No description available.

Segmented copolymer systems composed of an amorphous g1assy engineering polymer as one segment and a potentially anisotropic polyester as the second segment were synthesized and investigated. The engineering thermoplastic segment was based on various all aromatic poly(arylene ether sulfooes) derived from the nucleophilic aromatic substitution reaction between hydroquinone, biphenol, and dichlorodiphenylsulfone. This reaction was conducted in the presence of potassium carbonate and anhydrous aprotic dipolar solvents. Poly(biphenol terephthalate) and poly(oxybenzoate) were synthesized in situ as the second, potentially anisotropic, sem;crystalline segment. These segmented copolymers were synthesized either by solution t interfacial, or melt acidolysis techniques. The melt acidolysis technique was used to synthesize the segmented copolymers with high poly(arylate) contents. The morphology of the copolymers was found to be totally amorphous for those capolymers with low levels of the poly(arylates). They were semicrystalline when the poly(arylate) contents were increased beyond a critical value of about 15 weight percent. Differential scanning calorimetry, optical microscopy, and wide angle X-ray scattering were used to probe the copolymer morphology. The chemical structures of the segmented copolymers were studied through the use of Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy (both ¹H and ¹³C). As the weight percentage of the poly(arylate) was increased, a very significant improvement in the solvent resistance was noted. Evidence of anisotropy and liquid crystallinity in the copolymers was provided by optical microscopy, differential scanning calorimetry, and wide angle X-ray scattering. / Ph. D.

The concept of employing engineering thermoplastics as toughness modifiers for Bismaleimide resins was utilized to improve the fracture toughness properties of these important materials, which have applications as matrix resins for high performance composites. Modifier molecular weight, end group functionality, backbone structure and weight percent incorporation were all studied with respect to their influence on K_lc, fracture toughness properties. Increases in fracture toughness were created with thermoplastic oligomers without sacrificing high temperature properties and desirable hot-melt processing conditions. Investigations were also made to study the morphological features that develop within these modified thermosets and their resistance to specific environments. In addition, unidirectional carbon fiber composites were prepared and their mode I and II strain energy release rates measured. Respectable increases in the interlaminar fracture toughness were obtained, 15 and 20 percent by weight loadings of maleimide terminated polysulfone modifiers yielded G_lc values of 489±25 and 734±10 J/m² respectively, a substantial improvement over the control value of 359±17 J/m². Laminates were prepared using carbon fibers that had been investigated in terms of their surface energies using Inverse Gas Chromatography. It was illustrated how this technique could distinguish between the acid-base properties of fibers possessing different degrees of proprietary surface treatments. Fiber composites containing both contrasting and subtle changes at the fiber-matrix interphase were prepared and their mechanical properties evaluated using a variety of test methods. Dramatic increases in laminate properties were measured for composites possessing contrasting interphases. Furthermore, the mode II fracture toughness test was sensitive to interphase differences; however, the mode I fracture toughness test was not. Specimens subjected to the new Continuous Ball Indentation test method (meso-indentation) were compared with single fiber micro-indentation test results. Differences were detected in composites prepared using untreated and surface treated fibers. The new method was also sensitive to changes in matrix ductility. Certain anomalies that were noted to be surprising from micro-indentation measurements were not present in the meso-indentation test results. These observations brought to light certain limitations found within the micro-indentation test, but further supported the new test method as a potential technique for fiber-matrix interphase evaluation. / Ph. D.

Lewis acid/base interactions were shown to play an important role in the optimization of the interfacial adhesion of reinforcing carbon fibers to thermoplastic polymer matrices. Inverse gas chromatography (IGC) and x-ray photoelectron spectroscopy (XPS) were used to characterize the acid/base nature of the carbon fiber surfaces. Capillary column IGC (CIGC) was used to determine the acid/base nature of thermoplastic polymer surfaces. To quantify the non-dispersive (acid/base) interactions, the dispersive component had to be factored out by separate experiments. The carbon fibers (both surface pretreated and untreated) were found to be predominantly acidic while the polymer matrices (polysulfone, polycarbonate, and polyetherimide) exhibited basic properties. Single fiber fracture tests showed that increased acidity in the fiber surfaces (as a result of surface pretreatment) resulted in a significant improvement in the interfacial adhesion to the basic polymers. The acid/base interactions, however, were not solely responsible for the most favorable adhesion. The dispersive component and thus, the carbon fiber structure also played a role. / Master of Science

The present work presents the results of an investigation of properties of polyphenylene sulfide (PPS) reinforced with random, continuous glass fibers, approximately 30% by weight. The investigation included both characterization of the mechanical properties and nondestructive inspection of the material. The objectives of the nondestructive inspection program were twofold: i) to determine nondestructive testing techniques were most responsive to developing damage and ii) to identify the damage modes using the nondestructive testing methods. The mechanical testing program involved the study of three types of specimens: straight sided tensile coupon, dogbone, and streamline. The streamline specimen typically fails in the narrow region and therefore appears to be relatively unaffected by stress concentrations induced by the specimen geometry. Results are given for all three specimen types and comparisons made for the measured mechanical properties. Several nondestructive testing methods, including C-scan, ultrasonic attenuation, acoustic emission, X-ray radiography, and edge replication, were applied to study the damage developed under quasi-static tension loading of this material. The C-scan, edge replication, and X-ray radiography tests were performed both initially and after intermediate stages of loading. These three tests appear to be unresponsive to the developing damage. That is, these techniques were unable to detect any distinctive patterns around the regions of final failure. The most responsive NDT techniques are ultrasonic attenuation and acoustic emission. Both of these methods yield quite distinct changes with increasing load. The acoustic emission tests, for example, show an extremely rapid rise in count rate at loads of about two-thirds of ultimate. The ultrasonic attenuation measurements display maxima and minima when taken in real-time as the specimen is loaded. In an effort to determine the damage mechanisms in the material and to understand the results of the NDE tests, virgin and damaged specimens were destructively examined with the aid of a scanning electron microscope (SEM). The SEM appears to show that the acoustic emission production is corning from cracking of the transverse glass fibers. The results of all tests to date are presented together with recommendations and conclusions for the application of nondestructive test methods to PPS. / Master of Science

The objective of this study was to develop tests that could be used to characterize autohesive strength development in amorphous thermoplastic resins and fiber-reinforced thermoplastic prepregs. All tests were performed using polysulfone P1700 thermoplastic resin and AS4/P1700 graphite-polysulfone prepreg. Two test methods were examined to measure autohesion in neat resin samples. These included an interfacial tension test based on the ASTM tensile adhesion test (ASTM D897) and a fracture toughness test using a compact tension (CT) specimen (based on the ASTM toughness test for metals ASTM E399-83). The interfacial tensile test proved to be very difficult to perform and with an unacceptable amount of data scatter. The data obtained using the compact tension test were repeatable and could be correlated with temperature and contact time. Autohesive strength development in fiber-reinforced prepreg samples was measured using a double cantilever beam (DCB) interlaminar fracture toughness test. The fracture mechanisms were determined to be different in the healed DCB specimen than the virgin specimen due to resin flow at the crack plane during the healing tests. The CT test was found suitable for use in determining the autohesive properties and self-diffusion coefficient of neat resin. The DCB test, although not suitable for autohesive testing, indicated that repair of thermoplastic matrix composites is possible; however, the repair will not be as tough as the virgin material. / Master of Science

Novel perfectly alternating segmented copolymers containing imide junction points were synthesized via terminal amine-anhydride coupling from poly(dimethylsiloxane)s and either poly(arylene ether)s or polyimides. The copolymers were characterized in solution and the solid state. The -(-A-B-)-n architecture and molecular design of these linear systems afforded thermodynamically microphase separated systems which gave rise to interesting copolymer properties. Each controlled molecular weight oligomeric segment, or homopolymer, was initally synthesized with reactive endgroups and fully characterized prior to copolymerization. Thus, anhydride-terminated poly(dimethylsiloxane)s were prepared via cationic ring-opening polymerization in the presence of a "monofunctional" bis-norbornane anhydride disiloxane endcapping species. Aromatic amine-terminated engineering thermoplastics were synthesized through either nucleophilic aromatic substitution in the presence of a “monofunctional” aminophenol endcapper (as for poly(arylene ether ketone)s and poly(arylene ether sulfone)) or by solution imidization using a controlled excess of the diamine monomer. A solution imidization method was developed for the segmented copolymerization that simplified the typically two-step, two-solvent method into a one-step approach with a single solvent. Thus, a previously described condensation catalyst, 2-hydroxypyridine, was utilized which was demonstrated to be essential in obtaining high molecular weight copolymers. These segmented copolymers generally were fibrous and highly soluble in many common organic solvents. Creasable, transparent, solution-cast films were readily prepared. Thermal and morphological analyses demonstrated that the copolymers exhibited phase separation, and displayed lower and upper Tg's as a result of the two components employed. At short hard block lengths, uper Tg's were somewhat depressed, implying partial miscibility. / Master of Science

Master of Science

A non-isothermal autohesion model was developed by combining a transient finite element heat transfer model with the isothermal autohesion model. Heat transfer analyses and the interfacial strength development analyses were conducted using the non-isothermal autohesion model on a polysulfone (Udel P1700) compact tension specimen, a 64-ply graphic (Thomel T300)/P1700 unidirectional composite, and a 192-ply graphite (Hercules AS4)/P1700 unidirectional composite. A 64-ply T300/P1700 unidirectional composite was processed in a matched metal mold. Temperature data were taken and compared with the calculated values. Good agreement was observed between the calculated and the measured temperature values. A healing test which aimed at studying the interplay bond development in AS4/P1700 unidirectional composites was performed. The double cantilevered beam (DCD) Mode l fracture toughness test was selected. The DCB specimens were fractured and healed in a special fixture with different combinations of temperature pressure, and time. The healed DCB specimens were refractured and the critical strain energy release rates (G_IC) were measured. The pressure was found to be a key factor in the healing process. Temperature and time dependencies of the interply bond development were also observed. The non-isothermal autohesion model predicted a higher strength achieved in a shorter time. This was due to the extra time which was needed for the fracture interface to achieve intimate contact, and the assumption of the initial intimate contact achievement of the non-isothermal autohesion model. / Master of Science

Yes / Natural rubber (NR) and crosslinked polyethylene (XLPE) waste streams were devulcanized by solid state shear milling (S3M), producing a fine powder that may be more easily reprocessed. Understanding devulcanization and the nature of decrosslinked thermoset materials is of utmost importance for turning these waste steams into functional products. It was found that the devulcanized powders contained significant concentrations of radicals, which may be active in the subsequent revulcanization process. The produced devulcanized powders were converted into recyclable thermoplastic vulcanizates (TPVs) by twin screw extrusion. Reprocessing of these powders into value-added products is an important step in recycling and the use of extrusion allows for high throughput and industrial viability. Herein, we demonstrate that the optimal conditions for reprocessing are dependent upon the particle size of the devulcanized powder. Furthermore, dynamic vulcanization is affected by the nature of these recyclate powders. The successfully prepared TPVs showed similar properties to virgin materials, with a high elongation to failure. Therefore, the conversion of waste rubber into the rubber phase of a TPV shows significant promise in moving towards sustainable products, providing the revulcanization step can be well controlled. / EPSRC and NSFC for their funding of this work through the Joint UK-China Low Carbon Manufacturing Grant, Grant number EP/S018573/1.