Initiation reactions in thermal polymerization of vinyl monomers in the molten state

Evidence of the initiation process during uncatalyzed thermal polymerization of vinyl monomers is presented. DSC studies reveal a prominent endothermic effect just before the polymerization exotherm, which is substantiated by the identification of the free radicals produced in the initiation by a quick quenching technique and subsequent detection by ESR at low temperatures.     

Yields and average cross sections of recoil charged particle induced reactions on11B,12C,13C,14N,16O and18O

The yield and average cross section for the reactions¹¹B(p, n)¹¹C,¹²C(p, )¹³N,¹³C(p, n)¹³N, ₁₂ ¹² C(d, n)¹³N,¹⁴N(p, )¹¹C,¹⁶O(p, )¹³N,¹⁶O(d, n)¹⁷F,¹⁶O(t, n)¹⁸F, and¹⁸O(p, n)¹⁸F have been measured in different compounds. The charged particles were created in the samples themselves either through recoil by scattering of 14 MeV neutrons off hydrogen and deuterium, or by the (n, t) reaction on⁶Li using thermal neutrons. The yields of reactions¹²C(d, n);¹⁶O(p, );¹⁶O(t, n) and¹⁸O(p, n) have been measured using proton, deuteron and triton spectra generated by 14 MeV neutrons in the reactions D(n, p)2n;⁶Li(n, d);⁷Li(n, d) and¹⁰B(n, d);⁷Li(n, t) and¹⁰B(n, t), respectively.     

The influence of excess oxygen on the elastic properties of non-stoichiometric SrO crystals

Measurements have been carried out of the elastic constants of SrO in the virgin undoped state and of the changes produced in them by equilibrium doping with oxygen at ? 1200°C and oxygen partial pressure of 0.95 atm. The method used was Papadakis' pulse-echo overlap technique in conjunction with thermogravimetric analysis (T.G.A.) to determine mass and density changes due to oxygen doping.The values obtained for C₁₁, C₁₂ and C₄₄ of the virgin crystal at 23°C are

$\text{C}{}_{11}\text{= 17.60 ± 0.03 × 10}{}^{11}\text{dynes/cm}{}^2$

;

$\text{C}{}_{12}\text{= 4.808 ± 0.007 × 10}{}^{11}\text{dynes/cm}{}^2$

;

$\text{C}{}_{44}\text{= 5.577 ± 0.008 × 10}{}^{11}\text{dynes/cm}{}^2$

.(These values are in very good agreement with those of Son and Bartels [2].)Values for $\text{δC}{}_{11}\text{C}{}_{11}$ and $\text{δC}{}_{44}\text{C}{}_{44}$ were found to be ?1.74% and ?0.86% respectively. Accurate valu $\text{δC}{}_{12}\text{C}{}_{12}$ could not be obtained because of sample size limitations after quenching. However, C₁₂ was shown to definitely increase due to doping.Analysis of the results indicate that the elastic modulus changes can only be attributed to the formation of cation vacancies during doping. Analysis of the T.G.A. behavior indicates that this cation vacancy formation is probably associated with the presence of various tripositive cation and uninegative anion species depending upon the impurity concentrations of the sample. This implied impurity-controlled cation vacancy concentration is consistent with the earlier observed extrinsic nature of cation diffusion in SrO at 1200°C.     

Synthesis and characterization of biphenyl liquid crystal based on natural molecules and 2(5H)-furanone moiety

Using 4′-hexyloxybiphenyl-4-ol and N-(5-alkoxy-3-bromo-2(5H)-furanonyl) amino acids as reactants, a series of novel biphenyl liquid crystal compounds containing natural molecule moieties, such as menthol, borneol, and amino acids, were synthesized via esterification. The structures of all novel compounds were confirmed by FTIR, ¹H NMR, ¹³C NMR, MS, and elemental analysis, and the liquid crystal properties of target compounds were characterized with DSC, XRD, and POM. The introduction of hexyloxy made the biphenyl esters have a potential to appear in mesomorphic phase and have a higher Tm, and bornyl moiety was more beneficial for the liquid crystal performance than a menthyl unit. Most compounds were mesomorphic phase liquid crystal molecules, and POM and XRD showed that they existed in smectic phase. These researches provide a theoretical basis for the synthesis of biphenyl ester liquid crystal materials via the utilization of 2(5H)-furanone derivates and natural molecules.     

Enantioselective Total Synthesis of Four Styrylpyrone Derivatives

The first enantioselective total synthesis of 5-acetoxygoniothalamin 1 and 5-acetoxyisogoniothalamin oxide 2 was achieved through the Sharpless kinetic resolution of recemic secondary 2-furylmethanol 5 and the Mitsunobu reaction. At the same time we developed a short synthetic route for 6R-( )-goniothalamin 3 and (6R,7R,8R)-( )-goniothalamin oxide 4. And according to this route the configuration of 5-acetoxygoniothalamin 1 was confirmed as (5S,6S).     

Peak effect at microwave frequencies in swift heavy ion irradiated YBa2Cu3O7-δ thin films

The vortex dynamics at microwave frequencies in YBa₂Cu₃O_7-δ (YBCO) films have been studied. We observe a peak in the microwave (4.88 and 9.55 GHz) surface resistance in some films in magnetic fields up to 0.8 T. This is associated with the ‘peak-effect’ phenomenon and reflects the order-disorder transformation of the flux line lattice near the transition temperature. Introduction of artificial pinning centers like columnar defects created as a result of irradiation with 200 MeV Ag ion (at a fluence of 4×10¹⁰ ions/cm²) leads to the suppression of the peak in films previously exhibiting ‘peak effect’.     

Mechanistic studies on the pyrolysis and combustion of polystyrene/ammonium perchlorate propellants in the presence of transition metal oxides

The effect of transition metal oxides (Fe₂O₃, MnO₂, Ni₂O₃ and Co₂O₃) on polystyrene/ammonium perchlorate propellant systems has been examined. The mechanism of action of the oxides in increasing the burning rate was examined by studying the effect of the oxides on the thermal decomposition and combustion of the oxidizer and the propellant. It has been concluded that one of the mechanisms by which the oxides act is by promoting the charge-transfer process, which is indicated by the enhancement of the electron-transfer process in ammonium perchlorate and by the correlation between the redox potential of the metal ions and the corresponding burning rates of the propellant.     

Theory of insulator metal transition and colossal magnetoresistance in doped manganites

The persistent proximity of insulating and metallic phases, a puzzling characteristic of manganites, is argued to arise from the self-organization of the twofold degenerate e(g) orbitals of Mn into localized Jahn-Teller (JT) polaronic levels and broad band states due to the large electron-JT phonon coupling present in them. We describe a new two band model with strong correlations and a dynamical mean-field theory calculation of equilibrium and transport properties. These explain the insulator metal transition and colossal magnetoresistance quantitatively, as well as other consequences of two state coexistence.