结构色纤维/面料的制备及其光学性质研究
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摘要
中国是纺织工业大国，每年的贸易额约占全球的25%，然而，巨大的经济效益并不能掩盖纺织印染行业对环境造成的严重破坏。目前，传统的纺织印染行业已经成为我国高污染、高能耗和高排放的危害型行业。为了响应国家节能减排的政策要求，迫切需要发展一种不同于传统化学染料着色的纺织品显色技术。因此采用结构色这一绿色环保的显色方法对纺织品进行着色，降低传统印染工艺对环境造成的污染，开发出一种全新的纺织品显色方法，具有十分重要的意义。
本论文从纤维和面料这两个纺织品的基本构成单元出发，深入探讨了结构色纤维及面料的制备方法，微观结构，光学性质及力学强度等，拟开发出一种具有实际应用价值及工业化生产前景的结构色纤维及面料的制备方法，主要研究内容及结果如下：
（1）毛细管中胶体微球自组装法制备光子晶体结构色纤维：以类似纤维状的毛细管为模板，通过胶体微球自组装来验证制备结构色纤维的可行性。研究结果发现，通过PS微球自组装能够制备得到胶体晶体结构色纤维；并且通过改变微球的尺寸，能轻易调控结构色纤维的颜色；纤维沿径向不具有角度依赖性，沿轴向具有虹彩效应。毛细管中胶体微球自组装的方法验证了制备结构色纤维的可行性，为后续制备出具有较好力学性质，颜色可控的结构色纤维提供了理论基础。
（2）胶体静电纺丝法制备结构色纤维膜：通过胶体静电纺丝法，发展了胶体晶体纤维的快速、大批量的制备方法。研究发现，聚乙烯醇（PVA）包在胶体微球表面，起到粘结剂的作用，将胶体微球粘起来形成胶体晶体纤维；胶体晶体纤维中微球与微球空隙之间被PVA所填充，导致折射率差异非常小，从而使得制备得到的胶体晶体纤维膜呈现白色；通过水溶解去除掉部分PVA后，纤维膜呈现出明显的颜色，并且结构没有破坏，仍然保持纤维形貌；纤维膜的反射光谱和散射光谱都不具有角度依赖性，颜色没有虹彩效应，符合人眼的色彩感应习惯。
（3）纤维表面涂覆技术制备结构色纤维：采用类似光纤表面涂覆技术，开发出在纤维表面涂覆一层结构色涂层来制备结构色纤维的方法。研究发现，纤维表面微球堆积层数与纤维提拉速度呈现负相关，与乳液浓度、纤维尺寸呈现正相关；当纤维表面微球堆积层数超过10层的时候，其光学性质基本稳定而不发生变化；单根纤维沿径向不具有角度依赖性，沿轴向具有虹彩效应；通过调控微球的软硬度，及纤维表面的亲疏水性，在普通涤纶纤维表面涂覆一层无裂痕且力学性质非常好的结构色涂层，从而使得涤纶纤维具有颜色。这种基于普通纤维的结构色涂覆技术具有很好的实际应用意义及工业化前景。
（4）聚合物相分离方法制备类非晶结构色纤维：通过静电纺丝相分离技术，开发出制备多孔类非晶结构色纤维的方法。研究表明，纤维的颜色来源于结构色；SEM观察发现，纤维内部呈现无序多孔结构，通过二维傅里叶变换表明这种无序多孔结构具有径向的短程有序但长程无序性；制备得到的结构色纤维呈现明显的蓝色，颜色柔和不刺眼，并且通过显微角分辨光谱仪进行变角度反射光谱测量说明其颜色不具有虹彩效应。
（5）普通织物表面涂覆制备结构色面料：通过在普通织物表面直接浇铸的方法，深入研究了快速并且大量的制备结构色面料的可行性。研究发现，软聚合物微球乳液中无机纳米SiO2/CB颗粒的添加，形成具有折射率差异的周期性结构，得到高饱和度高亮度的结构色涂层；纳米复合胶体乳液在织物表面进行浇铸干燥过程中由于咖啡环效应，导致边缘和中间颜色出现偏差；结构色面料具有很好的与水与油颜色稳定性；较好的力学性质，完全满足实际应用中的服用性能；具有大面积制备的可行性，并且通过不同的筛网印花模具能够较容易的制备出具有不同形状不同颜色的结构色印花涂层。这种织物表面结构色涂层具有非常好的实际应用价值和工业化前景。
China has a significant influence on the textile industry, with an annual tradevolume that occupies25%of the world market. However, the economic benefits of thetextile dyeing and fishing industries do not cover the serious damages they cause to theenvironment. At present, the general Chinese public has become more aware of thehazards posed by the traditional dyeing and fishing industries, including drawbackssuch as high pollution, high energy consumption and high emissions. As a response tonational policies on energy-saving and emission-reduction, the textile coloring industryis required to develop a novel technology that is different from traditional chemicaldyeing processes. Therefore, we presented an idea that colors textiles based on physicalmethods that do not require the assistance of chemical dyes. We believe that thisenvironmentally conscious textile coloration strategy can reduce the pollution caused bythe traditional dyeing and finishing process.
In this dissertation, we studied the preparation methods, optical properties, andmechanical strength of structurally-colored fibers and fabrics. The goal was to develop apreparation method of structurally-colored fibers and fabrics with actual applicationvalues and industrial production prospects. The following several aspects were mainlydiscussed:
(1) Preparation of photonic crystal structurally-colored fibers through colloidalself-assemble in capillary: Structurally–colored fibers can be fabricated by soaking thecapillary tubes into PS microsphere dispersion through colloidal self-assembly. PSmicrospheres in the capillary tube formed a cylindrical colloidal crystal fiber as waterwas slowly evaporated. The colors of colloidal crystal fibers can be easily tuned byaltering the size of the PS microspheres. The reflective spectra in the radial direction were independent of the incident angle, while the spectra in the longitudinal directionnotably blue-shifted. The preparation method of colloidal self-assembly in capillary is atestament to the feasibility of preparing structurally-colored fibers, thus providing atheoretical basis for the subsequent studies.
(2) Preparation of structurally-colored fibrous membrane via colloidalelectrospinning technology: Colloidal crystal fibers were fabricated rapidly on a largescale, using the electrospinning process. PVA clung to the surface of colloidalmicrospheres and worked as an adhesive agent to adhere PS microspheres, forminguniform colloidal crystal fibers. The obtained fibrous membrane was white due to thelow refractive index contrast between PVA and PS. Interestingly, the membraneappeared in colors as it was immersed in water. The membrane preserved the fibrousshape after water treatment. A large amount of PVA was dissolved in water and removedfrom the structure, increasing the reflective index contrast. The fibrous membraneexhibited isotropic color properties, which is independent of incident and observingangles. Therefore, the coloration of the membrane is similar to the color property indyes, which adapt to certain shades based on interpretations made by human vision.
(3) Preparation of structurally-colored fibers through surface coatingtechnology: Inspired by the surface coating technology of optical fibers, we developeda new fabrication method for obtaining structurally-colored fibers by coating polymerfiber surfaces with colloidal crystal. The layers of colloidal microspheres showed anegative correlation with fiber lifting speed, and a positive correlation with the emulsionconcentration and fiber size. Interestingly, if number of colloidal layers reached10,further increasing the layers did not affect the color and reflective peaks of thestructurally-colored fiber. The fabricated structurally-colored PET fiber displayedexcellent mechanical property, which was possible via controlling the hardness ofmicrospheres and hydrophilicity of PET fiber.
(4) Preparation of structurally-colored fibers with porous quasi-amorphousstructure through polymer phase separation: The structurally-colored fibers werefabricated rapidly and on a large scale, via electrospinning technology. During the process, the quasi-amorphous structure formed inside the fibers as a result of phaseseparation, as confirmed by SEM observation. The results of Fourier transform revealeda disordered bicontinuous porous structure with radial short-range order and long-rangedisorder. The obtained fibers exhibited isotropic color properties, which is independentto the incident and observing angles.
(5) Preparation of structurally-colored fabrics through surface coatingtechnology: We fabricated structurally-colored fabrics on a large scale, though surfacecoating technology. The colorful fabric presented high brightness and saturation byadding inorganic nano SiO2/CB particles into soft polymer microsphere emulsion. Aperiodic structure with refractive index contrast was formed during the drying process.Due to the coffee-ring effect during the drying process of colloid emulsion, the color inlead edge was different from the middle portions. Colors of the obtained fabrics havegood stability when they were treated with water or oil. Excellent mechanical propertyof the structurally-colored fabric ensured the possibility of practical application.Coatings with different colors and shapes can be produced easily though screen-printingmode. This type of structurally-colored fabric has good practical value and prospect ofindustrialization.
本论文从纤维和面料这两个纺织品的基本构成单元出发，深入探讨了结构色纤维及面料的制备方法，微观结构，光学性质及力学强度等，拟开发出一种具有实际应用价值及工业化生产前景的结构色纤维及面料的制备方法，主要研究内容及结果如下：
（1）毛细管中胶体微球自组装法制备光子晶体结构色纤维：以类似纤维状的毛细管为模板，通过胶体微球自组装来验证制备结构色纤维的可行性。研究结果发现，通过PS微球自组装能够制备得到胶体晶体结构色纤维；并且通过改变微球的尺寸，能轻易调控结构色纤维的颜色；纤维沿径向不具有角度依赖性，沿轴向具有虹彩效应。毛细管中胶体微球自组装的方法验证了制备结构色纤维的可行性，为后续制备出具有较好力学性质，颜色可控的结构色纤维提供了理论基础。
（2）胶体静电纺丝法制备结构色纤维膜：通过胶体静电纺丝法，发展了胶体晶体纤维的快速、大批量的制备方法。研究发现，聚乙烯醇（PVA）包在胶体微球表面，起到粘结剂的作用，将胶体微球粘起来形成胶体晶体纤维；胶体晶体纤维中微球与微球空隙之间被PVA所填充，导致折射率差异非常小，从而使得制备得到的胶体晶体纤维膜呈现白色；通过水溶解去除掉部分PVA后，纤维膜呈现出明显的颜色，并且结构没有破坏，仍然保持纤维形貌；纤维膜的反射光谱和散射光谱都不具有角度依赖性，颜色没有虹彩效应，符合人眼的色彩感应习惯。
（3）纤维表面涂覆技术制备结构色纤维：采用类似光纤表面涂覆技术，开发出在纤维表面涂覆一层结构色涂层来制备结构色纤维的方法。研究发现，纤维表面微球堆积层数与纤维提拉速度呈现负相关，与乳液浓度、纤维尺寸呈现正相关；当纤维表面微球堆积层数超过10层的时候，其光学性质基本稳定而不发生变化；单根纤维沿径向不具有角度依赖性，沿轴向具有虹彩效应；通过调控微球的软硬度，及纤维表面的亲疏水性，在普通涤纶纤维表面涂覆一层无裂痕且力学性质非常好的结构色涂层，从而使得涤纶纤维具有颜色。这种基于普通纤维的结构色涂覆技术具有很好的实际应用意义及工业化前景。
（4）聚合物相分离方法制备类非晶结构色纤维：通过静电纺丝相分离技术，开发出制备多孔类非晶结构色纤维的方法。研究表明，纤维的颜色来源于结构色；SEM观察发现，纤维内部呈现无序多孔结构，通过二维傅里叶变换表明这种无序多孔结构具有径向的短程有序但长程无序性；制备得到的结构色纤维呈现明显的蓝色，颜色柔和不刺眼，并且通过显微角分辨光谱仪进行变角度反射光谱测量说明其颜色不具有虹彩效应。
（5）普通织物表面涂覆制备结构色面料：通过在普通织物表面直接浇铸的方法，深入研究了快速并且大量的制备结构色面料的可行性。研究发现，软聚合物微球乳液中无机纳米SiO2/CB颗粒的添加，形成具有折射率差异的周期性结构，得到高饱和度高亮度的结构色涂层；纳米复合胶体乳液在织物表面进行浇铸干燥过程中由于咖啡环效应，导致边缘和中间颜色出现偏差；结构色面料具有很好的与水与油颜色稳定性；较好的力学性质，完全满足实际应用中的服用性能；具有大面积制备的可行性，并且通过不同的筛网印花模具能够较容易的制备出具有不同形状不同颜色的结构色印花涂层。这种织物表面结构色涂层具有非常好的实际应用价值和工业化前景。
China has a significant influence on the textile industry, with an annual tradevolume that occupies25%of the world market. However, the economic benefits of thetextile dyeing and fishing industries do not cover the serious damages they cause to theenvironment. At present, the general Chinese public has become more aware of thehazards posed by the traditional dyeing and fishing industries, including drawbackssuch as high pollution, high energy consumption and high emissions. As a response tonational policies on energy-saving and emission-reduction, the textile coloring industryis required to develop a novel technology that is different from traditional chemicaldyeing processes. Therefore, we presented an idea that colors textiles based on physicalmethods that do not require the assistance of chemical dyes. We believe that thisenvironmentally conscious textile coloration strategy can reduce the pollution caused bythe traditional dyeing and finishing process.
In this dissertation, we studied the preparation methods, optical properties, andmechanical strength of structurally-colored fibers and fabrics. The goal was to develop apreparation method of structurally-colored fibers and fabrics with actual applicationvalues and industrial production prospects. The following several aspects were mainlydiscussed:
(1) Preparation of photonic crystal structurally-colored fibers through colloidalself-assemble in capillary: Structurally–colored fibers can be fabricated by soaking thecapillary tubes into PS microsphere dispersion through colloidal self-assembly. PSmicrospheres in the capillary tube formed a cylindrical colloidal crystal fiber as waterwas slowly evaporated. The colors of colloidal crystal fibers can be easily tuned byaltering the size of the PS microspheres. The reflective spectra in the radial direction were independent of the incident angle, while the spectra in the longitudinal directionnotably blue-shifted. The preparation method of colloidal self-assembly in capillary is atestament to the feasibility of preparing structurally-colored fibers, thus providing atheoretical basis for the subsequent studies.
(2) Preparation of structurally-colored fibrous membrane via colloidalelectrospinning technology: Colloidal crystal fibers were fabricated rapidly on a largescale, using the electrospinning process. PVA clung to the surface of colloidalmicrospheres and worked as an adhesive agent to adhere PS microspheres, forminguniform colloidal crystal fibers. The obtained fibrous membrane was white due to thelow refractive index contrast between PVA and PS. Interestingly, the membraneappeared in colors as it was immersed in water. The membrane preserved the fibrousshape after water treatment. A large amount of PVA was dissolved in water and removedfrom the structure, increasing the reflective index contrast. The fibrous membraneexhibited isotropic color properties, which is independent of incident and observingangles. Therefore, the coloration of the membrane is similar to the color property indyes, which adapt to certain shades based on interpretations made by human vision.
(3) Preparation of structurally-colored fibers through surface coatingtechnology: Inspired by the surface coating technology of optical fibers, we developeda new fabrication method for obtaining structurally-colored fibers by coating polymerfiber surfaces with colloidal crystal. The layers of colloidal microspheres showed anegative correlation with fiber lifting speed, and a positive correlation with the emulsionconcentration and fiber size. Interestingly, if number of colloidal layers reached10,further increasing the layers did not affect the color and reflective peaks of thestructurally-colored fiber. The fabricated structurally-colored PET fiber displayedexcellent mechanical property, which was possible via controlling the hardness ofmicrospheres and hydrophilicity of PET fiber.
(4) Preparation of structurally-colored fibers with porous quasi-amorphousstructure through polymer phase separation: The structurally-colored fibers werefabricated rapidly and on a large scale, via electrospinning technology. During the process, the quasi-amorphous structure formed inside the fibers as a result of phaseseparation, as confirmed by SEM observation. The results of Fourier transform revealeda disordered bicontinuous porous structure with radial short-range order and long-rangedisorder. The obtained fibers exhibited isotropic color properties, which is independentto the incident and observing angles.
(5) Preparation of structurally-colored fabrics through surface coatingtechnology: We fabricated structurally-colored fabrics on a large scale, though surfacecoating technology. The colorful fabric presented high brightness and saturation byadding inorganic nano SiO2/CB particles into soft polymer microsphere emulsion. Aperiodic structure with refractive index contrast was formed during the drying process.Due to the coffee-ring effect during the drying process of colloid emulsion, the color inlead edge was different from the middle portions. Colors of the obtained fabrics havegood stability when they were treated with water or oil. Excellent mechanical propertyof the structurally-colored fabric ensured the possibility of practical application.Coatings with different colors and shapes can be produced easily though screen-printingmode. This type of structurally-colored fabric has good practical value and prospect ofindustrialization.
引文
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