On the σ-dimerization of N,N-dimethyl-p-toluidine during anodic oxidation—A reinvestigation

The anodic oxidation of N,N-dimethyl-p-toluidine (2) was studied using cyclic voltammetry and spectroelectrochemistry. In contrast to former studies, the experimental measurements showed that the radical cations of 2 reversibly dimerize at the methyl substituted p-position of the dimethylamino group and form σ-dimers. Theses results again clearly demonstrate that σ-dimerization takes place even when reactive sites are blocked by substituents such as alkyl or phenyl groups. The findings are also relevant for the interpretation of σ-dimerization during electropolymerization and charging of conducting polymers.     

SrCo0.8Fe0.2O3−δ sorbent for high-temperature production of oxygen-enriched carbon dioxide stream

Perovskite-type SrCo_0.8Fe_0.2O_3−δ (SCF) has been prepared by a liquid citrate method and used to produce O₂-CO₂ gas mixture for oxyfuel combustion. Oxygen is desorbed and an oxygen-enriched carbon dioxide stream is obtained when SCF is exposed in a carbon dioxide stream at high temperature. Oxygen is adsorbed when SCF is regenerated in an air stream. A carbonation-reaction mechanism for O₂-desorption has been identified with the evidences of XRD and TGA analysis. It is found that the theoretical oxygen sorption capacity decreases with the increase of temperature. The sorption kinetics over a temperature range of 700-900 °C has been examined by TGA experiment. Both desorption and sorption processes exhibit a high reaction rate in an initial stage followed by a slower rate in a second stage. It is difficult to reach the theoretical oxygen sorption capacity during the whole temperature range due to the slow oxygen desorption rate. Optimal temperatures for oxygen sorption and desorption processes are determined to be 900 and 850 °C, respectively. Multiple sorption and desorption cycles indicate that SCF sorbent has high reactivity and cyclic stability. Comparison with the reference La_0.1Sr_0.9Co_0.5Fe_0.5O_2.6 (LSCF) and Sr_0.5Ca_0.5Co_0.5Fe_0.5O_2.47 (SCCF) sorbents shows that SCF has faster carbonation reaction at high temperature, i.e., 850 and 900 °C, and much higher theoretical oxygen sorption capacities.     

Effects of heating rate on microstructures and microwave dielectric properties of (1 − x)ZnAl2O4–xTiO2 (x = 0.21) ceramics

(1 − x)ZnAl₂O₄–xTiO₂ (x = 0.21) ceramics were synthesized at 1500 °C for 3 h using the solid-state reaction at a heating rate from 1 to 7 °C/min. The effects of heating rate on the microstructure, phase composition and oxidation state of titanium in the ceramics were investigated. The XRD results show that this system is composed of two phases, i.e. ZnAl₂O₄ spinel and rutile. The “black core” phenomenon resulting from reduction of Ti⁴⁺ ion valence appears after the ceramics are sintered at the speed of 1 and 3 °C/min. As the heating rate increases, the density and quality factor (Q·f) increase initially and reach the maximum value when the heating rate is 5 °C/min, and then reduce quickly to the minimum, while the dielectric constant (?_r) and temperature coefficient of resonator frequency (τ_f) nearly do not change. The optimal microwave dielectric properties can be achieved in (1 − x)ZnAl₂O₄–xTiO₂ (x = 0.21) ceramics sintered at a heating rate of 5 °C/min with an ?_r value of 11.6, a Q·f value of 74,000 GHz (at about 6.5 GHz), and a τ_f value of −0.4 ppm/°C.     

Compressive strength and preliminary in vitro evaluation of gypsum and gypsum–polymer composites in protein-free SBF at 37 °C

Gypsum is a bioresorbable material that has been used in many applications such as tissue regeneration. Mechanical properties of gypsum have limited its applications to non-load bearing sites. The current study aimed at studying the compressive strength and behaviour of gypsum–polymer composites in protein-free simulated body fluids (SBF). Polymers studied were poly(vinyl alcohol) (PVA) and its copolymers with vinyl acetate and itaconic acid in addition to vinyl acetate and vinyl chloride. Composites with the highest compressive strength results were chosen for the preliminary in vitro evaluation in protein-free SBF solutions. Changes in the concentrations of Ca²⁺ and PO₄³⁻ ions, weight loss and morphology of the solid samples were monitored after soaking them in SBF and 1.5 SBF solutions. Results showed resorption of gypsum, concurrently with deposition of apatite in all composites, including polymer-free gypsum. Mechanical integrities of all samples were maintained, suggesting their stabilities when used as bone cements.     

Synthesis and characterization of chiral polythiophenes: Poly [(R)-(−) and (S)-(+)-2-(3′-thienyl)ethyl N-(3″,5″-dinitrobenzoyl)-α-phenylglycinate]

(R)-(−) (1) and (S)-(+)-2-(3′-Thienyl)ethyl N-(3″,5″-dinitrobenzoyl)-α-phenylglycinate (2) monomers were synthesized, characterized, and polymerized in chloroform using FeCl₃ as an oxidizing agent. Molecular weights of 2.6 × 10⁴ and 3.2 × 10⁴ for poly1 and poly2, respectively, were determined by SEC analysis. FTIR spectra of the polymers indicated the coupling of monomers through the α positions. UV-vis spectra showed absorption bands at λ_max = 226 and 423 nm for poly1 and poly2, ascribed to transitions of side groups and polythiophene backbone, respectively. Poly1 and poly2 remained stable up to 210 °C. At higher temperatures, a two step weight loss degradation process was observed for both polymers by TGA analysis. ¹H NMR, in the presence of Eu(tfc)₃, and optical rotation measurements indicate the chiral properties of the monomers 1 ([α]_D²⁸ = −76.2) and 2 ([α]_D²⁸ = +76.0), and the maintenance of chirality after polymerization (poly1 [α]_D²⁸ = −29.0 and poly2 [α]_D²⁸ = +28.4, c = 2.5 in THF). According to scanning electron microscopic analysis, the polymers are highly porous.     

Immobilisation of α-amylase from Aspergillus niger onto polyaniline

α-Amylase from Aspergillus niger culture medium was immobilised on glutaraldehyde-modified polyaniline (PANIG-AMY) in a yield of 42% activity retention. Compared with the free enzyme, PANIG-AMY was less sensitive to inhibition by Zn²⁺, Cu²⁺ and Fe²⁺. The catalytic efficiencies of hydrolysis of starch (potato, cassava, wheat, maize and rice/maize) were similar for free and PANIG-AMY. Oligosaccharides were formed following the hydrolysis of potato starch by PANIG-AMY whereas the free enzyme produced oligosaccharides and glucose. PANIG-AMY retained 50% of its activity after repeated assay and storage at 5 °C and pH 7.0. The thermal stability of PANIG-AMY was increased by the presence of CaCl₂. The repeated batch-wise hydrolysis of potato starch using 5.0 mg of PANIG-AMY (0.8 U α-amylase) produced 1.7 μmol of reducing sugar per cycle, yielding a total of 25.5 μmol of reducing sugar after 15 cycles. The same yield would require 12.5 U of free α-amylase.     

Crystal structure and disorder in Poly(l-lactic acid) δ form (α′ form) and the phase transition mechanism to the ordered α form

Crystal structure of poly(l-lactic acid) (PLLA) α′ form (or the newly-termed “δ” form) has been analyzed on the basis of the X-ray diffraction data. The oriented δ form was obtained by stretching and annealing the melt-quenched sample at ca. 100 °C. The unit cell parameters were a = 10.80 Å, b = 6.20 Å, c (fiber axis) = 28.80 Å and α = β = γ = 90°. As seen from the lack of even-numbered 00l reflections (002, 004, ..) except the 0010 reflection, the chain conformation of the δ form was found to be more remarkably disordered than that of the regular α form. As already reported, the α form takes the (10/3) helix with approximately 2₁ screw symmetry although, more strictly speaking, this screw symmetry is not actually existent. The δ form does not possess any symmetry along the chain axis although the local torsional angles are not very much different from each other. As for the chain packing structure, the two different possibilities were assumed in the structural refinement procedure: (i) the corner and center chains direct upward and downward along the chain axis, respectively, just like the case of regular α form (alternate packing mode) and (ii) the upward and downward chains are located at the same lattice site at 50% probability (statistically-disordered packing mode). The structure analysis using the Bragg reflections suggested the preferability of the model (i). The diffuse and streaky lines were observed along the layer lines, originating from the relative-height disorder between the neighboring chains in the δ form. The X-ray diffuse scatterings coming from the various types of the disordered structure have been simulated, among which the disordered multi-domain structure model was found to be the most plausible model, where the domains constructed by the alternate arrangement of upward and downward chains are gathered together with the mismatch in the relative height between the neighboring domains. In this way the disorder-to-order phase transition from the δ to α form was found to occur through the conformational ordering of the chains accompanied with the chain packing regularization as well as the matching of the neighboring domain height to give a large single domain of the α form.     

Structural,dielectric and piezoelectric properties of xBiFeO3–(1−x)BaTi0.9Zr0.1O3 ceramics

Effect of BiFeO₃ (BFO) content on the microstructure and electrical properties of BaTi_0.9Zr_0.1O₃ (BTZ) ceramics prepared by the solid-state reaction technique was investigated. X-ray diffraction analyses show that BFO diffused into the lattice of BTZ to form a solid solution with perovskite structure. The relative density of the BTZ ceramics is increased by the introduction of BFO. The dielectric study reveals that the dielectric constant and the average dielectric loss of the solid solution decreased simultaneously with an increase in BFO content. The materials undergo a diffuse type ferroelectric phase transition. The diffusivity increases with increase in BFO contents in the studied composition range. On the other hand, the piezoelectric coefficient and electromechanical coupling coefficient decrease simultaneously with increasing the BFO content, whereas the mechanical quality factor increases gradually. The structure–property relationship and the mechanism associated with the change of the electrical properties are discussed intensively.     

Characterization of NdSrCo1−xFexO4+δ (0 ≤ x ≤ 1.0) intergrowth oxide cathode materials for intermediate temperature solid oxide fuel cells

NdSrCo_1−xFe_xO_4+δ (0 ≤ x ≤ 1.0) intergrowth oxides have been investigated as cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs). All the cathodes prepared by a glycine nitrate process (GNP) indicated single phase intergrowth oxides. The introduction of Fe for Co leads to decrease TEC values and electrical conductivity, and increase polarization resistance and oxygen content. The polarization resistance of NdSrCoO_4+δ composition is 0.16 Ω cm² at 800 °C in air atmosphere, which is the best electrochemical performance compared with other compositions.     

Electrocaloric effect based on the depolarization transition in (1−x)Bi0.5Na0.5TiO3–xKNbO3 lead-free ceramics

Lead-free ferroelectric ceramics (1−x)Bi_0.5Na_0.5TiO₃−xKNbO₃ (BNT–xKN) with x=0.00, 0.04, 0.06 and 0.08 were synthesized by the conventional solid state reaction method. The effects of the KNbO₃ addition on the dielectric behavior, ferroelectric properties, as well as electrocaloric effect of the ferroelectric ceramic BNT–xKN were investigated. The results show that the depolarization temperature decreases with the increment of KN content. A high ECE of 1.73 °C is achieved at 76 °C in BNT–0.06KN. The relation between electrocaloric effect and depolarization transition was discussed. This investigation indicates that the depolarization transition below Curie transition in BNT-based ceramics is a promising approach in ECE technique.     

RM57/28;TRM53.41;立磨

我公司现有两条5　000t/d生产线。1号线生料磨采用的是Polysius公司生产的RM57/28立磨,于2005年5月投料生产。2号线生料磨采用的是天津水泥工业设计研究院有限公司生产的TRM53.41立磨,于2011年2月投料生产。现就两种立磨生产运行情况做一对比分析。     

Comparison of Ti/BDD and Ti/SnO<Subscript>2</Subscript>–Sb<Subscript>2</Subscript>O<Subscript>5</Subscript> electrodes for pollutant oxidation

Anodic oxidation is a promising process for degrading toxic and biologically refractory organic pollutants present in wastewater treatment. Proper selection of electrodes is the key to reach effective and economic operation. In this study, two types of electrodes, i.e. the recently developed Ti/BDD and Ti/SnO₂–Sb₂O₅, which is generally believed to be superior to the conventional electrodes, were compared under the same conditions. It was found that the Ti/BDD electrode could mineralize both phenol and reactive dyes effectively. But the Ti/SnO₂–Sb₂O₅ electrode could only mineralize phenol. When oxidizing more refractory reactive dyes, it demonstrated very poor activity. In addition, the Ti/BDD electrode had a service life of 264 h in an accelerated life test, but the Ti/SnO₂–Sb₂O₅ was irreversibly damaged within several seconds. The direct experimental comparison in the present study indicates that the Ti/BDD electrode is much better than the Ti/SnO₂–Sb₂O₅ electrode for pollutant oxidation.     

Catalytic chemical vapor deposition synthesis of single- and double-walled carbon nanotubes from α-(Al1−xFex)2O3 powders and self-supported foams

An investigation of the potential interest of α-alumina-hematite foams, as opposed to powders, as starting materials for the synthesis of carbon nanotubes (CNTs) by catalytic chemical vapor deposition method was performed. The oxide powders and foams as well as the corresponding CNT-Fe-Al₂O₃ composite powders and foams are studied by X-ray diffraction, specific surface area measurements, electron microscopy, Raman spectroscopy and Mössbauer spectroscopy. The latter technique revealed that four components (corresponding to α-Fe, Fe₃C, γ-Fe-C and Fe³⁺) were present in the Mössbauer spectra of the composite powders, and that an additional sextet, possibly due to an Fe_1−yC_y alloy, is also present in the Mössbauer spectra of the composite foams. Contrary to some expectations, using foams do not lead to an easier reduction and thus to the formation of more α-Fe, Fe₃C and/or γ-Fe-C potentially active particles for the formation of CNTs, and hence to no gain in the quantity of CNTs. However, using foams as starting materials strongly favors the selectivity of the method towards SWCNTs (60% SWCNTs and 40% DWCNTs) compared to what is obtained using powders (5% SWCNTs, 65% DWCNTs and 30% MWCNTs).     

Ba1−xPrxCo1−yFeyO3−δ as cathode materials for low temperature solid oxide fuel cells

Ba_1−xPr_xCo_1−yFe_yO_3−δ (BPCF) perovskite oxides have been synthesized and investigated as cathode materials for low temperature solid oxide fuel cells (LT-SOFCs). Compared with those of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) and Sm_0.5Sr_0.5CoO₃ (SSCo) cathode materials, BPCF has a lower polarization resistance at decreased temperatures. In particular, Ba_0.5Pr_0.5Co_0.8Fe_0.2O_3−δ showed the lowest polarization loss among the different compositions as a cathode material for LT-SOFCs. The area specific resistance (ASR) of Ba_0.5Pr_0.5Co_0.8Fe_0.2O_3−δ as a cathode material is 0.70 and 0.185 Ω cm² at 500 °C and 550 °C, respectively. The maximum power density of the cell BPCF/SDC/Ni-SDC with humidified hydrogen as fuel and air as oxidant reaches 860 mW cm⁻² at 650 °C.     

Electrochemical properties of Sr1−xCexMnO3 (0.1≤x≤0.4) – GDC composite cathodes for IT-SOFCs

The electrochemical properties of Sr_1−xCe_xMnO₃ (SCM, 0.1≤x≤0.4)–Gd_0.2Ce_0.8O_2−x (GDC) composite cathodes were determined by impedance spectroscopy. The study focused on the doping effect of Ce in the composite cathodes. Single-phase perovskite was obtained for 0.1≤x≤0.3 in SCM. No reaction occurred between the Sr_0.7Ce_0.3MnO₃ electrode and the GDC electrolyte at an operating temperature of 800 °C for 100 h. In the single phase perovskite region, lattice expansion occurred due to the reduction of Mn⁴⁺ to Mn³⁺ at B-sites, and this was attributed to an increase in Ce content. Ce doping enhanced the electrode performance of SCM–GDC composite cathodes, and best electrode performance was achieved for the Sr_0.7Ce_0.3MnO₃–GDC composite cathode (0.93 Ω cm² and 0.47 Ω cm² at 750 °C and 800 °C, respectively). The improvement in electrode performance was attributed to increases in charge carriers induced by a shift of some Mn from +4 to +3 and to the formation of surface oxygen vacancies caused by Mn⁴⁺ to Mn³⁺ conversion at high temperatures.     

Bimetallic Pd–Cu/ZnO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Pd–Cu/ZrO<Subscript>2</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts for methanol synthesis

Monometallic copper and bimetallic palladium-copper catalysts supported on ZnO–Al₂O₃ and ZrO₂–Al₂O₃ were prepared by conventional impregnation method and tested in methanol synthesis reaction under elevated pressure (3.5 MPa) in gradientless reactor at 220°C. The physicochemical properties of prepared catalytic systems were studied using BET, X-ray, TPR-H₂, TPD-NH₃ techniques. The promotion effect of palladium on catalytic activity and selectivity of copper supported catalyst in methanol synthesis reaction was proven. The highest activity of this system is explained by the Pd–Cu alloy formation.     

Electrical conductivity of La1−xCaxFeO3−δ solid solutions

La_1−xCa_xFeO_3−δ solid solutions (x=0, 0.1, 0.2, 0.3, 0.4, 0.5 and 0.6) were investigated. The samples were prepared by the polymerizable complex route and characterized by X-ray diffraction and complex impedance spectroscopy techniques. Results reveal the formation of a single perovskite phase for the La_1−xCa_xFeO_3−δ (0≤x≤0.5) compositions. However, the La_0.4Ca_0.6FeO_3−δ sample is a mixture of many phases: perovskite, calcium ferrite and iron oxide. The unsubstituted lanthanum ferrite oxide, as well as the substituted samples, exhibits an orthorhombic symmetry. The direct current conductivity analyses reveal a typical negative temperature coefficient of the resistance behaviour for all the samples. The incorporation of calcium into the lanthanum ferrite lattice results in a significant improvement of the direct current conductivity. In fact, La_0.8Ca_0.2FeO_3−δ oxide shows the optimal conduction value. For all the studied compositions, a change in the activation energy is highlighted around 440 °C. This behaviour is attributed to the antiferromagnetic to paramagnetic transition of lanthanum ferrite. As for the alternating current conductivity, it obeys the Jonsher's power law. The correlated barrier hopping model is proposed to describe the transport mechanism in the studied matrix.     

Structural and thermal analysis of in situ synthesized C–WC nanocomposites

Nanostructure of carbon encapsulated tungsten carbide (WC@C) has been prepared using reaction between metallic magnesium (Mg), acetone (C₃H₆O) and tungsten trioxide (WO₃) in an autoclave at 600 °C. The resultant powders were characterized by X-ray diffraction (XRD), differential thermal analysis/thermal gravimetric analysis and transmission electron microscopy (TEM). The XRD results showed that the optimization of the reaction time facilitates the reduction as well as carburization of the tungsten source. The apparent activation energy for decarburization of carbide phase was also evaluated from the data of thermal analysis to find the thermal stability of carbide phase. TEM image showed that the synthesized sample consisted of particles with an average size of 35 nm.     

Hydroisomerization of Benzene-Containing Gasoline Fraction on Pt/B<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Pt/WO<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalysts

The effect of the hydroisomerization conditions of the benzene-containing fraction of catalytic reforming gasoline on the yield and composition of products is studied on Pt/B₂O₃–Al₂O₃ and Pt/WO₃–Al₂O₃ catalysts. These catalysts allow benzene to be completely removed from the raw material. At the same time, the greatest yields of liquid products are obtained with minimal losses of the octane number at 2 MPa, a mass feedstock hourly space velocity (MFHSV) of 2 h^?1, and 325°C: 96.3 and 95.4 wt % on Pt/B₂O₃–Al₂O₃ and Pt/WO₃–Al₂O₃ catalysts, respectively. The activity of the catalysts is maintained for 100 h during their operation.