G.

NALANKILLI
Bannari Amman Institute of Technology
Introduction
Industrially, are being used to modify a huge range of
material surfaces, including plastics, polymers and
resins, paper and board, metals, ceramics and
inorganics, and biomaterials.
Properties enhanced include wettability, adhesion,
biocompatibility, protection and anti-wear,
sterilisation, and chemical affinity or inertness.
• This enables a variety of generic surface processes
including
– Surface activation by bond breaking to create reactive
sites
– Grafting of chemical moieties and functional groups
– Material volatilisation and removal (etching)
– Dissociation of surface contaminants/layers (cleaning/
scouring) and
– Deposition of conformal coatings.

In all these processes a highly surface specific region of

the material (<1000 Å) is given new, desirable
properties without negatively affecting the bulk
properties of the constituent fibres.
 Plasma
Electrically neutral

+ve, -ve Charges,

Radicals,
Electrons,
Excited molecules, atoms.

Highly Reactive & Energetic

Sun

Hydrogen Bomb Fire

Potential Difference > Dielectric Strength , 13.56MHz RF Power
What is Plasma?
Matter within the universe is most commonly found in the
form of plasma rather than as a solid, liquid or gas.
Plasma is partially-ionized gas normally generated by an
electrical discharge at near-ambient temperatures.
Plasma, often considered as the fourth state of matter, is
composed of an ionized gas containing a mixture of ions,
electron, neutral and excited molecule, and photons.
This state of matter was first identified by Sir William
Crookes in 1879, and named 'plasma' by Irving Langmuir
in 1928.
What plasma consists of?
• The coupling of electromagnetic power into a process gas
volume generates the plasma medium comprising a
dynamic mix of ions, electrons, neutrons, photons, free
radicals, meta-stable excited species and molecular and
polymeric fragments, the system overall being at room
temperature.
• A plasma is an ionised gas, i.e. it contains electrons, ions
and neutral atoms and/or molecules
• This allows the surface functionalisation of fibres and
textiles without affecting their bulk properties. These
species move under electromagnetic fields, diffusion
gradients, etc. on the textile substrates placed in or passed
through the plasma.
Definition
A commonly accepted definition of plasma is: a
partially ionised gas composed of highly excited
atomic, molecular, ionic and radical species, as well as
photons and electrons

From 60s to 80s

In the 1960s, the main industrial applications of (low-
pressure) plasmas have been in the micro-electronic
industries.
In the 1980s their uses broadened to include many
other surface treatments, especially in the fields of
metals and polymers.
How depth it acts?
All these phenomena are limited to the most external
layer of the substrate. Normally, the effects do not
involve layers deeper than 10–100 nm. However, it
must be noticed also that ultraviolet (UV) or vacuum
ultraviolet (VUV) radiation (with wavelength <200
nm) is an important component of plasma. VUV
radiation can give rise to a variety of photochemical
interactions with the substrate, such as bond
breakage and formation of free radicals, reaching
inner layers (>10 nm) depending on the absorption
coefficient of the substrate
Generic Surface Engg. Process
Cleaning or etching: For such a phenomenon to occur, ‘inert’
gases (Ar, He, etc.), nitrogen or oxygen plasmas are typically
used. The bombardment of the substrate with the plasma
species causes the breakdown of covalent bonds. As a
consequence, detachment of low molecular weight species
(ablation) takes place. In this way, contaminants or even thin
layers of the substrate are removed, producing extremely ‘clean’
surfaces, modifications in the surface area, or controlled
reduction of weight of the exposed substrate.
The removal of bulk substrate material, occurs when the
interaction between the solid surface and the plasma generates
gas-state byproducts, which include atoms or molecules, from
the substrate. These desorbs from the surface and are carried
away from the substrate, thus removing bulk material.
Cleaning, the removal of contamination, is a form of etching
but with very high selectivity. Essentially, only the unwanted
surface contaminant is volatilized and removed while the
substrate remains untouched by the process.
Activation: Interaction with plasma may induce the
formation of active sites on the polymer surface (radicals or
other active groups, such as hydroxyl, carboxyl, carbonyl,
amine groups), which can give rise to chemical reactions, not
typical of the untreated material, with substances brought in
contact with the material after plasma processing. Activation,
enhancement of the surface energy, is the generation of
chemically reactive sites on a previously uncreative surface
resulting in a rise in surface tension.
Coating, deposition of a functional thin fi lm, occurs if the
plasma–solid surface interaction creates a solid phase
material. This remains on the surface and agglomerates over
time, e.g. micro-seconds, to generate a conformal film. This
process is sometimes called Plasma Enhanced Chemical
Vapor Deposition (PECVD) or plasma polymerization
Grafting: Radical species present in the plasma may be
directly grafted onto the polymer surface.

Polymerization: by using specific molecules, a process

known as plasma enhanced chemical vapour deposition
(PECVD) may occur. These molecules, activated in the
plasma, may react with themselves forming a polymer
directly on the surface of the substrate. Depending on the
different experimental conditions, chemically unique,
nanometric polymeric coatings are obtained and chemical,
permeation, adhesion and other properties of the starting
material can be dramatically modified.
Effect of plasma on fibres and polymers
• Textile materials subjected to plasma treatments undergo
major chemical and physical transformations including
(i) chemical changes in surface layers,
(ii) changes in surface layer structure, and
(iii) changes in physical properties of surface layers.
• Plasma treatment on fibre and polymer surfaces
results in the formation of new functional groups
such as —OH, —C=O, —COOH which affect fabric
wettability as well as facilitate graft polymerisation
which, in turn, affect liquid repellence of treated
textiles and nonwovens.
• Plasmas are acknowledged to be uniquely
effective surface engineering tools due to:

– Their unparalleled physical, chemical and thermal

range, allowing the tailoring of surface properties
to extraordinary precision.
– Their low temperature, thus avoiding sample
destruction.
– Their non-equilibrium nature, offering new
material and new research areas.
– Their dry, environmentally friendly nature.
Classification of Plasma
(i) On the basis of pressure in plasma chamber­- Atmospheric
Pressure and low pressure plasma.
(ii) On the basis of degree of ionization and the temperature
of electrons and ions-Hot and cold plasma.
(iii) On the basis of frequency of the power supply­DC and AC
plasma(RF, Microwave, GHz Plasma).
(iv) Depending upon the electron affinity of the process gases
used-Electropositive and electronegative gas plasma.
Any plasma reactor will be a combination of all of the above,
e.g. one atmosphere glow discharge cold plasma is based on
cold, AC and atmospheric pressure plasma.
 
Atmospheric Pressure Plasma
Traditional sources include transferred arcs, plasma torches,
corona discharges and dielectric barrier discharges.
In arcs and torches, the electron and neutral temperatures
exceed 3000°C and the densities of charge species range from 1016
cm-3 to 1019 cm-3.
Due to the high gas temperature, this plasma is used primarily in
metallurgy.
Corona and dielectric barrier discharges produce non­equilibrium
plasma with gas temperatures between 50°C and 400°C. Higher
voltages are required for gas breakdown at 760 torr and often
arcing occurs between the electrodes.
However, to prevent arcing and lower the gas temperature,
several schemes have been devised, such as the use of pointed
electrodes in corona discharges and insulating inserts in
dielectric barrier discharges
Advantages and Disadvantages of APP
The advantages of atmospheric pressure plasma are:
(i) continuous treatment can be given, and
(ii) it is cost effective process.
On the other hand, the disadvantages of atmospheric
pressure plasma are:
(i) difficulty of sustaining of glow discharge,
(ii) higher voltages are required for gas breakdown, and
(iii) difficult to form uniform plasma through out the
reactor volume.
Different types of atmospheric pressure plasma used are:
corona discharge, dielectric barrier discharge and plasma
jet.
Corona Discharge
 Corona treatment
• Corona discharge is characterized by bright filaments extending
from a sharp, high-voltage electrode towards the substrate.
• Corona treatment is the longest established and most widely used
plasma process; it has the advantage of operating at atmospheric
pressure, the reagent gas usually being the ambient air.
• This is obtained at atmospheric pressure by applying D.C., low
frequency or pulsed high voltage between two electrodes of very
different sizes. The corona consists of a series of rapid, non-
uniform, non-arcing discharges. Plasma density drops off rapidly
with increasing distance from the electrode.
Dielectric Barrier Discharge
 Dielectric barrier discharge
(Silent discharge)
This is an atmospheric-pressure plasma source.
In this case a pulsed high voltage power ranging
from low frequency AC to 100 kHz is applied
between electrodes, one or both of which is
covered by a dielectric layer. The purpose of the
dielectric layer is to terminate rapidly the arcs
that form in the region between electrodes. The
discharge consists of series of rapid micro
discharges
Plasma Jet
Low Pressure Plasma
Low pressure plasma has found wide applications in
materials processing and play a key role in manufacturing
semiconductor devices.
 They generate high concentrations of reactive species that
can etch and deposit thin films at the rates up to 10 m/min
The temperature of the gas is usually below 1500C, so that
the thermally sensitive substrates are not damaged.
The ions produced in the plasma can be accelerated toward
a substrate to cause directional etch at submicron level.
In addition, a uniform glow discharge can be generated, so
that the materials processing proceeds at the same rate over
large substrate areas.
Low-pressure plasmas
Low-pressure plasmas are a highly mature technology
developed for the microelectronics industry.
However, the requirements of microelectronics
fabrication are not, in detail, compatible with textile
processing

Vacuum vessel is pumped down to a pressure in the

range of 10-3 to 10 mbar with the use of high vacuum
pumps. The gas which is then introduced in the
vessel is ionised with the help of a high frequency
generator. The advantage of the low-pressure
plasma method is that it is a well controlled and
reproducible technique.
In a weakly ionized gas at low pressure, the electron
density ranges between 108cm-3 and 1013cm-3. Under these
conditions, the collision rate between electrons and
neutral molecule, insufficient to bring about thermal
equilibrium
Advantages & Disadvantages of low
pressure plasma
 Advantages:
(i) the generate high concentrations of reactive specie that can etch
and deposit thin films;
(ii) uniform glows is obtained;
(iii) the temperature of the gas is usually below 1500C, so that the
thermally sensitive substrates are not damaged;
(iv) low breakdown voltages; and
(v) a stable operating window between spark ignition and arcing.
 Disadvantages:
(i) vacuum systems are expensive and have high maintenance cost,
and
(ii) Size -of the object to be treated is limited by the size of the vacuum
chamber
Hot Plasma
Production in Universe is of hot plasma. Hot plasma
occurs when the temperature of electrons and atomic
and molecular species are extremely high. Ninety nine
per cent of the matter in the universe is in the plasma
state.
Hot plasma is nearly fully ionized which is actually
known as the fourth-state of matter. The Sun and the
stars in the universe consist entirely of hot plasma,
and the space within the stars of a galaxy is filled with
plasma.
Cold Plasma
Cold plasma occurs when the atomic and molecular
species are at ambient temperature, whereas the
electrons are at high temperatures. A small fraction of
the gas molecules (e.g. 1 %) is ionized. It has already
found uses in a variety of manufacturing processes. For
example, flat-screen televisions use cold plasma to
radiate light and create images.
Cold plasma can be used to treat surfaces (e.g. oxidation,
functionalization) or to deposit specific coatings onto
organic and inorganic substrates. Cold plasma can
produce ozone as its secondary offspring. Most
important, cold plasma is used to finely etch channels on
integrated circuits - the chips inside our desktop and
laptop computers that made the computer and internet
age possible
Cold plasma
Contrary to thermal plasmas, non-thermal plasmas are
‘cold’ plasmas and are produced at room temperature or a
little above room temperature. In this case, electrons
acquire higher energies than ions and molecules, their
energies ranging from 0.1 to some electron volts, and, due
to the low density of the gas, collisions with the other
species are relatively rare and thermal equilibrium is not
reached: the bulk temperature of the gas is comparable to
room temperature.
 Electron collisions with neutral species produce
additional electrons and ions. Thanks to the low operating
temperatures, cold plasmas can be put in contact with any
material, even delicate textiles, without problems.
DC & AC Plasma
AC discharges are preferred over DC-driven discharges in
plasma systems for a number of reasons.
First, as the frequency of AC increases, the energy transfer
into the discharge becomes more efficient, especially at
frequencies between ~100 kHz and 1GHz, the RF regime.
Also, in a DC discharge, charged particles from the plasma
can accumulate on the substrate surface causing
unwanted charging effects. By alternating the direction of
the current flow sufficiently rapidly, these charging effects
can be reduced.
At RF frequencies, this alternation is sufficiently rapid to
almost completely eliminate charging effects.
Electropositive and
Electronegative Gas Plasma
Most of the etching plasma used in the semiconductor
industry is formed from gases which readily form negative
ions, i.e. electronegative gases. Plasma is usually classified
into two different types depending upon the electron
affinity of the process gases used. Process gases can be
arranged roughly in the following order of increasing
electronegativity:
  Ar <=Nz < CF4 < CFzCl2 < Cl2 < CFCl3 < SF6 < CCl4
Electropositive (EP) Plasma
These are discharges consisting mainly of spices
which do not form negative ions easily. Examples are
all noble gases, such as Ar, He and some unreactive
gases like N2. In this plasma, the number of positive
ions is almost exactly equal to the number of
electrons, although both are still much smaller than
the number of neutrals.
 
Eleclronegative (EN) Plasma
 By contrast, EN plasma contains a significant number of species
which have a positive electron affinity. In these cases, the number
of free electrons is significantly reduced as a result of capture by
EN species to form negative ions. A typical reactions might be:
 
e + CCl4  CCl4  CCl3 + Cl­
 
 In CCl4 plasma, the number of electrons can be up to 100 times
less than the number of positive ions, with overall charge
neutrality being maintained by large numbers of negative ions. EN
plasma requires higher power to sustain and is difficult to initiate.
This make EN plasma unstable and often non-uniform. The
electron temperature is also much higher than in EP plasma.
 Glow Discharge Plasma
It is an ionized gas consisting of equal concentrations of
positive and negative charges and a large number of
neutral species.
In the simplest case, it is formed by applying a potential
difference (of a few 100 V to a few kV) between two
electrodes that are inserted on a cell (or that form the
walls of the cell).
The cell is filled with a gas (an inert gas or a reactive gas)
at a pressure ranging from a few mTorr to atmospheric
pressure.
This is obtained at low pressures, typically less than
10 mbar. The plasma is generated by antennas, fed with
electromagnetic fields at frequencies of 40 kHz or 13.56
MHz or microwaves (2.45 GHz).
Glow Discharge Plasma ….
 Due to the potential difference, electrons that are emitted from the
cathode by the omnipresent cosmic radiation are accelerated away from
the cathode, and give rise to collisions with the gas atoms or molecules.
 As a result of this excitation, the ionization and dissociation take place.
The excitation collisions give rise to excited species, which can decay to
lower levels by the emission of light.
 This process is responsible for the characteristic name of the "glow"
discharge.
  Glow discharge is characterised as a uniform, homogeneous and stable
discharge usually generated in helium or argon (and some in nitrogen).
Atmospheric Pressure Glow Discharge (APGD) offers an alternative
homogeneous cold-plasma source, which has many of the benefits of the
vacuum, cold-plasma method, while operating at atmospheric pressure.
One Atmosphere Uniform Glow Discharge
Plasma (OAUGDP)
 The OAUGDP is produced by applying a kilohertz electric field
between two parallel plates.
 The electric field required to initiate the OAUGDP is 8.5 kV/cm for
air, well below the DC electric field for sparking.
 Both electrodes may be covered with quartz, pyrex alumina or glass
insulating plates, the thickness of which is between 1mm and 3mm.
 The exposed samples are placed on the lower electrode. The working
gas is entered from one side and flows out through the other side.
 OAUGDP reactor is uniform without filamentary microdischarge if
the proper combination of gap distance, RF driving frequency and
rms voltage is selected to maintain ion trapping.
 The OAUGDP technology is simple, cost effective and suitable for
online treatment of fabrics and films.
Different APP & SURFACE MODIFICATIONS
 Why plasma processes at atmospheric pressure
are advantageous for the textile industry ?
 The typical working width of textile machines is between 1.5 and 10 meters.
Textile-suited plasma modules need to be scalable up to these dimensions, which
is easier for atmospheric-pressure techniques.
 Textiles have large specific surfaces compared to foils, piece goods or bulk solids.
Even with strong pumps, the reduced pressure which is necessary for low pressure
plasma will only be reached slowly due to the desorption of adsorbed gases.
 Depending on the fibre material, textiles can adsorb and absorb relatively large
amounts of water. To reduce the chamber pressure below the vapor pressure of
water (23.4 mbar at 20 ºC), a drying process is necessary. This is time consuming
because diffusion processes within the fiber and the cooling due to evaporation of
the water slow down the drying (vapour pressure of ice: 4.02 mbar at -5 ºC). The
evaporation time can be shortened by heating the substrate.
 Atmospheric-pressure processes can be combined with spraying or aqueous
aerosols.
 Atmospheric-pressure processes are in-line capable, in contrast to batch low-
pressure plasma processes.
 Investment and maintenance costs for atmospheric-pressure plasma modules are
moderate
What gas plasma, does what?
 Helium/oxygen plasma treatment of PP introduces oxidised functional groups
onto the surface, which may include alcohol, ketone, carboxy, ether, ester or
hydroperoxide. The introduction of polar groups onto the PP fi bres allows
chemical bonding with, for example, dye molecules, in contrast to the untreated
PP molecular chains which are non-polar giving a hydrophobic surface.
 Oxygen and oxygen-containing plasmas impart functional groups such as C-O,
C=O, O-C=O and C—O—O, as well as surface etching of fi bres, all enhancing
wettability and adhesion characteristics.
 Fluorine and fluorine containing gases (CF4, C2F6) result in the incorporation of
fluorine into the surface, resulting in hydrophobicity.
 Nitrogen and ammonia plasmas introduce amino (—NH2) and other nitrogen
containing functionalities onto natural and synthetic fibres. On wool, these are
dye sites increasing dye absorption.
 Treatment of PTFE with hydrogen-containing plasmas such as forming gas
(N2/H2::95%/5%) and ammonia results in large increase in surface energy due to
a high defluorination rate resulting in the formation of C—C, C—H and C=C
bonds and cross-links, and to nitrogen and oxygen species grafted onto the
treated surface
Breakdown Voltage
 To ignite plasma, the breakdown voltage for the gas must be
exceeded. This voltage depends on the electrode spacing d and the
pressure p as follows:
B p.d 
Vb 
In A p.d    In In1  1 /  sc  
 
where A and B are the constants found experimentally; and , the
secondary electron emission coefficient of the cathode. Breakdown
voltage (Vb) increases rapidly with pressure at constant electrode
spacing. For example, the breakdown voltage for argon is estimated to
be 2500 V at 760 torr and with a 5 mm gap distance. A narrow gap is
necessary to achieve a reasonable breakdown voltage at atmospheric
pressure.
Effect of Frequency
The electric fields in the one atmosphere glow discharge
plasma reactor are only a few kilovolts per centimeter;
values are usually too low to electrically break down the
background gas.
The most desirable uniform one atmosphere glow
discharge plasma is therefore created when the applied
frequency of the electric field is high enough to trap the
ions between the two parallel plates, but not so high that
the electrons are also trapped
Effect of Frequency……
If the frequency is so low that both the ions and the electrons can
reach the boundaries and recombine, the plasma will either not
initiate or form a few coarse filamentary discharges between the
plates.
 If the applied frequency is in a narrow band in which the ions
oscillate between the two plates, they do not have time to reach
either boundary during a half period of oscillation.
If the more mobile electrons are still able to leave the plasma volume
and impinge on the boundary surfaces, then the desirable uniform
plasma is produced.
If the applied frequency is still higher so that both electrons (e) and
ions (i) are trapped in the discharge, the discharge forms the
filamentary plasma.
Breakdown voltages and densities of charge
species in the plasma discharges

Source Breakdown Plasma

voltage (Vb), density cm-3
kV
Low pressure 0.2-0.8 108 -1013
discharge
Arc and plasma torch 10-50 1016 -1019
Corona 10-50 109 -1013
Dielectric barrier 5-25 1012 -1015
discharge
Plasma jet 0.05-0.2 1011 -1012
Mechanism of Surface Modification
Both vacuum and atmospheric pressure plasma achieve
their surface treatment effects as a result of the interaction
of one or more active species from the plasma with the
surface of interest. These active species are more
chemically reactive and more energetic than the species
associated with conventional chemical processing. Such
species may include
Ultraviolet photons which are capable of breaking
chemical bonds, and photons in the visible parts of the
spectrum which can produce a positive surface charge by
the photoelectric.
Mechanism of Surface Modification…
 Charges particles are a second major class of active species from
plasma; they include electron that either recombine on the surface or
build up a surface charge; ions that may be produced by ionization
events, attachment or charge exchange in the plasma; and free
radicals or other charge molecular fragments such as OH resulting
from plasma chemical reactions.
 A third major class of active species is neutral particles which can
include very reactive atoms such as monoatomic fluorine, oxygen or
other atomic fragments; atoms or molecule in excited atomic states;
and highly reactive molecular fragments, including monomers
produced in the plasma. Most of these active species are rarely present
or much less dense in ordinary chemical reactors, and their high
energy levels make possible surface treatment effects that can be
achieved only with difficulty, if at all, with conventional chemical
processing.
Surface Modifications Using Inert gas plasma
Ablation / etching – The ability of plasma processing to
break down weak covalent bonds in a polymer through
bombardment with high-energy particles is known as
ablation. This affects the outermost molecular layers of
the substrate exposed to the plasma which evaporated as
small volatile fragments. Desizing of cotton and antifelting
of wool are some examples.
Surface cross-linking – Cross-linking is the setting up of
multiple chemical links between the molecular chains of
polymers. Plasma processing with inert gases can be used
to crosslink polymers and produce a stronger and harder
substrate microsurface.
Surface Modification using Reactive Gases & Molecules

The replacement of surface polymer groups with chemical

groups from the plasma is called activation.  
During activation, the plasma breaks down weak bonds in
the polymer and converts them to highly functional
groups such as carboxyl, hydroxyl, etc. in the presence of
active species such as reactive gases and other small
organic compounds.
Surface Modification using Polymerizable Monomers
In this case, a thin polymer layer may be formed on the
substrate surface through polymerization of a monomer.
The monomer is directly polymerized on the surface
activated by plasma treatment. This is known as grafting
through plasma.
Grafting can be carried out in situ, where the monomer
gas is introduced within the plasma zone or carried out
subsequently, where the activated Surface is exposed to
polymerization conditions in the presence of a reactive
monomer such as vinyl monomer after the plasma
treatment.
 Depending on the selection of the gas, monomer and
process parameters, these thin coatings can be deposited/
grafted with various properties or physical characteristics
 Ageing of Plasma-treated Surfaces

Concentration of functional groups may change as a

function of time
Plasma Modification of Textile
 Some of the effects or characteristics that have been shown by cold
plasma treatment on textile substrates include crease-resistant
finishes, reduced felting of wool, antistatic finishes, improvement of
wetting, enhancement of dyeability or printability enhancement of
UV-protection, flame-retardant finishes, hydrophilic and hydrophobic
finishes, cleaning of surfaces such as desizing, scouring and bleaching
 In natural fibers, such as wool and cotton, the hydrophobic layer on
the surface is oxidized and partially removed (desizing). The specific
surface area is increased during plasma treatment, which is clearly
demonstrated by means of atomic force microscopy. Again, due to the
surface-directed activity of the plasma, the tenacity of the fibers is
hardly influenced. The chemical and physical surface modification
results in decreased shrinkage behaviour of wool top.
 Specific surface area of cotton also increases with oxygen plasma
treatment. In hydrophobic materials such as polypropylene, plasma
treatment significantly increases the hydrophilicity of the surface and
surface modifications are sustained for a long time.
Surface modification with inert gas plasma
Plasma treatment Effects
Atmospheric pressure; inert gases; up to 2.5
Adhesion enhancement by up to a factor of
min on LDPE/PET film. two to ten, depending on treatment time.
Atmospheric pressure; Gases: He, air/He,
Removed some PVA size and facilitated
Air/02/He; on PVA sized cotton fabric.
PVA removal by subsequent washing; did
not affect tensile strength significantly.
Weight loss and crystallinity decreased with
Vaccum plasma gas: O2; degummed silk
yam. time of treatment; strength not change
significantly.
Atmospheric pressure; gases: He/ Ar;
acetone/Ar; Marino wool. Dyeing rate increased with 30 s treatment
An increase in both the surface energy and
Vacuum plasma; gases: N2, Ar, He; up to 2.5 surface oxygen content causes an increase in
adhesive strength.
min on HDPE film.

DBD Plasma: not specified; on cotton, wool The hydrophobic character is changed to
become increasingly hydrophilic. Specific
and polypropylene. surface area is significantly increased during
plasma treatment from 0.1 m2/ g to 0.35 m2/ g
in cotton and wool; contact angle decreased
from 90° to 55° in PP.
Surface modification with reactive gases
and molecules in plasma
Plasma Treatment Effects
Atmospheric pressure glow plasma; gas; air; on The surface energy increased to > 70 dynes / cm by
nylon and PU melt blown and electrospun fibres. 5 s of plasma exposure; did not degrade
significantly up to 120 s treatment.

Vaccum plasma; gases; dichloromethane; on cotton Moisture content and dyeability were enhanced
and PET fabrics. without affecting other properties.

Total surface free energy of PBO increased from

43.3 mJm-2 to 61.1 mJm-2 (by 41%) with treatment
Vaccum; 70 W; gas; oxgen; on PBO, Kevlar and for 5 min and the interfacial shear strength of a
carbon fibres. model PBO/epoxy composite increased from 34.7
MPa to 44.7MPa (or 29%). Similar results for other
fibres.
Level of shrink resistance could be significantly
Vacuum; gas; oxygen; on wool subtrate. enhanced on application of polymers to wool fabric
after a 2 min treatment.

Atmosphere glow plasma; gases; He, Ar, air, carbon

dioxide and other gases; on PP melt blown. Increase in wettability.

DBD plasma; gas; hexafluoroethylene/H2; onnomex Plasma is used to apply a diffusion barrier layer to
fibres. the surface to improve the resistance to 85% H2SO4
(20 h at room temperature)
Plasma Treatment Effects

Vacuum plasma; gases; oxygen and Provide an effective barrier to aqueous

hexafluoroethane; on cotton fabric contamination.
Atmospheric pressure glow discharge and The atmospheric pressure glow discharge results
dielectric barrier discharge plasma; gas; air; on in .more uniform and effective than dielectric
PTEF. barrier discharge.
Atmospheric pressure; gases; Ar/fluorocarbon A small percentage admixture of hydrogen to
mixtures; on technical textiles. Ar/C3F8 resulted in increased deposition rate.
Plasma-post-treatment in etching gases can be
used to decrease the surface tension.­

Atmospheric pressure; gas; N2 & Hybrid organic-inorganic precursor resulted in

vinyltriethoxysilane; on PET substrate. better barrier properties against oxygen gas in
comparison to an organic precursor due to
organic and inorganic networks formation.

Atmospheric pressure; gases; helium / argon or Wettability increased with increased treatment
acetone/argon; on wool and PET fabric and time. The helium/argon plasma treatment more
film. effective than the acetone/ argon plasma.

Atmospheric pressure; gas: air; on Nylon-6,6 Surface contact angle decreased rapidly from
film. 83.5° to 35°.
Atmospheric pressure: gases; N2, H2, NH3 and Increase in surface energy was observed. From
mixtures; on HDPE and PP plates. the XPS analysis, the bonds C-H, C-C, C-N, C-
O-C and C-O-H were found in the surfaces of
the treated samples.
Surface modification with polymerizable monomers
Plasma Treatment Effects
Vacuum plasma; gas: Ar monomer: acrylonitrile; PPAN (plasma polymerized acrylonitri]e)
on PP fabric. surface grafted PP fabrics exhibit improve water
absorption and dyeing properties.
Vacuum of 0.2 mbar; gas: Ar; monomer: Treatment for 1 min gave water repellent
Perflouroacrylate; on cotton/PET fabrics. properties.
Increase in wettability, soiling resistance and
colour strength of polyester fabric was better by
Vacuum; gas: Ar; monomer: acrylic acid; on argon post-plasma polymerization of acrylic acid
PET fabric. compared to in situ polymerization
Atmospheric pressure; gases: He/O 2; monomer; Antireflection layer causes increase in colour
organosilicone; on PET fabric. intensity of the polymerized PET surfaces.
Vacuum; gas: Ar; monomer: fluoroacrylate in Fire-retardant coating; 50% decrease in peak
presence of vinyl crosslinking agents; on Nylon- value of rate of heat release.
6.
Vacuum; pretreatment with Ar/O2 followed graft Grafting yield varied depending upon the
polymerization by acrylamide, acrylic acids and parameters and monomers used; breaking
acrylates; on cellulosics, acetates, and acrylic strength decreased36 due to etching in the order:
substrates. cotton> acetate> acrylic
 Direct grafting of perfluoroalkyltrichlorosilanes. on
Atmospheric pressure; on PE for 10 s. activated PE occurs much more readily compared
to monochloro-substituted silanes.
Vacuum; gases: Ar, 02,N2 and organic solvents; Plasma induced grafting yield with different gases
monomers: glycidyl methacrylate, 2,2-diphenyl-l­ and their mixture is compared.
picrylhydrazyl; on cotton fabric for 60-300 s.

Vacuum; gases: air, Ar and O2; monomer: acrylic In situ plasma polymerization of acrylic acid
acid; resulted in improved wettability, dyeability and soil
on PET and polyamide fabric for 1-90 min. resistance.
Vacuum; gases: air, Ar and O2; monomers: acrylate The LOI value of PAN (18.5) increases by 4-8 units
containing phosphorus; on PAN fabric for 15 min. when treated with the flame retardant phosphate
and phosphonate monomers.
Vacuum; gas: Ar; monomer: 1,1,2,2,Tetra Graft-polymerization of monomer in direct contact
hydroperfluoro decyl acrylate; on PAN fabric for with the substrate surface required much smaller
10 min. amounts of fluorinated reactant to achieve water
and oil repellency.
Vacuum; gas: O2; monomer: 1.1.3.3 ­ Rate of heat release decreased by 30%. Many
tetramethyldisiloxane acrylate; on N-6 film for 20 different properties such as flame retardancy,
min. damping , film deposition or hindering of additive
diffusion out of the host matrix can be achieved
using this in a single stage, treatment.
Vacuum; gas: Ar; monomer: acrylic acid; on PE for Considerable increase in surface free energy and
1-4 min. wettability was observe within 1 min of plasma
treatment.
Vacuum; gas: oxygen; monomer: acrylic acid; on Etching + plasma polymer coating provided
PP. enhanced electrochemical properties.
Potential use of plasma treatments of
fibres, yarns and fabrics
• Anti-felting/shrink-resistance of woollen fabrics.
• Hydrophilic enhancement for improving wetting and dyeing.
• Hydrophilic enhancement for improving adhesive bonding.
• Hydrophobic enhancement of water and oil-repellent textiles.
• Facilitating the removal of sizing agents.
• Removing the surface hairiness in yarn.
• Scouring of cotton, viscose, polyester and nylon fabrics.
• Anti-bacterial fabrics by deposition of silver particles in the presence
of plasma.
• Room-temperature sterilisation of medical textiles.
• Improved adhesion between textiles and rubber.
• Plasma-treated fabrics with high hydrophilic stability when stored in
alkaline media.
• Graft plasma polymerisation for producing fabrics with laundry-
durable oleophobic, hydrophobic and stain-resistant finishes.
Potential use of plasma treatments of
fibres, yarns and fabrics
 Atmospheric plasma-based graft polymerisation of textiles and nonwovens
having different surface functional properties on the face and back side of the
fabric.
 A fabric which is coated with sizing agent inactive to plasma on one side and on
the other side left as hydrophobic or hydrophilic after size removal, the
resultant fabric having different functionality on its two sides.
 Flame-retardant coating using monomer vapour (halogen and/or phosphorus)
in combination with nitrogen and/or silicone.
 Silicone coating of air-bag fabrics using crosslinked silicone
(polyorganosiloxanes).
 Scouring of cotton, rayon, polyester fabrics using a non-polymerisable gas
(nitrogen, argon, ammonia, helium), followed by wet treatment for removing
the impurities.
 Prevention of readily-occurring colour variation in textiles.
 Durable antistatic properties using PU-resin and plasma processing.
 Shrink resistance of animal hair textiles using urethane-based resin and plasma
processing.
 Electro-conductivity of textile yarns by surface plasma deposition.
Potential use of plasma treatments of
fibres, yarns and fabrics
 Optical coatings
  Ultraviolet protective textiles – block UV radiation
  Far infrared textiles – fabric absorbs radiation and
re-radiates at lower wavelength to aid body warmth
 Conductive coatings
  Electromagnetic shielding textiles for medical
devices, safety and general uniforms, electronics,
assembly equipment, aprons, maternity wear, general
wear
Potential use of plasma treatments
of fibres, yarns and fabrics…..
 Hydrophobic or oleophobic finishing of Nomex fabrics
 Hydrorepellent finishing for polyamide fabrics for skiwear
 Antibacterial finishing for microfibre lining of shoes
 Flame-retardant finishing for home textiles
 coupling of polyester fabrics and polymeric membranes for
surgical Wear
 coupling of polyester fabrics and polymers for industrial
tapes
Characterisation
The techniques for surface analysis described are divided
into two main categories – those that assess physical and
topographical properties and those that assess chemical
properties.
The physical and topographical properties are measured by
scanning electron microscopy (SEM), transmission
electronic microscope (TEM) and atomic force microscopy
(AMF) techniques and the chemical properties are
measured using Fourier transform infrared (FTIR)
technique.
Other techniques such as X-ray photoelectron spectroscopy
(XPS) and the future possibilities of nanoindentation and
X-ray absorption spectroscopy (XAS).
Qualifier criteria for new textile technologies
Safety and handling: The new technology must be operated
safely, predominantly needing only the existing skill set of the
textile mills
Operating speed: Line speeds need to be as fast as or faster than
existing technologies to avoid bottlenecks
Production flexibility: Fast switching between fabric types and
effects must be available to allow for rapid adaptations in product
and process
Investment: The technology should offer a return on investment
in under 5 years and maintain or improve the profitability of the
mill
Environmental: The technology should comply with existing
legislation and improve compatibility with anticipated law
Major Parameters
Plasma reactors
Different types of power supply to generate the
plasma are

Low-frequency (LF, 50–450 kHz)

Radio-frequency (RF, 13.56 or 27.12 MHz)
Microwave (MW, 915 MHz or 2.45 GHz)

The power required ranges from 10 to 5000 watts,

depending on the size of the reactor and the
desired treatment.
Cold plasmas can be used for various treatments:
 plasma polymersation (gaseous monomers)
 Grafting
 deposition of polymers, chemicals and metal particles by
suitable selection of gas and process parameters
 plasma liquid deposition in vaporised form.

Gases commonly used for plasma treatments :

 Chemically inert (e.g. helium and argon).
 Reactive and non-polymerisable (e.g. ammonia, air, and
nitrogen).
 Reactive and polymerisable (e.g. tetrafluoroethylene,
hexamethyldisiloxane).
Plasma treatment vs. Traditional textile processing
 Examples of functional coatings that could be achieved by APP liquid
precursor coating include:
 Hydrophobic coatings for durable, breathable, water repellence, water
roll-off and inhibition of capillary fl ow; dry process for the
waterproofing of polyaramid fibres with no loss of fi bre strength, e.g.
for bulletproof vests.
 Hydrophilic response for water wicking for moisture transferring and
quick-drying textiles, e.g. sport, military; extra absorbance, e.g. easy
capillary fl ow; anti-fog; easy take-up and good coverage for painting,
coating, dyeing, etc.
 Oleophobic coatings with high oil, solvent, blood, etc. repellence and
durability to boiling water and solvent washes
 Low friction coatings with coefficient of friction comparable to PTFE
 Reactive coatings, e.g. chemically reactive and reagent-specific
filtration fabrics
 Non-stick/release – low release force; stain release, e.g. anti-dirt, easy
clean workwear, automotive upholstery
 Adhesion promotion coatings for outstanding bondability, coating
and lamination
 Bioactive coatings
 Anti-bacterial finishes for both general and medical use – inhibit bacterial
growth, achieve reduction in bacteria, e.g. anti-bacterial face masks
 Antifungal finish – inhibit growth of fungi on textiles
 Selective biological tethering sites – bio-receptors/bio-affinity,
biofunctional wound dressings
 Grafting of enzymes, proteins, cells
 Copolymers
  Multifunctional surfaces, e.g. dual function —NH2 with —COOH groups
  Smart/responsive surfaces, e.g. F + PEG – in air, stain-repellent F on
surface, in water, stain removing PEG on surface
 Trapped active coatings – The coating matrix encapsulates sophisticated
active molecules that can be released in a controlled manner over time or
through applied stimulus. Potential actives include anti-microbials,
enzymes and bio-molecules, pharmaceutical agents, cosmeceuticals,
fragrances, agro-chemicals, anti-oxidants, fl ame retardants, catalysts and
photochromic agents.
Substrate surfaces can be modified homogeneously in
short processing times without any change in bulk
properties.
A huge range of surface modifications are possible by
choosing appropriate plasma types, equipment, and gas or
liquid precursors.
Chemical consumption is low and the process is safer and
much more environmentally friendly.
Above all, APP processing, particularly liquid precursor
coating treatments, offers the textile industry extensive
potential for innovation and more flexible manufacturing
capabilities.
Hot/Thermal Plasma
Plasmas are generally classified as thermal or non-
thermal. Thermal (‘hot’) plasmas are characterised by
a condition of thermal equilibrium between all the
different species contained in the gas.
 In fact, if the gas density is sufficiently high, the
frequency of collisions between electrons, ions, and
neutral species composing the plasma is such that an
efficient energy exchange is possible. In thermal
plasmas, temperatures of several thousands degrees
are reached.
Results obtained on Textile Materials
Enhancement of both hydrophilic and hydrophobic properties.
This is one of the most widely studied plasma applications.
Oxygen, ammonia air, nitrogen, etc. plasmas have been used to
increase the wettability of synthetic polymers (PA, PE, PP, PET,
PTFE, etc.), while hydrophobic or oleophobic finishing of
natural fi bres (cotton, wool, silk, etc.) has been obtained by
using siloxanes, perfluorocarbons, SF6, acrylates, etc.

 Adhesion promotion. Good adhesion between fibres and matrix

is essential in the production of composites and laminates.
Plasma treatments can increase markedly the surface energy of
synthetic fibres, improving the mechanical characteristics of the
final products.
Results obtained on Textile Materials (Contd.)
 Dyeing and printing. Several studies have shown that dyeability or
printability of textiles can be markedly improved by plasma
treatments. This effect can be obtained on both synthetic and natural
fi bres. Capillarity improvement, enhancement of surface area,
reduction of external crystallinity, creation of reactive sites on the fi
bres and many other actions can contribute to the fi nal effect
depending on the operative conditions. Also production of colours on
fi bres exploiting diffraction effects has been attempted.

 Electrical properties. Antistatic properties have been conferred to artifi

cial or synthetic polymers. Moreover, studies have been carried out for
the creation of fabrics with very high conductive properties, suitable
for integrating electronic devices into fabrics.
Results obtained on Textile Materials (Contd.)
 Intelligent filtration properties. Filtration of gases or liquids is one of
the most common technical applications of fibres, fabrics or non-
wovens. Appropriate surface functionalisation can enhance chemical
selectivity of traditional filters based on more conventional
adsorption/absorption or physical separation processes.

 Other properties. The extreme versatility of the plasma processes is

shown by a very large number of investigations concerned with a wide
range of different properties of great importance for textiles, such as
flame retardancy, crease resistance, antimicrobic, antimicotic,
biological compatibility, antifelting for wool, UV-protection, as well as
‘hand’ modification, softening and antipilling.
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