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91.
N. Lee S. Obukhov 《The European Physical Journal B - Condensed Matter and Complex Systems》1998,1(3):371-376
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 相似文献
92.
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 相似文献
93.
The local structure of Al86Ni(8-x)Y6Agx (X = 0,1,2) molten and glassy alloy was investigated by ab initio molecular dynamics simulation. It transpired that the Al86Ni(8-x)Y6Agx 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. 相似文献
94.
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. 相似文献
95.
The influence of ultrasound-assisted rapid hydrothermal synthesis of aluminosilicate ZSM-5 catalysts was examined in this work. A series of MFI-type nanostructured materials with sonochemical approach and conventional heating were synthesized and evaluated for conversion of methanol to propylene reaction. The prepared samples were tested by characterization analyses such as XRD, FESEM, BET-BJH, FTIR, TPD-NH3 and TG/DTG. The obtained results confirmed that ultrasound treatment enhanced the nucleation process and crystal growth for ZSM-5 sample synthesized at moderate temperature of 250 °C. Therefore, it was found the formation of pure MFI zeolite with high crystallinity and improved textural, structural and acidic properties for ZSM-5(UH-250) sample compared with the other zeolites. This observation was attributed to the relationship between the perfect crystallization mechanism and catalytic properties, which led to producing an efficient MFI zeolite toward the optimal catalytic performance. In this manner, the methanol conversion and products selectivity of prepared materials were carried out in MTP reaction at 460 °C and atmospheric pressure. The ZSM-5(UH-250) zeolite with slower deactivation regime exhibited the constant level of methanol conversion (84%) and high propylene selectivity (78%) after 2100 min time on stream. Moreover, the synthesis pathway for MFI zeolite at moderate temperature and also deactivation mechanism of improved sample were proposed. 相似文献
96.
Feuz L Strunz P Geue T Textor M Borisov O 《The European physical journal. E, Soft matter》2007,23(3):237-245
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. 相似文献
97.
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. 相似文献
98.
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. 相似文献
99.
本文测定了Na4GeO4、Na2GeO3、Na2Ge4O9和Na4Ge9O20等晶体从273K到1413K升温及熔体的拉曼光谱,结合分析金红石型GeO2的相关结构和光谱,研究了其微结构单元在升温过程中的变化、熔体中的形态和锗的氧配位数及其温致变化。Na4GeO4和Na2GeO3晶体结构单元为GeO4四面体,在升温过程及其熔体中锗维持四配位。Na2Ge4O9和Na4Ge9O20晶体结构单元为GeO4四面体和GeO6八面体共存,升温过程中,GeO6八面体将发生结构转变,在熔融状态全部转变为GeO4四面体,并产生与钠离子等摩尔分数的非桥氧,在熔体中锗的氧配位数为4。研究还表明,桥氧的对称弯曲振动模可以反映不同微结构单元间的连接,并且随着温致结构的变化而产生特征性的变化。 相似文献
100.
Humberto Palza Ingo F. C. Naue Manfred Wilhelm 《Macromolecular rapid communications》2009,30(21):1799-1804
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.