Influence of third monomer on the crystal phase transition behavior of ethylene-tetrafluoroethylene copolymer

Crystal phase transition between the low- and high-temperature phases has been investigated for ethylene (E)-tetrafluoroethylene (TFE) alternating copolymer (ETFE) containing the third monomeric species by the temperature dependent measurements of wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) and differential scanning calorimetry. Nonafluoro-1-hexene (NFH) and hexafluoropropylene (HFP) were chosen as the third monomers, where they are different in the side-branch length, -(CF₂)₃CF₃ and -CF₃, respectively. In the case of E/TFE/NFH copolymer (ET-C4F9), the crystal phase transition temperature of the original ETFE two-components copolymer was not very much affected by the existence of NFH in the range of NFH content from 0.7 to 3 mol%. Contrarily, the crystal phase transition temperature of E/TFE/HFP copolymer (ET-CF3) was found to decrease drastically with increasing HFP content. The melting temperature and the higher-order structure were also affected sensitively depending on the HFP content. This difference in phase transition behavior between ET-C4F9 and ET-CF3 copolymers is reasonably interpreted as follows: the short side groups (-CF₃) of HFP monomeric unit are included in the crystal lattice of E/TFE chains and the unit cell is expanded gradually with an increment of the HFP content, resulting in the decrease in phase transition point because of easier thermal motion of the chains. On the other hand, the long side groups [-(CF₂)₃CF₃] of NFH monomeric units are excluded out of the crystal lattice and located on the lamellar surfaces or in the amorphous region and do not affect very much the phase transition temperature even when the NFH content is increased. In association with such a change in crystal structure, the long period of stacked lamellar structure was found to decrease remarkably in the case of NFH, whereas it does not change very much for HFP, consistent with the interpretation of the above-mentioned WAXD data.     

Current collecting efficiency of micro tubular SOFCs

In this study, current collecting efficiency of the micro tubular solid oxide fuel cell (SOFC) was estimated to determine optimum size of the micro tubular SOFC. Two models for collecting current from single terminal (ST) and double terminal (DT) of anode tube were proposed and used to calculate the current collecting efficiency as functions of anode thickness, tube length and operating temperature. It was shown that design of the cell geometry and current correcting method are significantly important to achieve high performance micro tubular SOFC stacks. The efficiency loss estimated from the DT model was about 2–4-fold lower than those of obtained from the ST model. The DT model was shown to be more effective for higher operating temperature and the tube length.     

Adsorption of urea,creatinine, and uric acid from three solution types using spherical activated carbon and its recyclability

In this paper, we propose that the urinary toxins from the wastewater be adsorbed on an adsorbent such as spherical activated carbon and the latter be regenerated by subjecting it to high temperatures to recycle activated carbon and also to recycle the water used in dialysis. We studied the adsorption of artificial waste dialysate, which is a mixed solution of urea, creatinine, and uric acid, and the separate solutions for each of these and found that their extents of adsorption onto the spherical activated carbon material were nearly identical. The amount of adsorption was approximately 1.4 mg·g^-1 for urea, 18 mg·g^-1 for creatinine, and 20 mg·g^-1 for uric acid. The urea, creatinine, and uric acid adsorbed onto the spherical activated carbon decomposed on heat treatment at 500℃, and the adsorption capacity of the spherical activated carbon was regenerated. Our study successfully demonstrated that the spherical activated carbon can be recycled in the waste dialysate treatment process.     

Removal of nonionic surfactant by systems based on chloromethylated polystyrene–poly(ethylene glycol)

For the purpose of obtaining compounds which can remove nonionic surfactants in water, chloromethylated polystyrene (CMPS) was allowed to react with triethylene glycol monomethyl ether (3EGMME), tetraethylene glycol (4EG), poly(ethylene glycol) (PEG) 200, 400, 600, 1000, and 1500. The amount of PEG groups combined with CMPS decreased with an increase in the molecular weight of PEG. The ability of the product to remove polyethylene glycol mono-p-nonyl phenyl ether (NP, n = 10), a nonionic surfactant, solutes in water was greater in the product with PEG of greater MW than that with PEG of smaller MW, and in the product with more PEG groups (mol/g prod.) than in that with less PEG groups. The removal behavior of the products conformed to Freundlich's adsorption formula. Constants of the formula, the effect of temperature on the constants, the effect of combined PEG groups on the removed amount, and the removal manner were studied.     

Determination of hydroperoxides and structures by high-performance liquid chromatography with post-column detection with diphenyl-1-pyrenylphosphine

A high-performance liquid chromatographic method, using post-column detection with diphenyl-1-pyrenyl-phosphine (DPPP), was developed for the quantitative and qualitative determination of isomeric lipid hydroperoxides (OOH). The OOH eluted from a normal-phase column were passed through a photodiode array detector and then mixed with DPPP solution in a reaction coil heated at 80°C. DPPP oxide formed by the reaction with OOH was determined by monitoring the fluorescence intensity at 380 nm and excitation at 352 nm. The conjugated diene OOH (13-cis, trans- and 9-cis, trans-OOH) and nonconjugated OOH (12-cis-trans- and 10-cis, trans-OOH) from photosensitized oxidation of methyl linoleate were determined in a molar ratio of 31∶29∶19∶21, respectively. However, only the two conjugated hydroperoxides were detected by ultraviolet absorption at 234 nm. Further applications were carried out for the determination of OOH of methyl oleate and methyl linolenate. This method proved to be useful for the determination of the OOH containing both conjugated and nonconjugated diene structures.     

Studies on miscibility in homopolymer/ random copolymer blends by equation of state theory

The miscibility of poly(methyl methacrylate) (PMMA) and styrene-acrylonitrile random copolymers (SAN) blends was investigated on the basis of the Flory—Orwoll—Vrij equation of state theory. To obtain the equation of state parameters (P*, V*_sp, T*: characteristic parameters), the pressure—volume—temperature (PVT) behaviour was measured for PMMA and a series of SANs with various acrylonitrile contents. The exchange energy parameter X_ij was also calculated by fitting the theory to some phase diagrams of PMMA/SAN blends. The Flory—Huggins interaction parameter χ was separated into two contributions based on the equation of state theory for mixtures: the exchange energy term χ_inter and the free volume term χ_free. Both the temperature and copolymer composition dependences of χ_inter and χ_free were estimated by calculations using the equation of state parameters. There exists a region in which χ_inter is negative, leading to a miscibility window in PMMA/SAN blends. However, the immiscibility at high temperatures in the blends cannot be explained only by χ_inter; it is caused by the free volume contribution, χ_free. The miscibility window behaviour in PMMA/SAN blends may be explained within the framework of the equation of state theory.     

Sintering of Ceria-Doped Tetragonal Zirconia Crystallized in Organic Solvents, Water, and Air

Amorphous CeO₂–ZrO₂ gels were prepared by coprecipitation in ammonia solutions. The onset of crystallization of the gels, from calcining in air, was 420°C, while 200° to 250°C in the presence of water and organic solvents such as methanol and ethanol. The sintering behaviors of CeO₂–ZrO₂ powders were sensitive to the crystallizing conditions, since hard agglomerates formed when the precipitated gels were crystallized by normal calcination in air, whereas soft agglomerates formed when they were crystallized in water or organic solvents. CeO₂–ZrO₂ powders crystallized in methanol and water at 250°C were sintered to full theoretical density at 1150° and 1400°C, respectively, whereas that crystallized by calcination in air at 450°C was sintered to only 95.2% of theoretical density, even at 1500°C.     

Gradient orientation pattern matching with the Hamming distance

This paper presents a novel pattern matching technique that is robust to illumination changes and the occlusion problem. The technique is based on the matching of gradient orientations in place of traditional image features such as intensities or gradients. Gradient orientations depend on the texture in an image. They are known to be insensitive to changes of image intensities that are often caused by time-varying illuminations or the auto-gain control (AGC) function of the camera. Moreover,the proposed method employs a voting strategy in the process of matching gradient orientations. The method works remarkably well even when a large part of the pattern is occluded with a foreign object. Consequently, the proposed method is robust to both irregular lighting conditions and the occlusion problem.     

Sulfur exchange on Co---Mo/Al2O3 hydrodesulfurization catalyst using S radioisotope tracer

A commercial Co---Mo/Al₂O₃ catalyst was labeled with the radioisotope ³⁵S in hydrodesulfurization (HDS) of ³⁵S-labeled dibenzothiophene (³⁵S-DBT) in a high-pressure flow reactor at 50 kg/cm². Then, HDS of 4-methyldibenzothiophene (4-MDBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) or sulfur exchange of H₂S were carried out on the labeled catalyst at 50 kg/cm² and 260–360°C. The amounts of labile sulfur participating in the reaction were determined from the radioactivity of ³⁵S---H₂S released from the ³⁵S-labeled catalyst. In the HDS reactions, the amount of labile sulfur participating in the reaction decreased in the order: DBT> 4-MDBT> 4,6-DMDBT. In the sulfur exchange reaction with H₂S, the adsorption of H₂S on the catalyst reached saturation above a H₂S partial pressure of 0.36 kg/cm². It was suggested that the release of H₂S from the labile sulfur may be the rate determining step of the HDS reaction.     

Structures and electronic properties of surface/edges of nanodiamond and nanographite

The structure, electronic and magnetic properties of nanodiamond and nanographite/nanographene are investigated. Detonation nanodiamond particles that are covered with amorphous graphitic composites are hydrothermally treated to remove the graphitic surface composites and to terminate the surface carbon atoms with hydrogen. The number of localized spins of dangling bonds and the hydrogen concentration increase upon the increase in the hydrothermal treatment time up to 40 h. Above 40 h, both drop discontinuously, a surface structural reconstruction was suggested. The creation of dangling bonds and an incomplete hydrogenation of the surface carbon atoms destabilize the surface, resulting in the structural reconstruction. Nanodiamond particles are thermally converted to nanographite/nanographene. A single nanographene sheet is successfully prepared by heat-treating nanodiamond particles. The edge of graphene sheet with its edge carbon atoms being hydrogen-terminated is investigated by UHV-STM/STS. Zigzag edges are found to have non-bonding π-state of edge origin, in good agreement with theoretical prediction.