Thermal reaction of clCH2CONH2 in molten acetamide

Mixtures composed of amides and electrolytes exhibit interesting properties such as viscoelastic behaviour and a megavalue of the dielectric constant. In order to improve the dielectric properties, the authors are investigating a large number of molten mixtures of CF₃COONa with different types of amides, including the ternary system sodium trifluoroacetate-chloroacetamide-acetamide. The experimental measurements showed that the ternary mixtures are thermally unstable. A yellow oily product is formed; this was purified and tested by means of IR and NMR techniques. The formula and the kinetic mechanism are proposed.     

Effect of structural variation within cationic azo-surfactant upon photoresponsive function in aqueous solution

The cationic azo-surfactants possessing different spacers and tail alkyl chain lengths have been synthesized by azocoupling ofp-alkylaniline orop-ethoxyaniline with phenol, followed by alkylation and quaternalization with dibromoalkane and trimethylamine, respectively. These surfactants showed a good solubility in water. A reversibletrans-cis isomerization of the azosurfactants by photoirradiation was assessed by UV-Vis absorption spectra. Due to a difference in HLB between thetrans- andcis-surfactants, the observed critical micelle concentration (CMC) values and the electric conductivity of the surfactant solution at above the CMC were significantly affected by the photoinducedtrans-cis isomerization. The azo-surfactants bearing moderate alkyl chain lengths such as surfactants 6 (R₂=C₂H₄, R₃=C₄H₉) and 9 (R₂=C₄H₈, R₃=C₂H₅) were found to be effective to achieve large CMC changes (3.6 mmol/L for 6 and 5.9 mmol/L for 9) by UV-light irradiation. The replacement of the tail chain species also affected the photoresponsive function. The surfactant 12, possessingp-ethoxy group as the tail chain, was found to form a stable micelle aggregation as compared with the structurally related surfactant 10 having ethyl unit as its tail group, but it exhibited a large CMC change (5.3 mmol/L) by UV-light irradiation.     

Thermal stability of poly(mono-n-alkylitaconates) and mono-n-alkylitaconate-co-vinylpyrrolidone copolymers I

Poly(monoitaconates) containing octyl, decyl and dodecyl groups and random monoalkylitaconate-co-vinylpyrrolidone copolymers were studied by thermogravimetric analysis. Copolymers of mono-n-octylitaconate (MOI), mono-n-decylitaconate (MDI), and mono-n-dodecylitaconate (MDoI), respectively, with N-vinyl-2-pyrrolidone (VP) of different compositions were studied by dynamic thermogravimetric analysis. The thermal stability of the copolymers depends on the structure of the monoitaconate comonomer and on the composition of the copolymer The kinetic analysis of the degradation data shows that the thermal decomposition of these copolymers can be described by several kinetic orders depending on the copolymer and on the composition. The relative thermal stability of the copolymers increases as the VP content increases and as the length of the side chain of the itaconate increases, following the same trend as the flexibility of the copolymers in solution.     

Near-field thermoelastic imaging coupled with infrared detection

Near-field thermoelastic imaging is a simple way to investigate the thermal and coupled thermoelastic properties of materials. A few microscopes, deriving from the atomic force microscope, have been used to observe and to quantify the samples observed. But the main problem is the absolute measurement of the temperature, because surface topography and thermal expansion contributions are not easily discernible. In the proposed SThEM (scanning thermoelastic microscope), the tip is excited at the resonance frequency of the cantilever and the sample is periodically heated by the Joule effect. Thus the static contributions (drift, topography) are reduced. Moreover, a radiometric sensor, operating in the far field, has been added in order to quantify the temperature. This multi-acquisition microscope enables one to investigate small objects at the nanoscale with complementary information at the micrometric scale.     

Dynamic mechanical analysis

Using dynamic mechanical analysis (DMA) we have studied thermal degradation for a system containing a diglycidyl ether of bisphenol A (DGEBA) and 1,3-bisaminomethylcylohexane (1,3-BAC). The changes of dynamic mechanical properties during thermal degradation indicated a shift of the glass transition temperature (T _g) to higher temperatures and a decrease in the peak value of the dynamic loss factor (tan δ) with an increasing of aging time. The value of dynamic storage modulus (E′) at the rubbery state showed an increase with aging time, whiteE′ at the glassy state only underwent a moderate change with increased thermal degradation. From these results it can be argued that thermal degradation during the stage prior to the onset of the severe degradation involves structural changes in the epoxy system, as further crosslinking and loss of dangling chains in the crosslinked network.     

A new technique for spatially resolved thermal lensing measurements

A new method is presented for spatially resolved thermal lensing measurements using multiple narrow probe beams and a two-dimensional array detector. The method is applied to an Er, Tm, Ho: YAG laser rod. No significant deviation from a parabolic temperature profile has been found although there is extraordinarily strong thermal lensing in the crystal. Thermo-optical constants of the material are reported.     

Thermal conductivity of poly(vinyl chloride)/polycaprolactone blends

Thermal diffusivity, heat capacity, and density of polyvinyl chloride/polycaprolactone (PVC/PCL) blends were measured by the laser flash method, DSC, and pycnometry, respectively. The thermal conductivity of the PVC/PCL blends was determined from the results. The miscibility of the blend and crystallinity of PCL were determined by DSC. The effect of blend structure on thermal conductivity is discussed. The phase compositions of the PVC/PCL blends are of three types depending on PCL content: i.e., up to 33%, from 33 to 70%, and above 70% PCL by weight. Thermal conductivity, thermal diffusivity, and heat capacity of the PVC/PCL blends are strongly affected by the phase composition of the blend, which changes in a complicated way with PCL content. © 1994 John Wiley & Sons, Inc.     

Towards understanding the increase in strength of thermotropic polyesters with heat treatment

Thermotropic copolyester fibers of oxynaphthoate and oxybenzoate have been subjected to conditions that promote solid-state polymerization as well as annealing. The annealing process causes the crystals to perfect with a simultaneous increase in heat of fusion and melting temperature. Solid-state polymerization, a reaction rate-controlled process, causes the polymer viscosity average molecular weight to increase by chain extension from about 14,000 g/mole to more than 87,000 g/mole with a simultaneous impressive increase in tenacity from about 10 g/d (1.2 GPa) to almost 30 g/d (3.7 GPa). To understand the changes in mechanical properties, we have modeled the fiber structure as short rod-like molecules poorly bonded to a continuous matrix of parallel molecules. Lengthening of the reinforcing molecules facilitates better transfer of load from matrix to molecules, resulting in higher tenacity fibers. © 1994 John Wiley & Sons, Inc.     

On interrelation between the internal pressure and the cohesion energy density

The question about the definition of the “internal pressure” concept is being discussed. It is shown that the previously found differential relation between the cohesion energy density and the internal pressure is one of the examples of an absolutely general interrelation between definitely connected differential functions. It is ascertained that the ratio (the internal pressure divided by the cohesion energy density) is a structuresensitive parameter inherent to the calorific (thermal) equation of a liquid state.     

硼中子俘获治疗的蒙特卡罗方法模拟

用通用蒙特卡罗程序MCNP模拟了粒子在人脑中的输运过程. 吸收剂量率主要来自以下四个反应:¹⁰B(n,α)⁷Li,¹⁴N(n,p)¹⁴C,¹H(n,γ)²D,快中子弹性散射反应.对肿瘤区的贡献主要来自硼中子吸收反应.结果表明,超热中子比热中子适合于深肿瘤的治疗,而热中子对浅肿瘤的治疗有优越性,比如皮肤癌.同确定论方法的结果相比,蒙特卡罗方法不失为一种模拟中子俘获治疗的好工具.