取向多孔导电聚乙烯醇（聚氨酯）基复合材料的制备及气敏行为
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摘要
作为气敏材料的导电高分子复合材料通常被热压或浇铸成数十至数百微米厚的薄膜使用，这是由于薄膜形状有利于有机气体对基体树脂特别是心层树脂的浸入与溶胀，以实现高气敏强度。然而，对于监测管道中流动气体的气敏材料而言，如此厚度的薄膜形态存在易破裂、作用面积小、稳定性不高等缺点。这成为阻碍导电高分子气敏材料进一步拓展其应用范围的重要因素。
从结构上看，如果在实体导电高分子材料内构建取向多孔气体通道，且孔径和孔壁尺寸小至微米或纳米级，那么这种取向多孔导电高分子材料将是一种理想的气敏材料。首先，超细泡孔的存在极大地增加了材料比表面积，从而加强了材料表面对气体分子的接触与吸附；其次，比普通薄膜材料更薄的聚合物层可提供更高的气敏响应强度；再者，取向通孔结构对气体流动影响较小，有利于高速流动气体的通过与检测；最后，三维构架材料可提供比薄膜材料更大的耐压性能，更适合于在具有一定气压差的环境下使用。
然而，取向多孔导电高分子材料结构的实现必须解决两个基本问题。其一是取向多孔结构在聚合物基体中的构建问题；其二是导电网络通路在取向多孔结构中的形成问题。就第一个问题而言，目前已有多种方法可用于实现在聚合物中构建取向微孔结构，如微加工法、光刻法、软光刻技术等。但这些方法所固有的成本高、效率低、对聚合物选择性强等缺点阻碍了其在聚合物加工中的应用。相比而言，新近发展起来的定向凝固干燥技术因其制备装置简单、效率高、不存在化学反应等优点而受到人们的广泛关注。
本文拟用定向凝固干燥法，构建具有取向多孔结构的导电高分子材料，并在获得了这种新型取向多孔导电高分子材料之后，研究了材料的制备参数与形态结构的关系、形态结构与电学性能关系、导电机理及对于动态有机气体的气敏响应行为及机理。
本研究主要结果有：
①聚乙烯醇取向多孔材料的制备
当PVA溶液以2mm/min的速度浸入液氮中，经定向凝固干燥后，观察到以1%的PVA溶液制备的样品断面呈纤维网状结构；而以5%的PVA溶液制备的样品呈比较规则的取向孔洞结构；随着PVA溶液浓度的增加，含PVA10%的溶液获得的样品呈现一种特殊的“鱼骨头”结构；当PVA溶液浓度高至15%时，样品断面结构呈仅有一定的取向趋势的微孔结构。
当PVA水溶液浸入液氮速度加快时（10mm/min），样品结构会有变化。同样是1%的PVA水溶液，以10mm/min的速度浸入液氮中，样品断面不再是纤维网状结构；PVA溶液浓度为5%时，以10mm/min浸入速度获得样品取向孔洞结构没有2mm/min的样品取向结构规整，孔洞之间有少量的桥接出现；PVA溶液浓度为10%时，样品断面形貌呈现特殊的“鱼骨头”结构；当PVA溶液浓度高至15%时，样品断面微孔结构的取向趋势没有2mm/min浸入液氮中的样品取向趋势明显。
对不同浓度的PVA溶液以4mm/min的速度浸入-70℃冷冻乙醇中所制备的样品断面微观组织分析后发现，当PVA溶液浓度极稀时（1%），与定向浸入液氮中所获得的样品断面呈纤维网状结构不同，断面呈团絮状结构；随着PVA溶液浓度的增加，浓度为5%及7.5%时，断面呈特殊的“鱼骨”形状，且“鱼骨”有增粗的趋势，取向趋势明显，这些“鱼骨”状结构的分支是由PVA溶质在大块冰晶边缘的排斥下形成的；在溶液浓度增加至10%及以上时，断面形貌逐渐转变为片层结构，取向趋势逐渐减弱，片层之间的间距也逐渐缩小。
②聚氨酯取向多孔材料的制备
a.以Bayer Impranil1380水性聚氨酯分散体为原料，对该溶液采用定向凝固干燥法制备样品。对于稀的Impranil1380水性聚氨酯分散体(5%)，以4mm/min浸入液氮后，与用稀PVA溶液（1%）制备的样品断面结构类似，断面呈纤维网状结构，纤维直径约2-3μm。而对于20%的Impranil1380水性聚氨酯分散体，浸入液氮定向凝固干燥后，获得的样品呈一定取向的多孔形貌，当Impranil1380水性聚氨酯分散体固含量增加至40%时，样品断面形貌仅呈一定的取向趋势，且只能观察到少量孔洞形貌。20%的Impranil1380水性聚氨酯分散体以4mm/min的速度浸入-50℃乙醇中，经定向凝固干燥后获得样品断面形貌呈解理状，无取向孔洞产生。
b.以Bayer UH240水性聚氨酯分散体为原料，用定向凝固干燥法制备样品。不同浓度的UH240水性聚氨酯溶液以4mm/min的速度浸入-70℃乙醇定向凝固干燥，以10%的UH240水性聚氨酯溶液制备的样品断面结构仅有一定取向趋势，而以20%的UH240溶液为原料所获得的样品断面呈非常规整的取向多孔结构，孔洞直径约为25μm，孔壁厚度约为4μm，孔洞结构在视场范围内保持连续，当UH240溶液浓度升高至40%时，样品断面显微组织仅呈一定的取向趋势。
把UH240水性聚氨酯溶液分别以1mm/min、10mm/min的速度浸入-70℃乙醇中发现，以10mm/min的速度浸入冷冻乙醇中后获得的样品孔洞直径、孔洞壁厚度要比1mm/min的速度浸入冷冻乙醇中后获得的样品略低。把20%的UH240水性聚氨酯溶液以4mm/min的速度分别浸入-50℃、-70℃、-90℃、-110℃的冷冻乙醇中，经定向凝固干燥后，所获得的样品断面都呈非常规整的取向多孔结构，且冷冻液温度越低，样品孔洞直径越小，孔洞壁厚度越薄。
③取向多孔导电聚乙烯醇基、聚氨酯基材料的制备及导电性能
在5%的PVA水溶液中添加炭黑、碳纳米管，20%的水性聚氨酯中添加碳纳米管后，以4mm/min的速度浸入-70℃乙醇，经定向凝固干燥后，成功获得了取向多孔导电炭黑/聚乙烯醇、碳纳米管/聚乙烯醇、碳纳米管/水性聚氨酯材料。复合材料（炭黑/聚乙烯醇、碳纳米管/聚乙烯醇、碳纳米管/水性聚氨酯）的电阻率与导电填料含量（炭黑或碳纳米管）关系曲线表明，在导电填料的含量增加到一定程度后，材料的电阻率显著降低；在降低到一定程度后，随着导电填料含量的继续增加，电阻率变化不大。用经典的逾渗理论方程对复合材料（炭黑/聚乙烯醇、碳纳米管/聚乙烯醇、碳纳米管/水性聚氨酯）的电阻率与导电填料含量（炭黑或碳纳米管）关系进行拟合，得出复合材料导电填料的逾渗值分别为12.5vol.%、6.2vol.%、2.0vol.%，临界电阻率指数分别为2.8、6.1、2.7，临界电阻率指数不在经典的逾渗理论所定义的范围之内，这是由于复合材料具有的特殊取向孔洞结构所导致。
④取向多孔导电聚乙烯醇基、聚氨酯基材料对流动气体的气敏行为
在利用定向凝固干燥法制备的取向多孔导电炭黑/聚乙烯醇、碳纳米管/聚乙烯醇、碳纳米管/水性聚氨酯复合材料的基础上，研究取向多孔导电炭黑/聚乙烯醇、碳纳米管/聚乙烯醇、碳纳米管/水性聚氨酯复合材料对流动气体的气敏行为。研究结果表明，取向多孔导电炭黑/聚乙烯醇、碳纳米管/聚乙烯醇、碳纳米管/水性聚氨酯复合材料对苯、四氢呋喃、丙酮等有机气体都具有很强的气敏响应，且对上述气体的响应率依次降低。对取向多孔导电碳纳米管/聚乙烯醇、碳纳米管/水性聚氨酯材料在不同温度的有机气体中的气敏响应研究发现，温度越高，响应率也就越高。
In the current practice, the conductive polymer composites as gas sensor are usuallyfabricated as films with the thickness from decades to hundreds of microns through hotpressing or casting, which is beneficial to vapor permeating, and resulting in high vaporsensitivity. However, when being used to monitor the flowing vapors in the pipes, thefilmy polymer sensors are seriously limited by easily getting ruptured, less operationarea, instability, and so on. Thus, it is still a tough challenge to establish alternativetechniques to fabricate polymer based gas sensor for flowing vapors in practicalapplication.
Structurally, the conductive polymer composites with an aligned porous structurewill be an ideal sensor when the diameter of the pores and thickness of the wall is tomicrons or to the nanometer level. Compared with the ordinary film-like polymer gassensors, this new aligned micro-porous composite sensor is much more suitable formonitoring flowing organic vapors based on the following reasons:
(1)The micro-pores greatly increase the surface area of the materials and intensifythe contact between the gas molecules and materials.
(2)The even thinner pore walls in the new aligned micro-porous sensor can result inhigher vapor sensitivity.
(3)One-dimensional micro-porous structure can facilitate the high speedtransportation of flowing vapors and benefit detection.
(4)This kind of sensor has stronger pressure resistance than the film sensors and ismore applicable under the condition of pressure difference.
However, there are two basic questions must be solved to achieve the alignedporous conductive composites. One is the construct of the aligned porous structure inpolymer matrix. The other is the formation of the conductive network in an alignedporous structure. For the first question concerned, there are a variety of methods can beused to realize the construction of an aligned porous structure in a polymer matrix, suchas micro processing method, photolithography, soft lithography, etc. But these methodshave shortcomings such as high cost, low efficiency and polymer selectivity andhindered the application in polymer processing. In contrast, the newly developeddirectional freeze-drying process has been paid much attention by the people because ofthe advantages such as simple preparation device, efficient and does not exist chemical reaction.
Herein, a conductive polymer composite with an aligned micro-porous structure isobtained through directional freeze-drying process. And, the relationship between thepreparation parameters and structure, the conductivity property and structure,conductivity mechanism, vapor-sensitive response behavior and mechanism are studiedin this paper.
The main results are listed below:
①Preparation of an aligned porous poly (vinyl alcohol)
When poly (vinyl alcohol)(PVA) solution was immersed in liquid nitrogen with thevelocity of2mm/min, after freeze-drying process, the fiber structure was observed inthe specimen’s cross section prepared from1%PVA solution. Regular aligned porousstructure was obtained from the specimen prepared from5%PVA solution. With theincrease of PVA solution concentration, the specimen prepared from10%PVA solutionis fish-bone like structure. And the micro-porous structure of the specimen preparedfrom15%PVA solution is only a trend to orientation.
The results show that the structure will change with the immersing velocity. WhenPVA solution was immersed in liquid nitrogen with the velocity of10mm/min, thespecimen prepared from1%PVA solution no longer is fiber network structures.Regular aligned porous structure can also be obtained from5%PVA solution, but thereare some bridges appeared between the pores. The specimen prepared from10%PVAsolution presents special fish-bone like structure. When the concentration of PVAsolution increased to15%, compared with the specimen prepared from2mm/min, theorientation trend of the specimen decreased.
When PVA solution was immersed into-70℃ethanol with the velocity of4mm/min, the structure of the specimen prepared from1%PVA solution is floe in group,that is different from the fiber structure. When the concentration of PVA solutionincreased to5%and7.5%, the structure of the specimen presents fish-bone likestructure and the fish-bone has the trend to been thicker. The branches of the fish-bonesare formed by the edge of the large ice crystals. When the concentration of the solutionincreased to10%or above, the morphology changed gradually to a layer structure andthe orientation trend decreased.
②Preparation of an aligned porous polyurethane
a. Bayer Impranil1380water-borne polyurethane dispersion was used as the rawmaterials for directional freeze-drying process in this section. When polyurethane dispersion was immersed in liquid nitrogen with the velocity of4mm/min, thespecimen prepared from5%polyurethane dispersion by directional freeze-dryingprocess is fiber network structures and the diameter of the fibers is about2-3μm. That issimilar to the structure of the specimen prepared from1%PVA solution. The specimenprepared from20%polyurethane dispersion presents an unobvious aligned porousstructure. And, when the concentration of polyurethane dispersion increased to40%,there are a few holes and only a trend to orientation in the micro-structure of thespecimen. When polyurethane dispersion was immersed in-50℃ethanol with thevelocity of4mm/min, the specimen presents a cleavage morphology and there is noaligned pores in it.
b. Bayer UH240water-borne polyurethane dispersion was used as the raw materialsfor directional freeze-drying process. When polyurethane dispersion was immersed in-70℃ethanol with the velocity of4mm/min, there are only a trend to orientation in themicro-structure of the specimen prepared from10%and40%polyurethane dispersionby directional freeze-drying process. However, the specimen prepared from20%polyurethane dispersion by directional freeze-drying process presents regular alignedporous structure, and the diameter of the pores is about25μm and pore wall thickness isabout4μm. When polyurethane dispersion was immersed in-70℃ethanol with thevelocity of1and10mm/min respectively, the result showed that the diameter of poresand pore wall thickness prepared by10mm/min were smaller than1mm/min. Whenpolyurethane dispersion was immersed in-50℃,-70℃,-90℃and-110℃respectively,the specimen prepared by directional freeze-drying process presents regular alignedporous structure. And the temperature of cryogenic lower, the smaller of diameter ofpores and pore wall thickness.
③Preparation and conductivity of aligned porous conductive poly (vinyl alcohol)and polyurethane composite
After carbon black or carbon nanotubes were added into5%PVA solution orcarbon nanotubes were added into20%polyurethane dispersion, the solutions wereimmersed in-70℃ethanol with the velocity of4mm/min. In this way, aligned porousconductive carbon black/poly (vinyl alcohol), carbon nanotube/poly (vinyl alcohol) andcarbon nanotube/polyurethane composites can be obtained by directional freeze-dryingprocess. Electrical conductivity of composites such as black/poly (vinyl alcohol),carbon nanotube/poly (vinyl alcohol) and carbon nanotube/polyurethane composites asa function of carbon black or carbon nanotubes content is obtained in this paper. These curves showed that the resistivity of the composite decrease significantly when theconductive filler increased to certain content. When the resistivity decreased to a certaindegree, as the conductive filler continue to increase, the resistivity change is not large.When these curves are fit using the percolation concept, the volume percolationconcentration of these composites were obtained as12.5%,6.2%and2.0%respectively.And, the resistivity critical exponents are2.8,6.1and2.7respectively and not in therange of percolation theory described.
④Aligned porous conductive poly (vinyl alcohol) or polyurethane composite usedas a sensor for flowing vapors.
When aligned porous conductive black/poly (vinyl alcohol), carbon nanotube/poly(vinyl alcohol) and carbon nanotube/polyurethane composites were obtained bydirectional freeze-drying process, the gas sensitive property of these composites toflowing vapors were studied in this paper. The electrical resistance responses of thesesaligned porous conductive composites against different flowing organic vapors weremeasured. The maximum response of these materials against benzene, tetrahydrofuranand acetone in turn reduced. The maximum response increased as the flowing vapourtemperature increase.
从结构上看，如果在实体导电高分子材料内构建取向多孔气体通道，且孔径和孔壁尺寸小至微米或纳米级，那么这种取向多孔导电高分子材料将是一种理想的气敏材料。首先，超细泡孔的存在极大地增加了材料比表面积，从而加强了材料表面对气体分子的接触与吸附；其次，比普通薄膜材料更薄的聚合物层可提供更高的气敏响应强度；再者，取向通孔结构对气体流动影响较小，有利于高速流动气体的通过与检测；最后，三维构架材料可提供比薄膜材料更大的耐压性能，更适合于在具有一定气压差的环境下使用。
然而，取向多孔导电高分子材料结构的实现必须解决两个基本问题。其一是取向多孔结构在聚合物基体中的构建问题；其二是导电网络通路在取向多孔结构中的形成问题。就第一个问题而言，目前已有多种方法可用于实现在聚合物中构建取向微孔结构，如微加工法、光刻法、软光刻技术等。但这些方法所固有的成本高、效率低、对聚合物选择性强等缺点阻碍了其在聚合物加工中的应用。相比而言，新近发展起来的定向凝固干燥技术因其制备装置简单、效率高、不存在化学反应等优点而受到人们的广泛关注。
本文拟用定向凝固干燥法，构建具有取向多孔结构的导电高分子材料，并在获得了这种新型取向多孔导电高分子材料之后，研究了材料的制备参数与形态结构的关系、形态结构与电学性能关系、导电机理及对于动态有机气体的气敏响应行为及机理。
本研究主要结果有：
①聚乙烯醇取向多孔材料的制备
当PVA溶液以2mm/min的速度浸入液氮中，经定向凝固干燥后，观察到以1%的PVA溶液制备的样品断面呈纤维网状结构；而以5%的PVA溶液制备的样品呈比较规则的取向孔洞结构；随着PVA溶液浓度的增加，含PVA10%的溶液获得的样品呈现一种特殊的“鱼骨头”结构；当PVA溶液浓度高至15%时，样品断面结构呈仅有一定的取向趋势的微孔结构。
当PVA水溶液浸入液氮速度加快时（10mm/min），样品结构会有变化。同样是1%的PVA水溶液，以10mm/min的速度浸入液氮中，样品断面不再是纤维网状结构；PVA溶液浓度为5%时，以10mm/min浸入速度获得样品取向孔洞结构没有2mm/min的样品取向结构规整，孔洞之间有少量的桥接出现；PVA溶液浓度为10%时，样品断面形貌呈现特殊的“鱼骨头”结构；当PVA溶液浓度高至15%时，样品断面微孔结构的取向趋势没有2mm/min浸入液氮中的样品取向趋势明显。
对不同浓度的PVA溶液以4mm/min的速度浸入-70℃冷冻乙醇中所制备的样品断面微观组织分析后发现，当PVA溶液浓度极稀时（1%），与定向浸入液氮中所获得的样品断面呈纤维网状结构不同，断面呈团絮状结构；随着PVA溶液浓度的增加，浓度为5%及7.5%时，断面呈特殊的“鱼骨”形状，且“鱼骨”有增粗的趋势，取向趋势明显，这些“鱼骨”状结构的分支是由PVA溶质在大块冰晶边缘的排斥下形成的；在溶液浓度增加至10%及以上时，断面形貌逐渐转变为片层结构，取向趋势逐渐减弱，片层之间的间距也逐渐缩小。
②聚氨酯取向多孔材料的制备
a.以Bayer Impranil1380水性聚氨酯分散体为原料，对该溶液采用定向凝固干燥法制备样品。对于稀的Impranil1380水性聚氨酯分散体(5%)，以4mm/min浸入液氮后，与用稀PVA溶液（1%）制备的样品断面结构类似，断面呈纤维网状结构，纤维直径约2-3μm。而对于20%的Impranil1380水性聚氨酯分散体，浸入液氮定向凝固干燥后，获得的样品呈一定取向的多孔形貌，当Impranil1380水性聚氨酯分散体固含量增加至40%时，样品断面形貌仅呈一定的取向趋势，且只能观察到少量孔洞形貌。20%的Impranil1380水性聚氨酯分散体以4mm/min的速度浸入-50℃乙醇中，经定向凝固干燥后获得样品断面形貌呈解理状，无取向孔洞产生。
b.以Bayer UH240水性聚氨酯分散体为原料，用定向凝固干燥法制备样品。不同浓度的UH240水性聚氨酯溶液以4mm/min的速度浸入-70℃乙醇定向凝固干燥，以10%的UH240水性聚氨酯溶液制备的样品断面结构仅有一定取向趋势，而以20%的UH240溶液为原料所获得的样品断面呈非常规整的取向多孔结构，孔洞直径约为25μm，孔壁厚度约为4μm，孔洞结构在视场范围内保持连续，当UH240溶液浓度升高至40%时，样品断面显微组织仅呈一定的取向趋势。
把UH240水性聚氨酯溶液分别以1mm/min、10mm/min的速度浸入-70℃乙醇中发现，以10mm/min的速度浸入冷冻乙醇中后获得的样品孔洞直径、孔洞壁厚度要比1mm/min的速度浸入冷冻乙醇中后获得的样品略低。把20%的UH240水性聚氨酯溶液以4mm/min的速度分别浸入-50℃、-70℃、-90℃、-110℃的冷冻乙醇中，经定向凝固干燥后，所获得的样品断面都呈非常规整的取向多孔结构，且冷冻液温度越低，样品孔洞直径越小，孔洞壁厚度越薄。
③取向多孔导电聚乙烯醇基、聚氨酯基材料的制备及导电性能
在5%的PVA水溶液中添加炭黑、碳纳米管，20%的水性聚氨酯中添加碳纳米管后，以4mm/min的速度浸入-70℃乙醇，经定向凝固干燥后，成功获得了取向多孔导电炭黑/聚乙烯醇、碳纳米管/聚乙烯醇、碳纳米管/水性聚氨酯材料。复合材料（炭黑/聚乙烯醇、碳纳米管/聚乙烯醇、碳纳米管/水性聚氨酯）的电阻率与导电填料含量（炭黑或碳纳米管）关系曲线表明，在导电填料的含量增加到一定程度后，材料的电阻率显著降低；在降低到一定程度后，随着导电填料含量的继续增加，电阻率变化不大。用经典的逾渗理论方程对复合材料（炭黑/聚乙烯醇、碳纳米管/聚乙烯醇、碳纳米管/水性聚氨酯）的电阻率与导电填料含量（炭黑或碳纳米管）关系进行拟合，得出复合材料导电填料的逾渗值分别为12.5vol.%、6.2vol.%、2.0vol.%，临界电阻率指数分别为2.8、6.1、2.7，临界电阻率指数不在经典的逾渗理论所定义的范围之内，这是由于复合材料具有的特殊取向孔洞结构所导致。
④取向多孔导电聚乙烯醇基、聚氨酯基材料对流动气体的气敏行为
在利用定向凝固干燥法制备的取向多孔导电炭黑/聚乙烯醇、碳纳米管/聚乙烯醇、碳纳米管/水性聚氨酯复合材料的基础上，研究取向多孔导电炭黑/聚乙烯醇、碳纳米管/聚乙烯醇、碳纳米管/水性聚氨酯复合材料对流动气体的气敏行为。研究结果表明，取向多孔导电炭黑/聚乙烯醇、碳纳米管/聚乙烯醇、碳纳米管/水性聚氨酯复合材料对苯、四氢呋喃、丙酮等有机气体都具有很强的气敏响应，且对上述气体的响应率依次降低。对取向多孔导电碳纳米管/聚乙烯醇、碳纳米管/水性聚氨酯材料在不同温度的有机气体中的气敏响应研究发现，温度越高，响应率也就越高。
In the current practice, the conductive polymer composites as gas sensor are usuallyfabricated as films with the thickness from decades to hundreds of microns through hotpressing or casting, which is beneficial to vapor permeating, and resulting in high vaporsensitivity. However, when being used to monitor the flowing vapors in the pipes, thefilmy polymer sensors are seriously limited by easily getting ruptured, less operationarea, instability, and so on. Thus, it is still a tough challenge to establish alternativetechniques to fabricate polymer based gas sensor for flowing vapors in practicalapplication.
Structurally, the conductive polymer composites with an aligned porous structurewill be an ideal sensor when the diameter of the pores and thickness of the wall is tomicrons or to the nanometer level. Compared with the ordinary film-like polymer gassensors, this new aligned micro-porous composite sensor is much more suitable formonitoring flowing organic vapors based on the following reasons:
(1)The micro-pores greatly increase the surface area of the materials and intensifythe contact between the gas molecules and materials.
(2)The even thinner pore walls in the new aligned micro-porous sensor can result inhigher vapor sensitivity.
(3)One-dimensional micro-porous structure can facilitate the high speedtransportation of flowing vapors and benefit detection.
(4)This kind of sensor has stronger pressure resistance than the film sensors and ismore applicable under the condition of pressure difference.
However, there are two basic questions must be solved to achieve the alignedporous conductive composites. One is the construct of the aligned porous structure inpolymer matrix. The other is the formation of the conductive network in an alignedporous structure. For the first question concerned, there are a variety of methods can beused to realize the construction of an aligned porous structure in a polymer matrix, suchas micro processing method, photolithography, soft lithography, etc. But these methodshave shortcomings such as high cost, low efficiency and polymer selectivity andhindered the application in polymer processing. In contrast, the newly developeddirectional freeze-drying process has been paid much attention by the people because ofthe advantages such as simple preparation device, efficient and does not exist chemical reaction.
Herein, a conductive polymer composite with an aligned micro-porous structure isobtained through directional freeze-drying process. And, the relationship between thepreparation parameters and structure, the conductivity property and structure,conductivity mechanism, vapor-sensitive response behavior and mechanism are studiedin this paper.
The main results are listed below:
①Preparation of an aligned porous poly (vinyl alcohol)
When poly (vinyl alcohol)(PVA) solution was immersed in liquid nitrogen with thevelocity of2mm/min, after freeze-drying process, the fiber structure was observed inthe specimen’s cross section prepared from1%PVA solution. Regular aligned porousstructure was obtained from the specimen prepared from5%PVA solution. With theincrease of PVA solution concentration, the specimen prepared from10%PVA solutionis fish-bone like structure. And the micro-porous structure of the specimen preparedfrom15%PVA solution is only a trend to orientation.
The results show that the structure will change with the immersing velocity. WhenPVA solution was immersed in liquid nitrogen with the velocity of10mm/min, thespecimen prepared from1%PVA solution no longer is fiber network structures.Regular aligned porous structure can also be obtained from5%PVA solution, but thereare some bridges appeared between the pores. The specimen prepared from10%PVAsolution presents special fish-bone like structure. When the concentration of PVAsolution increased to15%, compared with the specimen prepared from2mm/min, theorientation trend of the specimen decreased.
When PVA solution was immersed into-70℃ethanol with the velocity of4mm/min, the structure of the specimen prepared from1%PVA solution is floe in group,that is different from the fiber structure. When the concentration of PVA solutionincreased to5%and7.5%, the structure of the specimen presents fish-bone likestructure and the fish-bone has the trend to been thicker. The branches of the fish-bonesare formed by the edge of the large ice crystals. When the concentration of the solutionincreased to10%or above, the morphology changed gradually to a layer structure andthe orientation trend decreased.
②Preparation of an aligned porous polyurethane
a. Bayer Impranil1380water-borne polyurethane dispersion was used as the rawmaterials for directional freeze-drying process in this section. When polyurethane dispersion was immersed in liquid nitrogen with the velocity of4mm/min, thespecimen prepared from5%polyurethane dispersion by directional freeze-dryingprocess is fiber network structures and the diameter of the fibers is about2-3μm. That issimilar to the structure of the specimen prepared from1%PVA solution. The specimenprepared from20%polyurethane dispersion presents an unobvious aligned porousstructure. And, when the concentration of polyurethane dispersion increased to40%,there are a few holes and only a trend to orientation in the micro-structure of thespecimen. When polyurethane dispersion was immersed in-50℃ethanol with thevelocity of4mm/min, the specimen presents a cleavage morphology and there is noaligned pores in it.
b. Bayer UH240water-borne polyurethane dispersion was used as the raw materialsfor directional freeze-drying process. When polyurethane dispersion was immersed in-70℃ethanol with the velocity of4mm/min, there are only a trend to orientation in themicro-structure of the specimen prepared from10%and40%polyurethane dispersionby directional freeze-drying process. However, the specimen prepared from20%polyurethane dispersion by directional freeze-drying process presents regular alignedporous structure, and the diameter of the pores is about25μm and pore wall thickness isabout4μm. When polyurethane dispersion was immersed in-70℃ethanol with thevelocity of1and10mm/min respectively, the result showed that the diameter of poresand pore wall thickness prepared by10mm/min were smaller than1mm/min. Whenpolyurethane dispersion was immersed in-50℃,-70℃,-90℃and-110℃respectively,the specimen prepared by directional freeze-drying process presents regular alignedporous structure. And the temperature of cryogenic lower, the smaller of diameter ofpores and pore wall thickness.
③Preparation and conductivity of aligned porous conductive poly (vinyl alcohol)and polyurethane composite
After carbon black or carbon nanotubes were added into5%PVA solution orcarbon nanotubes were added into20%polyurethane dispersion, the solutions wereimmersed in-70℃ethanol with the velocity of4mm/min. In this way, aligned porousconductive carbon black/poly (vinyl alcohol), carbon nanotube/poly (vinyl alcohol) andcarbon nanotube/polyurethane composites can be obtained by directional freeze-dryingprocess. Electrical conductivity of composites such as black/poly (vinyl alcohol),carbon nanotube/poly (vinyl alcohol) and carbon nanotube/polyurethane composites asa function of carbon black or carbon nanotubes content is obtained in this paper. These curves showed that the resistivity of the composite decrease significantly when theconductive filler increased to certain content. When the resistivity decreased to a certaindegree, as the conductive filler continue to increase, the resistivity change is not large.When these curves are fit using the percolation concept, the volume percolationconcentration of these composites were obtained as12.5%,6.2%and2.0%respectively.And, the resistivity critical exponents are2.8,6.1and2.7respectively and not in therange of percolation theory described.
④Aligned porous conductive poly (vinyl alcohol) or polyurethane composite usedas a sensor for flowing vapors.
When aligned porous conductive black/poly (vinyl alcohol), carbon nanotube/poly(vinyl alcohol) and carbon nanotube/polyurethane composites were obtained bydirectional freeze-drying process, the gas sensitive property of these composites toflowing vapors were studied in this paper. The electrical resistance responses of thesesaligned porous conductive composites against different flowing organic vapors weremeasured. The maximum response of these materials against benzene, tetrahydrofuranand acetone in turn reduced. The maximum response increased as the flowing vapourtemperature increase.
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