On the Theory of Phase Transitions in Magnetorheological Suspensions

The “condensation” of the particles of magnetorheological suspensions (MRSs) under the action of an external magnetic field is theoretically studied. The analysis demonstrated that the formation of rather long linear chain aggregates preceded the condensation of particles into the dense phase. The phase transition of the “gas-liquid” type proceeded in a particle ensemble via the “condensation” of such chains caused by their magnetic interaction. In thin MRS layers oriented perpendicular to the external magnetic field, the scenario of phase transition differs from that observed in systems with infinite volume. After the completion of the phase transition, the ensemble of dense domains discretely distributed in dilute dispersion is formed in thin layers rather than two simple connected phases with different particle concentrations, as it takes place in infinite media. Under fairly strong external magnetic fields, the transition of the “gas-solid” type occurs in a system of particles.     

聚苯胺粒子悬浮液的电流变特性

将聚苯胺作为分散粒子，电绝缘油 分散介质组成电流变流体，研究了电场强度，温度等因素与ＥＲＦ的静态屈服应力和电流密度的关系。结果表明：τｓ和ｉ随电场强度的变化皆成指数关系。     

Electrorheological Response and Structure Growth of Colloidal Silica Suspensions

The electrorheological response and structure growth of colloidal silica suspension was studied with in situ measurements of the shear stress, electric conductivity, and dielectric permittivity of the suspension. The measurements were carried out under steady and sweep shears after the application of an electric field of alternative current (100 Hz) using silica particles with a diameter of 630 nm and a water content of 4.5 wt%. The measurements of the conductivity enabled the detection of structure growth formed by particle aggregation and clarified that the development of the particle aggregation enlarged the dielectric permittivity and the shear stress. Hysteretic behavior observed in the electrorheological response was explained by considering structure growth of the particle aggregation. The correlation equation for the shear stress and the dielectric permittivity obtained in our previous work (1) was found to be applicable to the present results. Copyright 2001 Academic Press.     

稀土掺杂聚苯撑ER流体的研究

选用CeCl4和FeCl3等对自制的对苯撑进行掺杂,将制得的高介电聚苯撑粉末加入到硅油中得到电流变体流体,测量了在电场作用下粘度和漏电流密度,以及相关的物理常数。讨论了电场强度、粒子浓度与粘度和漏电流密度的关系,粘度变化的响应速度和恢复时间,并探讨了其相关机制。     

Crystallographic and Magnetic Phase Transitions in the Layered Ruthenium Oxyarsenides TbRuAsO and DyRuAsO

The crystallographic and physical properties of TbRuAsO and DyRuAsO at and below room temperature are reported, including full structure refinements from powder X-ray diffraction data and measured electrical and thermal transport properties, magnetic susceptibility, and heat capacity. Both compounds are isostructural to LaFeAsO (ZrCuSiAs-type, P4/nmm) at room temperature. However, DyRuAsO undergoes a symmetry-lowering crystallographic phase transition near 25 K, and adopts an orthorhombic structure (Pmmn) below this temperature. This structural distortion is unlike those observed in the analogous Fe compounds. Magnetic phase transitions are observed in both compounds which suggest antiferromagnetic ordering of lanthanide moments occurs near 7.0 K in TbRuAsO and 10.5 K in DyRuAsO. The nature of the structural distortion as well as thermal conductivity and heat capacity behaviors indicate strong coupling between the magnetism and the lattice. The behaviors of both materials show magnetic ordering of small moments on Ru may occur at low temperatures.     

稀土掺杂TiO2颗粒的制备及其悬浮液的电流变特性

通过掺杂稀土元素,使TiO2电流变液的屈服强度提高到近5 kPa (3 kV/mm).用DSC-TG、 IR和XRD等手段对材料的Sol-gel制备过程和产物的晶体结构进行了分析.结果表明纯TiO2和掺杂稀土TiO2凝胶的分解分三阶段完成,并形成锐钛矿结构.掺杂浓度小于一定值时,稀土离子以置换Ti位固溶于TiO2晶格中并引起晶格膨胀.认为适当掺杂所导致的晶格常数变化改善了材料的介电性能,从而使TiO2的电流变性能优化.     

Structural Phase Transitions and Magnetic Superexchange in MIAgIIF3 Perovskites at High Pressure**

Pressure-induced phase transitions of M^IAg^IIF₃ perovskites (M=K, Rb, Cs) have been predicted theoretically for the first time for pressures up to 100 GPa. The sequence of phase transitions for M=K and Rb consists of a transition from orthorhombic to monoclinic and back to orthorhombic, associated with progressive bending of infinite chains of corner-sharing [AgF₆]⁴⁻ octahedra and their mutual approach through secondary Ag⋅⋅⋅F contacts. In stark contrast, only a single phase transition (tetragonal→triclinic) is predicted for CsAgF₃; this is associated with substantial deformation of the Jahn–Teller-distorted first coordination sphere of Ag^II and association of the infinite [AgF₆]⁴⁻ chains into a polymeric sublattice. The phase transitions markedly decrease the coupling strength of intra-chain antiferromagnetic superexchange in MAgF₃ hosts lattices.     

A Surfactant Bridge Model for the Nonlinear Electrorheological Effects of Surfactant-Activated ER Suspensions

In surfactant-activated electrorheological (ER) suspensions it is observed that the ER response shows linear ER behavior (F~E(2)) at small surfactant concentrations and nonlinear ER behavior (F~E(n), n approximately 1) at large surfactant concentrations. Here, a surfactant bridge model is developed to explain the nonlinear ER behavior of surfactant-activated ER suspensions. The model shows that the formation and size of a surfactant bridge depend on various variables, especially the electric field strength, the surfactant surface tension, and the initially adsorbed amount of surfactants on particles. The predicted dependence of the formation and size of a surfactant bridge on the electric field strength and the initially adsorbed amount of surfactants is consistent with the observations. Also, the model indicates that there is a critical minimum electric field E(crit) for the formation of a surfactant bridge, and the estimated E(crit) shows good agreement with the observations. The force acting between particles is composed of the electrostatic force and force associated with surface tension. However, it is found that the contribution of the force associated with surface tension can be ignored and the electrostatic force is dominant regardless of the formation of surfactant bridges between particles. When surfactant bridges are formed between particles, the predicted force shows nonlinear ER behavior (F~E(n), n approximately 1), consistent with the observed nonlinear ER behavior at large surfactant concentrations. When no surfactant bridge is formed, the predicted force is proportional to the electric field squared (F~E(2)), consistent with the interfacial polarization. The model can successfully predict the nonlinear ER behavior at large surfactant concentrations, confirming that the nonlinear ER behavior of surfactant-activated ER suspensions arises from the observed formation of surfactant bridges between particles. Copyright 2001 Academic Press.     

Coherent Disperse Structures in Magnetic Suspensions

Results of computer and physical simulation of cooperative behavior of a system of interacting ferroparticles in a liquid matrix under the action of rotating magnetic field are reported. It is shown that, under far from equilibrium (with respect to orientational variables) conditions, the phenomenon of dissipative self-organization arises resulting in the formation of coherent disperse structures.     

Phase Transitions in Solid Methanol

Neutron powder diffraction patterns were measured for the ordered α-phase and the disordered β-phase of deuterated methanol. The structure of the α-phase at 160 K is in agreement with that found earlier at 15 K. A complete refinement of the structure of the β-phase at 170 K was also carried out. The space groups are α-P2₁2₁2₁ and β-Cmcm. For the disordered phase, the thermal parameters indicate that the molecules are localized rather than being in free rotation. A transformation matrix was found that relates the unit cells of the two phases. The transition involves mainly the large-angle rotation of molecules in a plane. In a second experiment, the α- to β-phase transition in both deuterated and undeuterated solid methanol was examined using Raman spectroscopy and a metastable phase was produced, for the undeutered sample, by rapid quenching through the phase transition. Only two modes of the methyl groups in this metastable phase differ from the internal modes of the stable α-phase.     

Transitions of Chain＇s Conformation in the Lytropic Condensation of Macromolecules

详细讨论了稀溶液、亚浓溶液、浓溶液和极浓溶液中分子链构象的演变，考察了在溶致凝聚过程中分子链的链间相互作用、关联作用和分子链尺寸的变化规律，给出了排除体积的严格定义，引入热关联效应、长程关联效应和全高斯链浓度等概念。指出在不同浓度溶液中，分子链在不同尺度上构象状态不同；在从孤立单链态（良溶液中）向多链聚集态的溶致凝聚过程中，单链的尺寸一直在收缩，由Flory尺寸RF缩小至无扰尺寸Ro。这是大分子凝聚过程的一个特点。     

Some Aspects of Magnetic Filtration Theory for Removal of Fine Particles from Aqueous Suspensions

The magnetic filtration theory was evaluated to intensify the filtration of industrial fluids by magnetic filters. Effects of filtration velocity and external magnetic field intensity on filter performance were investigated and the dependence of the logarithmic efficiency coefficient on filtration velocity was questioned. It was concluded that change in the magnetic susceptibility of the dispersion particles, caused by external magnetic field, and change in the flow rate properties of the liquid alongside the filter pores are the most essential factors to be considered in the design, development, and modeling of magnetic filtration systems in various industrial areas.     

电流变技术中的控制理论及参数优化

针对ER型动力元件,阐述了含ER技术的机械系统控制方程的建立方法,运用控制理论建立了其状态方程.同时,对其进行了一般性分析及参数优化设计.发现电流变动力元件可以很简单地依靠调整工作位置来改善元件的动态性能.ER型流体控制元件属典型阻尼元件.     

Phase Transitions in Electro- and Magnetorheological Fluids

The model of internal structural phase transformations occurring in electro- and magnetorheological fluids under the action of external electric (magnetic) field is presented. The model describes both types of experimentally observed transformations such as the formation of linear chain clusters and bulk dense phases composed of suspension particles. The main qualitative result of this work is the conclusion that the appearance of chain clusters precedes the suspension separation into bulk phases with different particle densities and considerably affects the phase equilibrium diagrams. This conclusion agrees with the results of known experiments.     

On the Theory of Structural Transformations in Magnetic Fluids

Results of studying a new scenario of condensation phase transition in the ensemble of ferrofluid particles are reported. Phase transition in this ensemble starts with the formation of chain clusters. Chains whose length exceeds a certain critical value dependent on temperature and magnetic field undergo collapse and are transformed into very dense globules. The globule evolution leads to the separation of ferrofluid into two phases with different particle density. Initial (chain collapse) and final (equilibrium) stages of phase transition are investigated. Calculations of the critical length of a chain corresponding to its collapse, as well as the characteristics of dense phase at the final separation stage are in good agreement with the results of known experiments.     

Phase Transitions in Non-ionic Detergent Micelles

Differential scanning calorimetry (DSC) studies of micellar, 60 mM solutions of the octaethyleneglycol alkylethers C₁₄E₈ and C₁₆E₈ provide evidence for a narrow endothermic transition at 41 and 32°C,respectively, characterized by an enthalpy change of 2 kJ mol⁻¹ for both detergents. The observed thermal transition is indicative of a concerted transition of the surfactant molecules, as illustrated on the basis of a simple molecular model. The effect of co-solvents such as different alcohols on the thermal transition is investigated. Glycerol markedly lowers the transition temperature whereas the transition is absent in the presence of at least 10% ethanol. The calorimetric transition correlates with the temperature dependent increase of viscosity and static light scattering as well as with changes observed by small-angle neutron scattering (SANS). The SANS results provide clear evidence for a distinct structural change occurring at the transition temperature, which is interpreted as a sphere-to-rod transition of the detergent micelles. Moreover, the rod length increases with increasing temperature. We suggest that the process causing the thermal transition acts as the prerequisite of the growth process. This revised version was published online in August 2006 with corrections to the Cover Date.     

D-和L-丙氨酸的磁手性相变

利用变温直流磁化率测定, 在外加磁场强度为1 T, 磁场平行晶体c轴, 发现在温度270 K, D-和L-丙氨酸发生磁手性相变. 结合中子衍射确定磁手性相变机制为, D-和L-丙氨酸中的(N+H)有类金属氢原子特性, 在相变点270 K, 由(N+H)释放的电子自旋有磁手性. 用变温偏振拉曼光谱进一步证明, D-丙氨酸中的(N+H)的电子自旋(↑), 而L-丙氨酸中的电子自旋(↓), 处于高低不同的能态.磁手性相变(宇称和时间反演都破缺)能差为10^-4-10^-5 eV·molecule^-1.     

Magnetic Chirality Transitions of D- and L-Alanine

A chiral spin state of (N⁺H) in D- and L-alanine was established by monitoring the temperature dependence of dc-magnetic susceptibility (dc: direct current) under the external magnetic field of 1 T. An intrinsic spin chirality of electrons in the atomic magnetic dipole moment of (N⁺H) was also supported by polarized Raman spectroscopy. Magnetic chirality was associated with a strongly correlated electron system that was related to spin rigidity. Raman vibrational spectra were unrelated to structural chirality but could reflect spin chirality due to the reversal of motion breaking. The spin transition of (N⁺H) occured at 270 K without bond breaking but was assisted by an intermediate hydrogen bond elongation, splitting and reformation with NH₃⁺ torsion. The energy difference of spin chirality transitions between D- and L-alanine was around 10⁻⁴-10⁻⁵ eV·molecule⁻¹.     

Structural Changes and Phase Transitions in Whitlockite-Like Phosphates

New compounds with a g -Ca 3 (PO 4 ) 2 structure type were found in three systems: Sr 9+ x M 1.5 m x (PO 4 ) 7 ( M = Mn, Fe, Co, Ni, Cu, and Cd; space group R 3 m ; Z = 3), Sr 9 R (PO 4 ) 7 ( R = Al, Sc, Cr, Fe, Ga, In, and Gd-Lu; space group P 2/ c , Z = 4), and Sr 9+2 x M 1+ x A 1 m 6 x (PO 4 ) 7 ( M = Mn, Ni, Cd; space group R 3 c and Z = 6 for A = Na, K; space group P 2/ m and Z = 4 for A = Li). Crystal structures of these compounds were determined by time-of-flight neutron, synchrotron X-ray, and laboratory X-ray powder diffraction. Reversible polar-to-centrosymmetric phase transitions ( R 3 c {\begin{array}{c}\\[-14pt]\hspace*{.5pt}\to\\[-7pt]\hspace*{-.5pt}\gets \end{array}} R 3 m ) were observed at high temperatures in Ca 3 m x Sr x (PO 4 ) 2 (0 h x h 12/7), Ca 10.5 m 1.5 x Fe x (PO 4 ) 7 (0 h x h 1), and Ca 9 R (PO 4 ) 7 . Solid solutions Ca 3 m x Sr x (PO 4 ) 2 (13/7 h x h 16/7) are centosymmetric with space group R 3 m at room temperature. These phase transitions were studied by high-temperature X-ray diffraction, second-harmonic generation, DSC, electric-conductivity and dielectric measurements.