Mechanism of methanol decomposition on the Pd/WC(0001) surface unveiled by first-principles calculations

In this study, the decomposition of methanol into the CO and H species on the Pd/tungsten carbide (WC)(0001) surface is systematically investigated using periodic density functional theory (DFT) calculations. The possible reaction pathways and intermediates are determined. The results reveal that saturated molecules, i.e., methanol and formaldehyde, adsorb weakly on the Pd/ WC(0001) surface. Both CO and H prefer three-fold sites, with adsorption energies of −1.51 and −2.67 eV, respectively. On the other hand, CH₃O stably binds at three-fold and bridge sites, with an adsorption energy of −2.58 eV. However, most of the other intermediates tend to adsorb to the surface with the carbon and oxygen atoms in their sp³ and hydroxyl-like configurations, respectively. Hence, the C atom of CH₂OH preferentially attaches to the top sites, CHOH and CH₂O adsorb at the bridge sites, while COH and CHO occupy the three-fold sites. The DFT calculations indicate that the rupture of the initial C–H bond promotes the decomposition of CH₃OH and CH₂OH, whereas in the case of CHOH, O–H bond scission is favored over the C–H bond rupture. Thus, the most probable methanol decomposition pathway on the Pd/WC(0001) surface is CH₃OH → CH₂OH → trans-CHOH → CHO → CO. The present study demonstrates that the synergistic effect of WC (as carrier) and Pd (as catalyst) alters the CH₃OH decomposition pathway and reduces the noble metal utilization.     

1,5-己二烯交联烯烃聚合物的合成及其抗剪切稳定性

以金属配合物为催化剂、1,5-己二烯为交联剂,采用本体聚合法合成了交联超高相对分子质量烯烃类聚合物(简称交联聚合物)。用傅里叶变换红外光谱、核磁共振、凝胶渗透色潜表征交联聚合物的结构和相对分子质量。用旋转黏度计和超声波仪研究了1,5-己二烯用量对交联聚合物溶液表观黏度的影响及交联聚合物的相对分子质量对交联聚合物溶液抗剪切稳定性的影响。实验结果表明,在最佳聚合条件(单体80mL、助催化剂0．4mL、CS-1催化剂0．090g、1,5-己二烯0．40mL、0℃、24 b)下所合成的交联聚合物的重均相对分子质量为7．7×106,数均相对分子质量3．6×106。加入少量1,5-己二烯能提高交联聚合物的抗剪切能力,同时也能提高交联聚合物的相对分子质量。交联聚合物的相对分子质量越大,抗剪切稳定性越好。1,5-己二烯用量约为0．1 mL时(单体40 mL),交联聚合物溶液的表观黏度达到最大值(16．8 mPa·s)。     

On the origin of strain hardening in glassy polymers

The influence of network density on the strain hardening behaviour of amorphous polymers is studied. The network density of polystyrene is altered by blending with poly(2,6-dimethyl-1,4-phenylene-oxide) and by cross-linking during polymerisation. The network density is derived from the rubber-plateau modulus determined by dynamic mechanical thermal analysis. Subsequently uniaxial compression tests are performed to obtain the intrinsic deformation behaviour and, in particular, the strain hardening modulus. At room temperature, the strain hardening modulus proves to be proportional to the network density, irrespective of the nature of the network, i.e. physical entanglements or chemical cross-links. With increasing temperature, the strain hardening modulus is observed to decrease. This decrease appears to be related to the influence of thermal mobility of the chains, determined by the distance to the glass-transition temperature (T−T_g).     

泥页岩井壁稳定研究及在临盘地区的应用

从岩石力学和物理化学两个主要因素简要分析了井壁失稳的机理，指出泥页岩井壁失稳是由力学与化学两方面因素共同作用的结果。钻井液与泥页岩存在化学势差，并改变了井壁附近的孔隙压力，降低岩石强度。借助于井壁处有效应力的变化,将泥页岩与钻井液相互作用时页岩水化所产生的力学效应与纯力学效应结合起来，计算出任意井斜方位井眼围岩应力状态，利用测井资料求出有关岩石力学参数和Mohr Couloumb准则，计算得出防塌的临界钻井液密度。     

红外光谱法用于快速测定车用柴油酸度等性质的研究

针对车用柴油酸度等性质测定过程繁琐，采用衰减全反射样品池测定车用柴油的红外光谱，用偏最小二乘法（PLS）建立红外光谱测定车用柴油酸度、密度、闪点和凝点的4个校正模型，验证标准误差分别为0.46 mg/(100 mL),0.77kg/m3,2.60 ℃,2.77 ℃，该方法符合标准方法再现性要求。与标准方法相比，该方法具有无需预处理、操作简单、测量快速、重复性好等优点。     

凝胶渗透色谱法测定基础油PAO的相对分子质量及分布

聚α-烯烃是一种性能优良的润滑油基础油，其相对分子质量及分布直接影响宏观性能。本研究建立了一种用于表征1-癸烯齐聚物相对分子质量及分布的方法。采用带示差折光检测器的凝胶渗透色谱系统，综合考虑分离效果和测试可操作性，优化了流动相流速和凝胶色谱柱的组合方式。以四氢呋喃为流动相，流速为0.8 mL/min，色谱柱组合方式为Styragel HR 0.5,Styragel HR 1,PLGEL 3μm MIXED-E三柱串联，以聚苯乙烯作为标准样品，采用普适校正方法处理色谱流出曲线。此方法测得样品的质均相对分子质量与凝胶渗透色谱-光散射法所测定结果相比较，相对误差相对偏差在3%以内。     

低阻VDMOSFET的优化设计与制造

文章对9926型双N沟增强型VDMOSFET进行了结构和版图的优化设计。给出了该器件的纵横向结构参数,材料的物理参数和版图总体结构。单胞结构的优化设计使单胞密度达到204万个/cm2,比国际市场现有产品的单胞密度(156万个/cm2)提高了30%。这种设计采用浅n+注入工艺可使器件生产成本下降31%。最后对研制结果进行了分析讨论。     

RI/VI联用测定聚乙烯相对分子质量及其分布

150℃测试温度下，以1，2，4-三氯苯为溶剂，采用示差折光指数器，毛细管黏度计双检测器联用凝胶渗透色谱技术测定了聚乙烯的相对分子质量及其分布。与常规凝胶渗透色谱法对比，该方法不仅能直接得到聚乙烯较精确的相对分子质量和分布形态，同时可以得到聚乙烯的特性黏数分布。     

Simultaneous Measurement of Viscosity and Density with an Oscillating-Disk Instrument: The Effect of Fixed Plates

The period and damping of the free motion of a body oscillating in a fluid depend on the fluid's viscosity and density. Commonly, a working equation which expresses the damping as a function of the viscosity and density is solved for the viscosity, the damping being measured and the density being treated as an independently supplied parameter. Another working equation exists for the period, and, in general, the period depends on a combination of the viscosity and the density which is linearly independent of the combination that appears in the damping equation. It is, therefore, in principle, possible to determine both the viscosity and the density by a simultaneous solution of the two coupled working equations, since the period also is measured. In this paper, the working equations that describe the oscillating-disk viscometer are reviewed and their simultaneous solution is considered. The effect of fixed plates symmetrically located above and below the oscillating disk is of specific interest. The paper's main result is that fixed plates can dramatically increase the independence of the damping and period working equations, so that it becomes indeed feasible to determine the viscosity and the density of a fluid simultaneously from the damping and period of oscillating motion. A price is paid, however, because the instrument's working equations when plates are present have multiple solutions. Under special conditions, these multiple solutions can coalesce, and then one can only deduce the viscosity from the damping equation if the density is known a priori.     

电磁发射兵器用电容器的选取

本文首先从理论上论述了膜电容器的储能密度与寿命之间的关系，对国际电容器制造水平和趋势进行了分析，提出采用干式金属化膜电容器作为储能元件。最后，根据电磁发射兵器整体寿命配合原则，提出高储能密度脉冲电容器的合理寿命指标。