Starch and microbial exo-polysaccharides produced by prokaryotes (i.e. Eubacteria and Archaebacteria) and eukaryotes (i.e. phytoplankton, fungi, and algae) are recognized as a permanent source of biopolymers for the packaging industry. However, the unsuitable mechanical properties for thermoplastic applications and/or high cost of production have restricted their generalized use. Fungal isolates of the genus Ophiostoma are able to produce exo-polysaccharides or protein-like compounds in a medium containing starch as the substrate. Various analytical techniques were used as an approach to investigate the interaction between starch and the fungal extracellular metabolites and the effect of the molecular-structural modifications on the functional properties of the materials. Native starches were used as control in all experiments. Analyses performed by dynamic mechanical thermal analysis (DMTA), which provides information related to the viscoelastic properties, showed that the storage modulus (E') increased substantially after the modification of the starch showing a process of chain stiffness. The determination of the glass transition temperature (Tg) by tan  and loss modulus (E'') peaks showed various thermal transitions indicating a complex molecular aggregation due to the potential presence of dissimilar amorphous polymers. Experiments performed in DSC confirmed the presence of the various thermal transitions associated to the Tg of these materials. The first derivative of mass loss with respect to temperature during the thermogravimetric (TG) analysis was slightly lower compared with native starches (at ~630 and 650°C). However, modified starches can withstand high temperatures showing residues up to 20% at 1000°C. Studies on the characterization of the flow properties of the polymers by capillary rheology showed in both samples a shear thinning behavior. The double logarithmic plot of the shear rate vs. shear viscosity produced a straight line and in consequence a power law equation was used to describe the rheological behavior ( = K'n). The results showed that in order to achieve the same shear rate (') in both samples (modified and native starches) it is necessary to apply a higher shear stress () in the fungal treated materials. As a result, the consistency power law index (n) decreased and the consistency value increased (K). The practical consequence is that the melting point of these polysaccharides shifted to higher temperatures. By using various analytical techniques (including chromatography, spectroscopy, spectrometry) it was found that these phenomena may be due to the interaction of starch with protein-like or exo-polysaccharides or both which may influence the viscosity, bind adjacent molecules (i.e. network-like) and restrict the molecular motion. Evidences of the presence of pendant groups attached to high molecular weight compounds were also found. This information will give guidance to further structural studies and it is intended to pave the way for a variety of industrial applications.

Random Glass Mat Thermoplastic (GMT) composites are increasingly being used by the automotive industry for manufacturing semi-structural components. The polypropylene based materials are characterized by superior strength, impact resistance and toughness. Since polymers and their composites are inherently viscoelastic, i.e. their mechanical properties are dependent on time and temperature. They creep under constant mechanical loading and the creep rate is accelerated at elevated temperatures. In typical automotive operating conditions, the temperature of the polymer composite part can reach as high as 80°C. Currently, the only known report in the open literature on the creep response of commercially available GMT materials offers data for up to 24 MPa at room temperature. In order to design and use these materials confidently, it is necessary to quantify the creep behaviour of GMT for the range of stresses and temperatures expected in service. The primary objective of this proposed research is to characterize and model the creep behaviour of the GMT composites under thermo-mechanical loads. In addition, tensile testing has been performed to study the variability in mechanical properties. The thermo-physical properties of the polypropylene matrix including crystallinity level, transitions and the variation of the stiffness with temperature have also been determined. In this work, the creep of a long fibre GMT composite has been investigated for a relatively wide range of stresses from 5 to 80 MPa and temperatures from 25 to 90°C. The higher limit for stress is approximately 90% of the nominal tensile strength of the material. A Design of Experiments (ANOVA) statistical method was applied to determine the effects of stress and temperature in the random mat material which is known for wild experimental scatter. Two sets of creep tests were conducted. First, preliminary short-term creep tests consisting of 30 minutes creep followed by recovery were carried out over a wide range of stresses and temperatures. These tests were carried out to determine the linear viscoelastic region of the material. From these tests, the material was found to be linear viscoelastic up-to 20 MPa at room temperature and considerable non-linearities were observed with both stress and temperature. Using Time-Temperature superposition (TTS) a long term master curve for creep compliance for up-to 185 years at room temperature has been obtained. Further, viscoplastic strains were developed in these tests indicating the need for a non-linear viscoelastic viscoplastic constitutive model. The second set of creep tests was performed to develop a general non-linear viscoelastic viscoplastic constitutive model. Long term creep-recovery tests consisting of 1 day creep followed by recovery has been conducted over the stress range between 20 and 70 MPa at four temperatures: 25°C, 40°C, 60°C and 80°C. Findley’s model, which is the reduced form of the Schapery non-linear viscoelastic model, was found to be sufficient to model the viscoelastic behaviour. The viscoplastic strains were modeled using the Zapas and Crissman viscoplastic model. A parameter estimation method which isolates the viscoelastic component from the viscoplastic part of the non-linear model has been developed. The non-linear parameters in the Findley’s non-linear viscoelastic model have been found to be dependent on both stress and temperature and have been modeled as a product of functions of stress and temperature. The viscoplastic behaviour for temperatures up to 40°C was similar indicating similar damage mechanisms. Moreover, the development of viscoplastic strains at 20 and 30 MPa were similar over all the entire temperature range considered implying similar damage mechanisms. It is further recommended that the material should not be used at temperature greater than 60°C at stresses over 50 MPa. To further study the viscoplastic behaviour of continuous fibre glass mat thermoplastic composite at room temperature, multiple creep-recovery experiments of increasing durations between 1 and 24 hours have been conducted on a single specimen. The purpose of these tests was to experimentally and numerically decouple the viscoplastic strains from total creep response. This enabled the characterization of the evolution of viscoplastic strains as a function of time, stress and loading cycles and also to co-relate the development of viscoplastic strains with progression of failure mechanisms such as interfacial debonding and matrix cracking which were captured in-situ. A viscoplastic model developed from partial data analysis, as proposed by Nordin, had excellent agreement with experimental results for all stresses and times considered. Furthermore, the viscoplastic strain development is accelerated with increasing number of cycles at higher stress levels. These tests further validate the technique proposed for numerical separation of viscoplastic strains employed in obtaining the non-linear viscoelastic viscoplastic model parameters. These tests also indicate that the viscoelastic strains during creep are affected by the previous viscoplastic strain history. Finally, the developed comprehensive model has been verified with three test cases. In all cases, the model predictions agreed very well with experimental results.

Random Glass Mat Thermoplastic (GMT) composites are increasingly being used by the automotive industry for manufacturing semi-structural components. The polypropylene based materials are characterized by superior strength, impact resistance and toughness. Since polymers and their composites are inherently viscoelastic, i.e. their mechanical properties are dependent on time and temperature. They creep under constant mechanical loading and the creep rate is accelerated at elevated temperatures. In typical automotive operating conditions, the temperature of the polymer composite part can reach as high as 80°C. Currently, the only known report in the open literature on the creep response of commercially available GMT materials offers data for up to 24 MPa at room temperature. In order to design and use these materials confidently, it is necessary to quantify the creep behaviour of GMT for the range of stresses and temperatures expected in service. The primary objective of this proposed research is to characterize and model the creep behaviour of the GMT composites under thermo-mechanical loads. In addition, tensile testing has been performed to study the variability in mechanical properties. The thermo-physical properties of the polypropylene matrix including crystallinity level, transitions and the variation of the stiffness with temperature have also been determined. In this work, the creep of a long fibre GMT composite has been investigated for a relatively wide range of stresses from 5 to 80 MPa and temperatures from 25 to 90°C. The higher limit for stress is approximately 90% of the nominal tensile strength of the material. A Design of Experiments (ANOVA) statistical method was applied to determine the effects of stress and temperature in the random mat material which is known for wild experimental scatter. Two sets of creep tests were conducted. First, preliminary short-term creep tests consisting of 30 minutes creep followed by recovery were carried out over a wide range of stresses and temperatures. These tests were carried out to determine the linear viscoelastic region of the material. From these tests, the material was found to be linear viscoelastic up-to 20 MPa at room temperature and considerable non-linearities were observed with both stress and temperature. Using Time-Temperature superposition (TTS) a long term master curve for creep compliance for up-to 185 years at room temperature has been obtained. Further, viscoplastic strains were developed in these tests indicating the need for a non-linear viscoelastic viscoplastic constitutive model. The second set of creep tests was performed to develop a general non-linear viscoelastic viscoplastic constitutive model. Long term creep-recovery tests consisting of 1 day creep followed by recovery has been conducted over the stress range between 20 and 70 MPa at four temperatures: 25°C, 40°C, 60°C and 80°C. Findley’s model, which is the reduced form of the Schapery non-linear viscoelastic model, was found to be sufficient to model the viscoelastic behaviour. The viscoplastic strains were modeled using the Zapas and Crissman viscoplastic model. A parameter estimation method which isolates the viscoelastic component from the viscoplastic part of the non-linear model has been developed. The non-linear parameters in the Findley’s non-linear viscoelastic model have been found to be dependent on both stress and temperature and have been modeled as a product of functions of stress and temperature. The viscoplastic behaviour for temperatures up to 40°C was similar indicating similar damage mechanisms. Moreover, the development of viscoplastic strains at 20 and 30 MPa were similar over all the entire temperature range considered implying similar damage mechanisms. It is further recommended that the material should not be used at temperature greater than 60°C at stresses over 50 MPa. To further study the viscoplastic behaviour of continuous fibre glass mat thermoplastic composite at room temperature, multiple creep-recovery experiments of increasing durations between 1 and 24 hours have been conducted on a single specimen. The purpose of these tests was to experimentally and numerically decouple the viscoplastic strains from total creep response. This enabled the characterization of the evolution of viscoplastic strains as a function of time, stress and loading cycles and also to co-relate the development of viscoplastic strains with progression of failure mechanisms such as interfacial debonding and matrix cracking which were captured in-situ. A viscoplastic model developed from partial data analysis, as proposed by Nordin, had excellent agreement with experimental results for all stresses and times considered. Furthermore, the viscoplastic strain development is accelerated with increasing number of cycles at higher stress levels. These tests further validate the technique proposed for numerical separation of viscoplastic strains employed in obtaining the non-linear viscoelastic viscoplastic model parameters. These tests also indicate that the viscoelastic strains during creep are affected by the previous viscoplastic strain history. Finally, the developed comprehensive model has been verified with three test cases. In all cases, the model predictions agreed very well with experimental results.

Advancements in technologies such as microelectromechanical systems (MEMS), display devices, biomedical products have created an increasing requirement for miniature components on the scale of micrometers to nanometers. Currently, a commonly used fabrication for miniaturization is LIGA (Lithographie, Galvanoformung, and Abformung). It is a reliably manufacturing method for high-aspect-ratio microstructures with a precision of less than one micrometer. The use of electroplating within LIGA techniques, however, limits the range of materials that can be used. But the main disadvantage of LIGA is its cost: high-energy X-rays generated by synchrotron equipment. The homogeneous and isotropic characteristics of amorphous bulk metallic glasses (BMGs) due to the absence of crystallites, grain boundaries and dislocations lead to the scale of the metallic-glass structures can be miniaturized down to the atomic scale, which presents very high strength, hardness, elastic strain limit and corrosion resistance. In addition, the excellent workability and surface printability in the supercooled liquid state (the region defined from the glass transition temperature (Tg) to the crystallization temperature (Tx) of BMG) has been considered to be one of the most attractive properties of BMGs. The lighter Mg-based metallic glasses exhibit their superior glass forming ability (GFA). Consequently, the using of Mg-based BMGs can gain the goals of light devices and simplify manufacturing process. In this study, therefore, besides the study of LIGA process, a new process utilize the thermoplastic properties of BMGs is presented. First, UV (ultraviolet) -LIGA, a more economical process than LIGA, is used to fabricate the master mold with nickle-cobalt (Ni-Co) alloy. Then, this mold is applied to hot emboss on Mg58Cu31Y11 amorphous alloy to form a secondary mold. The hot embossing temperature is set at 423 K (150 oC) according to the Tg of the BMG around 413 K (140 oC). This embossing process shows that the thermoplastic forming ability of the BMG material is better than Polymethylmethacrylate (PMMA) which requires high hot embossing pressure. BMG is not only a good material for hot embossing process to fabricate microstructure directly, but also a fast-forming material for mold (or die) fabrication. On the other hand, other replicated-able moulds are presented to demonstrate the multifunctional ability of BMGs. First, a mold of oxygen free copper (OFC) with a very low hardness of 1.606 GPa, which is a popular material for machining due to its good machinability, is used to hot emboss on Mg58Cu31Y11 BMG with a higher hardness of 3.445 GPa. Second, micro triangular-pyramidal array (MTPA) on a tungsten (W) steel mold is transferred on Mg58Cu31Y11 BMG using this modified multi-step hot-embossing method to reduce the pattern size. In addition, scratch test with the Nano Indenter® XP system is used to study the mechanical behavior of the Mg58Cu31Y11 BMG for the application such as surface printability.

Various solar energy technologies are being developed to harness the available environmentally friendly and sustainable solar radiation. New ways of utilizing this "free" power for different energy consuming processes continue to be created. In this thesis, a multi-stage solar energy concentrating system has been developed and its feasibility as a radiation source for polymer processing has been explored. The solar energy concentrator (SEC) facility comprises a modified Cassegrainian configuration combined with auxiliary imaging and non-imaging optics, serving as an alternative energy source for polymer joining, ageing and adhesive curing. Modeling and improvement of various aspects of the operation and performance of the SEC facility have been implemented. Optical ray tracing models of the Cassegrainian concentrator with various conventional imaging components and nonimaging concentrators have been created to optimize the optical layout and system efficiency. On their basis, combined 3D ray tracing computer models integrated with the mechanical components have been developed to simulate the entire SEC facility and predict the image size, location and orientation. Additionally, the energy transfer, radiation absorption and heat generation and transfer in the irradiated polymer have been modeled in order to study the radiation-polymer interaction. One novel contribution of this research is the enhancement of the image forming concentrator with non-imaging cone-like concentrators (conical and compound parabolic concentrator (CPC)), utilizing their inherent disadvantage of excessive length. Compared to the refractive type means of transmitting concentrated solar radiation, the truncated cone and CPC concentrators have been found more efficient enhancing further the concentration and widening the utilized spectral range. The experimental studies have demonstrated that transparent and colored, similar and dissimilar polymers can be successfully joined using the SEC facility. The especially developed through-transmission technique removes the need to use a special absorbing medium of the radiant energy required by current advanced welding techniques. The tensile strengths of the joints achieved are comparable to those achieved for similar polymers with other advanced plastic joining methods. The results from the polymer ageing experiments have shown that ultraaccelerated exposure to concentrated sunlight can be performed with the SEC facility without introducing spurious failure mechanisms. Based on the preliminary investigation on adhesive curing utilizing concentrated solar radiation, it has been concluded that with carefully chosen light-curing adhesives solar radiation can be a useful radiation source for adhesive curing.

Thesis (Ph. D.)--Ohio University, November, 2000. / Title from PDF t.p.

Thesis (M.Sc.(Chemical Engineering))--University of Pretoria, 2007. / Abstract in English. Includes bibliographical references (leaves 74-80).

Thesis (Ph. D.)--University of Alabama at Birmingham, 2007. / Additional advisors: Derrick R. Dean, Alan W. Eberhardt, Ramana G. Reddy, Uday K. Vaidya. Description based on contents viewed Feb. 13, 2009; title from PDF t.p. Includes bibliographical references.

Thesis (Ph. D.)--Virginia Polytechnic Institute and State University, 1997. / "UMI number: 9724066"--T.p. verso. Vita. Includes bibliographical references (p. 182-189). Available electronically via Internet.

Thesis (M.S.)--Michigan State University. Dept. of Civil and Environmental Engineering, 2008. / Title from PDF t.p. (viewed on Aug. 3, 2009) Includes bibliographical references (p.129-132). Also issued in print.