在LiCl-KCl-AlCl3熔盐中直接电化学还原Sm2O3及Al-Sm合金的形成

在803 K LiCl-KCl熔盐中, 研究了通过添加助剂AlCl₃直接电化学还原Sm₂O₃和Al-Sm合金的形成。以SmCl₃为原料作为参照, 采用循环伏安和方波伏安方法, 研究了Sm₂O₃在LiCl-KCl-AlCl₃熔盐体系中的电化学行为。通过对比发现在两个体系中, 峰的数量和位置基本一致, 这说明在LiCl-KCl熔盐中, 加入AlCl₃之后, 可以将Sm₂O₃有效氯化。计时电位结果表明, 当阴极电流比-139.8 mA·cm^-2更负时, Al和Sm共同还原。为了提取Sm, 采用恒电流从LiCl-KCl-AlCl₃-Sm₂O₃熔盐中电解得到Al-Sm合金样品, 并进行XRD表征, 结果表明可以通过调节AlCl₃和Sm₂O₃的浓度得到不同相的Al-Sm合金。     

Multiple conformations in polyampholytes

We study the configurational statistics of a ring polyampholyte chain made of N randomly charged monomers with elementary charge .To a large extent, the overall structure of a polyampholyte is controlled by a total sum Q of all charges. When the total charge is smaller than , the polyampholyte has a compact globular structure. At charges larger than , the configuration has the form of a ring of small globules (beads) connected by strings. Between Q₁ and Q₂ we find a remarkable diversity of meta-stable configurations having the shapes of irregular clusters of small globules connected by the strings. We estimate the number of these configurations and the energy barriers between them. Between Q₁ and Q₂, the minimum energy configurations are completely controlled by randomness in the charge distribution along the chain. There are hysteresis effects in the shapes of the clusters. As the total charge increases, the linearly extended configurations become dynamically more preferable. When the charge decreases, the circular shapes are preferred. We remark on the probable connection with the multiple phase transitions observed in polyampholyte gels. Received: 10 July 1997 / Accepted: 13 October 1997     

Electrophoresis of a charge-inverted macroion complex: Molecular-dynamics study

We have performed molecular-dynamics simulations to study the effect of an external electric field on a macroion in the solution of multivalent Z : 1 salt. To obtain plausible hydrodynamics of the medium, we explicitly make the simulation of many neutral particles along with ions. In a weak electric field, the macroion drifts together with the strongly adsorbed multivalent counterions along the electric field, in the direction proving inversion of the charge sign. The reversed mobility of the macroion is insensitive to the external field, and increases with salt ionic strength. The reversed mobility takes a maximal value at intermediate counterion valence. The motion of the macroion complex does not induce any flow of the neutral solvent away from the macroion, which reveals screening of hydrodynamic interactions at short distances in electrolyte solutions. A very large electric field, comparable to the macroion unscreened field, disrupts charge inversion by stripping the adsorbed counterions off the macroion. Received 5 December 2001 and Received in final form 10 April 2002     

Influence of Ag substitution on the local structure and glass-forming ability of Al86Ni(8-x)Y6Agx (X = 0,1,2) liquids

The local structure of Al₈₆Ni_(8-x)Y₆Ag_x (X = 0,1,2) molten and glassy alloy was investigated by ab initio molecular dynamics simulation. It transpired that the Al₈₆Ni_(8-x)Y₆Ag_x alloy can be considered as a combination of Ni- and Y-centred Al clusters with Ag as ‘glue atoms’. First and second Ag–Ag coordination was scarcely found in Al₈₆Ni₇Y₆Ag₁, but a medium-range order between 7.5 and 9 Å was observed. The enhanced glass-forming ability and thermal stability of the alloy compared with Al₈₆Ni₈Y₆ can be attributed to the medium-range order of the Ag–Ag correlation. A second Ag–Ag coordination occurs in Al₈₆Ni₆Y₆Ag₂ and results in a decrease in glass-forming ability. The inter-atomic distances between all constituting elements increase during cooling. This increase is ascribed to a change in distribution of clusters around Al atoms towards clusters with higher coordination number around Al.     

Liquid–liquid phase equilibrium in ternary immiscible Al–Bi–Sn melts

In this paper, the liquid-phase separation of ternary immiscible Al–Bi–Sn melts was studied with resistivity and thermal analysis methods at different temperatures. The resistivity–temperature curves appear anomalous and abrupt change as rising temperature, corresponding to the distinctive and low peak of melting process in the differential scanning calorimetry (DSC) curves, indicative of the occurrence of the liquid-phase separation. The anomalous behaviour of the resistivity temperature dependence is attributable to concentration–concentration fluctuations. The microheterogeneity–microhomogeneity transformation causes large fluctuations in concentration, which make the randomness and chaos of the atoms larger, leading to the greater impediment to electron movement and the sharp rise of resistivity. The addition of tin to the Al–Bi immiscible alloys decreases the monotectic reaction. It is concluded that concentration–concentration fluctuations are responsible for the anomalous behaviour of resistivity and DSC methods.     

Conformation of poly(L-lysine)-graft-poly(ethylene glycol) molecular brushes in aqueous solution studied by small-angle neutron scattering

Small-angle neutron scattering (SANS) has been employed for the analysis of conformations of poly(L-lysine)-graft-poly(ethylene glycol) (PLL-g -PEG) molecular bottle brushes in aqueous solutions. The degree of polymerisation of the PEG chains was systematically varied in order to unravel dependence of the conformational properties of the bottle brushes on the molecular weight of the grafted chains. The grafting density was kept constant and high enough to ensure strong overlap of the PEG chains. The scattering spectra were fitted on the basis of the model of an effective worm-like chain with the account of average radial distribution and local fluctuations of the PEG density in the bottle brush. The results of the fits indicate that molecular brushes retain weakly bent configuration on the length scale of the order of (or larger than) the brush thickness. This finding is in agreement with earlier simulation and recent theoretical results.     

Melt fracture of entangled polymers*

We construct a model for a slippage plane in a sheared melt, based on a balance between reptation bridging and shear debonding. The resulting state could show up at rather low shear rates and be locally stable. But it is not easy to nucleate: the conventional entangled state is also locally stable. We propose that slippage occurs on solid walls: either at the container surface, or on dust particles floating in the melt. Slippage at solid/melt interfaces was studied (experimentally and theoretically) long ago. There is a critical stress for slippage: our estimate (for strong adsorption of melt chains on the solid) gives (plateau modulus) for typical cases. Thus, melt fracture is expected at moderate stresses, in agreement with observations by S.Q. Wang and coworkers.     

In situ mapping of high-pressure fluids using hydrothermal diamond anvil cells

We present new results combining high pressures and temperatures attainable in a diamond anvil cell with in situ synchrotron radiation induced micro-X-ray fluorescence measurements. Hydrothermal diamond anvil cells experiments have been performed by measuring the partitioning of Pb between aqueous fluids (pure water or NaCl-enriched water) and hydrous silicate melts of haplogranite composition using synchrotron X-ray fluorescence. The in situ measurements were performed in the range 0.3–1.2 GPa and 730–850 ^°C both in the aqueous fluid and in the silicate melts being in equilibrium. Pb is strongly partitioned into high-pressure–temperature hydrous melts when Cl is present in either the hydrous melt or the aqueous fluid. Moreover, our comparisons of in situ results with post-mortem results show that significant changes take place during rapid quenching especially when samples are small (few hundred of microns in diameter). Water exsolution is induced by the quench in the silicate melt showing the high mobility of Pb which immediately partitions into the water vapor phase during the quench. The current in situ approach offers thus a pertinent complementary method to the classical experimental petrology investigations.     

In situ Pressure Fluctuations of Polymer Melt Flow Instabilities: Experimental Evidence about their Origin and Dynamics

Despite the practical importance of polymer melt instabilities, there is still a lack of experiments able to characterize in situ the origin and behavior of these phenomena. In this context, a new set‐up consisting of high sensitive pressure transducers located inside a slit‐die and an advanced mathematical framework to process in situ measurements of polymer melt instabilities, are developed and applied. Our results show for the first time that pressure oscillations can actually be detected inside the die under sharkskin conditions. This originates from a factor of 10³ and 10² improvement in terms of time and pressure resolution. Furthermore, new evidence towards the propagation of the slip phenomena along the die in spurt instabilities are found.