The rheological behavior and dynamic mechanical properties of syndiotactic 1,2-polybutadiene

The rheological behavior and the dynamic mechanical properties of syndiotactic 1,2-polybutadiene (sPB) were investigated by a rotational rheometer (MCR-300) and a dynamic mechanical analyzer (DMA-242C). Rheological behavior of sPB-830, a sPB with crystalline degree of 20.1% and syndiotactic content of 65.1%, showed that storage modulus (G ') and loss modulus (G '') decreased, and the zero shear viscosity (eta(0)) decreased slightly with increasing temperature when measuring temperatures were lower than 160 degrees C. However, G ' and G '' increased at the end region of relaxation curves with increasing temperature and)10 increased with increasing temperature as the measuring temperatures were higher than 160 degrees C. Furthermore, critical crosslinked reaction temperature was detected at about 160 degrees C for sPB-830. The crosslinked reaction was not detected when test temperature was lower than 150 degrees C for measuring the dynamic mechanical properties of sample. The relationship between processing temperature and crosslinked reaction was proposed for the sPB-830 sample.

FT-Raman investigation of biodegradable polymers: Poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

This work presents a FT-Raman study (lambda(0) = 1064 nm) of naturally occurring polyester poly[(R)-3-hydroxybutyrate] (PHB) and its copolymer poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyvalerate] (PHBV) with 5,8 and 12 mol % of HV (hydroxyvalerate). The FT-Raman spectra of films indicate that full width at half height of the band centered at 1725 cm(-1) and relative intensity of bands at 1443 and 1458 cm(-1) can be use to estimate the crystalline degree in film samples. The similarity between Raman spectra of molten PHB and PHBV and theirs CDCl(3) solutions suggested that molten polymers present similar conformation than polymers in solution. Raman data of these samples showed that bands at 1220, 1402, 1725, 2998 and 3009 cm(-1) are due to crystalline helical structure and the bands at 1453, 1740, 2881, 2938 and 2990 cm(-1) are originated from disordered domains. It is shown that composition of PHBV samples can be estimated by analyzing the ratio of the intensity of the bands at 2938 cm(-1) (nu C-H) and 1740 cm(-1) (nu C=O) in the spectra of solutions and of bands at 1354 (wCH(2)) and 1740 cm(-1) (nu C=O) in spectra of molten polymers. (C) 2010 Elsevier B.V. All rights reserved.

Efeitos da história térmica nas propriedades do polímero pet: um experimento para ensino de análise térmica

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Use of high energy ball milling on the sintering optimization of alumina ceramics

In this work, the effect of the milling time on the densification of the alumina ceramics with or without 5wt.%Y 2O 3, is evaluated, using high-energy ball milling. The milling was performed with different times of 0, 2, 5 or 10 hours. All powders, milled at different times, were characterized by X-Ray Diffraction presenting a reduction of the crystalline degree and crystallite size as function of the milling time increasing. The powders were compacted by cold uniaxial pressing and sintered at 1550°C-60min. Green density of the compacts presented an increasing as function of the milling time and sintered samples presented evolution on the densification as function of the reduction of the crystallite size of the milled powders. © (2010) Trans Tech Publications.

Análise estrutural e morfológica de ferrita NiFe2O4 dopada com cromo

This paper reports on the effect of the substitution of Fe3+ for Cr3+ ions in the spinel lattice of the powders was investigated. Nickel ferrite powders with a NiFe2-xCrxO4 nominal composition (x = 0.0; 0.5; 1.0 and 1.5 mol of the chromium) were synthesized by combustion reaction using urea as fuel. The powders resulting were characterized by XRD, nitrogen adsorption by BET, SEM and Mössbauer spectroscopy (57Fe Mössbauer spectra). The results show that the substitution of the Fe3+ for Cr3+ions increased the crystalline degree of the phase, reduced the superficial area and consequently increased the particle size. The Mössbauer spectra of the samples also confirm the distribution of the particles size by the magnetic properties. Analyze of the spectra Mössbauer gives an estimate of the superparamagnetic and ferromagnetic particles behavior in each sample for several chromium concentrations.

Estudo do efeito da cristalinidade nas propriedades mecânicas de compósitos termoplásticos com aplicações aeronáuticas

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Nanopartículas lipídicas sólidas e vesículas cataniônicas contendo ftalocianina de cloro alumínio aplicadas nos processos fotodinâmicos

O trabalho apresentado foi realizado em duas etapas independentes e baseou-se no estudo de diferentes sistemas nanométricos para viabilizar a aplicação da ftalocianina de cloro alumínio (ClAlPc) na terapia fotodinâmica (TFD) para o tratamento do câncer de pele do tipo melanoma. O fármaco fotossensibilizante (FS) utilizado apresenta propriedades físico-químicas que lhe permitem exercer sua atividade fotodinâmica com excelência, sem a interferência do cromóforo endógeno melanina existente nas células melanocíticas. Para driblar sua elevada hidrofobicidade, ClAlPc foi encapsulada em sistemas nanométricos para administração em meio fisiológico. Inicialmente nanopartículas lipídicas sólidas (NLS) foram desenvolvidas por emulsificação direta, após um estudo de elaboração do diagrama de fases. O compritol foi o lipídio sólido escolhido para compor as NLS, com diferentes concentrações de ClAlPc. Todas as formulações desenvolvidas foram devidamente caracterizadas, com tamanho médio entre 100 e 200 nm, baixa polidispersão, potencial zeta adequadamente negativo (~|30| mV), drug loading de ClAlPc entre 76-94% (com pequena redução após 24 meses) e alta eficiência de encapsulação (E.E.). A morfologia arredondada das nanopartículas foi confirmada por microscopia eletrônica de transmissão e de força atômica. A estabilidade das NLS foi de 24 meses. A avaliação da cristalinidade do lipídio revelou a integração da ClAlPc à matriz lipídica da NLS, presença de estruturas polimórficas e grau de cristalinidade adequado, sem alterações após 24 meses. Nos estudos de difusão in vitro, observou-se que ftalocianina encapsulada nas NLS acumulam-se preferencialmente na epiderme e derme do que no estrato córneo, sem traços de permeação do ativo. Foi confirmado o caráter biocompatível das NLS sobre fibroblastos NIH-3T3. A ftalocianina encapsulada nas NLS não foi tóxica na linhagem de melanoma B16-F10 na ausência de luz, porém, apresentou excelente efeito fototóxico (0,75 ?g mL-1 de ClAlPc nanoencapsulada e irradiação entre 0,5 e 2,0 J cm-2), com redução da viabilidade celular de 87%. O segundo sistema de veiculação estudado foram as vesículas cataniônicas (VesCat), que se formam espontaneamente em água com o tensoativo TriCat 12. A obtenção das vesículas contendo ClAlPc envolve uma etapa adicional, para remoção de solvente orgânico, que foi aprimorada, reduzindo o tempo de produção em 55%. As VesCat/ClAlPc obtidas mantiveram suas propriedades físico-químicas e morfologia arredondada (confirmada por microscopia eletrônica de varredura), drug loading de 47% e alta E.E. Os resultados comprovaram que a aplicação desses dois sistemas nanométricos é altamente eficiente para aplicação da TFD no tratamento do câncer de pele do tipo melanoma ou outras doenças cutâneas, apresentando características favoráveis para avanços nos estudos de fase clínica e pré-clínica.

Molecular dynamics studies of the effects of branching characteristics on the crystalline structure of polyethylene

Molecular dynamics simulations were carried out on single chain models of linear low-density polyethylene in vacuum to study the effects of branch length, branch content, and branch distribution on the polymer’s crystalline structure at 300 K. The trans/gauche (t/g) ratios of the backbones of the modeled molecules were calculated and utilized to characterize their degree of crystallinity. The results show that the t/g ratio decreases with increasing branch content regardless of branch length and branch distribution, indicating that branch content is the key molecular parameter that controls the degree of crystallinity. Although t/g ratios of the models with the same branch content vary, they are of secondary importance. However, our data suggests that branch distribution (regular or random) has a significant effect on the degree of crystallinity for models containing 10 hexyl branches/1,000 backbone carbons. The fractions of branches that resided in the equilibrium crystalline structures of the models were also calculated. On average, 9.8% and 2.5% of the branches were found in the crystallites of the molecules with ethyl and hexyl branches while C13 NMR experiments showed that the respective probabilities of branch inclusion for ethyl and hexyl branches are 10% and 6% [Hosoda et al., Polymer 1990, 31, 1999–2005]. However, the degree of branch inclusion seems to be insensitive to the branch content and branch distribution.

A comparative study on the mineralogy, chemistry and chronology of the Apollo 16 crystalline impact melt breccias. Part II: Chronology.

The controversy on how to interpret the ages of lunar highland breccias has recently been discussed by James [1]. Are the measured ages testimony of true events in lunar history; do they represent the age of the ancient crustal rocks, mixed ages of unequilibrated matrix-phenocryst relationships, or merely thermal events subsequent to the formational event ? It is certain from analyses of terrestrial impact melt breccias that the melt matrix of whole impact melt sheets is isotopically equilibrated due to the extensive mixing process of the early cratering stage [2,3]. It has been shown that isotopic equilibration takes place between impact melt matrix and target rock clasts therein, with the intensity of isotopic exchange depending on the degree of shock metamorphism, thermal metamorphism and the size of the clasts [4]. Therefore, impact melt breccias - if they are relatively clast-poor and mineralogically well studied - can be considered to be the most reliable source for information on the impact history of the lunar highland.

Determination of degree of crystallinity of Nylon 1212 by wide-angle X-ray diffraction

Based on the X-ray scattering intensity theory and using the approximate expression for the atomic scattering factor, the correction factors for three crystalline peaks and an amorphous peak of Nylon 1212 were calculated and the formula of degree of crystallinity of Nylon 1212 was derived by a graphic multipeak resolution method. The degree of crystallinity calculated from the WARD method is compatible with those obtained by density and calorimetry methods.

Studies on the structure and properties of thermotropic liquid crystalline poly(aryl ether ketone)s

Series of thermotropic liquid crystalline poly (aryl ether ketone) s were synthesized by mucleophilic substitution reactions of 4,4'-biphenol and substituted hydroquinone with different difluoromonomers, The relationship between structure and properties of the novel copolymers was investigated. For the copolymers with liquid crystalline properties, their melting transition temperatures show no great change with increase the content of the crystal-disrupting unit. The reason is that the crystal phase is directly transformed from the ordered liquid crystal phase. Side-groups have important effect on mesophase stability, The temperature range of mesophase stability for the chloro-polymers is smaller than those of other series of copolymers (P-phenyl, t-butyl, methoxy, 3-trifluoromethylbenzene). This behavior indicates that the effect of geometric repulsive factor on the thermodynamic stability of the mesophase is much larger than that of the polarizability attractive factor. Different ordered liquid crystal phases are observed in the polymers with different molecular weights. At low molecular weight, highly ordered smectic liquid crystal phases form. With increasing the molecular weight, the ordered degree of the liquid crystals decreases, and only the nematic liquid crystal phase is observed in the polymer with higher molecular weight.

Synthesis and characterization of the side chain liquid crystalline poly(monoester {6-[4-(p-nitrophenyl)azo]phenoxy-1-hexyloxy} of maleic anhydride)

The poly(monoester (6-[4-(p-nitrophenyl) azo]phenoxy-1-hexyloxy) of maleic anhydride) shows a smectic phase with a focal conic fan texture. With the decrease of the monoestering degree the phase transition temperature decreases and the mesomorphic temperature range becomes narrow. The hydrogen bonding between two carboxylic acid groups was found to play a very important role in forming the smectic phase structure. The smectic bilayer structure has been built through self-assembly via. intermolecular hydrogen bonding.

Formation of nano-crystalline corrosion products on Zn-Al alloy coating exposed to seawater

Hot dip Zn-Al alloy coating performs better than hot dip galvanized coating and 55% Al-Zn-Si coating as well with regard to general seawater corrosion protection. A characterization of the corrosion products on Zn-Al alloy coating immersed in dynamic aerated seawater has been performed mainly based on transmission electron microscopy (TEM) for morphological analysis and X-ray diffraction (XRD) technique for crystalline phase identification. The XRD and TEM analyses showed that the corrosion products mainly were typical nanometer Zn4CO3(OH)(6).H2O, Zn-5(OH)(8)Cl-2 and Zn6Al2CO3(OH)(16). 4H(2)O microcrystals. This probably is connected to the co-precipitation of Zn2+ and Al3+ ions caused by adsorption. Zn-Al alloy coating being suffered seawater attacks, AI(OH)(3) gel was first produced on the coating surface. Zn and Al hydroxides would co-precipitate and form double-hydroxide when the concentration of adsorbed Zn2+ ions by the newly produced gel exceeded the critical degree of supersaturation of the interphase nucleation. However, because the growth of the crystals was too low to keep in step with the nucleation, a layer of nano-crystalline corrosion products were produced on the surface of the coating finally. (C) 2001 Elsevier Science Ltd. All rights reserved.

A new route to synthesize high degree polythiophene in a room temperature melt medium

Conducting polymers suffer from folds and kinks because of random nucleation and solvation of a free radical cation to yield a cross linked/disordered polymer and therefore a solvent free electrochemical polymerization in a room temperature melt medium is adopted to yield a high degree polymer with high electronic conductivity. Electropolymerization of thiophene was performed on platinum/ITO substrates using cyclic voltametry or galvenostatic mode in chloroaluminate room temperature melt medium to obtain a reddish brown free standing film which can be peeled off from the electrode surface after a minimum of 10 cycles. The conductivity was found to be around 102 S/cm. The degree of polymerization was calculated to be around 44 from IR studies. A layered structure supportive for high degree of polymerization was witnessed from potential step technique. From UV spectra the charge carriers were found to be bipolarons. The morphology of the film was found to be crystalline from SEM and XRD studies. Capacitative impedance properties for doped samples were interpreted from impedance spectroscopy.

Orientation effects in monodomain nematic liquid crystalline polysiloxane elastomers

A series of monodomain liquid crystalline (LC) elastomers based on a polysiloxane were synthesised. These elastomers were prepared either with one or two cross-linking agents in the presence of a mechanical field. By using the real-time X-ray facility at the University of Reading (AXIS), we have shown that the nematic order parameter 〈P2 〉 is dependent on both the extension λ value and the degree of cross-linking. We have also shown that the monodomain elastomers, exhibiting permanent alignment and 〈P2 〉 values of about 0.5, can be prepared by using only one cross-linking agent making the synthesis of these monodomain LC elastomers much more simple and cost effective than that proposed by Küpfer.