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Carbon fiber (CF) 8-harness satin weave, T650/Neximid system of [(+45/-45)/(0/90)]2S and [(0/90)]4S layup was manufactured using resin transfer molding (RTM). The material was cut into 3-point bending specimens and treated for 24 hours in a burn oven at T=(320,350,375,400,450 & 500)°C. The material was tested according to ASTM E1640-13 using dynamic mechanical thermal analysis (DMTA). Un-treated material showed Tg levels of 384°C and 392°C for the respective layups. It was found that pre-Tg treatment between 320-375°C affected this material parameter up to similar levels as previous studies of post Tg exposure for 2h to ~420°C [4]. Subjecting the material for post-Tg exposure at 400°C showed a rapid change up to ~480°C for [(0/90)]4S laminate. Indications that this resin system could reach levels above 500°C was found for [(+45/-45)/(0/90)]2S layup. However, one of these specimens were unfit for testing. DMTA tested material for 400°C showed indications of degradation, found by a broadening of the tan delta peak. This can be put in relation to epoxy where a similar behavior appear after 24h exposure at 150°C. Furthermore, it was showed that poor quality laminate, elevated mass loss at this temperature. When the material was subjected to as high temperatures as 450°C only remaining fibers were found. At 500°C these were almost fully oxidized. 400°C data was predicted by the use of activation energy along with TG extrapolation. It was possible to show that ~1/8 out of this 8-layered structure, (½ of each surface layer), was degraded after 400°C exposure for 24h, resulting in diffusion limited oxidation (DLO). Last but not least, DLO assumptions was used to predict the storage modulus change for thermo-oxidative degradation of 400°C samples with Classic Laminate Theory (CLT). A ~4% stiffness decrease was predicted by this method. The drop is regarded as a loss in tensile stiffness of the outer damaged layer. This was compared by 3-point bending DMTA data showing a ~7% decrease. This model could thus be regarded as a contributing factor for the stiffness decrease of this complex degradation process. / Kolfiber, 8-harness satin väv, T650/NEXIMID system med [(+45/-45)/(0/90)]2S och [(0/90)]4S orientering, tillverkades via RTM. Från materialet tillverkades 3-punkts böjprover. Dessa behandlades i 24 timmar vid T=(320, 350, 375, 400, 450 & 500)°C, i en brännugn. Materialet testades i enighet med ASTM E1640-13 via DMTA. Obehandlat material visade Tg nivåer av 384°C och 392°C för de respektive uppläggningarna. Pre-Tg exponering, vid 320-375°C, påverkade Tg upp till liknande nivåer som tidigare studier, (post-Tg 2h), ~420°C [4]. När materialet utsätts för post Tg exponering under 24 timmar vid 400°C kunde man se en snabb förändring av Tg, upp till ~480°C för [(0/90)]4S laminatet. Från [(+45/-45)/(0/90)]2S laminatet kunde man dessutom se indikationer på att nivån kunde nå över 500°C. Däremot var en av dessa prov inte kvalificerad för test efter behandlingen. DMTA testat material för 400°C visade indikationer av nedbrytning, via en breddning av piken för tan-delta kurvan. Det var dessutom möjligt att se att laminat av sämre kvalitet påverkade viktminskningen signifikant högre vid denna exponering. När material utsattes för så höga temperaturer som 450°C var endas fiber kvar efter test, vilket vid 500°C nästan var fullt nedbrutna. 400°C data förutspåddes via extrapolering av TG och Arrhenius beräkning. Beräkningen ledde till en övre gräns för nedbrytningen. Vidare var det möjligt att visa att ~1/8 av dessa 8-lager bröts ner efter 24 timmars exponering vid 400°C. Nedbrytningen motsvarar ½ av vartdera ytlager via diffusions begränsad oxidation (DLO). Sist men inte minst, kunskapen om DLO användes för att förutspå styvhetsförändringen vid termo-oxiderande nedbrytning med hjälp av klassisk laminat teori (CLT). DLO antogs resultera i en volymfraktionsförändring i det yttersta lagret. Detta implementerades i CLT där man kunde beräkna en ~4% styvhetsminskning via denna modell där det yttre skadade lagret har en reducerad dragstyvhet. Från testade böjprover i DMTA kunde man se en verklig ~7% styvhetsminskning för samma exponeringsvillkor. Modellen kan därmed ses som en bidragande del av denna komplexa nedbrytningsprocess.

O estudo do processo de fusão e solidificação da água contida dentro de materiais confinantes tem sido amplamente discutido em química, biologia, física, geologia, e com diversas aplicações tecnológicas, tais como aplicação na fabricação de etanol de segunda geração, ou etanol celulósico, separação de fases, fabricação de nanomateriais. Pesquisas mostraram que as temperaturas de transição da água nanoconfinada são muito sensíveis ao diâmetro do poro, mas que podem ser pouco afetadas pela natureza, hidrofóbica ou hidrofílica, da superfície do poro. Outra importante constatação em experimentos de fusão e congelamento em nanoporos é que nem toda água presente nos poros pode ser cristalizada até gelo. A existência de uma camada de água pré-fundida em nanoporos tem sido confirmada através de experimentos. Com o objetivo de entender mais profundamente como a temperatura de transição da água confinada depende da natureza da parede confinante e do tamanho do confinamento, propõe-se um modelo de nanoporos de celulose para o confinamento, onde varia-se o diâmetro e comprimento do nanoporo, além da natureza da parede do nanoporo. Nossos estudos, mostram que para sistemas hidrofóbicos, com formação de camada de água líquida na parede, as temperaturas de transição variam desde relativamente baixas, para menores valores de calor latente, até atingindo a temperatura de transição da água bulk, para calor latente mais alto. Enquanto que para sistemas hidrofílicos, para nenhum dos valores de calor latente trabalhados, e para nenhum tamanho do sistema, a temperatura de transição atinge o valor de bulk. / The study of the fusion process and water solidification inside confining materials has been widely discussed in Chemistry, Biology, Physics, and Geology, and has various technological applications as the usage and fabrication of second generation ethanol or cellulosic ethanol, phase separation, and nanomaterials fabrications. Researches have shown that nanoconfined water’s transition temperature are highly sensitive to the pore. Another interesting remark on freezing and fusion experiments on nanopores is that not all water present in pores can be crystallized into ice. The existence of a water layer pre-melted on nanopores has been confirmed through experiments. Aiming at understanding deeply how water’s transition temperature depends on the nature of the confining wall and size, a cellulose nanopore model is proposed to the confinement, where the nanopore diameter and length are varied, besides the nature of the wall of the nanopore. Our studies show that for hydrophobic systems, with the liquid water layer formation on the wall, the transition temperatures vary from relatively low latent heat to smaller values, even reaching the temperature transition on bulk water to higher latent heat. While for hydrophilic systems, for none of the latent heat used and no system size the transition temperature reaches bulk value.

Resumo: Este estudo avaliou o efeito da irradiação por microondas e da armazenagem em água sobre as propriedades viscoelásticas de duas resinas para base de prótese (Lucitone 550- L e Vipi Wave- VW) e duas resinas para reembasamento imediato (Kooliner- K e Tokuyama Rebase Fast II- TR II). Oito corpos-de-prova (40 x 10 x 3,3 mm) de cada material foram avaliados por meio de análise térmica dinâmico-mecânica (DMTA) após: acabamento (controle 1), armazenagem em água por 7 dias (controle 2), um (MW1) e 7 ciclos de irradiação por microondas (MW7). Para cada corpo-de-prova, ciclos de DMTA foram realizados dentro de intervalos de temperatura diferentes. Os valores do módulo de armazenamento (E') e de amortecimento mecânico (tan δ) a 37ºC foram obtidos no primeiro e último ciclos de DMTA. A partir do último ciclo, os valores de E' na temperatura de transição vítrea (Tg) e o máximo de tan δ também foram obtidos. Os dados foram submetidos à análise de variância a dois critérios e ao teste de Student-Newman-Keuls (α=0,05). Além disso, mensurações de temperatura no interior de corpos-de-prova de cada material, durante a irradiação por microondas (650 W/ 3 min), foram realizadas por meio da utilização de sensor de fibra óptica. Seis corpos-de-prova de cada material foram avaliados. Durante a irradiação por microondas, todos os corpos-de-prova atingiram a temperatura de ebulição da água em aproximadamente 130 s. A partir do primeiro ciclo de DMTA, MW 1 e controle 2 aumentaram significantemente os valores de E' e reduziram os valores de tan δ de K a 37ºC (P<0,05). No último ciclo de DMTA, o tan δ de K e TR II foi significantemente reduzido após MW1 (P<0,05). MW7 reduziu os valores de tan δ de K (P<0,05). Os valores de E' de L e VW foram semelhantes entre si e superiores aqueles produzidos por K e TR II (P<0,05). Na Tg, K produziu o menor E' e seu máximo... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This study evaluated the effect of microwave irradiation and water storage on the viscoelastic properties of two denture base resins (Lucitone 550-L and Vipi Wave-VW) and two reline resins (Kooliner-K and Tokuyama Rebase Fast II-TR II). Eight specimens (40x10x3.3mm) of each material were evaluated by dynamic mechanical thermal analysis (DMTA) after: processing, water storage for 7 days (WS), one (MW1) and 7 cycles of microwave irradiation (MW7). For each specimen, DMTA runs were carried out within different temperature intervals. Values of storage modulus (E') and loss tangent (tan δ) at 37ºC were obtained from the first and last runs. From the last run, values of E' at the glass transition temperature (Tg) and maximum tan δ were also recorded. Data were analyzed by 2-way ANOVA followed by Student-Newman-Keuls test (α=0.05). In addition, measurements of the inside temperature of each specimen during microwave irradiation (650W/3min) were conducted using a fiber optic temperature sensor. Six specimens of each material were evaluated. During microwave irradiation, all specimens reached the boiling temperature of water at approximately 130 s. From the first DMTA run, MW1 and WS significantly increased the E' and decreased the tan δ of K at 37°C (P<0.05). From the last run, the tan δ of K and TR II was significantly decreased after MW1 (P<0.05). MW7 decreased the tan δ of K (P<0.05). The E' of L and VW was similar and higher than K and TR II (P<0.05). At Tg, K produced the lowest E' and its maximum tan δ was increased after MW1 (P<0.05). The Tg mean values were arranged as: L>VW>TR II>K (P<0.05). Microwave irradiation and WS did not detrimentally affect the viscoelastic properties of the denture base and reline resins evaluated. / Orientador: Carlos Eduardo Vergani / Coorientador: Sebastião Vicente Canevarolo Júnior / Banca: Rafael Leonardo Xediek Consani / Banca: Ana Cláudia Pavarina / Mestre

Polymeric systems near their glass transition are known to exhibit heterogeneous dynamics that evolve both over space and time, yet many of the underlying principles of these dynamics are still poorly understood. In this thesis, experimental single molecule studies aimed at uncovering the dynamics of polystyrene near its glass transition temperature are described. In a first approach, the influence of temperature on the timescales associated with dynamic heterogeneity – also referred to as exchange times – are identified by following the dynamics of a fluorescent perylene diimide probe embedded in a high-molecular weight polystyrene host. No clear influence on the lifetime of dynamics is found in the temperature regime Tg to Tg + 10 K. In a second study, heterogeneous dynamics are investigated in the context of molecular weight and fragility. In a similar experimental approach to that of the first study, two fluorescent dyes are utilized to report on the rotational dynamics of low- to high-molecular weight polystyrene hosts. In accordance with previous reports, the stretching exponent, β, is found to be correlated with the system’s molecular weight, even on a single molecule level. However, no clear correlation with the system’s exchange time was found. In a final study, several single molecule approaches aimed at uncovering the dynamics in confined polystyrene films are described. As no evidence for previously-described mobile surface molecules has been found, this final chapter is meant to provide a basis for future single molecule studies in confined systems.

The flexible substrate was fabricated by BaTi4O9 mixed with O-Cresol Novolac Epoxy, polyether imide or surface active agents. The electrical and physical characteristic measured had been finished. The dielectric property influence of substrate was changed from percentage of BaTi4O9. The dielectric constant model was used by Jayasundere and Smith equation (J. S. eq.) and Lichtenecker equation (L. eq.) The study of crystalline grain, orientation and phase transfer temperature was used by SEM, XRD, and DSC, respectively. The dielectric constant and dielectric loss tangent of the composite was measured using an HP4294A impedance analyzer. The TM mode calculated by resonate frequency of the composite was measured using an HP4156C network analyzer. The dielectric constant was obtained to TM mode at high frequency. The result was showed that dielectric constant at low frequency of BaTi4O9, OCN Epoxy and PEI are 57, 5.8 and 3.65, respectively. OCN Epoxy is better than PEI of electrical characteristic. However, OCN Epoxy is not flexible. For this reason, the PEI was focused on electrical property at high frequency. The BaTi4O9 exhibited a dielectric constant of 39 at frequency during 3~10 GHz. The dielectric constant was measured of 10 at frequency during 2~16 GHz with 70 wt% PEI composite. The dielectric constant is higher than FR-4 substrate to 6.4 of the composite. The low dielectric constant is obtaining to reduce stuffing.

Using low-temperature (650¢J) Ce3+:YAG doped glass (LTCeYDG) phosphor layer instead of conventional Ce:YAG doped silicone phosphor layer applied to high-power phosphor-converted white-light-emitting diodes (PC-WLEDs) is demonstrated.The glass transition temperature (Tg) of silicone is 150¢J but glass is 750¢J,it shows the glass were employed in high power LED than silicon. The uniformity of phosphor powder doped glass is an important item to discriminates between good and bad. Quantize the uniformity of glass phosphor by image processing software and Distribution Uniformity (Du). Calculate the uniformity of phosphor powder mix with glass powder which has different particle size and measurement optical properties of glass phosphor which has different uniformity. The Du of glass phosphor are 64.46%, 84.65%, 85.24% , 91.85% and the quantum efficiency are 18.49%, 28.31%, 29.73%, 28.56% ,respectively. By using Ceramic tube and low temperature glass powder sintering glass phosphor is a new fabrication. Compare with last fabrication, new fabrication reduce 100¢Jfabrication temperature from 750¢J to 650¢J, 70% material savings and high luminous efficiency. The quantum efficiency and lumen per watt were improved about 7 percentage point from 22.3% to 29.1% and 4.2 lm/W from 36.4 lm/W to 40.68 lm/W. We used the XRD to analyze the glass phosphor of last fabrication and new fabrication and the results show that the higher thermal stress destroys the structure of YAG, lower fabrication temperature used to get higher luminous efficiency.

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The properties of polymers, thin films or bulk, are profoundly influenced by interactions at interfaces with dissimilar materials. Thin, supported, polymer films are subject to interfacial instabilities, due largely to competing intermolecular forces, that cause them to rupture and dewet the substrate. The addition of nanoparticles (such as clay sheets, metallic or semiconductor nanocrystals, carbon nanotubes, etc.) to polymers can substantially affect bulk properties, such as the glass transition and viscosity, and influence the processability of the material. In this dissertation, we contribute to a fundamental understanding of the role of interfacial interactions on both the instabilities exhibited by polymer thin films and the properties displayed by polymer-nanoparticle mixtures. While conditions under which the destabilization of compositionally homogeneous thin films occurs are relatively well understood, the mechanisms of film stabilization in many two-component thin film systems are still unresolved. We demonstrate that the addition of a miscible component to an unstable film can provide an effective means of stabilization. The details of the stabilization mechanism are understood in terms of the compositional dependence of both the macroscopic wetting parameters and the effective interface potential for the system. We find that the suppression of dewetting in the system is not an equilibrium stabilization process and propose a mechanism by which the increased resistance to dewetting may occur. There is also significant interest in understanding the extraordinary property enhancement of polymers that are enabled by the addition of only small concentrations of nanoparticles. If these effects could be distilled down to a few simple rules, they could be exploited in the design of materials for specific applications. In this work, the influence of C60 nanoparticles on the bulk dynamical properties of three polymers is examined. Based on the findings from a range of measurement techniques, including differential scanning calorimetry, dynamic mechanical analysis, dynamic rheology and neutron scattering, we propose that the changes in the glass transition temperature for the polymer-C₆₀ mixtures can be understood in terms of a percolation interpretation of the glass transition. The proposed mechanism is also characterized computationally. / text

Very specific protein-salt interactions are involved in a multitude of biological phenomena such as protein folding/stability, enzymatic activity, and signal transduction events. In this work, we used two very simple, protein-mimic model biopolymers to obtain a better understanding of specific cation effects operating in aqueous protein environments. The two biopolymers used were Elastin-like Polypeptides (ELPs) and poly(N-isopropylacrylamide) (PNIPAM). ELPs are an especially an ideal model system as these polypeptides can be easily genetically engineered to observe the effect of specific amino acid residues and peptide chain length on these salt interactions. Both of these biopolymers are also highly thermoresponsive as their aqueous solutions undergo a hydrophobic collapse/aggregation induced phase transition process above a lower critical solution temperature (LCST). Thermodynamic measurements of these biopolymers were carried out under various salt solution conditions. Additionally, both of these biopolymers are suitable for making surface specific spectroscopic measurements. Vibrational sum frequeny spectroscopy (VSFS), a non-linear interface sensitive spectroscopic technique, was employed here to investigate biologically relevant cation interactions which occur at peptide/protein surfaces. First, the LCST response of a non-polar ELP and a neutral biopolymer, PNIPAM, was investigated in the presence of 12 different alkali, alkaline-earth metal and transition metal chloride salts. Even though the salt interactions for uncharged proteins are dominated by anions, subtle specific cation effects were also observed. The results followed a direct Hofmeister series for cations. Most alkali cations are excluded from the polar amide regions of proteins. More polarizable cations, however, can solvate the hydrophobic moieties and somewhat counter the salting-out effect of the chloride anion. More charged and hydrated ions like lithium and divalent cations showed a weak interaction to the amide moiety through their hydration shell. The role of acidic amino acid residues in inducing cation specificities was investigated using an aspartate-rich ELP system. Both thermodynamic and spectroscopic data conclusively proved that the negative charge on protein surfaces is the main driving force for cation partitioning and specificity under physiological relevant concentration regimes. Apparent binding constants of carboxylate moieties with cations were determined. This is the first quantitative and thoroughly systematic study of such biologically relevant cation-carboxylate interactions prevalent in enzyme active sites and protein surfaces.