The quest for developing high performance materials, originally responsible for the birth and growth of the composites industry, is now responsible for the drive to produce composites which outperform those used today. A great deal of this interest lies in the use of thermoplastic polymers as the composite matrix. Thermoplastics offer the potential of improved mechanical performance, greater solvent resistance, better impact tolerance, as well as cost saving processing attributes such as infinite shelf life, the ability to be recycled, short processing time and repairability. Unfortunately, these advantages come at the expense of a very high melt viscosity which makes the prepregging process, where the fiber and polymer are combined, very difficult. To overcome this and associated difficulties a detailed analysis of thermoplastic matrix composite processing is developed. The primary area of focus involves the development of an electrostatic dry polymer powder prepregging facility. This unit is capable of the production of high quality towpreg from thermoplastic polymers and reinforcing fibers. Two approaches, statistical and stochastic, were employed to model the process of polymer deposition on the fibers in the prepregging process. These models are used to optimize the production of towpreg. A modification of the prepregging facility allows for the production of towpreg from very small (15 g) samples of polymer. This is extremely useful for analysis and performance verification of state of the art polymer systems. / Ph. D.

Fabrication of high-quality composites from thennoplastic prepregs requires careful selection of the processing cycles so that intimate contact at the ply interfaces is achieved resulting in the formation of strong interply bonds and the process-induced residual stress is minimized to ensure superior mechanical performance. The void formation and the consolidation mechanism were studied experimentally. A refined model was developed to relate the processing parameters of pressure, temperature and time to the interply intimate contact of thermoplastic composites. The model was developed by integrating a prepreg surface topology characterization with a resin flow analysis. Both unidirectional and cross-ply lay-ups were modeled. Two-ply unidirectional laminae fabricated from graphite-polysulfone and graphite-PEEK prepregs and [0/90/0]_T laminates were consolidated using different processing cycles. Optical microscopy and scanning acoustic microscopy were used to obtain the degree of intimate contact data. Agreement between the measured and calculated degree of intimate contact was good. A finite element model was developed to analyze residual stresses in thermoplastic composites by combining a plane-strain elasticity analysis and a temperature-dependent matrix properties. The residual stress model takes into account the mismatch of the thermal expansion coefficients and the crystallization shrinkage of the matrix. [O₁₀/90₆]_T graphite-PEEK laminates were manufactured at different cooling rates to verify the model. The induced residual thermal defonnations were measured by a shadow moire system. The model accurately estimated the out-of-plane displacement of the non-symmetrical laminates. / Ph. D.

The effect of the interphase/interface region on the static mechanical properties, creep and creep rupture behavior of thermoplastic (J2) composites was investigated. The mechanical properties of the J2 composites were altered by systematic changes in fiber surface chemistry. Four fiber systems were used including the AU4, AS4(1) & (2), and AS4CGP fibers. (AS4(1) and AS4(2) represent different batch numbers.) Surface energies and chemistry of carbon fibers were examined using the Dynamic Contact Angle (DCA) method and X-ray Photoelectron Spectroscopy (XPS), respectively. The meso indentation technique was used to measure the interfacial shear strengths (ISS) of the composites. For the same batch of the composites, the ISS ratios for AS4(2)/J2 to AU4/J2 and AS4CGP/J2 to AU4/J2 were 1.22 and 1.24, respectively. The mechanical properties of these composites in the fiber direction were insensitive to the ISS. The transverse and shear moduli of the J2 composites were also not affected by the ISS. The static strengths, in general, ordered themselves from strong to weak as follows: AS4(2)/J2> AS4CGP/J2> AU4/J2. However, the creep rupture strength revealed a different ordering: AS4CGP/J2> AS4(2)/J2> AU4/J2. This suggests that static mechanical properties may not be a good indicator for long term mechanical performance. Experimental results showed that the interphase/interface region did not affect the degradation rates of the creep rupture strength of the J2 composites. DMA creep tests were performed at elevated temperatures for J2 composites. A master curve of each composite was generated. The shift factors obeyed the Arrhenius type equation. The activation energies of composites were approximately the same. The creep response of the AU4/J2, AS4(2)/J2, and AS4CGP/J2 composites were not dependent upon the ISS. Severe delaminations were observed in the AS4(1)/Jd2 composite laminates. The ([±45/90₂]_s) laminate tensile strength of AS4(1)/J2 composite was less than that of AS4(2)/J2 and AS4CGP/J2 composite. The creep rupture strength of the AS4(1)/J2 composite laminates degraded about two times faster than that of the other three composite systems. / Ph. D.

Powder bed fusion (PBF) is one of seven technology modalities categorized under the term additive manufacturing (AM). Beyond the advantages of fabricating complex geometries and the "tool-less manufacturing" paradigm common to all types of AM, polymer PBF shows potential for significant industrial relevance through exploiting the technique's characteristic powder-filled bed (a.k.a. build piston) to utilize the full printer volume for batch-style production. Although PBF should be a suitable processing technique for all semi-crystalline polymers, the polyamide family currently occupies around 90% of the commercial market for polymer PBF. This commercial dominance of polyamides is mirrored in the focus of research publications. The lack of chemical variety in published research questions the universality of reported Structure-Property-Process and Process-Structure-Property relationships for PBF. This dissertation presents the findings from identifying Structure-Property-Process relationships critical to fabricate multi-layer parts for poly(phenylene sulfide) (PPS) by PBF towards expanding PBF material selection and evaluating universality of relationship guidelines. PPS is an engineering thermoplastic used for its high strength, rigidity, dielectric properties, and chemical resistance at elevated temperatures. These properties are attributed to PPS' highly crystalline morphology. Its current use in the automotive and aerospace industries, which are early adopters of AM technologies, makes PPS a prime candidate for AM applications. Therefore, the goal of this work is to demonstrate PPS printing by PBF, study its behavior throughout the PBF lifecycle, and abstract general trends in polymer PBF relationships. First, theoretical ranges for print parameter values are determined from properties of an experimental grade PPS powder feedstock. Successful printing of PPS by PBF is demonstrated in a way contrary to published empirical polymer-PBF relationships. Low temperature printing (i.e., bed temperature more than 15 °C lower than polymer peak melting temperature) of PPS successfully fabricated dimensionally accurate parts with reasonable mechanical properties compared against injection molding values. This distinct PPS behavior does not follow empirical guidelines developed for either polyamides or poly(aryl ether ketones). The unique success of low-temperature PBF prompted further investigation into potential benefits of low-temperature printing. Structure-Property-Process relationships were characterized over the course of simulated powder reuse to show that low-temperature printing prolonged the time when PPS powder properties remained in the "printable" range. Significantly re-used PPS powder was shown to be printable when print parameters were adjusted to accommodate structure and property changes. Successful prints from reused powder is uncommon among published reports of PBF printing of high-performance engineering thermoplastics. Observations of a change in molecular architecture through branching and crosslinking during simulated powder reuse motivated investigating if similar reactions occur in printed parts. PPS is commonly used at elevated temperatures in the presence of oxygen, which is the ideal environment for branching and crosslinking. Structural changes manifested in increased glass transition temperature and high temperature storage modulus. The relative change in structure when printed parts were thermo-oxidatively exposed was observed to be significant for parts printed from new powder, but minimal for parts printed from reused powder. This is a result of the structural changes occurring as powder feedstock during reuse over multiple builds. The changing architecture of reused PPS exposed shortcomings with print parameter value selection based solely on polymer thermal properties. Branching and crosslinking reduced crystallinity, resulting in calculated less energy required to melt; however, it also increased melt viscosity. This negative impact on coalescence behavior was not reflected in the methodology for process parameter value determination because current guidelines neglect rheological properties. These observations motivated proposing a method for selecting print settings based on polymer coalescence behavior. Because it is based on coalescence, this method can predict the transition in governing physics from viscous coalescence to bubble diffusion, which is accompanied by a change in the dependence of mechanical properties on laser energy density. Most work in polymer PBF has focused on "printed part triad'" Process-Property relationships. Work presented in this dissertation contributes to the "printability triad'" of Structure-Property-Process relationships and does so using the novel-to-PBF polymer, PPS. Additional polymers must be explored to continue to discern which polymer-manufacturing relationships are universal among all polymers and which are specific to one subset. The observations and connected interpretation to principles of polymer physics add to the body of knowledge for the polymer PBF field. These contributions will help pave the way for investigations into other polymer families and will re-shape the field's normative logic use when answering the question "what makes a polymer printable by PBF?" Understanding the connection between polymer properties and physical stimuli characteristic of PBF manufacturing will result in parts tailored for specific applications and more sustainable manufacturing, thus realizing additive manufacturing's full potential. / Doctor of Philosophy / Powder bed fusion (PBF) is one of seven distinct additive manufacturing (AM, also known as ``3D printing'') technologies. The manufacturing process creates solid, three-dimensional shapes through selectively heating, melting, and fusing together polymer powder particles in a layer-by-layer manner. Currently, organizations are interested in complementing existing manufacturing technology with PBF for one of three general reasons: (1) "complexity is free" PBF has the ability to make shapes that are difficult or expensive to fabricate using other manufacturing technologies. (2) "tool-less manufacturing" PBF only requires a digital design file to fabricate objects. This enables small changes to be easily made via computer-aided design (CAD) programs without the need to invest time and money into tooling (e.g., molds, jigs, fixtures, or other product-specific tools). This enables "mass customized" products (e.g., custom-fit medical devices and implants) to be economically feasible. (3) "material efficiency" AM is attractive as it often generates less waste than subtractive manufacturing techniques like milling. This is particularly a concern for organizations that manufacture parts from expensive, high-performance polymers, such as in the aerospace and medical industries. Despite these benefits, the state of the art for polymer PBF has room for improvement. Specifically, there are many details regarding material behavior during PBF manufacturing that are unknown; any unknown behaviors present challenges to building confidence in production quality. Additionally, approximately 90% of current PBF use is nylon-12 or else another material in the polyamide family of semi-crystalline thermoplastics. This limited selection of commercially available materials compared against other forms of manufacturing contributes to PBF's circular quandary: the manufacturing process physics are not robustly understood because most experimentation and research has been carried out on one family of polymers; however, a wider variety of polymers has not been developed because there is a limited understanding of the process physics. This dissertation presents research toward answering both PBF challenge areas. The first three chapters present investigations into relationships between the properties of a novel, experimental grade poly(phenylene sulfide) (PPS) semi-crystalline thermoplastic polymer powder, the stimuli imposed on this polymer during PBF processing, and the resultant properties of printed parts (i.e., "property-process-property relationships"). The target polymer, poly(phenylene sulfide), is a high-temperature, high-performance polymer that is traditionally melt processed, but has not yet been commercialized for PBF. Prior literature has established mathematical representation for the interaction between manufacturing energy input and the thermal response of the polymer resulting in melting. This framework has been created through studying the polyamide family. Work presented in this dissertation evaluates existing guidelines for PBF process parameter selection using measured thermal behavior of PPS (i.e., a polysulfide, not a polyamide) to predict the range of manufacturing energies affecting geometrically accurate printed parts of high density and strength. In addition, the impact of thermal exposure from repeated PPS powder reuse over the course of multiple PBF prints was evaluated on powder, thermal, and rheological properties identified as critical for PBF printing. Changes to the molecular structure and properties of reused PPS powder were observed to follow different trends than those reported for other materials traditionally used. The effect of thermal exposure on printed parts was also investigated to determine if the observed changes in molecular structure occurring during thermal exposure of the powder would result in changes to mechanical performance properties of printed parts. The importance of rheological flow properties in dictating printed part performance was observed to be a common theme throughout working with PPS. The final chapter presents a novel method for quantitatively predicting particle fusion during PBF and connecting the extent of particle fusion to mechanical properties of printed parts. The presented method is "polymer agnostic" and advances the state of the art in understanding the physics guiding polymer response to stimuli imposed during PBF AM.

Thermoplastic composite filament winding is an on-line consolidation process, where the composite experiences a complex temperature history and undergoes a number of temperature history affected microstructural changes that influence the structure's subsequent properties. These changes include melting, crystallization, void formation, degradation and consolidation. In the present study, models of the thermoplastic filament winding process were developed to identify and understand the relationships between process variables and the structure quality. These include models that describe the heat transfer, consolidation and crystallization processes that occur during fabrication of a filament wound composites structure. A comprehensive thermal model of the thermoplastic filament winding process was developed to calculate the temperature profiles in the composite substrate and the towpreg temperature before entering the nippoint. A two-dimensional finite element heat transfer analysis for the composite-mandrel assembly was formulated in the polar coordinate system, which facilitates the description of the geometry and the boundary conditions. A four-node 'sector element' was used to describe the domain of interest. Sector elements were selected to give a better representation of the curved boundary shape which should improve accuracy with fewer elements compared to a finite element solution in the Cartesian-coordinate system. Hence the computational cost will be reduced. The second thermal analysis was a two-dimensional, Cartesian coordinate, finite element model of the towpreg as it enters the nippoint. The results show that the calculated temperature distribution in the composite substrate compared well with temperature data measured during winding and consolidation. The analysis also agrees with the experimental observation that the melt region is formed on the surface of the incoming towpreg in the nippoint and not on the substrate. Incorporated with the heat transfer analysis were the consolidation and crystallization models. These models were used to calculate the degree of interply bonding and the crystallinity achieved during composite manufacture. Bonding and crystallinity developments during the winding process were investigated using the model. It is concluded that lower winding speed, higher hot-air heater nozzle temperature, and higher substrate preheating temperature yield higher nippoint temperature, better consolidation and a higher degree of crystallization. Complete consolidation and higher matrix crystallization will result in higher interlaminar strength of the wound composite structure. / Master of Science

High glass transition (eg. 360 °C) melt processable thermoplastic polyimide homopolymers and poly(imide-siloxane) segmented copolymers were prepared from a number of diamines and dianhydrides via solution imidization, polydimethylsiloxane segment incorporation and molecular weight control with non-reactive phthalimide end-groups. The adhesive bond performance of these polyimides was investigated as a function of molecular weight, siloxane incorporation, residual solvent, test temperature, and polyimide structure via single lap shear samples prepared from treated Ti-6AI-4V alloy adherends and compression molded film adhesives or scrim cloth adhesives. The adhesive bond strengths increased greatly with siloxane segment incorporation at 10, 20 and 30 weight percent, and decreased slightly with total polymer molecular weight. As the test temperature was increased, adhesive bond strength increased, decreased or showed a maximum at some temperatures depending on the polyimide structure and siloxane content. The presence of residual solvent increased adhesive bond strength at ambient temperature but decreased the strength at the elevated temperatures. The variation of adhesive bond strength with residual solvent, siloxane and test temperature was attributed to the influence of these parameters on the brittle-ductile transition behavior of the polyimide system. This conclusion was supported by stress-strain measurements which indicated that tensile strength and modulus decreased with siloxane concentration and test temperature, demonstrating that there was an optimum combination of strength and strain for maximum adhesive bond strength. A model was developed to describe this behavior. The poly(imide-30%siloxane) segmented copolymer and a miscible poly(ether-imide) also demonstrated excellent adhesive bond strength with poly(arylene ether ketone) PEEK®-graphite composites. Oxygen or ammonia gas plasma treatment was very effective in further improving adhesive bond strength of melt laminated PEEK®-graphite composites. / Ph. D.

O presente trabalho teve como proposta a preparação de amidos termoplásticos (TPS) e compósitos a partir de amido de arroz e subprodutos do processo de beneficiamento do arroz, no qual resulta em 20% de palha e 14% de grãos quebrados. Estudou-se o amido de arroz como nova fonte para preparação de termoplásticos, avaliou-se o efeito da incorporação de palha de arroz aos TPS a fim de superar as limitações apresentadas por estes tais como baixo desempenho mecânico e alta absorção de umidade, avaliou-se a possibilidade de preparação de termoplásticos diretamente dos grãos de arroz e quirera e investigou-se a influência das condições de processamento (tempo e temperatura) na preparação dos termoplásticos. O amido de arroz foi plasticizado com glicerol em proporções que variaram de 20 a 40%. Para os compósitos, o teor de reforço (palha) variou de 1 a 5% e o teor de glicerol foi fixado em 30%. Tanto os materiais de partida quanto os termoplásticos e compósitos obtidos foram caracterizados por MEV e difração de raios-X; quanto às propriedades térmicas por TG, DSC e DMTA; quanto às propriedades mecânicas por ensaio mecânico de tração. O comportamento frente à absorção de água também foi investigado. O estudo das condições de processamento foi feito com base nos resultados obtidos a partir da reometria de torque, difração de raios-X e MEV e demonstrou que a utilização de apenas uma das técnicas é insuficiente para determinação das condições de processamento que melhor contribuem para desestruturação do grânulo, mistura e homogeneização do TPS. Os TPS preparados a partir de amido de arroz e glicerol seguiram a mesma tendência de variação de suas propriedades em função do teor de plasticizante que os TPS preparados a partir de outras fontes de amido. Levando em consideração TPS preparados a partir de amido de mandioca, milho e batata, observa-se que os TPS preparados a partir de amido de arroz apresentaram a menor absorção de água. Em relação aos compósitos, a palha contribuiu para melhorar o desempenho mecânico, no entanto favoreceu o aumento da absorção de água. Foi possível obter termoplásticos preparados diretamente dos grãos de arroz (polido e integral) e da quirera. Em comparação com o TPS amido/glicerol, os TPS obtidos a partir dos grãos apresentaram maior cristalinidade, rigidez e temperatura de transição vítrea. No entanto, apresentaram menor estabilidade térmica, menor ductilidade e maior absorção de água. / This work aimed at preparation of thermoplastic starch (TPS) and composites from rice starch and byproducts of the beneficiation process of rice, which results in 20% of husk and 14% of broken grains. The rice starch was studied as a new source for preparing thermoplastics. The effect of incorporation of rice husk to the TPS was evaluated aiming to overcome the limitations presented by pure TPS such as poor mechanical properties and high moisture absorption. The preparation of thermoplastic directly from grain and broken rice was also studied. The rice starch was plasticized with glycerol in proportions ranging from 20 to 40%. For composites, the amount of husk ranged from 1 to 5% and glycerol content was 30%. The effect of processing conditions (time and temperature) in the preparation of thermoplastics were investigated. Starting materials, thermoplastics and composites were characterized by SEM and X-ray diffraction; the thermal properties by TG, DSC and DMTA; and mechanical properties by mechanical tests. The behavior in the water uptake was also investigated. The processing conditions study was based on the results obtained from the torque rheometry, X-ray diffraction and scanning electron microscopy and demonstrated that the use of only one technique is inadequate to determine the best processing conditions. The TPS prepared from rice starch and glycerol followed the same trend of variation of its properties as a function of plasticizer content when compared to TPS prepared from other starch sources. Considering TPS prepared from cassava starch, corn and potato, it was observed that the TPS prepared from rice starch presented a lower water uptake. For composites, husk has improved mechanical performance, but favors the increase in water uptake. It was possible to obtain thermoplastic prepared directly from grain rice (polished and integral) and broken grain. Compared to the starch/glycerol TPS, TPS obtained from the grains had higher crystallinity, and stiffness and glass transition temperature. However, had lower thermal stability, lower ductility and increased absorption of water.

As patologias que acometem os membros superiores são bastante incapacitantes para os seres humanos, pois elas são sua principal ferramenta de interação com o mundo tanto pelo papel nas tarefas cotidianas quanto pelo simbolismo que carregam. Na Terapia Ocupacional o objetivo é promover uma melhor qualidade de vida, maior autonomia e participação no cotidiano e, dentre os recursos e abordagens possíveis no processo de reabilitação, as órteses têm grande destaque, pois seu uso correto pode \"aumentar a função, prevenir ou corrigir deformidade, proteger estruturas em processo de cicatrização, restringir o movimento e permitir o crescimento ou remodelação tecidual\" (FESS, 2002, p.98). As órteses mais utilizadas na prática clínica são confeccionadas em material termomoldável de baixa temperatura. Não há opções nacionais deste material, implicando na necessidade de importação que pode gerar dificuldades no acesso a este tipo de material. Leite (2007) desenvolveu um poliuretano derivado do óleo vegetal (mamona) que se mostrou apto para a confecção de órteses após ensaios mecânicos, térmicos e clínicos, mas que necessita de melhorias, principalmente em relação aos aspectos de maleabilidade (moldabilidade) e memória do material. O presente trabalho tem como objetivos caracterizar o material desenvolvido e alguns existentes no mercado e modificar o material desenvolvido por Leite (2007). Para tanto, foram introduzidas modificações - acréscimo de cargas e mudanças na proporção poliol e pré-polímero - e realizados ensaios mecânicos e térmicos de Memória, Dureza, Moldabilidade, Análise Dinâmico-Mecânica, Tração, Temperatura no Contato com a Pele Humana e a velocidade de Resfriamento do material. Os resultados indicam que o acréscimo de Sílica Pirogênica e o aumento da proporção de poliol em relação ao pré-polímero melhoraram a moldabilidade do material e tornaram a memória adequada aos propósitos. Conclui-se que o novo material, o compósito CPU POS, é mais rígido que os importados, suportando maior carga, é seguro para o paciente do ponto de vista de temperatura e possui uma grande validade. A moldabilidade é rápida e necessita que o terapeuta posicione o material, pois ele não se acomoda com a ação da gravidade. A dureza foi diminuída, embora ainda seja maior que a dos materiais de comparação. Assim, o presente estudo contribuiu para um maior conhecimento dos termomoldáveis existentes no mercado utilizados para confecção de órteses e aponta o poliuretano derivado de óleo vegetal, modificado com cargas, como um material adequado para este propósito. / Pathologies that affect the upper limbs are very incapacitating to humans, because they are your primary tool for interaction with the world, both thé role of everyday tasks as the symbolism they carry. In Occupational Therapy the objective is promote a better quality of life, more autonomy and participation in daily life and, among the resources and possible approaches in the rehabilitation process, the orthosis have great prominence, because their correct use can \"enhance function, prevent or correct deformities, protect structures in the healing process, restrict movement and support the growth or tissue remodeling\" (FESS, 2002, p.98). The most used orthosis in clinical practice are fabricated with low temperature thermoplastic. There are no national options of this material, resulting in import which can create difficulties in accessing this type of material. Leite (2007) developed a vegetable (castor) oil based polyurethane that proved suitable for orthosis, after mechanical, thermal and clinical testing, but needs improvements especially aspects of malleability (moldability) and memory of the material. The current work aims at characterizing the material developed and some of the existing materials and modify the material developed by Leite (2007). Therefore, changes have been introduced - increase of fillers and changes in the proportion polyol to prepolymer - and performed mechanical and thermal tests of Memory, Hardness, Moldability, Dynamic Mechanical Analysis, Traction, Temperature in contact with human skin and the speed Cooling the material. The results indicate that the addition of Pyrogenic Silica and increased proportion of polyol in relation to the prepolymer improved moldability ofthe material and made appropriate memory to the purpose. We conclude that the new material, composite CPU POS, is more rigid than the imported, supporting higher load, it is safe for the patient in terms of temperature and has a great validity. The moldability is fast and requires the therapist to position the material, because it does not settle by gravity. The hardness was decreased, although it is still higher than the comparison material. Thus, the present study contributed to a better understanding of existing market thermoformables used for orthosis and points the polyurethane derived from vegetable oil, modified with fillers, as a suitable material for this purpose.

This thesis is an investigation of the TPE filament for Fused Deposition Modelling (FDM) manufacturing method. All the investigations aim to optimize the quality of the filament in order to make Thermoplastic Elastomer (TPE) material possible for FDM manufacturing method. Optimization experiments were made to find out key parameters in the extrusion process that determine the quality of the filament. With the optimal parameters, further investigation of the additive content in the TPE granulate was made to solve the current problem of the filament in practical 3D printing, which the high surface friction massively affects the FDM manufacturing feasibility. The filaments were manufactured by the desktop extruder 3devo filament extruder and the surface friction tests were performed on TribotesterTM. Additionally, discussion was made to summarize the pros and cons of TPE material as well as the significance of 3D printing TPE. Potential application and benefits are mentioned for combining the property of TPE and the advantage of FDM manufacturing. Current state-of-art extrusion equipment and FDM technology are also summarized.

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.