Surface modification of polymers for
biomedical applications
Chemical Engineering Department, University of Coimbra, Portugal
O
ne of the more frequent, expensive
and serious problems facing human
healthcare is the loss or failure of
organs or tissues. It is in providing solutions
to such problems that coating technologies
have much to offer. The medical need for
tissue and organ substitutes can arise from
trauma, infections, inherited or age-related
diseases and organ failure.1
The theme of biomaterials embraces a
wide range of materials and their
applications. Polymers have been
extensively used as coatings in biomedical
devices and in the devices themselves, such
as catheters, heart valves and dialysis
membranes. Many of these polymers were
originally developed for industrial
applications but were then adapted for use
as biomaterials, based on their favourable
characteristics.2
The performance of a material in a
biological environment is mainly mediated
by its surface properties and by the
combination of physical and mechanical
properties required for a specific
application, often achieved by appropriate
coating treatments. Among the surface
properties that can be achieved by the
judicious use of coatings, and of utmost
importance with respect to the
performance, are surface chemical
structure (such as inherent hydrophilicity),
the presence of functional groups on the
surface, (that could initiate
interaction/reaction with biological
systems, in biological media) and the
surface morphology (the distribution and
abundance of specified
hydrophilic/hydrophobic regions and the
presence of crystalline/amorphous phases)
and the overall surface topography.3
Factors affecting the choice
of materials
Many polymers, such as the polyolefins, the
polysiloxanes and the polyurethanes are
P Alves, P Ferreira and M H Gil
Outlines
l A large number of different materials are used in a wide range of biomedical
applications for which biocompatibility is essential. In order to combine this with
the desired bulk structural properties, it is frequently desirable to apply some form
of coating or other surface modification.
l Factors involved in the interactions between the body and implants are discussed.
The process of cell attachment to surfaces is complex and takes place in several
stages. Depending on the application, this attachment may be essential or highly
undesirable.
l Surface modification may be based on physical methods such as flame treatment,
corona discharge, UV radiation exposure or laser ablation. Chemical methods include
etching, surface oxidation, hydrolysis, chemical grafting and surface coating. Various
aspects and applications of these technologies are considered.
l Surface modification is a very important aspect of the creation of medically viable
polymeric and non-polymeric biomaterials and thus the use of coating techniques in
the creation of biomaterials has been growing over recent decades as they can
improve the application properties of materials in end uses ranging from catheters
to endoprostheses and cardiac valves.
commonly used as implants, as coatings Surface modification aims to tailor the
and as bulk materials. Their surface surface characteristics of a material for a
chemical properties are a major factor in specific application without detrimentally
determining the adhesion of proteins in ‘in affecting the bulk properties. This approach
vivo’ systems. This behaviour is directly provides a basis for increasing the success
related to the subsequent cellular of implant applications by increasing their
interactions with the coating/polymer and, service lifetime.
therefore, to the material’s
biocompatibility.
Also, it has to be recognised that if the Surfaces and cell adhesion
coating is inappropriately chosen,
When a biomaterial is implanted in a living
pathological microorganisms may easily
organism, several types of interactions are
adhere to the surfaces, causing infection.
established between the host tissue and the
The incidence of such infections varies
material and, more specifically, with its
from 1% for hip prostheses up to 100% for
surface. These interactions, although
urinary tract catheters and up to 50% in
classified as being normal, may lead, if not
aortic vascular graft infections.4
properly controlled, to a failure of the
An infection involves three major steps. implant and in the worst case scenario to
These are microbial adhesion, microbial
the host’s death.
proliferation and the formation of a
In order to understand, predict and avoid
bacterial film. To overcome this problem,
such effects, it is important to remember
the surface modification (coating and
that it is not only the effect of the implant
surface deactivation) of the material
on the host’s tissues that should be
substrate has, in the recent past, been one
considered. Another very important factor
of the more widely used and studied
involved in this tissue-coated biomaterial
approaches to resolving biofouling issues.
interface is the effect of the host on the
Surface Coatings International Issue 2013/3 1
 material and the consequences that such
an interaction might bring about. Several Table 1: Interactions commonly established between a coated biomaterial and a host tissue
effects arising from biomaterial-tissue Local effects Systemic/distant effects
interactions have been reported, and some
are detailed in Table 1. 1. Blood-material interactions (eg protein adsorption, 1. Embolisation (eg thrombus formation, …)
Immediately after implantation of a coagulation, haemolysis, platelet or 2. Hypersensitivity
leukocyte activation, …) 3. Mutagenicity
biomaterial, coated or otherwise,
adsorption of proteins to its surface takes 2. Toxicity 4. Teratogenicity
place. Among these proteins are usually the 3. Inhibition of normal healing (eg encapsulation,
immunoglobulins vitronectin, fibrinogen, foreign body reaction)
and fibronectin. This adsorption 4. Infection
phenomenon is due to the high abundance 5. Carcinogenesis
of these proteins in plasma as well as their
considerable mobility. Protein adsorption to
a surface is a highly complex and dynamic Figure 1: Representation of the Vroman effect: after exposure to the physiological medium, small and
process. In fact, with time, the initially abundant proteins (protein A) adsorb and interact with the polymeric surface. These weakly surface-active
adsorbed proteins are displaced by others proteins are subsequently displaced by other larger proteins having a greater affinity with the coated
that are larger and less motile, but have a material.7
more pronounced affinity for the material’s Protein A
surface. This phenomenon is commonly
known as the Vroman effect5 (see Figure 1).
The nature of the proteins’ adherence to
the coated biomaterial surface is a major
factor in influencing the attachment of
posterior cells and their behaviour, such as
the attachment and the activation of
neutrophils (white blood cells),
macrophages and other inflammatory cells.6

Protein adhesion initiates cell Exposure time

adhesion
Once attached to the material, a complex
system of communication, initiated by the
proteins, begins to take place, involving the
release of signals, the attraction of cells
and, finally, the adherence of these cells to
the surface.
The process of cell attachment to a
surface (coated or otherwise) occurs in
three consecutive stages:
l Attachment,
l Spreading and growth,
l The formation of focal adhesions and
stress fibres.8
Each of these stages can be recognised in
the development of interaction between
most non-biological coatings and their
substrate.
In the process of cell attachment, the first
stage is initiated by the contact between
those integrins (trans-membranar proteins
composed of an (alpha) sub-unit and a
(beta) subunit) and the proteins that are on
the coated surface. This phase will result in
the integrins becoming activated, a
phenomenon that includes their clustering
and the increase of their affinity towards
the coated surface.9
Protein B
Following this process, filaments of actin
(a protein capable of polymerisation) are
formed and the cells spread, enhancing
their surface contact area (second stage).
Finally, strong points of attachment, named
focal adhesions, are formed. These sites
work as linkage spots between the fibres of
actin and the extracellular medium, via the
transmembrane integrins. At the end of this
process, the cell is tightly attached to the
coated surface (see Figure 2).
When coated biomaterials are used, cell
adhesion may come either as an advantage
or as a shortcoming, depending on the
circumstances. While for some applications
it is vital that cells become attached,
spread and even divide on the surface, (as
Protein
displacement
in the case of the development of materials
for use in tissue engineering), in other
cases such processes will result in implant
failure and the need for removal and
replacement.
Biofilm formation
The most obvious example of undesirable
cell adhesion to a material is the case of
bacterial attachment. Bacterial attachment
and subsequent spreading on biomaterials
(commonly known as infection), results in
the formation of a secondary coating, a
biofilm, which is frequently associated with
the failure of implants, as in the case of
joint prostheses, heart valves, vascular
catheters and contact lenses.10

2 Surface Coatings International Issue 2013/3

 which works as an enclosing structure. The
Figure 2: Stages of cell adhesion to a coated surface: attachment, spreading and formation of focal adhesions
spreading of the resultant coating biofilm
and stress fibres9
is mainly due to the release of some
Stage 1 Stage 2 Stage 3 bacteria from the cluster structures, which
Cell attachment Cell spreading Focal adhesion then adhere to the coating surface and
Stress fibres start a new cycle.11
Integrin Actin filaments
Studies concerning the mechanisms of
bacterial adhesion, leading to an
understanding of how to avoid this
drawback, are constantly being updated.
However, the complexity of such processes
and all the factors of relevance (eg material
properties, bacterial strain type and patient
Strength of adhesion condition), makes it a difficult task to
accomplish.
Figure 3: Stages of biofilm development: (1) bacterial attachment to the coated surface; (2) synthesis of As previously mentioned, cell attachment
extracellular matrix; (3) formation of bacterial microcolonies; (4) maturation of biofilm architecture; (5) and consequent cell behaviour involves a
dispersion of bacteria complex set of occurrences which, in turn,
involve processes such as protein
adsorption and intercellular signalling that
Dispersion of bacteria
occur externally to the material. However,
these are fundamentally related to the
properties of the material. In fact, the
surface of the biomaterial is a key factor
determining the biological response and,
Beginning therefore, the biocompatibility, since most
of new biological reactions occur at the surfaces
cycle and interfaces.12
Properties such as the wettability,
chemical composition, porosity,
softness/stiffness, roughness and the
surface charge of the biomaterial, are
highly influential with respect to the effect
1 2 3 4 5 on the physiological environment (see
Figure 4).13 For such reasons, when
designing a biomaterial, all of these factors
Figure 4: Examples of key features of the material’s surface (coated or otherwise) that determine cell must be taken into consideration when
adhesion and spreading, following coating attempting to optimise features that are
related to the overall biocompatibility and
consequences of coating.
Charge Softness Two major strategies have been used by
researchers to increase the overall extent of
biocompatibility of coating compositions.
Wettability Chemical One involves the synthesis of new materials
composition and the other concerns the modification of
the surface of pre-existing materials, for
example by the use of appropriate coating
technologies and pretreatments. Here, some
of the available techniques that are used to
Roughness Porosity enhance biocompatibility are described and
Surface
properties examples of their application are given.

Biofilm formation occurs through several
consecutive stages (see Figure 3), starting
with the attachment of bacteria to the
surface, followed by cell-cell adhesion and
proliferation. Finally, cells begin to
accumulate in multilayer clusters and to
produce an extracellular matrix (mainly
composed of polysaccharidic species),
Enhancing biocompatibility
Surface modifications
In biomaterials, the surface and bulk
properties of the coated devices are

Surface Coatings International Issue 2013/3 3

 responsible for the success or failure of the
device. For a specific medical application,
the desired characteristic for the implant
must be known prior to its implantation.
Therefore, the implanted devices (coated or
otherwise), need to present specific bulk
and surface characteristics if they are to be
recognised and accepted by the medium in
which they are placed.
Usually a material is chosen according to
its bulk properties, such as the stiffness, the
polymer type, conductivity, optical
properties, degradation and strength.14,15
For most biomedical applications, the two
properties of greatest importance are the
strength (based on mechanical attributes)
and the surface reactivity and ease of
coating (based on chemical attributes).
Some synthetic materials have suitable bulk
properties. However, most such surfaces
have to be modified by coating, if they are
not to be recognised as a foreign material.
Thus, surface modification (coating) plays
an important role in the biomedical field
since this technique can be used to adapt
the surface to the desired characteristics
without compromising the bulk properties.
Surface modification techniques are used
in several distinct types of application, such
as biomedical polymers, textile materials,
microelectronics components and food
industry products. Thus, any successful
surface coatings related modification
method that is used will have been tried
and tested in a variety of fields, relevant to
different final applications of the material.
This reality gives confidence in the
appropriateness of the coating materials
and the modification techniques that are
available.
As previously mentioned, in the
biomedical field, one of the major causes of
device failure is biological response to the
implanted material. Therefore, it is crucial
to control the bio-interaction (if any) that
occurs between the modified (coated)
device and its surroundings.
Several methods for tailoring surfaces to
suit specific applications have been
reported. Biological methods, chemical
methods, physical methods and/or
physicochemical methods can be used for
these purposes. Some of these methods are
schematically illustrated in Figure 5.
Consequently, two major classes of
surface modification techniques can be
considered. The first concerns surface
modification by physical methods, which
include flame treatment, corona discharge
4 Surface Coatings International Issue 2013/3
Figure 5: Schematic representation of surface modification methods (adapted from references 16 and 17)
Original surface
Overcoat
– Solvent coating
– Grafted surface layer
Surface gradient
– Graft
– Interpenetrating network
treatment, plasma treatment, ultra-violet
(UV) radiation exposure, laser ablation
treatment, gamma irradiation and x-ray
treatments.
The second class includes surface
modification by using ‘chemical methods’
and incorporation of functional groups,
such as etching, surface oxidation,
hydrolysis, chemical grafting and surface
coating. Some of the common surface
modification techniques include plasma
techniques followed by polymerisation,
sputter coating and etching, spray coating,
dip coating, graft copolymerisation at the
surface, UV, gamma radiation and laser
treatment, biomolecule attachment and the
use of self-assembling coatings.16
Over the years, several surface
modification methods have been
developed. Some of these are summarised
here:
l The physical deposition of active
compounds to the surface by coating;18
l The covalent immobilisation of polymer
chains onto a surface by chemical
reactions, taking place after the
coating has been applied;19
l The grafting of polymer chains on the
surface, during/after plasma
treatment;20,21 by corona
discharge,22,23 and by grafting that has
been initiated by radiation pre-
treatment.24,25
Surface modification by ultraviolet
radiation
Some of the surface modification methods
that have been previously mentioned might
not give rise to a ‘permanent’ change and
the benefits might also considerably impair
the required bulk properties of the
material. Surface graft polymerisation with
ultraviolet (UV) irradiation induced
initiation (see Figure 6) has been proven to
offer some advantages over alternative
Surface active bulk additive
H H H CH3 CH3 CH3
O O O O O O
Surface chemical reaction
Etching and roughening
treatments. These include fast reaction
rates, the low cost of such processing, the
availability of relatively simple formulations
and equipment, relatively facile
development on an industrial scale and,
probably most importantly, the distribution
of the grafted chains is limited to the
surface of the material.26
Such grafting can be viewed as a
controlled coating option. Surface
modification by the photo-grafting of
coating formulations provides another basis
for the modification of the surface
properties without interfering with the
bulk material.
The first work on photografting
polymerisation that was initiated by UV
radiation was published in the 1950s by
Oster and Shibata.27 Surface graft
polymerisation after coating, by using
simultaneous UV radiation
induction/initiation, is usually performed in
the presence of a photoinitiator or a
photosensitiser.
This photoinitiator (after its
photodecomposition), along with
monomers can induce the formation of
monomer radicals, leading to subsequent
atom abstraction processes, (usually
involving H-atoms), resulting in radicals on
Figure 6: Schematic representation of surface graft
polymerisation by UV irradiation
UV irradiation
Monomer
Initiator
Surface graft
polymerisation
the backbone of the substrate surface,
thereby initiating graft
photopolymerisation through the usual
routes of propagation and eventual chain
termination.28–30
Benzophenone (BP), thioxanthones,
chlorinated acetophenones and their
derivatives are among the more common
photoinitiators that are used in this
context. These allow the initiation of the
grafting process by inducing radical
formation. The radical produced may be
symmetrical or asymmetrical, depending on
the molecular structure of the initiator.
Thus, frequently used photoinitiators, such
as the isopropylthioxanthone, xanthone,
anthraquinone, 2,2-azo-bisisobutyronitrile
and Irgacure 2959, among others, are used
for non-aqueous media.26
Water-soluble derivatives of these
initiator types are used when aqueous-
based formulations are required, the water
solubility being provided by the use of the
appropriate quaternary salt or sulphonic
acid salt. The curing reaction time and the
wavelength of the radiation that is used in
the reaction are determined by the chosen
photoinitiator and the spectral output of
the radiation source.
1-[4-(2-hydroxyethoxy)-phenyl]-2-
hydroxy-2-methyl-1-propane-1-one
(Irgacure 2959), is a highly efficient non-
yellowing radical photoinitiator that is used
for the UV curing of systems comprising of
unsaturated monomers and pre-polymers.
This photoinitiator has been very much
used since Williams et al31 studied its
biocompatibility, along with that of other
photoinitiators. In their study, Irgacure
2959 gave the best results in terms of
cytocompatibility.
Other applications of UV in the field
Despite the main application of UV
radiation in the biomaterial field being
targeted towards the modification of
surfaces, in some cases, such as in the
improvement of biocompatibility and
haemocompatibility, UV irradiation can be
also used to modify the bulk properties and
composition of the material. Moreover,
cross-linked materials and cell
immobilisation systems,32,33 anti-fouling
surfaces34 and bio-scaffolds for tissue
engineering35,36 can be prepared by UV
irradiation-based techniques.
Surface modification by plasma
treatment
Nowadays, plasma technologies are being
widely used to tailor the surface properties
of polymers without affecting their bulk
properties. The hydrophilicity, chemical
structure and roughness are some of the
surface properties that can be modified by
plasma treatment in order to adapt a
material for a specific application. Plasma
treatment can also be used to clean
polymer surfaces from organic
contamination.37
A plasma is a mixture of highly excited
electrons, negatively charged particles and
positively charged particles, neutral atoms
and molecules. For this reason, the plasma
state is sometimes referred to as the fourth
state of matter.
Plasma polymerisation has been studied
intensively since the 1950s and especially
in the 1960s. Over the years, it has gained
importance as a surface modification
technique and nowadays is a well-
recognised method38, especially in the
biomedical field. This is because it is a
relatively economical and effective
technique for the processing of polymeric
materials. Table 2 lists some of the common
research areas and applications in which
plasma treatment is used for the creation
of more effective coated biomaterials.39
As previously mentioned, a plasma can be
used for cleaning, for activation and for
the etching of a surface (metal, ceramics,
glass and plastics) as well as for coating by
plasma polymerisation. The various effects
of the plasma treatment of a polymer
surface may be categorised as surface
Table 2: Common research areas and applications of plasma treatment in biomaterials, adapted from
reference 39
Areas
Blood-containing surfaces
Non-fouling surfaces
Tissue engineering and cell culture
Sterilisation of surgical tools and devices
Biosensors
Barrier coatings
Surface Coatings International Issue 2013/3
modification, coating, grafting and film
deposition (plasma polymerisation).40
How plasma treatment functions
The surface treatment of polymers is widely
achieved by using gases such as argon,
helium, nitrogen and oxygen, among
others. This treatment leads to the
formation of free radicals at the surface of
the polymer. These radicals are, under
appropriate circumstances, able to react
with the excited species in the plasmas.
Therefore, treatment with O2, N2 or inert
gases leads to the formation of
functionalities containing oxygen atoms,
such as hydroxyl groups, carbonyl groups
and, in some cases carboxylic groups.
In the biomedical field, plasma surface
modifications are mostly used to improve
adhesion, increase surface wettability and
induce surface roughness. Thus, plasma
surface modifications include:37
l removing surface contaminants such as
air pollutants or fingerprints;
l etching, leading to an increase of the
surface roughness by selective removal
of surface material by chemical
reaction and/or physical sputtering;
l substitution of chemical groups on the
surface by other groups or
functionalities that might allow
covalent bonding, by the modification
of the surface characteristics with
reactive gases.
Plasma grafting/coating
Plasma grafting is a two-step incorporation
process whereby functional groups and
reactive sites can be created on the
Applications
Vascular grafts, catheters, stents, heart valves,
membranes (haemodialysis), filters (blood cell
separation)
Intraocular lenses, contact lenses, wound healing,
catheters, biosensors
Cell growth, antibody production, essays, vascular
grafts
Cutting tools of surgeons, tweezers
Biomolecules immobilised on surfaces
Drug-release, gas-exchange membranes, device
protection, corrosion protection, reduction of leaching
(many of these involving the correct use of additives
and plasticisers)
5
 polymer surface. Using inert gas plasmas,
free radicals can be formed on the surface.
To generate a grafted/coated polymer on
this surface, a monomer solution is
introduced into the reaction chamber,
allowing the monomer to react with the
surface free radicals, resulting in a
grafted/coated surface treatment (Inagaki,
1996).40
Alves et al41 have introduced carboxylic
groups onto a thermoplastic polyurethane
substrate using the plasma method. In this
way, the authors graft/coated acrylic acid
and methacrylic acid onto the surface of
the polymeric substrate to improve
wettability and reduce cell adhesion.
Poly(dimethyl siloxane) surfaces can be
modified by low pressure plasmas in order
to improve their characteristics for
biomedical applications. Pluronic F-68 (a
surfactant) and poly(ethylene glycol)
methyl methacrylate can be grafted to
poly(dimethyl siloxane) surfaces to improve
the wettability of the surface and reduce
bacterial adhesion.42
These surface modification findings allow
these kinds of materials (polyurethanes and
poly(dimethyl siloxane)) to be used as
medical devices (eg catheters, vascular
grafts and voice prostheses) without
leading to a biofouling mechanism.
Plasma Polymerisation
Plasma polymerisation leads to the
formation of a thin coating film that can
possess unique chemical properties and
physical properties. In order for the
polymerisation process to occur, radicals
can be formed in the presence of a gas in
which a monomer is usually mixed. Then, as
the molecular weight of the polymer in the
chamber increases, the polymer is deposited
as a coating on the surface of the
substrate.
The deposition of the polymers is mainly
mediated by the geometry of the plasma
system, the working gas pressure, the
power and frequency of the signal, the
temperature of the substrate and the flow
rate and reactivity of the monomer. This
technique leads to coated thin films that
are highly cross-linked and are strongly
bound to the surface.37,40
Vilani et al43 studied the influence of the
parameters associated with the plasma
treatment during the use of acrylic acid on
polysiloxane and polyurethane substrates.
They treated both surfaces using a RF
(radio frequency), low-pressure plasma with
6 Surface Coatings International Issue 2013/3
acrylic acid being the plasma monomer. The
authors concluded that the coated thin
film was formed was chemically similar to
poly(acrylic acid).
Biomolecule attachment
As mentioned previously, the
adsorption/desorption behaviour of blood
proteins and the adhesion and proliferation
of different types of cells on polymeric
materials depends mainly on surface
characteristics such as the wettability, the
degree of hydrophilicity/hydrophobicity, the
bulk chemistry, the surface charge, the
surface charge distribution and the surface
roughness44 In order to accommodate
these issues, the surface modification of
biomaterials, using proteins to control cell
adhesion and the subsequent cellular
response to material surfaces, has been
reported.44–48
For this purpose, molecules such as
laminin, fibronectin, collagen, and the
Arg–Gly–Asp (RGD) peptide can be used.
Some studies have shown that by
modifying the biomaterial surface with
molecules that induce cell adhesion, such
as fibronectin, an improvement of the
cellular response and of tissue repair can be
achieved.
Some serum proteins, such as fibronectin
and vitronectin, show a preferential
adsorption onto moderately wettable
surfaces. These proteins are also known as
cell-adhesive proteins. Thus, if a surface
offers the ideal hydrophilicity, these
proteins can adhere on the surface and
consequently can improve cell adhesion,
spreading, and growth.44 Thus if a surface
is tailored to have the ideal hydrophilicity
the cellular response can be controlled.
The RGD peptide sequence is known as a
cell recognition site for numerous adhesive
proteins that are present in the
extracellular matrix (ECM) and in blood.
Surface-immobilised RGD groups are
known to enhance cell attachment, while
RGD components that are present in
solution can inhibit cell attachment by
competing with endogenous ligands for the
same recognition site).49
Bovine serum albumin (BSA) protein has
different responses to different interfacial
environments. BSA is often used to coat
biomedical devices. Albumin is often used
for the coating of vascular grafts to
passivate those surfaces that are in contact
with blood and thus minimise surface-
induced platelet activation. Albumin
reduces both the number of adherent
platelets and the extent of platelet
activation on the albumin-adsorbed
surface.50
Poly-D-lysine (PDL) is a synthetic
polypeptide that is used as a culture
substrate to enhance cell attachment, after
coating on plastic and on glass surfaces.
PDL is also widely used with a wide variety
of cell cultures, particularly neurons, glial
cells and transfected cells. In addition, PDL
coated surfaces are often used to reduce
cell detachment that might otherwise
occur during the multiple washing steps
that are associated with cell assays.50,51
Conclusions
The modification of surfaces is a very
important aspect of the creation of
medically viable polymeric and non-
polymeric biomaterials (metals, ceramics).
The use of coating techniques in the
creation of biomaterials field has been
growing over recent decades due to the
developed abilities to improve the
application properties of such materials
when they are used in several biomedical
applications, such as catheters, artificial
veins, endoprostheses, cardiac valves and
voice prostheses.
The efforts of researchers towards
reaching ideal, designed surface
modifications are converging towards the
introduction of desired functional
properties without leading to irregular
etching or producing significant hazardous
wastes. At the same time, it is
recognised/proposed that the nature of
these functional properties must be
provided by species that are as close to
being a monolayer as possible.
From all the methods available for surface
modification, the radiation treated-
chemical related (ultraviolet and gamma
radiation-plasma systems) have been shown
to be among the simpler, faster and more
effective methods. One of the more
important characteristics of the UV
irradiation or plasma methods is that their
action takes place only on thin surface
layers, permitting the bulk of the sample to
remain unchanged, the modified material
being thus able to retain its mechanical
properties.
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