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Ftee 75 98
Ftee 75 98
Ftee 75 98
*Stefan Połowiński,
Effect of the Corona Discharge Treatment
Dorota Kowalczyk,
Iwona Karbownik,
of Polyester Fabrics on their Adhesive
Grażyna Malinowska Properties
Textile Research Institute, Abstract
Department of Non-conventional Techniques This paper presents the results of studies carried out at the Textile Research Institute, Łódź,
and Textiles, Poland with the use of original experimental equipment for the generation and applica-
ul. Gdańska 118, 90-520 Łódź, Poland tion of corona discharge. The construction of this generator was described in our previous
paper. It was found that the treatment of polyester fibres/fabrics with corona discharge
*Technical University of Łódz;
Department of Physical Chemistry of Polymers, brings about some significant changes, both in the physical and chemical structures of the
ul. Żeromskiego116, 90‑924 Łódź;, Poland
surface layer, which results in considerable changes in the technological and performance
properties of textile fabrics. Changes in adhesive properties are of the greatest importance
and their range depends on the process conditions of the treatment used, especially on
the unit energy of modification, the properties of the fibres modified, the environment in
which the discharges occur and the constructional features of the generator. The test re-
sults presented concern changes in the physical state of the surface layer, measured by
means of scanning electron microscopy (SEM) and atomic force microscopy (AFM). The
free surface energy and contact angle were assessed by tensiometric measurements. The
wettability of fibres and the chemical structure of the surface layer were also tested. The
molar oxygen to carbon ratio (O/C) and the concentration of functional groups containing
oxygen were measured by the techniques of photo-electron spectroscopy (XPS) and X-ray
micro-analysis. The changes occurring in the technological properties of polyester fabrics,
especially the forces of delamination of the coat layers and the quality of polymeric coat
bonding, resulting from the corona treatment are also presented. It was found that any
change in the charge sign on the activated fabric resulted in an almost double increase in
the delamination force.
Key words: polyester woven fabric, corona discharge, adhesion, surface energy, polarity,
wettability, fibre surface properties.
98 Brzeziński S., Połowiński S., Kowalczyk D., Karbownik I., Malinowska G.; Effect of Corona Discharge Treatment of Polyester Fabrics on Their Adhesive Properties.
FIBRES & TEXTILES in Eastern Europe 2009, Vol. 17, No. 4 (75) pp. 98-102.
rate in m/min.; B - discharge power in Measuring the contact angle and free Testing the adhesive properties of
% ; L – the length of discharge electrode surface energy PET fabrics treated with corona
in cm. The contact angle of the fabrics tested discharge – Determination of the
was measured by the dynamic method delamination force of laminates
Microscopic examination using a Sigma 701 tensiometer (KSV In- In order to assess changes in the adhesive
of the fibre surface struments Ltd., Finland). This method properties of fabrics treated with corona
This examination was performed at a consists in recording the force acting on discharge, the delamination forces of two
micro-scale with the use of the SEM a sample of the fabric tested, which is im- laminated fabrics were determined. The
method and at a nano-scale by means of mersed in and emerged from the meas- bonding agent used was a self-crosslink-
the AFM technique. uring liquid at the same rate. Distilled ing acrylic-vinyl copolymer in the form
water and ethylene glycol were used as of an anion-active 50% aqueous disper-
For the observation of the PET fabric sion under the name of Evo-Fin ATR,
test liquids. The surface free energy and
surface, a JSM35C scanning electron mi-
its components were calculated using the provided by DyStar (Germany). Tests
croscope from JEOL was used. Fabric
Wu equation [6]. were carried out in accordance with
samples were dusted with gold by means
Standard PN-P-04950:1988 [9]
of a JFC 1100 duster from JEOL. gS = gSL + gL·cosΘL
γS = γSd + γSp
Morphological and topographic changes
γSL = γS + γL ‑ 4·γSd·γLd·(γSd + γLd)‑1 + n Results and discussion
in the polyester fibre surface at a nano-
‑ 4·γSp·γLp·(γSp + γLp)‑1
scale brought about by corona discharge The treatment of polyester fabrics with
where:
were examined by means of an atomic corona discharge with various values of
γL – free surface energy of test liquid
force microscope, Nanoscope IIIA from unit energy results in several significant
Digital Instruments/Veeco (USA), oper- γLd – non-polar component of free changes in the physical and chemical
ated in the tapping mode. Rectangular surface energy of test liquid structures of the surface layer. The range
silicon cantilevers, model RTESP7 (Na- γLp – polar component of free sur- of these changes depends on the process
nosensors, Wetzlar-Blankenfeld, Germa- face energy of test liquid conditions of the treatment used.
ny), were used throughout the study. γS – free surface energy of fabric
γSd – non-polar component of free Morphological changes in the surface of
Testing the chemical properties surface energy of fabric modified PET fabrics were assessed by
of the fibre top layer γSp – polar component of free sur- means of scanning electron microscopy.
Photon-electronic spectroscopy XPS face energy of fabric The SEM photographs taken allowed us to
All spectra were recorded on a Physical γSL – fabric-liquid interfacial free energy select preliminary activation conditions,
Electronics PHI 5000 Versa Probe scan- Θ – contact angle. under which one could avoid any notice-
ning spectrometer using monochromatic able destruction of fibres. Figures 1.a,
Al Ka X-rays working with a power of Wettability testing 1.b and 1.c (see page 100) show SEM
25 W. An X-ray beam was focused to a Wettability tests were carried out photographs of untreated and modified
diameter of 100 mm; the area measured in accordance with Standard PN-P- fabrics with unit activation energies of
was defined as 250 x 250 mm. The hemi- 04633:1967 [7]. A description of this 37.8 J/cm2 and 75.6 J/cm2, respectively
spherical electron energy analyser was method and determination procedure are
operated at a pass energy of 117.4 eV for given in [6]. The use of atomic force microscopy
the survey scan and 23.50 eV for all high (AFM) allowed us to observe, at an nano-
resolution measurements. All measure- Tensile strength testing scale, changes in the physical state of the
ments were conducted under a vacuum Tensile strength tests were performed ac- surface layer after corona discharge treat-
below 3×10-8 mbar, with the use of a neu- cording to Standard PN-EN ISO 13934- ment. As is seen in Figures 2.b & 2.c (see
traliser, working with both low energy 1:2002 [8] using a Zwick tester, model page 100), fibres of the modified fabrics
electrons and low energy Ar+ ions. PHI 1120 (Germany). show characteristic changes in the nan-
Multipak software was used to evaluate otopography of their surface, which are
the XPS data (Shirley type background Determination of charges on the fabric absent in the case of unmodified fibres/
subtraction). For final calibration of the surface fabrics (Figure 2.a).
spectra, the peak C1s of an aromatic ring A sample of the fabric tested was me-
with binding energy values = 284.70 eV chanically disintegrated into single fila- The activation of PET fabrics with coro-
was used as an internal standard. ments with a length not exceeding 1 mm. na discharge results in the development
About 0.25 g of these filaments was im- of a specific surface structure, as shown
X-ray micro-analysis (EDX) mersed in 10 ml of distilled water, inten- by the increase in nanocoarseness RMS.
For the purpose of qualitative and quan- sively stirred and placed in the vessel of
titative chemical analysis of the surface a Particle Charge Detector (BTG Műtek The RMS value of unactivated fabric
composition, the X radiation was record- GmbH, Germany). amounts to 1.7 nm and increases up to 11
ed by means of an EDX micro-analyser nm after treatment with corona discharge
of the ISIS Link System from Oxford In- Depending on the charge sign, the of 37.8 J/cm2 and can go up to 13 nm
strument. The topography of the surfaces filament dispersion was titrated with when the activation energy is 75.6 J/cm2.
tested was observed by means of a Vega a solution of poly(acrylic acid) or Similar changes in the form of spherical
TS 5135 MM electron scanning micro- poly(allylamine hydrochloride). The outgrowths with nanodimensions on the
scope from Tesca. The resolution of the concentration of the solution to be titrat- surface of polymeric films were observed
X-ray micro-analysis was about 0.5 μm. ed was 1×10-3 mol/dm3. by Strobel et al. [10] when such films
FIBRES & TEXTILES in Eastern Europe 2009, Vol. 17, No. 4 (75) 99
a) b) c)
Figure 1. SEM photographs of PET fibres: a) unmodified fibres, b) fibres activated with corona discharge with a unit activation energy of
37.8 J/cm2, c) fibres activated with corona discharge with a unit activation energy of 75.6 J/cm2.
a) b) c)
Figure 2. AFM photographs: a) unmodified PET sample; b) PET sample activated with an energy of Ej = 37,8 J/cm2; c) PET sample acti-
vated with an energy of Ej = 75,6 J/cm2, showing the profiles of the PET surface coarseness.
were treated with corona discharge. The almost unchanged, and the amount of ex- angle values obtained, the free surface
authors explained that this phenomenon tract was insignificantly low (lower than energy, γS, was calculated (Table 1). An
was due to the formation of water-soluble 0.5%). increase in the unit activation energy is
oligomers. An analogous phenomenon in accompanied by an increase in both fi-
relation to the effect of the corona dis- The change in the specific surface of fi- bre wettability and free surface energy.
charge treatment of PET film was also bres in the PET fabric samples tested also
An increase in the free surface energy
reported by Laurens et al. [11]. brings about a change in their surface
is mostly due to an increase in the polar
energy. The measurements performed
component, which indicates the presence
In order to compare our results with by the tensiometric method show that
of polar groups in the surface layer of the
those reported in [10], the sample ac- activation with corona discharge de-
tivated was extracted with hot water. It samples tested.
creases contact angles with both water
was found that its surface structure was and ethylene glycol. Based on the contact The changes in wettability were con-
firmed by wettability tests.
Table 1. Average values of the contact angle and free surface energy, γS, including the
dispersive (γSd) and polar (γSp) components of the PET fabric versus the unit activation The results of wettability tests are given
energy Ej.
in Table 2. The analysis of the results
Contact angle, deg obtained shows directly that the samples
Ej, J/cm2 γS, J/cm2 γSd, J/cm2 γSp, J/cm2
water ethylene glycol modified by means of corona discharge
0 65.35 59.09 38.45 12.74 25.71 are characterised by better wettability
18.90 52.10 53.47 47.60 12.34 35.26 than that of unmodified samples. An in-
37.80 49.31 55.87 49.03 12.63 36.40 crease in wettability occurs in both the
75.60 51.03 58.52 48.16 12.52 35.64
longitudinal and cross directions, which
100 FIBRES & TEXTILES in Eastern Europe 2009, Vol. 17, No. 4 (75)
Table 2. Effect of the unit activation energy, an unactivated sample and a sample ac- Table 4. Values of the electric charges on
Ej, on the wettability of PET samples in the tivated with an energy of 75.6 J/cm2. It the PET fabric surface; * activation with
longitudinal and cross direction. was found that the O/C of the unactivated 75.6 J/cm2.
sample was 0.269, while that of the ac-
Wettability, cm
tivated sample amounted to 0.485. The No. of The sequence Charge quantity
Ej, J/cm2 Longitudinal Cross sample of operation coulomb/g ×106
direction direction increase in O/C (∆O/C) clearly indicates
Padding with
0 5.45 6.90 the oxidation of the top layer of the PET 1
no activation
+ 1,0
26
warp
24
weft
22
Delamination force, N
20
18
16
14
12
10
0 20 40 60 80
Ej, J/cm 2
Figure 3. Effect of the unit activation energy, Ej, on the delamina- Figure 4. Titration by 0.001 M poly(allyl-amine hydrochloride):
tion force of two PET fabrics bonded with a bonding agent. Serie 1 – activated 37.8 J/cm2; Serie 2 – unmodified.
FIBRES & TEXTILES in Eastern Europe 2009, Vol. 17, No. 4 (75) 101
Figure 5. Delamination forces: 1 – PET fabric; 2 – PET fabric Figure 6. Effect of the unit activation energy, Ej, on the delamina-
padded with PDAMA; 3 – PET fabric activated with an energy of tion force of PET fabric, padded with PDAMA.
75.6 J/cm2 and padded with PDAMA.
methacrylate) (PDAMA), a substance The modification of PET fabrics with co- Discharge Air-Plasmas: Chemical and
with a strong positive charge, which rona discharge increases the fibre’s sur- Morphological Effects.
changes the fabric charge from negative face energy, wettability and the wettabil- 4. C-P Klages, K. Hőpfner, N. Kläke, R.
ity of the samples activated. Thyen; Plasma and Polym. 5 79 (2000)
to positive. The charges of the fabric sur-
Surface Functionalization at Atmospheric
face after the padding process are given
The increased oxygen to carbon ratio in- Pessure by DBD-Based Pulsed Plasma
in Table 4 (see page 101). Polymerization.
dicates the formation of a great number
5. M. Lejeune, L. Lacroix, F. Brétagol, A.
As is seen, the best variant of treatment of functional polar groups in the top fi-
Valsesia, P. Colpo, F. Rossi; Plasma-ba-
consists in activation followed by pad- bre layer of PET fabrics activated with sed Processes for Wetability Modification;
ding with PDAMA. The charge obtained corona discharge. Langmuir 22 3057 (2006).
in this case is positive and amounts to 6. S. Brzeziński, M. Żenkiewicz, S. Poło-
10.5 × 10-6 coulomb/g. Due to the development of the fibre’s wiński, D. Kowalczyk, I. Karbownik, S.
specific surface and the elimination of di- Lutomirski, G. Malinowska; Polimery 54
The use of padding with PDAMA to rect contact between the negative charge (2009) No 7/8 pp. 552-558.
change the sign of charge on the fabric accumulated on the surface of activated 7. Standard PN-67/P-04633 “Determination
activated resulted in a considerable, al- PET fabric and the bonding agent used, of capillarity of textiles”.
most double, increase in the delamination the adhesive capabilities of such fabrics 8. Standard PN-EN ISO 13934-1:2002
force, as shown in Figure 5. are considerably improved, as shown by „Tensile properties of fabrics - Part:1
an appreciable increase in the delamina- Determination of maximum force and
The adhesion test results obtained, i.e. elongation at maximum force using the
tion force.
the increased delamination force, can be strip method”.
9. Standard PN-88/P-04950 „Laminated
explained as follows: the padding of fab-
and nonwoven fabrics. Determination or
rics with PDAMA changed the charge ac- Acknowledgments resistance to delaminating”.
cumulated on the activated fabric surface 10. M. Strobel, V. Jonem, C.S. Lyons, M.
from negative to positive, which brought n The research was financially supported
Ulsh, M.J. Kusher, R. Dorai, M.C. Branch;
by the Polish Ministry of Science and Hi-
about a significant improvement in mak- Plasmas Polym. 8 61 (2003) A Compa-
gher Education in 2006‑2009. Research
ing use of the chemical activation of the Project No. 3 R08 035 01.
rison of Corona-Treated and Flame-Tre-
fibre’s top layer to create a chemical bond n The authors also wish to express their
ated Polypropylene Films.
with the bonding agent and, consequent- thanks to Professor Adam Tracz, D. Sc. 11. P. Laurens, S.Petit, F. Arefi-Khonsari.
ly, to increase the force of delamination. of the Centre of Molecular and Supermo- Plasmas Polym. 8 281 (2003).
12. G. Borcia, C.A. Anderson, N.M.D. Brown;
As is seen, the application of PDAMA lecular Research, the Polish Academy
of Science, Łódź, for performing AFM Surface treatment of natural and synthetic
quickly increases the delamination force.
measurements of the changes in fibre textiles using a dielectric barrier dischar-
A further increase is due to the activa- ge; Surface and Coatings Technology,
surface caused by corona discharge.
tion process. The larger this increase is, Volume 201 3074 (2006).
the higher the unit activation energy of 13. R. Morent, N. De Geyter, J. Verschuren,
the corona discharge is, as illustrated by K. De Clerck, P. Kiekens, C. Leys; “Non-
Figure 6. References thermal plasma treatment of textiles
“Surface and Coatings Technology,
1. S. Brzeziński, M. Żenkiewicz, S. Poło-
Volume 202, Issue 14, 15 April 2008,
wiński, D. Kowalczyk, I. Karbownik, S.
n Conclusions Lutomirski, G. Malinowska; Polimery 8
Pages 3427-344.
14. S. Brzeziński: Wybrane zagadnienia z
Corona discharge causes characteristic (2009) (in press).
chemicznej technologii włókna. vol.. II,
2. R. Shishoo (Ed.) „Plasma Technologies
changes in the physical and chemical chapter 8.3.1.1. p. 119. Ed. Bielsko-Biała
for textiles” Woodhead Pub. Lim. Cam-
state of the top layer of PET fabrics, re- bridge England (2007).
Branch of the Technical University of Łódź
sulting in an increase in surface nano- 3. R. Seeböck, H. Esrom, M. Charbonnier, 1999, ISBN 83-87087-36-X.
coarsness (RMS) and the formation of M. Romand; Plasma Polym. 5 103 (2000)
polar groups in the fibre’s top layer. Modification of Polyamide in Barrier Received 27.02.2009 Reviewed 27.05.2009
102 FIBRES & TEXTILES in Eastern Europe 2009, Vol. 17, No. 4 (75)