One of the main objectives of this thesis is to disperse double-walled carbon nanotubes (DWNT) in a polyvinylidene fluoride (PVDF) matrix, and to characterize the resulting composite using electrical, thermal, and mechanical characterization techniques. DWNTs are successfully dispersed in the PVDF, and this dispersion is assessed by using optical microscopy and both scanning and transmission electron microscopy. The second objective of this study is to investigate the morphology of the PVDF after adding the carbon nanotubes. The results using the x-ray diffraction technique do not show change in the PVDF morphology with addition of DWNTs. In Differential scanning calorimetry study the results show that the melting temperature does not vary much with addition of DWNTs. An increase in the crystallization temperature and a decrease in the percent crystallinity is also observed as DWNT content increases. The electrical and mechanical properties of the composites are measured and data is used to calculate the percolation volume fraction using electrical conductivity. The results show that the percolation threshold occurs at 0.23 vol%, which is a low volume fraction further indicating a good dispersion. The critical exponent implies a three dimensional dispersion. The predicted volume fraction at percolation using the excluded volume approach indicates that the DWNTs are dispersed in small bundles of seven hexagonally closed packed tubes. The mechanical properties are done using dynamic mechanical analysis to study the effect of the nanotubes on the mechanical properties. The results show that the storage modulus is enhanced 84% by adding 4.51 vol% DWNT-PVDF below the glass transition temperature which is in a -45°C region and it is increased by about 97% at 40°C. Electromechanical performance of the composites is assessed by testing the actuation behavior using DC voltage. The results show no actuation for volume contents below percolation, and a measurable actuation at volume contents above percolation. Results from the different characterization techniques indicate that the DWNTs are successfully dispersed. An enhancement in electrical conductivity and dielectric constant is achieved by addition of DWNTs. At DWNT volume content above percolation, both mechanical and electromechanical enhancements are observed, as evidenced by DMA and electroactive characterization techniques.

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Polyvinylidene fluoride (PVDF) and its copolymer with trifluoethylene (PVDF-TrFE) have been widely investigated. This is largely attributed to their ferroelectric properties, which are present in a limited number of polymers. In comparison with the more widely used ferroelectric ceramics, the ease of their fabrication makes them attractive in flexible electronic devices. Despite many advances in their application, we are still lacking a complete fundamental understanding of the relationship between their structure and the functional properties. The melt-extrusion of PVDF revealed that the α-phase is predominantly formed in films. The ferroelectric β-phase PVDF was obtained by high temperature drawing of the α-phase of as-extruded films. It was observed that a minimum draw ratio of 3 is required to generate the β-phase. Chain mobility is crucial to the formation of β-phase. Too high chain mobility when drawing at temperatures above 100 °C can only orientate the pre-existing α-crystals without making the chain conformation change to form the β-crystals. Furthermore, the comparison between the produced α- and β-PVDF films is summarized. The α-PVDF films crystallized into spherulites with random orientation, while β-PVDF films displayed fibriliar structure showing preferred orientation of the polymer chains along the drawing direction. The overall crystallinity obtained from DSC data hardly varied, however, the drawn β-PVDF films had a lower melting temperature, which was also confirmed from the dielectric temperature spectra. The drawn β-PVDF films showed higher dielectric constant and larger remnant polarization compared with the as-extruded α-PVDF films, which is mainly ascribed to their higher β-phase content and preferred orientation. Highly aligned PVDF-TrFE films were processed using a melt extrusion processing route. Crystalline structure and orientation were optimized by controlling the melt extrusion conditions. XRD patterns suggested that there was nearly perfect alignment of the c-axis (polymer chain direction) along the extrusion direction in the optimized as-extruded films. SEM analysis confirmed the morphology of the crystalline phase, showing edge-on lamellae stacked perpendicular to the extrusion direction. DSC data indicated high crystallinity and well-ordered ferroelectric structure of the extruded films. FTIR spectroscopy revealed strong intermolecular dipole-dipole interaction in the extruded films. Accordingly, the optimized as-extruded PVDF-TrFE films exhibited a coercive field of 24 kV/mm, half of the commonly reported values for bulk films (~ 50 kV/mm) and a remnant polarization of 0.078 C/m2 which further increased to 0.099 C/m2 after annealing. This value is close to the theoretical limit (0.102 C/m2) assuming perfect in-plane c-axis orientation and 100% crystallinity. The typical limitations of PVDF - low crystallinity and indirect ferroelectric β-phase crystallization - and PVDF-TrFE - higher materials and processing costs and a low Curie point - are tackled by a simple and industrially viable melt blending approach. Despite the immiscible nature of PVDF and PVDF-TrFE, strong interactions exist between the two polymers when co-melt processed, which substantially affect the morphology and texture of the blends as well as their dielectric and ferroelectric properties. Surprisingly, minor amounts of PVDF-TrFE led to a significant increase in the β-phase content and preferred orientation of PVDF, well beyond the rule-of-mixtures. Moreover, the blends exhibited maximum increases in the dielectric constant of 80% and 30%, respectively compared with pure PVDF and PVDF-TrFE. The ferroelectric remnant polarization increased from 0.040 to 0.077 C/m2, while the coercive field decreased from 75 to 32 kV/mm with increasing PVDF-TrFE from 0 to 40 wt. %. The enhancement of properties is explained by the strong interactions at the interfaces between PVDF and PVDF-TrFE, which also suppresses the Curie transition of PVDF-TrFE, providing a potentially increased working temperature range for blended films, which is important in applications like non-volatile energy storage devices, ferroelectric field-effect transistors and touch sensors. Ferroelectric composites, integrating dielectric ceramic fillers with mechanically flexible polymers, are promising materials for flexible electronic applications. Numerous research works have demonstrated enhanced dielectric and ferroelectric properties of composite materials. However, the mechanisms responsible for these enhancements are not completely understood. Herein, PVDF and BaTiO3 (BTO) were used to study the effect of dielectric filler on the crystallization, phase transformation and dielectric properties of PVDF. The crystallization of α-PVDF was not affected by the presence of BTO particles, but small amounts of BTO (< 3 vol. %) made PVDF crystallize into larger spherulites. This is linked to crystallization kinetic studies, which showed that BTO acted as a nucleation agent for large full ring banded spherulites when its content was less than 1 vol. %. Furthermore, solid state drawing in the presence of BTO particles promoted the formation of β-PVDF with more pronounced crystalline orientation at high drawing temperatures (120 °C). The dielectric and ferroelectric properties were enhanced with BTO filling. The 100 °C oriented drawn PVDF tape exhibited a dielectric permittivity of 14 (100 Hz) and remnant polarization of 0.080 C/m2 (10 Hz), which increased to 20 and 0.095 C/m2, respectively, after filling with 5 vol. % BTO; neither resulting in high dielectric loss tangent (~ 0.02) nor obvious current leakage. Moreover, the coercive field decreased from 80 to 50 kV/mm with increasing BTO content from 0 to 5 vol. %.

The applications of membrane technologies have dramatically increased during the last few decades due to technology improvement and cost reduction. Membrane applications can be found in water and wastewater treatment, pharmaceutical industry, chemical processing industry, food industry, etc. However, the membrane technology faces two major challenges: membrane fouling and membrane lifetime. During the membrane filtration process, membrane fouling caused by natural organic matter (NOM) is an inevitable phenomenon, and physical cleaning or chemical cleaning are required for recovering the performance of membrane. As a result of these cleaning processes, membrane lifetime is shortened. For this reason, it is necessary to improve membrane's fouling resistance and lifetime in order to apply membrane technology in large-scale facilities. This dissertation focuses on improving the fouling resistance and flux performance of polyvinyl chloride (PVC) membrane and polyvinylidene fluoride (PVDF) membrane. Specifically, it is comprised of four parts. First, I prepared PVC membranes by adding different amounts of amphiphilic copolymer (Pluronic F 127) into PVC casting solutions. I optimized the performance of PVC membranes by changing the amount of Pluronic F127 used in the casting solution. The results show that with the increase of Pluronic F 127 content, the pore size and pore density both decrease. Moreover, the membrane surface becomes more hydrophilic as indicated by lower contact angles. In addition, the PVC membrane exhibits remarkable antifouling characteristics after adding Pluronic F 127. Second, I synthesized PVDF membranes by adding PVDF graft poly(ethylene glycol) methyl ether methacrylate (PEGMA) (PVDF-g-PEGMA) as additive in casting solutions via the phase inversion method. The synthesized PVDF membranes have unique pillar-like structures on surfaces, which gives the PVDF membrane a defect-free feature and allows it to generate high flux under low pressure. Third, I investigated the forming mechanism of the pillar-like structure from aspects of solvent and additive. Finally, I investigated the influence of PEGMA dose on the performance of PVDF membranes. I changed the amount of PEGMA used in the casting solution and compared the performance of the synthesized PVDF membranes. To summarize, this dissertation has deepened our understanding of how to improve the fouling resistance and flux performance of PVC membranes and PVDF membranes by using amphiphilic copolymer. In addition, the PVDF membrane I synthesized has unique pillar-like structures that give it defect-free and high flux properties. Overall, the results of this study provide valuable information for PVC and PVDF membrane synthesis for large-scale production.

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第22796号 / エネ博第410号 / 新制||エネ||78(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 坂口 浩司, 教授 佐川 尚, 准教授 高井 茂臣 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

<p>The clogging of filtration membrane by particles otherwise known as fouling is a major concern in membrane filtration technology due reduction of flux, membrane lifespan and system performance, with an associated increase in process and operating costs in industries that utilize membrane in their production process. Cleaning or replacement of a fouled membrane requires production to be interrupted or the entire system to be shut down. This is because the cleaning or replacement of the fouled membrane requires production to be interrupted for the cleaning process or the entire system to be shut down for the replacement process to take place, leading to great losses to the industries involved. Many approaches have been devised over the years to tackle this problem, of which not only undermine the performance of the filtration membrane but also contribute to great losses to industries that apply them. Cheaper and more efficient means of fouling control remains the key to solving this problem. </p> <p> </p> <p>A water filtration system is proposed that uses piezoelectric crystals attached on a tubular polyvinylidene fluoride (PVDF) membrane to increase flux and delay the clogging of the pores of the filtration membrane (by particles). Filtration tests with mud solution showed that the membrane vibrated with piezoelectrics reduced the clogging of the pores and increased permeate flux of the filtration process as compared to the non-vibrated membrane. To optimize the permeate flux production of the system and fouling reduction, the effects of voltage, concentration and location of piezoelectric crystals<a> were investigated. An equation to best fit the experimental data was developed which can help in the optimization of the variables.</a></p> <p> </p> <p> </p> <p> </p> <p> </p> <p> </p>

With the increase of population every year, fresh water scarcity has rapidly increased and it is reaching a risky level, particularly in Africa and the Middle East. Desalination of seawater is an essential process for fresh water generation. One of the methods for desalination is membrane distillation (MD). MD process separates an aqueous liquid feed across a porous hydrophobic membrane to produce pure water via evaporation. Polyvinlidene fluoride (PVDF) membranes reinforced with a polyester fabric were fabricated as potential candidates for MD. Non-solvent induced phase separation coupled with steam treatment was used to prepare the PVDF membranes. A portion of the prepared membrane was coated with Teflon (AF2400) to increase its hydrophobicity. In the first study, the fabricated membranes were characterized using scanning electron microscopy and other techniques, and they were evaluated using direct contact MD (DCMD). The fabricated membranes showed a porous sponge-like structure with some macrovoids. The macrovoid formation and the spongy structure in the membrane cross-sections contributed significantly to a high permeate flux as they provide a large space for vapor water transport. The modified PVDF membranes with steaming and coating exhibited a permeate flux of around 40 L/h m2 (i.e. 27-30% increase to the control PVDF membrane) at temperatures of 60 °C (feed) and 20 °C (permeate). This increase in the permeate flux for the modified membranes was mainly attributed to its larger pore size on the bottom surface. In the second study, the control PVDF membrane was tested in two different module designs (i.e. semi-circular pipe and rectangular duct module designs). The semi-circular module design (turbulent regime) exhibited a higher permeate flux, 3-fold higher than that of the rectangular duct module design (laminar regime) at feed temperature of 60 °C. Furthermore, a heat energy balance was performed for each module design to determine the temperature polarization coefficients (TPC). The turbulent module design showed higher TPC (0.5-0.58) than the laminar module (0.1-0.14) (i.e. a poor module design). This indicates that the effect of temperature polarization on the laminar flow was significant, which is below the reported TPC range of 0.4-0.70.

The growth of sensors and sensing technologies have made significant impact in our day-to-day life. The five principle sensory organs of our body should perform effectively, so that we can lead a good healthy life. Apart from these natural sensors, there are man-made sensors that helps us to cope with diseases, organ failure etc. and enable us to lead a normal life. In recent years, with the prevalence of new kind of diseases, the need for new type of biomedical sensors is becoming very important. As a result, sensors used for biomedical applications have become an emerging technology and rapidly growing field of research. The aim of the present thesis work is to use the piezoelectric property of Polyvinylidene Fluoride (PVDF) film for the development of biomedical sensor and studying its application for human respiration/breathing related abnormalities. PVDF nasal sensor was designed in cantilever configuration and detailed theoretical analysis of the same was performed. Based on theoretical and experimental results, the PVDF nasal sensor dimensions were optimized. Suitable signal conditioning circuitry was designed and a measurement system for biomedical application was developed. The developed PVDF nasal sensor was calibrated using MEMS low-pressure sensor. The PVDF nasal sensor system has been applied in different biomedical applications namely, (i) to monitor human respiration pattern, (ii) to identify different Respiration Rates (RR), (iii) to evaluate Deviated Nasal Septum (DNS) in comparison with other objective method and, (vi) to clinically investigate nasal obstruction in comparison with subjective method. The thesis is divided into seven chapters. Chapter 1 This chapter gives a general introduction about biomedical sensors, piezoelectric sensing principle and PVDF polymer films along with the relevant literature survey. The brief introduction as well as literature survey of techniques used to monitor human respiration and to measure nasal obstruction is also included in this chapter. Chapter 2 This chapter gives details about the design of the PVDF nasal sensor in the cantilever configuration for sensing nasal airflow along with the relevant theoretical equations. Also, the details on the optimization of the PVDF nasal sensor dimensions based on the theoretical and experimental analysis are presented. Chapter 3 This chapter reports the designing of the necessary signal conditioning hardware along with the data acquisition unit for the PVDF nasal sensor. The signal conditioning hardware unit made consists of charge amplifier, low-pass filter and an amplifier. Besides, a complete measurement system for biomedical application was developed using PVDF nasal sensor and its merits and demerits were discussed. Chapter 4 In this chapter, an experimental set-up for measuring human respiration/breathing pressure using water U-tube manometer has been described. Also, the calibration procedure followed for the developed PVDF nasal sensor using a Micro Electro Mechanical Systems(MEMS) low pressure sensor is reported. Apart from these, the details on the measurement of deflection of the PVDF cantilever sensing element using laser displacement setup are provided. In addition, the PVDF nasal sensor was also calibrated for various air flow rates. At the end, a study has been reported on optimizing the position the PVDF nasal sensor with respect to human nose. Chapter 5 This chapter is divided into two sections, Section 5.1: This section describes the applicability of the PVDF nasal sensor using its piezoelectric property to monitor the human respiration pattern of each nostril simultaneously. The results of the PVDF nasal sensor have also been evaluated by comparing with Respiratory Inductive Plethysmograph(RIP) technique in normal subjects. Section 5.2: In this section, PVDF nasal sensor, RIP and Nasal Prongs (NP) techniques were used to measure the RR of healthy adults. The aim here was to evaluate the presently developed PVDF nasal sensor for identifying different RR compared to „Gold standard‟ RIP and NP methods. Chapter 6 This chapter is divided into two sections. Section 6.1: This section reports about the utilization of the developed PVDF nasal sensor for clinical application on the patient population. For this purpose, the performance of the PVDF nasal sensor measurements has been compared with the Peak Nasal Inspiratory Flow(PNIF) objective technique and visual analog scale (VAS). Section 6.2: This section describes about the use of PVDF nasal sensor system to measure nasal obstruction caused due to DNS objectively. Further, the results of the PVDF nasal sensor were compared with subjective techniques namely, VAS and clinician scale in patients and control group. Chapter 7 This chapter is composed of two sections. Section 7.1: This section summarizes the salient features of the work presented in this thesis. Section 7.2: This section reports a scope for carrying out further work.

In this study, membranes were made from three polyvinylidene fluoride (PVDF) polymers individually and the blend systems of high (H) and low (L) molecular weight PVDF by phase inversion process. After investigating membrane casting solutions’ viscous and thermodynamic properties, the membranes so fabricated were characterized by scanning electron microscopy, gas permeation tests, porosity measurement, contact angle (CA) and liquid entry pressure of water (LEPw) measurement, and further subjected to vacuum membrane distillation (VMD) in a scenario that was applicable for cooling processes, where the feed water temperature was maintained at 27℃. It was found that PVDF solutions’ viscosities and thermodynamic instabilities were determined by the types of PVDF employed in single polymer systems and the mixing ratios of two PVDF polymers in blend systems. Thus the membrane properties and performances were influenced by the aforesaid factors as well. In single polymer systems, it was found that the membrane surface roughness and porosity increased with an increase in molecular weight. Among all the membranes casted in this study, the water vapor flux of VMD was found to be the highest at the intermediate range of H:L ratio, i.e., 4:6, at which the thickness of the sponge-like layer showed a minimum, the finger-like macro-voids formed a more orderly single-layer structure, and the LEPw showed a minimum. A conclusion can be made that blend systems of high molecular weight PVDF polymers and low molecular weight PVDF polymers could be used to optimize membrane performance in vacuum membrane distillation.

This study used electrospinning to fabricate a polyvinylidene fluoride (PVDF) piezoelectric nanofiber harvesting device with interdigitated electrode to capture ambient energy. According to d33 mechanical-electric energy conversion mode, the energy harvesting device can be applied on the low frequency ambient vibration and impact abilities for the transformation mechanical energy into electrical energy effectively. First, the PVDF powder was mixed in acetone solution uniformly and the dimethyl sulfoxide (DMSO) was mixed with multi-walled carbon nanotube (MWCNT) to prepare PVDF macromolecular solution. The mixed solution was filled in a metals needle injector and contacted hundreds of voltage. After the PVDF drop in the needle was subjected to high electric field, the drop overcame surface tension of the solution itself, then extremely fine PVDF fiber was formed and spun out. The electrospun was collected orderly using X-Y digital control stage and the linear diameter of electrospun can be controlled easily by adjusting the travelling speed of the stage. In the spinning process, as affected by stretching strain and electric field at the same time, the PVDF piezoelectric fiber resulted in electric polarization and transformed £] piezoelectric crystal phase, in which the dipoles are oriented in the same direction. Furthermore, MWCNT was added to improve the mechanical properties of fiber and increase £] phase, to enhance the tensile strength and piezoelectric property of PVDF fiber effectively. Finally, the photolithography was used to fabricate interdigitated electrodes with 100£gm gap on the flexible PI substrate. The PVDF fibers, with a length and diameter of approximately 1cm and 700-1000nm, were aligned on interdigitated electrodes and packaged with the PI film. In order to increase the conversion efficiency of piezoelectric fiber in d33 mode, the PVDF fibers were repolarized in a high electric field. The results showed that the PVDF fiber energy harvesting device can generate 15mV open-circuit voltage under low frequency vibration of 4Hz and generate above 30mV open-circuit voltage under 6Hz vibrations. As compared with the piezoelectric fiber not repolarized by interdigitated electrode, its output voltage was increased by1- 2 times.