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1.
2.
Creep and differential scanning calorimetry (DSC) measurements have been used to study the physical aging behavior of a polyetherimide. Isothermal aging temperatures ranged from 160°C to Tg with aging times ranging from 10 min to 8 days. The only measurable effect of physical aging on the short-time creep curves is a shift of the creep compliance to longer times. Andrade plots of the compliance versus the cube root of time are linear at short times with the slope β decreasing with increasing aging time to a constant value once equilibrium is reached. Log β3 is related directly to the degree to which the creep curves shift to longer times with physical aging, and is used in this work as a measure of physical aging. A reduced curve of log β3 versus log aging time is obtained for the aging temperatures investigated by appropriate vertical and horizontal shifts. The enthalpy change during aging increases linearly with the logarithm of the aging time, ta, leveling off at equilibrium at values which increase with decreasing aging temperature. Hence, both nonequilibrium and equilibrium temperature shift factors can be calculated from the DSC data. Good agreement is observed between the equilibrium temperature shift factors obtained from the creep and DSC data. The temperature dependence of the nonequilibrium temperature shift factors is found to be an order of magnitude smaller than that of the equilibrium shift factors. The time scales to reach equilibrium for enthalpy and for mechanical measurements are found to be the same within experimental error. © 1995 John Wiley & Sons, Inc.  相似文献   
3.
Homopolymers and blends of polycarbonate/ThermX have been investigated by differential scanning calorimetry, dynamic mechanical analysis, density measurements, and positron annihilation lifetime spectroscopy. The study focuses on the chain mobility and free volume in the amorphous miscible regions of the blends and how this mobility and free volume are affected by increasing crystallinity. It is proposed that judicious annealing, which results in increasing crystallinity (while avoiding ageing or transesterification), induces a constraint on the amorphous region leading to an increase in Tg and coalescence of free volume sites. © 1994 John Wiley & Sons, Inc.  相似文献   
4.
Summary A reproducible method is described for the separation and simultaneous and specific quantitation of ascorbic acid and dehydroascorbic acid by ion-pairing reversed-phase HPLC with fluorometric detection. Copper sulphate and copper acetate were compared as oxidizing reagents for ascorbic acid and 1,2-diaminobenzene dihydrochloride and 1,2-diamino-3,4-dimethylbenzene dihydrochloride as derivatising reagents. The HPLC-method was applied to human plasma. The detection limit reaches 16 ng for ascorbic acid and 3 ng for dehydroascorbic acid. Sample preparation is carried out by solid phase extraction with a recovery of 98%; it is compared with conventional precipitation of plasma proteins by metaphosphoric acid.  相似文献   
5.
Hermann M. Niemeyer 《Tetrahedron》1978,34(18):2757-2762
Chelates formed by carbocations and cyclic polyethers and polyamines are studied with semiempirical and ab initio MO methods.  相似文献   
6.
A model is presented that describes quantitatively the condensation of analytes in pico- and nanogram masses sampled with electrothermal vaporization (ETV). It presumes that the analyte vapor condensation of such low amounts occurs mainly heterogeneously, predominantly on growing carbon particulates originating from the graphite furnace before the analyte vapor achieves saturation via cooling. The model regards the coagulation of carbon particles and the diffusion of analyte atoms. The criterion whether or not an analyte atom sticks to a colliding particle is chosen as a function depending on its temperature and on the common GFAAS pretreatment temperatures. Heterogeneous condensation of six analytes with different volatilities, Ag, Cu, Fe, Ni, Mn, and Pb, is calculated for the ETV unit with an axially focusing convection upstream described in Part I. Modifier effects are taken into account. The results are compared to measured data.  相似文献   
7.
Quantum chemical calculations are used to explore the proton-transfer reactivity of O-protonated vinyl alcohol, CH2CHOH2+, with phosphorus nitride, PN. This reaction is relevant to the chemical evolution of interstellar clouds, since O-protonated vinyl alcohol has been postulated (and tentatively identified) as a product of the association reaction between interstellar H3O+ and C2H2, while PN is the most widespread and abundant phosphorus-containing molecule seen in astrophysical environments. Furthermore, the reaction exhibits an unusual mechanistic feature, namely, an extended "proton-transport catalysis" mechanism, which we characterize here as a "proton-transfer triple play". The reaction proceeds initially by proton transfer from CH2CHOH2+ to PN, then from PNH+ to CH2CHOH, and finally from CH3CHOH+ to PN, where the emphasized atom indicates the resultant site of protonation/deprotonation. Thus, the ultimate overall bimolecular proton-transfer reaction is expected to occur as CH2CHOH2+ + PN --> CH3CHO + PNH+; that is, the apparent favored product channel exhibits not only proton transfer but also keto/enol tautomerization. The triple-play mechanism can be rationalized in terms of the proton affinities of vinyl alcohol, acetaldehyde, and phosphorus nitride, which here are satisfactorily reproduced by high-level ab initio calculations. Other neutrals with a proton affinity appropriate for the possible triple-play mechanism converting CH2CHOH2+ to CH3CHO are also identified, with a view to encouraging experimental investigation of this mechanism.  相似文献   
8.
The principal goal of this paper is to investigate the representation theory of double coset hypergroups. IfK=G//H is a double coset hypergroup, representations ofK can canonically be obtained from those ofG. However, not every representation ofK originates from this construction in general, i.e., extends to a representation ofG. Properties of this construction are discussed, and as the main result it turns out that extending representations ofK is compatible with the inducing process (as introduced in [7]). It follows that a representation weakly contained in the left-regular representation ofK always admits an extension toG. Furthermore, we realize the Gelfand pair (where are a local field andR its ring of integers) as a polynomial hypergroup on ℕ0 and characterize the (proper) subset of its dual consisting of extensible representations.  相似文献   
9.
We have investigated the dielectrophoretic assembly of colloidal gold, carbon black, and carbon nanotubes into electrical wires. The resulting microwires have diameters less than 1 microm, with lengths ranging from 5 microm to 3 mm. Current-voltage curves for these wires indicate an ohmic response, where the resistance is determined by the type of colloid and by the frequency of the alternating field used to grow the wires. The predicted frequency dependence of dielectrophoresis is confirmed by experiment. Measurements of the threshold voltage for initial wire growth are also presented. These experiments demonstrate that a variety of nanoparticles can be assembled into microwires for sensor applications.  相似文献   
10.
We define a gravitational field strength in theories of the Einstein-Cartan type admitting a Killing vector. This field strength is a second rank, antisymmetric, divergence-free tensor, whose (Komar) integral over a closed 2-surface gives a physically meaningful quantity. We find conditions on the Lagrange density of the theory which ensure the existence of such a tensor, and show that they are satisfied forN=2-supergravity and for a special case of the bosonic sector ofN=4-supergravity. We discuss a possible application of the generalized Komar integral in the theory of stationary black holes. We also consider the field strength problem in Kaluza-Klein theory, where the application to black holes is particularly interesting.  相似文献   
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