Side-chain functionalized liquid crystalline polymers and blends, 10: phase behavior and structure of side-chain liquid crystalline ionomers containing ions of d-metals

Novel side-chain liquid crystalline (LC) ionomers containing d-metals Co(II) and Ni(II) were synthesized and characterized. Both families of the ionomers are characterized by the same influence of charged group content in polymer on their phase behavior. The incorporation of 2-3 mol% of metal ions in the nematic polymer matrix leads to the induction of SmA phase and rise in the clearing point. The peculiarity of their phase behavior in comparison with the earlier investigated LC ionomers with alkaline or alkali-earth metals is the full destruction of the mesophase at the concentration of d-metal higher than 12 mol%. This phenomenon was associated with the well-known ability of the transition metal ions to form various complexes that, in the case of LC ionomers, can negatively influence the ordering of the side mesogenic groups. The proposed structure of the LC ionomers is discussed in comparison with the metallomesogenic polymer systems.     

Phase Diagram for Liquid Crystalline Polymer/ Polycarbonate Blends

A novel mechanism to form binary polymer blends is through phase separation by spinodal decomposition in the unstable region of the phase diagram. The present work investigates the effects of thermally‐induced phase separation by spinodal decomposition on the morphology development of liquid crystalline polymer/polycarbonate blends. Moreover, a thermodynamic binary phase diagram is obtained using a twin‐screw extruder at various processing melt temperatures. Differential scanning calorimetry and scanning electron microscopy were used to study the miscibility of the blends and the resulting morphology. A thermodynamic binary phase diagram exhibiting a lower critical solution temperature was obtained. The droplet size distribution of the blend was also obtained and discussed in light of the Cahn‐Hilliard theory.     

油水气三相流液体流量调节系统研究与设计

针对油水气三相流研究试验平台液体流量调节范围宽、范围度大的问题,提出采用3条主回路与3条旁通回流调节支路来覆盖所有的流量范围,设计了液相系统原理图及管路布置图,对3条旁通回流调节支路中调节阀的计算流量、计算压差及Kv值进行了计算,并对调节阀的开度及实际可调比进行了验算,结果表明选定的调节阀性能满足油水气三相流研究试验的要求。     

Theory of chromatography of complex cyclic polymers: eight-shaped and daisy-like macromolecules

A theory of chromatography of eight-shaped, trefoil-shaped and daisy-like polymers is developed. For a model of an ideal chain in a slit-like pore exact equations and a number of approximate formulae for the distribution coefficient K of these polymers are derived. All modes of chromatography of complex macrocycles of arbitrary molar mass in both narrow and wide pores are covered by the theory. It is shown that complex macrocycles always elute after linear polymers and rings of the same contour length. The effective chromatographic radius of eight-shaped and daisy-like macromolecules, which determines retention in size-exclusion chromatography are calculated. The increase in the retention with molar mass is predicted for all types of macrocycles at the critical interaction condition. Non-monotonous molar mass dependences of K are found at pre-critical interaction. We simulate separation of complex cyclic polymers from linear and ring precursors, discuss possibilities to separate symmetric and asymmetric eights, and speculates on the use of chromatography for separating knotted and unknotted polymer rings. According to the theory, the chromatography under the critical and pre-critical interaction conditions is expected to be especially efficient in these and similar problems. Boundary conditions for the theory and its applicability to real systems are discussed.     

液晶聚酯的液晶行为与加工性能

液晶聚酯由于具有特异的液晶行为和高强高模性能而越来越受到人们的关注。本文对液晶聚酯的液晶态形成原因、液晶态类型与链结构的关系、液晶态热稳定性及其成型加工性能进行了讨论，指出了提高液晶态热稳定性的方法及液晶聚酯的发展趋势。     

Mobile phase composition for resolving whey proteins in reversed-phase high performance liquid chromatography

Reversed-phase high-performance liquid chromatography was successfully developed for the simultaneous and rapid separation for the main whey proteins, α-Lactalbumin and β-Lactoglobulin. This method consisted of a linear gradient of the two mobile phases of 0.1% trifluoroacetic acid in water and 0.1% trifluoroacetic acid in acetonitrile. The total run time for this separation was approximately 30 min, and α-Lactalbumin was eluted followed byβ- Lactoglobulin. The injection volume was fixed at 20 μl and the flow rate was 1 ml 1/min. The optimum mobile phase composition and gradient conditions to separate α-Lactalbumin and β-Lactoglobulin (A+B) were experimentally obtained at the 15 μm particle with a pore size of 300 Å on the linear-gradient mode.     

Effects of the boundary layer and interfacial reaction on the time lag in supported liquid membranes

A mathematical model is proposed to describe the effects of boundary layer resistance and interfacial reaction on the time lag in supported liquid membranes for metal ion separation. The model shows that the presence of boundary layer resistance and interfacial reaction delays the time-lag, compared with the limiting case that rapid equilibrium at the interfaces and negligible boundary layer resistance are assumed. Calculated result describes the expected trend and the model equation allows one to predict the lumped parameters which represent the ratios of the diffusion time in the membrane to the characteristic time for boundary layer transfer and interfacial reactions.     

Heat capacities of polyethylene and linear fluoropolymers

Heat capacities at constant pressure, C_p, and at constant volume C_v, were calculated with the help of normal mode frequency spectra and compared to experimental data for crystalline or semicrystalline polyethylene, poly(vinyl fluoride), poly(vinylidene fluoride), polytrifluooroethylene and poly(tetrafluoroethylene). A calculation scheme using a Tarasov function for 2N skeletal vibrational modes and an approximation of the residual 7N normal modes from known data on polyethylene and polytetrafluoroethylene is developed for all homologous, linear fluoropolymers. N is the number of carbon backbone atoms of the repeating unit. Calculations can be carried out over the whole temperature range 0 K to melting. For the two theta temperatures and the constant A₀ used for C_v to C_p conversion, fluorine-concentration dependent curves are given. The relations are expected to hold also for copolymers and blends of intermediate fluorine contents. Recommended experimental (data bank) heat capacities agree to ±2.5% with the calculations.     

Crystalline complex between poly(γ-methyl l-glutamate) and dimethyl phthalate

The crystalline complex between poly(γ-methyl l-glutamate) (PMLG) and dimethyl phthalate (DMP) has been formed in films cast from a solution in dichloroethane. It has the stoichiometry of 1 mol of DMP to three or four residues of PMLG and shows two definite characteristics in X-ray diffraction patterns; one is the large hexagonal unit cell with the edge of around 28 Å and another the ‘extra’ 5.07 Å meridional reflection which can not be interpreted by a PMLG α-helical conformation. The structural examination for the films with various DMP contents is carried out by X-ray, viscoelastic, and d.s.c. measurements and the following structure is proposed for the crystalline complex. Four PMLG are associated to form a group which is hexagonally packed and DMP molecules, located in the gaps between groups, form a specific favourable helical structure along PMLG chains in which the van der Waals stacking of benzene rings of DMP is significant.