近场纺丝制备聚合物微/纳米纤维及其应用研究
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摘要
一维纳米结构具有大的比表面积、特殊的光学、电学、磁学性能,已经成为当今世界材料科学研究的热点。其中聚合物纳米纤维材料由于其良好的柔韧性,引起了人们高度的研究兴趣。静电场纺丝是制备各种纳米纤维材料的一种常用方法,纤维的直径一般从几纳米到几微米。然而传统静电纺丝制备的纳米纤维大多呈无序状态,限制了其应用范围。因此本文提出了一种有序静电场纺丝技术-近场纺丝,制备了多种聚合物微/纳米纤维图案,并基于制备的聚合物纤维制作了多种微/纳器件,如聚偏二氟乙烯(PVDF)纤维压电执行器、聚苯胺(PANI)静电执行器和微/纳流体通道。其主要内容包括以下几个方面:
1.提出了一种有序静电场纺丝技术-近场纺丝,并用来直接、连续、可控地沉积聚合物微/纳米纤维。近场纺丝中,将喷丝头与收集器间的距离减小到几毫米,从而得到稳定的聚合物射流,以实现有序的微/纳米纤维沉积。通过一个可编程的X-Y平台来控制收集器的运动轨迹和运动速度,制备了各种聚氧化乙烯(PEO)、PVDF和PANI微/纳米纤维图案。采用电子扫描显微镜(SEM)对制备的微/纳米纤维的形貌进行了分析表征,并讨论了电纺参数对纤维直径的影响。这种技术使得静电纺丝成为直接写微/纳米制造技术的一种潜在工具,从而应用于各种微/纳米器件的制造,如发电机、传感器、执行器、微/纳流体器件等。
2.电纺聚合物微/纳米纤维在执行器方面的应用。(1)研究了直接写的两端固定、悬空的PVDF纤维的压电驱动性能。近电纺丝技术中的实时电极化过程赋予了PVDF纤维良好的压电性能。试验中,在应用的电场下PVDF纤维既产生压电响应,也产生静电响应,采用双层电极结构削弱了静电作用对测试结果的影响。近场纺丝制备的PVDF纤维压电系数d33的平均值为-57.6pm/V,约为文献中报道的PVDF薄膜的2倍。(2)基于电纺的PANI纳米纤维,制作了悬臂梁结构的静电执行器,并测试了PANI悬臂梁在静电力作用下的位移。当应用的电压为270V时,PANI悬臂梁自由端的位移为1.2μm。
3.电纺聚合物纤维在微/纳流体通道制备技术方面的应用。采用近场纺丝沉积在硅基底上的PVDF和PEO微/纳米纤维图案作为模板,在PDMS上制备了微/纳流体通道。由于近场纺丝工艺具有高度的控制性,因此根据不同的应用需要,可以制备各种图案的流体通道。基于近场纺丝技术,制备了平行的流体通道阵列、交叉相连的通道网络、‘Cal’、‘A’和‘O’通道图案,并在SEM下观测了流体通道的截面,在荧光显微镜下测试了通道的连通性。
One-dimensional nanostructures, which have large specific surface area and special optical, electrical and magnetic properties, have been the hotspot of material research in the today’s world. Among them, the polymeric nanofibers have attracted tremendous research interests due to their good flexibility. Electrospinning is a common method to produce nanofibers of different kinds of materials ranging from a few micrometers down to a few nanometers. However, the nanofibers fabricated by conventional electrospinning are random, which has limited their application. Therefore, an orderly electrospinning technique, Near-field electrospinning (NFES), has been developed, and used to fabricate various polymeric micro/nanofiber patterns. Based on electrospun polymeric fibers, several micro/nanodevices have been created, such as Poly (vinylidene fluoride) (PVDF) piezoelectric actuator, polyaniline (PANI) electrostatic actuator and micro/nanofluidic channels. The main research contents were as follows.
1. An orderly electrospinning technique, NFES, has been developed to deposit polymeric micro/nanofibers in a direct, continuous, and controllable manner. In NFES, the distance between spinneret and collector is decreased to a few millimeters to achieve stable polymer jet, thus enabling orderly deposition of micro/nanofibers. Using a programmable X-Y stage to control the trajectory and moving speed of the collector, we fabricated various poly (ethylene oxide) (PEO), PVDF and PANI micro/nanofiber patterns. Scanning Electron Microscope (SEM) has been used to investigate the morphology of fabricated micro/nanofibers, and the influence of electrospinning parameters on fiber diameter has been discussed. This technique makes electrospinning a potential tool in direct-write micro/nanofabrication for possible applications in micro/nanodevices, such as generator, sensor, actuator and micro/nanofluidic devices.
2. The application of electrospun polymeric micro/nanofibers in actuators. (1) Piezoelectric actuation of doubly clamped, suspended PVDF fibers fabricated by a direct-write process has been demonstrated. NFES technique was utilized to fabricate PVDF fibers with good piezoelectric properties by means of the in situ electrical poling process. Experimentally, PVDF fibers have responded to both piezoelectric and electrostatic effects in applied electric field, and double-layer electrodes have been used to minimize the contribution of electrostatic effect to the measured results. The electrospun PVDF fibers have an average piezoelectric coefficient d33 of -57.6pm/V, which is nearly twice of the value reported in PVDF thin films. (2) The electrostatic actuator with cantilever structure was fabricated based on electrospun PANI nanofiber, and the displacement of PANI cantilever beam under electrostatic force was measured. When the voltage of 270V was applied, the free end of PANI cantilever beam had a displacement of 1.2μm.
3. The application of electrospun polymeric micro/nanofiber in micro/nanofluidic channel fabrication. PVDF and PEO micro/nanofibers were patterned on a Si substrate using NFES technique to serve as a template to form micro/nanochannels in PDMS. Due to high control of our NFES process, diverse patterns could be realized corresponding to desired applications. Based on NFES technique, we created various micro/nanochannel patterns, such as parallel channel array, cross-linked microchannels,‘Cal’,‘A’and‘O’channel patterns. The cross section of fabricated channels was investigated under SEM and the accessibility of channels was tested under fluorescence microscope.
1.提出了一种有序静电场纺丝技术-近场纺丝,并用来直接、连续、可控地沉积聚合物微/纳米纤维。近场纺丝中,将喷丝头与收集器间的距离减小到几毫米,从而得到稳定的聚合物射流,以实现有序的微/纳米纤维沉积。通过一个可编程的X-Y平台来控制收集器的运动轨迹和运动速度,制备了各种聚氧化乙烯(PEO)、PVDF和PANI微/纳米纤维图案。采用电子扫描显微镜(SEM)对制备的微/纳米纤维的形貌进行了分析表征,并讨论了电纺参数对纤维直径的影响。这种技术使得静电纺丝成为直接写微/纳米制造技术的一种潜在工具,从而应用于各种微/纳米器件的制造,如发电机、传感器、执行器、微/纳流体器件等。
2.电纺聚合物微/纳米纤维在执行器方面的应用。(1)研究了直接写的两端固定、悬空的PVDF纤维的压电驱动性能。近电纺丝技术中的实时电极化过程赋予了PVDF纤维良好的压电性能。试验中,在应用的电场下PVDF纤维既产生压电响应,也产生静电响应,采用双层电极结构削弱了静电作用对测试结果的影响。近场纺丝制备的PVDF纤维压电系数d33的平均值为-57.6pm/V,约为文献中报道的PVDF薄膜的2倍。(2)基于电纺的PANI纳米纤维,制作了悬臂梁结构的静电执行器,并测试了PANI悬臂梁在静电力作用下的位移。当应用的电压为270V时,PANI悬臂梁自由端的位移为1.2μm。
3.电纺聚合物纤维在微/纳流体通道制备技术方面的应用。采用近场纺丝沉积在硅基底上的PVDF和PEO微/纳米纤维图案作为模板,在PDMS上制备了微/纳流体通道。由于近场纺丝工艺具有高度的控制性,因此根据不同的应用需要,可以制备各种图案的流体通道。基于近场纺丝技术,制备了平行的流体通道阵列、交叉相连的通道网络、‘Cal’、‘A’和‘O’通道图案,并在SEM下观测了流体通道的截面,在荧光显微镜下测试了通道的连通性。
One-dimensional nanostructures, which have large specific surface area and special optical, electrical and magnetic properties, have been the hotspot of material research in the today’s world. Among them, the polymeric nanofibers have attracted tremendous research interests due to their good flexibility. Electrospinning is a common method to produce nanofibers of different kinds of materials ranging from a few micrometers down to a few nanometers. However, the nanofibers fabricated by conventional electrospinning are random, which has limited their application. Therefore, an orderly electrospinning technique, Near-field electrospinning (NFES), has been developed, and used to fabricate various polymeric micro/nanofiber patterns. Based on electrospun polymeric fibers, several micro/nanodevices have been created, such as Poly (vinylidene fluoride) (PVDF) piezoelectric actuator, polyaniline (PANI) electrostatic actuator and micro/nanofluidic channels. The main research contents were as follows.
1. An orderly electrospinning technique, NFES, has been developed to deposit polymeric micro/nanofibers in a direct, continuous, and controllable manner. In NFES, the distance between spinneret and collector is decreased to a few millimeters to achieve stable polymer jet, thus enabling orderly deposition of micro/nanofibers. Using a programmable X-Y stage to control the trajectory and moving speed of the collector, we fabricated various poly (ethylene oxide) (PEO), PVDF and PANI micro/nanofiber patterns. Scanning Electron Microscope (SEM) has been used to investigate the morphology of fabricated micro/nanofibers, and the influence of electrospinning parameters on fiber diameter has been discussed. This technique makes electrospinning a potential tool in direct-write micro/nanofabrication for possible applications in micro/nanodevices, such as generator, sensor, actuator and micro/nanofluidic devices.
2. The application of electrospun polymeric micro/nanofibers in actuators. (1) Piezoelectric actuation of doubly clamped, suspended PVDF fibers fabricated by a direct-write process has been demonstrated. NFES technique was utilized to fabricate PVDF fibers with good piezoelectric properties by means of the in situ electrical poling process. Experimentally, PVDF fibers have responded to both piezoelectric and electrostatic effects in applied electric field, and double-layer electrodes have been used to minimize the contribution of electrostatic effect to the measured results. The electrospun PVDF fibers have an average piezoelectric coefficient d33 of -57.6pm/V, which is nearly twice of the value reported in PVDF thin films. (2) The electrostatic actuator with cantilever structure was fabricated based on electrospun PANI nanofiber, and the displacement of PANI cantilever beam under electrostatic force was measured. When the voltage of 270V was applied, the free end of PANI cantilever beam had a displacement of 1.2μm.
3. The application of electrospun polymeric micro/nanofiber in micro/nanofluidic channel fabrication. PVDF and PEO micro/nanofibers were patterned on a Si substrate using NFES technique to serve as a template to form micro/nanochannels in PDMS. Due to high control of our NFES process, diverse patterns could be realized corresponding to desired applications. Based on NFES technique, we created various micro/nanochannel patterns, such as parallel channel array, cross-linked microchannels,‘Cal’,‘A’and‘O’channel patterns. The cross section of fabricated channels was investigated under SEM and the accessibility of channels was tested under fluorescence microscope.
引文
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