Crystallization of micelles and matrix in dilute diblock copolymer/homopolymer solutions

The crystallization, morphology, and crystalline structure of dilute solid solutions of tetrahydrofuran-methyl methacrylate diblock copolymer (PTHF-b-PMMA) in poly(ethylene oxide) (PEO) and PTHF have been studied with differential scanning calorimetry (DSC), X-ray, and optical microscopy. This study provides a new insight into the crystallization behavior of block copolymers. For the dilute PTHF-b-PMMA/PEO system containing only 2 to 7 wt % of PTHF content, crystallization of the PTHF micellar core was detected both on cooling and on heating. Compared the crystallization of the PTHF in the dilute solutions with that in the pure copolymer, it was found that the crystallizability of the PTHF micellar core in the solution is much greater than that of the dispersed PTHF microdomain in the pure copolymer. The stronger crystallizability in the solution was presumably due to a softened PMMA corona formed in the solution of the copolymer with PEG. However, the "soft" micelles formed in the solution (meaning that the glass transition temperatures (T-g) of the micelle is lower than the T-m of the matrix phase) showed almost no effects on the spherulitic morphology of the PEO component, compared with that of the pure PEO sample. In contrast, significant effects of the micelles with a "hard" PMMA core (meaning that the T-g of the core is higher than the T-m of the PTHF homopolymer) on the nucleation, crystalline structure, and spherulitic morphology were observed for the dilute PTHF-b-PMMA/PTHF system. (C) 1998 John Wiley & Sons, Inc.

Microstructural evolution and formation of nanocrystalline intermetallic compound during surface mechanical attrition treatment of cobalt

Nanocrystalline intermetallic Co3Fe7 was produced on the surface of cobalt via surface mechanical attrition (SMA). Deformationinduced diffusion entailed the formation of a series of solid solutions. Phase transitions occurred depending on the atomic fraction of Fe in the surface solid solutions: from hexagonal close-packed (<4% Fe) to face-centered cubic (fcc) (4-11% Fe), and from fcc to body-centered cubic (>11% Fe). Nanoscale compositional probing suggested significantly higher Fe contents at grain boundaries and triple junctions than grain interiors. Short-circuit diffusion along grain boundaries and triple junctions dominate in the nanocrystalline intermetallic compound. Stacking faults contribute significantly to diffusion. Diffusion enhancement due to high-rate deformation in SMA was analyzed by regarding dislocations as solute-pumping channels, and the creation of excess vacancies. Non-equilibrium, atomic level alloying can then be ascribed to deformation-induced intermixing of constituent species. The formation mechanism of nanocrystalline intermetallic grains on the SMA surface can be thought of as a consequence of numerous nucleation events and limited growth. (C) 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Enhanced luminescence from transparent Ni2+-doped MgO-Al2O3-SiO2 glass ceramics by Ga2O3 addition

Transparent Ni2+-doped MgO-Al2O3-SiO2 glass ceramics without and with Ga2O3 were synthetized. The precipitation of spinel nanocrystals, which was identified as solid solutions in the glass ceramics, could be favored by Ga2O3 addition and their sizes were about 7.6 nm in diameter. The luminescent intensity of the Ni2+-doped glass ceramics was largely enhanced by Ga2O3 addition which could mainly be caused by increasing of Ni2+ in the octahedral sites and the reduction of the mean frequency of phonon density of states in the spinel nanocrystals of solid solutions. The full width at half maximum (FWHM) of emissions for the glass ceramics with different Ga2O3 content was all more than 200 nm. The emission lifetime increased with the Ga2O3 content and the longest lifetime is about 250 mu s. The Ni2+-doped transparent glass ceramics with Ga2O3 addition have potential application as broadband optical amplifier and laser materials. (C) 2007 Elsevier Ltd. All rights reserved.

Effect of partial site occupation on the magnetic properties of Nd2Fe17-xSix by supercell calculation

The magnetic properties of the Nd2Fe17-xSix intermetallic compounds are studied by means of spin-polarized supercell calculations in which the selected sites of substitution are close to the situations in real samples. It is shown that the average Fe moment increases with x and saturates near x = 3. This correlates quite well with the experimental dependence of Te on x. The difference between supercell and unit cell calculations are pointed out and the influence of Si atoms on the density of states of the nearby Fe atoms is emphasized. (C) 1997 American Institute of Physics.

Preparation and Electrical Properties of New Oxide Ion Conductors Ce6-xGdxMoO15-delta (0.0 <= x <= 1.8)

A series of oxide ion conductors Ce6-xGdxMoO15-delta (0.0 <= x <= 1.8) have been prepared by the sol-gel method. Their properties were characterized by differential thermal analysis/thermogravimetry (DTA/TG), X-ray diffraction (XRD), Raman, IR, X-ray photoelectron spectroscopy (XPS), and AC impedance spectroscopy. The XRD patterns showed that the materials were single phase with a cubic fluorite structure. The conductivity of Ce6-xGdxMoO15-delta increases as x increases and reaches the maximum at x = 0.15. The conductivity of Ce4.5Gd1.5MoO15-delta is sigma(t) = 3.6 x 10(-3) S/cm at 700 degrees C, which is higher than that of Ce4.5/6Gd1.5/6O2-delta (sigma(t) = 2.6 x 10(-3) S/cm), and the corresponding activation energy of Ce4.5Gd1.5MoO15-delta (0.92 eV) is lower than that of Ce4.5/6Gd1.5/6O2-delta (1.18 eV).

Calculation of bulk modulus on carbon nitrides with chemical bond method

The bulk moduli of some superhard materials were calculated by using the chemical bond method. For simple crystals, such as diamonds, c-BN, SiC, Si, BP, and Ge, the calculated results agree with experimental and theoretical values. For crystals of complex structure, such as beta-BC2N crystal and various structural C3N4 crystals, the results indicate that their bulk moduli are large, but do not exceed that of diamond.

Grain boundary conductivity of high purity neodymium-doped ceria nanosystem with and without the doping of molybdenum oxide

Solid solutions of Ce1-xNdxO2-x/2 (0.05 <= x <= 0.2) and (Ce1-xNdx)(0.95)MO0.05O2-delta (0.05 <= x <= 0.2) have been synthesized by a modified sol-gel method. Both materials have very low content of SiO2 (similar to 27 ppm). Their structures and ionic conductivities were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM) and electrochemical impedance spectroscopy (M). The XRD patterns indicate that these materials are single phases with a cubic fluorite structure. The powders calcined at 300 degrees C with a crystal size of 5.7 nm have good sinterability, and the relative density could reach above 96% after being sintered at 1450 degrees C. With the addition Of MoO3, the sintering temperature could be decreased to 1250 degrees C. Impedance spectroscopy measurement in the temperature range of 250-800 degrees C indicates that a sharp increase of conductivity is observed when a small amount of Nd2O3 is added into ceria, of which Ce0.85Nd0.15O1.925 (15NDC) shows the highest conductivity. With the addition of a small amount Of MoO3, the grain boundary conductivity of 15NDC at 600 degrees C increases from 2.56 S m(-1) to 5.62 S m(-1).

Synthesis, reactive mechanism and thermal stability of W1-xAlxC (x=0.33, 0.5, 0.75, 0.86) nanocrystalline

W1-xAlxC (x = 0.33, 0.50, 0.75, 0.86) solid solutions have been synthesized directly by ball-milling tungsten powder, aluminum powder and activated carbon. The structural development of W0.5Al0.5C phase with the milling times up to 160 h has been followed using X-ray diffraction. X-ray photoelectron spectra demonstrate that Al atom takes the place of W. High temperature annealing experiment reveals that Al is stable in hexagonal structure to 1873 K. Transmission electron microscopy image shows that the grain size of the prepared powders is about 5 nm.

海相碳酸盐－稀土元素共沉淀过程中的分异作用研究

本文主要运用稳定加液－反应系统对海水中方解石和文石形成时稀土元素的共沉淀现象进行了分析，研究了稀土元素在固-液体系中的迁移、转化和分配。进而在对其定量描述的前提下，研究了稀土元素共沉淀对各种反应条件的响应，并对共沉淀行为的机制进行了探讨。 本实验首先运用pH测试、高精度滴定分析等手段测定了实验中的一些基本参数，如[H+]、碱度和[Ca2+]，根据计算结果获得了各碳酸体系要素，并以此为基础建立了5℃、15℃和25℃及pCO2=0.003atm下海水中方解石或文石的沉淀动力学方程。实验结果表明： 1）在各条件下，方解石或文石的沉淀速率（R）和其在海水中过饱和度（Ω）存在很好的线性相关性，即海相碳酸盐的沉淀动力学方程可以通过下面的基本表达式来表示：LogR=k*Log(Ω-1)+b ； 2）过高的稀土元素浓度会对文石或方解石的沉淀产生抑制作用，进而对共沉淀过程中YREEs的分异和分馏产生一定的影响。相比方解石而言，文石的沉淀动力学过程承受稀土元素的干扰能力更强； 3）不同温度下得到的方解石或文石各自的沉淀动力学方程存在明显的差异，表明这一过程受热力学因素控制。相对于方解石而言，温度对文石的沉淀动力学的影响更为显著。 与前人研究不同的是，本实验中YREEs的浓度设定在非常低的范围内，从而避免了过高浓度YREEs对方解石或文石沉淀动力学过程的干扰。在最终的反应液中，各种实验条件非常接近自然环境。有关稀土元素的共沉淀行为主要得出以下定性或定量化结论： 1）YREEs在随方解石或文石的共沉淀过程中，均发生了强烈的分异作用。在方解石实验中，稀土元素的分异系数分布曲线呈凸状分布；而在文石实验中，稀土元素的分异系数随原子序数的增加逐渐减小，遵循镧系收缩的规律。总的来说，稀土元素，尤其轻稀土元素在文石中的分异作用要强于方解石。 2）无论是方解石还是文石，沉淀速率对YREEs的分异作用都有着明显的影响。在方解石中，YREEs的分异系数随沉淀速率的增加呈一致性递减趋势；而在文石中，其分异系数对文石沉淀速率有着截然不同的响应：轻稀土元素（La, Ce, Nd, Sm, Eu, Gd）的分异系数随文石沉淀速率的增加而下降，而重稀土元素（Ho, Y, Tm, Yb , Lu）的分异系数则随文石沉淀速率的增加呈上升趋势。 3）在方解石中YREEs的分异系数之间存在非常好的相互关系，表明这些元素是以成比例的方式参与共沉淀。整个谱系呈现中等强度的分馏，MREE相对于LREE和HREE要更为富集；在文石中由于沉淀速率的作用不同，只有Y、Ho、Yb、Lu等元素的分异系数之间有较好的相互关系。YREEs出现了差异性的强烈分馏，在新生成沉淀中轻稀土元素相对于重稀土元素强烈富集。 4）YREEs在溶液中和碳酸盐晶体表面的碳酸根配位形式对YREEs在共沉淀过程中的分异作用极为重要，YREEs在碳酸盐晶体表面的吸附是整个谱系发生分馏效应的关键环节。对于文石来讲，晶体中有效YREE离子和Ca离子半价大小之间的相近程度是其分馏效应的关键因素；而对于方解石来说，YREEs在方解石晶格中的安置就是其分馏效应的关键控制因子，但在晶格安置中起到关键作用的是YREEs和方解石中O原子之间离子键M-O的键长，而非离子半径。 5）综合YREEs在方解石中的分异作用和分馏效应，我们认为M2(CO3)3-CaCO3和MNa(CO3)2-CaCO3是最为可能的两种固体溶液形成模式。 最为重要的是，对比我们的实验结果与前人在灰岩、叠层石、微生物成因碳酸盐等方解石质载体中的研究成果，两者之间出现了非常好的一致性。我们认为方解石质载体将是重建古海水中稀土元素相关信息的重要工具。相比之下，文石质载体不适合作为类似的载体。

Damage analysis of tetragonal perovskite structure ceramics implicated by asymptotic field solutions and boundary conditions

Cracking of ceramics with tetragonal perovskite grain structure is known to appear at different sites and scale level. The multiscale character of damage depends on the combined effects of electromechanical coupling, prevailing physical parameters and boundary conditions. These detail features are exhibited by application of the energy density criterion with judicious use of the mode I asymptotic and full field solution in the range of r/a = 10(-4) to 10(-2) where r and a are, respectively, the distance to the crack tip and half crack length. Very close to the stationary crack tip, bifurcation is predicted resembling the dislocation emission behavior invoked in the molecular dynamics model. At the macroscopic scale, crack growth is predicted to occur straight ahead with two yield zones to the sides. A multiscale feature of crack tip damage is provided for the first time. Numerical values of the relative distances and bifurcation angles are reported for the PZT-4 ceramic subjected to different electric field to applied stress ratio and boundary conditions that consist of the specification of electric field/mechanical stress, electric displacement/mechanical strain, and mixed conditions. To be emphasized is that the multiscale character of damage in piezoceramics does not appear in general. It occurs only for specific combinations of the external and internal field parameters, elastic/piezoelectric/dielectric constants and specified boundary conditions. (C) 2002 Published by Elsevier Science Ltd.

SOLID DEFECT STRUCTURE AND CATALYTIC ACTIVITY OF PEROVSKITE-TYPE CATALYSTS LA1-XSRXNIO3-LAMBDA AND LA1-1.333XTHXNIO3-LAMBDA

Two series of La1-xSrxNiO3-lambda and La1-1.333xThxNiO3-lambda catalysts have been prepared, and the relationships between the solid defect structure and catalytic activity for NH3 oxidation were measured. The results showed that in the range of x < 0.3, the samples possessed single perovskite-type structure, and as the content of Sr2+ decreased and that of Th4+ increased the catalytic activity increased which was paralleled with the Ni3+ concentration within the catalysts. The active oxygen species (O- or O2(2-)) were present not only on the surface but also in the bulk of the samples. The synergistic effect of transition metal ions with higher oxidation states and randomly distributed oxygen vacancies was the key factor determining catalytic activity of perovskite-type oxides. A redox mechanism for NH3 oxidation over ABO3 is proposed.

A Crack Perpendicular to the Bimaterial Interface in Finite Solid

The dislocation simulation method is used in this paper to derive the basic equations for a crack perpendicular to the bimaterial interface in a finite solid. The complete solutions to the problem, including the T stress and the stress intensity factors are obtained. The stress field characteristics are investigated in detail. It is found that when the crack is within a weaker material, the stress intensity factor is smaller than that in a homogeneous material and it decreases when the distance between the crack tip and interface decreases. When the crack is within a stiffer material, the stress intensity factor is larger than that in a homogeneous material and it increases when the distance between the crack tip and interface decreases. In both cases, the stress intensity factor will increase when the ratio of the size of a sample to the crack length decreases. A comparison of stress intensity factors between a finite problem and an infinite problem has been given also. The stress distribution ahead of the crack tip, which is near the interface, is shown in details and the T stress effect is considered.

Finite Element Solutions for Plane Strain Mode I Crack with Strain Grading Effect

In this paper, a new phenomenological theory with strain gradient effects is proposed to account for the size dependence of plastic deformation at micro- and submicro-length scales. The theory fits within the framework of general couple stress theory and three rotational degrees of freedom omega(i) are introduced in addition to the conventional three translational degrees of freedom mu(i). omega(i) is called micro-rotation and is the sum of material rotation plus the particles' relative rotation. While the new theory is used to analyze the crack tip field or the indentation problems, the stretch gradient is considered through a new hardening law. The key features of the theory are that the rotation gradient influences the material character through the interaction between the Cauchy stresses and the couple stresses; the term of stretch gradient is represented as an internal variable to increase the tangent modulus. In fact the present new strain gradient theory is the combination of the strain gradient theory proposed by Chen and Wang (Int. J. Plast., in press) and the hardening law given by Chen and Wang (Acta Mater. 48 (2000a) 3997). In this paper we focus on the finite element method to investigate material fracture for an elastic-power law hardening solid. With remotely imposed classical K fields, the full field solutions are obtained numerically. It is found that the size of the strain gradient dominance zone is characterized by the intrinsic material length l(1). Outside the strain gradient dominance zone, the computed stress field tends to be a classical plasticity field and then K field. The singularity of stresses ahead of the crack tip is higher than that of the classical field and tends to the square root singularity, which has important consequences for crack growth in materials by decohesion at the atomic scale. (C) 2002 Elsevier Science Ltd. All rights reserved.

Nontoxic electrodes of solid amalgams

This is a review of electrodes based on nontoxic solid amalgams (MeSAE) (prepared by amalgamation of soft metal powders) in connection with some other kinds of voltammetric electrodes is given. Information is summarized on various types of MeSAEs (esp. AgSAE, CuSAE, AuSAE), pretreatment of their surfaces, their hydrogen overvoltage in aqueous solutions, conditions for their testing, electroanalytical parameters and use, in compared with the hanging mercury drop electrode (HMDE). Although the solid amalgam electrodes do not reach the quality of the HMDE, in many cases they represent its possible alternative. The broad range of voltammetric applications of the MeSAEs, especially of the AgSAEs, their good mechanical stability, simple handling, and new aspects of their use in electrochemical techniques are documented by numerous examples.

The solid-liquid extraction of yttrium from rare earths by solvent (ionic liquid) impreganated resin coupled with complexing method

A kind of solvent (ionic liquid) impreganated resin (IL-SIR) was developed herein for ameliorating imidazolium-type IL-based liquid-liquid extraction of metal ions. In this study, [C(8)mim][PF6] containing Cyanex923 was immobilized on XAD-7 resin for solid-liquid extraction of rare earth (RE). The solid-liquid extraction contributed to ameliorating mass transfer efficiency, i.e. shortening equilibrium time from 40 min to 20 min, increasing extraction efficiency from 29% to 80%. In additional, the novel IL-SIR could separate Y(III) from Sc(III), Ho(III), Er(III), Yb(III) effectively by adding water-soluble complexing agent.