Capillary-driven interdiffusion along interphase boundaries in solids

We consider chemical interdiffusion along interphase boundary (IB) between two immiscible solid phases. We derive explicit expressions for capillary-related excess chemical potentials of the atoms diffusing along the IB. The obtained expressions contain both a local term which depends on local curvature of the IB, and a non-local one which depends on overall system geometry and on energy of all surfaces and interfaces in the system. The obtained expressions are employed for describing the sintering of two immiscible two-dimensional solid particles controlled by surface and IB diffusion processes. We demonstrate that the sintering of particles is accompanied by relative rigid-body rotation of the particles even for fully isotropic surfaces and interphase boundaries.     

Dislocation content of geometrically necessary boundaries aligned with slip planes in rolled aluminium

Previous studies have revealed that dislocation structures in metals with medium-to-high stacking fault energy, depend on the grain orientation and therefore on the slip systems. In the present work, the dislocations in eight slip-plane-aligned geometrically necessary boundaries (GNBs) in three grains of near 45° ND rotated cube orientation in lightly rolled pure aluminium are characterized in great detail using transmission electron microscopy. Dislocations with all six Burgers vectors of the ½?1?1?0? type expected for fcc crystals were observed but dislocations from the four slip systems expected active dominate. The dislocations predicted inactive are primarily attributed to dislocation reactions in the boundary. Two main types of dislocation networks in the boundaries were identified: (1) a hexagonal network of the three dislocations in the slip plane with which the boundary was aligned; two of these come from the active slip systems, the third is attributed to dislocation reactions (2) a network of three dislocations from both of the active slip planes; two of these react to form Lomer locks. The results indicate a systematic boundary formation process for the GNBs. Redundant dislocations are not observed in significant densities.     

Magnetic phases in Mn<Subscript>1</Subscript>_<Subscript>x</Subscript>Fe<Subscript>x</Subscript>WO<Subscript>4</Subscript> studied by neutron powder diffraction

The magnetic structures of Mn_1-xFe_xWO₄ with x = 0.0, 0.16, 0.21, 0.225, 0.232, 0.24, 0.27, 0.29, and 1.0 were refined from neutron powder diffraction data. The magnetic phase diagram could be completed in the coexistence range of different magnetic structures up to x = 0.29. For the magnetic state at 1.5 K a commensurate antiferromagnetic structure with a propagation vector = (±1/4, 1/2, 1/2) was found for x ⩽ 0.22 while the magnetic spins order with = (1/2, 0, 0) for x ≥ 0.22. In the latter phase, additionally, weak magnetic reflections indexed to an incommensurate ordering with = (- 0.214, 1/2, 0.457) occur in the diffraction pattern up to x = 0.29 indicating the occurence of a reentrant phase. For 0.12 ⩽ x ⩽ 0.29 the low temperature phases are separated from a magnetic high temperature phase showing only magnetic reflections indexed to a spin arrangement with = (1/2, 0, 0). The magnetic phase diagram is discussed qualitatively considering random superexchange between the statistically distributed Mn²⁺- and Fe²⁺-ions in the coexistence range 0.12 ⩽ x ⩽ 0.29 of different magnetic structures related to those of pure MnWO₄ and FeWO₄. Received 9 October 2002 Published online 14 March 2003     

The reduction of rotational ambiguity in soft-modeling by introducing hard models

Rotational ambiguity is a major problem in the application of soft-modeling analysis to a variety of multivariate mixture resolution problems and particularly important in the analysis of kinetic data. Soft-modeling analyses rely on constraints that restrict the concentration profiles and/or the spectral responses of all components. The main goal of this work is to demonstrate how a hard-modeling constraint on concentration profiles drastically decreases the extent of the rotational ambiguity. Therefore, in the present paper the discussion is focused on systems in which hard-modeling information is available. The results of simulated examples reveal that the utilized hard constraint decreases the rotational ambiguity in estimated concentration profile even components that do not take part in the explicit model. In addition, the rate constant of known reaction is determined in this method.     

Gd0.2Ce0.8O1.9纳米颗粒对固体氧化物电解池La0.6Sr0.4Co0.2Fe0.8O3-δ阳极 析氧反应的影响

化石燃料的使用排放了大量CO2,对气候和环境造成了日益严重的危害.固体氧化物电解池(SOEC)能够利用可再生能源产生的电能将CO2高效转化成CO,降低CO2排放的同时,又能减少化石燃料的使用,近年来受到研究者的广泛关注.相比于低温液相CO2电还原,SOEC高的运行温度保证了其较高的反应速率,即较高的电流密度.典型的SOEC单电池由多孔阴极、致密电解质和多孔阳极以三明治的方式组装而成.CO2分子在阴极得到两个电子解离成CO和一个O2–;生成的O2–通过致密电解质传导至阳极,在阳极失去四个电子发生析氧反应(OER)生成一个O2.相比于两电子的阴极反应,阳极四电子的析氧反应更难进行,可能是整个电极过程的速控步,因此开发高性能的阳极材料有望显著提高SOEC的CO2电还原性能.La0.6Sr0.4Co0.2Fe0.8O3-δ(LSCF)因具有较高的混合离子-电子导电性而被用作SOEC阳极材料,但受LSCF-气体两相界面的限制,其OER性能较低.研究表明,LSCF-掺杂的CeO2-气体所构成的三相界面相比于LSCF-气体两相界面具有更高的电化学反应活性,即OER反应更易在三相界面进行.因此,本文将Gd0.2Ce0.8O1.9(GDC)纳米颗粒浸渍到SOEC LSCF阳极来提高其OER活性,考察了纳米颗粒浸渍量(3,5,10和20 wt%)对SOEC电化学性能的影响.结果表明,SOEC的电化学性能随浸渍量的增加而逐渐升高,当GDC纳米颗粒浸渍量为10 wt%时(10GDC/LSCF),SOEC的电化学性能达到最高,在800 oC和1.6 V的电流密度为0.555 A cm–2,是LSCF阳极SOEC性能的1.32倍.继续增加浸渍量到20 wt%,电化学性能反而开始下降.电化学阻抗谱测试结果表明,GDC纳米颗粒的加入减小了SOEC的极化电阻.对应的弛豫时间分布函数解析结果表明10GDC/LSCF阳极上的OER由四个基元反应构成.电镜和O2-程序升温脱附结果表明,GDC纳米颗粒的加入显著增加了10GDC/LSCF阳极三相界面和表面氧空位的数量以及体相氧的流动性,从而促进了OER四个基元反应的反应速率,降低了这几个过程的极化电阻,因而降低了OER反应的极化电阻,提高了SOEC电还原CO2的电化学性能.     

Accurate determination of extra-column band broadening using peak summation

The present contribution addresses the problem of the accurate determination of the extra-column band-broadening dispersion by applying the method of moments (MOM) on pulse response experiments. The MOM provides the only mathematically rigorous way to determine the variance of a pulse response, but suffers from the fact that the obtained variance values usually depend very strongly and unpredictably on the selected integration boundaries. In the present study, it is investigated whether the MOM cannot be made more accurate by repeating the pulse response experiment a number of times, then add all measured peaks (after retention time alignment) and subsequently perform the integration on this summed peak. Testing this approach for a number of different integration boundary detection methods consistently more accurate results are obtained than when the different repeat response pulses are integrated individually and the variances are averaged afterwards. It was also found that adding five repeats already leads to a significant improvement of the variance estimate, whereas the addition of 10-20 repeats is needed before the variance estimate converges to a steady value.     

Dislocation Analysis for Large-sized Sapphire Single Crystal Grown by SAPMAC Method

In this paper,large-sized sapphire (230×210 mm,27.5 kg) was grown by SAPMAC method (sapphire growth technique with micro-pulling and shoulder-expanding at the cooled center). Dislocation peculiarity in large sapphire boule (0001) basal plane was investigated by chemical etching,scanning electron microscopy and X-ray topography method. The triangular dislocation etch pit measured is 7.6×101～8.0×102 cm-2,in which relative high-density dislocations were generated at both initial and final stages of crystal growth. The analysis of single-crystal X-ray topography shows that there are no apparent sub-grain boundaries; the dislocation lines are isolated and straight. Finally,the origins of low-density dislocation in sapphire crystal are discussed by numerical analysis method.     

Enhanced Physical and Mechanical Properties of Nitrile-Butadiene Rubber Composites with N-Cetylpyridinium Bromide-Carbon Black

The physical and mechanical properties of nitrile–butadiene rubber (NBR) composites with N-cetylpyridinium bromide-carbon black (CPB-CB) were investigated. Addition of 5 parts per hundred rubber (phr) of CPB-CB into NBR improved the tensile strength by 124%, vulcanization rate by 41%, shore hardness by 15%, and decreased the volumetric wear by 7% compared to those of the base rubber-CB composite.     

On isoperimetric problems for domains with partly known boundaries

In the present paper, we discuss the isoperimetric problems for domains with partly known boundaries, i.e., the problem of determining a domain that minimizes the capacity functional in the class of plain double-connected domains having the same fixed area and outer boundary. The formulas for capacity variations obtained in this paper allows us to formulate necessary conditions.It is proved that the convexity of the fixed outer boundary implies the convexity of the inner boundary corresponding to an optimal domain. Then, we discuss the case where the fixed part of the boundary is a square.Further, we consider similar problems with more complicated functionals. We introduce the concept of a minimal function in the class of equimeasurable functions. This concept allows us to unify the approach to all of these problems. At the end, we produce a hypothesis that, if proved, would enable us to characterize the shape of the optimal domains in the isoperimetric problems mentioned above.The author wishes to express his appreciation to Dr. K. A. Lurie for his help and unceasing attention.     

Atomic Structure and Properties of the (310) Symmetrical Tilt Grain Boundary (STGB) in SrTiO3 Part II: Comparison with Experimental Studies

The atomistic simulation results presented in Part I for SrTiO₃ (310) symmetrical tilt grain boundary (STGB, the so-called = 5 GB with 36.8° symmetrical misorientation about [001]) are analyzed in the context of available experimental studies. In particular, atomic imaging studies of SrTiO₃ GBs via high resolution TEM and incoherent Z-contrast STEM imaging; and determination of oxygen positions by combining electron energy loss spectroscopy (EELS) and bond-valence-sum rules, are compared with simulation results. The atomistic simulation data on the GB energies are compared with relative experimental estimates obtained via a novel approach of faceting of focused ion beam (FIB) induced microvoids.While there are considerable differences in details of simulation and experimental results, some basic trends seem to emerge about the core structural framework of GBs in SrTiO₃. The paper highlights the limitations of both, experimental and simulation techniques, and argues in favor of synergistic use of diverse experimental and simulation approach to determine the atomic structure and properties of GBs.