The effect of hBN on the flame retardancy and thermal stability of P-N flame retardant PA6

A novel thermally conductive Polyamide 6 (PA6) with good fire resistance was prepared by introducing a phosphorous-nitrogen flame retardant (FR) and platelet-shaped hexagonal boron nitride (hBN) into the matrix. With high thermal conductivity and good flame retardancy, the material is suitable for applications in electronic and electrical devices. The limiting oxygen index (LOI) changes for various loadings content of FR. However this formulation still does not show an ideal fire resistance, due to the appearance of melt dripping behavior during the UL 94 test. With the extra introduction of 3 vol% and 5 vol% hBN, the melt dripping behavior during the burning process completely disappeared. The hBN also increased the thermal conductivity. Furthermore PA6 compounded with FR and hBN showed a better thermal stability than neat PA6. The morphology of the char residues was investigated by scanning electron microscopy (SEM). The flaky hBN acted as the framework in the char structure and the rigid hBN could effectively break the bubble-shaped char on the surface of the residues which resulted in the enhancement of the strength and compactness of the char.     

Experimental investigation of the muon transfer reaction from deuterium to helium isotopes

Muon transfer from the ground state of muonic deuterium to a helium atom proceeds mainly via the formation of a muonic molecule in an excited state. A large number of decay X rays ( 6.8 keV) from these (dµHe)^* molecules were observed for the⁴He as well as for the³He case. The time distributions of these X rays allow the determination of the ground state transfer rate. The simultaneous employment of Ge/Si-detectors and CCDs for the same target conditions allows the determination of the branching ratio of radiative to nonradiative decay for the first time.     

First measurement of the polarisation transfer on the proton in the reactionsH(\vec e,e'\vec p) andD(\vec e,e'\vec p)

The measurement of the polarisation transfer to the proton in the reactions $H(\vec e,e'\vec p)$ and $D(\vec e,e'\vec p)$ performed with longitudinally polarised electrons in quasi-free kinematics is presented. The coincidence measurement was executed atQ ²≈8fm ^?2 using the 855 MeV, c.w. beam of the Mainz Microtron MAMI. The recoil polarisation was determined by means of a carbon analyser. The experiment shows that the binding of the nucleon does not modify the polarisationP _x of the recoil proton within an error ofΔ P _x/P_x≈10%. The measured polarisation agrees with recent theoretical predictions. Implications for the measurement of the electric form factor of the neutron using the $D(\vec e,e'\vec n)$ reaction are discussed.     

Effect of a Phosphazene Base on the Diastereoselectivity of Addition of alpha-Sulfonyl Carbanions to Butyraldehyde and Isopropylideneglyceraldehyde

The effect of tBuP4, a strong and cation-free base, on the yield and diastereoselectivity of additions of thus formed "naked" alpha-sulfonyl carbanions to achiral butyraldehyde and chiral isopropylideneglyceraldehyde was studied. It has been found that with tBuP4 a reasonable yield ( approximately 55%) and a slightly better diastereoselectivity (72% of the anti diastreomer) are obtained with achiral and nonfunctionalized butyraldehyde while with isopropylideneglyceraldehyde the use of tBuP4 allowed us to greatly increase the yields (up to 95-100%) and the diastereoselectivities (83-89% of a single diastereomer over the four possible diastereomers). It was also shown that the extra oxygen atom in the alpha-position plays a determinant role in this effect.     

Field emission from a metal covered with a semiconducting layer: A model calculation

The electron field emission from a metal covered with a thin layer of a semiconductor with electron affinity and dielectric constant is considered. The model takes into account the metal-semiconductor (Schottky) barrier of height _b, the conduction current inside the semiconductor, and the band bending at the semiconductor-vacuum interface due to the external field penetration. For thick films under moderately high electric fields, the metal-semiconductor interface does not influence the emission behaviour whereas for thin films, the interface plays an important role, depending on the barrier heights. In particular, for /_b<^2/3 the I–V characteristics will, for strong fields, be dominated by the field emission process at the interface. In such cases important deviations from Fowler-Nordheim behaviour are found.     

A novel bornane synthesis by an old idea

Aiming at a synthesis of spiro[2.4]hepta-4,6-dienes with a carbon substituent at C-4, we investigated solvolysis reactions of the thiatricycle 2, obtained from spiro[2.4]hepta-4,6-diene (1) and thiophosgene by [4 + 2] cycloaddition. With methanol or ethanol a mixture of the esters 7 and 8 was formed. Desulfurization of the thionoesters 8 gave methyl and ethyl spiro[2.4]hepta-4,6-diene-4-carboxylate (10a,b). The corresponding alcohol (11) was prepared from 10b by LiAlH(4) reduction. Ethenetetracarbonitrile combined with the 4-substituted spiro[2.4]hepta-4,6-dienes to give the [4 + 2] cycloadducts 12a-c. Diels-Alder reaction between 11 and 2-chloroacrylonitrile afforded the spiro(bicyclo[2.2.1]hept-5-ene-7,1'-cyclopropane) derivative 14a that was transformed in three steps to rac-10-hydroxycamphor (17). This synthesis of a bornane derivative opens opportunity for variations and thus may find further applications.     

Factors Controlling the Addition of Carbon-Centered Radicals to Alkenes-An Experimental and Theoretical Perspective

The successful exploitation of syntheses involving the generation of new carbon-carbon bonds by radical reactions rests on some prior knowledge of the rate constants for the addition of carbon-centered radicals to alkenes and other unsaturated molecules, and of the factors controlling them. Two former classical reviews in Angewandte Chemie by Tedder (1982) and by Giese (1983) provided mechanistic insight and led to various qualitative rules on the complex interplay of enthalpic, polar, and steric effects. In the meantime, the field has experienced very rapid progress: many more experimental absolute rate constants have become available, and there have been major advances in the efficiency and reliability of quantum-chemical methods for the accurate calculation of transition structures, reaction barriers, and reaction enthalpies. Herein we review this progress, recommend suitable experimental and theoretical procedures, and display representative data series for radical additions to alkenes. On this basis, and guided by the pictorial tool of the state-correlation diagram for radical additions, we then offer a new and more stringent quantification of the controlling factors. Our analysis leads to a partial revision of the previous qualitative rules, and it more clearly exhibits the interplay of the reaction enthalpy effects, polar charge-transfer contributions, and steric substituent effects on the reaction energy barrier. The various contributions are cast into the form of new, simple, and physically meaningful but non-linear, predictive equations for the preestimation of rate constants. These equations prove successful in several tests but call for additional theoretical and experimental foundation. The kinetics of related reactions such as polymer propagation, copolymerization, and the addition of radicals to alkynes and aromatic compounds is shown to follow the same principles.