Influence of the sulfonate countercation on the thermal stability of nafion perfluorosulfonate membranes

We report a strong dependence of the thermal stability of Nafion® perfluorosulfonate ionomer on the nature of the counterion associated with the fixed sulfonate site. These results were obtained using thermal gravimetric analysis on a series of alkali metal and alkyl ammonium cation-exchanged Nafion films. We have found that the temperature of decomposition of Nafion is inversely dependent on the size of the exchanged cation; i.e., Nafion films show improved thermal stability as the size of the counter cation decreases. We attribute this inverse relationship of thermal stability with counterion size to an initial decomposition reaction which is strongly influenced by the strength of the sulfonate-coun-terion interaction. © 1993 John Wiley & Sons, Inc.     

THERMAL AND THERMO-ELASTIC-PLASTIC RESPONSE OF CERAMIC-METAL FUNCTIONALLY GRADED MATERIALS—THERMAL SHOCK PROBLEM

The thermal and thermo-elastic-plastic response of newly developed ceramic-metalfunctionally graded materials under a thermal shock load is studied.The materials are heated at the ce-ramic surface with a sudden high-intensity heat flux input,and cooled at the metal surface with aflowing liquid nitrogen.Emphasis is placed on two aspects:(1)the influence of the graded composi-tion of the materials on the temperature and stress response;and(2)the optimum design of the gradedcomposition from a unified viewpoint of the heat insulation property and stress relaxation property.Moreover,a comparison between the thermoelastic stress and the thermo-elastic-plastic stress is alsomade to indicate the plasticity effect.     

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.     

Metal complexation of crosslinked polyacrylamide-supported dithiocarbamates: Effect of the molecular character and extent of crosslinking on complexation

Dithiocarbamate functions were incorporated into different polyacrylamide matrices crosslinked with a flexible and hydrophilic crosslinking agent, tetraethyleneglycol diacrylate (TEGDA), and their complexation behaviours were investigated. Crosslinked polyacrylamides with varying extents of the tetrafunctional TEGDA crosslinks were prepared by free radical solution polymerization at 60°C using potassium persulphate as initiator in ethanol. The dithiocarbamate functionality was incorporated into these polyacrylamides by a two-step polymer-analogous reaction involving (i)trans-amidation with ethylenediamine and (ii) dithiocarbamylation of the aminopolyacrylamide with carbon disulphide and alkali. The complexations of dithiocarbamate with Cu(II), Ni(II), Zn(II), Co(II) and Hg(II) ions were followed under different conditions. The metal ion intake varied with the extent of the crosslinking agent and the observed trend in complexation is Hg(II) > Cu(II)> Zn(II)> Co(II)> Ni (II). The time-course of complexation, the possibility of recycling, swelling characteristics, and spectral and thermal analyses were carried out. The thermal stability increases upon complexation with metal ions.     

狭义相对论效应──运动时钟变慢的计算机模拟演示实验

利用精炼的C语言进行程序设计，定量模拟狭义相结论的运动时钟变慢，并对处于两种不同时空观的时钟运行进行对比，使得时间膨胀效应变得直观。     

A review of the role of DSC analysis in the design of fluorozirconate glasses for fibre optic applications

The relatively poor thermal stability of fluorozirconate glasses is a major factor preventing the realisation of their true potential for fibre optic applications. A range of methods based on both isothermal and non-isothermal DSC techniques, which can be employed to evaluate the thermal stability of fluorozirconate glasses, are described. The relevance of these thermal stability criteria to the design of fluorozirconate compositions capable of yielding high quality optical fibres is discussed.     

Thermal Behaviour of the N-donor Adducts of Metal Saccharinates III. Imidazole saccharinates of Co(II), Ni(II) and Cd(II)

The complexes [M(HIm)₄(H₂O)₂](sac)₂ (M=Co, Ni) and [Cd(HIm)₂(sac)₂]₂ with saccharin (sac) and imidazole (HIm) were synthesized and their thermal (TG, DTG and DTA) behaviour in the interval from room temperature up to 1000°C in a static air atmosphere was investigated. Irrespectively of whether the deprotonated saccharinato residues are present as ligands or ions or both as ligands and ions, the anhydrous complexes regularly decompose in two stages. The thermal data of 16 saccharinato complexes (including the title compounds) were correlated with the respective structural data. The general thermal stability order of the saccharinato complexes can be represented as: Pb(II)<Zn(II)<Co(II)Ni(II)<Cd(II) (the stability of the Cu saccharinates depends on the particular compound) and is dictated by several structural factors, e.g. metal ionic radii, participation of the water in the coordination sphere of the metal and other structural characteristics. This revised version was published online in August 2006 with corrections to the Cover Date.     

Palladium-catalyzed ring expansion reaction of 1-alkynylcyclobutanols with aryl iodides: an efficient route to 2-disubstituted methylenecyclopentanones

The reaction of 1-alkynylcyclobutanols with aryl iodides in the presence of Pd(OAc)₂ and Et₃N in acetonitrile at 80°C for 24 h gives 2-disubstituted methylenecyclopentan-1-ones in modest to good yields. The tandem insertion-ring expansion process proceeds via the formation of an alkynyl π-complex, followed by migration of a carbon-carbon bond of the tert-alkanol to form the cyclopentanones stereoselectively.     

Cathodoluminescence Depth Profiling in SiO2:Ge Layers

 For investigation of the luminescent center profile cathodoluminescence measurements are used under variation of the primary electron energy E ₀ = 2…30 keV. Applying a constant incident power regime (E ₀·I ₀ = const), the depth profiles of luminescent centers are deduced from the range of the electron energy transfer profiles dE/dx. Thermally grown SiO₂ layers of thickness d = 500 nm have been implanted by Ge⁺-ions of energy 350 keV and doses (0.5–5)10¹⁶ ions/cm². Thus Ge profiles with a concentration maximum of (0.4 – 4) at% at the depth of d_m≅240 nm are expected. Afterwards the layers have been partially annealed up to T _a = 1100 °C for one hour in dry nitrogen. After thermal annealing, not only the typical violet luminescence (λ = 400 nm) of the Ge centers is strongly increased but also the luminescent center profiles are shifted from about 250 nm to 170 nm depth towards the surface. This process should be described by Ge diffusion processes, precipitation and finally Ge nanocluster formation. Additionally, a Ge surface layer is piled-up extending to a depth of roughly 25 nm.