X-Ray, Micro-Raman, Optical Absorption/Emission Studies of ErNbO4 Grown by Vapor Transport Equilibration

Vapor transport equilibration (VTE) treatments were performed on a Y-cut bulk Er (1.6 mol%)-doped congruent LiNbO₃ crystal and an X-cut pure congruent crystal, on one surface of which a 40 nm-thick film of erbium metal was coated before the VTE treatment. Scanning electron microscope, powder or single-crystal X-ray diffraction (XRD), polarized infrared absorption/emission of Er³⁺ as well as micro-Raman spectroscopy were used to study the two VTE crystals. The results are discussed in comparison with a corresponding as-grown bulk Er-doped crystal, calcined ErNbO₄ powder, and a locally Er-doped congruent LiNbO₃ crystal prepared by using the standard Er-diffusion technique. The experimental results show that the VTE treatment induces the formation of micrometer-sized ErNbO₄ precipitates with the crystallographic morphology of a flat polyhedron not only on the surfaces of both crystals but also in the bulk of the homogeneously Er-doped one. The optical absorption and emission studies show that the formation of the precipitates results in substantial spectral changes in both the 0.98 and 1.5 μm regions. The micro-Raman studies allow to resolve four additional Raman peaks around 800 cm⁻¹ in the E(TO) spectra of the two VTE crystals. These additional Raman peaks are associated with the characteristic vibrations with respect to the NbO₄³⁻ group. Characteristic XRD, optical absorption, and emission and Raman peaks for identifying the ErNbO₄ phase are proposed. Finally, the formation mechanism and light-scattering effect of the precipitates are discussed.     

Synthesis of carbon nanocapsules containing Fe, Ni or Co by arc discharge in aqueous solution

A simple, inexpensive and one-step synthesis method of metal-containing carbon nanocapsules using an arc discharge in aqueous solution is reported. It was found that Ni, Co and Fe nanoparticles could be in situ encapsulated in carbon shells when the arc was performed respectively in aqueous solutions of NiSO₄, CoSO₄ and FeSO₄. Transmission electron microscopy, energy dispersive X-ray spectroscopy and electron diffraction patterns of selected areas were used to determine the crystalline phase of the metal cores. To explain the formation mechanism of metal-containing carbon nanocapsules, a model of discharge in solution is proposed. This result presents a simply controllable way to synthesize metal-containing carbon nanocapsules.     

Synthesis and characterization of copolythiophene

Copolythiophenes (Co‐PTs), poly(3‐hexylthiophene‐co‐3‐thiophene carboxylic acid) (P3HT‐TCa), poly(3‐hexyloxylthiophene‐co‐3‐thiophene carboxylic acid) (P3HOT‐TCa), and poly(3‐phenylthiophene‐co‐3‐thiophene carboxylic acid) (P3PhT‐TCa), were synthesized by chemical oxidized polymerization to investigate the effect of copolymerization on the properties of polythiophenes (PTs). Gel permeation chromatography showed that the molecular weight (MW) of Co‐PT was lower than that of homopolythiophene. Fourier transform infrared (FTIR) spectra indicated that the copolymerization was successful between the monomers. The λ_max of Co‐PTs gave a “blue shift” in ultraviolet‐visible (UV‐VIS) spectra. Photoluminescence (PL) spectra showed that the PL intensity of Co‐PT became weaker than that of homopolythiophene and the disappearance of PL had been observed in P3HOT‐TCa. The thermal stability of Co‐PT was influenced by the carboxyl for its low decomposition temperature. Furthermore, the copolymerization between multi‐wall carbon nanotube containing thiophene ring (MWNT‐Th) and 3‐hexyloxylthiphene could also take place successfully. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Morphologies-Controlled Synthesis and Optical Properties of Bismuth Tungstate Nanocrystals by a Low-Temperature Molten Salt Method

Well-crystallized bismuth tungstate (Bi₂WO₆) powders with different morphologies were successfully synthesized via a low-temperature molten salt method. The powders were characterized by X-ray diffraction, transmission electron microscopy, and UV-Vis, respectively. It was found that the variation of morphology of the obtained Bi₂WO₆ powder mainly depends on the different reaction temperatures and the weight ratio of LiNO₃–NaNO₃ salt to precursor. In addition, the UV-Visible absorption spectra showed that the synthesized powders had strong light absorption properties not only in the ultraviolet light but also in the visible light region.     

Evaluation of sorbents for thiophene removal from liquid hydrocarbons

Thiophene is a commonly occurring sulfur compound in liquid hydrocarbon streams produced in a petroleum refinery. The concentration of thiophene often needs to be reduced to very low levels for most applications. Selective adsorption of thiophene is investigated in n-heptane, 1-octene and xylenes and their mixtures. A variety of adsorbents were tested for their selectivity and adsorption capacity. Improvements in adsorption capacity were attempted based on analysis of the adsorption mechanism. Adsorption capacity of NaX zeolite was found to be highest among tested adsorbents. However, competitive adsorption from xylenes reduced adsorption capacity for thiophene from mixtures containing large concentration of xylenes. Langmuir model is applied to describe observed competitive adsorption. Selective adsorption of organic sulfur compound could be used as a polishing step in a purification scheme which allows sulfur removal from hydrocarbons at low temperature and without the use of expensive hydrogen.     

Effects of the reinforcement and toughening of acrylate resin/CaCO3 nanoparticles on rigid poly(vinyl chloride)

Novel composite particles based on nanoscale calcium carbonate (nano‐CaCO₃) as the core and polyacrylates as the shell were first synthesized by in situ encapsulating emulsion polymerization in the presence of the fresh slush pulp of calcium carbonate (CaCO₃) nanoparticles. Subsequently, these modified nanoparticles were compounded with rigid poly(vinyl chloride) (RPVC) to prepare RPVC/CaCO₃ nanocomposites. At the same time, the effects of the reinforcement and toughening of these modified nanoparticles on RPVC were investigated, and the synergistic effect of modified nanoparticles with chlorinated polyethylene (CPE) was also studied. The results showed that in the presence of nano‐CaCO₃ particles, the in situ emulsion polymerization of acrylates was carried out smoothly, and polyacrylates successfully encapsulated on the surface of nano‐CaCO₃ to prepare the modified nanoparticles, breaking down nano‐CaCO₃ particle agglomerates, improving their dispersion in the matrix, and also increasing the particle–matrix interfacial adhesion. Thus, the effects of the reinforcement and toughening of these modified nanoparticles on RPVC were very significant, and the cooperative effect of the nanoparticles with CPE occurred in the united modification system. Scanning electron microscopy analyses indicated that large‐fiber drawing and network morphologies coexisted in the system of joint modification of nanoparticles with CPE. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3940–3949, 2007     

Volatilisation and catalytic effects of alkali and alkaline earth metallic species during the pyrolysis and gasification of Victorian brown coal. Part VII. Raman spectroscopic study on the changes in char structure during the catalytic gasification in air

FT-IR/Raman spectroscopies have been used to identify the structural features of Victorian brown coal chars during the gasification in air at 400 °C. The deconvolution of the Raman spectra has allowed us to identify the main structural sites in char where preferential reaction with O₂ takes place. The presence of Na and Ca catalysts is shown to alter the reaction pathways between char and O₂. In the absence of a catalyst, the O-containing functional groups formed in char during gasification were closely associated with the aromatic structure and thus tended to loosen the aromatic structure. The non-catalysed gasification was slow and took place on some specific (especially sp³-rich or sp²–sp³ mixture) sites distributed throughout the char. In the presence of a catalyst (Na or Ca), the O-containing functional groups were not closely associated with the main aromatic structure throughout the char. The catalytic gasification reactions were localised on the sites associated with the catalysts. The preferential removal of smaller aromatic ring systems and the persistence of cross-linking structures in the presence of a catalyst mean that the large aromatic ring systems were increasingly concentrated with little flexibility, affecting the dispersion of catalyst.     

Research on the friction and wear mechanism of Poly(vinyl alcohol)/hydroxylapatite composite hydrogel

Poly(vinyl alcohol)/Hydroxylapatite (PVA/HA) composite hydrogel was prepared with poly(vinyl alcohol) and hydroxylapatite as raw materials, using the method of repeated freezing and thawing. The morphologies of PVA/HA composite hydrogel were observed by means of high-accuracy 3D profiler and scanning electron microscope (SEM). The compressive elastic modulus and the stress relaxation characteristics of PVA/HA composite hydrogel were measured using the flat-head cylinder indenter. The friction and wear tests between PVA/HA composite hydrogel and bovine knee articular cartilage were performed on the micro-tribometer. The worn morphologies of PVA/HA composite hydrogel were observed with environmental scanning electron microscope (ESEM). The results showed that PVA/HA composite hydrogel has the cross-link network microstructure which is similar to that of the natural bovine knee articular cartilages. With the increase of freezing-thawing cycles and the HA content, the degree of cross-link and the crystallization of PVA/HA composite hydrogel both increase, the elastic modulus increases evidently, the rate of stress relaxation is improved and the value of balance stress decreases. The friction coefficient decreases with the increase of the freezing-thawing cycles and the HA content. The more the freezing-thawing cycles are, the earlier the friction coefficient reaches the stable balance value. The friction deformation depth between PVA/HA composite hydrogel and bovine knee articular cartilage is inversely proportional to freezing-thawing cycles and the HA content. The main wear mechanisms of PVA/HA composite hydrogel are plastic flowing and adhesive flaking. The wear severity degree decreases with the increase of freezing-thawing cycles and the HA content. Supported by Key Program of the National Natural Science Foundation of China (Grant No. 50535050), Program for New Century Excellent Talents in University (Grant No. NCET-06-0479) and Natural Science Foundation of Jiangsu Province (Grant No. BK2005403)     

高速钢表面PN＋PVD复合处理工艺和性能研究

采用多弧离子镀设备,在高速钢W18Cr4V上先进行等离子氮化,再沉积TiN薄膜,研究了不同渗氮温度和时间对PN＋TiN薄膜组织和性能的影响。结果表明,温度为500℃左右和时间为2h以上条件下对W18Cr4V进行渗氮处理后再沉积TiN薄膜,可以得到最佳的薄膜表面显微硬度（1800～2000HV0.05）和膜／基结合力（50N）,涂层耐磨性也得到明显提高。     

Differential Thermal Calorimetric Determination of the Thermodynamic Properties of Kaolinite

Four samples of kaolinite were investigated to determine the exothermic reaction enthalpy by differential thermal calorimetry. The measured 9 kcal/mol for the 980°C exothermic reaction enthalpy corresponds to the calculated heat of crystallization of silica at this temperature. Literature evidence discounts the crystallization of the other participating phases, mullite and silicon spinel. An NaOH extraction technique was used to remove the amorphous silica from a kaolinite fired at 850°C; this extraction removed the 980°C exotherm. It is tentatively suggested, therefore, that most of the heat release at 980°C on firing kaolinite accompanies the reaction SiO₂(amorphous) → SiO₂(β-quartz).