Synthesis and properties of novel side-chain-sulfonated polyimides from bis[4-(4-aminophenoxy)-2-(3-sulfobenzoyl)]phenyl sulfone

A novel side-chain-sulfonated aromatic diamine of bis[4-(4-aminophenoxy)-2-(3-sulfobenzoyl)]phenyl sulfone (BAPSBPS) was synthesized. Sulfonated copolyimides were synthesized by random and sequenced block copolymerization of 1,4,5,8-naphthalene tetracarboxylic dianhydride, BAPSBPS and nonsulfonated diamine. They displayed good solubility in common aprotic solvents and high desulfonation temperature of 350 °C, suggesting the high stability of sulfonic acid groups. The reduced viscosity was in the range of 0.4-1.8 dl/g at 0.5 g/dl and 35 °C. Flexible and tough membranes with reasonably high mechanical strength were prepared. They showed anisotropic membrane swelling with larger swelling in thickness than in plane. They displayed reasonably high proton conductivity (σ), taking their lower ion exchanging capacity (IEC) into account. For example, the membrane with IEC of 1.54 mequiv/g showed σ values of 81 and 11 mS/cm in water and 70% RH, respectively, at 60 °C.     

Studies on the biaxial stretching of polypropylene film. XI. Type II orientation during [2-2FI]-type stretching and its change by subsequent thermal contraction

In order to study the deformation mechanism of type II stretching, the change in orientation during the restretching and subsequent thermal contraction was investigated by x-ray diffraction method. When a uniaxially oriented film is restretched, the lamellae which are stacked in the stretching direction by the stretching rotate as a whole toward the restretching axis. They rotate backward nearly reversibly during the thermal contraction, unless the restretching exceeds a balancing state, where the orientation in the film plane are equal in all directions. However, when the restretching degree is so high and the film orientation exceeds the balancing state, the lamellar rotation is accompanied by a complex phenomenon. It is considered from the wide-angle and small-angle x-ray diffraction patterns that the lamellar surface becomes indented because of slippage between microfibrils composing the lamellae, and the microfibrils themselves bend at the boundary between the amorphous and crystalline regions within which the tilting of c-axis also occurs. Upon contracting of the film; these changes recover, but even in the last stage of contraction the orientation approaches the symmetrical biaxial orientation but not the uniaxial orientation from which the biaxial orientation is started. These orientation and disorientation behaviors are not affected basically by a slight change in the restretching temperature and the degree of stretching.     

An Application of Silica‐Based Monolithic Membrane Emulsification Technique for Easy and Efficient Preparation of Uniformly Sized Polymer Particles

Summary: Uniformly sized polymer particles were prepared by an emulsification and polymerization technique utilizing a silica monolithic membrane, namely the “silica monolithic membrane emulsification technique”. In this paper, we utilized silica monolithic membrane as a device for the preparation of uniformly sized polymer particles. A mixture of monomers, diluents and oil‐soluble initiator was emulsified into a continuous medium through the silica monolithic membrane and polymerized. The particles obtained had a higher size uniformity than that of particles prepared by previously reported membrane emulsification techniques, such as the Shirasu Porous Glass (SPG) emulsification technique. Through the silica monolithic membrane emulsification technique, we could prepare particles having availability as a possible packing material for solid‐phase extraction (SPE) and high performance liquid chromatography (HPLC).

SEM photograph of silica particles prepared through capillary plate membrane.     

Structural characterization of 1,2-polybutadiene by 13C-n.m.r. spectroscopy: 2. Sequence distribution of 1,2-unit in hydrogenated polybutadienes

The configurational sequences of 1,2-unit in a series of hydrogenated syndiotactic 1,2-polybutadienes were determined in relation to the sequence distribution of 1,2- and 1,4-units on the basis of the ¹³C-n.m.r. signal assignment of the methyl carbons. The observed triad distributions of 1,2- and 1,4-units and configurational distributions of the 1,2-unit are in good agreement with the calculated distributions from transition probabilities. The number average sequence lengths of the 1,2-unit and the 1,2-unit in the racemic addition are 5.7 to 8.0 and 4.1 to 5.4, respectively. From the extrapolation of the plot of the number average sequence length against the crystallinity of the starting 1,2-polybutadienes, the minimum sequence length for crystallization is estimated to be 3.7 for the 1,2-unit in the racemic addition.     

Fat Bloom Caused by Partial De-Oiling on Chocolate Surfaces after High-Temperature Exposure

Fat bloom in chocolate is a substantial problem that affects its sensory properties, such as texture and appearance. This phenomenon is because of diffuse light reflection on a roughened surface of chocolate, caused by structural changes of fat crystals subjected to various temperature conditions. The purpose of this study is to characterize the fat bloom formed through gradual two-step cooling after exposure to temperatures (35–37 °C) slightly above the cocoa butter Form βV melting point (33.8 °C). To clarify the fat bloom formation process, the structural changes in cocoa butter and on the chocolate surface, at the dynamic thermal condition for bloom formation, was investigated using X-ray diffraction (XRD), fluorescence light microscopy, and scanning electron microscopy (SEM). The results revealed that an entirely light brown fat bloom occurred, even in the absence of the Form βVI or other polymorphic transformation. Microscopic observation showed that the light brown appearance was because of the porous structure on the chocolate surface. This porous structure was formed by liquid oil moving inside of chocolate from the surface. The formation of a coarse network and the subsequent de-oiling, because of movement of unsolidified liquid fat into the chocolate, appeared to be the main causes of bloom formation. Therefore, a coarsened fat network and oil movement besides the conventional principles of polymorphic transformation of cocoa butter should be considered.     

Pressure effects on the low temperature state of the α-(BEDT-TTF)2MHg(SCN)4 organic conductor family

Systematic magnetotransport measurements as a function of hydrostatic pressure have been made on four members of the α-(BEDT-TTF)₂MHg(SCN)₄ organic conductor family (M = K, Tl, Rb, NH₄). Applied pressure above about 6 Kbar removes the density wave state for M = K, Tl, and Rb. For M = NH₄ the superconducting state is removed with pressure as dT_c/dP = − 0.25 K/Kbar. In all cases the Shubnikov de Haas oscillation frequency increases with pressure, including the β orbit (which involves the entire Brillouin zone), and new orbits involving very small fractions of the Fermi surface are formed.     

Differences between corrosion products formed on copper exposed in Tokyo in summer and winter

We analyzed the copper corrosion products that formed during a month in summer and a month in winter at three sites in Tokyo using several analytical techniques. The X-ray diffraction patterns revealed that cuprite Cu₂O and posnjakite Cu₄SO₄(OH)₆·H₂O formed on copper exposed in summer. By contrast, only cuprite was found in winter exposed copper. The X-ray fluorescence results indicated that the amounts of sulfur and chlorine on the copper plates exposed in summer were much greater than those in winter. This could be explained by the change in particulate sulfate and sea salt concentrations. Depth profiling analysis by Auger electron spectroscopy revealed that the oxide layer formed in summer was thicker than that in winter. This difference in oxide layer thickness could have been due to the differences in temperature, relative humidity, and the amount of sulfur and chlorine on the copper plate.     

Measurement of self-diffusion coefficients in Li ionic conductors by using the short-lived radiotracer of 8Li

For the effective use of short-lived radioactive beams, soon to be available at the Tokai Radioactive Ion Accelerator Complex, the authors have developed a radiotracer method for diffusion studies in solids. The experimental test was performed by the measurement of the diffusion coefficients of Li in a sample of the compound βLiAl using an α-emitting radiotracer of ⁸Li (T_1/2=0.84 s). It was found that the time-dependent yields of the α particles from the diffusing ⁸Li that was initially implanted in the sample could be used as a measure of the diffusivity of the tracer in a nondestructive way. The method was applied to measure the self-diffusion coefficients of Li in βLiGa, and for investigating how the Li diffusion in the Li ionic conductors is affected by the concentration of atomic defects (i.e., the existence of the atomic vacancies of Li and the defects in Ga sites that are replaced by Li).     

Variable space diversity, crossover and mutation in MOEA solving many-objective knapsack problems

In this work, we analyze variable space diversity of Pareto optimal solutions (POS) and study the effectiveness of crossover and mutation operators in evolutionary many-objective optimization. First we examine the diversity of variables in the true POS on many-objective 0/1 knapsack problems with up to 20 items (bits), showing that variables in POS become noticeably diverse as we increase the number of objectives. We also verify the effectiveness of conventional two-point and uniform crossovers, Local Recombination that selects mating parents based on proximity in objective space, and two-point and uniform crossover operators which Controls the maximum number of Crossed Genes (CCG). We use NSGA-II, SPEA2, IBEA _??+? and MSOPS, which adopt different selection methods, and many-objective 0/1 knapsack problems with $n=\{100,250,500,750,\mbox{1,000}\}$ items (bits) and m?=?{2,4,6,8,10} objectives to verify the search performance of each crossover operator. Simulation results reveal that Local Recombination and CCG operators significantly improve search performance especially for NSGA-II and MSOPS, which have high diversity of genes in the population. Also, results show that CCG operators achieve higher search performance than Local Recombination for m?≥?4 objectives and that their effectiveness becomes larger as the number of objectives m increases. In addition, the contribution of CCG and mutation operators for the solutions search is analyzed and discussed.     

Fabrication of large area diffraction grating using LIGA process

X-ray imaging is a very important technology in the fields of medical, biological, inspection, material science, etc. However, it is not enough to get the clear X-ray imaging with low absorbance. We have produced a diffraction gratings for obtaining high resolution X-ray phase imaging, such as X-ray Talbot interferometer. In this X-ray Talbot interferometer, diffraction gratings were required to have a fine, high accuracy, high aspect ratio structure. Then, we succeeded to fabricate a high aspect ratio diffraction grating with a pitch of 8 μm and small area using a deep X-ray lithography technique. We discuss that the diffraction gratings having a narrow pitch and an large effective area to obtain imaging size of practical use in medical application. If the pitch of diffraction gratings were narrow, it is expected high resolution imaging for X-ray Talbot interferometer. We succeeded and fabricated the diffraction grating with pitch of 5.3 μm, Au height of 28 μm and an effective area of 60 × 60 mm².