Visible-light photocatalytic activity of TiO2−x by heat treatment and plasma-heat treatment

The partial reduction of TiO₂ was attempted by heat treatment and plasma-heat treatment and it was carried out to investigate the photocatalytic characteristics of partially reduced TiO₂ (TiO_2?x) in the visible-light region. As a result, the plasma-heat treatment shows significantly stronger than the heat treatment for the visible-light photocatalytic activity of TiO₂. The red-shifted absorption bands in the visible-light region of TiO_2?x by plasma-heat treatment gave broader than one by heat treatment. The TiO_2?x by heat treatment and plasma-heat treatment was changed white to beige color, and white to navy, respectively.     

Hydrolytic degradation of poly(L-lactic acid): Combined effects of UV treatment and crystallization

Amorphous and crystallized poly(L -lactic acid) (PLLA) films were prepared and the hydrolytic degradation of the ultraviolet (UV)-treated and UV-nontreated films was investigated. This study reveals that the combination of UV and thermal treatments can produce the PLLA materials having different hydrolytic degradation profiles and that the UV-irradiation in the environment will affect the design of recycling process for PLLA articles. In an early stage, the degrees of hydrolytic degradation monitored by weight loss (W_loss), number-average molecular weight (M _n), and melting temperature (T _m) were higher for the UV-treated films than for the UV-nontreated films. In a late stage, the trend traced by W_loss was reversed, and the difference in the degrees of hydrolytic degradation between the UV-treated and UV-nontreated films monitored by M _n and T _m became smaller, with the exception of the degrees of hydrolytic degradation of the amorphous films traced by T _m. Also, in the early stage, the degrees of hydrolytic degradation monitored by W_loss and M _n were higher for the crystallized films than for the amorphous films. In the late stage, this trend was reversed, with the exception of the degrees of hydrolytic degradation of the UV-treated films monitored by M _n. The main factors that determined the W_loss and T _m were the molecular weight and initial crystallinty but not the molecular structures such as terminal CC double bonds and crosslinks. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Disorders and oxygen vacancies in p-type Sn2B2O7 (B = Nb,Ta): Role of the B-site element

Sn₂Nb_2−xTa_xO₇ (x = 0.0–2.0) with pyrochlore structure is a promising material for p-type oxide semiconductors. A systematic study of its Nb/Ta ratio indicated that the hole–generation efficiency of the Nb end (Sn₂Nb₂O₇) was an order of magnitude lower than that of the Ta end (Sn₂Ta₂O₇). Although this occurs due to differences in oxygen-vacancy formation, the origins of the hole–generation efficiencies remain unclear due to limited information on local and global crystal-structure disorders in pyrochlore Sn₂Nb₂O₇ and Sn₂Ta₂O₇. In this study, the crystal structures of Sn₂B₂O₇ (B = Nb, Ta), composed of BO₆ octahedra and Sn₄O tetrahedra, were investigated using X-ray absorption spectroscopy and X-ray diffraction. A detailed investigation of the local and global crystal structures indicated a larger amount of disorder in the Sn₄O tetrahedra in Sn₂Nb₂O₇ compared to Sn₂Ta₂O₇; disorder in the BO₆ octahedra occurred only in Sn₂Ta₂O₇. This study indicates that an appropriate selection of the B-site element is vital for suppressing defect and disorder formation in Sn₄O tetrahedra and subsequently improving the hole–carrier–generation efficiency.     

Sintering Behavior of Pt Metal Particles Supported on Silica-Coated Alumina Surface

The sintering behavior of Pt metal particles was studied by supporting them on silica-coated alumina. Silica coating was found to be effective for the retention of a large surface area of alumina even after calcination at elevated temperatures. Before sintering, the size of Pt metal particles on all the silica-coated aluminas, including the uncoated alumina, was identical, while the particle size was larger on silica than on alumina. After sintering the Pt catalyst at 1073 K, the particle size increased on uncoated alumina as well as on alumina coated with thicker silica layers, especially on the supports previously calcined at >1473 K. On the other hand, the size of Pt metal particles did not increase much on alumina coated with monolayer silica. The observed suppression of sintering of Pt metal particles resulted from the retention of a large surface area of alumina with a thinner silica layer. In the case of a thicker silica layer, although a large surface area was maintained after calcination at elevated temperatures, the existence of a bulk silica-like property of the support did not favor the suppression of sintering of Pt metal particles.     

N-Alkylation of chitin and some characteristics of the novel derivatives

Summary Introduction of simple alkyl groups at the C-2 nitrogen of chitin and some properties of the resulting N-alkyl-chitins have been examined. Chitosan was fully deacetylated and treated with three kinds of aldehydes, formaldehyde, acetaldehyde, and pentanal. The Schiff bases of chitosan, whose extents of substitution were dependent on the amount of aldehydes, were reduced with sodium cyanoborohydride to N-alkylated chitosans. The N-alkyl-chitosans were then transformed into the corresponding N-alkyl-chitins by acetylation with acetic anhydride followed by transesterification to remove partly formed O-acetyl groups. The resulting N-methyl-, ethyl-, and pentyl-chitins were amorphous and showed improved affinity for organic solvents. Received: 13 December 2001/Revised version: 11 January 2002/Accepted: 17 January 2002     

Adsorption isotherms of pigments from alkali-refined vegetable oils with clay minerals

Adsorption isotherms of pigments from alkali-refined oils (rapeseed, soybean, wheatgerm, safflower, corn, cottonseed and sunflower) were measured to investigate the applicability of the Langmuir and Freundlich equations and to elucidate the adsorption characteristics of pigments on sepiolites and standard activated clay. The Freundlich equation was more applicable to the experimental adsorption isotherms. The equilibrium amount adsorbed, acidity, pore size distribution and inflection of the Freundlich isotherms could be explained by assuming that pigments were adsorbed on the stronger acid sites in smaller pores at low concentration, and then in the larger ones when the concentration increased. The amount adsorbed increased with a rise in adsorption temperatures from 70 to 110°C, and the heat of adsorption was below 10 kcal/mol. The results indicate that pigments were physically adsorbed on the acid sites activated at higher adsorption temperatures.     

Effect of Grain Boundaries on Thermal Conductivity of Silicon Carbide Ceramic at 5 to 1300 K

The thermal conductivity of a SiC ceramic was measured as 270 W·m⁻¹·K⁻¹ at room temperature. At low temperatures ( T < 25 K), the decrease in the conductivity was proportional to T ³ on a logarithmic scale, which indicated that the conductivity was controlled by boundaries. The calculated phonon mean free path in the ceramic increased with decreased temperature, but was limited to ∼4 μm, a length almost equal to the grain size, at temperatures below 30 K. We concluded that the thermal conductivity of the ceramic below 30 K was influenced significantly by grain boundaries and grain junctions.     

Hydrodechlorination of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) over supported ruthenium and other noble metal catalysts

The hydrodechlorination of CCl₂F–CClF₂ (CFC-113) was studied using silica- and activated carbon-supported Ru, Rh, Pd, and Pt catalysts. The activity of the catalysts changed with time-on-stream. Ru was most stable among the four noble metals and gave a simple product distribution yielding CClF=CF₂ (CFC-1113) and CHClF–CClF₂ (HCFC-123a) as main products. Over silica-supported Ru, CFC-1113 yield decreased gradually with time-on-stream but HCFC-123a yield did not change throughout the reaction, suggesting that these products were formed on different sites of Ru. XRD studies and temperature-programmed reduction of the spent catalyst revealed that the deactivation was caused by halogen-containing carbonaceous species accumulated on the Ru surface during the reaction. The carbonaceous species seemed to be formed on the active site for CFC-1113 formation. Because CFC-1113 selectivity was higher over the catalyst having higher Ru dispersion, it was assumed that the hydrodechlorination of CFC-113 is structure-sensitive and CFC-1113 formation is promoted by Ru having highly unsaturated coordination sphere.     

EFFECT OF HEATING MODES ON INTERNAL STRAIN-STRESS FORMATION DURING DRYING OF MOLDED CERAMICS

Parametric analyses in drying processes of molded ceramics are performed to investigate the influence of heating modes on the formation of drying-induced strain-stress as well as the drying characteristic. The transient three-dimensional problem of strain-stress and heat and moisture transfer in a slab is solved simultaneously by the finite element method. Three modes of hot air, intermittent and internal heating are compared by modeling in the normalized parameters. The tensile and compressive stresses fluctuate, and fall remarkably during the low Biot number period when the slab is heated intermittently. In the internal heating mode, the drying rate is the fastest but stress formation is maintained at the lowest level among the three modes. This effectiveness of the internal heating is investigated experimentally by employing the microwave heating as well.     

Dehydrogenative polycondensation of telechelically bis(dimethylsilyl)functionalized oligo(dimethylsiloxane)s or aromatics and 1,3,3,5,5,7,7,7-octamethyltetrasiloxane

Telechelically bis(hydrodimethylsilyl)-functionalized oligo(dimethylsiloxane)s or aromatics were found to give polymers constituting of alternating disilylene and oligodimethylsiloxane or 4,4′-diylaromatics as repeating units by dehydrogenative coupling reaction in the presence of palladium dibenzylideneacetone complex. The same catalyst gave polysilylenes with trisiloxane pendant from 1,1-dihydro-1,3,3,5,5,7,7,7-octamethyltetrasiloxane. Received: 18 October 1996/Accepted: 31 October 1996