Tao Fan, Xiaomeng Han, Zulan Liu, Lanqian Li, Yiping Li, Ming Lu

(1.Chongqing Engineering Research Center of Biomaterial Fiber and Modern Textile,Chongqing 400716,China;2.College of Textile Garment, Southwest University, Chongqing, 400716, China)



UV-Blocking Property of Silk Fabrics Coate with ZnO Nanorod arrays

Tao Fan1,2, Xiaomeng Han1,2, Zulan Liu1,2, Lanqian Li1,2, Yiping Li1,2, Ming Lu1,2

(1.Chongqing Engineering Research Center of Biomaterial Fiber and Modern Textile,Chongqing 400716,China;2.College of Textile Garment, Southwest University, Chongqing, 400716, China)

The shielding against the UV radiation is one of the practical requirements for the textile industry. The in-situ synthesis process of ZnO nanorod arrays on silk fabric by the application of a hydrothermal method was described in this paper. Experimental parameters (concentration, temperature, time) were adjusted systematically to obtain the optimum. The results indicated that ZnO nanorod arrays grew well on silk fabric surface and enhanced UV-blocking property of the silk fabric.

ZnO nanorod array Silk fabric UV - blocking

0　Introduction

UV-blocking property is one of important issues of textile industry. The UV radiation transmitted through the fabric interacts with the skin and can induce acute and chronic illnesses, as skin damage and allergies[1]. The UV-A radiation (100-280 nm) can induce a very high damage of the human skin, the UV-B radiation (280-320 nm) pigments of epidermal melanoma or skin cancer, and UV-C radiation (320-400 nm) deep penetration induces skin premature aging[2]. Zinc oxide (ZnO) anano-particle are semiconductor material and widely used due to their particular physical and chemical properties[3-7], such as Nano-particle has surface effect, quantum dimension effect, and macro quantum effect and so on. ZnO is known as a UV-blocking material[8], especially in the UVA region. At present, One-dimensional ZnO nanostructures have been synthesized by a wide variety of techniques, including chemical methods[9,10], physical vapor deposition[11], pulsed laser deposition and so on. Among them, hydrothermal technique is a low cost, green and scalable method for the fabrication of ZnO nanostructures. In this paper, hydrothermal method was applied to grow ZnO nanorod arrays on silk fabric. Parameters of growing ZnO nanorod arrays on silk fabrics were adjusted systematically to obtain the optimal UV-blocking properties. The scanning electron microscopy (SEM) images of fabric samples were taken to study the surface morphology of pure silk and ZnO-coated silk fabrics. Energy-dispersive X-ray spectrometry (EDS) is applied to observe the elements of the silk fabric treated with ZnO nanorod arrays. UPF and UV transmittance at various waves were used to evaluate UV-blocking property.

1　Experiment

1.1Materials

Silk fabrics were purchased from the market of China. Ethyl alcohol was obtained from Zhejiang Tianbao Technology Development Co.Ltd. Zinc acetate, Zinc nitrate, sodium hydroxide and hexamethylenetetramine (99%, HMTA) was purchased from the Tianjin Guangfu Technology Development Co. Ltd. All reagents were of analytical grade and were used without further purification.

1.2Preparation of layers of Zno seeding on fabrics

1.35g of zinc acetate was slowly added into 60 mL ethyl alcohol under vigorous stirring and at 60℃. In order to get ZnO/Zn(OH)2colloid, sodium hydroxide/ethyl alcohol solution prepared (0.75gNaOH/65ml alcohol) was blended with the above solution drop by drop with violent stirring at 60℃. Silk fabrics were immersed into the colloidal solution mentioned previously for 2min at room temperature, followed by nipping. After that, fabrics were drid at 80℃ for 10 min. The process was repeated for several times until a smooth and homogeneous layer of ZnO seeds stuck to the surface of silk fabrics.

1.3Preparation of Samples used in this Study

100 mL zinc ion solution was prepared at a stainless steel tank containing different concentrations (0,0.0003,0.001,0.003,0.01mol) of zinc nitrate hexahydrate (Zn(NO3)2·6H2O) in addition to equal to the mole number of hexamethylenetetramine (HMTA:C6H12N4). After that, the sample with ZnO seeds layers was immersed in the above solution and heated while being stirred. In order to obtained the optimum conditions of grawing of ZnO nanorod arrays, different treatment time (30, 60, 120, 180min) and treatment temperature (30, 60, 90℃) were controlled. Then, treated samples were dried at 70℃ for 1 hour. Finally, samples treated were dried at 70℃ for 1 hour.

1.4Analytical Method

The scanning electron microscopy (SEM) images of fabric samples were taken by an FEI Quanta-250 scanning electronic microscope to study the surface morphology of pure silk and ZnO-coated silk fabrics. Energy-dispersive X-ray spectrometry (EDS) is an analytical technique used for chemical characterization of a sample and detection of the elements using X-rays. A TU-1901 UV/Vis spectrometer (Beijing general analysis general instrument co., Ltd.) was employed for transmittance measurements.

2　Results and Discussion

2.1Morphology of Samples

Fig.1 exhibits the surface morphologies of untreated samples and samples treated with ZnO nanorod arrays.

将1424例到我院诊断冠心病的患者作为研究主体，研究时间选取为2017年1月1日—2018年1月1日，将冠脉造影检查作为诊断金标准，全部患者均行256排螺旋CT冠脉成像检查。参与本实验的1424例冠心病患者中，男性患者为769例，患者的年龄在50～74岁之间，患者的平均年龄为（62.99±4.25）岁，女性患者为655例，患者的年龄在52～75岁之间，患者的平均年龄为（63.07±4.36）岁。

Fig. 1SEM images of (a)the sanple without any treatments, (b)the sample treated with ZnO.

It is clearly found that the surface of original silk sample is smooth and clean in Fig.1(a). After the treatment, the treated silk samples show a coarse surface for a layer of ZnO nanorod arrays film in Fig.1(b). ZnO nanorod arrays with alignment and compactness which was grown at 0.003mol/L zinc acetate with 90℃ for 1 hour. Diameter of ZnO nanorod is 100-300nm approximately, which can be caused by crystal growth of ZnO.

2.2EDS spectrum

Fig. 2EDS of (a)the sanple without any treatments, (b)the sample treated with ZnO.

The chemical composition of the ZnO Nanorod arrays coated silk fabric is further ascertained by the EDS shown in Fig.2. Results indicate that zinc element is introduced into treated silk. The mass ratio of zinc element is 19.90%, furtherly suggesting that ZnO is certainly deposited on the surface of silk fibers.

2.3UV-Blocking Property of Samples

Fig.3-5 displays ultra-violet protection factor (UPF) of sample via surface finishing. UPF is defined as the ratio of the potential ultraviolet radiation effect to the actual ultraviolet radiation effect by the radiation transmitted through the fabrics.

Fig. 3The effect of concentration of Zn(NO3)2on UV-blocking of fabrics.

Fig. 4The effect of temperature on UV-blocking of fabrics.

Fig.5The effect of time on UV-blocking of fabrics.

The untreated silk fabrics show a UPF of 7.92. All the silk fabrics assembled with ZnO Nanorod array layers show UPF value of 50. These data indicate that silk fabrics already have UV-blocking performance. After being treated with ZnO, samples show a great UPF of 50 which is completely in accordance with national standards.

Apart from the UPF, another important parameter to assess the UV-blocking property of a fabric is transmission between 200 and 400 nm of UV radiation region. The average transmittance values of UV-A (315-400 nm) and UV-B (280-315 nm) are given in Fig.5-7.

Fig.6The effect of concentration of Zn(NO3)2on UV-blocking in different wave band.

After coated with ZnO Nanorod array layers, the surface of modified silk fabrics shows typical UV blocking behavior. The transmittance percentage value decreased rapidly from 7.89% to 0.24% in UVA band, from 8.06% to 0.24 in UVB band when the concentration of zinc ion increased from 0 to 0.1 mol/L.

Fig.7The effect of temperature on UV-blocking in different wave band.

The Transmittance of the treated silk fabrics is shown in Fig.7. The ZnO-coated silk fabrics have a great capability of shielding ultraviolet rays owing to the intrinsic UV-absorption property of ZnO nanocrystalline. The transmittance percentage of ZnO-coated silk fabrics decreased significantly increasing the temperature of ZnO crystal growth. This advanced shielding ultraviolet rays property may be ascribed to better ZnO crystal structure, which improve reflection and absorption towards ultraviolet rays.

Fig.8The effect of time on UV-blocking in different wave band.

Fig.8 is the effect of time on UV-blocking in different wave band. It is obviously that time of ZnO crystal grownth has little effect on the ultraviolet ray transmittance percentage of the treated samples.

3　Conclusion

Acknowledgments

This work was financially supported by the Fundamental Research Funds for the Central Universities (XDJK2013B026), National Training Programs of Innovation and Entrepreneurship for Undergraduates (201410635013).

References

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纳米棒状氧化锌整理蚕丝织物的抗紫外性能

樊涛1,2, 韩晓蒙1,2, 刘祖兰1,2, 李兰倩1,2, 刘一萍1,2, 卢明1,2

(1.西南大学 纺织服装学院, 重庆北碚 400716；2.重庆市生物质纤维材料与现代纺织工程技术研究中心, 重庆北碚 400716)

轻薄蚕丝织物具有较高的紫外线透过率，有必要提高蚕丝织物的抗紫外线能力。采用水热法将纳米棒状氧化锌原位组装于蚕丝织物表面，探讨了锌离子浓度、氧化锌晶体生长温度和时间对织物抗紫外性的影响。结果表明，蚕丝织物表面可以形成氧化锌纳米棒阵列，以及整理后蚕丝织物的UPF值在50以上，具有良好的抗紫外性能，。

氧化锌纳米棒阵列蚕丝织物抗紫外性

TS101

A

1008-5580(2016)03-0052-05

TS101 Document code: A Article ID: 1008-5580( 2016) 03-0052-05

date：2016-04-20

Ming Lu(1978-)，Male,Associated professor.