Viscoelasticity and birefringence of polyisoprene

The complex Young's modulus, E^*(ω), and the complex strain-optical coefficient, O^*(ω), which is the ratio of the birefringence to the strain, were measured for polyisoprene (PIP) over a frequency range of 1 ～ 130 Hz and a temperature range of 22 ～ ?100°C. The imaginary part of O^*, O″, was positive at low frequencies and negative at high frequencies. The real part, O′, was always positive and showed a maximum. The complicated behavior of O^* could be understood by the assumption that E^* = E_R^* + E_G^* and O^* = C_RE_R^* + C_GE_G^*, where E_R^* and E_G^* were complex quantities and C_R and C_G were constants. The C_R value, equal to the ordinary stress-optical coefficient measured in the rubbery plateau zone, was 2.0 × 10^?9 Pa^?1. The C_G value, defined as the ratio O″/E″ in the glassy zone, was ?1.1 × 10^?11 Pa^?1. The E_G^*, which was the major component of E^* in the glassy zone, showed almost the same frequency dependence as that of polystyrene and polycarbonate. The E_R^*, which was dominant in the rubbery zone, was described well by the bead-spring theory. The temperature dependence of the E_G^* was stronger than that of the E_R^*. This difference caused the breakdown of the thermorheological simplicity for E^* and O^* around the glass-to-rubber transition zone. © 1995 John Wiley & Sons, Inc.     

Gelation with N-lauroyl-L-glutamic-α,γ-dibutylamide for liquid scintillation counting of low specific activities of35S and32P

A gelling agent, N-lauroyl-L-glutamic-,-dibutylamide, was applied for liquid scintillation counting of inorganic³²P and³⁵S. The gel with toluene cocktail is transparent and rigid for a long time. Several grams of ammonium magnesium phosphate or barium sulfate can easily be measured without complicating procedures.     

Rheology of polystyrene solutions around the coil overlapping concentration: A phenomenological description of stresses in simple shear flow

Linear viscoelasticity behavior is described with the sum of two terms for polystyrene solutions in tricresyl phosphate around the coil overlapping concentration (K. Osaki, T. Inoue, & T. Uematsu, J Polym Sci Part B: Polym Phys 2001, 39, 211). One is a Rouse–Zimm (RZ) term represented by the Zimm theory with arbitrarily chosen values of the hydrodynamic interaction parameter and the longest relaxation time (τ_RZ). The other (the L term) consists of a relaxation mode with a single relaxation time (τ_L > τ_RZ) and a high‐frequency limiting modulus proportional to the square of the concentration. In this study, we describe the viscosity (η) and first normal stress coefficient (Ψ₁) in steady shear with simple formulas. The stress due to the L term is assumed to be given by a Kaye, Bernstein, Kearsley, and Zapas (K‐BKZ) equation with the damping function h(γ) = (1 + 0.2γ²)^?1/2, where γ is the magnitude of shear. Contributions to η and Ψ₁ from the RZ term are derived from the RZ model, in which the relaxation time in steady flow is given by τ_st = τ + (τ_RZ ? τ)/(1 + 0.35τ_RZ γ˙) instead of τ_RZ. Here, γ˙ is the rate of shear, and τ is the τ_RZ value at the infinite dilution limit. η and Ψ₁ at various concentrations for two polystyrene samples (with molecular weights of 2890 and 8420 kg mol^?1) are well described with parameters derived from dynamic viscoelasticity. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1038–1045, 2002     

In Situ Processing of Nano Crystalline Oxide Particles/Polymer Hybrid

Nano sized crystalline particles/polymer hybrids were synthesized form designed metal-organic precursors. The newly developed method is composed of the synthesis of organic matrix by polymerization and the in situ nucleation and growth of crystalline oxide particles in the organic matrix below 100°C. The design of metal-organic precursor modified with polymerizable ligand and the selection of reaction conditions does influence the size and crystallinity of ceramic particles in organic matrix. The nano-sized magnetic particle/polymer hybrid exhibits the interesting feature of superparamagnetism and quantum size effect. The crystalline particles of BaTiO₃/, PbTiO₃/, and KNbO₃/polymer hybrids behave to be dielectric and show the typical electro-rheological behavior.     

Kinetic studies of CO2dissociation on supported Ni catalysts

Summary In order to investigate the kinetics of CO₂dissociation on supported nickel catalysts, a novel technique, which can give the surface reaction rate constants with no information on the number of active sites, was developed. It was revealed that CO₂dissociation was more enhanced on TiO₂support than on other metal oxide ones. The activity pattern and activation energies were in good agreement with those obtained by a conventional pulse technique using the number of active sites, suggesting the validity of the present technique for investigating the kinetics of the surface reaction.</o:p>     

Allylation of methylenecyclopropanes with allylindium reagents

Methylenecyclopropanes carrying a hydroxymethyl group at the ring underwent stereoselective allylindation with allylindium sesquiiodide to afford the allylated products, in which the allyl group was delivered at the external sp² carbon via cyclopropylindium intermediates. The reaction of ethyl 2-cyclopropylideneacetate and triallylindium afforded the 1,4-adduct along with dimeric products.     

On the damping function of shear relaxation modulus for entangled polymers

Published data of the damping function of the shear relaxation modulus, h(), are reviewed. This is the ratio of the relaxation modulus measured at a finite magnitude of shear, , to that at the limit of = 0. Majority of the data are in accord with the universal function of the Doi-Edwards tube model theory, in which the damping or the decrease of h() is attributed to the contraction along the tube of extended polymer chains. The weaker damping seems to be attributed to 1) comb-branching such as in LDPE; 2) lack of entanglement in too short chains; 3) bimodal molecular weight distribution. However, a star-branching does not cause a deviation from the tube model theory and a broadness of molecular weight distribution is not a major origin of a weaker damping. A star-branched polystyrene with 15 arms exhibits no strain dependence: h() = 1. For highly entangled systems with more than 50 entanglement points per molecule, the strain dependence is stronger than that of the Doi-Edwards theory. This could be due to a slip or an instability of deformation in the material.     

Nonlinear rheological behavior of a concentrated spherical silica suspension

Linear and nonlinear viscoelastic properties were examined for a 50 wt% suspension of spherical silica particles (with radius of 40 nm) in a viscous medium, 2.27/1 (wt/wt) ethylene glycol/glycerol mixture. The effective volume fraction of the particles evaluated from zero-shear viscosities of the suspension and medium was 0.53. At a quiescent state the particles had a liquid-like, isotropic spatial distribution in the medium. Dynamic moduli G^* obtained for small oscillatory strain (in the linear viscoelastic regime) exhibited a relaxation process that reflected the equilibrium Brownian motion of those particles. In the stress relaxation experiments, the linear relaxation modulus G(t) was obtained for small step strain (0.2) while the nonlinear relaxation modulus G(t, ) characterizing strong stress damping behavior was obtained for large (>0.2). G(t, ) obeyed the time-strain separability at long time scales, and the damping function h() (–G(t, )/G(t)) was determined. Steady flow measurements revealed shear-thinning of the steady state viscosity () for small shear rates (< ^–1; = linear viscoelastic relaxation time) and shear-thickening for larger (>^–1). Corresponding changes were observed also for the viscosity growth and decay functions on start up and cessation of flow, + (t, ) and _– (t, ). In the shear-thinning regime, the and dependence of ₊(t,) and _–(t,) as well as the dependence of () were well described by a BKZ-type constitutive equation using the G(t) and h() data. On the other hand, this equation completely failed in describing the behavior in the shear-thickening regime. These applicabilities of the BKZ equation were utilized to discuss the shearthinning and shear-thickening mechanisms in relation to shear effects on the structure (spatial distribution) and motion of the suspended particles.Dedicated to the memory of Prof. Dale S. Parson     

Synthesis of stereoarray isotope labeled (SAIL) lysine via the "head-to-tail" conversion of SAIL glutamic acid

A stereoarray isotope labeled (SAIL) lysine, (2S,3R,4R,5S,6R)-[3,4,5,6-(2)H(4);1,2,3,4,5,6-(13)C(6);2,6-(15)N(2)]lysine, was synthesized by the "head-to-tail" conversion of SAIL-Glu, (2S,3S,4R)-[3,4-(2)H(2);1,2,3,4,5-(13)C(5);2-(15)N]glutamic acid, with high stereospecificities for all five chiral centers. With the SAIL-Lys in hand, the unambiguous simultaneous stereospecific assignments were able to be established for each of the prochiral protons within the four methylene groups of the Lys side chains in proteins.