用于纸基材料抗老化的纳米TiO_2制备及结构表征
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摘要
目的对纳米TiO_2进行有机无机改性,使其保持原有的抗紫外特性,同时降低光催化活性,实现对纸基材料的抗老化保护。方法以正硅酸乙酯(TEOS)为前驱体,通过溶胶-凝胶法在纳米TiO_2表面包覆纳米二氧化硅(SiO_2)壳层,再用硅烷偶联剂KH570进行有机改性,制备无机-有机复合微粒,对试样进行SEM, TEM, UV-Vis, XRD, FT-IR分析表征,探讨TEOS用量对复合微粒形貌、抗紫外效果以及光催化性的影响。结果经过改性后SiO_2以无定形态成功包覆于纳米TiO_2表面,且以Si—O—Ti键结合,复合微粒的分散性得到明显提高。包覆层的厚度与TEOS用量有关,随着TEOS用量的增加,在不影响复合微粒紫外屏蔽效果的同时,复合微粒的光催化性能明显降低。结论复合改性降低了纳米TiO_2的光催化性,而对抗紫外性的影响较小,这对于其在纸质文物抗老化保护液中的应用非常有利。
The work aims to conduct organic-inorganic modification of nano-TiO_2 to keep the original anti-UV properties and reduce the photocatalytic activity, so as to realize the anti-aging protection of paper-based materials. Sol-gel method was applied to prepare SiO_2 coatings on the surface of nano-TiO_2 with tetraethoxysilane(TEOS) as precursor and then silane coupling agent of γ-(Methacryloxypropyl) trimethoxy Silane(KH570) was used for organic modification to prepare inorganic-organic composite particles. The sample was characterized and analyzed by Scanning electron microscopy(SEM), Transmission electron microscope(TEM), Fourier transform infrared spectroscopy(FT-IR), X-ray Diffraction(XRD) and Ultraviolet-visible spectroscopy(UV-Vis). The influence of TEOS dosage on the microstructure, UV resistance and photocatalysis performance of composite particles was explored. The modified SiO_2 was ly coated on the surface of nano-TiO_2 in amorphous state and bonded as Si-O-Ti. The dispersibility of composite particles was improved obviously. The coating thickness was related to TEOS dosage. With the increase of TEOS dosage, the photocatalytic property of composite particles was significantly decreased, while the UV resistance capability almost remained the same. The composite modification of nano-TiO_2 reduces its photocatalytic activity, but has little effect on its UV resistance, which is very beneficial to its application in the anti-aging protection solution of paper cultural relics.
The work aims to conduct organic-inorganic modification of nano-TiO_2 to keep the original anti-UV properties and reduce the photocatalytic activity, so as to realize the anti-aging protection of paper-based materials. Sol-gel method was applied to prepare SiO_2 coatings on the surface of nano-TiO_2 with tetraethoxysilane(TEOS) as precursor and then silane coupling agent of γ-(Methacryloxypropyl) trimethoxy Silane(KH570) was used for organic modification to prepare inorganic-organic composite particles. The sample was characterized and analyzed by Scanning electron microscopy(SEM), Transmission electron microscope(TEM), Fourier transform infrared spectroscopy(FT-IR), X-ray Diffraction(XRD) and Ultraviolet-visible spectroscopy(UV-Vis). The influence of TEOS dosage on the microstructure, UV resistance and photocatalysis performance of composite particles was explored. The modified SiO_2 was ly coated on the surface of nano-TiO_2 in amorphous state and bonded as Si-O-Ti. The dispersibility of composite particles was improved obviously. The coating thickness was related to TEOS dosage. With the increase of TEOS dosage, the photocatalytic property of composite particles was significantly decreased, while the UV resistance capability almost remained the same. The composite modification of nano-TiO_2 reduces its photocatalytic activity, but has little effect on its UV resistance, which is very beneficial to its application in the anti-aging protection solution of paper cultural relics.
引文
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[16]LI C,SUN Y,CHENG M,et al.Fabrication and Characterization of a TiO2/Polysiloxane Resin Composite Coating with Full-thickness Super-hydrophobicity[J].Chemical Engineering Journal,2018,333:361-369.
[17]REN Y,CHEN M,ZHANG Y,et al.Fabrication of Rattle-type TiO2/SiO2 Core/Shell Particles with Both High Photoactivity and UV-shielding Property[J].Langmuir,2010,26(13):11391-11396.
[2]MOMENTI M M,GHAYEB Y,GHONCHEGI Z.Fabrication and Characterization of Copper Doped TiO2,Nanotube Arrays by in Situ Electrochemical Method as Efficient Visible-light Photocatalyst[J].Ceramics International,2015,41(7):8735-8741.
[3]SOLTANI M,ROHANI A A,RAMAZANI O,et al.UV-curable Coating Process on CMYK-printed Duplex Paperboard,Part II:Effects of Nano-TiO2 Modification[J].Bioresources,2016,11(1):1930-1940.
[4]JIANG B,HUANG Y D,ZHAO L W.Diffusion Process of an Ink Drop in Core-shell Silica-titania Pigment Particles[J].Materials&Design,2016,92:114-119.
[5]刘德飞,郑育英,黄慧民.水热法制备核壳型纳米TiO2/Al2O3粉体的研究[J].材料工程,2008(10):342-345.LIU De-fei,ZHENG Yu-ying,HUANG Hui-min.Hydrothermal Synthesis and Characterization of Core-shell TiO2/Al2O3 Nano Material[J].Journal of Materials Engineering,2008(10):342-345.
[6]赵冬梅.纳米二氧化钛表面改性及其对玻璃涂料性能影响的研究[D].北京:中国科学院大学,2013.ZHAO Dong-mei.Surface Modification of Nano-TiO2and Its Influence on the Performances of Glass Coatings[D].Beijing:University of Chinese Academy of Sciences,2013.
[7]SIKORA P,CENDROWSKI K,MARKOWSKA-SZCZUPAK A,et al.The Effects of Silica/Titania Nanocomposite on the Mechanical and Bactericidal Properties of Cement Mortars[J].Construction&Building Materials,2017,150:738-746.
[8]程学群,陈琳,杨丽霞,等.微波法改性纳米二氧化钛工艺及机理探讨[J].材料保护,2003,36(11):35-37.CHENG Xue-qun,CHEN Lin,YANG Li-xia,et al.Process and Mechanism of Nano Titanium Dioxide Modified by Microwave Irradiation[J].Materials Protection,2003,36(11):35-37.
[9]LIU J H,YU J,LU S J.Influence of KH570 on the Graft Modifying Nano-silica[J].Chinese Journal of Colloid&Polymer,2010,28(1):19-21.
[10]ZHOU Y,YU J,WANG X,et al.Preparation of KH570-SiO2 and Their Modification on the MF/PVAComposite Membrane[J].Fibers&Polymers,2015,16(8):1772-1780.
[11]BAI Y,LI Z,CHENG B,et al.Higher UV-shielding Ability and Lower Photocatalytic Activity of TiO2@SiO2/APTES and Its Excellent Performance in Enhancing the Photostability of Poly(P-phenylene Sulfide)[J].Rsc Advances,2017,7(35):21758-21767.
[12]张亮,陈胜利,王秀通,等.纳米CdTe/TiO2复合材料对304不锈钢的光生阴极保护行为[J].表面技术,2016,45(7):80-84.ZHANG Liang,CHEN Sheng-li,WANG Xiu-tong,et al.Nano-CdTe/TiO2 Composite Material for Photogenerated Cathodic Protection of 304 Stainless Steel[J].Surface Technology,2016,45(7):80-84.
[13]薛朝华,张平,姬鹏婷,等.TiO2/SiO2核壳结构微粒的合成及超疏水防紫外线功能织物的制备[J].陕西科技大学学报,2013,31(6):45-50.XUE Chao-hua,ZHANG Ping,JI Peng-ting,et al.Preparation of TiO2/SiO2 Core-shell Particles and Their Coating on Fibers for Superhydrophobic Textiles with UV-shielding Property[J].Journal of Shannxi University of Science&Technology,2013,31(6):45-50.
[14]WEN B,WANG F,ZHANG S M,et al.ZnO and ZnO-SiO2 Core-shell Structured Fillers on Properties of Polycarbonate Nanocomposites[J].Plastics Rubber&Composites,2010,39(9):419-424.
[15]尚超红,罗春荣,向礼琴,等.仙人球状Ag/TiO2@PMMA超材料的制备与纳米平板聚焦效应[J].材料导报,2013,27(8):1-4.SHANG Chao-hong,LUO Chun-rong,XIANG Li-qin,et al.Preparation and Nano Slab Focusing of Cactus-like Ag/TiO2@PMMA Metamaterial[J].Materials Review,2013,27(8):1-4.
[16]LI C,SUN Y,CHENG M,et al.Fabrication and Characterization of a TiO2/Polysiloxane Resin Composite Coating with Full-thickness Super-hydrophobicity[J].Chemical Engineering Journal,2018,333:361-369.
[17]REN Y,CHEN M,ZHANG Y,et al.Fabrication of Rattle-type TiO2/SiO2 Core/Shell Particles with Both High Photoactivity and UV-shielding Property[J].Langmuir,2010,26(13):11391-11396.