No description available.

The effects of loading polyacrylonitrile (PAN) single fibers with carbon nanotubes (CNTs) on mechanical damage accumulation processes are explored in this thesis. Tensile, fatigue, and creep experiments were conducted to establish the effects of CNTs on the strength, fatigue lifetime, and viscoelastic/plastic (creep) damage accumulation. Three different configurations were tested: neat PAN fibers, PAN fibers loaded with multi-walled CNTs (MWCNTs) in the core, and PAN fibers loaded with few-walled CNTs (FWCNTs) uniformly throughout. The tensile results yielded load and displacement data from which failure stress was determined for all three fiber groups. During stress-life fatigue tests (runout lives ~600,000 cycles) the fibers displayed similar fatigue susceptibilities, but in static load creep tests, the different fiber configurations led to a wider range of responses. The different fiber processing parameters used for each fiber group lead to a variety of viscoelastic and viscoplastic properties within each system, resulting in a range of damage accumulation mechanisms.

No description available.

Blown films of high molecular weight high density polyethylene (HMW-HDPE) were produced from two resins of differing molecular weight (MW) and molecular weight distribution (MWD) using a high stalk bubble configuration. The processing conditions were varied such that three film gauges, each fabricated at three frost line heights (FLH), were produced. Crystalline orientation and tear resistance properties of the films were measured. Under appropriate conditions, the formation of two populations of lamellar stacks with their surface normals orthogonal to one another were observed. Increasing the FLH increased the amount of transverse direction (TD) stacked lamellae. This finding was related to bubble shape and relaxation behavior. Balanced in plane crystalline orientation was noted to give the best dart impact performance. Interestingly, for the lower Mw resin in the study, this could be achieved by down gauging. In a second project, structure-property-processing relationships were investigated in a series of high density polyethylene (HDPE) blown films. The use of metallocene and chromium oxide based resins allowed the effects of MW and MWD on orientation behavior to be studied. All films possessed Keller-Machin low stress morphologies oriented along the film MD. Under identical processing conditions, the narrower MWD resins produced films with greater orientation than the broader MWD resins of equivalent weight average MW. Greater processing stresses and shorter quench times were noted to produce higher levels of orientation. Moisture vapor transmission rate (MVTR) performance of these films was also measured. Orientation effects were seen to influence MVTR as permeation behavior did not scale directly with the crystalline content in the films. Additional studies investigated the relationship between comonomer content and the thermal and structural properties of novel poly(acrylonitrile-co-methyl acrylate) materials. Five polymers were studied with methyl acrylate (MA) content varying between 0 and 15 mol%. The MA decreased both the glass transition and melting temperatures. Melting point depression was sufficient in the two highest MA content copolymers to allow for complete melting prior to the onset of thermal degradation using modest heating rates (20 ºC/min). Insight into the heterogeneous structure of poly(acrylonitrile) homopolymer was gained through both conventional and modulated differential scanning calorimetry. / Ph. D.

No description available.

An effort concerned with the feasibility of achieving melt-processable polyacrylonitrile copolymer system precursors for producing high modulus carbon fibers is detailed. High molecular weight poly(acrylonitrile-ran-methyl acrylate) (PAN-MA) copolymer with high acrylonitrile content were mixed with various water containing binary melting point modifiers to produce systems that formed stable melts at temperatures below the temperature corresponding to the onset of PAN-MA crosslinking. The structure of the copolymer was found to be 96.5 ± 0.13 mole % acrylonitrile and 4.40 ± 0.13 mole % methyl acrylate by 1H-NMR with an Mw ]= 238 kDa and dispersity of 1.9 determined by size exclusion chromatography. A reduction in the Tm of the copolymer of 200 C was established for a copolymer/melting point modifier system containing copolymer mixed with water and acetonitrile with the following composition: PAN-MA/ACN/H2O 55/25/20 wt:wt:wt. This corresponds to the greatest reduction in a PAN-based copolymer melting temperature yet reported. From isothermal DSC and pressurized capillary rheometry experiments it was found that the stability of the resulting melts shows a strong temperature dependence, but does not show a strong dependence on shear rate. Copolymer mixtures with H2O and acetonitrile or H2O and adiponitrile were found to be suitable for melt-extrusion at 170 C with viscosities ranging from 1800-2000 Pa*s with stabilities greater than 1 hour. The modification of membranes to improve gas separation properties is of considerable interest. Crosslinking is one route to modify membranes, but the resulting effects on thin membranes have yet to be investigated to understand the impact of such modification at thicknesses that are relevant to industrial membranes. In this study, the influences of UV irradiation and physical aging on O2 and N2 gas permeation properties of thin (~ 150 nm) glassy poly(arylene ether ketone) (PAEK) films at 35 C and 2 atm were investigated. Thin PAEK films prepared from tetramethyl bisphenol A and 4,4'-difluorobenzophenone were UV irradiated on both sides in air or N2 at wavelengths of 254 nm or 365 nm. This induced crosslinking and, in some cases, photooxidation. Gas permeability decreased and O2/N2 selectivity increased as UV irradiation and aging time were increased. At 254 nm, samples irradiated in air had lower permeability coefficients and higher selectivities than samples irradiated in N2, and this was ascribed to additional decreases in free volume due to photooxidation in air-irradiated samples. Additionally, air-irradiated samples at 254 nm exhibited less physical aging than non-crosslinked and N2-irradiated samples at 254 nm, possibly due to interactions among photooxidative polar products that may restrict polymer chain mobility, thereby lowering the aging rate. The influence of water vapor on physical aging of air-irradiated samples was examined. Finally, irradiation at 254 nm leads to more extensive crosslinking and/or photooxidation than irradiation at 365 nm, possibly due to greater UV absorption by the polymer and the higher probability of radical formation at the lower wavelength. Poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) is utilized for gas separation membranes. It has a relatively high free volume with high gas permeabilities but suffers from low selectivities. PPO polymers with Mn's from 2000-22,000 g/mole were synthesized and blended with a poly(arylene ether ketone) derived from bisphenol A and difluorobenzophenone (BPA-PAEK). DSC showed that the blends with all but the lowest molecular weight PPO had two Tgs, thus suggesting that two phases were present. The ketone carbon and benzylic methyl groups on the BPA-PAEK and the PPO polymers crosslinked upon exposure to UV light. The gel fractions after UV exposure were high and the tensile properties were similar to the PPO control polymer that is currently used as a gas separation membrane. The crosslinked blends had improved gas selectivities over their linear counterparts. The 90/10 wt/wt 22k PPO/BPA PAEK crosslinked blends gained the most O2/N2 selectivity and maintained a high permeability. Two series of high molecular weight disulfonated poly(arylene ether sulfone) random copolymers were synthesized as proton exchange membranes for high temperature water electrolyzers. These copolymers differed based on the position of the ether bonds on the aromatic rings. One series was comprised of fully para-substituted hydroquinone comonomer and the other series incorporated 25 mole % of a meta-substituted comonomer, resorcinol, and 75 mole % hydroquinone. The influence of the substitution position on water uptake and electrochemical properties of the membranes were investigated and compared to the state-of-the-art membrane, Nafion. Mechanical properties of the membranes were measured for the first time in fully hydrated conditions at room and elevated temperatures. While submerged in water, these hydrocarbon-based copolymers had moduli an order of magnitude higher than Nafion membrane. Selected copolymers of each series showed dramatically increased proton conductivity at elevated temperature and fully hydrated conditions while their H2 gas permeabilities were well controlled over a wide range of temperatures. These improved properties were attributed to the high glass transition temperature of poly(arylene ether sulfone)s. / Ph. D. / In this work, the author is attempting to create precursor material for carbon fiber that is melt-processable. Currently, carbon fibers are produced from precursor fibers which were spun from organic solvent solutions. This method is more expensive and less environmentally friendly than producing the precursor fibers from the melt. The precursor polymer has a tendency to crosslink and degrade at temperatures that are less than its melting point, thus preventing is from being melt-processed. By creating formulations with the precursor polymer and various modifiers, the author was able to produce materials that could be melted without significant degradation and could therefore potentially be used to melt-process carbon fiber precursor fibers.

Polyacrylonitrile (PAN) fiber is one of the most important synthetic fibers in the world because it is a precursor to carbon fiber. Compared to the traditional solution spinning process, the melting spinning process of PAN is less costly and can further reduce the price of PAN fiber. This dissertation is concerned with the objective of establishment of conditions (temperature, plasticizer type, and plasticizer composition) that a PAN copolymer is able to be stable melt spun with water based plasticizers. More specifically, PAN/water/acetonitrile (70/15/15) mixture is considered as reference sample in this study because it was proposed in a BASF patent in which it was claimed it could be stably melt spun. We are looking for a more benign plasticizer so that the use of acetonitrile can be avoided and PAN can still be stably melt spun. To achieve this objective, the first step is to measure the melting point (Tm) of PAN copolymer with various plasticizers and compositions by using differential scanning calorimetry (DSC). The results indicate the Tm of PAN copolymer can be reduced to around 160 oC with water only as a plasticizer, which is lower than the degradation temperature of PAN (180 oC). Moreover, using a water/ethanol mixture and water/acetonitrile as plasticizers can further reduce the melting point of PAN to 150 oC and 135 oC, respectively. The second step is conducting rheological measurements on the PAN/plasticizers mixture. A pressure chamber was designed and attached to the capillary rheometer in order to prevent the foaming and evaporation of plasticizers during the viscosity experiments. Both steady-shear and time-dependent viscosity measurements were conducted. The rheological measurement results indicate that PAN can keep stable for more than 120 minutes with all plasticizers under 170 oC, and it starts to degrade in 60 minutes at 180 oC, except samples plasticized with 30 wt% of water (which keep stable for 120 minutes as well). The steady-shear viscosity results indicate the shear-thinning behavior is observed for the PAN/plasticizer mixtures at a temperature ranging from 170 oC to 190 oC and provide the fundamental viscosity data which can be applied to the extrusion process. In conclusion, the rheological measurements show PAN/Water (70/30 wt%) at 180 oC and PAN/EtOH/Water (70/15/15) at 170 oC are two potential systems for carrying out the PAN melt spinning process. Scanning electron microscopy (SEM) images were taken for the reference state and potential conditions. These images show that the copolymer strands have more and larger voids when plasticized with water only compared to those plasticized with water/acetonitrile and water/ethanol mixture. In this case, PAN/EtOH/Water (70/15/15) at 170 oC is considered to be the most benign system for that PAN melt spinning. / Doctor of Philosophy / The melt spinning process of polyacrylonitrile (PAN) has been studied in the past few decades. Compared to the traditional solution spinning process, it does not require toxic organic solvents. The major problem of the PAN melt spinning process is the melting point (Tm) of PAN is much higher than its degradation temperature. However, by adding plasticizers the Tm of PAN can be significantly reduced, which makes PAN melt spinning feasible. In this work we discuss the feasibility of the melt spinning process of polyacrylonitrile (PAN) copolymer plasticized with water based plasticizers by using differential scanning calorimetry (DSC) and rheological methods. The objective is to use water only as a plasticizer to melt spin PAN under specific conditions (composition, temperature etc). The melting point and rheological measurements have been conducted by DSC and a modified capillary rheometer, respectively, for this plasticized system. The DSC results show that the melting point of the PAN copolymer can be reduced below the degradation temperature of PAN, and the rheological results show that the PAN copolymer can be extruded with a reasonable viscosity at 15-20 o v above its melting point, and also the stability and viscosity are strongly dependent on temperature and the plasticizer type and content. Furthermore, the Scanning electron microscopy (SEM) images show the copolymer strands extruded from PAN/H2O mixture have many more and larger voids than PAN/H2O/EtOH mixture. In conclusion, the results indicate that the most appropriate condition for PAN melt spinning is PAN/H2O/EtOH mixture of 70/15/15 wt% ratio at a temperature of 170 oC

Au cours de la dernière décennie, une nouvelle classe de composés de coordination, à base de métaux et de ligands organiques de pontage, connus sous le nom de «Metal Organiques Frameworks (MOFs)» a été largement étudiée. Ces composés ont été popularisés par Yaghi et ses collaborateurs en 1995 et ont attiré l'attention considérablement en raison de leur structure hautement modulable, leur large gamme de tailles de pores avec une grande surface et leurs fonctionnalités facilement adaptables. Ces matériaux offrent un grand potentiel pour diverses applications, en particulier dans le domaine de la catalyse, du stockage et de séparation des gaz.Malgré leurs applications diverses, en particulier dans la séparation de gaz, il y a très peu de rapports concernant la croissance des MOFs sous forme des films minces ou de membranes synthétiques. Dans ce travail, nous décrivons l'utilisation de l'électrofilage pour construire des structures hiérarchiques et des membranes autosupportées de MOF. En fait, l'électrofilage est une technique simple et polyvalente pour produire des libres continues avec des diamètres moyens allant de quelques nanomètres à quelques micromètres.Deux stratégies, basées sur l'utilisation des nanofibres de différents polymères, ont été adoptées : pour produire des membranes auto­ supportées, différents composites polymère/MOF ont été d'abord électrofilés, puis les nanofibres obtenues ont été exposées à des différentes solutions contenant un mélange cation/linker. En conséquence, après la croissance des MOFs, des membranes auto­supportées ont été obtenues avec les nanofibres servant de matrice.D'autre part, pour construire des structures hiérarchiques, des mélanges polymère/cation ont été électrofilés et les nanofibres obtenues ont été immergées dans des solutions de linkers pour la croissance de différents MOFs sur les fibres. Les méthodes décrites ont été testées avec succès en utilisant deux polymères différents (PVA, PAN) et quelques MOFs (MOF-5, HKUST-1, ZIF-8). En effet, ces structures font partie des structures les plus représentatives de celle classe de composés hybrides. Enfin, les différents matériaux obtenus ont été caractérisés par la microscopie électronique à balayage (MEB), la spectroscopie infrarouge à transformée de Fourier, la diffraction des rayons X sur poudre et l'analyse thermogravimétrique / Ln the last decade, a novel class of coordination compounds comprising metal-based nodes and bridging organic linkers known as «Metal Organic Frameworks (MOFs) » has been extensively studied. These compounds were popularized by Yaghi et al. around 1995 and have attracted enormous attention due to their highly designable structure, their wide range of pore sizes with a large surface area and their easily tailorable functionalities. These materials offer a great potential for various applications especially in the field of catalysis, gas storage and gas separation. Despite the huge potential especially in the gas separation, there are few reports about the growth of MOFs as thin films or synthetic membranes.In this work, we describe the use of electrospinning for building hierarchical structures and auto-supported membranes of MOFs. ln fact, the electrospinning is a simple and versatile technique to produce continuous fibers with average diameters in the range of nanometers to a few micrometers.Two strategies were adopted: for producing auto-supported membranes, different polymer/MOF composites were firstly electrospun, then, the obtained nanofibers were exposed to solutions containing different cation/linker mixtures. Accordingly, after the MOFs' growth, auto-supported membranes were obtained with the nanofibers serving as backbone. ln another hand, for building hierarchical structures, polymer/cation mixtures were electrospun and the obtained nanofibers were immersed in linkers' solutions for growing different MOFs on the fibers. The described methods were successfully tested using 1\\0 polymers (PVA,P/\N) and different metal organic frameworks (MOF-5. I IKUST- 1 and ZIF-8). Indeed, these MOFs are among the most representative metal organic frameworks. Finally, the different obtained materials were characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy, powder X-ray diffraction and thermogravimetric analysis.

Due to its unique characteristics, carbon fiber is one of the leading materials for light weight, high strength and stiffness applications in composite materials. The development of carbon fibers approaching theoretical strengths and stiffness is a continuing process which has led to improved mechanical and physical properties over the recent years. Improvements in carbon fiber properties are directly dependent on the quality of the precursor fiber. Research and development of PAN precursor fiber requires extensive experimentation to determine how processing conditions affect the structure and properties of the precursor fibers. Therefore, it is the goal of this thesis to analyze the results of varying coagulation rates on fiber shape, density and porosity, to determine the effect of cross-sectional shape, density, and fiber diameter on the tensile strength of the fiber, and to investigate the most effective method for the reduction of fiber diameter. Results indicate a low temperature, high solvent concentration coagulating bath leads to a rounder cross section with lower void content. Reduction in fiber diameter was found to increase tensile strength while increased molecular orientation experienced during high draw down ratios led to an increase in fiber modulus.

Carbon fiber is one of the leading materials for high strength and modulus, and light weight applications. Improvements in carbon fiber properties are directly dependent on all aspects of manufacture, especially the process of stabilization. Therefore, it is the goal of this thesis to study the effects of the temperature and strain profile of the stabilization process, and the resulting carbon fiber tensile properties. In addition, the precursor fibers used were spun under two different draw ratios, to study the effects of the spinning parameters. Results indicated through DMA studies that completeness of stabilization reactions can be gauged by the peak and leveling of induced stress while fibers are stabilized in isostrain conditions. Through this method, carbon fiber tensile properties were maintained from the prior methods, but saved significant time for processing. Stress vs. strain tests throughout the stabilization process created a baseline for understanding the maximum capable strain on fibers throughout the stabilization process. Lastly, this information was summarized, combined, and basic mechanical engineering principles discussed for a continuous stabilization furnace with strain control, so that further research into the stabilization process can incorporate carbon fibers made with in situ stretch control.