Synthesis of side‐chain liquid‐crystalline homopolymers and triblock copolymers with p‐methoxyazobenzene moieties and poly(ethylene glycol) as coil segments by atom transfer radical polymerization and their thermotropic phase behavior

A series of side‐chain liquid‐crystalline (LC) homopolymers of poly[6‐(4‐methoxy‐4′‐oxy‐azobenzene) hexyl methacrylate] with different degrees of polymerization were synthesized by atom transfer radical polymerization (ATRP), which were prepared with a wide range of number‐average molecular weights from 5.1 × 10³ to 20.6 × 10³ with narrow polydispersities of around 1.17. Thermal investigation showed that the homopolymers exhibit two mesophases, a smectic phase, and a nematic phase, and the phase‐transition temperatures of the homopolymers increase clearly with increasing molecular weights. A series of novel LC coil triblock copolymers with narrow polydispersities was synthesized by ATRP, and their thermotropic phase behavior was investigated with differential scanning calorimetry and polarized optical microscopy. The LC coil triblocks were designed to have an LC conformation of poly[6‐(4‐methoxy‐4′‐oxy‐azobenzene) hexyl methacrylate] with a wide range of molecular weights from 3.5 × 10³ to 1.7 × 10⁴ and the coil conformation of poly(ethylene glycol) (PEG) (number‐average molecular weight: 6000 or 12,000) segment. Their characterization was investigated with ¹H NMR, Fourier transform infrared spectra, and gel permeation chromatography. Triblock copolymers exhibited a crystalline phase, a smectic phase, and a nematic phase. The phase‐transition temperatures from the smectic to nematic phase and from the nematic to isotropic phase increased, and the crystallization of PEG depressed with increasing molecular weight of the LC block. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2854–2864, 2003     

Atom transfer radical polymerization directly from poly(vinylidene fluoride): Surface and antifouling properties

The direct preparation of grafting polymer brushes from commercial poly (vinylidene fluoride) (PVDF) films with surface‐initiated atom transfer radical polymerization (ATRP) is demonstrated. The direct initiation of the secondary fluorinated site of PVDF facilitated grafting of the hydrophilic monomers from the PVDF surface. Homopolymer brushes of 2‐(N,N‐dimethylamino)ethyl methacrylate (DMAEMA) and poly (ethylene glycol) monomethacrylate (PEGMA) were prepared by ATRP from the PVDF surface. The chemical composition and surface topography of the graft‐functionalized PVDF surfaces were characterized by X‐ray photoelectron spectroscopy, attenuated total reflectance/Fourier transform infrared spectroscopy, and atomic force microscopy. A kinetic study revealed a linear increase in the graft concentration of poly[2‐(N,N‐dimethylamino)ethyl methacrylate] (PDMAEMA) and poly[poly(ethylene glycol) monomethacrylate] (PPEGMA) with the reaction time, indicating that the chain growth from the surface was consistent with a controlled or living process. The living chain ends were used as macroinitiators for the synthesis of diblock copolymer brushes. The water contact angles on PVDF films were reduced by the surface grafting of DMAEMA and PEGMA. Protein adsorption experiments revealed a substantial antifouling property of PPEGMA‐grafted PVDF films and PDMAEMA‐grafted PVDF films in comparison with the pristine PVDF surface. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3434–3443, 2006     

Effect of glass bead packing on the fibrillation of liquid‐crystalline polymer in polycarbonate

Polycarbonate (PC) was melt blended with small amount of liquid‐crystalline polymer (LCP) and various contents of glass beads (GB) having different diameters. The rheological measurements indicated that the GB addition increased the viscosity ratio and seemed unfavorable to the LCP fibrillation. However, the morphological observation showed that the LCP fibrillation was promoted by the GB addition and varied with the GB packing. With the increased GB packing by increasing the GB content and/or decreasing the GB diameter, LCP deformed from spheres and ellipsoids into stretched ellipsoids at lower shear rates and into long fibrils at higher shear rates. Although higher content of smaller GB jammed into the larger LCP droplets and inhibited the LCP fibrillation, very long LCP fibrils formed at higher shear rates at a high enough packing of GB. The relationship between GB packing and LCP fibrillation revealed two kinds of hydrodynamic effects of GB promoting the LCP fibrillation: at lower GB packing, the shear flow was enhanced by the high local shear between GB, in quantity; and for a high enough GB packing, the shear flow was changed, in quality, into elongational flow, which was more effective for the LCP fibrillation. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1020–1030, 2006     

Effective potential for local composite operators and the problem of factorization of multi-field condensates

A new formulation of effective potential for local composite operators is given. The two-fermion condensate \(\langle \bar \Psi \Psi \rangle \) and four-fermion condensate \(\langle \bar \Psi \Psi \bar \Psi \Psi \rangle \) are calculated simultaneously in the Gross-Neveu model up to next-to-the-leading order in 1/N expansion. It is shown that factorization \(\langle \bar \Psi \Psi \bar \Psi \Psi \rangle = C_1 \langle \bar \Psi \Psi \rangle ^2 \) holds only in theN→∞ limit and the non-factorized part of \(\langle \bar \Psi \Psi \bar \Psi \Psi \rangle \) contributed by the order-1/N terms is comparable to \(C_1 \langle \bar \Psi \Psi \rangle ^2 \) when takingN=3.     

Indirect laser photoacoustic detection for trace samples on membranes

An indirect laser photoacoustic technique is described. The basic principle, the experimental set-up and the influencing factors are discussed in detail. This method was used to quantify phenylamine, arginine and methylene blue on membranes. The linear ranges of the calibration curve are up to two orders of magnitude. With 1 microliter of sample solution, the detection limits are 0.25, 1.52 and 0.14 pmol for phenylamine, arginine and methylene blue, respectively.     

Molar conductivity calculation of Li-ion battery electrolyte based on mode coupling theory

A method is proposed to calculate molar conductivity based on mode coupling theory in which the ion transference number is introduced into the theory. The molar conductivities of LiPF6, LiClO4, LiBF4, LiAsF6 in PC (propylene carbonate) are calculated based on this method. The results fit well to the literature data. This presents a potential way to calculate the conductivities of Li-ion battery electrolytes.