Adhesion Mechanisms of Polyurethanes to Glass Surfaces. III. Investigation of Possible Physico-Chemical Interactions at the Interphase

Surface free energies of polyurethanes made from toluene diisocyanate and 1, 4 butanediol-based hard segments and caprolactone polyol-based soft segments were calculated using additive functions. Good agreement was found between the calculated values based on additive functions and the calculated values based on contact angle measurements. The phase-separated polyurethanes were found to have a higher polar surface free energy component (γ^P). This was linked to the preferential segregation of butanediol/butanediol-derived moieties to the polyurethane surfaces due to phase separation. The adhesion values of these polyurethanes to soda-lime glass were correlated with their respective γ^P values and a linear relationship was found. It was also shown that the adhesion values of the low γ^P polyurethanes improved substantially when the glass surfaces were coated with a thin layer of butanediol prior to the bonding. The modulus of the interphase region rich in butanediol was evaluated. Although a modulus increase was found at the interface, this increase was found to play a secondary role in the adhesion. The chemical interactions at the polyurethane/glass interphase were investigated by pre-treating the glass surfaces with methyl-trimethoxysilane and trimethylchlorosilane prior to adhesion testing. The adhesion data showed no significant difference between the uncoated and the silane-treated glass substrates. Based on this experimental evidence, the possibility of any covalent or ionic bonding at the polyurethane/glass interphase was assumed negligible. It was determined that the mechanism of adhesion between the polyurethanes and the glass surface could be through the formation of an interphase region in which hydrogen bonding between the butanediol-rich interphase region and the hydroxylated glass surface plays a key role.     

Effect of sintering zirconia with calcia in very low partial pressure of oxygen

Samples of zirconia containing 0, 8 and 15 mol % calcia were sintered in very low partial pressure of oxygen ( 10^–6 Pa) and the resulting phases, lattice parameters and electrical conductivity studied. The cubic phase was found to be partially stabilized in the calcia-free samples while complete stabilization occurred in the samples containing 8 and 15 mol calcia. The lattice parameter of the cubic phase showed dependence on the calcia content and the concentration of vacancies at the anion sites. The concentration of these vacancies in the calcia-containing samples is estimated to be 21 % and is limited by the appearance of metallic zirconium located in isolated pockets. Electrical conductivity measurements also indicated that the metallic phase was not continually connected. A peak and a minimum in the conductivity-temperature plot are believed to be due to the removal of excess oxygen vacancies introduced during sintering.     

Nanogoldpharmaceutics (i) The use of colloidal gold to treat experimentally-induced arthritis in rat models; (ii) Characterization of the gold in Swarna bhasma, a microparticulate used in traditional Indian medicine

Nanosized gold particles (27 +/− 3 nm) have been proven to be effective in ameliorating the symptoms of mycobacterial-, collagen- and pristane-induced arthritis in rat models. This contrasts with the drug sodium aurothiomalate that was only effective against mycobacterial-induced arthritis but not to the same extent as Au⁰. Gold in the traditional Indian Ayurvedic medicine,Swarna bhasma (gold ash), has been characterized as globular particles of gold with an average size of 56–57 nm.     

Adhesion Mechanisms of Polyurethanes to Glass Surfaces I. Structure-Property Relationships in Polyurethanes and Their Effects on Adhesion to Glass

Polyurethanes were prepared from toluene diisocyanate (TDI), 1-4-butane diol (BDO) and polycaprolactone-based triols with varying molecular weights. Among each molecular weight triol-based urethane, hard segment content was varied from 20% to 70%. Differential scanning calorimetry, tensile testing, and Iosipescu shear testing were done on all the various urethanes prepared. Thermal characterization data revealed the dependence of phase separation on hard segment content as well as on the triol molecular weight. Tensile data and Iosipescu shear data further confirmed the observations made from the DSC data. The data further indicated that phase separation can greatly improve the modulus of cross-linked segmented urethanes. Adhesion of these urethanes to glass surface was evaluated using soda-lime float glass plate. Urethane samples were cast on the air side of the glass plates and adhesion was measured in shear mode. Adhesion data indicated that in addition to hard segment content, modulus, cross-link density, and molecular weight of the triols, phase separation seems to be a major factor in controlling adhesion. Surfaces of the failed adhesion samples were also analyzed and the failure mode was found to be cohesive, in varying degree, with the different urethane systems.     

Separation of kinetics and mass-transfer in a batch alkoxylation reaction

The quantitative aspects of the role of interfacial mass-transfer and reaction kinetics in ethoxylation of lauryl alcohol were examined in a batch recirculation reactor. The liquid droplets falling through a gas column were obtained by utilizing a recirculation loop and a set of spray nozzles. The CO₂/NaOH reaction was employed to characterize the interfacial area. The alkoxylation reaction was studied at temperatures between 124°C and 171°C, at catalyst levels between 0.09 and 0.50 weight percent and at ethylene oxide partial pressures between 68 kPa and 204 kPa. A model was developed which permits the prediction of reactor performance at various operating conditions. The mass-transfer during free fall dominates the interfacial mass-transfer and the contributions during the drop formation and coalescence stages are small. The rate of ethylene oxide (EO) addition to lauryl alcohol was constant during the batch run, indicating similar activity for the unreacted lauryl alcohol and the lauryl alcohol ethoxylated to varying extents. The rate of ethoxylation is first-order in both catalyst and ethylene oxide concentrations. The liquid-phase reaction kinetics and interfacial mass-transfer occur in series, with kinetics dominating the overall ethoxylation rate. As expected, an increasing role of mass transfer is observed at higher temperatures, and/or higher catalyst concentrations where the kinetic rate becomes significantly high. The intrinsic activation energy for the ethoxylation of lauryl alcohol is 55.2 kJ/mole.     

Improvement of Crystallinity of KZr2P3O12 by Sol-Gel Synthesis

The X-ray diffraction pattern for potassium-zirconium phosphate is significantly improved when the material is prepared by the sol-gel route rather than the powder method. Peaks at high, low, and intermediate angles are presented and compared for the two methods. It is assumed that the more nearly homogeneous mixing of the elements in the sol-gel process is responsible for the significant improvement in crystallinity.     

Injection-molding process control—A review

This paper reviews control strategies employed in the injection-molding process. For clarity, the controlled variables have been categorized into all-phase control, phase-dependent control, and cycle-to-cycle control. All-phase control includes variables that must be monitored and controlled at all times; i.e., in all the phases. Control of variables that are triggered during a specific phase are discussed under phase-dependent control. In cycle-to-cycle control, previous data are used to predict future trends and take appropriate corrective actions, The cyclic, dynamic, and unsteady state nature of the injection-molding process is discussed with respect to the conventional proportional-integral (PI) and proportional- integral-derivative (PID) controllers as well as the more advanced control schemes such as self-tuning control, optimal control, and statistical process control. Suggestions involving specific advanced control schemes and recommendations for future research in injection-molding process control also are made.     

The inhibition of corrosion and hydrogen embrittlement of AISI 410 stainless steel

A study was carried out on the inhibition of corrosion and hydrogen embrittlement of AISI 410 stainless steel by two organic inhibitors, namely benzotriazole and benzonitrile. Tensile testing, scanning electron microscopy, weight loss measurements and potentiodynamic polarization were the techniques used for this study. Tensile tests showed that 410 steel is highly susceptible to hydrogen stress cracking. Scanning electron microscopic observations of fracture surfaces showed a brittle quasi-cleavage type of failure when the steel was hydrogen charged from 0.5m H₂SO₄. Both inhibitors reduced hydrogen induced ductility loss though the fracture mode was unaltered. They showed increasing inhibition efficiencies for corrosion as well as cathodic hydrogen evolution as their concentration in H₂SO₄ increased from 3.9×10^–5 m to 8.4×10^–3 m. Benzonitrile was found to be a more efficient inhibitor than benzotriazole for AISI 410 stainless steel exposed to 0.5m H₂SO₄.     

Kinetics of esterification of cycloaliphatic epoxies with methacrylic acid

The esterification of cycloaliphatic epoxy resins CER I and CER II containing glycidyl and cyclohexane epoxy groups, respectively, as their reactive units was carried out using a 1 : 0.9 stoichiometric ratio of resin and methacrylic acid in the presence of triphenylphosphine. The reaction was performed at 80, 85, 90, 95, and 100°C and it followed second‐order kinetics. The specific rate constants, calculated by regression analysis, were found to obey an Arrhenius expression. Kinetic and thermodynamic parameters, activation energy, frequency factor, entropy, enthalpy, and free energy of the reaction, revealed that the reaction was spontaneous and irreversible and produced a highly ordered activated complex. The reactivity of CER II was found to be higher than that of CER I. The difference in the reactivity of the cycloaliphatic epoxies was explained by proposing a reaction mechanism. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3197–3204, 2002