proliferation
on the implant surface to form a healthy endothelium [Source: Biosurface and Biotribology, 1,
146 (2015)].
precisely-defined, grating-based surface terned Ti stents that were compatible with
patterns on planar Ti foils with minimum conventional balloon catheter deploy-
feature sizes as small as 0.15 μm that ment techniques [6].
created cylindrical stents from micro-
machined planar Ti foils. They showed Concluding Remarks
integration of these processes to produce Vacuum-assisted deposition meth-
the first submicrometer-scale surface-pat- ods have been proven to be important to

Vacuum Technology & Coating • January 2017 www.vtcmag.com  3

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