CORRELATION OF DIFFUSION COEFFICIENTS FOR LIQUIDS AND DENSE FLUIDS WITH TEMPERATURE AND PRESSURE

On the basis of the free volume theory and activation energy concept,a fundamental equation whichtakes into account the effects of temperature and pressure has been developed.By introducing differentexpressions for the free volume and activation energy,several equations for fluid diffusion coefficients were derivedaccordingly.With the van der Waals free volume and intermal energy formula,a three-parameter model for fluiddiffusion coeffficients at moderate pressure was obtained.The grand average absolute deviation percent of 345data points (44 systems)for self-and infinite dilute inter-diffusivities is 2.32,against the results of the model ofCohen and Turnbull,4.13.In particular,by means of the modified Carnahan-Starling free volume equation,afour-parameter model with average abosolute deviation percent 2.64(30 systems,644 data points)for theestimation of dense fluid inter-and self-diffusivities at high pressures and in supercritical conditions was derived.The derived model is superior to the method of L     

On the oxidation kinetics and mechanisms of various SiC-coated carbon-carbon composites

SiC coatings on the surface of C-C were produced by either silicone resin impregnation/ pyrolysis or reaction sintering. Cycles of resin impregnation/pyrolysis produced an SiC coating, on the walls of fine open pores, which was effective in reducing the oxidation rate of C-C and in shifting the transition temperature to a higher value. Unless it is pre-coated with a pyrocarbon layer before sintering, plain reaction sintered SiC has oxidation behaviors similar to those of the above-mentioned SiC. The dense pyrocarbon film deposition on the surface of C-C could form a better SiC film than others. The carbon film homogenized the surface of C-C and a dense SiC film was established. The oxidation of the coated C-C can be modelled by a set of “oxidation resistors” in series and/or in parallel, with each resistor corresponding to an oxidation element. The controlling mechanism can be resolved from the activation energy. A combined resistant layer, consisting of resin impregnation, pyrocarbon film and reaction sintering SiC, showed the best oxidation resistance of any single-layer coated C-C composite.     

微悬浮聚合法合成聚醋酸乙烯酯的动力学研究

采用微悬浮法合成聚醋酸乙烯酯,对其聚合反应的动力学进行了研究。考察了引发剂浓度、乳化剂浓度、单体浓度以及温度对聚合反应速率的影响。结果表明,聚合反应速率对引发剂浓度、乳化剂浓度和单体浓度的反应级数分别为0．45,0．28,1．90,单体浓度对聚合反应速率的影响最大,反应体系的表观活化能为105．96 kJ/mol。     

预处理工艺对钛合金电镀镍-磷合金的影响

采用不同工艺预处理(包括活化、活化+化学预镀镍和阳极氧化)TC4钛合金后再电镀Ni–P合金,对比了所得Ni–P合金镀层的表面粗糙度、显微硬度、微观形貌和结合力。"活化+预镀镍"预处理工艺(即砂纸打磨→除油→粗化→酸洗→活化→蒸馏水洗涤→化学预镀镍→蒸馏水洗涤)效果最好,所得Ni–P合金镀层平整、致密,厚度分布均匀,结合力好,显微硬度为625 HV,表面粗糙度为0.626μm。     

桥面不平度随机激励模型

桥面不平度是影响车辆-桥梁振动的主要因素,定量地研究桥面的凹凸不平对车辆-桥辆振动的影响程度,关键是要能够建立一个能正确模拟实际桥面状况的桥面不平度模型.指出了传统的用周期性函数表示不平度模型的缺点,引入随机不平度理念,建立了一种用路面功率谱函数表示桥面不平度的方法,并建立了桥面不平度随机激励时域模型.通过对比分析发现,建立的桥面不平度模型是可信的,从而提供了一种在缺少实测数据时如何通过计算机模拟获得桥面不平度仿真数据的方法.     

Viscosity of binary mixtures. I. mono-, di-, and tri-n-butyl and -n-octylamine with cyclohexane

Viscosities for six binary mixtures of n-butylamine, di-n-butylamine, tri-n-butylamine, n-octylamine, di-n-octylamine, and tri-n-octylamine with cyclohexane have been measured at 303.15 K with an Ubbelohde suspendedlevel viscometer. Deviations of viscosities from a rectilinear dependence on mole fraction are attributed to H-bonding and to the size of alkylamine compounds. The application of the Eyring's theory of activation energy is examined. The free volume theory of Prigogine-Flory-Patterson (PFP) and the experimental excess enthalpy have been used to estimate excess viscosity ln = (ln / ₁ ⁰ – x ₂ ln ₂ ⁰ / ₁ ⁰ ) and corresponding free volume, enthalpy, and entropy contributions for five binary mixtures of tri-n-alkylamine: triethyl, tripropyl, tributyl, trihexyl, and trioctylamine with cyclohexane. A comparison of experimental and theoretical excess viscosities indicates a failure of the PFP theory when two components of the mixture differ considerably in size. The size difference contribution to excess viscosity is related to (V ₂ ^*1/2 – V ₁ ^*1/2 ), where V ₁ ^* and V ₂ ^* are hard-core volumes of two components of the mixture.     

中子辐照SiC晶格肿胀及退火回复机理研究

为研究辐照缺陷产生及其热稳定性,对SiC晶体实施了不同通量中子辐照.利用高分辨X射线衍射和单晶X射线衍射研究了中子辐照6 H-SiC晶体的肿胀效应以及退火对肿胀的回复作用.研究结果表明,SiC晶体经中子辐照后产生的主要缺陷是点缺陷,中子辐照通量越大,SiC晶体肿胀效应越显著.在2.85×1024 n/m2辐照通量下,SiC晶体未出现非晶化.高温退火可使肿胀的SiC晶格回复,1450℃退火275 min晶胞参数回复至辐照前水平.退火过程晶胞体积回复符合一级反应方程,利用等温退火方法计算分析迁移能分布.实验发现不同缺陷迁移能分别对应不同退火温度阶段:0.16 eV对应200～500℃退火;0.24 eV对应600～1100℃退火;1.15 eV对应1200～1400℃退火.200～500℃温度区间主要是C的Frenkel缺陷复合;600～1100℃温度区间主要是Si的Frenkel缺陷复合;更高温度区间1200～1400℃则对应C、Si间隙原子复合.实验结论对全面掌握晶体测温技术、提高测温精度具有一定的指导意义.     

空间金字塔分解的深度可视化方法

针对基于深度卷积神经网络的图像分类模型的可解释性问题,通过评估模型特征空间的潜在可表示性,提出一种用于改善理解模型特征空间的可视化方法.给定任何已训练的深度卷积网络模型,所提出的方法在依据原输入图像使得模型类别得分激活最大化时,首先对反向传播的梯度进行归一化操作,然后采用带动量的随机梯度上升训练策略,反向回传修改原输入图像.引入了通过激活最大化获得的图像可解释性的正则化方法,常规正则化技术不能主动调整模型特征空间的潜在可表示性,结合现有正则化方法提出空间金字塔分解方法,利用构建多层拉普拉斯金字塔主动提升目标图像特征空间的低频分量,结合多层高斯金字塔调整其特征空间的高频分量得到较优可视化效果.通过限制可视化区域,提出利用类别显著性激活图技术加以压制上下文无关信息,可进一步改善可视化效果.对模型学习到的不同类别和卷积层中单独的神经元进行合成可视化实验,实验结果表明提出的方法在不同的深度模型和不同的可视化任务中均能取得较优的可视化效果.     

大规模体积压裂诱发的地质灾变问题研究综述

页岩储层大规模体积压裂对储层实施改造,是实现非常规油气资源工业化开发的核心技术,但目前该技术的机理研究和应用都处于起步发展阶段。大规模体积压裂可能带来潜在的地质灾害风险,主要包括淡水资源的消耗、浅水层的污染、断层活化诱发地质灾害和地表侵蚀、甲烷泄露致空气污染、植被破坏等问题。从体积压裂机理入手,研究了上述存在的地质灾变风险及灾害发生机制,并从勘探调研合理的页岩气开采区块、设计科学的钻井完井方式、压裂液注入速率方案、实时监测断层破裂带应力及滑移状态以及废水废气回收处理等角度提出对应的科学指导和防范措施,对国内页岩气顺利开展工业化开采、避免潜在的地质环境灾变对人类产生危害具有重要的指导意义。     

Theoretical Study on the C-H Activation in Decarbonylation of Acetaldehyde by NiL_2(L=SO_3CH_3) Using Density Functional Theory

Density functional theory calculations were carried out to explore the potential energy surface(PES) associated with the gas-phase reaction of Ni L2(L=SO3CH3) with acetone. The geometries and energies of the reactants, intermediates, products and transition states of the triplet ground potential energy surfaces of [Ni, O, C2, H4] were obtained at the B3LYP/6-311++G(d,p) levels in C,H,O atoms and B3LYP/ Lanl2 dz in Ni atom. It was found through our calculations that the decabonylation of acetaldehyde contains four steps including encounter complexation, C-C activation, aldehyde H-shift and nonreactive dissociation. The results revealed that C-C activation induced by Ni L2(L=SO3CH3) led to the decarbonylation of acetaldehyde.