页岩气中CH4-C2H6吸附-扩散分子动力学研究

本文采用巨正则蒙特卡洛(GCMC)和分子动力学(MD)模拟方法,对比分析了不同温度、压力和孔径对二元气体(CH4-C2H6)在K-伊利石中的吸附-扩散的影响.结果表明,在低压条件下,K-伊利石对C2H6的吸附能力大于CH4, C2H6优先吸附在K-伊利石孔隙表面.热力学因子随着孔径的增加而减小,C2H6的热力学因子大于...     

退火处理对磁控溅射制备LaCoO_3薄膜性能的影响

采用磁控溅射法在硅衬底上制备了LaCoO_3(LCO)薄膜,研究了退火温度对LCO薄膜组织结构、表面形貌及热电特性的影响,并利用X射线衍射仪、原子力显微镜(AFM)、激光导热仪等对LCO薄膜的晶体结构、表面形貌、热扩散系数等进行测量与表征.结果表明:退火温度对LCO薄膜的结晶度、晶粒尺寸和薄膜表面形貌都有较大影响;退火前后LCO薄膜的热扩散系数都随温度的升高而减小,且变化速率逐渐减缓; LCO薄膜的热扩散系数随退化温度的升高先增大后减小.LCO薄膜经过700℃退火后得到最佳的综合性能,其薄膜表面致密、平整,结晶质量最好,热扩散系数最小,热电性能最好.     

在NaCl和HTAB共存条件下甲基纤维素溶液凝胶化行为

利用流变仪研究了甲基纤维素(MC)溶液在NaCl、十六烷基三甲基溴化铵(HTAB)以及两者共存下MC溶液的凝胶化行为,发现其凝胶化温度随着NaCl浓度的增加而下降,随着HTAB浓度的增加而上升;但是MC/NaCl的凝胶化温度保持不变,与HTAB浓度 无关,而MC/HTAB溶液的凝胶化温度则随着NaCl浓度的增加而下降．以上的实验结果表明,在NaCl存在下,HTAB将被诱导形成胶束,因此MC/NaCl的凝胶化温度保持不变;反之,当NaCl不存在时,HTAB将优先吸附到MC上而不会在溶液中形成胶束,尽管其浓度     

异质原子对液体气泡成核影响的分子动力学模拟

采用分子动力学方法模拟了池沸腾中液体层加入异质原子对气泡成核的影响.分析了异质原子能量参数对液体起始气泡成核时间和温度的影响及其机理.结果表明,当异质原子能量参数小于液氩能量参数时,液体起始气泡成核时间缩短,起始温度降低.当异质原子剂能量参数大于液氩能量参数时,液体起始气泡成核时间增加,起始温度升高.异质原子在壁面上的吸附及在液体中的扩散行为影响固液界面性质,较大能量参数的异质原子扩散系数较小,更多能量参数较大的原子吸附在固体表面上使得壁面势能壁垒增加,导致沸腾时间延迟,液体需要吸收更多的热量克服势能壁垒,进而提高沸腾起始温度.能量参数较小的异质原子扩散系数较大,异质原子更容易分散到液体中,使得壁面附近液体层势能减小,液体层更容易气泡成核行为.     

纳米MgO掺杂聚乙烯微观特性的分子动力学模拟研究

电力系统高压电缆的主要绝缘材料为聚乙烯,为了提升聚乙烯的热稳定性以及减弱水分对其的渗透能力,采用纳米MgO掺杂聚乙烯,利用分子动力学模拟方法建立包含低密度聚乙烯(LDPE)、不同颗粒半径的MgO纳米团簇以及相同质量分数水分的复合模拟模型.研究结果表明,水分会降低复合体系的玻璃化温度,MgO的掺杂则会提高复合体系的玻璃化温度,减弱聚乙烯分子链的运动并减小复合体系的自由体积,使得复合体系结构更加稳定,从而增强了聚乙烯材料的热稳定性能.此外发现水分子的扩散随着温度的上升而增大,纳米MgO的添加会与水分子形成氢键抑制水分子的扩散,同时自由体积的缩减使水分子的溶解度系数与扩散系数都减小,导致水分子的渗透能力减弱,更难以渗透进聚乙烯材料破坏其结构.研究结果可为聚乙烯的水树枝生长以及老化过程的抑制提供有益的参考.     

Study on the deterioration process of a chromium-free conversion coating on AZ91D magnesium alloy in NaCl solution

The morphology of a chromium-free conversion coating for AZ91D magnesium alloy was observed with an Atomic Force Microscopy. The results showed the uniform conversion coating has a relatively smooth appearance with shallow valleys. The EDX results indicated that the compositions of the coating were mainly compounds of Mg, Al, Mn, P, Ca and O. The XRD result showed that the coating contained amorphous materials and a small quantity of crystalline compound. The pitting product of the coating in NaCl water solution mainly composed of Mg, Cl, Mn, P, Ca and O. The corrosion behavior of the samples in NaCl solution was also studied by electrochemical impedance spectroscopy (EIS), which was characterized by one capacitive loop and one inductive loop. Based upon study on both a mathematical model for Faradic admittance of coating in NaCl solution and EIS, it could be considered that the inductive loop was caused by the adsorption of Cl anion and the appearance of pitting corrosion. A degradation mechanism of the coating in NaCl solution is set forth: dissolution velocity of the Cl⁻ adsorption regions of the coating is higher than those non-adsorption regions, for Cl⁻ anions are selective adsorption at some regions of coating surface. When the adsorption regions of coating layer are penetrated by dissolution, the pitting comes into being. The degradation mechanism of conversion coating and the mathematical model are consistent with the EIS results, polarization measurement results and coating's corrosion test results.     

离子浓度及表面结构对岩石孔隙内水流动特性的影响

酸性环境引发的岩石孔隙表面溶解增加了孔隙内水溶液的盐离子浓度,破坏了孔隙的表面结构.本文采用分子动力学模拟的方法研究了纳米级岩石孔隙内水溶液的流动特性,分析了盐离子浓度和孔隙表面结构对水流速度分布的影响及原因.研究结果表明:纳米级岩石孔隙内的水溶液流动符合泊肃叶流动特性,流速呈"抛物线"分布;随盐离子浓度增加,水溶液内部氢键网络变得更为致密,水黏度随其呈线性增长;水溶液中离子浓度越大,孔隙表面对水流动的阻力越大,最大流速越小,速度分布的"抛物线"曲率半径越大;岩石孔隙表面结构的破坏改变了流动表面的粗糙程度,增加了孔隙表面对H2O分子的吸引力.随表面结构破坏程度的增大,水溶液在近壁区域的密度增大,流速降低;当表面破坏程度达到50%时,水溶液在近壁区域出现了明显的负边界滑移现象.     

析晶与颗粒混合污垢的实验研究

在实验室实验研究了CaCO3和Al2O3或MgO混合污垢特性,考察了颗粒浓度、工质流速和水浴温度的影响。结果表明:混合污垢热阻值比纯粹的析晶污垢的污垢热阻值大,流速增大,其污垢热阻渐近值减小,颗粒浓度增大,混合污垢渐近值增大,但当浓度达到某一值后再增加时,混合污垢渐近值基本维持常数,水浴温度在实验范围内变化对结垢影响不大。     

Properties of aqueous NaCl solutions in external electromagnetic fields

Molecular dynamics simulations are performed to investigate the effects of an external electromagnetic field on aqueous NaCl electrolyte solutions at a temperature of 298 K. The simulations assume that the electromagnetic waves propagate in the x-axis direction with a frequency of 50, 100 or 200 GHz. The intensity of the electromagnetic field is assumed to vary in the range 0.1–0.3 V/Å. The simulations are conducted for two different NaCl solution concentrations, namely 1 m and 5 m (molality). The results indicate that as the intensity of the electromagnetic field is increased, the re-orientation of the water molecules becomes more pronounced and the diffusion coefficient of the aqueous NaCl solution increases. It is also shown that in both the low-concentration and high-concentration solutions, the diffusion coefficients of water molecules and ions increase as the frequency and intensity of the electromagnetic field increase.     

氚在锆合金包壳材料中的扩散行为模拟

基于氚扩散基本模型建立了氚扩散行为一维模拟程序,对模拟程序进行了典型实验验证,模拟结果与实验结果符合较好。分析了不同氚浓度、温度分布对锆合金包壳材料中氚的扩散行为的影响。分析结果表明:包壳-芯块间隙内氚浓度的升高会导致进出包壳的氚扩散通量提高,渗透通量增大;由于包壳氧化层相对较低的扩散系数,包壳氧化层的存在对氚渗透有较大的限制作用;温度对氚扩散速率的影响很显著,温度越高,扩散速度越快;锆合金外表面氧化层的相对低温限制了氚渗透出包壳管的速率,温度梯度导致的热致扩散有利于氚向包壳冷测扩散。     

Effect of molecular weight on the ultrasonic degradation of poly(vinyl-pyrrolidone)

The ultrasonic degradation of poly(vinyl-pyrrolidone) (PVP) of different initial molecular weights was studied at a fixed temperature. The effect of solution concentration on the rate of degradation was investigated. A method of viscometry was used to study the degradation behavior and kinetic model was developed to estimate the degradation rate constant. The results were indicated that the rate of ultrasonic degradation increased with increasing molecular weight. It was found that rate constant decreases as the concentration increases. The calculated rate constants correlated in terms of inverse concentration and relative viscosity of PVP solutions. This behavior in the rate of degradation was interpreted in terms of viscosity and concentration of polymer solution. With increasing solution concentration, viscosity increases and it causes a reduction in the cavitation efficiency thus, the rate of degradation will be decreased. The experimental results show that the viscosity of polymers decreased with ultrasonic irradiation time and approached a limiting value, below which no further degradation took place. This study confirms the general assumption that the shear forces generated by the rapid motion of the solvent following cavitational collapse are responsible for the breakage of the chemical bonds within the polymer. The effect of polymer concentration can be interpreted in terms of the increase in viscosity with concentration, causing the molecules to become less mobile in solution and the velocity gradients around the collapsing bubbles to, therefore, become smaller.     

高压热处理对铝青铜热物理性能的影响

在5 GPa压力下对铝青铜进行750℃、保温15 min的高压热处理,对高压热处理前后铝青铜的电导率以及25～600℃温度范围内的热扩散系数、热容和热导率进行测试,结合显微组织的观察结果,探讨了高压热处理对铝青铜热物理性能的影响。研究表明:高压热处理能增大铝青铜的热扩散系数,减小热容;对热导率而言,温度低于400℃时高压热处理能增大铝青铜的热导率,而温度高于400℃时高压热处理能减小铝青铜的热导率。分析认为,产生变化的主要原因是高压热处理使铝青铜的微观组织发生了变化。     

MgO（001）表面上沉积MgO薄膜过程的分子动力学模拟

采用分子动力学方法模拟了MgO分子连续沉积于MgO（001）表面上的薄膜生长过程,分析了衬底温度和分子入射能对MgO分子在衬底表面上的扩散能力以及对衬底表面覆盖率的影响.模拟结果表明,随着衬底温度的升高,在衬底表面上沉积的MgO分子扩散能力增强,MgO薄膜层中空位缺陷变少.低温下,分子入射能的增大有助于提高衬底表面覆盖率;高温下,表面覆盖率随入射能增大到3.0 eV时达到最大值,入射能继续增大,表面覆盖率减小. 关键词： MgO薄膜生长 分子动力学 计算机模拟 表面扩散     

紫外光谱法研究黄药在黄铜矿表面的吸附热力学与动力学

在紫外吸收光谱范围内对黄药溶液进行扫描,发现在波长226.5和300 nm处有两个明显吸收峰,且300 nm处的吸收峰强于226.5 nm处的。采用标准曲线法对不同浓度的标准样品进行浓度测量,对所得数据进行线性拟合,结果表明：在波长226.5和300 nm处的线性相关性均较好,但在波长300 nm处的相关性更佳,在226.5 nm处进行高浓度黄药溶液测量,可在300 nm处进行低浓度黄药溶液测量。在300 nm下对不同浓度黄药溶液进行定量分析,结果表明,最大吸光度为1.672,最小吸光度为0.032时,黄药溶液标准曲线的线性相关性仍很好,吸光度继续增大时,相关系数降低,在进行定量分析时,黄药浓度最好不要超过20 mg·L-1。在不同pH条件下,在300 nm处对黄药溶液进行浓度测量,发现pH为3时,吸光度下降,黄药开始分解,当溶液pH为2时,所测吸光度为0,黄药已完全分解,pH值在5~10范围内,黄铜矿对黄药吸附较好,溶液最佳吸附pH值为9。在300 nm处测量黄药在黄铜矿表面吸附量,分别采用Freundlich和Langmuir等温吸附模型方程、准一级和准二级动力学方程模型对所得实验数据进行拟合,研究其在黄铜矿表面的吸附动力学和热力学。结果表明：在288～303 K范围内,温度变化对吸附量多少影响不大,黄药在黄铜矿表面的吸附等温线更符合Langmuir等温线模型,黄铜矿对黄药的实际平衡吸附量Q_e均小于或接近理论单层饱和吸附量,Q_m值均与实验值极为接近,说明黄药在黄铜矿表面的吸附以单层化学吸附为主。随着温度升高,吸附量增加,说明升高温度有利于吸附过程进行,黄铜矿对黄药的吸附为吸热过程,但吸附量增加幅度很小,说明黄药在黄铜矿表面吸附受温度影响较小。该吸附过程是一个熵增、吸热、自发进行的过程,热力学参数可通过范特霍夫方程计算得到,吸附焓变ΔH为48.703 41 kJ·mol-1,熵变ΔS为219.403 88 J·(mol·K)-1,吸附自由能变ΔG为-16.054 93 kJ·mol-1,推测该吸附过程属于化学吸附;黄铜矿对黄药的吸附更符合准二级动力学方程模型,Q_t值随着温度升高而增大,且变化幅度很小,表明黄药在黄铜矿表的吸附过程为吸热过程,但受温度变化较小,这与热力学分析的结论一致,对方程拟合所得Q_e值均与实验值极为接近。     

液体表面张力系数、声波在液体中传播速度与液体浓度关系的研究

通过实验的手段研究了氯化钠与蔗糖溶液的表面张力系数及声波在其中的传播速度与浓度关系,发现随着浓度的增加,表面张力系数与液体中的声波传播速度近似于线性变化。然而,两种液体中两个物理量的变化快慢不同,氯化钠溶液明显比蔗糖溶液变化快;从分子动理论角度,对此现象作了圆满的解释,说明两个物理量之间有着较密切的关联,也研究了温度变化时,两个物理量的变化情况。     

Single-phase model of recrystallization of molybdenum activated by diffusion of nickel impurities

A new model of the activated recrystallization of molybdenum under the diffusion action of a nickel coating is proposed. In the context of this model, dependences of the thickness of the recrystallized layer and of the velocity of motion of the recrystallization front on the annealing time have been derived analytically. It has been revealed that an increase in nickel concentration on the surface increases, whereas an increase in average size of recrystallized grains decreases the recrystallization velocity in molybdenum. A temperature dependence of the thickness of the recrystallized molybdenum layer has also been derived. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 50–55, November, 2007.     

超临界CO2-丙烷混合物管内传热特性数值研究

采用SST k-w湍流模型对超临界CO₂/丙烷混合工质水平管内的传热特性进行数值模拟研究。管径d=4 mm,加热段L₂=800 mm;混合工质浓度配比为100/0、95/5、90/10、85/15、80/20、75/25;质量流速为150～250 kg·m^?2·s^?1;热流密度为30～40 kW·m^?2,入口温度293 K,入口压力7.5～30 MPa。随着丙烷浓度的增加,CO₂/丙烷二元混合工质的临界压力降低,临界温度升高,丙烷浓度从5%增加到25%,换热系数峰值降低6.19%～31.45%,但增加丙烷浓度可提高拟临界温度后的换热效果。P=7.5～8.5 MPa,换热系数有明显峰值;P=20～30 MPa,换热系数变化规律无明显峰值,并随压力的升高而减小。混合工质的换热系数随质量流速的增大而增大。同一流体温度所对应的换热系数,随着热流密度的增加而减小。     

考虑介质膨胀速率的锂离子电池管状电极中扩散诱导应力及轴向支反力分析

硅作为锂离子电池阴极材料相对于传统负极材料具有高比容量,价格低廉等优势.本文针对充电过程中锂离子电池中电极建立力学模型和扩散模型,并在扩散模型引入考虑介质膨胀速率的影响.以硅空心柱形电极为例,分析了恒流充电下介质膨胀速率对电极中扩散诱导应力分布的影响,并研究了不同内外半径比、充电速率、材料参数以及锂化诱导软化系数(lithiation induced softening factor,LISF)对轴向的支反力达到临界欧拉屈曲力所需时间的影响.结果表明,随着电极中锂浓度上升,介质膨胀速率对应力分布的影响增大,对轴向的支反力影响较小.弹性模量和应力成正比,但其与轴向的支反力达到临界欧拉屈曲力所需时间无关;扩散系数与所需时间成反比;偏摩尔体积增大时,达到临界屈曲力所需时间减少;随着LISF绝对值增大,完全锂化时轴向力降低.     

超临界CO2-丙烷混合物管内传热特性数值研究

采用SST k-w湍流模型对超临界CO₂/丙烷混合工质水平管内的传热特性进行数值模拟研究。管径d=4 mm,加热段L₂=800 mm;混合工质浓度配比为100/0、95/5、90/10、85/15、80/20、75/25;质量流速为150～250 kg·m^?2·s^?1;热流密度为30～40 kW·m^?2,入口温度293 K,入口压力7.5～30 MPa。随着丙烷浓度的增加,CO₂/丙烷二元混合工质的临界压力降低,临界温度升高,丙烷浓度从5%增加到25%,换热系数峰值降低6.19%～31.45%,但增加丙烷浓度可提高拟临界温度后的换热效果。P=7.5～8.5 MPa,换热系数有明显峰值;P=20～30 MPa,换热系数变化规律无明显峰值,并随压力的升高而减小。混合工质的换热系数随质量流速的增大而增大。同一流体温度所对应的换热系数,随着热流密度的增加而减小。     

Study on Hydrate Production Behaviors by Depressurization Combined with Brine Injection in the Excess-Water Hydrate Reservoir

Depressurization combined with brine injection is a potential method for field production of natural gas hydrate, which can significantly improve production efficiency and avoid secondary formation of hydrate. In this work, the experiments of hydrate production using depressurization combined with brine injection from a simulated excess-water hydrate reservoir were performed, and the effects of NaCl concentration on hydrate decomposition, temperature change, and heat transfer in the reservoir were investigated. The experimental results indicate that there is little gas production during depressurization in a excess-water hydrate reservoir, and the gas dissociated from hydrate is trapped in pores of sediments. The high-water production reduces the final gas recovery, which is lower than 70% in the experiments. The increasing NaCl concentration only effectively promotes gas production rate in the early stage. The final cumulative gas production and average gas production rate have little difference in different experiments. The NaCl concentration of the produced water is significantly higher than that which is in contact with hydrate in the sediments because the water produced by hydrate decomposition exists on the surface of undissociated hydrate. The high concentration of NaCl in the produced water from the reactor significantly reduces the promoting effect and efficiency of NaCl solution on hydrate decomposition. The injection of NaCl solution decreases the lowest temperature in sediments during hydrate production, and increases the sensible heat and heat transfer from environment for hydrate decomposition. The changes of temperature and resistance effectively reflect the distribution of the injected NaCl solution in the hydrate reservoir.