Clustering in ternary III–V semiconductors2

The difference between the bond probability between identical cations (anions) in a quasi-chemical and random solid solution is used as a quantitative measure of the tendency for clustering to occur in ternary III–V semiconductors. GaAlAs, GaAsP, InGaAs and InGaP are examined in some detail and the antimonides, InGaSb, InAsSb and GaAsSb, are discussed briefly. It is shown that the tendency to cluster increases more rapidly with increasing mole fraction than it does with decreasing temperature. It is also suggested that the segregation effects observed in GaAlAs in GaAs/GaAlAs quantum well structures is due to kinetic, as opposed to thermodynamic, effects.     

Viscoelastic properties of 1,2-polybutadiene—comparison with natural rubber and other elastomers

Viscoelastic properties of uncrosslinked 1,2-polybutadiene (91.5% vinyl, 7.0% cis, 1.5% trans, number-average molecular weight 99,000) were studied by dynamic shear measurements between 0.15 and 600 cps (torsion pendulum and Fitzgerald transducer) and shear creep measurements over time periods up to 3.7 × 10⁴ sec., in the temperature rang from 5 to 50°C. More limited dynamic measurements were made on a sample of unvulcanized natural rubber with number-average molecular weight 350,000 at frequencies from 0.4 to 400 cps and temperatures from 13 to 48°C. All data were reduced to 25°C. by shift factors calculated from equations of the WLF form with the following coefficients: 1,2-polybutadiene, c₁ = 6.23, c₂ = 72.5; natural rubber, c₁ = 5.94, c₂ = 151.6. In the transition zone, the relative positions of the loss tangent curves on the logarithmic frequency scale for these and other rubbers (1,4-polybutadiene with 50% trans configuration; styrene–butadiene rubber with 23.5% styrene content; and polyisobutylene) provided relative measures of local segment mobility. At 25°C., these ranged over a factor of 3700 with 1,2-polybutadiene and polyisobutylene the lowest and 1,4-polybutadiene the highest. When the frequency scale of each rubber was reduced to a temperature 100°C. above its glass transition temperature, however, the loss tangent curves for all except polyisobutylene were nearly coincident; the latter still showed a lower mobility by a factor of about 1/800. The terminal relaxation time and steady-state compliance for the 1,2-polybutadiene calculated from the Rouse theory were larger than those observed experimentally. The level of compliance corresponding to the entanglement network of 1,2-polybutadiene, J_eN, was calculated by integration over the loss compliance, J″, to be 1.62 × 10^?7 cm.²/dyne; integration over G″ to obtain the corresponding modulus gave reasonable agreement. From such J_eN, values, the average number of chain atoms between entanglement points, jZ_e, was estimated as follows: 1,2-polybutadiene, 132; natural rubber, 360; 1,4-polybutadiene, 110; styrene–butadiene rubber, 186; polyisobutylene, 320. Values of jZ_e were also estimated from the minimum in the loss tangent and compared with those reported from the molecular weight dependence of viscosity. The three sources were in generally good agreement.     

Dynamic mechanical properties of two copolymers of styrene and n-hexyl methacrylate

The storage (J′) and loss (J″) shear compliances have been measured for two random copolymers of styrene and n-hexyl methacrylate with styrene contents of 18% and 30% (by weight) in the frequency range 45–4400 Hz and the temperature range 31–107°C. The data at different temperatures were combined by the method of reduced variables, and the WLF coefficients were calculated from the temperature shift factors by the method of Pierson and Kovacs. The data were compared with earlier data for the two homopolymers. The thermal expansion coefficient of the fractional free volume, and the free volume at the glass transition temperature, varied monotonically with composition, but the fractional free volume at a reference temperature of 100°C appeared to pass through a maximum as a function of concentration. Comparison of isothermal plots of J′ at 100°C, plots of the relaxation spectrum at 100°C, the monomer friction coefficient and its temperature dependence, and isochronal plots of the storage shear moduls at 100 radians/see all show that the properties of poly(n-hexyl methacrylate) are very slightly affected by incorporation of 18% styrene and only moderately affected by 30% styrene. By contrast, comparison of styrene–butadiene rubber with 1,4-polybutadiene shows a very large effect of incorporation of 23.5% styrene. These differences may be associated with local packing relations of the comonomer residues and suggest that copolymer properties cannot be readily predicted from those of the component homopolymers.     

Molecular friction coefficients in polymers and their temperature dependence

Colloid and Polymer Science - Analysis of the temperature dependence of viscoelastic and dielectric relaxation processes in several individual polymers by the equation of Williams, Landel, and...     

Strategic views of accreditation

This paper summarises the experience we gained while going through an accreditation process in accordance with the requirements of ISO/IEC 17025 Standard. We propose in this paper an initial path finding study stage to evaluate the laboratory's predisposition for, and the benefits of, accreditation. We also present a conceptual framework as part of the path finding study stage to identify and classify different groups of activities in a laboratory into separate business domains. The objective of the study is to assess, for each business domain, the approach, the benefits, costs and implications of working with a systematic QA and then design a priori appropriate working systems tailored to the real needs of each business. Such a study should naturally lead to an appropriate definition of accreditation scope.

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Acidity in Nafion

Hammett acidity functions have been measured for Nafion films equilibrated with a series of nitroaniline dyes in hydrochloric acid solutions. The effect of ionic strength of alkali metal and tetraalky-lammonium bromides on the ability of the Nafion film to donate a proton to Bronsted bases is the reverse of that expected for acid in solution. Absorption of neutral and charged dye is also influenced by the concentration and hydrophobicity of the salt in solution. An interpretation based upon structural spectroscopic studies is discussed.     

Gelatin‐Methacrylamide Hydrogels as Potential Biomaterials for Fabrication of Tissue‐Engineered Cartilage Constructs

Gelatin‐methacrylamide (gelMA) hydrogels are shown to support chondrocyte viability and differentiation and give wide ranging mechanical properties depending on several cross‐linking parameters. Polymer concentration, UV exposure time, and thermal gelation prior to UV exposure allow for control over hydrogel stiffness and swelling properties. GelMA solutions have a low viscosity at 37 °C, which is incompatible with most biofabrication approaches. However, incorporation of hyaluronic acid (HA) and/or co‐deposition with thermoplastics allows gelMA to be used in biofabrication processes. These attributes may allow engineered constructs to match the natural functional variations in cartilage mechanical and geometrical properties.

     

Least‐square collocation and Lagrange multipliers forTaylor meshless method

A recently proposed meshless method is discussed in this article. It relies on Taylor series, the shape functions being high degree polynomials deduced from the Partial Differential Equation (PDE). In this framework, an efficient technique to couple several polynomial approximations has been presented in (Tampango, Potier‐Ferry, Koutsawa, Tiem, Int. J. Numer. Meth. Eng. vol. 95 (2013) pp. 1094–1112): the boundary conditions were applied using the least‐square collocation and the interface was coupled by a bridging technique based on Lagrange multipliers. In this article, least‐square collocation and Lagrange multipliers are applied for boundary conditions, respectively, and least‐square collocation is revisited to account for the interface conditions in piecewise resolutions. Various combinations of these two techniques have been investigated and the numerical results prove their effectiveness to obtain very accurate solutions, even for large scale problems.