Morphology and crystalline transition of poly (3-butylthiophene) associated with its polymorphic modifications

Poly (3-butylthiophene) (P3BT) is a much less studied conjugated polymer despite its high crystallizability and thus excellent electrical property. In this work, morphology of P3BT at different crystalline polymorphs and solvent/thermal induced phase transition between form I and U modifications have been intensively investigated by using optical microscopy, electron microscopy, differential scanning calorimetry, and X-ray diffraction. It is shown that a direct deposition from carbon disulfide (CS2) at fast evaporation results in P3BT crystals in form I modification, giving typical whiskerlike morphology. In contrast, low evaporation rate from CS, leads to formation of form II crystals with spherulitic morphology, which is so far scarcely observed in polythiophene.

Transformation from ordered islands to holes in phase-separating P2VP/PS blend films by adding triton X-100

Our previous investigation showed that the ordered hexagonal island pattern in the phase-separating polymeric blend films of polystyrene and poly(2-vinylpyridine) (PS/P2VP) formed due to the convection effect by proper control of PS molecular weight, solvent evaporation rate, and the weight ratio of PS to P2VP. In this paper, we further illustrate that, by adding a proper amount of the surfactant Triton X-100 to the PS/P2VP toluene solution, the ordered hexagonal island pattern can be transformed to the ordered honeycomb pattern. The effects of the amount of Triton X-100 on the surface morphology evolution and the pattern transformation are discussed in terms of the collapse of Triton X-100, phase separation between Triton X-100/P2VP and PS, the interfacial interaction between Triton X-100/P2VP and the mica substrate, and the Benard-Marangoni convection.

Surface morphology evolution of poly (styrene-block-4-vinylpyridine) (PS-b-P4VP)(H+) and poly(methyl methacrylate)-dibenzo-18-crown-6-poly(methyl methacrylate) (PMCMA) supramolecular film

Well-ordered nanostructured polymeric supramolecular thin films were fabricated from the supramolecular assembly of poly(styrene-block-4-vinylpyridine) (PS-b-P4VP)(H+) and poly(methyl methacrylate)-dibenzo-18-crown-6-poly(methyl methacrylate) (PMCMA). A depression Of cylindrical nanodomains was formed by the block of P4VP(H+) and PMCMA associates surrounded by PS. The repulsive force aroused from the incompatibility between the block of P4VP(H+) and PMCMA was varied through changing the molecule weight (M-w) of PMCMA, the volume fraction of the block of P4VP(H+), and annealing the film at high temperature. Increasing the repulsive force led to a change of overall morphology from ordered nanoporous to featureless structures. The effects of solvent nature and evaporation rate on the film morphology were also investigated. Further evolution of surface morphologies from nanoporous to featureless to nanoporous structures was observed upon exposure to carbon bisulfide vapors for different treatment periods. The wettability of the film surface was changed from hydrophilicity to hydrophobicity due to the changes of the film surface microscopic composition.

Effects of casting solvents on the formation of inverted phase in block copolymer thin films

Previously, an inverted phase (the minority blocks comprising the continuum phase) was found in solution-cast block copolymer thin films. In this study, the effect of casting solvents on the formation of inverted phase has been studied. Two block copolymers, poly(styrene-b-butadiene) (SB) (M-w = 73 930 Da) and poly(styrene-b-butadiene-b-styrene) (SBS) (M-w = 140 000 Da), with comparable block lengths and equal polystyrene (PS) weight fraction (similar to30 wt %) were used. The copolymer thin films were cast from different solvents, toluene, benzene, cyclohexane, and binary mixtures of benzene and cyclohexane. Toluene and benzene are good solvents for both PS and PB, but have a preferential affinity for PS, while cyclohexane is a good solvent for PB but a Theta solvent for PS (T-Theta = 34.5 degreesC). The differential solvent affinity for PS and PB was estimated in terms of a difference between the polymer-solvent interaction parameter, chi, for each block. Under an extremely slow solvent evaporation rate, the time-dependent phase behavior during such a solution-to-film process was examined by freeze-drying the samples at different stages, corresponding to different copolymer concentrations, rho.

Ordered macroporous films from self-assembly of two-armed polymer with a crown ether core

Highly ordered honeycomb-like macroporous films were obtained via self-assembly of a two-armed polymer with a crown ether core under controlled conditions. A possible mechanism is speculated, primarily based on the strong affinity between the crown ether cores. The pore size and arrangement are sensitive to the solvent evaporation rate and the solution concentration. Upon spontaneous drying, the pore diameter (D) depends on the concentration (c) by a relation of D=518c(-0.610).

Tunable ordered droplets induced by convection in phase-separating P2VP/PS blend film

Ordered hexagonal droplets patterns in phase-separating polymeric blend films of polystyrene and poly(2-vinylpyridine) (PS/PVP) formed due to the convection effect by solvent evaporation. The influences of PS molecular weight, solvent evaporation rate, and the weight ratio of PS to PVP on the PVP-rich domains pattern formation and distributions were investigated by atomic force microscope (AFM). Only in an appropriate range of molecular weight of PS, can the ordered pattern form. Too low or too high molecular weight of PS led no ordered pattern due to the viscosity effects. The increase of solvent evaporation rate decreased the mean radius of the PVP-rich domains and the intervals between the centers of the domains due to the enhancement of the viscosity on the top layer of the fluid film. The increase of the weight ratio of PS to PVP decreased mean radius of the PVP-rich domains whereas the intervals between the centers of droplets remained constant. Therefore, the size and the distributions of ordered patterns can be tuned by the polymer molecular weight, the weight ratio of the two components and the solvent evaporation rate.

Study on the origin of inverted phase in drying solution-cast block copolymer films

In a previous study, we reported observation of the novel inverted phase (the minority blocks comprising the continuum phase) in kinetically controlled phase separating solution-cast poly(styrene-b-butadiene-b-styrene) (SBS) triblock copolymer films [Zhang et al. Macromolecules 2000, 33, 9561-7]. In this study, we adopt the same approach to investigate the formation of inverted phase in a series of solution-cast poly(styrene-b-butadiene) (SB) asymmetric diblock copolymers having nearly equal polystyrene (PS) weight fraction (about 30 wt %) but different molecular weights. The microstructure of the solution-cast block copolymer films resulting from different solvent evaporation rates, R, was inspected, from which the kinetically frozen-in phase structures at qualitatively different block copolymer concentrations and correspondingly different effective interaction parameter, chieff, can be deduced. Our result shows that there is a threshold molecular weight or range of molecular weight below which the unusual inverted phase is accessible by controlling the solvent evaporation rate. In comparing the present result with that of our previous study on the SBS triblock copolymer, we find that the formation of the inverted phase has little bearing on the chain architecture. We performed numerical calculations for the free energy of block copolymer cylinders and found that the normal phase is always preferred irrespective of the interaction parameter and molecular weight, which suggests the formation of the inverted phase to have a kinetic origin.

A cunning strategy in design of polymeric nanomaterials with novel microstructures

A relative approach, based on the dynamic density functional theory, for simulating the solvent evaporation rate dependence of self-assembly process of block copolymers in solution is proposed. The di- and triblock copolymers are first chosen as the candidates for exploration of novel microstructures. The results reveal that asymmetrical block copolymers with unequal block length, which generally exhibit disordered microdomain patterns in melts, have the ability to assemble into periodic ordered microdomain patterns by properly controlling solvent evaporation rate, e.g., diblock copolymers may assemble into lamellar microstructures with lamellar thickness proportional to individual block length. This simulation suggests a strategy of design and manufacture of polymeric nanomaterials with novel microstructures.

中国南方热带地区田洋玛珥湖24万年以来的气候变化及湖泊演变

A continuous long (224m) and high-resolution core TY2 was recovered from paleo-maar-lake Tianyang, tropical South China. Based on the diatom records of the upper 130-m core, this paper focuses on exploring climate change and the lake evolution history in tropical South China during the past 240ka. The most typical and unique characteristics of the diatom assemblages is that, Aulacoseira granulata was dominant or absolutely dominant species (80-90%) during most parts of the 130-m core, while Cyclotella stelligera var. tenuis and Fragilaria construens var. venter were subdominant species in only limited parts of the lower and upper core, respectively. Time scale is always the biggest problem for the study of TY2 core, so although diatom is seldom used for establishing time scale, here we attempt this by correlating the diatom-reconstructed temperature sequence with the time scale of ODP core 806B from Equatorial Western Pacific. Verified by the few most reliable ages from TY2 core and the parallel core TYl, a rather reasonable and reliable time scale was established. 01S 7/6 falls at the depth of 100m (ca. 194kaBP), OIS 6/5 at 75m (ca. 132kaBP), OIS 5/4 at 46m (ca. 75kaBP), OIS 4-3 at 35m (ca. 60kaBP). Qualitative and quantitative environmental reconstructions are made on the basis of diatom assemblage ecotype and EDDI dataset. Correlation of diatom-reconstructed temperature and moisture changes of Core TY2 with pollen-reconstructed temperature and rainfall sequence of Core TYl proves that the results are quite consistent in most periods. Thus the reconstruction results from diatom are quite reliable, and probably have a much higher resolution than pollen results. Combined with lithological and magnetic susceptibility variations, the diatom analysis reveals that, the general climate in tropical South China during the past 240ka was warm and wet. On the time scale of glacial-interglacial, warm and wet, cool and dry are not always synchronous. It was relatively warm-wet during the penultimate interglacial, cool-dry during the penultimate glacial, warm-dry during the last interglacial, and cooler-drier during the last glacial. In contrast, on the time scale of subglacial-subinterglacial scales, warm and dry, cool and wet corresponds very obviously, showing very clear 21-23 ka precession cycle. Analysis also shows that, the water of Tianyang paleo-maar-lake was generally warm, turbulent, turbid, meso-trophic, slightly alkaline, low conductivity and fresh during the past 240 kaBP, with small variations in some parts. Tianyang paleolake experienced shallow to semi-deep lake in OIS7d, open shallow lake in OIS7c-OIS5b, shallow coastal lake in OIS5a-OIS4c, swamp in OIS4b, and then completely dried up in OIS3c. The lake evolution was mainly controlled by temperature and precipitation changes in tropical China. While temperature and precipitation changes were probably controlled by the migrations of monsoon rainband and the evaporation rate, which was in turn controlled by the evolution of East Asian monsoon. Therefore, when the summer monsoon was strongest the climate was warm-dry, when stronger the climate was warm-wet; when the winter monsoon was strongest the climate was cool-dry, stronger cool-wet. This mechanism caused the warm-dry sub interglacial and cool-wet subglacial climate in the tropical South China.

ELM-induced transient tungsten melting in the JET divertor

The original goals of the JET ITER-like wall included the study of the impact of an all W divertor on plasma operation (Coenen et al 2013 Nucl. Fusion 53 073043) and fuel retention (Brezinsek et al 2013 Nucl. Fusion 53 083023). ITER has recently decided to install a full-tungsten (W) divertor from the start of operations. One of the key inputs required in support of this decision was the study of the possibility of W melting and melt splashing during transients. Damage of this type can lead to modifications of surface topology which could lead to higher disruption frequency or compromise subsequent plasma operation. Although every effort will be made to avoid leading edges, ITER plasma stored energies are sufficient that transients can drive shallow melting on the top surfaces of components. JET is able to produce ELMs large enough to allow access to transient melting in a regime of relevance to ITER.

Transient W melt experiments were performed in JET using a dedicated divertor module and a sequence of I-P = 3.0 MA/B-T = 2.9 T H-mode pulses with an input power of P-IN = 23 MW, a stored energy of similar to 6 MJ and regular type I ELMs at Delta W-ELM = 0.3 MJ and f(ELM) similar to 30 Hz. By moving the outer strike point onto a dedicated leading edge in the W divertor the base temperature was raised within similar to 1 s to a level allowing transient, ELM-driven melting during the subsequent 0.5 s. Such ELMs (delta W similar to 300 kJ per ELM) are comparable to mitigated ELMs expected in ITER (Pitts et al 2011 J. Nucl. Mater. 415 (Suppl.) S957-64).

Although significant material losses in terms of ejections into the plasma were not observed, there is indirect evidence that some small droplets (similar to 80 mu m) were released. Almost 1 mm (similar to 6 mm(3)) of W was moved by similar to 150 ELMs within 7 subsequent discharges. The impact on the main plasma parameters was minor and no disruptions occurred. The W-melt gradually moved along the leading edge towards the high-field side, driven by j x B forces. The evaporation rate determined from spectroscopy is 100 times less than expected from steady state melting and is thus consistent only with transient melting during the individual ELMs. Analysis of IR data and spectroscopy together with modelling using the MEMOS code Bazylev et al 2009 J. Nucl. Mater. 390-391 810-13 point to transient melting as the main process. 3D MEMOS simulations on the consequences of multiple ELMs on damage of tungsten castellated armour have been performed.

These experiments provide the first experimental evidence for the absence of significant melt splashing at transient events resembling mitigated ELMs on ITER and establish a key experimental benchmark for the MEMOS code.

Post-frying oil drainage from potato chips and french fries: a comparative study of atmospheric and vacuum drainage

This paper represents a study of the transient changes occurring in temperature, and moisture and oil contents during the so called “post-frying drainage”—which is the duration for which a product is held in the head space of the fryer after it is removed from the oil. Since most of the oil adhering to the product penetrates into the structure during this period, this paper examines the effects of applying vacuum during drainage (1.33 kPa) to maintain the product temperature consistently above the water saturation temperature corresponding to the prevailing pressure (11 °C), which potentially eliminates water condensation and prevents the occluded surface oil from penetrating into the product structure. Draining under vacuum significantly lowers the oil content of potato chips by 38% compared to atmospheric drainage. This phenomenon can be further confirmed by confocal laser scanning microscopy (CLSM) images, which show that the boundary between the core and the crust regions is clearly visible in the case of vacuum drainage, whereas in the case of atmospheric drainage, the oil is distributed throughout the structure. Unfortunately, the same approach did not reduce the oil content of French fries—the oil content of vacuum-drained product was found similar to the product obtained by draining under atmospheric pressure. This is because the reduction in oil content only occurs when there is net moisture evaporation from the product and the evaporation rate is sufficient to force out the oil from the product; this was clearly not the case with French fries. The CLSM images show that the oil distribution in the products drained under atmospheric pressure and vacuum was similar.

Characteristics of thin cellulose ester films spin-coated from acetone and ethyl acetate solutions

Spin-coated films of cellulose acetate (CA), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB) and carboxymethylcellulose acetate butyrate (CMCAB) have been characterized by ellipsometry, atomic force microscopy (AFM) and contact angle measurements. The films were spin-coated onto silicon wafers, a polar surface. Mean thickness values were determined by means of ellipsometry and AFM as a function of polymer concentration in solutions prepared either in acetone or in ethyl acetate (EA), both are good solvents for the cellulose esters. The results were discussed in the light of solvent evaporation rate and interaction energy between substrate and solvent. The effects of annealing and type of cellulose ester on film thickness, film morphology, surface roughness and surface wettability were also investigated.

Latent heat loss of Holstein cows in a tropical environment: a prediction model

Nove vacas Holandesas lactantes com 526 ± 5 kg de peso corporal (cinco predominantemente pretas e quatro predominantemente brancas), criadas em região tropical e manejadas em pastagens, foram observadas com os objetivos de determinar simultaneamente as taxas de evaporação cutânea e respiratória em ambiente tropical e desenvolver modelos de predição. Para a medição da perda de calor latente pela superfície corporal, utilizou-se uma cápsula ventilada e, para a perda por respiração, utilizou-se uma máscara facial. Os resultados mostraram que as vacas que tinham maior peso corporal (classe 2 e 3) apresentaram maiores taxas evaporativas. Quando a temperatura do ar aumentou de 10 para 36ºC e a umidade relativa do ar caiu de 90 para 30%, a eliminação de calor por evaporação respiratória aumentou de aproximadamente 5 para 57 W m-2 e a evaporação na superfície corporal passou de 30 para 350 W m-2. Esses resultados confirmam que a eliminação de calor latente é o principal mecanismo de perda de energia térmica sob altas temperaturas (>30ºC); a evaporação cutânea é a maior via e corresponde a aproximadamente 85% da perda total de calor, enquanto o restante é eliminado pelo sistema respiratório. O modelo para predizer o fluxo de perda de calor latente baseado em variáveis fisiológicas e ambientais pode ser utilizado para estimar a contribuição da evaporação na termorregulação, enquanto o modelo baseado somente na temperatura do ar deve ser usado apenas para a simples caracterização do processo evaporativo.

Análise de algumas variáveis fisiológicas para avaliação do grau de adaptação de ovinos submetidos ao estresse por calor

Investigaram-se a temperatura retal, a freqüência respiratória e a taxa de evaporação total de ovinos Corriedale sob três temperaturas ambientes, visando uma melhor compreensão dos mecanismos de termorregulação desses animais. Inicialmente, 21 animais adultos foram alojados em câmara climática à temperatura de 45ºC, e pressão parcial de vapor (PV) variável, registrando-se a freqüência respiratória (FR) e a temperatura retal (TR). Baseando-se na FR e TR, foram selecionados 10 animais, cinco com os valores mais baixos, assumindo-os como mais adaptados ao calor (grupo 1) e cinco com valores mais altos, assumindo-os como menos adaptados (grupo 2). Os animais selecionados foram mantidos em câmara climática, onde mediram-se novamente TR, FR e taxa de evaporacão total (TET), sob 20, 30 e 40ºC de temperatura do ar e PV variável. Não houve diferença estatística entre os grupos classificados, para todas as variáveis medidas. Concluiu-se que a utilização das variáveis fisiológicas TR e FR como parâmetros únicos para a seleção destes animais não é suficiente para avaliar o grau de adaptação a temperaturas elevadas.

Avaliação da aplicação de modelos para a secagem de pastas e suspensões em leito de jorro com alimentação contínua

This work studies the development, implementation and improvement of a macroscopic model to describe the behavior of the spouted bed dryer with continuous feeding for pastes and suspensions drying. This model is based on the CST model (Freire et al., 2009) and the model of Fernandes (2005), whose theoretical foundation is based on macroscopic mass and heat balances for the three phases involved in the process: gas, liquid and solid. Because this technique is quite relevant, the studies of modeling and simulation of spouted bed drying are essential in the analysis of the process as a whole, because through them it is possible to predict and understand the behavior of the process, which contributes significantly to more efficient project and operation. The development and understanding of the phenomena involved in the drying process can be obtained by comparing the experimental data with those from computer simulations. Such knowledge is critical for choosing properly the process conditions in order to obtain a good drying efficiency. Over the past few years, researches and development of works in the field of pastes and suspensions drying in spouted bed has been gaining ground in Brazil. The Particulate Systems Laboratory at Universidade Federal do Rio Grande do Norte, has been developing several researches and generating a huge collection of experimental data concerning the drying of fruit pulps, vegetables pastes, goat milk and suspensions of agro-industrial residues. From this collection, some data of goat milk and residue from acerola (Malpighia glabra L.) drying were collected. For the first time, these data were used for the development and validation of a model that can describe the behavior of spouted bed dryer. Thus, it was possible to model the dryer and to evaluate the influence of process variables (paste feeding, temperature and flow rate of the drying air) in the drying dynamics. We also performed water evaporation experiments in order to understand and to study the behavior of the dryer wall temperature and the evaporation rate. All these analysis will contribute to future works involving the implementation of control strategies in the pastes and suspensions drying. The results obtained in transient analysis were compared with experimental data indicating that this model well represents the process