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The performance of polymeric diphenylmethane diisocyanate (PMDI) resin is known to be highly dependent on the wood species. This species dependence may be due to differences in: cure chemistry, interphase morphology, or both of these factors. This study addresses aspects of the cure chemistry and interphase morphology of wood/PMDI bondlines; specifically these effects are compared using two woods: yellow-poplar and southern pine. In this study, the cure chemistry of wood-PMDI system was analyzed with solid state NMR (SSNMR) using wood samples cured with doubly labeled (15N,13C) PMDI resin. The kinetics of PMDI cure in the presence of wood was analyzed with differential scanning calorimetry. Thermogravimetric analysis was used to analyze the effect of resin impregnation on the degradation patterns of wood. The wood-PMDI bond morphology was probed with dynamic and static (creep) mechanical analyses in both dry and plasticized conditions. The effect of resin on wood polymer relaxations was quantitatively analyzed by both the time-temperature superposition principle and the Kohlrausch-Williams-Watts equation. The presence of a small but statistically significant species effect was observed on both the cure chemistry and bond morphology of wood-PMDI system at low cure temperatures. The cure of PMDI resin was found to be significantly faster in pine relative to corresponding poplar samples. Resin impregnation showed a significant species dependent effect on the wood mechanical properties; the resinated pine samples showed increase in compliance while the corresponding poplar samples became stiffer. The in situ lignin relaxation was studied with both dynamic and static modes, using plasticized wood samples. Results showed that the lignin relaxation was slightly affected by resin impregnation in both woods, but the effect was relatively larger in pine. Static experiments of dry wood samples showed a significant reduction in the interchain interactions of wood polymers in pine samples, exclusively. Investigation of plasticized pine samples, which focuses on the in situ lignin relaxations, showed only minor changes with resin impregnation. This led us to hypothesize that the large changes observed in dry samples, were due to the in situ amorphous polysaccharides. The wood-PMDI interactions were significantly reduced upon acetylation of wood. This study also discusses three new and highly sensitive methods for the analysis of wood-resin interactions. / Ph. D.

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Made available in DSpace on 2016-06-02T19:19:58Z (GMT). No. of bitstreams: 1 OLIVEIRA_Robson_2013.pdf: 4428066 bytes, checksum: aefeb43146df9afeba619c532fb8d2f6 (MD5) Previous issue date: 2013-09-13 / Composite technology of a polymer matrix reinforced with artificial fibers, like fiberglass, Kevlar, carbon, etc., has become specialty in recent times moved by advances in technology in some sectors such as automotive and aerospace. The composites already have come a long way in replacing conventional materials like metals and Woods. However with the goal to reduce costs and provide a sustainable growth, science has directed his attention in reinforced compounds with renewable material such as natural fibers. In this work, a study was conducted of the dynamic behavior-mechanical and thermodynamic transitions of second order, as is the case of the glass transition temperature, matrix composite polyurethane elastomers with jute fiber reinforcement. The relaxation that occurs in glassy transition region, also called primary relaxation or relaxation α to amorphous polymers, molecular movements resulting from long distances, involving the main polymer chain segments. The matrix was formed by a MDI-BDO system provided by the company Metso Brazil, PU Division. Metso Brazil manufactures PU screens used in crushing sieves in the mining industry, and this work studied replacing the pure PU fiber by composite reinforced with jute. The material was prepared in an open heated to 100º C with controlled temperature, the system was synthesized in a mixer pre-polymer ratio automatic PU of Baulé on following conditions: MDI, 45º C to 9.5 bar; BDO, 45 C 5.7 bar and D20, 69 C a11 .2 bar. For the characterization of mechanical properties of composite dynamic-mechanical analysis was performed in tension in a temperature range of 35 to 160° C and bending creep. The results showed that the composite had formed showed lower creep deformation in bending test compared to pure polyurethane, but higher strain compared to the composite fiberglass. The flexural modulus (E ') of jute fiber composite showed a higher value at higher temperatures than the unreinforced material. The composi / A tecnologia de compósitos de uma matriz polimérica reforçada com fibras artificiais, com fibra de vidro, Kevlar, carbono, etc., tornou-se de grande interesse nos últimos tempos com os avanços da tecnologia em alguns setores como automobilístico e aeroespacial. Os compósitos já percorreram um longo caminho na substituição dos materiais convencionais como metais e madeiras, no entanto com o objetivo de reduzir custos e proporcionar um crescimento sustentável, a ciência tem direcionado sua atenção em compostos reforçados com material de fontes renováveis como as fibras naturais. No presente trabalho, foi realizado um estudo do comportamento dinâmico-mecânico e transições termodinâmicas de segunda ordem, como é o caso da transição vítrea, em compósito de matriz poliuretana elastomérica com reforço de fibra de juta. A matriz foi formada por um sistema MDI/BDO (reação entre um diisocianato de 4-4'-difenilmetano (MDI) e o 1,4-butanodiol (BDO), fornecida pela empresa Metso Brasil, divisão PU. A Metso Brasil fabrica telas de PU usadas em peneiras de britagem na indústria de mineração, sendo que o presente trabalho estudou a substituição do PU puro pelo compósito com fibra de juta. O material foi vazado em molde aberto na empresa em mesa aquecida a 100ºC com temperatura controlada. O sistema prepolímero foi sintetizado em um misturador automático de PU da Baulé nas seguintes condições: MDI 45ºC a 9,5 bar; BDO, 45ºC a 5,7 bar e D20, 69ºC a11,2 bar. Para a caracterização das propriedades mecânicas desse compósito foi realizada análise dinâmico-mecânica (DMA) em ensaios de tensão no intervalo de temperatura de 35 a 160 ºC. Os principais resultados mostraram que o compósito formado apresentou menor deformação de fluência em ensaio de flexão em relação ao poliuretano puro, porém maior deformação quando comparado com o compósito com fibra de vidro. O módulo flexural (E ) do compósito de fibra de juta apresentou um maior valor em temperaturas mais elevadas que o do material sem reforço. O compósito de fibra de juta foi solicitado no modo de tração e teve um comportamento de material menos dúctil.

Fibre Reinforced Polymer Composites are extensively used in aircraft structures because of its high specific stiffness, high specific strength and tailorability. Though Fibre Reinforced Polymers offer many advantages, they are not free from problems. The damage of different nature, e.g., service mechanical damages, fatigue damage or environmental damage can be observed during operating conditions. Among all the damages, manufacturing or service induced, delamination related damage is the most important failure mechanisms of aircraft-composite structures and can be detrimental for safety. Delamination growth under fatigue loading may take place due to local buckling, growth from free edges and notches such as holes, growth from ply-drops and impact damaged composites containing considerable delamination. Delamination growth can also occur due to interlaminar stresses, which can arise in complex structures due to unanticipated loading. The complex nature of composite failure, involving different failure modes and their interactions, makes it necessary to characterize/identify the relevant parameters for fatigue damage resistance, accumulation and life prediction. An effort has been made in this thesis to understand the fatigue behavior of carbon fibre reinforced epoxy laminates under aircraft wing service loading conditions. The study was made on laminates with different lay-up sequences (quasi-isotropic and fibre dominated) and different geometries (plain specimen, specimen with a hole and ply-drop specimen). The fatigue behaviour of the composite was analyzed by following methods: . Ultrasonic C-Scan was used to characterize the delamination growth. . Dynamic Mechanical Analysis (DMA) was done to study the interfacial degradation due to fatigue loading. In this analysis, the interfacial strength indicator and interfacial damping were calculated. The DMA also provides the storage modulus degradation under fatigue loading. . Scanning electron microscope examination was carried out to understand the fatigue damage mechanisms. . A semi-empirical phenomenological model was also used to estimate the residual fatigue life. This research work reveals that the Carbon Fibre Reinforced Polymer laminates are in the safe limit under service loading conditions, except the specimen with a hole. The specimen with a hole showed delaminations around the hole due to stress concentration and higher interlaminar stresses at the hole edges and this delamination is found to be associated with fibre breakage and fibre pullout. The quasi-isotropic laminate is found to show poorer fatigue behaviour when compared to fibre dominated laminate and ply-drop also shows poor performance due to high stress concentration in the ply-drop region.

No description available.

Wood is a widely used construction material that has many advantageous properties, and some drawbacks. These drawbacks are mainly associated with the porous vascular structure of wood that makes it a high water-absorbent material. In addition, wood’s properties alter substantially with respect to the moisture content. Amongst the treatment techniques that limit the water uptake capacity of wood, vacuum-aided impregnation has exhibited promising results. However, little research has explored the effect of key parameters (such as the vacuum pressure) on the effectiveness of the impregnation. This study aims to optimize the performance of SiO2 impregnation of spruce wood under vacuum pressures. The main objective of this research is to overcome wood’s weakness by reducing its water uptake capacity through a vacuum-aided impregnation technique and study its effect on the physico-mechanical properties of wood under dry and saturated conditions. The study was conducted in two parts. In the first part, wood samples underwent impregnation under atmospheric and three vacuum pressures. Density measurements, water uptake tests, microscopy examination, thermogravimetric analysis, and dynamic mechanical analysis were conducted on non-treated and SiO2-treated samples. Quantitative and qualitative analyses demonstrated that SiO2 impregnation performed under -90 kPa was able to effectively enhance the wood’s properties compared to the other conditions. The SiO2 impregnation under high vacuum pressure demonstrated an effective increase in the density of the wood and achieved a significant reduction in the water uptake capacity. The analysis of the wood’s viscoelastic properties revealed that SiO2 impregnation under atmospheric and vacuum conditions triggered two different reinforcing mechanisms: a solid film, causing stick-slip oscillation, and particle diffusion, causing particle-particle and particle-lumen wall friction, respectively. For the second part, characterization methods such as Impact test, DMA, SEM, EDS, Porosity, and SAXS tests were conducted on non-treated and -90 kPa treated spruce wood samples in dry, saturated, and submerged states in order to reveal the synergistic effect of the SiO2 impregnation pressure and water uptake on the wood’s properties. The results showed that high vacuum impregnation pressure has a significant positive reinforcing effect on the wood’s properties. It increased the impact resistance of wood in dry and saturated conditions. A high vacuum impregnation was able to overcome the softening effect of water and caused a significant increase in the Storage modulus by strengthening the wood’s vascular structure, which accordingly increased the wood’s capacity to absorb energy. High vacuum impregnation was also able to counteract the plasticizing effect of water and significantly increased the Loss modulus by increasing the internal friction in the wood with the diffusion of the nanoparticles in the wood’s cell walls and vascular structure. This phenomenon increased the wood's capacity to absorb and dissipate energy under dry and submerged conditions.

New resin-based composites and resin-infiltrated ceramics are used to fabricate computer-aided design (CAD) and computer-aided manufacturing (CAM)-based restorations, although little information is available on the long-term performance of these materials. The aim of this investigation was to determine the effects of storage time (24 h, 90 days, 180 days) on the thermophysical properties of resin-based CAD/CAM materials. Thermogravimetric Analysis (TGA), differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were used in the study. TGA provided insight into the composition of the resin-based materials and the influence of internal plasticization and water sorption. Resin-based composites showed different decomposition, heat energy and mechanical behavior, which was influenced by storage time in water. Individual materials such as Grandio bloc showed lower influence of water storage while maintaining good mechanical properties.

No description available.

Este trabalho apresenta o estudo de um sistema polimérico bi-componente formado por Poli(Ácido carboxílico)-Poli(Eter-poliol), constituído primariamente de um polímero acrílico polimerizado pelo processo de polimerização em solução aquosa por mecanismo de radicais livres ao qual foi adicionado seqüencialmente, um Poli(Eter-poliol), ambos de baixo peso molecular médio. Tal sistema tem por finalidade atuar como dispersante-ligante em sistema cerâmico à base de caulim CADAM, uma vez que este sistema apresenta propriedades termoplásticas e termorrígidas a diferentes temperaturas. Foram sintetizados 03 protótipos de um sistema polimérico e o critério para escolha teve como base o pH do sistema em sentido generalizado, isto é, compreendendo as diversas fases de preparação dos polímeros e sua aplicação final. É do conhecimento comum que a reação de esterificação entre grupos COOHOH requer catálise ácida para ocorrer, o qual usualmente é realizada em pH abaixo de 4 e, neste ensaio, este pH ácido é devido à presença de ácido para-toluenosulfônico, que atua como catalisador de esterificação. Em tal intervalo de pH, em virtude do ponto isoelétrico do caulim ser comumentemente abaixo de 4, a estabilização da dispersão de caulim por repulsão eletrostática utilizando polímeros sintéticos é improvável de ocorrer, razão pela qual buscou-se mecanismos alternativos para obtenção de uma tal estabilização, entre os quais o mecanismo estérico surge como opção. O sistema polimérico do presente estudo apresenta-se na forma de uma solução aquosa sendo, de fato, uma mistura homogênea de um copolímero de ácido acrílico, N- metiloacrilamida e metacrilato de metoxipolietileno glicol e um poli(eter-poliol). O poli(eter-poliol) e N-metilolacrilamida presentes no sistema polimérico são principais fontes de grupo hidroxila para reação de poliesterificação e formação de ligações cruzadas à temperatura de 150 a 200 °C. No estado termoplástico o sistema polimérico produzido pela mistura poli(ácido carboxílico)-poli(eter-poliol) pode ser utilizado como dispersante de argilas com especial fóco sobre caulim como tratado neste trabalho. A propriedade dispersante pode ser atribuida à presença de grupos carboxílicos e metoxipolietilenoglicol aleatoriamente distribuídos ao longo da cadeia polimérica e, também, ao baixo peso molecular médio. A temperaturas entre 150 a 200 °C, o polímero é reticulado (crosslinked) por reação de poliesterificação, catalisada por ácido, entre grupos carboxila e grupos hidroxila, sendo as hidroxilas provenientes tanto de poliol como de N-metilolacrilamida (NMAM). Assim, do ponto de vista térmico comporta-se como termorrígido, sendo nesta condição insolúvel em água e adequado atuar como ligante na manufatura de materiais cerâmicos. Medidas de mobilidade eletroforética e viscosidade são aplicadas à caracterização de caulim e do sistema polimérico a fim de avaliar a potencialidade de aplicação como dispersante desta argila. Também, as transições dos estados termoplásticos para termorrigidos foram determinadas por análise termogravimétrica (TG) e análise dinâmico mecânica (DMA) nos polímeros isoladamente e depois com medidas de resistência mecânica do sistema caulim/polímero. O sistema apresentou comportamento dispersante em água e ligante após cura. Um sistema polimérico assim sintetizado foi propriamente curado por calor tornando- se, na forma termorrígida, um ligante para peças cerâmicas com propriedades mecânicas de alto desempenho, como resistência a flexão no estado cru (green strenght). / This work presents the study of a polymeric bi-component system made from Poly(carboxylic acid)-Poly(ether-polyol) primarily constituted of an acrylic acid polymerized through the process of aqueous solution polymerization by free radical mechanism, to which a poly(ether-polyol) has been sequentially added, both of them of low average molecular weight. Such a system has the aim to act as dispersing-binding balance on CADAM kaolin targeting to evaluate the applicability potential or the preparation of ceramic bodies as this polymeric system presents thermoplastic and thermosetting properties at different temperatures. Were made the synthesis of 03 polymeric system prototypes which criteria for choice was based on pH of the system at whole sense, that is, regarding the several steps for polymers preparation and its final application. It is knowledge that esterification reaction between COOH-OH groups requires acid catalyst to occur, which usually is done at pH below 4 and, in this work this pH is due to p-toluene sulfonic acid that act as esterification catalyst. In this range of pH, due to the isoeletric point of kaolin to be below 4 the electrostatic stabilization of dispersion is unlikely to occur, from which reason was looked for an alternative mechanism to achieve the dispersion stabilization, among them the steric mechanism arises an option. The polymeric system of this study is the form of an aqueous solution, which actually is a homogeneous blend of a copolymer of acrylic acid, N-Methylolacrylamide Methoxypolyethyleneglycol Methacrylate (MPEGMA) and Poly(ether-polyol). The Poly(etherpolyol) and the N-Methylolacrylamide presents at the polymeric system are the main sources of hydroxyl groups to enhance the polyesterification reaction for further crosslinking at temperatures from 160 to 200 °C. At the thermoplastic state the polymeric system made by Poly(carboxilic acid)poly(ether-polyol) macromolecules may be used as clay dispersant focusing on kaolin for this work. The dispersant property may be attributed to the carboxylic and methoxypolyethyleneglycol group randomly distributed along the polymeric chain backbone and, also to the low average molecular weight. At temperatures between 150 to 200 °C, the polymer is crosslinked by polyesterification reaction catalized by acid between carboxyl groups and hydroxyl groups, in such way that hydroxyls groups comes both from the polyol base polymer and NMethylolacrylamide (NMAM) present at first polymer backbone. Thus, through a thermal standpoint it behaves as thermoset being that, under this condition, water insoluble and adequate to act as binder for manufacturing of ceramic materials. Electrophoretic mobility and viscosity measurements were applied for the characterization of kaolin and the polymeric system targeting to the evaluation its potential application as a dispersant for this clay. Also, the transitions from the thermoplastic to the thermoset state have been determined by thermo-gravimetric analysis (TG) and dynamicmechanical analysis (DMA) for the Poly(carboxylc acid)poly(ether-polyol) polymers alone and further by mechanical resistance measurements for a clay-polymer system. The system has presented both dispersant behavior on aqueous media and binder just afterward cure. A polymeric system thus synthesized was properly cured by heat turning and then, at the thermoset state, become suitable for act as a binder for ceramic bodies with high performance mechanical properties measured as flexural resistance at green strength.