Prediction of Experimental Methanol Decomposition Rates on Platinum from First Principles

A microkinetic model for methanol decomposition on platinum is presented. The model incorporates competitive decomposition pathways, beginning with both O–H and C–H bond scission in methanol, and uses results from density functional theory (DFT) calculations [Greeley and Mavrikakis, J. Am. Chem. Soc. 124 (2002) 7193, Greeley and Mavrikakis, J. Am. Chem. Soc. 126 (2004) 3910]. Results from reaction kinetics experiments show that the rate of H₂ production increases with increasing temperature and methanol concentration in the feed and is only nominally affected by the presence of CO or H₂ with methanol. The model, based on the values of binding energies, pre-exponential factors and activation energy barriers derived from first principles calculations, accurately predicts experimental reaction rates and orders. The model also gives insight into the most favorable reaction pathway, the rate-limiting step, the apparent activation energy, coverages, and the effects of pressure. It is found that the pathway beginning with the C–H bond scission (CH₃OH→H₂COH→HCOH→CO) is dominant compared with the path beginning with O–H bond scission. The cleavage of the first C–H bond in methanol is the rate-controlling step. The surface is highly poisoned by CO, whereas COH appears to be a spectator species.     

丙烯酸接枝线形低密度聚乙烯的热学行为及结晶形态

利用差示扫描量热仪研究了丙烯酸接枝线形低密度聚乙烯（PE-LLD-g-AA）的热学行为，结果表明，与纯线形低密度聚乙烯（PE—LLD）相比，PE-LLD-g-AA的熔融温度（Tm）略有增加，结晶温度（Tc）增加大约4℃，熔融焓（AHm）随AA含量的增加而降低。还利用差示扫描量热仪研究了PE—LLD和PE—LLD-g—AA的等温结晶动力学，用扫描电子显微镜观察了PE—LLD-g—AA等温结晶形态。结果表明，PE-LLD-g-AA的结晶速率大于纯PE—LLD的，随着接枝率的增加，PE-LLD的球晶半径减小，接枝到PE—LLD分子链上的AA分子起到了成核剂的作用。     

Sintering of Ceramic Particulate Composites: Effect of Matrix Density

Composites consisting of a fine-grained, polycrystalline zinc oxide matrix and <10 vol% coarse, rigid silicon carbide inclusions were prepared by the same mixing procedure and then compacted to produce samples with matrix densities of 0.45 and 0.68 of the theoretical. The samples were sintered under identical temperature profiles in separate experiments that employed either a constant rate of heating of 4°C/min or near isothermal heating at 735°C. The ratio of the densification rate of the composite matrix to the densification rate of the unreinforced zinc oxide was found to be independent of the initial matrix density. This ratio increased significantly with temperature in the constant-heating-rate experiments but was relatively constant in the isothermal experiments. The results indicate that microstructural coarsening may be an important mechanism for explaining the reduced sinterability of polycrystalline matrix composites.     

YS-842催化剂在Hypol工艺PP中试装置上的应用

将Ziegler-Natta高效载体催化剂YS—842在Hypol工艺聚丙烯(PP)中试装置上进行应用考核，考察了该催化剂的适应性及共聚合性能。试验表明，YS—842催化剂活性高(达1．2Mg／g)、寿命长、氢调敏感性好：用YS—842催化剂生产的聚合物流动性好，粒径分布窄，细粉少，平均粒径为640μm；等规指数大于98．5％，堆密度大于0．45g／mL；试生产的F401、J340，其机械性能与使用进口催化剂生产的产品相当。     

HDPE新牌号树脂的研究

根据扬子石化公司开发HDPE新牌号产品的生产经验,从分子量及分子量分布与树脂性能的关系、密度对HDPE性能的影响、HDPE的共聚改性、HDPE的共混改性、添加剂与HDPE改性等5个方面讨论了HDPE新牌号产品开发的方法。     

Structural material from waste plastic

In efforts to contribute to community development, particularly in the context of Egyptian communities, waste plastics materials were successfully recycled without the difficult task of separation and reused to economically produce new structural material. Recycling was performed by mixing molten waste plastics with sand to produce these new materials. Samples with different percentages of plastics and different particle sizes of sand were used in the process. Materials showed acceptable density and high compressive strength, which was shown to be at a maximum with contents of about 30–40% waste plastic. Furthermore, certain types of sand having different colors were used to produce attractive materials, suitable for decorative uses. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2543–2547, 2004     

PTA生产中浆料浓度的先进控制

在PTA生产过程中,TA浆料浓度是一个极其重要的工艺变量,该变量控制的好坏直接影响最终产品的产量和质量。首先分析了浆料浓度的特性,然后根据其特性提出了非线性补偿+预测控制的先进控制策略。实际应用表明,这一控制策略可以显著减少浆料浓度波动、提高装置处理能力。     

Mechanical properties and crosslink density of rare earth‐modified high‐abrasion furnace‐filled powdered natural rubber

High‐abrasion furnace‐filled powdered natural rubber [P(NR/HAF)] has more advantages than traditional HAF‐filled bale NR (NR/HAF) because of its better environmental performance and easier processing quality, but its lower mechanical properties are disadvantageous. To improve the mechanical properties, rare earth‐modified HAF‐filled powdered NR [P(NR/HAF‐Ln)] (Ln = Sm,La,Pr) was prepared by means of coacervation–coprecipitation, using rare earth‐modified HAF as separant and filler. The effect on mechanical properties of P(NR/HAF‐Ln) vulcanizate exerted by the emulsifier/HAF ratio, powdering temperature, Ln/HAF ratio and type of Ln, and HAF content were studied. The results indicated that when optimum formulation, the mechanical properties of P(NR/HAF‐Ln) vulcanizate were better than P(NR/HAF) vulcanizate. In addition, the relationship of the apparent crosslink density and HAF content of P(NR/HAF‐Ln), P(NR/HAF), NR/HAF vulcanizates was also investigated, along with their SEM microphotographs of tensile fracture surface, which indicated that the excellent mechanical properties of P(NR/HAF‐Ln) vulcanizate was attributed to correct amount of Ln that could increase crosslink density and reinforce the interface structure of NR matrix/HAF‐Ln particle. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1755–1762, 2006     

基于密度调整的改进自适应谱聚类算法

针对谱聚类存在构造相似度矩阵时对尺度参数敏感以及处理多重尺度数据集效果不理想的缺陷, 提出一种基于密度调整的改进自适应谱聚类算法. 该算法将样本点所处领域的密度引入谱聚类, 利用密度差来调整样本点之间的相似度, 使其更符合实际簇类中样本点间的内在关系, 在一定程度上解决了多尺度聚类问题; 同时, 通过样本点的近邻距离自适应得到尺度参数, 使算法对尺度参数相对不敏感. 仿真实验验证了所提出算法的有效性和优越性.

     

Physicochemical properties of irradiated and loaded LDPE films with polyfunctional monomers

Polyfunctional monomers (PFMs), namely, trimethylol propane trimethacrylate (TMPTMA), trimethylol propane triacrylate, ethylene glycol dimethacrylate, and diethylene glycol diacrylate were blended with low‐density polyethylene (LDPE) and exposed to different doses of EB irradiation. Fourier transform infrared and ultraviolet and UV–vis spectroscopy of the unirradiated, irradiated, unloaded, and PFMs‐loaded LDPE films were studied under various irradiation doses up to 300 kGy. The degree of crosslinking and oxidative degradation, as measured by the spectroscopic parameters, were dependent on both the irradiation dose and the type of loaded PFMs. For all of the loaded monomers, the extent of crosslinking increased at different rates as a function of irradiation dose. TMPTMA monomer was the most efficient in enhancing the crosslinking of LDPE films compared to the other loaded monomers. However, the unloaded LDPE film showed the least extent of crosslinking. In addition, the EB‐radiation‐induced changes, such as trans‐vinylene formation, a decrease in vinyl and vinylidene unsaturation; and carbonyl double‐bond formation and change in crystallinity were correlated. The importance of these results on the prediction of the role of polyfunctional monomers in the production of crosslinked polymers is discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2025–2035, 2003