Current Applied Physics 15 (2015) 1075e1083

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Current Applied Physics

journal homepage: www.elsevier.com/locate/cap

New insights into corona discharge surface ionization of polyethylene

terephthalate via a combined computational and experimental
assessment
Mazeyar Parvinzadeh Gashti a, *, Izadyar Ebrahimi b, Mohammad Pousti c
a
Department of Textile, College of Engineering, Yadegar-e-Imam Khomeini (RAH) Branch, Islamic Azad University, PO Box 15735/334, Tehran, Iran
b
Young Researchers and Elites Club, Yadegar-e-Imam Khomeini (RAH) Branch, Islamic Azad University, Tehran, Iran
c
D
epartement de Chimie, Universit e Laval, 1045 Avenue de la M
edecine, Qu
ebec, QC G1V0A6, Canada

a r t i c l e i n f o a b s t r a c t

Article history: The aim of the present work is to demonstrate the influence of corona discharge ionization on chemical
Received 23 May 2015 and physical properties of polyethylene terephthalate (PET) fibers using computational and experimental
Received in revised form studies. In the computational section, the vibrational frequencies of proposed models for PET before and
16 June 2015
after corona discharge treatment were predicted in the liquid phase at both the B3LYP/6-31G/COSMO
Accepted 18 June 2015
Available online 17 July 2015
and B3PW91/6-31G/COSMO level of theories using the harmonic approximation. When compared to
B3LYP, the frequencies obtained for the B3PW91 show a better linear correlation with the experimental
data. Furthermore, experimental studies were carried out by the use of Fourier transform infrared
Keywords:
Corona discharge process
spectroscopy (FTIR), X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), and reflec-
Polyethylene terephthalate tance spectroscopy (RS). Experimental evidence indicated that the corona discharge modifies the surface
Computational chemistry of fibers and also increases the reactivity of PET toward cationic dyes. Our combined computational and
IR spectra experimental parametric study clearly confirms that the changes occurred on the PET surface due to
corona discharge ionization.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction surface modifying and enhancing the dyeability of textile products

Polyethylene terephthalate (PET) is one of the great man-made
fibers that is widely used in the textile industry due to its light
weight and resistance to shrinking, stretching, mildew, and
creasing [1]. Despite these desired properties of PET, it has resis-
tance to coloration by dyes and finishing with various reagents due
to the limited ionic groups and relatively high crystallinity [2,3]. In
this regard, several research groups have proposed physical
modification techniques to enhance hydrophilicity and dye recep-
tivity including ultrasonic vibration [4], microwave heating [5],
gamma irradiation [6e10], ozone gas treatment [11,12], CO2 laser
radiation [13,14], ultraviolet irradiation [15e18] and electron beam
irradiation [19]. Adeel et al. studied the influences of UV and
gamma irradiations on natural and synthetic dyeing of cotton,
wool, silk and polyester fibers. They demonstrated that these two
modification methods are environmentally friendly procedures for
* Corresponding author.
E-mail address: mparvinzadeh@gmail.com (M. Parvinzadeh Gashti).
[7e10,16e18]. Also, plasma functionalization has been considered
for modification of different polymers in the last decade due to the
energy-efficient dry-state processing, continuous on-line applica-
bility, and minimal precursor quantity requirements and positive
environmental impact. Moreover, it modifies the surface of poly-
mers without any undesirable side effects on the bulk and me-
chanical properties [20,21]. Sapieha et al. studied the lamination
properties of polyethylene and PET after air plasma treatment and
found that generation of hydroxyl, ether, and epoxy groups on films
results in maximum adhesion [22]. Wang et al. evaluated the
penetration of helium/oxygen plasma surface treatment into the
fabric layers. The pore size of the fabric was a critical parameter on
penetration depth of chemically active species into the textile
structure [23,24]. Plasma treatment was found to be useful for
improving the adhesive capabilities of PET fabrics with poly(-
dimethylaminoethylene methacrylate) and poly(allyl-amine hy-
drochloride) [25]. Shakeri Siavashani stated that corona discharge
treatment is not only able to influence the surface morphology, but
it also changes the mechanical properties, air permeability, abra-
sion resistance, and pilling of cotton and PET-cotton fabrics [26].

http://dx.doi.org/10.1016/j.cap.2015.06.009
1567-1739/© 2015 Elsevier B.V. All rights reserved.
1076 M. Parvinzadeh Gashti et al. / Current Applied Physics 15 (2015) 1075e1083

We have recently evaluated the coating ability of PET with different

lubricating agents and hydroxyapatite. Plasma treatment showed a
drastic improvement in the reactivity of substrate toward emul-
sions as well as calcium and phosphate ions [27e30].
Another field of interest for textile chemists is the enhancement
of dyeability of PET through plasma functionalization. Many
research works focus on the dyeability of plasma-treated PET with
disperse, acid, reactive, and natural dyes [31e35], but only two
researches have reported dyeing of PET with cationic dyes. Re-
searchers demonstrated that plasma increases remarkably the
dyeing speed, dye-uptake, and fastness properties, which are
strongly dependent on the plasma exposure time, gaseous mixture,
and energy input [36]. Another study was carried out on PET by in
situ polymerization of acrylic acid using a low temperature plasma
treatment, and it significantly increased the dyeability with basic
dyes [37].
Thus, in order to fulfill a combined study on the chemical
changes that occur on the PET surface by corona discharge treat-
ment, the present research work focuses on computational, spec-
troscopic, and microscopic tools. In this regard, a quantum
mechanical calculation is used to validate the experimental results
and to give deeper insight into the reaction mechanisms on PET
after corona discharge treatment. Among the different types of
quantum mechanical calculations, DFT methods have been able to
incorporate electron correlation effects in the definition of molec-
ular force fields and also show a competitive computational cost
when compared with other post-HartreeeFock methods [38].
Another objective of this work is to compare the performance of
two famous DFT methods (B3LYP and B3PW91) at the same basis
sets in predicting the vibrational spectrum of PET macromolecules
after corona discharge treatment.
Fig. 1. Chemical structure of cationic dyes used in this study.

2. Experimental
basic dyes (6 and 8% owf), sodium sulphate (2% owf), wetting agent
A plain weave PET fabric with an area density of 150 g/m2, 20 (1% owf), and acetic acid (5% v⁄v) at a liquor to goods ratio of 40:1.
warps and wefts per 1 cm, and warp and weft yarn counts of 160 The dyeing process was the same as for corona-treated fabrics.
denier and 27 mm thickness was used. Nonionic detergent, acetic The effect of the corona treatment on the chemical structure of
acid (98%), sodium sulphate, and sodium carbonate were produced the PET fabric was examined by Fourier transform infrared spec-
by Merck (Germany), and they were used for scouring and dyeing of troscopy (FT-IR) [Bomem-MB100 Series (Hartmann & Braun,
PET fabrics. The wetting agent was TECHWET CXD supplied by Germany)].
Dyetech Inc. for dyeing process. The basic dyes used were Cationic The crystalline morphology of the fibers was characterized with
Blue X-GRL (C.I. Basic Blue 41) from Hebei Youhao Chemical Co., a wide angle X-ray diffractometry using a computerized XRD in-
Cationic Red GT (C.I. Basic Red 18) from Rifa Industrial Co., and strument (XPERT-MPD, PHILIPS). Ni-filtered Cu Ka radiation
Cationic black X-2RL from Zhejiang Zhenguang Chemical Co. for generated at 40 kV (k 1⁄4 0.1542 nm) and 30 mA was used. As re-
dyeing of untreated and corona-treated PET fabrics. Fig. 1 shows the ported before, the crystallinity percentage of untreated and corona
chemical structure of the cationic dyes used in this study. discharge-treated fabrics was according to the following equation
Fabric samples were first scoured with 2 g/l nonionic detergent [34]:
to remove impurities. The liquor to goods ratio of the scouring bath
was kept at 50:1 for 20 min at 40
C. The samples were fully dried at
70
C in an oven.
The corona discharge process was carried out on PET samples
using a laboratory prototype as shown in Fig. 2. The instrument
consists of two electrodes: a metal electrode roll with silicon
coating and an aluminum electrode parallel to it. The distance be-
tween electrodes is 3 mm. The samples were treated with corona
discharge at different voltages (5, 8, and 10 kV) and different turns
around the cylinder (30 and 40). The turning velocity of the corona
instrument was set at 5.1 m/min.
For cationic dyeing of corona-treated PET fabrics, solutions were
prepared by adding the basic dyes (4% owf), sodium sulphate (2%
owf), wetting agent (1% owf), and acetic acid (5% v⁄v) at a liquor to
goods ratio of 40:1. The dyeing process was started at 40
C, and the
temperature was raised to 100
C over 30 min and then held at that
temperature for 50 min. Dyeing of untreated fabrics were carried
out for comparison with corona-treated samples by adding the Fig. 2. Laboratory prototype corona discharge instrument used for PET treatment.
 M. Parvinzadeh Gashti et al. / Current Applied Physics 15 (2015) 1075e1083 1077

peak changes are in favor of produced carboxylic groups [45e47].

Cx % ¼ Ic =ðIc þ Ia Þ  100 (1)
where Cx % is the crystallinity percentage of polymer, Ic is the in-
tensity of the X-ray diffraction of the crystalline region, and Ia is the
intensity of the X-ray diffraction of the amorphous area.
A surface morphology analysis of the fabrics was carried out
using a EM3200, KYKY scanning electron microscope. Samples
Calculated IR spectra of untreated and corona discharge treated
PET by two different computational models are shown in Fig. 4. The
main peaks of PET by FTIR spectroscopy are also compared with
those calculated frequencies by the B3LYP and B3PW91 models;
results are shown in Table 1. The relative deviations are accounted
for each selected bands according to Eq. (3):
 
were covered with an Au layer under vacuum conditions prior to
the measurements.
The reflectance of the dyed samples was recorded using a Tex-
flash, Data Color spectrophotometer integrated with an IBM per-
sonal computer. CIELAB colour coordinates (L*, a* and b*) were
calculated from the reflectance data for a 10
observer and illumi-
nant D65 source. The L* represents the lightness of fabrics inde-
pendent of color hue. The a* stands for the horizontal red-green
color axis. The b* represents the vertical yelloweblue axis. The
maximum wavelength of absorbency (lmax) in reflectance curves
was also used for calculation of the colour strength (K/S) of the
samples by means of the KubelkaeMunk equation:
K=S ¼ ð1  RÞ2 =2R
where R is the observed reflectance, K the absorption coefficient,
and S the light scattering coefficient.
3. Computational studies
For modeling PET before and after corona discharge treatment,
two hybrid density functional theory (DFT) methods, Becke's three-
parameter gradient exchange correction functional (B3) in combi-
nation with LeeeYangeParr gradient-corrected correlation func-
tional (LYP) and PerdeweWang 91 (PW91) abbreviated as B3LYP
and B3PW91 were used, respectively. All quantum mechanical
calculations were carried out using ORCA version 3.0.3 software
code [30]. At first, all models' structures were optimized without
any geometrical constraint, then vibrational (IR) spectra were
calculated for the optimized structures at the same level of theory.
A standard 6-31G basis sets were used for all atoms. The solvent
effect was simulated using the conductor-like screening model
(COSMO). For visualizing the models, wxMacMolPlt v7.5 was used
[39].
4. Results and discussion
4.1. Chemical and computational analyses
The experimental infrared spectra of untreated and corona
discharge-treated PET at 10 kV and 40 cylinder turns are shown in
Fig. 3. In PET, CH3 asymmetric stretching, CH3 bending, and CH2
out-of-plane bending vibrations are indicative by the peaks at
2923, 2858, 1458, 1411, 1361, 1245, 875, and 725 cm1, respectively.
The bands at 3433 and 1014 cm1 are characterized by intermo-
lecular OeH bonded to C]O groups and OeH out-of-plane bending
in terminal carboxylic domains of polymer [40e42]. The bands at
1515 and 1095 cm1 are assigned to CeC and CeOeO stretching
vibrations. A strong band observed at 1724 cm1 is related to C]O
symmetric stretching of carbonyl groups [43,44].
Several changes were observed on PET after corona discharge
treatment as shifting of the peaks from 2923, 1515, 1361, 1245, and
1095 cm1 to 2931, 1504, 1380, 1253, and 1103 cm1, respectively.
Furthermore, new peaks appeared at 2970, 1573, 964, and 840 cm1
related to CH stretching, asymmetric stretching of carboxylate an-
ions, and CH out-of-plane bending of PET. Here we confirm that the
content of oxygen atoms are increased on the fiber surface, and the
pK  pKexp 
cal
RD ¼ (3)
pKexp
%MRD ¼ 100*SRD=n (4)
From the results shown in Table 1, the percentage of mean
relative deviations (Eq. (4) where n is the number of degrees of
freedom) with experiment of 1.21 and 1.15 are obtained for PET at
B3LYP and B3PW91, respectively; this proves that our model is
probably reasonable, and it also indicates that the frequencies ob-
tained for the B3PW91, when compared with B3LYP, show a slightly
better linear correlation with experimental data. Therefore, it is
(2) clear that the theoretical values are in good agreement with
experimental results as expected, so we can conclude that the
proposed models can be used for surface modification procedure of
PET by corona discharge treatment.
The assignments of these vibrational modes can be also exam-
ined based on quantum calculations. In the present study, molec-
ular structures of PET before and after corona discharge treatment
were investigated by means of density functional theory (DFT) at
B3LYP and B3PW91 levels with the 6-31G basis set. All the geom-
etries of the proposed models were optimized without any
geometrical constraint in aqueous solution using the COSMO
model, which represents solvent as a dielectric polarizable con-
tinuum. Also, the Hessian matrix and vibrational spectra were
calculated at the same level that were used for optimization. No
imaginary frequencies were detected, which indicates that we
probably found the global minima of the potential surface. Scale
factors of 0.968 and 0.952 were accounted for in the B3LYP and
B3PW91 IR spectra, respectively. The molecular structure of PET
were drawn by the B3PW91 model and shown in Fig. 5. Table 2
shows the geometrical parameter for the proposed models of un-
treated and corona discharge-treated PET. We believe that the
proposed polymer chain models are valuable to include all types of
atoms involved for DFT calculation of IR spectrum. It should be
considered that we only compared the frequency sequence be-
tween experimental and theoretical IR bands; we did not compare
the intensity due to the lack of the local field and chemical effects
involved in experiment.
Our former research demonstrated that plasma treatment
changes the surface energy levels of PET and generates the CeH
radical groups by splitting the CeC bonds of polymeric chains. This
enhances the bonding ability of ionic and silicone softeners on PET
fabric [27e30]. These computational results clearly state that
corona discharge treatment changes the bonding length of PET at
the molecular level. Moreover, several groups elucidated that
amorphization of the crystalline fraction of PET and scission of the
main chain at para position of disubstituted benzene rings resulted
in an increase in the intensity of bands [48,49]. As stated by Wang
et al., the plasma treatments has enough energy level to break
benzene rings and produces active species [23,24].
4.2. Evaluation of morphology by XRD
The XRD patterns and the calculated parameter for the un-
treated PET as well as the samples treated with corona discharge at
1078 M. Parvinzadeh Gashti et al. / Current Applied Physics 15 (2015) 1075e1083

Fig. 3. FTIR spectra of the samples: (a) untreated polyester and (b) polyester treated with corona discharge at 10 kV and 40 cylinder turns.

different voltages and cylinder turns are shown in Fig. 6 and Table 3.
Diffraction peaks of untreated PET are characteristic with three
reflections at 2q ¼ 17.6, 22.73, and 25.6, representing d (010),
d (110), and d (100) Bragg's reflections [50]. We observed that the
reflection degree did not considerably change for PET after corona
discharge treatment. However, as seen in Fig. 6 and calculated by
Eq. (1), the intensity of the diffraction peaks were decreased and
became broader. Moreover, the crystallinity percent and crystal size
for PET fabric treated with corona discharge at 5 kV and 40 cylinder
turns were decreased and continued to decrease with increasing
corona discharge voltage up to 10 kV (Table 3). On this basis and
results obtained by FTIR, we concluded that corona discharge
treatment must therefore be confined to the PET surface. By
comparing the results from Tables 2 and 3, it can be postulated that
the crystallinity of PET at the surface is influenced by bonding
length changes as reported in Table 2. The changes in crystallinity
and the crystallite size on the fiber surface can contribute to the
improvement in adsorption kinetics of different compounds [51].
We recently confirmed this phenomenon after the crystallinity
measurement of cotton in a case where ozone was applied for
grafting of fluoromonomers [52].

4.3. Microscopic characterization of fibers

Fig. 4. Calculated IR spectra of untreated PET models at a) B3PW91 and b) B3LYP and
treated PET models at c) B3PW91 and d) B3LYP.
Fig. 7 shows the SEM images of the untreated PET together with
the corona discharge-treated samples at different voltages and
cylinder turns. As can be seen from Fig. 7a, the surface of the un-
treated fiber is relatively smooth with no damage from the corona
discharge treatment. However, the fiber surface is dramatically
damaged and is rough with blisters and hills. These changes are not
uniformly distributed on the surface, showing that the corona
discharge is dependent on both treatment voltage and number of
turns.
We have previously postulated that the surface degradation
occurs on PET after corona discharge treatment by two phenomena.
The first reason is entrapment of low molecular weight polymeric
chains in internal gas bubbles after bombardment of ions and
 M. Parvinzadeh Gashti et al. / Current Applied Physics 15 (2015) 1075e1083 1079

Table 1
The comparison of experimental and theoretical frequencies together with the percentage of mean relative deviation for B3LYP and B3PW91 levels. The relative deviation of
both models in different frequencies is shown in parenthesis.

Sample Experimental (cm1) B3LYP (cm1) B3PW91 (cm1)

Untreated PET 725 703 (3.03E-2) 694 (4.28E-2)

875 885 (1.14E-2) 870 (5.71E-3)
1014 1015 (9.86E-4) 1001 (1.28E-2)
1095 1089 (5.48E-3) 1085 (9.13E-3)
1245 1240 (4.02E-3) 1230 (1.20E-2)
1361 1339 (1.62E-2) 1384 (1.69E-2)
1411 1436 (1.77E-2) 1415 (2.83E-3)
1458 1455 (2.06E-3) 1468 (6.86E-3)
1515 1504 (7.26E-3) 1484 (2.05E-2)
2923 2985 (2.12E-2) 2942 (6.50E-3)
Corona discharge treated PET 725 752 (3.72E-2) 747 (3.03E-2)
790 800 (1.27E-2) 798 (1.01E-2)
840 817 (2.74E-2) 817 (2.74E-2)
875 874 (1.14E-3) 873 (2.29E-3)
964 958 (6.22E-3) 968 (4.15E-3)
1014 1009 (4.99E-3) 999 (1.48E-2)
1103 1110 (6.35E-3) 1102 (9.07E-4)
1253 1232 (1.68E-2) 1258 (3.99E-3)
1346 1331 (1.11E-2) 1336 (7.43E-3)
1380 1396 (1.16E-2) 1384 (2.90E-3)
1504 1494 (6.65E-3) 1484 (1.33E-2)
2931 2950 (6.48E-3) 2931 (0.00E00)
%MRD e 1.21 1.15

electrons. The second can be due to destruction of crystalline re-
gions at the fiber surface to amorphous domains and to relaxing at
fiber surface in disordered forms. This resulted in changes to the
surface energy and roughness of the polymers and improves the
coating ability against different emulsions and resins [53,54]. This is
in good agreement with the results obtained from the FTIR spectra.
4.4. Dyeability studies
The L*, a*, b* and K/S values as well as reflectance curves of
untreated and corona discharge treated/dyed with different
cationic dyes are given in Table 4 and Figs. 8e10. It is well known
that L*, K/S, and reflectance curves are key measurements to
indicate the dyeability of textile products. Any decrease in L* and
increase in K/S could be concluded as the more dye absorption into
the fibers. As seen from the L* and K/S values, the corona discharge
influences positively on PET fabric and improves the dyeability of
PET with cationic dyes. The reflectance curves of corona discharge-
treated fabrics also showed a great decrease after dyeing with
different dyes used in respect to untreated samples.
Note, however, that the dyeability of corona discharge-treated
samples showed a correlation to the applied voltage and cylinder
turns. As can be seen from the samples dyed with cationic blue dye,
the K/S value showed an increase with the increase of cylinder turns
from 30 to 40 at constant applied voltages of 5 kV and 8 kV. This
was also observed for those corona discharge treated fabrics at

Fig. 5. The optimized structures of a) untreated PET and b) treated PET at DFT-B3PW91/6-31G/COSMO. Green, gray, and red balls are H, C, and O atoms, respectively. (For inter-
pretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
1080 M. Parvinzadeh Gashti et al. / Current Applied Physics 15 (2015) 1075e1083

Table 2 voltages of 5 kV and 10 kV after dyeing with cationic red and black
Acquired geometrical parameter for the proposed model's skeleton of untreated and dyes. This observation implies that an increase in the amount of
treated PET at B3PW91 and B3LYP. Bond lengths are in Angstroms.
active species is expected on the PET surface with increasing the
Corona discharge treated PET Untreated PET applied voltage.
Bond length (A
) Bond length (A
) We have demonstrated that the dyeing behavior of PET depends
on different parameters, including the affinity of the dye to the
Bond B3PW91 B3LYP Bond B3PW91 B3LYP
polymer, chemical structure of dye, existence of functional sites,
O1 e C 2 1.4498 1.4573 C1 e O2 1.4706 1.4785
and crystallinity percent in the polymer [2,3]. Conventional PET
C2 e C3 1.5195 1.5230 O2 e C3 1.3603 1.3659
C 3 e O4 1.4725 1.4802 C3 e O4 1.2432 1.2454 textiles have no affinity to cationic dyes due to a lack of hydrophilic
O4 e C 5 1.3616 1.3670 C3 e C5 1.4800 1.4833 groups. Introduction of different functional domains such as car-
C 5 e O6 1.2427 1.2448 C5 e C6 1.4036 1.4063 boxylic, hydroxyl, or amine groups to PET can thus change their
C5 e C7 1.4794 1.4831 C6 e C7 1.3919 1.3939 properties and markedly enhances their affinity to cationic or
C7 e C8 1.4036 1.4062 C7 e C8 1.4043 1.4069
C8 e C9 1.3919 1.3940 C8 e C9 1.4038 1.4065
anionic dyes. Our computational studies showed that carboxylic
C9 e C10 1.4044 1.4069 C9 e C10 1.3920 1.3941 acid groups are generated on the PET surface due to corona
C10 e C11 1.4038 1.4064 C8 e C11 1.4779 1.4812 discharge treatment. As a result, the affinity of PET to cationic dyes
C11 e C12 1.3919 1.3939 C11 e O12 1.2419 1.2441 is improved due to electrostatic bonding between the negatively
C10 e C13 1.4780 1.4816 C11 e O13 1.3650 1.3707
charged carboxylic groups in PET and positively charged nitrogen
C13 e O14 1.2419 1.2439 O13 e C14 1.4683 1.4759
C13 e O15 1.3647 1.3704 C14 e C15 1.5132 1.5170 atom of cationic dyes. Another reason for improving dyeability of
O15 e C16 1.4685 1.4762 C15 e O16 1.4683 1.4759 PET could be explained as production of the rougher surface and
C16 e C17 1.5132 1.5167 O16 e C17 1.3650 1.3707 decrement of crystallinity, which improves the accessibility of
C17 e O18 1.4687 1.4763 C17 e O18 1.2419 1.2440 cationic dyes into the fiber structure. This result is incidentally
O18 e C19 1.3646 1.3701 C17 e C19 1.4779 1.4812
consistent with our other results obtained from XRD and SEM
C19 e O20 1.2418 1.2438 C19 e C20 1.4038 1.4065
C19 e C21 1.4782 1.4820 C20 e C21 1.3920 1.3941 analyses.
C21 e C22 1.4037 1.4062 C21 e C22 1.4043 1.4069 It is important to note that the dyeing procedure of PET gener-
C22 e C23 1.3918 1.3939 C22 e C23 1.4036 1.4063 ally consumes a lot of energy, water uptake, and dyes, which in-
C23 e C24 1.4042 1.4068 C23 e C24 1.3919 1.3939
creases the manufacturing costs. In this sense, plasma technology is
C24 e C25 1.4037 1.4062 C22 e C25 1.4800 1.4833
C25 e C26 1.3919 1.3939 C25 e O26 1.2431 1.2454 an environmentally friendly process to reduce the chemicals dos-
C24 e C27 1.4771 1.4803 C25 e O27 1.3603 1.3659 ages and production costs.
C27 e O28 1.2426 1.2443 O27 e C28 1.4706 1.4785
C27 e O29 1.3624 1.3686

Fig. 6. XRD patterns for different samples used in this study: (a) The untreated polyester, (b) polyester fabric treated with corona discharge at 5 kV and 40 cylinder turns, and (c)
polyester fabric treated with corona discharge at 10 kV and 40 cylinder turns.

Table 3
XRD parameter calculated by Eq. (1) for untreated polyester together with different corona discharge-treated samples.

Sample Crystallinity (%) 2q (
) d-spacing (Å) for d(100) Bragg's reflections Crystal size (nm)

Untreated PET 5.87 3.56 25.62 50.28

PET treated at 5 kV and 40 cylinder turns 5.32 3.52 25.88 47.25
PET treated at 10 kV and 40 cylinder turns 4.78 3.54 25.72 41.62
 M. Parvinzadeh Gashti et al. / Current Applied Physics 15 (2015) 1075e1083 1081

Fig. 7. SEM images for different samples used in this study: (a) The untreated polyester, (b) polyester fabric treated with corona discharge at 5 kV and 40 cylinder turns, (c) polyester
fabric treated with corona discharge at 8 kV and 40 cylinder turns, (d) polyester fabric treated with corona discharge at 10 kV and 30 cylinder turns, (e) polyester fabric treated with
corona discharge at 10 kV and 40 cylinder turns.

Table 4
Color coordinates and color strength of untreated and corona discharge treated/dyed with different cationic dyes.

Samples Dye (%) and name L* a* b* K/S

Untreated PET 4%-Cationic blue X-GRL 58.49 19.91 3.07 1.81

PET treated at 5 kV and 30 cylinder turns 44.98 14.31 5.76 3.68
PET treated at 5 kV and 40 cylinder turns 44.54 16.26 5.84 4
PET treated at 8 kV and 30 cylinder turns 39.54 10.69 11.42 4.45
PET treated at 8 kV and 40 cylinder turns 39 17.917 6.053 6.21
PET treated at 10 kV and 30 cylinder turns 42.58 14.57 7.1 4.25
PET treated at 10 kV and 40 cylinder turns 44.62 14.78 7.96 3.71
Untreated PET 4%-Cationic red GT 60.34 26.73 11.49 1.79
PET treated at 5 kV and 30 cylinder turns 49.72 30.45 17.96 4.32
PET treated at 5 kV and 40 cylinder turns 48.51 29.88 16.55 4.53
PET treated at 8 kV and 30 cylinder turns 46.9 32.65 20.25 5.74
PET treated at 8 kV and 40 cylinder turns 47.18 32.8 20.22 5.59
PET treated at 10 kV and 30 cylinder turns 49.99 30.57 17.83 4.21
PET treated at 10 kV and 40 cylinder turns 47.19 31.16 18.88 5.34
Untreated PET 4%-Cationic black X-2RL 59.41 25.65 5.3 2.39
PET treated at 5 kV and 30 cylinder turns 53.11 16.73 0.44 2.55
PET treated at 5 kV and 40 cylinder turns 45.47 24.37 5.57 5.89
PET treated at 8 kV and 30 cylinder turns 46.81 11.71 2.65 3.07
PET treated at 8 kV and 40 cylinder turns 49.06 14.07 0.72 2.97
PET treated at 10 kV and 30 cylinder turns 49.8 16.36 1.59 2.96
PET treated at 10 kV and 40 cylinder turns 48.4 15.08 2.6 3.06
1082 M. Parvinzadeh Gashti et al. / Current Applied Physics 15 (2015) 1075e1083

Fig. 8. Reflectance curves of untreated and corona discharge treated/dyed with Cationic Blue X-GRL. (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)

5. Conclusion induced changes in chemical properties, crystallinity percent, and

The performance of corona discharge ionization on PET fabric
has been studied computationally and experimentally. DFT calcu-
lations on the molecular structure and vibration spectra of PET
before and after corona discharge have been carried out. It is
remarkable that the B3PW91/6-31G level is superior to the B3LYP
level in predicting the vibration spectra of untreated and treated
PETs. Our computational study of corona discharge-treated PET
clearly indicates the surface changes occurred on the polymer
surface at the molecular level. Exposing fabrics to corona discharge
the crystallite size on the fiber surface. This results in a significant
roughness dependent on treatment voltage and number of turns.
Our results also showed that corona discharge generated the
cationic dyeable PET due to electrostatic bonding between func-
tional domains of polymer and cationic dyes. Dye absorption was
also influenced by the production of a rough surface and decrement
of the surface crystallinity. Our computational studies also
confirmed a salient feature of the corona discharge process by
enhancement of surface functionality of PET polymer as an envi-
ronmental bonus.

Fig. 9. Reflectance curves of untreated and corona discharge-treated/dyed with Cationic Red GT. (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)
 M. Parvinzadeh Gashti et al. / Current Applied Physics 15 (2015) 1075e1083 1083

Fig. 10. Reflectance curves of untreated and corona discharge-treated/dyed with Cationic black X-2RL.

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