Progress in Organic Coatings 76 (2013) 1858–1862

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Progress in Organic Coatings

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

Surface modification of polypropylene fiber for hydrophilicity

enhancement aided by DBD plasma
A. Mercado-Cabrera a,∗ , B. Jaramillo-Sierra b , R. López-Callejas a,b , R. Valencia-Alvarado a ,
A. de la Piedad-Beneitez b , R. Peña-Eguiluz a , S. Barocio-Delgado a,1 , A. Muñoz-Castro a ,
B. Rodríguez-Méndez a
a
Instituto Nacional de Investigaciones Nucleares, AP 18-1027, 11801 México, D.F., Mexico
b
Instituto Tecnológico de Toluca, AP 890, Toluca, Estado de México, Mexico

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

Article history: Low-wetting low-hydrophilicity polipropylene fiber has been treated by means of non-thermal dielectric
Available online 24 June 2013 barrier discharge plasma. The fiber has been characterized before and after the treatment by scanning
electron microscopy (SEM), X-ray diffraction, atomic force microscopy (AFM) and industrial tests of sub-
Keywords: mersion in water. The cold plasma was generated in a helium–air mixture at a 2 kHz frequency and
Polypropylene fiber 12–18 kV potential. The treatment periods ranged from 1 min up to 3 min. The results present an increase
Plasma treatment
in the oxygen content which rose from 2.5% to 4.8%. SEM analysis reveals a surface change of the fiber
SEM
with the formation of nodules, which is confirmed by AFM. Water submersion experiments show an
X-ray diffraction
enhancement of the hydrophilic capability of the samples.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction solutions during its manufacture [1]. However adverse environ-

mental consequences can be generated using these softeners or
Polymers are widely used in the production of textiles and acconditioning solutions due to the wastewater production. Non-
coatings. Sometimes polymers are required to provide high wett- thermal plasma can oxidize the polypropylene surface (dry process)
ability, hydrophilicity, adhesivity, reactivity, and printability. These grafting a polar group containing oxygen on the surface generat-
properties do not always easy to be achieved given the nonpo- ing functional groups like: ketones, alcohols or carboxylic acids
lar character of some polymers. Non-thermal plasma has been without changing the structural properties of polypropylene. The
applied for polymers treatment with the aim of increasing such present work reports the feasibility of increasing the hydrophylic-
properties [1–4] or in other cases, sterilization avoiding the growth ity of polypropylene fibers used in decorative sheet manufacture
of microorganisms [5]. In all case, non-thermal plasma capability applying dielectric barrier discharges in He–air mixtures. It is
to make possible oxidation processes on surface materials with important to indicate that commercially PP fiber was treated with-
high sensitivity to heat has utilized. Allowing adequate plasma out any previous special preparation in molecular weight, density,
working conditions, it is possible to generate some active species crystalinity and thickness.
like: free radicals, low-energy ions, and high-energy free electrons,
which are able to cleaning, etching or oxidize polymer surface
[6–8]. A particular case is the polypropylene (PP) used for auto- 2. Experimental
mobile parts manufacture, medical devices, laboratory material,
sanitary clothes, etc. Specific aplication of polypropylene under Commercial polypropylene fiber was cut into 1 cm long seg-
fiber form is to reinforce and exibilize resin sheets in the decoration ments, Fig. 1(a), approximately. The diameter of the fiber was
and carpet industries. The fiber presents a nonpolar characteris- measured ∼40 ␮m. A single dielectric circular reactor, Fig. 1(b), was
tic which hinders its association in aqueous media. Thus, in order used for the generation of the dielectric barrier discharge. The set-
to increase its hydrophilicity, fiber surface is traditionally mod- up is showed in Fig. 1(c). A known amount of polypropylene was
ified by conventional chemical processes: soaked in tensoactive placed on the lower electrode dielectric, Fig. 1(b). The upper elec-
trode was placed 3 mm away from the dielectric. The gas input was
located in a perpendicular way to (and at the center of) the upper
∗ Corresponding author. electrode in order to saturate the sample. A He–air gas mixture was
E-mail address: [email protected] (A. Mercado-Cabrera). injected at a rate of 0.5 LPM. The gas flowed through a water con-
1
In memoriam. tainer so as to add humidity to the reactor. A power supply system

0300-9440/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.porgcoat.2013.05.029
 A. Mercado-Cabrera et al. / Progress in Organic Coatings 76 (2013) 1858–1862 1859

Fig. 1. Experimental set-up.

[10] providing 12–18 kV voltages at 2 kHz frequency was used to except in the case of high power and long treatment time (Fig. 2,
generate the non-thermal plasma discharge. The relative humidity Table 1). Also, it was possible to observe that treatment time should
(% R.H.) was measured with an HD500 Extech Instruments psy- be lower than 3 min for similar working conditions. Otherwise,
chrometer. The treated samples were analyzed by SEM, AFM, X-ray long exposure times will oxidize and destroy the material with
diffraction and water submersion tests. the generation of CO2 [11]. The oxygen presence in the polypro-
pylene surface is linked to the enhancement of its hydrophylicity
3. Results and discussion capacity [8,9]. 10–12 kV SEM potentials were used for the elemen-
tal analyses and 20 kV were applied for the picture frame when it
3.1. SEM analysis was possible.
SEM micrographs (Fig. 3) show the evolution of the fiber sur-
The elemental content was determined before and after the face topography along the treatment for differents power applied
treatment by EDX analysis. The output showed an increment of the and the untreated one. In the first seconds of treatment, Fig. 3(b), it
atomic oxygen % as the power and time of treatment were increased observes an increase of the roughness (not measured). The helium

Fig. 2. Atomic oxygen % at (a) 16.70 W and (b) 31.2 W.

1860 A. Mercado-Cabrera et al. / Progress in Organic Coatings 76 (2013) 1858–1862

Table 1
SEM measured elemental percentage.

Elements Before treatment After treatment at 16.70 W

1 min 2 min 3 min

C (%) 97.44 95.78 95.33 95.3

O (%) 2.56 4.22 4.67 4.70

After treatment at 31.20 W

C (%) 97.44 95.38 93.37 93.8
O (%) 2.56 4.62 6.63 6.2

addition to the mixture allowed to diminish the breakdown poten- along with the treatment duration. Contrary to results in [13], the
tial of the discharge and so the treatment temperature sufficiently fiber did not require being washed to be AFM analyzed.
low to avoid the streamers formation that could damage the fiber
as happened with air.
3.3. X-ray diffraction analysis

3.2. AFM analysis X-ray diffraction revealed that important damages had not been
made to the polypropylene fiber and that it preserved its structure
The samples of polypropylene fiber, untreated and treated, were in general, as shown in Fig. 5.
analyzed by AFM using non-contact procedure. The results showed The conditions prevailing during the X-ray difractometry were:
changes on the surface of the fiber. Before the treatment the mate- 35 kV, 25 mA acceleration voltage and current respectively, a char-
rial presented a flat surface with some depth on the surface. In acteristic  = 1.5406 CuK␣ line wavelength of the copper target, a
general, after plasma treatment, it can be observed an etching 2 range within 10◦ –30◦ , and a 0.030◦ angular step size.
effect over PP surface resulting in a regular pattern. As non-thermal The diffractogrammes of the untreated and treated polypropyl-
plasma treatment time was increased several nodules were formed ene are shown in Fig. 5. A broadening was not observed in the
on the surface of the fiber, as seen in Fig. 4(b)–(d), in agreement with treated samples spectra but a slight 2 shift of the main peaks
previous reports [12,13]. The size of such formations was increased to the right with respect to the untreated sample. The relative

Fig. 3. SEM images of the PP fiber samples: (a) untreated sample and treated samples for 3 min at 71.2% R.H., (b) 10.0 W, (c) 16.70 W, (d) 32.10 W.
 A. Mercado-Cabrera et al. / Progress in Organic Coatings 76 (2013) 1858–1862 1861

Fig. 4. AFM images of PP fiber samples for: (a) untreated sample and samples treated at 16.70 W and 71.2% R.H. for: (b) 1 min, (c) 2 min, (d) 3 min.

intensities of industrial polypropylene fiber were compared to (9) (0 1 2), 28.278◦ . Only the first plane (1 1 0) in 14.089◦ and the
those of the 00-054-1936 JCPDS data file. It should be observed that sixth plane (n 5 1) in 25.580◦ were straightforwardly identified. The
the intensities reported on this data file refer to a sample of polypro- other intensities and planes of the untreated polypropylene were
pylene crushed to a powder and prepared with calcium carbonate. shifted to the left or right with respect to those reported on the
Nevertheless, the main polypropylene peaks shown in Fig. 5 were 00-054-1936 data file. Specifically, these are: the second at 16.93◦ ,
largely coincident and therefore identifiable. the third at 18.58◦ , the fourth at 21.82◦ and the ninth at 28.39◦ .
According to the 00-054-1936 JCPDS data file, the difraction The presence of the rest of the peaks was not observed in the
planes and the difraction 2 angles are: (1) (1 1 0), 14.089◦ , (2) untreated sample, indicating that it presents a crystalinity differ-
(n 4 0), 17.087◦ , (3) (1 3 0), 18.485◦ , (4) (1 4 0), 21.783◦ , (5) (1 5 0), ent to that of the polypropylene reported on the JCPDS data file.
25.080◦ , (6) (n 5 1), 25.580◦ , (7) (n 6 0), 26.079◦ , (8) (2 0 0), 27.278◦ , The results of X-ray difraction also indicated that, (1) the intensity
of the peaks was increased on all the samples whereby it can be
considered that the treated sample acquired a better crystalinity
due of the structural arrangement of the atoms in the polypro-
pylene, (2) some peaks were practically not observed before the
treatment and they became more visible afterwards, i.e., the plane
(0 1 2) near to 28.278◦ , (3) a slight 2 shift of the peaks is observed
to the right of those of the untreated sample, (4) the polypropyl-
ene was not substantially modified and the material conserves its
structural properties, as X-ray spectrum taken after the treatment
showed.
Moreover, the wide-angle X-ray scattering spectra from X-ray
diffraction was used to determine the cristallinity of the sample
[14]. The cristallinity was calculated by dividing the total area
of cristalline peaks by the total area under the diffraction curve
(crystalline plus amorphoud peaks). Therefore, the crystallinity
percentage was estimated around ∼46.45% for the untreated PP
sample and ∼50.01% for the treated PP sample with 1 min of treat-
ment (red line, Fig. 5).
The method of contact angle does not an appropriate technique
to measure the hydrophylicity of a fiber due to its irregular and
cylindrical nature [4], and because the porous structure can absorb
the liquid. In their place we used a direct industrial technique
Fig. 5. X-ray diffraction for untreated and treated samples. to evaluate the hydrophylicity in a bulk of the treated fibers. It
1862 A. Mercado-Cabrera et al. / Progress in Organic Coatings 76 (2013) 1858–1862

Table 2
Water submersion experimental results.

Visualization time (min) Untreated Treated 16.70 W treatment time

1 min 2 min 3 min

10

15

consisted in placing a weighted amount of treated PP fiber segments Acknowledgements

in a measured volume of water, shaking it vigorously, allowing it
to settle and finally comparing it with a similar preparation made This work received financial support from CONACYT, Mexico,
with the untreated PP fiber segments. The results showed that, after under contracts 288097/229210. The authors appreciate the tech-
15 min, the untreated polypropylene continued oating in the water, nical support received from M.T. Torres Martínez, P. Angeles
as seen on the photographic Table 2. Espinosa and I. Contreras Villa.

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