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Surface modification of textiles by plasma treatment for imparting certain desired properties in terms of wettability,
adhesion promotion, surface energy improvement and host of other characteristics has been the subjects of interest to
researchers in the last few years. The plasma technology for textiles has emerged from conceptual embryonic stage to
growth stage, where considerable research is yet to be carried out to translate the potential into industrial reality. This review
aims at reporting the current status of the atmospheric pressure plasma technology in surface treatment of textiles, its effect
on certain properties and the techniques used for characterisation of plasma-treated textile materials. The review paper also
covers the studies carried out so far on the effect of atmospheric pressure plasma generated from non-polymerising gases
like helium, argon, air, oxygen and nitrogen on the surface properties of both natural as well as synthetic textiles along with
the changes in chemical and morphological characteristics of plasma-treated textile material using different qualitative and
quantitative characterisation techniques, such as measurement of wicking height, contact angle, surface energy, SEM, AFM,
FTIR and XPS.
Keywords: Atmospheric pressure plasma, Non-polymerising gases, Surface modification, Surface characterization techniques
Use of plasma for improving surface energy, 3.2 Measurement of Zeta Potential
especially of low surface energy textiles like Zeta potential is the charge developed at the
polyethylene, polypropylene and polyester, is well interface between a solid surface and its liquid
established. Geyter et al.31 have investigated the effect medium. The net charge at the textile surface affects
of plasma treatment on the surface energy of the ion distribution in the nearby region, which leads
polyethylene. Surface free energy of PE was to increase in the concentration of counter ions. An
increased to 56.2 mJ/m2 from initial value of 31.3 electrical double layer is formed in the region of the
mJ/m2. Moreover, the increase in the surface free particle-liquid interface.
energy was observed with the increase in plasma Guo et al.26 have studied the zeta potential of air
exposure time. The increase in the surface energy can plasma-treated woven PET fabric. The negative zeta
be attributed to the introduction of oxygen-containing potential was increased after plasma treatment which
hydrophilic functionalities on the PE surface. Increase indicates the higher number of carboxyl groups at the
in surface energy of the textile material after fibre surface. The atmospheric air plasma-treated
atmospheric pressure plasma treatment was also samples exhibited more number of carboxyl groups at
corroborated by Leroux et al34. Similar kind of the surface. Moreover, increase in the discharge
increase in surface energy has been corroborated by power led to increase in the carboxyl groups. Wakida
the studies of others35-38. There are different methods et al.39 have studied the zeta potential of wool and
available for measuring surface free energies of a nylon 6 fibres treated with oxygen plasma. The zeta
solid. It can be derived from the contact angle data of potential of the fibres was measured by the streaming
different test liquids. Some researchers have used potential method. The zeta potentials of both fibres
formic acid solutions of different concentrations for increased the negative charge over the pH range
measuring surface energy after plasma treatment8,17. measured. The plasma interaction with substrate
In this method, a drop of formic acid solution is causes polymer chain scission resulting in formation
placed on the fabric surface. If drop is absorbed by the of reactive radicals and end groups such as carbonyl,
fabric within 5 s, the surface energy of the fabric is carboxyl and hydroxyl groups. Chemical nature of the
considered equivalent to surface tension of that liquid. species formed at the surface of plasma-treated
Samanta et al.8 have used oxygen, air, argon and textiles can be known by zeta potential method.
helium for the plasma treatment of PET. Considerable
3.3 Surface Morphology
increase in the surface energy of PET from 40
dynes/cm to 71 dynes/cm was observed after plasma 3.3.1 Scanning Electron Microscopy
treatment for 60 s. The scanning electron microscope (SEM) uses a
Pascual et al.32 have reported the effect of ageing focused beam of high energy electrons to generate a
on the surface free energies of the corona treated variety of signals at the surface of solid specimens.
polyethylene. The environmental or storage When beam of electrons strike the surface of the
conditions were found to have significant effect on specimen and interact with the atoms of the samples,
the ageing process of plasma-treated substrate. The signals in the form of secondary electrons are
influence of relative humidity and temperature during generated which give information about surface
the aging was studied with three different storage topography of the substrate40.
conditions, such as aging at room temperature, aging Plasma treatment with non-polymerising gases
at 23°C/50% RH, and ageing at 50° C/ 40% RH. The leads to mechanisms like etching, cleaning and
ageing process was accelerated by the temperature of activation. Due to bombardment of highly energetic
the storage. Decrease in the surface energy during the ions and radicals, ablation of atoms/molecules at the
ageing process can be attributed to the loss in surface surface of textile fibre takes place, resulting in
functionalities due to re-arrangement of the polar alteration in surface morphology. Zhongfu et al.41
groups. Plasma treatment with non polymerising have investigated the surface morphology of plasma-
gases is not a permanent one and hydrophobic treated polyester fabric. Polyester fabric treated with
recovery takes place with successive ageing period. argon-oxygen plasma exhibited rough surface
The stability of the new functional groups formed at morphology due to etching. The surface morphology
the surface of textiles may not be good which results of wool and cotton after plasma treatment has been
in their rearrangements. studied by Sun et al42. The SEM micrographs of O2
294 INDIAN J. FIBRE TEXT. RES., SEPTEMBER 2011
plasma-treated wool and cotton fabrics revealed holes plasma treatment (Fig.4) revealed that fibres with
on the fibres surface. Tissington et al.19 have studied lower moisture regain exhibit little etching effect,
the morphology of polyethylene monofilaments. whereas severe etching was observed in samples
Fibriller structure of polyethylene resulted in the having higher moisture, leading to almost complete
formation of pitted cellular structure. Longer removal of scales. The chlorination is the
treatment duration caused extensive pitting of the conventional process for scale removal in wool.
surface which resulted in improved adhesion due to However, it creates pollution and environmental
mechanical keying effect. However, they have not related problems. The plasma technology for scale
studied changes in the surface chemistry and ageing removal seems to be a promising environment-
effect after plasma treatment. Studies by other friendly alternative to the chlorination process.
researchers have corroborated change in the surface However, application focused research is required in
topography after plasma treatment of different the plasma assisted scale removal of wool by
textile fibres like Jute33, polyester43, cotton44 and comparing the conventional chlorination process and
polypropylene45. plasma process. Performance of the fabric treated
Plasma treatment for scale removal and for anti- with dry and environment-friendly technique like
felting property of wool has been the subject of plasma needs to be evaluated. Commercial
interest to many researchers. Xu et al.46 have exploitation of plasma technology especially for wool
investigated the morphology of weft knitted wool seems to have promising future.
fabric after helium and He-O2 plasma treatment. In 3.3.2 Atomic Force Microscopy
case of both helium and He-O2 plasma, SEM of fibre Atomic force microscopy (AFM) is a newly
surface exhibited relatively smooth morphology due developed high resolution technique to study the
to removal of scales. The presence of moisture in the surface morphology. It is possible to directly obtain
sample during the plasma treatment is very critical three dimensional topographic images of the surface
factor. The study of Xu et al.46 showed almost up to atomic level resolution27. Preparation of samples
complete removal of scales in wool samples which such as heavy metal coating, involved in SEM and
were conditioned at 100% RH before plasma TEM, is not needed for AFM. AFM is capable of
treatment. Moreover, lowest shrinkage ratio of 5.2% investigating surfaces of both conductors and
was obtained with wool fabrics conditioned at 100% insulators on an atomic scale.
RH. Similar kind of studies pertaining to the effect of Shin et al.27 have reported mean surface roughness
moisture on plasma treatment of wool was also (Ra) from AFM images of He/O2 plasma-treated PET
reported by Zhu et al47. SEM photographs after nonwoven at different exposure times varying from 0s
Fig.4—SEM images of control and plasma-treated wool with different moisture regain [(a) control, (b) 4.51 % moisture regain, plasma
treated, (c) 12.1% moisture regain, plasma treated, and (d) 26.6 % moisture regain, plasma treated47]
KALE & DESAI: ATMOSPHERIC PRESSURE PLASMA TREATMENT OF TEXTILES 295
to 90s. The mean roughness recorded for untreated (electron spectroscopy for chemical analysis). It is
sample was 0.805 nm, which then increased to 1.305 very powerful surface analysis technique where
nm after exposure for 90 s. Koo et al.48 have studied chemical characterization near the surface region up
the surface roughness of the cellulose triacetate to 1-2 nm can be determined12. In the XPS, X-rays hit
treated with argon plasma. It was observed that the sample and produce photoelectrons whose energy
smooth structure of untreated cellulose triacetate has is measured. The XPS technique is highly surface
gradually changed into irregular structure after plasma specific due to the short range of the photoelectrons
treatment. Increase in the treatment time led to that are excited from the solid. The energy is specific
increase in the surface roughness value. Processes like to each element and can be used to identify all the
etching, re-deposition, and cross-linking which occur elements present in the outer 10 nm of the surface.
during plasma treatment affect surface morphology Guo et al.26 have investigated the effect of
and lead to micro-roughness. atmospheric air-plasma treatment on surface
The effect of air plasma treatment on the PET fibre chemistry of PET woven fabrics. The XPS analysis
surface topography was investigated by Wei et al.16 revealed oxidation of the fibre surface, leading to
using tapping mode AFM images. Significant changes formation of hydroxyl, carboxyl and carbonyl groups.
in the original topography of the PET fibres were Increase in the O/C atomic ratio was reported after the
observed after plasma treatment. Similar kind of plasma treatment. Shin et al.27 have reported the
alteration in the surface topography of plasma-treated increase in O1s/C1s ratio of nonwoven PET surface
PET is reported by Ricardi et al.18 (Fig.5). Surface after He/O2 plasma treatment. The XPS analysis
morphology and roughness of aramid fibres after revealed increase in the O/C atomic ratio
oxygen plasma treatment was studied by Wang et al49. progressively from 0.37 to 0.46 as plasma exposure
Oxygen plasma caused increase in the surface time was increased (Fig. 6).
roughness value (Ra) of aramid fibres from 153.8 nm Morent et al.29 have reported similar kind of
to 329.1 nm after 20 min of treatment. increase in the O/C atomic ratio of plasma-treated PP
Plasma treatment is basically a surface treatment. and PET nonwovens. The O/C ratio of PP and PET
Therefore, many times topographical changes occur at nonwoven after plasma treatment is found to be
very limited depth on the fibre surface, which cannot PP—2.4 (untreated) & 17.5 (plasma treated); and
be detected or quantified by SEM. In such cases, PET—31.0 (untreated) & 47.7(plasma treated). They
AFM is a very useful tool. However, due to irregular have also determined the effect of ageing on O/C
structure of textiles AFM may not always yield ratio. The O/C atomic ratio decreased with
accurate results due to non-uniform surfaces. increasing ageing time until a plateau value was
Therefore, technique for assessing surface reached. However, the plateau value of the O/C
morphological changes requires to be selected ratios after ageing was considerably higher than the
depending upon the nature of substrate. O/C ratios of the untreated textile samples. The
effect of ageing on the O/C ratio of plasma treated
3.4 Surface Chemical Analysis surface was also studied by Riccardi et al.18 and
3.4.1 X-ray Photoelectron Spectroscopy Pascual et al32. The oxygen content of the plasma-
X-ray photoelectron spectroscopy (XPS) is the treated surface decreases during aging period.
most widely used surface analysis technique for Wang et al.49 have found that surface-oxygen
plasma modified surfaces and plasma enhanced concentrations in plasma-treated fibres are higher
deposited thin films. The XPS is also known as ESCA than that in the untreated one.
FTIR spectra of PVA films after plasma treatment times. Similar kind of decrease in the fibre tenacity
showed enhanced peaks of alcohol (O-H stretch), and modulus after argon plasma treatment was
aldehyde (C=O stretch) and carboxylic acid (COOH corroborated by the study of Sinha.33
stretch). Wong et al.52 have studied the effect of low
FTIR analysis of argon plasma treated jute fibres temperature plasma on weight loss of linen. The
carried out by Sinha33 has shown decrease in the oxygen plasma treated samples showed increase in
phenolic and secondary alcoholic groups, resulting weight loss with the increase in both discharge power
in development of hydrophobicity. Usually, increase and treatment time. Shin et al.27found that He/O2
in the hydrophilic character is expected after the plasma treated PET nonwoven fabric shows higher
argon plasma treatment. Further research is required weight loss with increased plasma exposure time.
in the plasma treatment studies of jute fibres with Hwang and McCord59 and Bhat et al.60 have also
more advanced characterisation techniques to showed similar increase in % weight loss at higher
understand the mechanism between the plasma and plasma exposure time. Matthews et al.61 have
the substrate. thoroughly investigated the mechanism of etching for
Plasma treatment is a surface treatment and the PET treated with He and He-O2 plasma. It was
depth of effect achieved in the plasma treatment is observed that weight loss gradually increases with
approximately up to 10 nm or less. On the other hand, exposure time up to saturation value. Further increase
sampling depth of ATR-FTIR techniques is many in exposure time led to re-deposition of previously
times too large to detect structural alteration after etched film material. The weight loss of plasma
plasma treatment56. This is why, most of the times treated PET samples was determined by Vesel et al.62.
XPS is preferred over the FTIR for surface In their study, the etching rates of 12.9 nm/s and
characterization of plasma treated fabric. Geyter et al. 3.3 nm/s were obtained after oxygen and nitrogen
31
have compared the XPS and FTIR techniques for plasma treatment of PET respectively.
surface characterization of dielectric barrier discharge Kan and Yuen63 have revealed that low temperature
treated polypropylene. Their study showed that ATR- oxygen plasma treatment on wool influences
FTIR analysis can only give qualitative information mechanical properties as well as properties like air
about the change in surface chemistry, whereas XPS permeability and thermal properties. Morent et al.29
can provide quantitative chemical analysis. have shown that the efficient hydrophilization of
Similar kind of comparison between XPS and nonwovens could be achieved without affecting the
FTIR was also carried out by Mercx57on air and mechanical properties. The tensile strength of rayon
ammonia plasma treated polyethylene tapes. Though yarns after air–O2–He and air–He plasma was
XPS revealed the oxidation and amination of PE measured by Cai et al. 64. They have reported that
surface, IR spectroscopy did not show any signs of atmospheric plasma treatments did not have a
either oxidation or amination due to air or ammonia negative effect on the tensile strength of the viscose
plasma. Usually, shallow penetration is more fabric. It can be inferred that mild plasma treatment
prevalent in case of plasma generated by non- does not affect the tensile properties of textile
polymerising gases. In such cases, XPS would material. However, higher discharge power or longer
provide better sensitivity for surface chemical treatment time during plasma treatment may lead to
analysis than FTIR. However, in case of plasma loss in tensile properties due to excessive etching.
polymerisation, where continuous deposition of
plasma polymer takes place at longer depths, FTIR is 4 Conclusion
also very important surface analysis tool to Atmospheric pressure plasma treatment can modify
understand the mechanism of plasma polymerisation. the textile surfaces in variety of ways and can impart
desired functional properties to the textile substrate.
3.5 Mechanical Properties Treatment of textiles with plasma generated from
Cioffi et al.58 have conducted tensile tests on non-polymerising gases improves wettability,
monofilaments of radio frequency plasma treated hydrophilicity and adhesion. It brings about chemical,
PET. Oxygen and argon plasma treatment resulted in physical and morphological changes in the textiles.
a decrease in the average tensile strength as compared Plasma treatment offers unique advantages of being
to the untreated fibres. Moreover, higher tensile dry and environment-friendly process. However, like
strength reduction was observed for longer treatment other industries, plasma has not found the same
298 INDIAN J. FIBRE TEXT. RES., SEPTEMBER 2011
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