溶胶—凝胶技术在羊毛防毡缩整理中的应用研究
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摘要
溶胶-凝胶(Sol-Gel)技术是胶体化学中一项古老的技术,是在制备玻璃、陶瓷等无机材料领域中发展、成熟起来的。近些年来,这一技术已扩展到有机/无机复合材料中。目前国际上对它在纺织品上的应用研究刚刚起步。利用有机改性的金属醇盐制备的溶胶,可以在较低的处理温度下,在基质物表面形成均一性好、透明多孔、结合牢固,且具有一定柔顺性和弹性的薄膜,此薄膜可包覆功能性的材料,从而实现基质材料的表面改性和功能整理。
羊毛是具有典型鳞片结构的一种天然纤维,这一特殊结构使其具有与众不同的缩绒性。未经防缩处理的羊毛织物容易产生毡缩,并出现尺寸收缩、变形、增厚等不良现象,使织物丧失原有优异的服用性能。目前工业化的防毡缩技术主要是氯化-树脂法,可达到良好的防毡缩效果。但存在羊毛易泛黄和弹性受损等缺点,特别是会在废水排放中产生有机氯(AOX)污染,从而限制了这一技术的应用。
溶胶-凝胶技术属于非氯的环保型防毡缩技术,论文在本课题组原有的工作基础上,进一步深入探索了溶胶-凝胶技术在羊毛织物防毡缩功能整理上应用的可行性,并希望将其产业化。论文工作首先通过比较各种有机改性烷氧基硅烷的水解性能及其在羊毛织物上的防毡缩效果,在实验数据的基础上确定选用γ-缩水甘油醚氧丙基三甲氧基硅烷(GPTMS)作为烷氧基硅烷溶胶前驱体。同时分析研究了影响GPTMS溶胶的形成和稳定性的各项因素,如pH值、浓度、温度、溶剂等,提出了可以长期存放的制备GPTMS溶胶的最佳工艺条件。通过测定水洗(IWS TM No.31)后羊毛织物的面积收缩率,优选了羊毛织物整理过程中的工艺参数(包括pH值、工作液浓度、浸轧工艺、烘干和焙烘的时间及温度等),分析了影响羊毛织物整理效果、手感和耐久性的因素。
羊毛整理后的各项测试数据表明,经溶胶-凝胶处理后,透明多孔的网状薄膜均匀地沉积在羊毛纤维上,覆盖了羊毛的鳞片层,减小羊毛纤维的定向摩擦效,防毡缩效果达到国际羊毛局TM31的标准。
另外,论文工作还探索制备稳定的纳米水Al_2O_3分散的两种方法,研究了将纳米材料和有机改性硅溶胶复合的整理技术。结果表明,在GPTMS溶胶中混合纳米水Al_2O_3分散液,对羊毛织物的防毡缩性略有改善。
本论文的研究结果,对利用溶胶-凝胶技术结合纳米材料在纺织品的表面改性方面指出了一条新的可行之路,这将给纺织行业带来巨大的经济价值。
Sol-gel technique is one of venerable techniques in the neoteric colloid chemistry. It is presently the initiative step where sol-gel technique is used in functional finishing of fabric. When organic modified silane is applied to textile fabric, sol can produce an even, transparent, porous and functional membrane with flexibility on a variety of substrates, which can be filled with functional materials. So the surface modification or functional finishing of substrates can be carried out by this way.
Wool is an important textile raw material and has a lot of excellent features, such as soft handle, good elasticity, excellent hygroscopy. Wool can be used to make all kinds of superior fabrics. But because of the shrinking of wool, fabric shrinks during home-laundering, which greatly affects the use of fabric. Due to environmental pollute by using Chlorine/Resin process with higher values of AOX in wastewater for shrink-resist treatments, the researches and techniques focus on non-chlorine shrink-resist treatments.
Sol-gel technique, as a non-chlorine easy care finishing of wool, is investigated in this paper. On the basis of former research, the feasibility of this new application is further discussed.
GPTMS (3-glycidyloxypropyltrimethoxysilane) is prehydrolyed and then the finishing of anti-felting of wool fabric is carried out by pad-dry-cure process. The influence of sol forming and sol stability, pH value, concentration, temperature and different solvents, the parameter of pad-dry-curing process (pH values, concentration, curing temperature and curing procedure), as well as the influence of treating qualities on handle and durability of treated wool is researched. By means of comparing the shrink proof properties of treated fabric, shrink-resist treatment is optimized. Other physical properties of treated and untreated wool fabrics is measured and evaluated. The SEM pictures are taken simultaneously to investigate the surface structures with and without sol-gel treating.
Based on the experiment result, after sol-gel treatment, a transparent netted thin film deposited on the surface of the wool may decrease the levelness and close the scales effectively, which endows wool fibers an anti-felting property, which could measure up the standard of shrink proof of IWS TM No.31.
Different methods of preparing stable nano-Al_2O_3 disperse solution and nano-materials combined with sol-gel technique applied in shrink-resist treatment are also investigated.
The conclusion in the thesis indicated a feasible method to surface modification of textiles by utilizing nano-materials combined with sol-gel technique. It is an innovation and will bring the whole textile industry considerable economic effect.
羊毛是具有典型鳞片结构的一种天然纤维,这一特殊结构使其具有与众不同的缩绒性。未经防缩处理的羊毛织物容易产生毡缩,并出现尺寸收缩、变形、增厚等不良现象,使织物丧失原有优异的服用性能。目前工业化的防毡缩技术主要是氯化-树脂法,可达到良好的防毡缩效果。但存在羊毛易泛黄和弹性受损等缺点,特别是会在废水排放中产生有机氯(AOX)污染,从而限制了这一技术的应用。
溶胶-凝胶技术属于非氯的环保型防毡缩技术,论文在本课题组原有的工作基础上,进一步深入探索了溶胶-凝胶技术在羊毛织物防毡缩功能整理上应用的可行性,并希望将其产业化。论文工作首先通过比较各种有机改性烷氧基硅烷的水解性能及其在羊毛织物上的防毡缩效果,在实验数据的基础上确定选用γ-缩水甘油醚氧丙基三甲氧基硅烷(GPTMS)作为烷氧基硅烷溶胶前驱体。同时分析研究了影响GPTMS溶胶的形成和稳定性的各项因素,如pH值、浓度、温度、溶剂等,提出了可以长期存放的制备GPTMS溶胶的最佳工艺条件。通过测定水洗(IWS TM No.31)后羊毛织物的面积收缩率,优选了羊毛织物整理过程中的工艺参数(包括pH值、工作液浓度、浸轧工艺、烘干和焙烘的时间及温度等),分析了影响羊毛织物整理效果、手感和耐久性的因素。
羊毛整理后的各项测试数据表明,经溶胶-凝胶处理后,透明多孔的网状薄膜均匀地沉积在羊毛纤维上,覆盖了羊毛的鳞片层,减小羊毛纤维的定向摩擦效,防毡缩效果达到国际羊毛局TM31的标准。
另外,论文工作还探索制备稳定的纳米水Al_2O_3分散的两种方法,研究了将纳米材料和有机改性硅溶胶复合的整理技术。结果表明,在GPTMS溶胶中混合纳米水Al_2O_3分散液,对羊毛织物的防毡缩性略有改善。
本论文的研究结果,对利用溶胶-凝胶技术结合纳米材料在纺织品的表面改性方面指出了一条新的可行之路,这将给纺织行业带来巨大的经济价值。
Sol-gel technique is one of venerable techniques in the neoteric colloid chemistry. It is presently the initiative step where sol-gel technique is used in functional finishing of fabric. When organic modified silane is applied to textile fabric, sol can produce an even, transparent, porous and functional membrane with flexibility on a variety of substrates, which can be filled with functional materials. So the surface modification or functional finishing of substrates can be carried out by this way.
Wool is an important textile raw material and has a lot of excellent features, such as soft handle, good elasticity, excellent hygroscopy. Wool can be used to make all kinds of superior fabrics. But because of the shrinking of wool, fabric shrinks during home-laundering, which greatly affects the use of fabric. Due to environmental pollute by using Chlorine/Resin process with higher values of AOX in wastewater for shrink-resist treatments, the researches and techniques focus on non-chlorine shrink-resist treatments.
Sol-gel technique, as a non-chlorine easy care finishing of wool, is investigated in this paper. On the basis of former research, the feasibility of this new application is further discussed.
GPTMS (3-glycidyloxypropyltrimethoxysilane) is prehydrolyed and then the finishing of anti-felting of wool fabric is carried out by pad-dry-cure process. The influence of sol forming and sol stability, pH value, concentration, temperature and different solvents, the parameter of pad-dry-curing process (pH values, concentration, curing temperature and curing procedure), as well as the influence of treating qualities on handle and durability of treated wool is researched. By means of comparing the shrink proof properties of treated fabric, shrink-resist treatment is optimized. Other physical properties of treated and untreated wool fabrics is measured and evaluated. The SEM pictures are taken simultaneously to investigate the surface structures with and without sol-gel treating.
Based on the experiment result, after sol-gel treatment, a transparent netted thin film deposited on the surface of the wool may decrease the levelness and close the scales effectively, which endows wool fibers an anti-felting property, which could measure up the standard of shrink proof of IWS TM No.31.
Different methods of preparing stable nano-Al_2O_3 disperse solution and nano-materials combined with sol-gel technique applied in shrink-resist treatment are also investigated.
The conclusion in the thesis indicated a feasible method to surface modification of textiles by utilizing nano-materials combined with sol-gel technique. It is an innovation and will bring the whole textile industry considerable economic effect.
引文
[1]田志荣,赵先丽.羊毛防防缩整理剂WSP在精纺毛织物中的应用[J].毛纺科技,2000,(4):37～40.
[2]王菊生,孙凯.染整工艺原理第二册[M].北京:纺织工业出版社,1982:240.
[3]林子务等.毛织物的防缩整理[J].广西纺织科技,1998,(2):24～27.
[4]罗敏,等.溶胶-凝胶法与固色整理[J].国际纺织导报,2004,(1):72～76.
[5]Piere A.C.“Introduction to Sol-Gel Processing”[M].Kluwer Academic Publishers,Boston,Dordrecht,London,1998:1～4.
[6]Mahltig B.,B(o|¨)ttcher H.Refining of Textiles by Nanosol Coating[J].Melliand Textilberichte,2002,(4):E50～51.
[7]钱海霞,等.Sol—Gel法合成有机/无机纳米复合材料的研究进展[J].材料导报,1993,(5):443～450.
[8]张剑锋,等.溶胶—凝胶法制备高分子/无机复合材料[J].功能材料,2004,(4):357～360.
[9]张永化等.Sol-Gel法制备有机/无机纳米复合材料的进展[J].高分子材料科学与工程,1997,(4):14～18.
[10]Zhou Han.Study of Preparation of Organic/Inorganic Hybrid Biomaterials Through Sol-Gel Process[J].Chinese J.Biomedicals Engineering(English Edition),1997,(4):275～276.
[11]成凤桂等.Sol—Gel固定磷钨酸催化合成乙酸丁酯[J].中南民族学院院报(自然科学版),2001,(2):68～72.
[12]吴洪等.溶胶—凝胶法包埋生物活性分子[J].现代化工,2002,(7):60～63.
[13]张立德,牟季美.纳米材料和纳米结构[M].科学出版社,2001:136～137.
[14]B(o|¨)ttcher P.Sol-Gel Coating on Textiles—Possibilities and Problems[J].Textilveredlung,2001,(36):19～21.
[15]Mahltig B.,B(o|¨)ttcher P.,Light Fading and Wash Fastness of Dyed Nanosol-Coated Textiles[J].Textile Res.J.,2004,74(60):521～527.
[16]Yan kelu,Zhang Yapeng,Song Fengxia,Karola Schaefer.Hartwig Hoecker Permanent Finishing of UV Protecting Textiles with Nano-Particles by Using the Sol-Gel Technique[M].DWI Reports,2003,V127.
[17]张亚鹏.溶胶-凝胶技术在织物抗紫外功能整理中的应用研究[M].东华大学硕士学位论文,2003(2).
[18]陈水林,徐鹏.棉织物的溶胶凝胶抗紫外整理方法[M].200410053058.3.
[19]Luo Min,Zhang xiaoli,Chen Shuilin.Enhancing the wash fastness of dyeing by a sol-gel process[J].Coloration Technology(UK),2003,(119):297～300.
[20]杜鹃.溶胶凝胶法的固色作用[M].东华大学博士学位论文,2005(5).
[21]Textor T.;Bahner T.;Schollmeyer E.,Inorganic organic hybrid polymers to protect technical textiles[J].Technical Textiles,2002,(45),E103～105.
[22]Textor T.,Bahners T,Schollmeyer E.Coating Wool and Silk by Sol-Gel-Technique[M].The 10~(th)International Wool Textile Research Conference,2000,F1-12:1～5.
[23]Textor T.,Bahners T,Schollmeyer E.Surface modification of textile fabrics by coating based on the Sol-Gel process[J].Melliand Textilberichte,1999,(10):E229(G847～848).
[24]Textor T.,Bahners T,Schollmeyer E.Organically modified ceramics for coating textile materials[J].Progr Colloid Polym Sci,2001,(117):76～79.
[25]Yoldas B.E.,J.Non-Cryst[J].Solids,1986,81:227～234.
[26]吴翠明,等.无机—有机复合膜的制备技术进展[J].无机材料学报,2002,(4):641～648.
[27]章基凯,等.有机硅材料[M].中国物质出版社,1999:339～389.
[28]周宁琳.有机硅聚合物导论[M].科学出版社,2000:168～195.
[29]Smaihi,M.;Jermoumi,T.;Marignan,J.;Noble,R.D.,Organic-inorganic gas separation membranes:preparation and characterization[J].J.Membr.Sci.,1996,(116):211～220.
[30]莫百春.纳米材料在功能纺织品上的应用[J].国外丝绸,2003,(2):33～35.
[31]高善民,孙树声.纳米材料的制备[J].现代化工,1999,(10):46～48.
[32]王春兰译.纺织品功能整理(下册)[M].纺织工业出版社,1999年5月第一版:31～35.
[33]王维,李伟.精防毛织品防缩整理工艺技术应用与实践[J].毛纺科技,1998,(5):8～12.
[34]林子务,等.毛织物的防缩整理[J].广西纺织科技,1998,(2):24～27.
[35]姚金波,等.毛纤维新型整理技术[M].中国纺织出版社,2000年4月,第一版:1～21.
[36]周公度.结构与物性[M].高等教育出版社,2000,第二版:304～305.
[37]夏海涛.物理化学[M].哈尔滨工业大学出版社,2004.
[38]Fardad M.A.;Yeatman E.M.;et al.Effect of H_2O on structure of acid-catalyzed SiO_2 Sol-Gel films[J].J.Non-Cryst.Solids,1995,(183):260～267.
[39]Pope E.J.A.;Mackenzie J.O.J.Non-Cryst.Solids[J].J.Non-crystalline Solids,1986,(87):188～198.
[40]Sakka S.,In Ultrastructure Processing of Advanced Ceramics[M],Wiley,NY,1988:159.
[41]Fardad M.A.,Catalysts and the structure of SiO_2 Sol-Gel films[J].J.Mater.Sci.,2000,(35):1835～1841.
[42]R.Nass,E.Arpac,W.Glaubitt,H.Schmidt,Modelling of Ormocer Coating by Processing[J],J.of Non-crystalline Solids,1990,(121):370.
[43]周艺,何小川,王炎根.Tween-80和SDBS对纳米TiO_2在水溶液中分散稳定性的影响[J].长沙电力学院学报(自然科学版),2002,(4):72～75.
[2]王菊生,孙凯.染整工艺原理第二册[M].北京:纺织工业出版社,1982:240.
[3]林子务等.毛织物的防缩整理[J].广西纺织科技,1998,(2):24～27.
[4]罗敏,等.溶胶-凝胶法与固色整理[J].国际纺织导报,2004,(1):72～76.
[5]Piere A.C.“Introduction to Sol-Gel Processing”[M].Kluwer Academic Publishers,Boston,Dordrecht,London,1998:1～4.
[6]Mahltig B.,B(o|¨)ttcher H.Refining of Textiles by Nanosol Coating[J].Melliand Textilberichte,2002,(4):E50～51.
[7]钱海霞,等.Sol—Gel法合成有机/无机纳米复合材料的研究进展[J].材料导报,1993,(5):443～450.
[8]张剑锋,等.溶胶—凝胶法制备高分子/无机复合材料[J].功能材料,2004,(4):357～360.
[9]张永化等.Sol-Gel法制备有机/无机纳米复合材料的进展[J].高分子材料科学与工程,1997,(4):14～18.
[10]Zhou Han.Study of Preparation of Organic/Inorganic Hybrid Biomaterials Through Sol-Gel Process[J].Chinese J.Biomedicals Engineering(English Edition),1997,(4):275～276.
[11]成凤桂等.Sol—Gel固定磷钨酸催化合成乙酸丁酯[J].中南民族学院院报(自然科学版),2001,(2):68～72.
[12]吴洪等.溶胶—凝胶法包埋生物活性分子[J].现代化工,2002,(7):60～63.
[13]张立德,牟季美.纳米材料和纳米结构[M].科学出版社,2001:136～137.
[14]B(o|¨)ttcher P.Sol-Gel Coating on Textiles—Possibilities and Problems[J].Textilveredlung,2001,(36):19～21.
[15]Mahltig B.,B(o|¨)ttcher P.,Light Fading and Wash Fastness of Dyed Nanosol-Coated Textiles[J].Textile Res.J.,2004,74(60):521～527.
[16]Yan kelu,Zhang Yapeng,Song Fengxia,Karola Schaefer.Hartwig Hoecker Permanent Finishing of UV Protecting Textiles with Nano-Particles by Using the Sol-Gel Technique[M].DWI Reports,2003,V127.
[17]张亚鹏.溶胶-凝胶技术在织物抗紫外功能整理中的应用研究[M].东华大学硕士学位论文,2003(2).
[18]陈水林,徐鹏.棉织物的溶胶凝胶抗紫外整理方法[M].200410053058.3.
[19]Luo Min,Zhang xiaoli,Chen Shuilin.Enhancing the wash fastness of dyeing by a sol-gel process[J].Coloration Technology(UK),2003,(119):297～300.
[20]杜鹃.溶胶凝胶法的固色作用[M].东华大学博士学位论文,2005(5).
[21]Textor T.;Bahner T.;Schollmeyer E.,Inorganic organic hybrid polymers to protect technical textiles[J].Technical Textiles,2002,(45),E103～105.
[22]Textor T.,Bahners T,Schollmeyer E.Coating Wool and Silk by Sol-Gel-Technique[M].The 10~(th)International Wool Textile Research Conference,2000,F1-12:1～5.
[23]Textor T.,Bahners T,Schollmeyer E.Surface modification of textile fabrics by coating based on the Sol-Gel process[J].Melliand Textilberichte,1999,(10):E229(G847～848).
[24]Textor T.,Bahners T,Schollmeyer E.Organically modified ceramics for coating textile materials[J].Progr Colloid Polym Sci,2001,(117):76～79.
[25]Yoldas B.E.,J.Non-Cryst[J].Solids,1986,81:227～234.
[26]吴翠明,等.无机—有机复合膜的制备技术进展[J].无机材料学报,2002,(4):641～648.
[27]章基凯,等.有机硅材料[M].中国物质出版社,1999:339～389.
[28]周宁琳.有机硅聚合物导论[M].科学出版社,2000:168～195.
[29]Smaihi,M.;Jermoumi,T.;Marignan,J.;Noble,R.D.,Organic-inorganic gas separation membranes:preparation and characterization[J].J.Membr.Sci.,1996,(116):211～220.
[30]莫百春.纳米材料在功能纺织品上的应用[J].国外丝绸,2003,(2):33～35.
[31]高善民,孙树声.纳米材料的制备[J].现代化工,1999,(10):46～48.
[32]王春兰译.纺织品功能整理(下册)[M].纺织工业出版社,1999年5月第一版:31～35.
[33]王维,李伟.精防毛织品防缩整理工艺技术应用与实践[J].毛纺科技,1998,(5):8～12.
[34]林子务,等.毛织物的防缩整理[J].广西纺织科技,1998,(2):24～27.
[35]姚金波,等.毛纤维新型整理技术[M].中国纺织出版社,2000年4月,第一版:1～21.
[36]周公度.结构与物性[M].高等教育出版社,2000,第二版:304～305.
[37]夏海涛.物理化学[M].哈尔滨工业大学出版社,2004.
[38]Fardad M.A.;Yeatman E.M.;et al.Effect of H_2O on structure of acid-catalyzed SiO_2 Sol-Gel films[J].J.Non-Cryst.Solids,1995,(183):260～267.
[39]Pope E.J.A.;Mackenzie J.O.J.Non-Cryst.Solids[J].J.Non-crystalline Solids,1986,(87):188～198.
[40]Sakka S.,In Ultrastructure Processing of Advanced Ceramics[M],Wiley,NY,1988:159.
[41]Fardad M.A.,Catalysts and the structure of SiO_2 Sol-Gel films[J].J.Mater.Sci.,2000,(35):1835～1841.
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