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APPLICATION OF ARGON PLASMA TREATMENT FOR IMPROVING FIXATION

PROCESS

Chapter · July 2011

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 APPLICATION OF ARGON PLASMA TREATMENT FOR IMPROVING
FIXATION PROCESS
Jelena HAČKO1, Slavica ANDRIĆ1, Sanja ERCEGOVIĆ RAŽIĆ1
1University of Zagreb, Faculty of Textile Technology, Department of Materials, Fibers and Textile
testing, Prilaz baruna Filipovića 28a, HR-10 000 Zagreb

Abstract: In this paper low-pressure plasma was used for surface treatment of cellulose cotton
fabrics of defined structural characteristics. Plasma treatment processes were carried out by
activation of the surface with oxygen at defined plasma parameters. After surface activation of the
cotton by plasma treatment, fabrics were treated with succinic acid as cellulose cross linking agent.
At the end of treatment, fixation process for better cross linking effects between carboxylic groups
of succinic acid and cellulose functional groups were carried out with two processes: curing process
at high temperature and argon (Ar) plasma fixation at room temperature.
The changes in chemistry were analyzed using FTIR-ATR technique. Changes of mechanical
properties were analyzed using Strength Tester. The obtained results indicate that the argon
plasma treatment certainly improved fixation process of carboxylic groups of succinic acid on the
cotton supstrate. Also, the obtained results of mechanical properties indicated on the lower
reduction of breaking strength after plasma fixation process, in relation to the curing process
where the reduction of breaking strength is evident.

Keywords: argon plasma treatment, cotton fabrics, succinic acid, fixation process

1. Introduction
Plasma treatment is a physical method used for surface modification, as it affects the surface both
physically and chemically without altering the material bulk properties. It is known that plasma
appears when a gas at low pressure and near ambient temperature is exposed to an
electromagnetic field. These plasmas are known also as non-equilibrium plasma, or as low-
temperature plasma. Generally, cold plasmas can be classified as either low-pressure of
atmospheric plasmas. Both types could be used for improving properties, acting especially on the
exposed materials surface, by process of cleaning, activation, etching, oxidation, cross linking,
grafting, deposition and materials fixation. The efficiency of plasma process treatments depends
of treatment conditions - pressure, time, power, gas flow rate and gas [1].
In this paper laboratory low-pressure LF-40 kHz plasma system (by Diener Electronic) was used for
surface treatment of cellulose cotton fabrics defined structural characteristics. Treatment
processes were carried out by proposed experimental procedures:
1. Activation of the surface using oxygen plasma at defined process parameters;
2. After surface activation of the cotton surface, fabrics were treated with succinic acid (with and
without catalyst) as cellulose cross linking agent, using exhaustion method;
3. Fixation process for better cross linking effects between carboxylic groups of succinic acid and
cellulose functional groups were carried out with two processes: curing process at high
temperature and argon (Ar) plasma fixation at room temperature.

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2. Materials and Methods

2.1. Materials
Scoured and de-sized cotton woven fabric (mass per unit area 130.6 g/m2; number of threads per
cm 25/20; thickness 0.35 mm) was used in experiment. Raw cotton fabrics were additionally pre-
treated with sodium hydroxide to partially remove hydrophobic compounds from the fibre
surfaces.

2.2. Treatment with Low - pressure plasma system

Low-pressure (LP) - plasma NANO LF laboratory system of 40 kHz low-frequency generator and
maximum power of 300 W was used for fabric treatments. One electrode and the four trays were
placed inside the cylindrically vacuum chamber of 24 L volume. A standard part of the plasma
system was a conventional rotary vane pump, type D8B, suction power of the approx. 8 m3/hour,
with an electromagnetic valve, which prevented the return of the oil vapour into the vacuum
chamber. Brass needle valves (max. flow rate of 400 sccm), with pressure reducers specified for
each type of gases applied, provided constant gas flow rate during plasma processes performed.
The workings were controlled fully automatically.
Experimental procedure
Untreated cotton fabric

Surface activation by
Oxygen plasma

Working gas: oxygen (O2 )

Pressure: 0,34 mbar
Power: 300 W
Gas flow rate: 40 sccm ACTIVATED SURFACE
Treatment time: 5 min
Working frequency: 40 kHz
0,6 M Succinic acid 0,6 M Succinic acid
with NaH2PO2 without catalyst

Exhaustion method
Bath ratio 1:20; 1 hour ; pH 2,2; 22 C
Drying : 100 C, 10 min

Plasma fixation Curing

Working gas : argon (Ar) Curing : 170 C, 3 min

Pressure : 0,30 mbar
Power : 300 W
Gas flow rate : 40 sccm
Treatment time : 5 min
After treatment all the samples were scoured in
dest. water at 40 C for 10 min and dryed at
100 C for 10 min.

2.3. Treatment with succinic acid

Fabric were treated with 0.6 M Succinic acid with 0.6 M sodium hypophosphite monohydrate as
catalyst for better crosslinking of cellulose, by using exhaustion method, according to conditions
presented in experimental procedure.

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Six sequences realized during study, according to schematic experimental conditions for the
treatment of the cotton fabrics:

Untreated cotton fabric 0,6 M Succinic acid with NaH2 PO 2 170 C, 3 min
Exhaustion method Curing

Ar plasma, 5 min
Untreated cotton fabric 0,6 M Succinic acid with NaH2 PO2 Exhaustion method Plasma fixation

Oxygen plasma pretreated 170 C, 3 min

0,6 M Succinic acid with NaH2 PO2 Exhaustion method Curing
cotton fabric

Oxygen plasma pretreated 0,6 M Succinic acid with NaH2 PO 2 Ar plasma, 5 min
Exhaustion method Plasma fixation
cotton fabric

0,6 M Succinic acid without catalyst Ar plasma, 5 min

Untreated cotton fabric Exhaustion method Plasma fixation

Oxygen plasma pretreated Ar plasma, 5 min

0,6 M Succinic acid without catalyst Exhaustion method Plasma fixation
cotton fabric

2.4. Methods of analysis

FTIR-ATR analysis
A Fourier transform infrared spectrometer Spectrum 100 FT-IR (Perkin Elmer) with attenuated
total reflectance (ATR) detector, was used in this experiment to detect the changes in the cotton
fibre chemical structure at the fabric surface of the untreated sample and samples treated with
succinic acid as cross linking agent of cellulose. The spectra were recorded over the range of 4000-
500 cm-1, with resolution of 4 cm-1 and per 32 scans. The FTIR spectra were normalized to the
absorption band at 1314 cm-1.

Strength Tester
A tensile testing machine Strength Tester 3000 (Mesdan, Italy) is used for testing the mechanical
properties of cotton fabrics. Measurements were performed on cotton woven fabric samples
which were prepared according the standard HRN EN ISO 13934-1:2008. The fabric sample was
exposed to tensile loading of maximum strain on a tensile test machine. For every fabric sample,
three tests were performed. Measurements were performed under standard testing conditions
(65±2% relative humidity and 20±2°C).

3. Results and discussion

 Analysis of the changes of cellulose functional groups induced by plasma and carboxylic acid
In order to determine the chemical changes of functional groups of cellulose after its
modifications, the spectral analysis of untreated and treated cotton samples using oxygen plasma
and succinic acid (SA) as cross linking agent was performed. The FTIR-ATR spectra of studied
fabrics are illustrated in Figures 1 and 2.
Spectra shown in Figure 1 reveals the presence of absorption bands at 1706 cm -1 and 1721 cm-1,
attributed to the carbonyl group of the ester and/or carboxyl groups. The intensity of this
absorption bands could indicate on the amount of generated ester linkages between the hydroxyl
groups of the cellulose and the carboxyl groups of the carboxylic acid such modified cellulose.
Additionally, the intensity of the absorption band at 1721 cm-1 of pretreated oxygen plasma
samples was higher in relation to the sample without oxygen plasma pretreatment. According to
this approach it can be assumed that the processing of succinic acid anhydride with a curing
catalyst under conventional cure process have proved to be the effective system to give a great

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number of chemical species on the treated surface, which can act as active centers on cellulose
capable to creation a new plasma reactions using different chemical agents, e.g. metal ions.
0,220

0,21

0,20

0,19

0,18

0,17

0,16

0,15

0,14

0,13 1 - untreated cotton

2 - cotton_oxygen plasma_0.6 SA+SHP_plasma fixation
0,12 3 - cotton_0.6 SA+SHP_cured
4 - cotton_oxygen plasma_0.6 SA+SHP_cured
0,11 3332,47 5 - cotton_0.6 SA+SHP_plasma fixation
A 814,81
0,10

0,09 1314,70

0,08

0,07 2899,29
1706,62

0,06
1721,52
0,05
5
0,04
4
3
0,03
2
1
0,02

0,01

0,000
4000 ,0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 500,0
cm-1

Figure 1: FTIR-ATR spectra of cottons treated with SA+SHP under different process conditions

The similar investigations were performed with polycarboxylic acid (BTCA) as cross linking agent of
cellulose [2]. The mechanism for crosslinking hydroxyl groups of cellulose with succinic acid as a
result forming cyclical anhydride, was proposed according scheme:

(1)

The presence of absorption band at 1706 cm-1 of the treated sample fixed using Ar plasma is
attributed to the carbonyl band of the carboxylic acid. Contrary, the cotton sample pretreated
using O2 plasma, revealed absence of absorption band in spectral region between 1800-1500 cm-1.
This may indicate to reduction of the –OH functional groups of cellulose after oxygen plasma
activation, which is necessary in mechanisms of the reaction that takes place over the succinic acid
anhydride. The more intensity of the absorption bands were revealed at 3334 cm-1, 2899 cm-1,
1365 cm-1 i 1314 cm-1 which indicate the intensive vibrations on the –OH functional groups of
cellulose as well as deformation at δ(OHO), δ(C–H), δ(CH2) and δ(CH3) linkages. However, reliable
response to the resulting reaction required further investigations and separated of ester
absorption bands on the bands which belongs carboxyl and carbonyl groups.

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 0,220

0,21

0,20

0,19

0,18

0,17

0,16

0,15

0,14

0,13

0,12

0,11 3333,04
A 1 - untreated cotton
0,10 2 - cotton_0.6 SA_plasma fixation
1314,58
3 - cotton_oxygen plasma_0.6 SA_plasma fixation
0,09

0,08

0,07
2898,91

0,06 1713,08

0,05

0,04

0,03
3
2
0,02
1
0,01

0,000
4000 ,0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 500,0
cm-1

Figure 2: FTIR-ATR spectra of cottons after treatments with SA using Ar plasma for fixation process

Figure 2 shows the spectra obtained for the samples treated with SA without catalyst and fixed
using Ar plasma, were compared to the untreated cotton sample. Additionally, one cotton sample
was pretreated using O2 plasma. The spectra were recorded in spectral region between 4000-500
cm-1, since the spectral region between 1800-1500 cm-1 is of high interest. The band at 1713 cm-1
is attributed to the carbonyl band of the free carboxylic acid. Based on these results, it can be
presumed a higher efficiency of the plasma acting, as a pretreatment and as a fixation process,
and representing a new environmental and economic process, because it does not use a catalyst,
and reaction occurring at room temperature.

 Changes of mechanical properties treated cotton samples

Table 1: Results of breaking strength [N] and breaking elongation [%] of tested samples
Sample CO CO 0.6M CO 0.6M CO O2/ CO O2/ CO 0.6M CO O2/0.6M
untreated SA+SHP/ SA+SHP/ 0.6MSA+SHP/ 0.6MSA+SHP/ SA/plasma SA/plasma
Properties
cured plasma fixed cured plasma fixed fixed fixed
warp 422.8 307.8 400.2 345.0 455.2 430.3 360.8
BF [N]
weft 365.5 187.7 332.1 265.1 329.5 234.9 290.8
warp 1.3 38.3 17.1 13.1 10.3 3.9 14.9
CV [%]
weft 0.1 19.5 4.1 11.8 16.7 8.1 6.5
warp 11.2 8.9 10.0 9.3 11.9 10.8 10.3
BE [%]
weft 24.6 18.8 19.3 17.9 21.4 15.9 20.3
warp 3.5 15.7 11.3 3.5 7.1 3.2 8.4
CV [%]
weft 2.0 8.2 8.9 5.3 2.0 24.7 3.6
BF - breaking strength [N]; BE - breaking elongation [%]; CV - coefficient of variation [%]

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 Generally, the obtained results presented in Table 1 indicate the lower reduction of breaking
strength and breaking elongation after plasma fixation process, in relation to the curing process
where the reduction of breaking strength and elongation is evident, both in warp and weft
direction. It is believed that O2 plasma treatment caused etching and ablation action on the
substrate surface, resulting in roughening effect on the fabric surface [3]. The rougher surface
might impart more contact points within the fibers and yarns, resulting in enhanced inter-yarn and
fiber friction and contributing to increased of physical properties at macrostructure level (e.g.
increased of thickness, mass per unit area, number of threads and reducing of volume porosity)
[4]. Additionally, the Ar plasma treatment was expected to affect the crosslinking structure and
agent distribution to improve the physical-chemical properties of the finished fabrics [5], with less
or no reduction of mechanical properties of the treated fabrics, as well.

4. Conclusions
 The results of FTIR-ATR analysis indicate that the argon plasma treatment certainly improved
fixation process of carboxylic groups of succinic acid on the cotton supstrate in comparison to the
thermofixation process.
 Oxygen plasma pretreatment increase the intensity of the absorption band at 1721 cm -1 which
indicate on the amount of generated ester linkages between the hydroxyl groups of the cellulose
and the carboxyl groups of the carboxylic acid such modified cellulose.
 Results of mechanical properties indicate on the lower reduction of breaking strength and
breaking elongation after plasma fixation process (reduction of breaking strength amounts approx.
from 5% to 15%), in relation to the curing process where the reduction of breaking strength and
breaking elongation is evident (reduction of breaking strength amounts approx. from 15% to 40%).
 If the processes of plasma fixation were durable in application conditions, it would be a good
basis for the substitution of conventional method with environmentally more favorable one.

5. References
[1]Shishoo R.: Plasma technologies for textiles, Published by Woodhead Publising Limited in
association with The Textile Institute, ISBN 978-1-84569-257-5, Cambridge, England, (2007).
[2]Šauperl O. & Stana-Kleinschek K., Differences Between Cotton and Viscose Fibers Crosslinked
with BTCA, Textile Research Journal, 80 (2010) 4, pp. 383-392, ISSN 0040-5175.
[3]Sun D. and Stylios G.K.: Investigating the Plasma Modification of Natural Fiber Fabrics - The
Effect on Fabric Surface and Mechanical properties, TRJ, 75 (2005.) 9, 639-644, ISSN 0040-5175.
[4]Ercegović Ražić S.: Target modification of textile material properties using plasma and metal
compounds, Doctoral Thesis, Faculty of Textile Technology, University of Zagreb, 2010.
[5]Chen C.-C. et al.: Argon Plasma Treatment for Improving the Physical Properties of Crosslinked
Cotton Fabrics with Dimethyldihydroxyethyleneurea-Acrylic Acid, Textile Research Journal, 80
(2010) 8, pp. 675-682, ISSN 0040-5175.

Aknowledgements
The research was funded by the Croatian Ministry of Science, Education and Sports, project
"Multifunctional textile materials for personal protection" (No. 117-1171419-1393). We would like
to express our appreciation to the Assoc. Prof. Sandra Bischof Vukušić, PhD, at Department of
Textile Chemistry and Ecology of the Faculty of Textile Technology, for the support and confidence
in work with FTIR-ATR spectrophotometer.

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