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Optics & Laser Technology 40 (2008) 113119 www.elsevier.com/locate/optlastec

Impact on textile properties of polyester with laser


C.W. Kan
Institute of Textiles and Clothing, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, China Received 14 November 2006; received in revised form 2 March 2007; accepted 16 March 2007 Available online 30 April 2007

Abstract Modication of the textile properties of polyester due to laser irradiation were studied and these properties included bre weight and diameter, tensile strength and elongation, yarn abrasion, bending, surface lustre, wetting, air permeability as well as crystallinity. Properties such as wettability and air permeability were positively affected while properties of bre weight and diameter, tensile strength, yarn abrasion and bending were adversely affected. In this study, laser irradiation used was not found to affect the bulk properties of polymer due to its low penetration depth, and hence, the effect of laser irradiation on bulk and structural properties was limited. However, the performance and comfort properties of the laser-irradiated polyester could be signicantly affected by laser irradiation. r 2007 Elsevier Ltd. All rights reserved.
Keywords: Polyester; Laser; Textile

1. Introduction In the last decade, considerable effort has been made in developing surface treatments such as UV irradiation, plasma, electron beam and ion beam to modify the properties of textile materials. Laser modication on material surface is one of the most studied technologies. It has been shown that materials like polymers, woods, metals, semiconductors, dielectrics and quartz modied by laser irradiation often exhibit physical and chemical changes in the materials surface. In the case of polymers, some well-oriented structure of grooves or ripple structures with dimensions in the range of micrometre are developed on surface with irradiation uence above the so-called ablation threshold, e.g. a polyester irradiated by a laser of wavelength 248 nm with energy of about 30 mJ/cm2 [1,2]. The laser irradiation of highly absorbing polymers such as polyester can generate characteristic modications of the surface morphology [3,4]. The physical and chemical properties are also affected after laser irradiation [57]. Hence, it is reasonable to believe that such surface modication of a polymer may have an important impact on its textile properties [810]. In order to nd out which
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property of polyester is affected by laser irradiation, different experiments and testing instruments were used to characterize the treated samples. In this paper, the inuence of laser irradiation on some of the important textile properties of polyester was studied. These properties include bre weight and diameter, tensile strength and elongation, yarn abrasion, bending, surface lustre, wetting, air permeability and crystallinity. 2. Experimental All measurements were undertaken with 5% tolerance limit. 2.1. Material Commercially available poly(ethylene (polyester) bre, yarn and fabric were used All samples were conditioned for at least experiment under the standard conditions 65% relative humidity. 2.2. Laser irradiation Both high- and low-uence laser irradiations were conducted [810]. Irradiation was performed using a commercial terephthalate) for the study. 24 h prior to at 20 1C and

E-mail address: tccwk@inet.polyu.edu.hk. 0030-3992/$ - see front matter r 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.optlastec.2007.03.005

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pulsed UV excimer laser (Lambda Physik COMP EX 205) under atmospheric conditions in air. The laser was operated with KrF gas and a wavelength of 248 nm was produced. In high-uence laser irradiation, samples were irradiated directly from the laser beam without using either special photomask or focusing lens. The laser energies in terms of applied uence and number of pulses varied in different experiments. The laser uence was regulated in the range from 50 to 150 mJ/cm2 and the number of pulses varied between 0 and 200. In low-fIuence laser irradiation, only the highly polarization beam method was employed and the uence was controlled to 2000 pulses at 6 mJ/cm2. For both types of laser irradiation, the pulse repetition was kept constant at 1 Hz to avoid any possible heat accumulation. 2.3. Morphological study The morphology of samples was investigated by Scanning Electron Microscopy (SEM) (Lecia Stereoscan 440). 2.4. Bulk and structural properties The degree of crystallinity was determined by integrating the peak area of a differential scanning calorimetry curve. This method is based on a thermodynamic denition of order and it requires the absolute value of the ideal polymer crystals heat of fusion (DH of melting peak of ideal polyester crystal 119.8 J/g) [11]. The heat of fusion obtained from this is directly proportional to the crystallinity. The measurement was conducted by using a Mettler DSC Model 25 under thermally controlled conditions with a heat rate of 10 1C/min in a nitrogen atmosphere with the scanning ranging from 30 to 300 1C. The degree of crystallinity was calculated based on the following equation [11]: degree of crystallinity DH of melting peak DH of melting peak of ideal polyester crystal 100%.

with a silicon carbide waterproof abrasive paper 100 (etectro-coated) for the creation of abrasion against the specimens. KES-F (Kawabata Evaluation System for Fabrics) Bending Tester was employed for measuring both the bending rigidity, B, and hysteresis, 2HB, of the yarn samples. Specimen each comprised of 82 ends was tested. The glossiness of the fabric samples was measured by a Goniophotometer (Model VG-ID, Nippon Denshoku Kogyo Co. Ltd.) designed according to Japanese Industrial Standard 28741. During the experiment, the incident angle of light was always xed at 601 while the receiving angle varied from 01 to 851 at the interval of 51. This measurement method is widely used since it facilitates subjective evaluation in which the incident light and the fabric sample are both xed while the position of the observer is varied. The glossiness index expressed in terms of percentage was measured in both warp and weft directions. 2.7. Comfort properties The vertical drop test of fabrics was measured in accordance with BS 4554. A drop of distilled water was placed onto the fabric sample and the time, Ts, for which the liquid required to sink into the fabric completely (i.e. the liquid is no longer visible from the surface of the fabric) was recorded. The shorter the time, the more wettable was the fabric. A Shirley air permeability tester was employed to measure the air permeability of the fabric samples based on BS 5636 and the air permeability in this test is dened as the volume of air in milliliters passed in 1 s through 100 s mm2 of the fabric at a pressure difference of 10 mm head of water. Specimens with size 15 cm2, avoiding selvages, crease and fold, were used. The equation shown below was used to calculate the air permeability of the samples. Air permeability Air flow . 5:08

3. Results and discussion 2.5. Weight and bre diameter change These experiments were designed to compare the sample weight and bre diameter before and after laser irradiation; the percentage change of the sample weight and bre diameter could then be obtained. The bre diameter was obtained directly from microscopic measurement. 2.6. Performance properties The tensile strength and elongation-at-break of the bres were measured in accordance with ASTM D2101-2005 using an Instron Tensile Tester 4466. The yarn abrasion of the bres was examined by a Shirley Yarn Abrasion Tester 3.1. Degree of crystallinity Table 1 shows the degree of crystallinity of the laserirradiated polyester. The change of crystallinity of polyester as a result of laser irradiation was 2% for high uence; no change was observed under low-uence irradiation. It seems that the overall change in the degree of crystallinity is insignicant. The relatively small difference in the degree of crystallinity between the laser-irradiated and untreated polyester is expected and explainable, although it is reasonably believed that the surface of the high-uenceirradiated polyester would become highly amorphous due to ablation. The small change may be due to the nature of laser irradiation as it generates only surface morphological

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C.W. Kan / Optics & Laser Technology 40 (2008) 113119 Table 1 Degree of crystallinity of laser irradiated polyester: high uence 5 pulses at 70 mJ/cm2 and low uence 2000 pulses at 6 mJ/cm2 Degree of crystallinity (%) Control High-uence irradiated Low-uence irradiated 44 43 44 % Changes over control k2 115

modication where the bulk properties of polymer remain unchanged. In fact, the penetration depth of laser energy is limited to a few micrometres under high-uence irradiation and even less for the low-uence counterpart, while crystallinity is a bulk internal property of polymer. 3.2. Morphological study Fig. 1 shows the surface structure of the untreated polyester bre and a smooth surface is noted. With the inuence of laser irradiation under high uence, certain roughness or periodic roll was developed on the polyester bre surface as shown in Fig. 2, which is called roll-like or ripple-like structure. The orientation of this kind of ripplelike structure is strictly perpendicular to the brillar orientation of the bre. On the other hand, periodic surface structure of sub-micrometre size was developed when the polyester surface was irradiated with low uence as shown in Fig. 3. In Fig. 3, the polyester has submicronmetre ($200 nm) ripple spacing on the surface and some with granule structure on the two sides after laser irradiation. The granules are distributed quite randomly which may be due to the geometry effect of the curved surface. 3.3. Weight and bre diameter change The weight change of polyester caused by high-uence laser irradiation is shown in Fig. 4. It can be observed that the weight change correlated well with laser uence and the number of pulses applied during laser irradiation, i.e. an increasing uence and number of pulses resulted in an increasing level of weight loss. In the rst few pulses, the weight loss was insignicant but increasing the pulse counts would further increase the weight loss. However, no saturation of weight loss was seen against the pulse counts. The reduction in weight with increased laser irradiation may be due to the etching effect induced by the highuence ablation as the polyester bre was etched pulse-bypulse during uence above the ablation threshold [12]. In the case of high-uence irradiation, materials were etched away and ejected from the surface into the atmosphere during ablation. On the other hand, no signicant weight change was recorded for the low-uence irradiation. The energy involved in low-uence treatment was limited to a
Fig. 2. Surface structure of polyester bre under high uence (5 pulses at 100 mJ/cm2). Fig. 1. Surface structure of untreated polyester bre.

very low level and hence no obvious ablation was resulted and no material would be removed or etched from the polyester surface signicantly under such irradiation [13]. Fibre diameter measurement is shown in Fig. 5 for highuence-irradiated samples only as no signicant change in bre diameter was recorded for low-uence counterparts. In the high-uence irradiation, an increase in the number of pulses was resulted with an increase in diameter reduction. For the rst 10 pulses, the reduction was almost insignicant but once the pulse count went beyond 20, the reduction became more severe. 3.4. Tensile strength and elongation The results of the breaking load and elongation-atbreak of the polyester samples with and without laser irradiation are listed in Table 2. Under the high-uence

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116 C.W. Kan / Optics & Laser Technology 40 (2008) 113119 Table 2 The breaking load and elongation-at-break of laser-irradiated polyester: high uence 10 pulses at 50 mJ/cm2 and low uence 2000 pulses at 6 mJ/cm2 Breaking load (N) Percentage of elongationat-break (%) 11.67 10.44(k11%) 11.30(k3%)

Control High-uence irradiated Low-uence irradiated

0.106 0.095(k10%) 0.103(k3%)

The percentages in the parentheses indicate the increase/decrease in the value of irradiated samples compared with the control.

Fig. 3. Surface structure of polyester bre under low uence (2000 pulses at 6 mJ/cm2).

Table 3 Yarn abrasion of laser-irradiated polyester: high uence 10 pulses at 50 mJ/cm2 and low uence 2000 pulses at 6 mJ/cm2 Mean revolutions % Changes over control k13 k10

25 Reduction in weight (%) 20 15 10 5 0 0 50 100 No. of laser pulses 150 200

Control High-uence irradiated Low-uence irradiated

68 59 61

Fig. 4. Weight reduction of polyester after laser irradiation (~: 50 mJ/cm2, : 150 mJ/cm2).

25 Diameter reduction (%) 20 15 10 5 0 0 50 100 150 200 250 300 No. of laser pulses

extensibility. Another reason may be due to the deposition of debris as the debris could give a harder surface to polyester, making it more rigid resulting in lower strength and elongation. After low-uence irradiation, no signicant change in tensile strength and elongation was observed. The small reduction in the breaking load and elongation of the irradiated sample has little meaning statistically. It may be argued that the ripples induced by irradiation will result in more weak points to the bre; hence the tensile strength should be reduced [8]. However, bearing in mind that the depth of ripples is in the range of the sub-micrometre level, as shown in Fig. 3, the weakening effect to the strength and elongation should be very little. 3.5. Yarn abrasion Table 3 shows the yarn abrasion results; a reduction of approximately 13% and 10% for high- and low-uenceirradiated polyester yarn was recorded, respectively. Unlike previous results, no obvious difference was noted between both the high and low uence of laser irradiation. The yarn abrasion tester employs the principle of using a rotary rod wrapped with abrasive paper creating abrasion against the yarn specimen. Hence, laser-irradiated yarn would obviously have a lower abrasion resistance since it is full of periodical ripple-like structures and these structures would largely reduce the contact areas between the abrasive paper and the yarn [9]. Also, these laser-developed structures induced more weak points to the yarn sample and therefore when the yarn was under tension, the bre arrangement would be changed resulting in lower yarn abrasion resistance.

Fig. 5. Fibre diameter change after laser irradiation: at 50 mJ/cm2.

laser irradiation, irradiation could reduce both the breaking load and elongation of the sample. The rate of reduction for both properties was similar in terms of percentage, which was about 10%. The reduction could be due to the fact that the induced high-uence ripples on the surface, as shown in Fig. 2, created more weak points to the bre and eventually reduced both strength and

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3.6. Bending property The bending properties have important effects on both the handle and tailoring performance of textile materials. Table 4 shows the bending properties of the laser-irradiated polyester yarn, including bending rigidity and bending hysteresis. The results in Table 4 indicated that the bending rigidity and bending hysteresis increased for both types of laser irradiations. A higher increment was observed for high-uence-irradiated samples as the bending rigidity and bending hysteresis increased by 20% and 50% respectively. Under low-uence irradiation, the increment was relatively small. The bending rigidity and bending hysteresis increased by 7% and 25% respectively. The increase in the bending properties may result in difculties in manufacturing, especially for the dramatic increase in bending hysteresis. Generally speaking, the smaller the values of the bending hysteresis, the better will be the fabric bending recovery ability. The tremendous increase in the bending properties of the laser-irradiated yarn may nally decrease the fabric exibility and elastic recovery from bending action [14], which may in turn affect the fabric tailorability, draping quality and wear. Highly skill operators may therefore be needed to deal with the problem and thus the cost of manufacturing may increase. Although the bre diameter was reduced after laser irradiation, the ripples were formed on the polyester bre surface. Thus, during the bending process, the ripples so formed on the polyester bre surface may increase the friction between the bre in the yarn which restricts the bending moment of yarn and hence the bending property changed. 3.7. Surface lustre Surface lustre is the term generally accepted to describe the glossiness of a textile material and is dened as the intensity of directionally reected light from a surface. The glossiness indexes of the polyester fabrics before and after laser irradiations were measured in both warp and weft directions as shown in Figs. 6 and 7 respectively. The glossiness distribution curves in warp and weft directions produced similar trends for the sample tested.
Table 4 The bending properties of laser-irradiated polyester: high uence 10 pulses at 50 mJ/cm2 and low uence 2000 pulses at 6 mJ/cm2 Bending rigidity, B (gfcm2/cm) Control High-uence irradiated Low-uence irradiated 0.0015 0.0018 (m20%) 0.0016 (m7%) Bending Hysteresis, 2HB (gfcm/cm) 0.0004 0.0006 (m50%) 0.0005 (m25%)

3.5 3 2.5 Glossiness 2 1.5 1 0.5 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 Recevier angle

Fig. 6. The glossiness distribution curve (warp direction) of laserirradiated polyester. n Control, } 5 pulses at 100 mJ/cm2 and o 2000 pulses at 6 mJ/cm2.

3.5 3 2.5 Glossiness 2 1.5 1 0.5 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 Recevier angle

Fig. 7. The glossiness distribution curve (weft direction) of laserirradiated polyester. n Control, } 5 pulses at 100 mJ/cm2 and o 2000 pulses at 6 mJ/cm2.

The percentages in the parentheses indicate the increase/decrease in the value of irradiated samples compared with the control.

No prominent peak value appeared in either direction where the glossiness in warp was slightly higher than that of the weft. Fig. 2 illustrates the effect of high-uence laser irradiation on the polyester bre surface. It was observed that the ripples structure was formed perpendicularly to the bre axis with the mean roll distance of approximately 1mm. While in the low-uence laser treatment, ripples were also formed but the effect was not as signicant as in the highuence treatment. High-uence-irradiated sample would have a lower level of glossiness index, whereas low-uenceirradiated counterparts would increase the overall glossiness index. Laser irradiation is claimed to largely lower the glossiness index of textile material with sharp peaks thus making the material more silk-like [15] because the surface of laser-irradiated area would diffuse the incident light more evenly and eventually reduce the specular reection. However, it is not known that why there would be an overall increase in the glossiness index for the low-uenceirradiated sample. At the present stage, the most possible explanation would be because the process of low-uence irradiation could be able to clean up the surface of the irradiated part such as removing the dust particles and minimizing the manufacturing defect by smoothing the surface. Such effects would eventually increase the glossiness index.

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118 C.W. Kan / Optics & Laser Technology 40 (2008) 113119 Table 6 Air permeability of laser-irradiated polyester: high uence 10 pulses at 50 mJ/cm2 and low uence 2000 pulses at 6 mJ/cm2 ml/(cm2s) Control High-uence irradiated Low-uence irradiated 19.6 20.9 21.1 % Changes over control m 6.6 m 7.7

3.8. Wetting Table 5 shows the vertical drop test result for both highand low-uence-irradiated samples. It was observed that high-uence laser irradiation increased greatly the wetting time of the polyester fabric from 470 to 4900 s (exceeding 900 s). The large increment in the wetting time was believed to be closely related to the ripple-like structure. The ripple structure increased the roughness of the surface and this kind of increased roughness enhanced the unwettability of the fabric, resulting in an increase in the wetting time. Researchers have experimentally proved that surface roughness decreases the wettability of a hydrophobic material [15]. Many models have been proposed in explaining this phenomenon. Besides, if the surface is sufciently rough, a liquid with a large contact angle may not completely wet the surface. This incompletely wetted surface provides room for air to be trapped between the liquid and solid interface (Fig. 8), resulting in a composite interface. This composite interface prevents water penetration and this mechanism has already been adopted by some Japanese manufacturers in producing high-tech water repellent textile materials. In addition, under high-uence laser irradiation, the surface of aromatic polymer-like polyester will normally result in the deposition of some yellow to black materials often known as debris. This debris was ionized and carbonrich materials nally condensed to form high aggregates [16,17], resulting in a more hydrophobic surface. Such reduced surface oxygen content may also be part of the reason for the increase in the wetting time. A reduced wetting time was observed for the lowuence-irradiated sample, which is completely opposite to the high-uence result. It means that the wettability of lowuence-irradiated sample has increased (hydrophilicity increased). The ripples induced by low uence were in the

range of nanometer level and it is reasonable to believe that air could not be able to be trapped inside the gaps between ripples due to size constraints. Hence, the effect of a composite interface could not take place. The increased surface oxygen content and the reduced contact angle measurement could help reduce the time for the droplets of water to sink into the sample. This is because the polar radicals of the low-uence-irradiated polyester have increased. This increased polarity will lead to the increase in the attraction force between the modied surface and the polar water molecules.

4. Air permeability Air permeability is one of the major properties of textile materials and is governed by factors like the fabric structure, density, thickness and surface characteristics. Table 6 indicates that both laser irradiations could increase the air permeability of the fabric samples. It is believed that the contributing factor is the surface modication of the bres [10]. The laser irradiation induced ripple structures on the surface of the bres, which eventual1y provided more air space between bres and fabric and therefore it is possible for more air to pass through the fabric resulting in better air permeabi1ity. No obvious difference between high- and low-uence irradiations was noted.

Table 5 Results of vertical drop test of laser-irradiated polyester: high uence 10 pulses at 50 mJ/cm2 and low uence 2000 pulses at 6 mJ/cm2 Seconds Control High-uence irradiated Low-uence irradiated 470 s 4 900 s 330 s % Changes over control Immeasurable 30

5. Conclusions In this paper, some common textiles properties of polyester were studied after the high- and low-uence laser surface morphological treatment. Some properties were affected signicantly while the others were found unchanged. In fact, depending on the end-uses of the materials, for example, increased wettability of polyester may be good for ordinary textile functions but bad for water resistant functional garments. It is therefore suggested that the correct selection of surface treatment parameters is of prime importance. In general, laser irradiation could not affect the bulk properties of a polymer due to its low penetration depth, and hence, the effect of the treatment on the bulk and structural properties are limited. However, the performance and comfort properties of the irradiated polyester could be largely affected by laser irradiation as these properties could have been changed considerably if the surface is modied.

Fig. 8. The effect of surface roughness on wetting.

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