燃料电池阴极扩散层扩散特性研究

本文采用粗粒化分子动力学方法研究了燃料电池阴极扩散层的扩散特性。采用全原子方法的计算结果校验了粗粒化方法的准确性,并提出了一种定量校正方案。分析了碳纳米管气体扩散层中气体和水的扩散特性,其中气体和水的扩散存在各向异性,气体和水两者在碳纳米管中轴向的扩散系数均较低,且气体和水的轴向扩散系数也随着该分子比例的降低而进一步降低;对带缺陷气体扩散层的研究表明气体扩散层中缺陷的形态对其扩散性能有显著的影响。     

氢及其同位素在聚苯乙烯与Cu界面的扩散

为了探索气体在固体表面高分子链中的扩散,使用分子动力学（MD）的方法,对H2,D2,T2在聚苯乙烯与金属铜（PS-Cu）界面的扩散进行了计算模拟,通过所得到气体的均方位移计算了气体在不同金属表面与聚苯乙烯界面中的扩散系数。结果显示:气体在界面的扩散系数比在聚苯乙烯本体中的扩散系数小,气体在PS-Cu(110)界面的扩散系数最大,在PS-Cu(111)界面的扩散系数最小。计算和分析了PS与金属表面的相互作用,发现其相互作用能越大,气体在此界面的扩散系数越小。同时,金属表面的晶面密度对气体在界面中的扩散也有一定的影响。     

多组分气体在多孔介质中扩散过程的数值模拟

通过对已有的多组分气体在多孔介质中的扩散模型与实验结果对比,发现尘气模型(DGM)与实验结果吻合较好,并利用该模型对CH_4/O_2/N_2三元混合气体在不同孔径的多孔介质内扩散过程进行了数值模拟,分析了扩散与对流两种机理在有/无压差下对扩散通量的影响,对比分析了干燥和含水非饱和多孔介质中的扩散过程.结果表明在无压差的扩散过程中也存在对流;气体的扩散速度随孔径的减小先增大后减小;含水非饱和多孔介质中扩散速度减弱。     

EPT／BIIR橡胶密封材料制备及其性能

为了探索具备低水蒸气透过系数、低透气系数、低压缩永久变形以及良好耐老化性能的新型橡胶密封材料，鉴于影响并用胶性能的主要因素是共混相容性以及硫化速度，从实现并用胶优势互补角度出发，优选综合性能较好的三元乙丙橡胶（EPT）和溴化丁基橡胶（BIIR），开展了EPT／BIIR共混共硫化技术研究，并开展了DBPMH／HVA-2过氧化物硫化体系在EPT／BIIR并用胶中的应用研究。     

分子动力学模拟玻璃微球充气保气性能的机理

为了探讨载能重粒子辐照改善惯性约束聚变中所用玻璃微球的充气性能,以及热弛豫过程中改善其保气性能的微观机制,利用分子动力学的方法对载能重粒子辐照前后的SiO₂玻璃在内部形成气体扩散微通道的机理进行了模拟研究。结果表明,重粒子辐照可以在SiO₂玻璃中形成明显的扩散通道,说明辐照后的玻璃更适合通入Ar等较大尺寸气体;在高温高压的条件下,形成的扩散通道有逐渐关闭的趋势,辐照产生的缺陷能够在一定程度上得到修复。因此,利用重粒子辐照的方法,可在玻璃体中产生充气的微通道,该通道在高温高压下可实现关闭,从而起到开关的作用。模拟结果可为实验上通过重粒子辐照提升微球玻璃充气保气性能的方法提供理论支持,说明该方法具有可行性。     

电厂烟羽中SO2柱浓度的紫外非色散二维成像

鉴于近年来突发事故和雾霾等污染现象时有发生,其危害范围广、危害程度深,因此迫切需要掌握污染影响的区域、范围、强度以及污染扩散的趋势。而污染源、污染气体的二维快速成像分布在确定气体泄漏源定位、鉴别突发事件以及鉴定污染范围和污染影响的过程中占绝对优势。基于面阵CCD探测器,利用紫外滤光片分光的成像技术实现了对丰台电厂烟囱排放的烟羽进行快速成像测量;采用烟气在线监测技术获取的SO2实时浓度作为参考浓度,经转换之后标定成像系统,标定结果表明SO2斜柱浓度与光学厚度呈线性关系,相关系数0.958,满足成像理论可被解析的先决条件;考虑到成像系统视场角小,使镜头在上风向偏离烟羽区域拍摄的图片作为背景,任取背景图上的一行像素,这些像素的光学强度表明上风向强度均匀,无其他干扰影响;测量过程中,为了减小烟羽变化带来的误差,鉴别目标气体的310 nm滤光片与祛除气溶胶影响的330 nm滤光片对烟羽交替成像;最后根据线性最小二乘拟合获取了2017年5月20日12点30分左右的SO2斜柱浓度的二维分布及其时序图。测量结果显示在烟囱出口附近出现SO2斜柱浓度高值,SO2斜柱浓度高值约为1.7×1017 molec·cm^-2;SO2斜柱浓度分布图直观显示SO2浓度的扩散趋势,表明下风向SO2斜柱浓度沿着烟羽的扩散轴减小缓慢,在大气浮力、烟羽流体动力学以及风向共同作用下,垂直于烟羽扩散轴的方向上,扩散轴上方的SO2斜柱浓度小于其下方浓度,但基本趋势是垂直于扩散轴的两侧SO2斜柱浓度衰减很快;在下风向距离烟囱中心28米的区域,取SO2斜柱浓度与高斯曲线进行拟合,拟合系数0.747,表明风向方向:SO2斜柱浓度扩散遵循高斯扩散;根据SO2斜柱浓度时序图,获得了烟羽的传播速度约为1.2 m·s^-1;为了验证紫外非色散成像系统测量结果的可靠性,在已知烟羽SO2排放量(9.2 g·s^-1)、烟羽速度(1.2 m·s^-1)、烟羽高度(约140 m)及周边环境的情况下,采用高斯烟羽扩散模型进行理论预测,成像系统的测量结果与烟羽模型的模拟结果对比表明:SO2斜柱浓度的测量值及扩散趋势与理论预测基本一致。利用基于滤光片的快速成像方法实现了对固定点源排放的污染气体SO2斜柱浓度的成像测量,最终成功获取了烟羽中SO2斜柱浓度的分布及扩散的趋势,测量结果与模型模拟的一致性表明该成像方法有望为定量、定性评估污染危害提供测量依据。     

PEMFC气体扩散层内各向异性传递过程数值模拟

质子交换膜燃料电池(PEMFC)气体扩散层(GDL)具有各向异性属性,常规数值模拟对GDL采取均匀模型,忽略了各向异性传递过程对PEMFC性能的影响。本文发展了一个三维非等温单相模型,在GDL平面内和GDL厚度方向采用不同的传递系数,模拟了各向异性传递系数对PEMFC整体和局部性能的影响。在本文计算条件下,GDL各向异性和均匀模型模拟得到的电池极化曲线几乎完全相同,但电池电流密度分布和温度分布等局部特性存在很大差异。该结果进一步证明了不能单独用极化曲线来验证电池数学模型的正确性。     

Kr/Xe气体在塑料闪烁体表面的吸附与扩散行为研究

采用基于Compass力场的分子动力学(MD)方法,研究了惰性气体氙(Xe)和氪(Kr)在塑料闪烁体(聚乙烯基对甲苯)的平整和粗糙表面的吸附和扩散行为.由惰性气体吸附曲线的均方根位移(MSD),得到了Xe/Kr气体在聚乙烯基对甲苯表面的扩散系数.研究结果表明,Kr/Xe气体均被稳定地吸附在塑料闪烁体表面,其稳定性随着温度的升高而增加,Xe分子的吸附性强于Kr分子. Kr/Xe气体在聚乙烯基对甲苯表面具有较强的扩散性能,扩散深度随着温度与厚度的增加而增加,最大为22.865?,Kr分子扩散能力强于Xe分子.基底粗糙表面增加了两种惰性气体分子的吸附和扩散.     

硫酸钡微球掺杂聚碳酸酯材料的光散射特性模拟分析

基于多重米氏(Mie)散射理论和蒙特卡罗(Monte Carlo)方法, 对掺杂硫酸钡(BaSO4)微球体的散射型聚碳酸酯(PC)光散射材料进行了数值模拟。研究了BaSO4粒子粒径、浓度及样品厚度等光学参量对PC材料透光率、扩散率、照度角分布等光学性能的影响, 并进行了设计评估。通过比较不同材料参数下光散射材料光学性能的差别, 总结出了获得良好光学性能所需的合适材料参数。模拟结果为高性能光散射材料的实验制备提供了理论参考。     

PEM燃料电池中的两相传质及其影响

建立了一个新的二维、两相流模型来研究质子交换膜(PEM)燃料电池中的两相传质及其对质子膜阻抗和阴极性能的影响。模型不仅将催化剂层(CL)包含在电极中,还考虑了电池中相变及其对传质的影响。模型可同时使用在电池的阴极和阳极。主要模拟了电池阴极中两相传质、质子膜阻抗、阴极有效孔隙率和电流密度。模拟结果显示,提高加湿温度可以降低质子膜的阻抗,但过高的加湿温度会降低阴极气体扩散层(GDL)的有效孔隙率,降低阴极的性能。     

Novel volumetric analysis technique for characterizing the solubility and diffusivity of hydrogen in rubbers

We introduce a volumetric analysis technique to characterize the solubility of hydrogen dissolved in polymers and its diffusion coefficient by electrical capacitance measurement electrodes to determine the water level in graduated cylinders. This new and simple technique measures the volume of hydrogen released from rubber inside a graduated cylinder after a sample is exposed to high-pressure hydrogen and subsequent decompression. A diffusion analysis program is utilized to determine the total uptake (C₀) and diffusivity (D) of hydrogen, which are used to calculate the solubility (S) and permeability (P). This method is applied to spherical rubber samples of nitrile butadiene rubber (NBR), ethylene propylene diene monomer (EPDM), and fluoroelastomer (FKM), which are potential sealing materials for H₂ energy infrastructures. C₀ follows Henry's law for all samples. No sample size and pressure dependence is observed for S, whereas an appreciable size dependence for the three rubbers is detected for D. The uncertainty is evaluated by considering uncertainty factors that affect the measurement. The correlation between D and density of rubber is found. The developed method can be utilized as a standard test for the transport properties versus pressure of various polymer membranes regardless of the sample shapes and size.     

First-principles investigation on diffusion behaviours of H isotopes: From W(110) surface into bulk and in bulk W

The diffusion behaviours of hydrogen (H), deuterium (D), and tritium (T) from W(110) surface into bulk and in bulk W are investigated using a first-principles calculations combined with simplified models. The diffusion energy barrier is shown to be 1.87 eV from W(110) surface to the subsurface, along with a much reduced barrier of 0.06 eV for the reverse diffusion process. After H enters into the bulk, its diffusion energy barrier with quantum correction is 0.19 eV. In terms of the diffusion theory presented by Wert and Zener, the diffusion pre-exponential factor of H is calculated to be 1.57×10^-7 m²·s^-1, and it is quantitatively in agreement with experimental value of 4.1×10^-7 m²·s^-1. Subsequently, according to mass dependence (√1/m ) of H isotope effect, the diffusion pre-exponential factors of D and T are estimated to be 1.11×10^-7 m²·s^-1 and 0.91×10^-7 m²·s^-1, respectively.     

Effects of the Be_(22)W phase formation on hydrogen retention and blistering in mixed Be/W systems

We have performed first-principles density functional theory calculations to investigate the retention and migration of hydrogen in Be_(22) W, a stable low-W intermetallic compound. The solution energy of interstitial H in Be_(22) W is found to be 0.49 eV lower, while the diffusion barrier, on the other hand, is higher by 0.13 eV compared to those in pure hcp-Be. The higher solubility and lower diffusivity for H atoms make Be_(22) W a potential beneficial secondary phase in hcp-Be to impede the accumulation of H atoms, and hence better resist H blistering. We also find that in Be_(22) W, the attraction between an interstitial H and a beryllium vacancy ranges from 0.34 eV to 1.08 eV, which indicates a weaker trapping for hydrogen than in pure Be. Our calculated results suggest that small size Be_(22) W particles in hcp-Be might serve as the hydrogen trapping centers, hinder hydrogen bubble growth, and improve the resistance to irradiation void swelling, just as dispersed oxide particles in steel do.     

First-principles investigation of diffusion behaviours of H isotopes:From W(110) surface into bulk and in bulk W

<正>The diffusion behaviours of hydrogen（H）,deuterium（D）,and tritium（T） from W（110） surface into bulk and in bulk W are investigated using first-principles calculations combined with simplified models.The diffusion energy barrier is shown to be 1.87 eV from W（110） surface to the subsurface,along with a much reduced barrier of 0.06 eV for the reverse diffusion process.After H enters into the bulk,its diffusion energy barrier with quantum correction is 0.19 eV. In terms of the diffusion theory presented by Wert and Zener,the diffusion pre-exponential factor of H is calculated to be 1.57×10^-7 m²·s^-1,and it is quantitatively in agreement with the experimental value of 4.1×10^-7 m²·s^-1. Subsequently,according to mass dependence(（1/m）^1/2) of H isotope effect,the diffusion pre-exponential factors of D and T are estimated to be 1.11×10^-7 m²·s^-1 and 0.91×10^-7 m²·s^-1,respectively.     

Diffusion of hydrogen in metals

The present status of our understanding of the diffusion of hydrogen in metals, both experimental and theoretical, is reviewed. Discussions are focused on the mechanism of diffusion of hydrogen isotopes H, D and T in f.c.c. and b.c.c. metals; the positive muon (μ ⁺) is referred to where appropriate. An up-to-date compilation of diffusion data as a function of temperature and isotope mass has been made, and a clear distinction in general diffusion behaviour in f.c.c. and b.c.c. metals is noted. Subsequently, the results obtained from the Gorsky effect, nuclear magnetic resonance and quasi-elastic neutron scattering that provide information on elementary jump processes are discussed.

A conceptual framework of the quantum diffusion of light interstitials in metals is given, including the recent Kondo theory that emphasizes the crucial importance of particle-conduction electron interactions in the diffusion process, especially at low temperatures. It is shown with the help of recent estimates of the tunneling matrix element that the overall feature of diffusion of hydrogen isotopes in b.c.c. metals as well as μ ⁺ in f.c.c. metals can be explained consistently within the frame presented here.

Finally, recent advances in the diffusion studies on hydrogen in b.c.c. metals are described. They include a re-analysis of quench-recovery experiments that manifested nearly athermal diffusion of H, D and T in Ta at low temperatures, and an enormous enhancement of the diffusivity under stress (superdiffusion) observed for H and D in V.     

Substitution effects on the hydrogen storage behavior of AB2 alloys by first principles

The hydrogen storage behavior of the TiCr₂ and ZrCr₂ alloys substituted with the third components (Zr, V, Fe, Ni) have been studied using first-principles calculations. The change of the hydrogen absorption energies caused by metal doping is arising from the charge transfer among the doped alloys interior. Zr and V atoms devoted abundant electrons, leading to a great enhancement of the H absorption energy, while Fe and Ni atoms always accepted electrons, yielding a remarkable decrease of the H absorption energy. The hydrogen diffusion energy barrier is closely correlated with the geometry effect rather than the electronic structure.     

Interaction of hydrogen and deuterium with intrinsic atomic defects in high-purity electron-irradiated nickel

Abstract

High-purity nickel was irradiated with 2 MeV electrons at temperatures below 80 K to a dose of 1 × 10²³ e^?/m² in the as-prepared state and after charging with H or D. By means of magnetic after-effect measurements relaxations of anisotropic radiation-induced defects and of defect-hydrogen complexes were investigated in the temperature range between 4.2 and 500 K. The isochronal annealing behaviour of these relaxations and the isochronal recovery of the residual resistivity was measured simultaneously on the same specimens. At temperatures below the hydrogen mobility (< 160 K) in charged irradiated specimens relaxation maxima are observed at 45, 100, 115 and 140 K which show no isotope shift for H and D charging. The maxima below 160 K are explained by defect-hydrogen complexes, where radiation-induced defects reorient around immobile hydrogen atoms. Above 160 K, where hydrogen atoms get mobile, in charged irradiated specimens a broad relaxation maximum appears at 170 K which shows an inverse isotope shift for H and D charging. This 170 K maximum anneals in Stage III. A hydrogen diffusion maximum observed in charged specimens at 215 K prior to irradiation is missing after electron irradiation. The 170 K relaxation is explained by defect-hydrogen complexes, where hydrogen atoms reorient around immobile radiation-induced defects while the long-range hydrogen diffusion is suppressed by these defects. In such relaxation measurements hydrogen and deuterium atoms are used as a “probe” to investigate radiation-induced defects.     

Effect of Soret diffusion on lean hydrogen/air flames at normal and elevated pressure and temperature

The influence of Soret diffusion on lean premixed flames propagating in hydrogen/air mixtures is numerically investigated with a detailed chemical and transport models at normal and elevated pressure and temperature. The Soret diffusion influence on the one-dimensional (1D) flame mass burning rate and two-dimensional (2D) flame propagating characteristics is analysed, revealing a strong dependency on flame stretch rate, pressure and temperature. For 1D flames, at normal pressure and temperature, with an increase of Karlovitz number from 0 to 0.4, the mass burning rate is first reduced and then enhanced by Soret diffusion of H₂ while it is reduced by Soret diffusion of H. The influence of Soret diffusion of H₂ is enhanced by pressure and reduced by temperature. On the contrary, the influence of Soret diffusion of H is reduced by pressure and enhanced by temperature. For 2D flames, at normal pressure and temperature, during the early phase of flame evolution, flames with Soret diffusion display more curved flame cells. Pressure enhances this effect, while temperature reduces it. The influence of Soret diffusion of H₂ on the global consumption speed is enhanced at elevated pressure. The influence of Soret diffusion of H on the global consumption speed is enhanced at elevated temperature. The flame evolution is more affected by Soret diffusion in the early phase of propagation than in the long run due to the local enrichment of H₂ caused by flame curvature effects. The present study provides new insights into the Soret diffusion effect on the characteristics of lean hydrogen/air flames at conditions that are relevant to practical applications, e.g. gas engines and turbines.     

Theory of hydrogen solubility in binary iron alloys based on ab initio calculation results

Interaction of hydrogen atoms with three substitutional impurities (X?=?Pd, Ti, Cr) in bcc iron base solid solution was modelled ab initio using the WIEN2k package. It was shown that in spite of attraction between H and X atoms, excess energy of the H atom in tetrahedral sites in the first sphere of coordination of the X atom has a significant positive value, while the lowest negative values are observed in the second (Pd, ?0.087?eV; Ti, ?0.091?eV) or the third (Cr, ?0.032?eV) sphere. A new thermodynamic theory of hydrogen solubility in dilute bcc Fe–X alloys was developed on the basis of these results. The resulting equation was used to analyze existing experimental data on H solubility in a number of Fe–X alloys, and X–H interaction energies were determined for each case. The energies determined from high-temperature solubility data for Fe–Pd, Fe–Ti and Fe–Cr are somewhat greater than those obtained in ab initio calculations. The theory gives a new basis for analyzing hydrogen behaviour in iron-base solid solutions.     

Effect of metal catalyst on the mechanism of hydrogen spillover in three-dimensional covalent-organic frameworks

Hydrogen spillover mechanism of metal-supported covalent-organic frameworks COF-105 is investigated by means of the density functional theory, and the effects of metal catalysts M_4(Pt_4, Pd_4, and Ni_4) on the whole spillover process are systematically analyzed. These three metal catalysts exhibit several similar phenomena:(i) they prefer to deposit on the tetra(_4-dihydroxyborylphenyl) silane(TBPS) cluster with surface-contacted configuration;(ii) only the H atoms at the bridge site can migrate to 2,3,6,7,10,11-hexahydroxy triphenylene(HHTP) and TBPS surfaces, and the migration process is an endothermic reaction and not stable;(iii) the introduction of M_4 catalyst can greatly reduce the diffusion energy barrier of H atoms, which makes it easier for the H atoms to diffuse on the substrate surface. Differently, all of the H2 molecules spontaneously dissociate into H atoms onto Pt_4 and Pd_4clusters. However, the adsorbed H2 molecules on Ni_4 cluster show two types of adsorption states: one activated state with stretched H–H bond length of 0.88 ?A via the Kubas interaction and five dissociated states with separated hydrogen atoms. Among all the M_4 catalysts, the orders of the binding energy of M_4 deposited on the substrate and average chemisorption energy per H2 molecule are Pt_4Ni_4Pd_4. On the contrary, the orders of the migration and diffusion barriers of H atoms are Pt_4Ni_4Pd_4, which indicates that Pt_4 is the most promising catalyst for the hydrogen spillover with the lowest migration and diffusion energy barriers. However, the migration of H atoms from Pt_4 toward the substrate is still endothermic. Thus direct migration of H atom from metal catalyst toward the substrate is thermodynamically unfavorable.