Structural development in cycloolefin copolymers under uniaxial elongational flow

Development of structures in new cycloolefin copolymers (COCs) of ethylene–norbornene (E–NB) and ethylene–tetracyclododecene (E–TD) of different NB/TD compositions were investigated under uniaxial elongational flow. For E–NB copolymer, which has multiblock sequences, a shoulder in WAXD at 0.76 nm was evident besides its amorphous halo, and the relative intensity of the peak increased with increasing comonomer content (NB). The appearance of a new peak for E–TD copolymer, and a relatively higher intense peak for E–NB copolymer at the same position of 0.76 nm, indicated that local ordering of the segments occurred when the COC was subjected to uniaxial flow. A lower comonomer composition of elongated COC, at a constant Hencky strain rate, exhibited two T_g values, whereas a higher composition showed a single T_g. Both local ordering and segmentization occurred in low comonomer content COCs but only local ordering occurred in higher comonomer content COCs. Both the shear viscosity and roll processing experiments exhibited similar phenomena of segregation. A model is proposed to illustrate the structure of COC after uniaxial elongation/deformation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3421–3427, 2004     

金属离子掺杂二氧化钛及水体光催化脱氮研究

采用溶胶-凝胶法制备了掺杂Ce^3＋、La^3＋、Ag^＋、Fe^3＋的TiO2光催化剂，以考察其薄膜和粉体形式对水中无机氮的光催化去除效果和活性．用所制备的催化剂对含氨氮-亚硝酸氮的混合液进行了光催化脱氮研究．本文利用UV—Vis吸收光谱、XRD和TEM对催化剂进行了表征．同时，对影响TiO2光催化效率的因素：如掺杂金属离子的种类、浓度、涂膜层数、反应液中有无Fe^2＋、不锈钢和玻璃载体、反应器的构型等进行了探讨，并对今后的研究进行展望．经过2h紫外光照射反应，实验最佳脱氮效果：金属离子掺杂TiO2薄膜型催化剂总氮去除率在30％左右，金属离子掺杂粉末型催化剂光催化最高总氮去除率可达41．7％．     

Influence of compaction on the interfacial transition zone and the permeability of concrete

The interfacial transition zone (ITZ) is regarded as a key feature for the transport properties and the durability of concrete. In this study one self-compacting concrete (SCC) mixture and two conventionally vibrated concrete (CVC) mixtures are studied in order to determine the influence of compaction on the porosity of the ITZ. Additionally oxygen permeability and water conductivity were measured in vertical and horizontal direction. The quantitative analysis of images made with an optical microscope and an environmental scanning electron microscope shows a significantly increased porosity and width of the ITZ in CVC compared to SCC. At the same time oxygen permeability and water conductivity of CVC are increased in comparison to SCC. Moreover, considerable differences in the porosity of the lower, lateral and upper ITZ are observed in both types of concrete. The anisotropic distribution of pores in the ITZ does not necessarily cause anisotropy in oxygen permeability and water conductivity though.     

Dynamics in input and output coefficients for land use studies: a case study for nitrogen in crop rotations

Increasingly, model-based approaches play a role in the design and development of new land use systems. Simulation modeling may play a role in the generation of land use systems for land units, and optimization modeling (e.g. linear programming – LP) may be used in the upscaling to farm and region. In the quantification of new land use systems for land units, often equilibrium conditions with respect to soil resources are assumed, following a so-called target-oriented approach. This facilitates ex ante computation of inputs and emissions of nutrients and allows their use in static optimization models based on LP. The condition of equilibrium in soil resources is often not met, nor is it the ultimate aim. Hence, the dynamics in new systems are insufficiently dealt with. This paper presents an approach for the design of land use systems (crop rotations) and their quantification in terms of input and output coefficients, using particular yields and dynamics in soil resources as targets. Interactions between N input and output of succeeding crops are explicitly taken into account. A simple N-balance model is used describing major processes affecting soil N-dynamics. For the Koutiala region in Mali five crop rotations are evaluated that differ in target crop yield, crop choice, crop residue management and external N source. Modeled crop rotations aiming at high yields, in combination with incorporation of crop residues and legumes, result in depletion of soil N stock. Only in crop rotations aiming at high yields and with incorporation of crop residues combined with a supply of large quantities of animal manure, soil N depletion can be prevented. Four approaches are presented of how to use the dynamic input–output coefficients of these systems in land use studies using LP: (i) use of average coefficients, (ii) use of discounted coefficients, (iii) use of pessimistic estimates of coefficients in an optimization of the land use allocation followed by a recalculation of the objective values for the optimized land use with optimistic coefficients, and (iv) a combined use of systems characteristics, i.e. cumulative N-inputs of land use systems over the time horizon and the magnitude of the soil N pool at the end of the time horizon, which can be used as filters for land use systems. Though none of the approaches completely captures the dynamics in input–output coefficients, they enable a well-founded consideration of the consequences of dynamics in, for instance, soil N stocks in static optimization approaches for farm and regional studies.     

Synthesis and characterization of novel polyesterimides

A series of soluble novel polyesterimides was synthesized from diamines [a mixture of 2,2‐bis(4‐(4‐aminophenoxy)phenyl)propane (BAPP) with amine‐terminated polysiloxane (ATPS) in various mole ratios] and the ester‐group‐containing dianhydrides. The ester group containing dianhydrides in turn was synthesized by the transesterification reaction of trimellitic anhydride (TMA) with diacetate ester of hydroquinone (HQ), 4,4′‐dihydrophenyl (BP), 1,6‐hexanediol, or ethylene glycol. The resulted polyesterimides were characterized by using Fourier‐transform infrared spectroscopy, inherent viscosity, solubility, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The polyesterimides of BP and HQ had relatively high glass transition temperatures in the range of 214.7–227.2 and 195.7–210.5°C, respectively. The glass transitions decreased rather slowly with the increase in polysiloxane content. Thermal stability and the weight‐loss behavior of polyesterimides were studied by TGA. All polyesterimides of BP and HQ (BPI and HQI) showed no significant weight loss below 500°C in a N₂ environment, and the decomposition temperatures (T_d5%) of BPI and HQI were >520°C. Most polyesterimides were soluble in polar aprotic solvents and m‐cresol. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 730–738, 2004     

地层主曲率在研究储层裂缝发育中的应用

曲面曲率的几何意义可以反映曲面一点邻近区域的具体形态和变形特征,因而可以用主曲率法来评价和预测油气储层裂缝分布和发育程度,应用这种方法对泌阳深凹陷中心安棚鼻状构造带进行了评价。研究结果表明,采用主曲率法预测的结果与地质解释、钻井和测井资料吻合较好,具有很好的应用前景。     

Bi2—xPbxSr2Ca2Cu3Oy系高Tc超导体相变的研究

用DSC研究了高T_e超导体B_(2-r)Pb_rSr_2Ca_2Cu_sO_v(x=0,0.2,0.4,0.6)从室温至600℃范围内的相变。在320℃和440℃附近有二个吸热蜂,每一个峰对应一个相变过程。440℃附近的相变是不可递的,其原子激活能为1.37eV,是由高T_e相向低T_e相的转变。而320℃附近的相变则与超结构的形成有关。     

纤维素衍生物液晶相转变和织态结构

本文综述了纤维素衍生物液晶态相转变和织态结构。描述了纤维素衍生物从各向同性态向液晶态的转变过程和液晶态的织构特征。讨论了溶液浓度和温度对液晶相织构的影响。探讨了各种因素,如溶剂、取代基含量、外加力场和外加磁场等对液晶相的形成及织态结构的影响。     

Mechanisms of hydrocarbon conversion reactions on heterogeneous catalysts: analogies with organometallic chemistry

Catalysis is central to most industrial processes for chemical manufacturing. As catalytic processes have become more complex and more demanding, selectivity has become the central issue in their design. Selectivity is defined by the relative rates of competing reaction pathways available to crucial intermediates, and can be controlled by subtle changes in the nature of the catalyst, the reactants, and/or the reaction conditions. In order to be able to do this in a systematic manner, a good understanding of the catalytic reaction mechanisms is needed. Here a connection is drawn between the key elementary steps comprising hydrocarbon conversion reactions on surfaces and those known to occur on discrete organometallic complexes. This way, the hydrogenation, dehydrogenation, hydrogenolysis, chain growth, and isomerization reactions typical in heterogeneous catalysis are redefined in terms of hydride elimination, oxidative addition, reductive elimination, migratory insertion, and 1, 2-shift elementary steps, among others. It is suggested that the knowledge already available from organometallic chemistry can be used to further advance the understanding of the surface science involved in heterogeneous catalysis. Thanks to the commonality of the chemistry involved, a better synergy could also be established between homogeneous and heterogeneous catalytic development. These ideas are discussed in this article in a critical and personal way.*Invited contribution to the special volume entitled The Interface between Heterogeneous and Homogeneous Catalysis, stemming from contributions at the recent International Symposium on Relations between Heterogeneous and Homogeneous Catalysis, and dedicated to the memory of Robert L. Burwell.