【作者】 殷允杰；

【导师】 王潮；

【作者基本信息】 江南大学 ， 纺织工程， 2013， 博士

【摘要】 纺织品印染污染严重、能耗大、工艺繁琐，使得整个纺织行业面临的压力越来越大。印染行业对现代织物加工提出了生态、节能减排、高产品附加值、回收再利用等技术革新要求，要求织物加工节能省水，无废水排放，能通过简短工艺实现织物的功能化、智能化加工，提高产品附加值，并实现废弃纤维或织物的绿色回收和再利用等。基于溶胶-凝胶原位修饰技术将色素、硅烷偶联剂、TiO₂等杂化到硅溶胶中，从分子层次上设计并分别构筑色素杂化SiO₂溶胶、X-Si（OC2H5）3/SiO₂杂化溶胶、TiO₂/SiO₂杂化溶胶等体系，通过旋转涂层、静电自组装等方法对织物基材进行表面功能改性，赋予织物优良的颜色、牢度、力学等性能等。同时通过功能硅烷偶联剂等的杂化作用实现改性织物的疏水疏油、润湿可控、抗菌、防紫外等功能，旨在解决织物湿处理过程中工艺繁琐、污染严重、能耗大等问题，为印染加工技术提供新途径。主要结论如下：通过将染料和涂料原位杂化到SiO₂溶胶中制备色素杂化硅溶胶，用于织物改性以赋予织物颜色并改善织物的色牢度。通过分析染料和涂料杂化SiO₂溶胶的稳定性、颜色等，研究了染料和涂料杂化SiO₂溶胶在织物上成膜后对织物颜色和牢度性能的改善作用。染料或涂料杂化到SiO₂溶胶后体系最大吸收波长（λmax）没有发生变化。染料和涂料杂化SiO₂溶胶薄膜表面会有较大突起，其粒径与对应的杂化SiO₂溶胶中的粒径尺寸相接近。C.I.直接红23和C.I.涂料红23杂化硅溶胶染色织物K/S值分别较直接染色对照样提高了11.1%和45.4%，而且织物颜色λmax仍然无变化，说明染料或涂料发色基团织物改性过程中没有发生变化。染料杂化SiO₂溶胶染色织物干湿摩擦牢度分别提高1级；C.I.涂料红23杂化SiO₂溶胶染色织物湿摩擦牢度提高了半级，表明色素杂化SiO₂溶胶改性可在完成织物染色的同时并达到固色目的，实现染色固色一步法工艺。为赋予织物疏水或疏油性，将十六烷基三甲氧基硅烷（HTEOS）、γ-氯丙基三乙氧基硅烷（CPTS）、十三氟辛基三乙氧基硅烷（FAS）原位杂化到硅溶胶中，并用于处理棉、丝绸、羊毛等纤维织物，同时将C.I.直接红23杂化到硅溶胶中制备CPTS/SiO₂色素杂化溶胶，并通过旋转涂层方式实现棉织物着色，使织物同时具有良好的颜色性能和疏水性。棉织物经HTEOS/SiO₂杂化溶胶改性后接触角达到139.8°，耐静水压从原来的1.8KPa增大到4.1KPa。棉织物经色素杂化硅溶胶改性后，接触角增大到112.4°；当棉织物经CPTS/SiO₂色素杂化溶胶处理后，接触角增大到131.5°；织物耐静水压值为4.5KPa，与未处理棉织物耐静水压值相比增大136.7%。FAS/SiO₂杂化溶胶对织物改性后，棉、丝绸和羊毛织物对辣椒油的接触角分别为98.5°、111.6°和122.2°。染色织物经FAS/SiO₂杂化溶胶处理后，织物K/S值变化率小于8%。与用直接染料液直接染织物色K/S值3.95相比，经CPTS/SiO₂色素杂化溶胶改性织物的K/S值提高到5.15，提高了30.4%。经C.I.直接红23杂化硅溶胶改性织物干湿摩擦牢度分别提高到3级和2-3级，水洗变色和沾色牢度分别提高到3级和3-4级，证明了CPTS/SiO₂色素杂化溶胶一步法处理织物的可行性。基于棉织物防紫外/抗菌复合功能以及分散染料转移印花性能，利用正硅酸四乙酯（TEOS）、钛酸四正丁酯（TBT）、多聚季铵盐制备了阳离子TiO₂/SiO₂杂化溶胶并用于织物改性。从TEM可看出阳离子TiO₂/SiO₂杂化溶胶粒子呈椭圆形，杂化溶胶前驱体TEOS和TBT会发生脱水缩合，形成Si-O-Si、Ti-O-Ti和Si-O-Ti等结构。从XPS谱图可知，未经处理棉织物含56.4%的炭和43.6%的氧，织物改性后表面含33.2%炭元素、48.4%氧元素、18.1%硅元素含量、0.3%钛元素。未经溶胶改性棉织物全波段紫外透过率URT高于7.0%，而经杂化溶胶改性棉织物大部分波段URT低于5.0%，水洗30次后URT仍然低于6.0%。棉织物经阳离子TiO₂/SiO₂杂化溶胶改性后对大肠杆菌和金黄色葡萄球菌的抗菌率分别达到90.9%和95.2%，水洗30次后抗菌率仍可达到61.1%和71.5%，说明阳离子TiO₂/SiO₂杂化溶胶优异的防紫外/抗菌复合功能以及耐洗性。未经改性棉织物分散染料转移印花K/S值为2.4，织物经阳离子TiO₂/SiO₂杂化溶胶改性后其转移印花K/S值增大到10.1；未经改性棉织物分散染料转移率仅为21%，而经阳离子TiO₂/SiO₂杂化溶胶改性再热转移印花，分散染料转移率为89%。改性后的棉织物转移印花K/S值曲线较尖锐，织物颜色鲜艳度高，而且其对应的λmax没有变化，织物颜色色相没受影响。从转移的印花图案可看出未改性棉织物转移印花图案清晰度较差，颜色深度低，而经改性后棉织物转移印花图案鲜艳，线条精细，颜色较深。经阳离子TiO₂/SiO₂杂化溶胶改性，织物湿摩擦牢度由4级增大到4-5级，但织物的拉伸性能有所下降。为了提高织物抗菌防紫外复合功能改性时的力学性能，设计并制备了染料杂化硅溶胶、酸性TiO₂溶胶和阳离子酸性硅溶胶，通过棉织物上层层自组装制备出多组分多功能有色织物。棉织物经溶胶层层自组装，不同涂层间存在Si-O-Ti的交联反应，织物的K/S值提高15.8%。棉织物经溶胶层层自组装后，织物防紫外/抗菌性能较优异，全波段URT从10.6%下降到1.3%，织物对大肠杆菌和金黄色葡萄球菌抗菌率分别提高到95.3%和96.1%。织物干湿摩擦牢度分别提高了1级，水洗褪色率由31.5%下降到18.2%，而且织物的拉伸断裂强力和断裂伸长率基本无变化。与阳离子TiO₂/SiO₂杂化溶胶改性相比，溶胶层层自组装改性织物机械性能、防紫外/抗菌性等提高更明显。基于UV和暗处条件驱动纳米TiO₂中的Ti4+Ti3+相互转换原理，制备了改性TiO₂杂化溶胶，用于织物改性后赋予了改性织物UV光开关可控亲水-疏水功能性和循环可逆性，实现织物光控动态润湿性，并对接触角衰减的原理深入讨论。TiO₂/SiO₂杂化溶胶改性棉织物水接触角为121.3°，织物呈现疏水性。经UV光照射18h后，接触角减小到0°，织物呈现亲水性。UV照射后织物在暗处放置12h，织物接触角增大到93.2°，接触角实现回复，接触角疲劳衰减的现象是由于硅烷偶联剂分子极性影响造成的。织物再经UV光照射和暗处放置可逆循环10次后，织物接触角可在0°和94°之间转换，实现了织物亲水-疏水的可逆转换。织物紫外透射谱图表明，UV光照射和暗处放置前后织物紫外透过率会分别下降和增强，并且由于受硅烷偶联剂水解产物弱极性的影响，使得织物疏水接触角仅在第一次放置黑暗后衰减。为提升织物润湿可控性及接触角变化的幅度，用FAS对TiO₂溶胶杂化改性（TiO₂/FAS杂化硅溶胶）。TiO₂/FAS杂化硅溶胶粉末晶体类型为锐钛矿/金红石型混合晶型。棉织物和涤纶织物润湿变化循环时间分别为84h和168h。未经照射的TiO₂/FAS杂化硅溶胶粉末放置水后几乎全部漂浮在水面上，当粉末经UV光照射再放置水面后大部分粉末会沉入水底部。UV光照射后的粉末再放入黑暗环境中恢复一段时间，放入水面后粉末又会漂浮在水面上。改性棉织物和涤纶织物在UV光照射呈亲水状态，而再经黑暗放置后织物恢复疏水性。织物结构及纤维表面形貌分析表明纤维表面形貌对润湿变化周期的影响比织物组织结构更显著。织物透水量和保水量的变化进一步证实了TiO₂/FAS杂化硅溶胶改性织物的UV光照润湿可变性。采用共溶液法将钡、镁、铁、氟、氮等离子杂化TiO₂溶胶中，处理后的棉织物经UV光照射，杂化2.0%氟离子试样正面接触角衰减最快，而60℃有利于在黑暗条件下接触角的恢复。利用热解法打开连接二异氰酸根与二胺中间的含脲连接基使氨纶组分降解和分离，并将回收来的废旧氨纶溶解成聚氨酯高分子（PU）溶液，并原位杂化到于硅溶胶体系中，制备PU/SiO₂杂化溶胶。尼龙/氨纶织物经干态常压法处理，在220℃处理2h，经乙醇在70℃下洗涤60min后，氨纶组分几乎被完全分离。将废旧氨纶溶解后杂化到碱性硅溶胶中，制备成PU/SiO₂杂化溶胶处理棉织物，可赋予棉织物良好的抗皱性和织物风格。与未处理棉织物经纬向急弹折皱回复角54.6°和47.1°，缓弹折皱回复角65.5°和60.0°相比，经PU/SiO₂杂化溶胶改性棉织物经纬向急弹折皱回复角分别为69.5°和68.2°，缓弹折皱回复角分别为82.5°和77.0°。经PU/SiO₂杂化溶胶改性后，棉织物的拉伸性能、弯曲性能均有所改善，使得废旧氨纶织物绿色回收并在棉织物抗皱上再利用。更多还原

【Abstract】 Dyeing and finishing industry is typical on severe pollution, more energy-wasting andcomplicated process, and the textile industry suffers enormous pressure. Therefore, the dyeingindustry is requested to use ecological, energy-saving, emission-reduction, high of additionalvalue and recyclable new technologies. Fabrics should also present non-polluting, functional,intelligent and reusable characteristics after treatment process.According to in-situ decorated sol-gel technology, colorant, silane coupling agent,polyurethane were doped into silica sol to prepare functional sols. dye/SiO₂hybrid sol,dye/CPTS/SiO₂hybrid sol and cationic TiO₂/SiO₂hybrid sol were prepared. After the hybridsol was treated on fabric by spin-coating, layer-by-layer electrostatic self-assembly, and otherprocesses, the color property, fastness and mechanical property of fabric were improved.Meanwhile, the fabric treated by the functional silane coupling agent will present goodhydrophobic and oil repellent property, controlled wettability, anti-bacterial property,anti-ultraviolet behavior, and the mechanical property. This method will shorten the treatingprocess, reduce the pollution and energy, and provide a novel dyeing and printing method.According to the sol types and the coating functionalities, the main conclusions on this topicare listed as following:The preparations of the silica sol doped with colorants are investigated according toin-situ decorated organic-inorganic hybrid technology. Sol properties, including stability andcolor properties are analyzed, and the color and fastness of the treated fabric by the hybridsilica sol also are discussed. In the silica sol doped with organic dye or pigment, themaximum absorption wavelength is consistent with that of the pigment disperse solution.From atomic force microscope （AFM）, there are scraggly micro-surface topographies on thedoped silica film, and the peak sizes in the AFM are inconsistent with the particle sizes of thesilica sols. The color strengths （K/S value） of the coated fabric with doped silica sol are higherthan that of the dye solution or pigment dispersion, and the maximum absorption wavelengthdoes not change. With the dye/SiO₂coating, the dry and wet rubbing fastnesses are increasedby one grade, and the washing change and staining fastnesses are enhanced by half a grade,respectively, while the dry and wet rubbing fastnesses with the pigment/SiO₂coating areincreased by half a grade, and the washing change and staining fastnesses are enhanced morethan half a grade, respectively. These results indicate that the fabric modification withdye/SiO₂presents good color and fastness properties via the wastewater-free and one-stepprocess.Modified silica sols are in-situ prepared by doping hexadec-ltrimethoxysilane,（HTEOS） γ-chloropropyltriethoxysilane （CPTS）, and tridecafluorooctyltriethoxysilane （FAS） to obtainthe hydrophobic or oil repellent coatings on cotton, silk and wool fabrics. Also, a sol-gelderived hybrid silica sol consisting of C.I. Direct Red23dye and inorganic silica issuccessfully synthesized by adding coupling agent CPTS, and via spin-coating, the fabric canobtain good hydrophobicity and color properties. After coated with HTEOS/SiO₂hybrid sol,the fabric could support a subglobose water droplet, and the contact angle is increased to139.8°. The hydrostatic pressure of fabric coated with hybrid HTEOS/SiO₂hybrid sol is4.1KPa, which is significantly higher than that of the control sample （1.8KPa）. The contact angleof the treated fabric with dye hybrid silica sol is increased to112.4°and the contact angle isincreased to131.48°when the fabric was treated with CPTS/dye hybrid silica sol. Thehydrostatic pressure of the cotton fabric coating with CPTS/dye hybrid silica sol is4.5KPaand increased by136.7%compared with that of the untreated fabric. The K/S value （5.15） ofthe dye/CPTS/SiO₂hybrid silica coated cotton fabric is increased by higher30.4%than thatof the control coated sample （3.95）. The dry and wet rubbing fastness with dye/CPTS/SiO₂hybrid silica coating are increased to3and2-3grades, respectively, and the washing changesand stain fastnesses are enhanced to3and3-4grades, respectively. These indicate excellentcolor and hydrostatic properties.An integrated approach to preparing a novel cationic TiO₂/SiO₂hybrid sol withanti-ultraviolet and anti-bacterial performances is investigated by Tetraethoxysilane （TEOS）,Tetrabutyl titanate （TBT） and Polyquaternium. The particle is elliptic from the TEMphotograph, and from FIRT spectrum, the Si-O-Si, Ti-O-Ti and Si-O-Ti bonds are formed inthe cationic TiO₂/SiO₂hybrid coating. From XPS spectra, only the characteristic bands C andO are presented for the original cotton fabric （56.4%C1s and43.6%O1s）. After coated withCSTHS, besides33.2%C1s and48.4%O1s,18.1%Si2p and0.3%Ti2p are confirmed in thecoating. During the UVB （280-320nm） and UVC （200-280nm） wave bands, the lowest URTof the original cotton fabric without washing is higher than7.0%, but the URT of the coatedcotton fabric is almost smaller than5.0%and after washing the URT is lower than6.0%. Thebacteriostatic capabilities of the coated cotton fabric to Gram-negative bacteria E. coli andGram-positive bacteria S. aureus are90.9%and95.2%, respectively, while the antibacterialratios are decreased to61.1%and71.5%during washing respectively, which indicate a goodwashing fastness. The K/S value of the original cotton fabric printed with disperse dye is2.4at520nm wavelength. After modification with CSTHS, the K/S value of the cotton fabric isenhanced to10.1at the same wavelength （520nm）, and the K/S value is sharply increased by320%. The transfer rate of disperse dye is increased to89%from21%. The peaks of the K/Svalue curve for the coated fabric are high and narrow, which indicates that the color vividness is increased relative to the original cellulose fabric. The λmaxof the coated cellulose fabric isunchanged, and it is coincident with the maximum absorption wavelength of the untreatedcellulose fabric, which indicates that the treatment presents little effect on the color hue. Thesharpness and the color strength of the treated cellulose fabric are improved. The wet rubbingfastness is improved from4grade to4-5grade, whereas the tensile property of the treatedfabric was decreased severely.In order to obtain excellent mechanical properties of the treated fabrics during functionalmodification, directional coatings with alkaline SiO₂, TiO₂and acidic cationic SiO₂sol aredesigned and prepared on fabric. The K/S value of the coated fabric via layer-by-layerself-assembly is increased15.8%. Compared to the average ultraviolet radiation transmittance（URT） and bacterial reduction （R） of the control sample, the URT of the treated fiberdecreases from10.6%to1.3%and the anti-bacterial activities to the Gram-negative bacteria E.coli and Gram-positive bacteria S. aureus are increased to95.3%and96.1%, respectively. Forthe treated fabric, the dry and wet rubbing fastness is enhanced by1grade, respectively, thewashing fade rate is decreased to18.2%from31.5%. And the mechanical properties of thetreated fabrics via layer-by-layer self-assembly are better than that with TiO₂/SiO₂hybrid sol.According to the mechanism of the conversion between Ti4+Ti3+under UV lightand dark, modified TiO₂hybrid sol is prepared and coated on fabric to presenthydrophobic-hydrophilic switchable property via UV response. The contact angle of thecoated fabric is121.3°and hydrophobic, but after radiated in UV for18h, the contact angle is0°and hydrophilic. When the radiated fabric is kept in dark place for12h, the contact angle isincreased to93.2°from0°. The difference of the contact angle between93.2°and121.3°iscaused by the polarity of the silane coupling agent. When the fabric is kept in UV and darkplace for10times, the contact angle is switched between0°and94°, and the fabric showshydrophobic-hydrophilic switchable property. From the ultraviolet spectrum, the ultravioletradiation transmittances of the coated fabrics are decreased slightly via radiation UV for18h,whereas, the ultraviolet radiation transmittances are increased when the radiated fabric is keptin dark place for12h. This change of the ultraviolet radiation transmittances verifies themechanism of switchable wettability.Silane coupling agent FAS was in-situ doped in TiO₂sol （TiO₂/FAS hybrid silica sol） toimprove the switchable wettability and the rangeability of contact angle. The anatasecomponent in TiO₂/FAS hybrid silica powder is mixed with rutile component from XRD, andthe crystal component is unchanged in UV light and dark store condition. The switchablecycle of the cotton is84h, while the switchable cycle of the polyester is168h. The TiO₂/FAShybrid silica powder floats on the water surface for its excellent hydrophobicity, and the sample deposits at the bottom of water as the wettability of coated fabric increased via UVirradiation. The irradiated sample floats on water again when it is placed in dark. The coatedcotton and polyester fabric is hydrophilic with UV irradiation, and shifts to be hydrophobic indark. The effect of the fiber morphology on the cycle is more important than that of the fabricconstruction. The water diffusivity and permeable capacity further confirmed the excellentswitchable wettability of coated fabrics by F/TiO₂hybrid sol through UV irradiation orstorage in dark. Some ions, including Ba2+, Mg2+, Fe3+, F-, N3+were doped into the TiO₂hybrid sol via by co-solution method, and the cotton fabric coated with the hybrid sol wasirritated under UV light. The F/TiO₂hybrid sol shortened the damping time of the frontcontact angle and the60°C condition was beneficial to the recover of contact angle in dark.To separate spandex from the waste polyamide/spandex fabric and improve themechanical properties of the cotton fabric, ureido between the isocyanate and diamine wasbroken during heating process, leading to the spandex degradation. After washed with ethanol,the spandex component and nylon component are separated. The spandex component isdissolved in N,N-dimethylformamide （DMF）, and then in-situ doped in silica sol.Nylon/Spandex fabric is treated with dry and opened heating method （DOHM） at220°C for2h, and then washed with ethanol at60°C for60min. The spandex is almost separated andextracted. After coating, the wrinkle resistance and fabric style of the coated the fabric areimproved. The fast wrinkle recovery angles of the treated fabric in warp and weft directionsare improved by27.3%and44.8%, and the slow wrinkle recovery angles in warp and weftdirections are improved by26.0%and28.3%, respectively. With the silica treatment, thecompressing, shearing, tensile strength, bending and washing properties of the fabric are alsoenhanced significantly. The enhancements of these properties are the coatings of the PU/SiO₂hybrid sol on fiber, which is a good pathway for waster spandex recycle.更多还原