Monolayers of graft and block copolymers

Surface pressure-area isotherms for monolayers from graft copolymers with one branch (or four) and diblock copolymers were determined at air/aqueous medium interfaces. The dependence of surface pressure on area for poly(vinyl acetate) (PVAc)-polystyrene(PS) graft and block copolymers was identical to that of pure PVAc at the large areas, while a sharp increase in pressure appeared with further compression. The surface pressure of PVAc-PS graft copolymer at the air/0. 2 N NaOH interface decreased with time, but the critical area at which the surface pressure increased rapidly remained constant, regardless or hydrolysis time. When a poly(vinyl alcohol) (PVA)-PS graft or block copolymer was spread over water, the surface pressure originating from the PVA chain was too small to be observed, and merely that of the PS sequence appeared. It was concluded that the PS sequence was always present in the form of a tightly coiled sphere at the interfaces, whereas the PVAc sequence was spread as a monomolecular film on water but diffused into the alkaline substrate as a result of the hydrolysis to PVA. Thus the PVA-PS graft and block copolymers spread on water seem to be so oriented that the PVA chain “dissolved” in water is supported at the interface by the compact, monomolecular particle of PS on the surface.     

Elastic properties,Debye temperature,density of states and electron–phonon coupling of ZrB12 under pressure

The structural parameters, elastic constants and the electronic density of states of ZrB₁₂ under pressure are determined using first-principles calculations with plane-wave pseudopotential density functional theory, within the generalized gradient approximation. From the elastic constants the elastic parameters and Debye temperature were calculated. They increase as the pressure is increased. The density of states at the Fermi level decreases as pressure is increased, changing from 0.576 to 0.515. Using the Debye temperature and the McMillan equation, the electron–phonon coupling constant was obtained as a function of pressure. It is found that the electron–phonon coupling constant is proportional to the logarithm of the ratio between the value of the Debye temperature and the value of the superconducting critical temperature.     

The immutability of the critical current under any sample cross-sectional form modification

The temperature and size dependences of the critical currents in bismuth-based high-temperature superconducting ceramic samples consisting of randomly oriented grains have been studied in zero magnetic field. It is shown that the critical current is a function of the sample cross-sectional area only. At constant sample cross-sectional area the value of the critical current is independent of any variation of a sample cross-sectional shape. At the same time the distributions of the critical current density and induced magnetic field in ceramics are functions of the sample cross-sectional shape. These values very in accordance with a change of the sample cross-sectional shape (at constant cross-sectional area i.e. at constant value of the critical current). The field and current distributions in the rectangular sample are reported.     

超临界CO_2在岩石孔隙内流动状态的分子模拟

本文采用分子模拟的方法研究了地质封存条件下超临界CO_2在镁橄榄石孔隙内的流动,分析了孔隙尺寸、温度、压强对超临界CO_2的密度分布和流动速度的影响.研究结果表明,只有当孔隙尺寸大于5.0 nm时,超临界CO_2分子在岩石孔隙内的流动才符合Poiseuille流动;同时,超临界CO_2分子在岩石近壁面存在1.5 nm的密度震荡,当孔隙尺寸小于15 nm时,密度振荡现象会影响CO_2分子在岩石孔隙内的平均密度;升高温度、降低压强的方法可以减小密度震荡的第一峰值,减弱岩石壁面与CO_2的相互作用,使得CO_2的流动速度增加.     

Thermoreversible,epitaxial fcc<-->bcc transitions in block copolymer solutions

Uncharged block copolymer micelles display thermoreversible transitions between close-packed and bcc lattices for a range of concentration, solvent selectivity, and copolymer composition. Using small-angle x-ray scattering on shear-oriented solutions, highly aligned fcc crystals are seen to transform epitaxially to bcc crystals, with fcc/bcc orientational relationships that are well established in martensitic transformations in metals. The transition is driven by decreasing solvent selectivity with increasing temperature, inducing solvent penetration of the micellar core.     

Effect of confinement in nano-porous materials on the solubility of a supercritical gas

By combining Gibbs Ensemble Monte Carlo simulations and density functional theory, we investigate the influence of confinement in a slit-shaped carbon pore on the solubility of a supercritical solute gas in a liquid solvent. In the cases studied here, competing adsorption of the solvent and solute determines whether the solubility is enhanced or suppressed for larger pores. We find that the solubility in the confined system is strongly dependent on pore width, and that molecular packing effects are important for small pore widths. In addition, the solubility decreases on increase in the temperature, as for the bulk mixture, but the rate of decrease is greater in the pore due to a decrease in the partial molar enthalpy of the solute in the pore; this effect becomes greater as pore width is decreased. The solubility is increased on increasing the bulk pressure of the gas in equilibrium with the pore, and obeys Henry's law at lower pressures. However, the Henry constant differs significantly from that for the bulk mixture, and the range of pressure over which Henry's law applies is reduced relative to that for the bulk mixture. The latter observation indicates that solute–solute interactions become more important in the pore than for the bulk at a given bulk pressure. Finally, we note that different authors use different definitions of the solubility in pores, leading to some confusion over the reported phenomenon of ‘oversolubility’. We recommend that solubility be defined as the overall mole fraction of solute in the pores, since it takes into account the increase in density of the solvent in the pores, and avoids ambiguity in the definition of the pore volume.     

Dielectric and thermodynamic properties of CHF3 near the critical temperature

We report here some measurements of the complex dielectric constant of CHF₃ near the critical temperature from the low pressure gas densities up to the compressed liquid ones. The behaviour of the complex dielectric constant, measured at about 10 GHz, is compared with the provisions of some recent theories. The dielectric relaxation time is derived and an interpretation of the relaxation mechanisms in the whole explored density range is proposed. The pressure second virial coefficient is also obtained.     

Constant chemical potential,pressure and temperature profiles in liquid–vapour equilibrium obtained by spinodal decomposition

Constant chemical potential, pressure and temperature profiles across a slab of liquid in equilibrium with its vapour confirm that, the spinodal decomposition procedure carried on the NVT ensemble simulated via molecular dynamics produce an equilibrium system. An initial homogeneous crystalline configuration of fluid is kept in a cell with a parallelepiped shape at a density near the critical density and a temperature between the triple and critical temperatures, form a slab of liquid in equilibrium with its vapour by the spinodal decomposition phenomenon if the simulation is performed in the NVT ensemble. An elongated box favours the formation of two planar parallel surfaces along the largest side of the box. We show in this paper that the ‘three conditions’ for thermodynamic equilibrium: constant temperature, constant pressure and constant chemical potential are met for such a system.     

A statistical thermodynamic approach to sonochemical reactions

The calculation of the equilibrium constants K of the sonolysis reactions of CO2 into CO and O atom, the recombination of O atoms into O2 and the formation of H2O starting with H and O atoms, has been studied by means of statistical thermodynamic. The constants have been calculated at 300 kHz versus the pressure and the temperature according to the extreme conditions expected in a cavitation bubble, e.g. in the range from ambient temperature to 15200 K and from ambient pressure to 300 bar. The decomposition of CO2 appears to be thermodynamically favored at 15200 K and 1 bar with a constant K1=1.52 x 10(6), whereas the formation of O2 is not expected to occur (K2=1.8 x10(-8) maximum value at 15200 K and 300 bar) in comparison to the formation of water (K3=3.4 x 10(47) at 298 K and 300 bar). The most thermodynamic favorable location of each reactions is then proposed, the surrounding shell region for the thermic decomposition of CO2 and the wall of the cavitation bubble for the formation of water. Starting from a work of Henglein on the sonolysis of CO2 in water at 300 kHz, the experimental amount of CO formed (7.2 x 10(20)molecules L(-1)) is compared to the theoretical CO amount (1.4 x 10(27)molecules L(-1)) which can be produced by the sonolysis of the same starting amount CO2. With the help of the literature data, the number of cavitation bubble has been evaluated to 6.2 x 10(15) bubbles L(-1) at 300 kHz, in 15 min. This means that about 1 bubble on 1900000 is efficient for undergoing the sonolysis of CO2.     

Preparation and properties of sulfonated polybenzimidazole-polyimide block copolymers as electrolyte membranes

Sulfonated polybenzimidazole-polyimide block copolymers are synthesized through condensation polymerization at high temperature. The length of the polyimide chain is varied to give a series of block copolymers with various block lengths. The as-synthesized block polymers are used to prepare the corresponding membranes through the solvent evaporation method. The structure of the block copolymers is characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR). Their mechanical strength, thermal behavior, water uptake, swelling ratio, and proton conductivity, as well as oxidative stability are also investigated. All the block copolymers exhibit good thermal stability, dimensional stability, mechanical strength, and proton conductivity. Compared to the random sulfonated polyimide-containing benzimidazole membranes with the same degree of sulfonation, the membranes prepared from the block copolymers show higher proton conductivities. The proton conductivities of the block copolymer membranes range from 6.2?×?10^?4 to 1.1?×?10^?2?S cm^?1 at 105 °C. The block copolymer membrane doped with phosphoric acid exhibits proton conductivity higher than 0.2 S cm^?1 at 160 °C, indicating its potential applications in proton exchange membrane fuel cells operated under high temperature and low humidity conditions.     

Pressure dependence of acoustic behaviors and refractive index of amorphous Kel F-800 copolymer studied by Brillouin spectroscopy

The pressure dependences of the longitudinal sound velocity and the refractive index of amorphous Kel F-800 copolymer were investigated for pressures up to 13 GPa using high-pressure Brillouin spectroscopy combined with a diamond-anvil-cell technique. The sound velocity increased rapidly with increasing pressure at pressures below ～2 GPa, whereas it showed a mild change at higher pressure values. This was attributed to substantial collapse of effective free volume in this amorphous material. The refractive index could be measured by comparing the Brillouin spectra measured from backward and forward, symmetric scattering geometries. The pressure–density relationship could be obtained by using Lorentz–Lorenz equation based on an assumption of constant polarizability, which was consistent with that reported by previous study.     

Refractive indices and thermo-optical properties of dye laser solvents

By measuring the wavelength tuning of a distributed feedback dye laser, solvent refractive-index changes as small as 0.0002 may be determined. This technique hence allows precise measurement of refractive-index dependence on temperature (dn/dT) and therefore enables the thermo-optical properties of solvents used in dye lasers to be assessed. In addition to single component solvents, the thermo-optical properties of solvent mixtures and additives are reported here. The refractive-index change with temperature (dn/dT) is related to solvent density change with temperature (dq/dT) through molecular polarizability.     

An isothermal titration calorimetry study of the interactions between an oxyphenylethylene/oxyethylene diblock copolymer and sodium dodecyl sulfate

Interactions between the diblock copolymer S₁₅E₆₃ and the surfactant sodium dodecyl sulfate (SDS) have been investigated by isothermal titration calorimetry (ITC) in the temperature range 10–40°C. At 20°C, the block copolymer is associated into micelles with a hydrodynamic radius of 11.6?nm, which is composed of a hydrophobic styrene oxide (S) core and a water-swollen oxypolyethylene (PEO) corona. The copolymer/surfactant system has been studied at a constant copolymer concentration of 0.25?wt% and over a wide range of surfactant concentration, from 7.5?×?10^?6 up to 0.3?M. The titration calorimetric data for SDS in the temperature range 10–20°C presents a first endothermic increase indicating the formation of mixed copolymer rich-surfactant micelles. From that point, important differences in the ITC plots for surfactant titrations in the presence and in the absence of the copolymer are present. A shallow second endothermic peak is assigned to the interaction between SDS molecules and copolymer molecules resulting from the beginning of micelle disruption. An exothermic peak indicates the end of this disruption where only SDS micelles attached to single copolymer monomers are present, as shown by DLS in a previous paper. At higher temperatures in the range 25–40°C, the first endothermic maximum is not totally shown because interactions between surfactant and block copolymer start at very low SDS concentrations. Moreover, the second endothermic peak is absent and the exothermic minimum is less pronounced as a consequence of the increased micellization of the block copolymer.     

Interaction between solute molecules in medium density solvents

Solvation properties of solutes in supercritical, medium density solvents have been analysed using hypernetted-chain theory with the emphasis on the solvent-mediated interaction between solute molecules. The solvent and solute molecules are Lennard-Jones particles, and the solute is present at infinite dilution. Also a pair of solute molecules separated by different distances has been considered using reference interaction site model theory. Mainly, solvents at two typical densities (1.09_pc and 2.91_pc; pc is the critical density) that are in medium and high density regions, respectively, are treated. The temperature is set at 1.04T_C (T_c is the critical temperature). When the solute size is larger than the solvent size and the strength of the solute-solvent attractive interaction is greater than that of the solvent-solvent in the medium density region, the solvent structure confined between a pair of solute molecules is largely different from that near a single solute molecule. The confined solvent becomes denser and more stabilized as the distance between the solute molecules decreases, and an attractive interaction is induced between them. The interaction becomes even more attractive as the strength of the solute-solvent attractive interaction increases. The observations are qualitatively different from those in the high density region. Another high density region, which is well below the critical temperature, has been considered, but the behaviour observed is similar to that in the high density region above the critical temperature.     

Thermo-responsive copolymer coatings for flow regulation on demand in glass microcapillaries

This study presents thermo-responsive on-demand regulation of water flow rate in glass microcapillaries with a recently developed water-stable, stimuli-responsive poly(methyl methacrylate/N-isopropyl acrylamide) [P(MMA/NIPAM)] copolymer grafted at the inner walls. It is shown that the grafted coatings are stable and can withstand significant tractions under temperature variation. Such microcapillaries allow flow regulation on demand by changing temperature across the lower critical solution temperature (LCST) of the copolymer layer, which makes it swell or shrink, thus changing the bore available for pressure-driven flow. The grafted copolymer layers were subjected to different pressure drops applied to the capillary open ends, as well as to periodic temperature variation across the copolymer LCST to determine the best grafting conditions for microfluidic operation. Then, by varying the temperature, the flow rate in the capillaries was changed periodically on demand due to the swelling/shrinkage of the grafted copolymer layer. It was also shown that the entrapped air bubbles are present in the coating which can result in an apparent slip.     

HCFC133a的热力学性质的实验研究

l引言替代工质和替代技术的研究，都离不开工质准确而可靠的热物性数据。HFC134a是目前国际上公认的制冷剂CFC12的替代物之一，而HCFC133a是合成替代工质HFC134a过程中的中间产物。为了提纯HFC134a，需要设计分离装置，这就必需知道HCFC133a的热力学性质。但是，目前公开发表的HCFC133a的热力学性质数据很少。本研究的目的就是测量HCFC133a的热力学性质，为HFC134a的合成工艺设计和其它工业应用提供基础的物性数据。2实验装置、实验方法及其可靠性检验本研究工作是在我室于1985年建成，并经过多次改进的定容法PVTX试验台上进…     

Selectivity and temperature dependence of phase and phase transition in diblock copolymer solution

In order to study the effects of solvent selectivity and temperature on phase behavior and transition of diblock copolymer solution, self-consistent field theory is modified to incorporate the short-range interaction and non-local effects. Inhomogeneous free-energy density is shown to be dependent on solvent selectivity, temperature and copolymer concentration. Enthalpic quantity and entropic contributions are crucial to phase diagrams of diblock copolymer solution. Three selective strengths of solvent --weak, moderate and strong-- are chosen for comparison. For a weakly selective solvent, theoretical and experimental results illustrate the same variation tendency in the phase boundary of the order-disorder transition for a symmetric diblock of polystyrene and polyisoprene. Self-consistent field equations can be used to calculate the exact FCC-BCC structural phase transition temperatures in moderately and strongly selective solvents. Detailed comparison with the experimental phase diagrams including lamellar, cylindrical and spherical structures is presented.     

Solvent effects for CO and H2 adsorption on Cu2O (1 1 1) surface: A density functional theory study

To investigate solvent effects, CO and H₂ adsorption on Cu₂O (1 1 1) surface in vacuum, liquid paraffin, methanol and water are studied by using density functional theory (DFT) combined with the conductor-like solvent model (COSMO). When H₂ and CO adsorb on Cu_cus of Cu₂O (1 1 1) surface, solvent effects can improve CO and H₂ activation. The H-H bond increases with dielectric constant increasing as H₂ adsorption on O_suf of Cu₂O (1 1 1) surface, and the H-H bond breaks in methanol and water. It is also found that both the structural parameters and Mulliken charges are very sensitive to the COSMO solvent model. In summary, the solvent effects have obvious influence on the clean surface of Cu₂O (1 1 1) and the adsorptive behavior.     

Electrical transport properties of dense bulk YBa2Cu4O8 produced by hot isostatic pressing

Highly dense sintered YBa₂Cu₄O₈ has been produced by hot isostatic pressing (HIP). The electrical resistivity of this material has been measured as a function of temperature T and pressure in the range 40–650 K and 0–0.7 GPa. Both the temperature dependence and the pressure dependence of are found to be well described by a model based on the standard Bloch-Grüneisen theory. It is pointed out that is liner in T only under isobaric conditions, while is strongly nonlinear in all high-T_c superconductors under isochoric (constant volume) conditions. The critical current density of the material is 900 A/cm² at 4 K, while the resistivity is 630 μΩ cm at 294 K.     

Harbingers and latecomers – the order of appearance of exact coherent structures in plane Poiseuille flow

The transition to turbulence in plane Poiseuille flow (PPF) is connected with the presence of exact coherent structures. We here discuss a variety of different structures that are relevant for the transition, compare the critical Reynolds numbers and optimal wavelengths for their appearance, and explore the differences between flows operating at constant mass flux or at constant pressure drop. The Reynolds numbers quoted here are based on the mean flow velocity and refer to constant mass flux. Reynolds numbers based on constant pressure drop are always higher. The Tollmien–Schlichting (TS) waves bifurcate subcritically from the laminar profile at Re = 5772 at wavelength 6.16 and reach down to Re = 2610 at a different optimal wave length of 4.65. Their streamwise localised counter part bifurcates at the even lower value Re = 2334. Three-dimensional exact solutions appear at much lower Reynolds numbers. We describe one exact solutions that has a critical Reynolds number of 316. Streamwise localised versions of this state require higher Reynolds numbers, with the lowest bifurcation occurring near Re = 1018. The analysis shows that the various branches of TS-waves cannot be connected with transition observed near Re ≈ 1000 and that the exact coherent structures related to downstream vortices come in at lower Reynolds numbers and prepare for the transition.