环氧树脂改性双环戊二烯型氰酸酯树脂固化反应性

采用凝胶试验、FTIR和DSC等手段研究了环氧E-51与双环戊二烯型氰酸酯（DCPDCE）共聚体系的固化反应性以及阶梯固化过程中一OCN基、三嗪环、唑啉、嗯唑啉酮的变化情况。结果表明，环氧树脂既能够催化氰酸酯本身三聚成环反应，又对氰酸酯三聚成环反应有稀释作用。当环氧树脂含量（环氧占混合物总量的质量百分比）大于5wt％时，催化效果增加不明显，稀释作用加强；当环氧树脂含量约为25wt％时，以上两种作用效果基本平衡，改性体系的固化反应活性和纯DCPDCE相当。阶梯固化时，低温阶段（160～180℃）主要发生生成三嗪环和唑啉的反应，高温阶段（200-220℃）主要发生三嗪环和唑啉向嘌唑啉酮的转化反应。另外，～OCN基的低温转化率随着环氧树脂含量的增大而提高，固化树脂的最终结构组成和环氧树脂的含量有关。

含芳环脂肪胺的固化反应性研究

含芳环脂肪胺兼具脂肪胺和芳香胺的优点 ,在高性能室温固化环氧树脂体系中受到极大的重视。对 3种新型含芳环脂肪胺的固化反应性进行了初步研究 ,并与A - 5 0 (间苯二甲胺丙烯腈改性物 )的相应性能作了比较。

纳米TiO_2对改性BMI树脂固化反应及热稳定性影响

将芳香二胺、N-取代苯基马来酰亚胺等组分引入双马树脂以降低固化物交联密度 ,研究了纳米 Ti O2 对该改性双马树脂固化反应性和固化树脂热稳定性的影响。利用差热分析、凝胶特征曲线对树脂的固化反应性进行研究 ,采用热重分析和红外分析表征固化树脂的热稳定性和树脂固化前后 IR光谱变化特征。结果表明 :该系列树脂基体具有较低的熔点 (70～ 90℃ ) ,良好的溶解性 ,大多数预聚体可溶解于丙酮溶剂 ;纳米 Ti O2 的引入可使固化温度下降 45～ 10 5℃ ,固化物的耐热温度指数提高 19～ 2

基于改性亚麻仁油的有机/无机光固化膜的光固化机理及其反应性研究

用亚麻仁油和环戊二烯合成了改性亚麻仁油(NLO)光固化低聚物,其结构用红外光谱(FT-IR)进行了表征.基于改性亚麻仁油、巯基硅氧烷和光引发剂制备了有机/无机杂化光固化膜,对其光固化机理进行了分析,对无机粒子在改性亚麻仁油中的分布用AFM(原子力显微镜)进行了观测,建立了该有机/无机杂化体系的光固化模型.对杂化膜光固化反应性用Photo-差示扫描热分析仪(Photo-Differential Scanning Calorimeter)进行了测试,Photo-DSC测试结果表明:巯基硅氧烷能大大提高改性亚麻仁油体系光固化速率,环烯键对硫醇十分敏感.

注射环氧树脂应用研究

研讨了自动压力凝胶工艺用环氧树脂应用的有关问题 :流动性、工艺性。

Schottky Barrier Characteristics of Polycrystalline and Epitaxial CoSi_2/n-Si(111) Contacts Formed by Solid State Reaction

Polycrystalline and epitaxial CoSi 2 films are formed on the n-Si (111) substrates by solid state reaction of the as-deposited Co single-layer and Co/Ti bilayer with Si,respectively at different annealing phase.The CoSi 2/Si Schottky contacts are measured with the current-voltage and capacitance-voltage (I-V/C-V) techniques within the range of temperature from 90K to room temperature.The measured I-V characteristics have been analyzed with a model based on the inhomogeneity in Schottky barrier height,i.e.,at high temperatures (≥～200K) or low temperatures but with a large bias,the I-V curves can be described by using the thermionic emission theory with a Gaussian distributed barrier height over the whole junction,while at low temperatures and with a small bias,the current is dominated by some small patches with low barrier height.It results in a plateau-like section in the low temperature I-V curves around 10 -7 A.At room temperature,the barrier height of polycrystalline CoSi 2/Si deduced from the I-V curve is about 0 57eV.For epitaxial CoSi 2,the barrier height depends on its final annealing temperature and increases from 0 54eV to 0 60eV with the annealing temperature increasing from 700℃ to 900℃.

Comparison of Fe^(2+) oxidation by Acidithiobacillus ferrooxidans in rotating-drum and stirred-tank reactors

Fe2＋ oxidation by Acidithiobacillus ferrooxidans（At.ferrooxidans） under different solid contents by adding inert Al2O3 powder was examined in rotating-drum and stirred-tank reactors.The results show that the bioactivity of At.ferrooxidans in the stirred-tank is higher than that in the rotating-drum in the absence of Al2O3 powder,but the biooxidation rate of Fe2＋ decreases markedly from 0.23 g/（L·h） to 0.025 g/（L·h） with increasing the content of Al2O3 powder from 0 to 50%（mass fraction） in the stirred-tank probably due to the deactivation of At.ferrooxidans resulting from the collision and friction of solid particles.The increase in Al2O3 content has a little adverse effect on the bioactivity of At.ferrooxidans in the rotating-drum due to different mixing mechanisms of the two reactors.The biooxidation rate of Fe2＋ in the rotating-drum is higher than that in the stirred-tank at the same content of Al2O3 powder,especially at high solid content.The higher bioactivity of At.ferrooxidans can be maintained for allowing high solid content in the rotating-drum reactor,but its application potential still needs to be verified further by the sulfide bioleaching for the property differences of Al2O3 powder and sulfide minerals.

Coating of LiNi_(1/3)Mn_(1/3)Co_(1/3)O_2 cathode materials with alumina by solid state reaction at room temperature

Alumina coated LiNi1/3Mn1/3Co1/3O2 particles were obtained by a simple method of solid state reaction at room temperature. The reaction mechanism of solid state reaction at room temperature was investigated. The structure and morphology of the coating materials were investigated by XRD, SEM and TEM. The electrochemical performances of uncoated and Al2O3-coated LiNi1/3Co1/3Mn1/3O2 cathode materials were studied within a voltage window of 3.00?4.35 V at current density of 30 mA/g. SEM, TEM and EDS analytical results indicate that the surface of LiNi1/3Mn1/3Co1/3O2 particles is coated with very fine Al2O3 composite, which leads to the improved cycle ability though a slight decrease in the first discharge capacity is observed. It is proposed that surface treatment by solid state reaction at room temperature is a simple and effective method to improve the cycle performance of LiNi1/3Co1/3Mn1/3O2 particles.

Kinetic study on carbothermic reduction of ilmenite with activated carbon

The carbothermic reduction of Panzhihua ilmenite with various additions of activated carbon was investigated byisothermal experiments over the temperature range of1373to1773K in the argon atmosphere.According to the reaction kineticsrecorded by the infrared gas analyzer,it was found that the amount of carbon addition had little influence on the reaction rates atvarious temperatures except1473K.When the reaction temperature was above the eutectic temperature of1427K of Fe?C binarysystem,part of carbon would dissolve into Fe to form a liquid phase,which made the liquid Fe as a diffusion channel of carbon todiffuse to the reaction interface.The carbothermic reduction above1573K obeyed the shrinking-core model.The mass fraction ofTiC could be determined by the standard addition technique.

Mechanism of Clay Mineral Affect on Strength of Solidification Sludge

To solve the problem of vast cement and low strength in the treated sludge, clay mineral used for accessorial solidification material was applied to advance strength. The principle of solidification sludge strength because of clay mineral is not clear and has not supported the choice of clay mineral. The mineral and pore water is analyzed in order to contrast clay mineral added or not based on the XRD and pore water chemical character. The result shows that the absorbed quantity of Ca2~ was reduced by sludge because of clay mineral added, the hydrated reaction was advanced and integrated solidified materials was formed.

Preparation of SO_4^(2-)/TiO_2-MoO_3 Solid Superacid and Its Catalytic Activity in Acetalation and Ketalation

SO4^2-/TiO2-MoO3, a novel solid superacid, has been prepared and its catalytic activity at different synthetic conditions was examined with esterification of n-butanoic acid and n-butyl alcohol as probing reaction.The optimum conditions were also found, that is, the mass ratio of MoO3 used in the compound is 25%, the calcination temperature 450℃, and the soaked consistency of H2SO4 is 0.5mol.L^-1. Then it was applied in the catalytic synthesis of six similar important ketals and acetals as catalyst and revealed high catalytic activity. Under the condition that the molar ratio of aldehyde/ketone to glycol was 1:1.5, the mass ratio of the catalyst to the reactants was 0.5% and the reaction time 1.0 h, the yield of ketals and acetals reached up to 63.2%. The catalyst can be easily recovered and reused.

Selective Removal of Nitrogen-Containing Heterocyclic Compounds from Transportation Diesel Fuels with Reactive Adsorbent

This paper presents a new selective adsorbent to remove nitrogen-containing heterocyclic compounds from model and commercial transportation diesel fuels based on characteristic reaction designed to occur in the pores of substrate.This reactive adsorbent is composed of formaldehyde,phosphotungstic acid and Santa Barbara USA(SBA)-15.The experiment was based on assumed hydroxymethylation reaction of nitrogen-containing heterocyclic compounds with formaldehyde using phosphotungstic acid as catalyst in batch and fixed-bed systems.The nitrogen concentration in the model fuel was 237.33 ng.μl-1,carbazole and toluene were used as model nitrogen-containing heterocyclic compound and solvent,respectively.The effectiveness of reactive adsorbent for removal of nitrogen-containing heterocyclic compounds from commercial 0# diesel fuel containing 224.86 ng.μl-1 nitrogen was examined in a fixed-bed reactor at 70 ℃.The results showed that nitrogen in the model fuel was very low and the nitrogen concentration in the commercial diesel reduced to 2.44 ng.μl-1.The demand for transportation fuel with ultra-low nitrogen is satisfied.

Synthesis and electrochemical performance of Li_3V_2(PO_4)_3 by optimized sol-gel synthesis routine

Li3V2（PO4）3 samples were synthesized by sol-gel route and high temperature solid-state reaction. The influence of Li3V2（PO4）3 as cathode materials for lithium-ion batteries on electrochemical performances was investigated. The structure of Li3Va（PO4）3 as cathode materials for lithium-ion batteries and morphology of Li3V2（PO4）3 were characterized by X-ray diffractometry （XRD） and scanning electron microscopy （SEM）. Electrochemical performances were characterized by charge/discharge and AC impedance measurements. Li3V2（PO4）3 with smaller grain size shows better performances in terms of the discharge capacity and cycle stability. The improved electrochemical properties of Li3V2（PO4）3 are attributed to the refined grains and enhanced electrical conductivity. AC impedance measurements also show that the Li3V2（PO4）3 synthesized by sol-gel route exhibits significantly decreased charge-transfer resistance and shortened migration distance of lithium ions.

Oxidative Desulfurization over Molybdenum-containing MCM-41

Two series of molybdenum-containing MCM-41 catalysts were prepared for oxidative desulfurization ofdibenzothiophene （DBT） using t-butylhydroperoxide （TBHP） as the oxidant. The electronic properties, pore dimension and hydrophilic properties of the catalysts were studied by XRD, BET, and 1R spectrometry. The Mo-Al2O3 catalyst and TiMCM-3% were also studied for comparison. The two series of MCM-41 zeolite with MoO3 in the framework or impregnated on the surface exhibited considerable activities at low MoO3 content and both were faxbetter than the Mo-Al2O3 catalyst, but had lower activities as compared to the TiMCM-3% catalyst. The catalysts with the highest activity were evaluated in a fixed-bed reactor. The concentration of DBT in model diesel upon oxidative desulfurization was successfully reduced from 5000 ppm to less than 150 ppm, but the catalysts were deactivated very fast. The probable reason was the high affinity of DBTO2 to the MCM-41 skeleton, especially to MoO3. The catalysts could restore most of its original activity by treating with alcohol.

Growth of Hierarchically Structured High-Surface Area Alumina on FeCralloy~ Rods

The formation of metastable alumina phases due to the oxidation of commercial FeCralloy（R） rods （0.5 mm thickness） at various temperatures and time periods has been examined. This structured layer acts as an anchor to bind additional coatings of alumina via wash-coat techniques, thereby improving the layer thickness and increasing adhesion of the catalytic surface. Optimisation of the layer thickness and catalytic properties were conducted, using a range of analytical systems [scanning electron microscope （SEM）, energy dispersive X-ray （EDX） and X-ray diffraction （XRD）]. The modified FeCralloy（R） rods were tested in a fixed bed reactor rig to assess the impact on yield for the dehydrogenation of methylcyclohexane.

Axial Liquid Dispersion in Gas-Liquid-Solid Circulating Fluidized Bed

The effects of liquid viscosities, solid circulating rates, liquid and gas velocities and phase holdups on the axial dispersion coefficient, Dax, were investigated in a gas-liquid-solid circulating fluidized bed (GLSCFB).Liquid viscosity promotes the axial liquid backmixing when solid particles and gas bubbles are present. Increases in gas velocities and solid circulating rates lead to higher Dax. The effects of liquid velocity on Dax are associated with liquid viscosity. Compared with conventional expanded beds, the GLSCFBs hold less axial liquid dispersion,approaching ideal plug-flow reactors.

Preparation and properties of pectinase immobilized on chitosan support

Pectinase was immobilized onto chitosan support itsing glutaraldehyde as a coupling agent to obtain high activity and stability of pectinase.x A maximum residual activity of 55% was obtained with 0.4 mg proteirdg chitosan （w/w）, 5% （v/v） g/utara/dehyde, and 4℃ for the crosslinking reaction. The optimal pH and temperature for pectinase activity changed from 3.0 and 40℃ to 3.5 and 50℃, respectively, after immobilization The immobilized enzyme exhibited higher stability under varying conditions of pH and temperature and better reusability than the free enzyme.

A thermodynamic framework for thermo-chemo-elastic interactions in chemically active materials

In this paper, a general thermodynamic framework is developed to describe the thermo-chemo-mechanical interactions in elastic solids undergoing mechanical deformation, imbibition of diffusive chemical species, chemical reactions and heat exchanges. Fully coupled constitutive relations and evolving laws for irreversible fluxes are provided based on entropy imbalance and stoichiometry that governs reactions. The framework manifests itself with a special feature that the change of Helmholtz free energy is attributed to separate contributions of the diffusion-swelling process and chemical reaction-dilation process. Both the extent of reaction and the concentrations of diffusive species are taken as independent state variables, which describe the reaction-activated responses with underlying variation of microstructures and properties of a material in an explicit way. A specialized isothermal formulation for isotropic materials is proposed that can properly account for volumetric constraints from material incompressibility under chemo-mechanical loadings, in which inhomogeneous deformation is associated with reaction and diffusion under various kinetic time scales. This framework can be easily applied to model the transient volumetric swelling of a solid caused by imbibition of external chemical species and simultaneous chemical dilation arising from reactions between the diffusing species and the solid.

Curing kinetics and mechanical properties of bio-based composite using rosin-sourced anhydrides as curing agent for hot-melt prepreg

In this study, a novel bio-based thermosetting system has been developed from epoxy resin （EP）, with rosin-sourced anhydrides （maleopimaric acid, RAM） as curing agent and imidazole type latent catalyst （two amino imidazole salt complex, IMA）, to be used as matrix for hot-melt prepreg curing at mid-temperature. For comparison, the epoxy resin system with petroleum sourced hardener methylhexahydrophthalicanhydride （MHHPA） was also examined. The curing behaviour and mechanism were investigated by non-isothermal differential scanning calorimeter （DSC） analysis and Fourier transform infrared （FTIR） spectra. The results showed that the curing course of bio-based epoxy resin system containing RAM included two stages, which were the reaction between the free carboxyl group of RAM and oxirane ring under the acceleration of IMA, and the main reaction attributed to the reaction between anhydride and oxirane. According to Kissinger method, the reaction activation energy （E,） of two stages were 68.9 and 86.5kJmo1-1, respectively. The Eo of EP/MHHPA and EP/IMA resin system were 81.04 and 77.9kJmol-I. The processing property of EP/RAM/IMA system, i.e. the relationship between viscosity-temperature-time, was characterized by cone-plate viscometer aim to decide the processing parameter ofprepreg preparation. The effect of RAM content on mechanical performance and dynamic mechanical property was investigated. Noteworthily, compared with the laminates with EP/MHHPA as matrix, the laminates with RAM as hardeners achieved a 44%, 73% and 70℃ increase in bending strength, bending modulus and the glass transition temperature, respectively, due to the bulky hydrogenated phenanthrene ring structure incorporated into the cross-linking networks. When the fiber volume fraction reached 47%, the mechanical property of the laminates prepared with hot melt prepreg was superior or comparable to that of composites with pure petroleum sourced matrix. RAM as cross-linking agent of epoxy resin holds a great potential to satisfy the requirement of composites such as structure and secondary structure parts preparation.