Polymerization of silylacetylenes by W and Mo catalysts

Polymerization of HC?CSiMe₃ homologues (HC?CSiMe₂R; R = n-C₆H₁₃, CH₂CH₂Ph, CH₂Ph, Ph, and t-Bu) was studied by use of W and Mo catalysts. W catalysts provided polymers in good yields from all these monomers. Mo catalysts gave mainly a polymer from HC?CSiMe₂–t-Bu, but virturally only cyclotrimers from sterically less croweded monomers (R = n-C₆H₁₃, CH₂CH₂Ph, CH₂Ph, and Ph). Polymers with flexible R groups (n-C₆H₁₃, CH₂CH₂Ph, and CH₂Ph) were totally soluble, their number-average molecular weights being 7000–18,000. Polymers with inflexible R groups (Ph and t-Bu) were partly insoluble. Every polymer was a yellow rubber or powder, and had the structure, \documentclass{article}\pagestyle{empty}\begin{document}$ \rlap{--} [{\rm CH} = {\rm C}\left( {{\rm SiMe}_{\rm 2} {\rm R}} \right)\rlap{--} ]_n $\end{document}. The results were compared with the polymerization and polymer of HC?CSiMe₃.     

Nonlinear viscoelastic properties and change in entanglement structure of linear polymer

Simultaneous measurements of stress relaxation and differential dynamic modulus were made at 268 K over a time scale of 10 to 10⁴⁵ s for nearly monodisperse polybutadiene (M _w =2.2x10⁵, 1,2-structure 70%, M _e =3600) and also one having coarse cross-linking (M _c =29000). Static shear strain ranged from 0.1 to 2.0. In a long-time region (t> _k ), the relaxation modulus G (; t) could be expressed by the product G (0; t) h (y). The observed h() agreed well with the Doi-Edwards theory without use of IA approximation. Both the cured and uncured samples showed initial drop of the differential storage modulus G (), ; t) followed by gradual recovery, but did not attain the value before shearing G (, ; t) for the uncured sample showed smaller values than that for the cured one in the whole measured time scale at the higher strain, confirming the two origins of nonlinear viscoelasticity of well entangled polymer; induced chain anisotropy and induced decrement in entanglement density. G (, ; t) curves for the cured sample agreed well with the BKZ predictions. But the curves for the uncured sample agreed well with the BKZ prediction only at the time scale of t< _k . BKZ prediction showed significant upward deviations at t> _k . Such the differences are discussed in terms of the two origins.Dedicated to Prof. John D. Ferry on the occasion of his 85th birthday.     

Theoretical calculation of structures and proton transfer in hydrated ammonia-hydrogen chloride clusters

Ab initio molecular orbital calculations have been performed to investigate the structures and quantum effects of the proton motion in NH(3):HCl:(H(2)O)(n) (n = 0-3) clusters using a MP2/aug-cc-pVDZ level of theory. Three new stable structures and one transition-state structure are investigated for these clusters. The detailed analyses of the intermolecular interactions suggest that three-body interactions play an important role to determine the relative stability in each size of cluster. The quantum effects of the proton motion result in frequency shifts for proton-stretching modes. Our one-dimensional and two-dimensional models fairly closely reproduce the experimental proton-stretching vibrational frequency of the NH(3):HCl cluster. The most stable isomer for n = 1 has a proton-transfer structure, which is weakened by the quantum effects of the proton motion.     

Cavitation in elastomeric solids: I—A defect-growth theory

It is by now well established that loading conditions with sufficiently large triaxialities can induce the sudden appearance of internal cavities within elastomeric (and other soft) solids. The occurrence of such instabilities, commonly referred to as cavitation, can be attributed to the growth of pre-existing defects into finite sizes. This paper introduces a new theory to study the phenomenon of cavitation in soft solids that: (i) allows to consider general 3D loading conditions with arbitrary triaxiality, (ii) applies to large (including compressible and anisotropic) classes of nonlinear elastic solids, and (iii) incorporates direct information on the initial shape, spatial distribution, and mechanical properties of the underlying defects at which cavitation can initiate. The basic idea is to first cast cavitation in elastomeric solids as a homogenization problem of nonlinear elastic materials containing random distributions of zero-volume cavities, or defects. This problem is then addressed by means of a novel iterated homogenization procedure, which allows to construct solutions for a specific, yet fairly general, class of defects. These include solutions for the change in size of the defects as a function of the applied loading conditions, from which the onset of cavitation — corresponding to the event when the initially infinitesimal defects suddenly grown into finite sizes — can be readily determined. In spite of the generality of the proposed approach, the relevant calculations amount to solving tractable Hamilton-Jacobi equations, in which the initial size of the defects plays the role of “time” and the applied load plays the role of “space”. When specialized to the case of hydrostatic loading conditions, isotropic solids, and defects that are vacuous and isotropically distributed, the proposed theory recovers the classical result of Ball (1982) for radially symmetric cavitation. The nature and implications of this remarkable connection are discussed in detail.     

Effect of refraction index and thickness of the light guide in the position-sensitive gamma-ray detector using compact PS-PMTs

We constructed a position-sensitive gamma-ray detector consisting of an array of BGO scintillators, a light guide and compact PS-PMTs. The effects of refractive index and thickness of the light guide of a glass plate on the detector performance were investigated. A light guide with higher refractive index and smaller thickness is found better for a good spatial resolution.     

Total synthesis of fumitremorgin B

Total synthesis of fumitremorgin B, one of the potent tremorgic mycotoxins, was achieved in 7 steps.     

Study of buried Si(1 1 1)-5 × 2-Au by surface X-ray diffraction

The structure of buried Si(1 1 1)-5 × 2-Au capped with amorphous Si was investigated using surface X-ray diffraction. It was found that the 5 × 2 structural periodicity is kept under the amorphous Si from the in-plane measurement. Furthermore, the intensity variation along the fractional-order rod indicates that Au atoms are located almost on the same plane.     

The role of a radial ion-track distribution in semiconductors studied by numerical simulations

The effect of radial ion-track distribution on the transient current in semiconductors caused by a high-energy heavy ion strike was studied. Reasonable agreement was observed in experimental and calculated transient currents for ion energies ranging from several to several hundred MeV when the radius of the ion track used in the numerical simulations was shorter or equivalent to that of the penumbra radius.