Identification of Metal Contaminants on FCC Catalyst

FCC Catalyst deactivation is a major source of expense in the refining industry. Of concern is the deposition of contaminant metals onto the catalyst particles, leading to premature deactivation. Samples of used catalyst were collected from a working refinery using the standard sampling ports. These samples were subjected to surface examination by Scanning Electron Microscope, and to X‐ray Micro Analysis to determine elementary composition of key metals. Particle mapping was conducted to obtain cross sectional composition of both used and fresh catalyst. It was found that metals preferentially deposit onto the outside of the catalyst particles, presumably causing premature de‐activation to occur. Although the particles are found in a high attrition environment, the metal deposits formed a rough outer surface on the particle. Mild attrition of these particles was found to remove this outside layer of material and help to restore the original chemical make up of the particles surface. This work has shown how refineries can investigate metal deposition onto particles surfaces which will help them better manage FCCU catalyst usage.     

密度泛函理论研究碱金属原子在完美氧化镁(001)表面的吸附

基于平面波赝势法的密度泛函理论系统地研究了孤立碱金属原子(锂、钠、钾、铷、铯)在完美氧化镁(001)表面的吸附. 锂在氧位表面上的吸附能是0.72 eV,大约是其它碱金属的3倍. 锂和表面氧之间较强的相互作用主要是来源于共价键的作用,这可由态密度和差分电荷密度的分析所证实. 讨论碱金属在MgO(001)表面吸附的成键机理.     

金属表面荧光增强的物理增强机制

具有特殊形貌及构型的表面(如金属薄膜)能够使位于其邻近的荧光分子的荧光信号得到增强, 这种现象被称之为表面增强荧光(Surface Enhanced Fluorescence, SEF)。有关表面增强荧光效应的研究探讨已有许多报道,并先后提出了多种增强机理以试图理解和解释观测到的实验现象。本文将在总结归纳已有机理研究的基础上,从物理学的角度出发分析理解局域场增强、能量转移以及辐射衰减速率增加等理论模型,并对衬底表面与荧光分子之间的间距变化对增强效果的影响进行探讨。     

纳米金属粉对高氯酸铵热分解动力学的影响

用TG和DSC研究了普通级和纳米级的铝、镍金属粉对普通高氯酸铵热分解特性的影响 .结果表明 ,普通级和纳米级铝粉对普通高氯酸铵热分解几乎没有影响 ,纳米镍粉对普通高氯酸铵的热分解 ,特别是高温阶段的促进作用最明显 .这种促进作用随着纳米镍粉含量的减少而逐渐减弱 .利用Coats Redfern积分法计算了超细高氯酸铵热分解的动力学参数 ,结果显示纳米镍粉使超细高氯酸铵热分解的表观活化能从 15 7.9kJ/mol下降为134.9kJ/mol,而其热分解的机理函数都同属于“成核和核成长”的Avrami Erofeev方程系列的函数 ,同时还探讨了纳米镍粉对高氯酸铵热分解促进作用的机理 .     

Resolution Enhancement of Plasmonic Sensors by Metal‐Insulator‐Metal Structures

Optical sensors based on surface plasmons have attracted much attention over the past decades owing to the wealth of applications in bio‐ and chemical and gas sensing. In surface plasmon resonance sensors, a single metal layer is commonly used, but its resolution is limited because of broad resonances. In this context, we have developed a sensor chip based on a stack of metals and a dielectric, e.g. a metal‐insulator‐metal structure, consisting of a thick insulator layer sandwiched by metal layers, that exhibits a sharp resonance due to the excitation of surface plasmon polaritons hybrid modes. We have performed both experiments and theoretical simulations to estimate the enhancement of the sensitivity of such a structure. By changing the refractive index of an aqueous solution of glucose on top of the sensor chip, we found that the use of a metal‐insulator‐metal structure improves the figure of merit of the sensor 7.5 times compared to that of a conventional surface plasmon resonance sensor chip.     

Fluorescence Spectroscopy of Polymer Systems Doped with Rare-Earth Metal Ions and Their Complexes

Abstract

There has been an increased attention to explore the possibility of using polymer materials with rare-earth (RE) metal ions and their complexes as potential optical materials due to their capability of exhibiting novel and unusual properties. The fluorescence characteristics of polymer systems doped with RE metal ions and/or their complexes were analyzed and the effects of the doping metal ion/metal complexes as well as nature of the material were discussed. Electron transitions of REs can be manipulated by efficient ligand designs and proper doping into the polymer matrix. Emphasis was especially focused on the accommodation of the metal ion/metal complex in polymer matrix as well as its role in fluorescence. The photochemistry of the fluorescent polymer matrices with RE complexes is expected to open up frontier fields that lie between photophysics and materials science. Recent developments on a new aspect of these technologies related to the fluorescence dynamics in polymer analysis will also be discussed in this present review.     

过渡金属元素氢化物发生-原子荧光增敏效应研究

基于反应介质酸度对Zn,Cd,Cu和Ni的氢化物发生影响的考察,揭示了氢转移过渡中间态[H+BH-₄]*分解反应氢化物生成机理。分别考察了Co2+离子、Ni2+离子、邻菲咯啉、羟基喹啉对Zn,Cd,Cu和Ni氢化物发生原子荧光信号的影响,探讨了其增敏机理。由于Co和Ni的挥发性物种分解抑制了Cd和Zn氢化物在传输过程中的分解损失,明显提高了Cd和Zn氢化物的传输效率。邻菲咯啉与Co2+离子或8-羟基喹啉与Co2+离子对Zn和Cd信号均具有协同增敏效应,8-羟基喹啉和邻菲咯啉对Zn和Cd信号则没有协同增敏效应。考察了阳离子、阴离子和非离子表面活性剂对氢化物发生的促进作用。结果证实阳离子和非离子表面活性剂均对分析物信号有明显的增敏效果,其原因在于表面活性剂的存在引起溶液的表面张力显著的降低。以石墨炉原子吸收法进一步考察了分析物从表面活性剂吸收液中逸出特性,提出了表面活性剂在氢化物发生和传输过程中的增敏机理。     

Metal Nanoparticle–Microbe Interactions: Synthesis and Antimicrobial Effects

Metal nanoparticles (NPs), chalcogenides, and carbon quantum dots can be easily synthesized from whole microorganisms (fungi and bacteria) and cell-free sterile filtered spent medium. The particle size distribution and the biosynthesis time can be somewhat controlled through the biomass/metal solution ratio. The biosynthetic mechanism can be explained through the ion-reduction theory and UV photoconversion theory. Formation of biosynthetic NPs is part of the detoxification strategy employed by microorganisms, either in planktonic or biofilm form, to reduce the chemical toxicity of metal ions. In fact, most reports on NP biosynthesis show extracellular metal ion reduction. This is important for environmental and industrial applications, particularly in biofilms, as it allows in principle high biosynthetic rates. The antimicrobial and antifungal effect on biosynthetic NPs can be explained in terms of reactive oxygen species and can be enhanced by the capping agents attached to the NP during the biosynthesis process. Industrial applications of NP biosynthesis are still lagging, due to the difficulty of controlling NP size and low titer. Further, the environmental assessment of biosynthetic NPs has not yet been carried out. It is expected that further advancements in biosynthetic NP research will lead to applications, particularly in environmental biotechnology.     

利用ICP-MASS研究有机培肥土壤重金属淋溶特征

以下辽河平原11年长期定位试验为平台,采用原状土柱淋溶实验,通过比较不同用量有机肥处理土壤重金属积累情况及其淋溶特征,探讨了雨养农业条件下有机培肥措施对土壤表层重金属（Cu,Zn,Cd和Cr）积累的影响,阐述了重金属在土壤表层(0～20 cm)中的积累特征明确了重金属元素的淋溶特点和垂直迁移规律(0～60 cm)。研究表明,随着有机肥用量增加,表层土壤中Cu,Zn,Cd和Cr的含量都随之升高,积累速度为Cd＞Cu＞Zn＞Cr。根据中国土壤环境质量标准(GB15618-1995),即使施入50 t·ha-1有机肥料,也未造成表层土壤Cr, Cu和Zn的污染,其中Cr仍符合Ⅰ类土壤质量标准,而Cu和Zn符合国家Ⅱ类土壤质量标准,但对Cd而言,此时表层土壤含量已接近国家Ⅲ类土壤质量标准阈值,存在较大风险,应引起足够重视。土柱淋溶实验表明,只有个别淋溶液Cu和Cd浓度属于国家Ⅲ类水质量标准（GB/T14848—93）,其余均符合国家Ⅱ类及以上水质标准,且所有淋溶液Cr的含量都符合国家Ⅰ类水质标准,表明在下辽河平原,即使有机肥使用量达到50 t·ha-1时,仍未对地下水构成任何风险。另外,淋溶液中的重金属含量均随土层深度增加呈现下降趋势(Cr除外),表现出重金属不易下移的特点,但相对而言,Zn和Cr向深层土壤淋溶能力较强,Cu和Cd则更易积累在表层土壤。     

酞菁铜/金属薄膜界面电位与光二次谐波特性分析

采用Kalvin探针和光二次谐波 (SecondHarmonicGeneration ,SHG)方法研究了铜酞菁衍生物 (Coppertetra tert butylPhthalocyanine ,CuttbPc )LB(Langmuir Blodgentt)膜与金属 (Al、Au)界面的空间电荷现象与非线性光学效应 .检测到空间电荷感应电场 (SpaceChargeInducedElectricField ,SCIEF)形成的表面电位与金属功函数有关 ,并随膜厚变化趋于饱和值 .尽管酞菁分子为中心对称体系 ,但仍有SHG效应 ,并观察到CuttbPc/Al样品在 12 6 0nm附近有异常增强的SH信号 ,而CuttbPc/Au样品未见该峰 .根据样品结构的物理模型 ,运用电磁场理论分析了界面电介质的非线性极化特性和光学效应产生机制 ,初步认为CuttbPc/Al的SH增强峰源于SCIEF形成的较强表面电位 ,说明SH信号的产生与界面静电现象有密切关系 .     

Absorption and Recurrence Spectra of Nonhydrogenic Rydberg Atom Near a Metal Surface

Multielectron to theoretical treatments atoms near a metal surface are essentially more complicated than hydrogen atom with regard By using the semicalssical dosed orbit theory generalized to the multielecton atoms, we study the dynamical properties of the Rydberg lithium atom near a metal surface. The photoabsorption spectra and recurrence spectra of this system have also been calculated. Considering the effect of the ionic core potential of the Rydberg lithium atom, the number of the closed orbits increases, which leads to more peaks in the recurrence spectra than the case of hydrogen atom near a metal surface. This result shows that the core-scattered effects play an important role in nonhydrogenic atoms. This study is a new application of the closed-orbit theory and is of potential experimental interest.     

金属纤维烧结过程的分数阶模型

基于金属纤维烧结结点的几何模型,运用Caputo分数阶微分方程,建立时间分数阶表面扩散模型,使用有限差分法求数值解,实现金属纤维烧结过程的数值模拟.对不同的阶数进行模拟,得到0~1阶烧结过程数值结果及颈长变化规律;在阶数为0.9阶时,模拟初始夹角为0°、30°、60°、90°时的烧结过程.结果表明：阶数等于1时的结果与整数阶扩散模型一致;烧结的初始阶段,整数阶与分数阶模拟的颈半径迅速生长,随着烧结的进行,分数阶模拟的烧结颈长出现局部波动,最后以大于整数阶的增长速率增长;阶数固定时,初始夹角越小,增长速率越大.分数阶表面扩散模型比整数阶表面扩散模型能更好地描述纤维烧结过程中烧结结点的复杂变化.     

脉冲激光诱导Cu靶产生发光羽的特性分析

通过在不同的环境气压下拍摄脉冲激光烧蚀金属Cu诱导产生的发光羽,获取了不同区域具有不同颜色特征的发光羽照片.结果发现:发光羽的颜色随环境气压的改变而变化.采用空间分辨光谱技术,测定了激光诱导金属Cu靶产生发光羽辐射强度的空间分布,以及不同烧蚀环境气压对发光羽辐射强度的影响.研究了脉冲激光烧蚀Cu表面诱导发光的动力学过程,建立了可能的发光羽分区模型,对发光羽的不同区域发光粒子的激发机理进行了探讨,并用之定性地解释了所观察的实验现象.结果分析表明:脉冲激光诱导Cu产生的发光羽可以分为三个区域,不同区域的发光机理不同,Cu原子和Cu离子的激发机理不完全相同.     

低温光滑壁面上水滴撞击结冰行为

采用高速摄像技术测试低温光滑壁面上水滴撞击结冰过程, 分析了撞击速度、壁面温度和材料热导率对水滴撞击铺展、振荡及结冰行为的影响规律. 结果表明, 低温壁面造成水滴最大铺展直径缩小, 且结冰时间随温度降低而缩短; 当撞击We数提高时, 水滴最大铺展直径增大, 而振荡和结冰时间减小; 同时材料热导率越高, 最大铺展直径越小, 结冰越迅速. 另外, 从热力学角度推导出水滴撞击结冰时间的理论公式, 预测误差<5.3%.     

金属电子逸出功的测定的计算机数据处理

通过测量金属电子逸出功实验,通过简单软件进行数据处理,使实验数据处理更直观,快捷。     

金属异质波导阵列中的表面等离激元传播特性

提出了一种新的一维金属异质波导阵列的设计方案,即波导芯区周期调制的金属波导阵列.数值模拟的结果表明,金属波导芯区的周期调制引起波导中传播的表面等离激元有效折射率的周期调制,从而可在特定的波段打开一个表面等离激元带隙(如1550nm附近).通过引入合适的缺陷波导单元,可获得特定波长的高品质因子(Q=556)的表面电磁模共振.这一结果可用于设计亚波长的布拉格反射器、光发射器、滤波器等,有可能被用于未来的集成光路.     

Third-Order Optical Nonlinearity in Two-Dimensional Transition Metal Dichalcogenides

We present a detailed calculation of the linear and nonlinear optical response of four types of monolayer twodimensional (2D) transition-metal dichalcogenides (TMDCs), having the formula MX₂ with M=Mo, W and X=S, Se. The calculations are based on 6-band tight-binding model of TMDCs, and then performing a semi-classical perturbation analysis of response functions. We numerically calculate the linear χ_μν⁽¹⁾ (-ω;ω) and nonlinear surface susceptibility tensors χ_μνζη⁽³⁾(-ω_Σ; ω_r; ω_s; ω_t) with ω_Σ=ω_r+ω_s+ω_t. Both non-degenerate and degenerate cases are studied for thirdharmonic generation and nonlinear refractive index, respectively. Computational results obtained with no external fitting parameters are discussed regarding two recent reported experiments on MoS₂, and thus we can confirm the extraordinarily strong optical nonlinearity of TMDCs. As a possible application, we demonstrate generation of a π/4-rotated squeezed state by means of nonlinear response of TMDCs, in a silica micro-disk resonator covered with the 2D material. Our proposed method will enable accurate calculations of nonlinear optical response, such as four-wave mixing and highharmonic generation in 2D materials and their heterostructures, thus enabling study of novel functionalities of 2D photonic integrated circuits.     

Effect of spin-orbit interaction on a magnetic impurity in the vicinity of a surface

We propose a new mechanism for surface-induced magnetic anisotropy to explain the thickness dependence of the Kondo resistivity of thin films of dilute magnetic alloys. The surface anisotropy energy, generated by spin-orbit coupling on the magnetic impurity itself, is an oscillating function of the distance d from the surface and decays as 1/d2. Numerical estimates based on simple models suggest that this mechanism, unlike its alternatives, gives rise to an effect of the desired order of magnitude.     

Grain Boundary Grooving Accelerated by Local Plasticity as a Possible Mechanism of Liquid Metal Embrittlement

Kinetic mechanism of premature grain boundary (GB) failure under simultaneous action of tensile stress and wetting liquid metals (LME) is not clear yet. We summarize briefly the stress intensity, surface energy and GB segregation effects in LME crack kinetics and the explanations that have been put forward. A possible mechanism of LME is outlined. It is proposed that GB cracks under LME propagate by Mullins grooving controlled by bulk diffusion in liquid and dramatically accelerated by periodic blunting of the groove tip by local plastic flow. It is found that this GALOP (Grooving Accelerated by Local Plasticity) mechanism captures the major experimental observations of stress intensity, surface energy and GB segregation effects in LME fairly well. A parallel between the GALOP mechanism and the GB subcritical crack growth under creep in inert atmosphere is mentioned.