A dynamic method of determining the modulus of elasticity of refractories at high temperatures and automation of the tests

Conclusions Laboratory apparatus was designed for determining the elastic properties with automatic regulation of the temperature schedule and automatic registration of the basic type of frequency of oscillation during heating to 1400°C. In comparison with the manual regulation, more detailed characteristics for the change in elastic properties during heating are obtained and subjective errors are also excluded.The new equipment was used to elucidate the dependence of the frequency of bending oscillations and the modulus of elasticity of various refractories on temperature.     

Modeling of free radical polymerization up to high conversion. I. A method for the selection of models by simultaneous parameter estimation

A systematic quantitative method for the selection of models for the high-conversion free radical polymerization exhibiting gel and glass effects has been developed. Four representative models were selected from the literature and were compared on the basis of the same experimental data. All models describe the isothermal time-conversion data over the entire conversion range for a single type and loading of initiator well. Models that are not considering the effect of molecular weight of the polymers on the diffusion of macro radicals fail to describe the time-conversion data if the concentration of the initiator varies at the same time. By simultaneous fitting of the conversion and polymerization degree data it was shown that the Marten-Hamielec model and its extended form (Panke-Stickler-Hamielec model) were not able to describe the number average polymerization degree Pn at the final conversion, where the glass effect occurs. This occurred because both models neglect the change of the radical efficiency f in this region, which has more effect on Pn than the change of the propagation rate coefficient (see part II of this series). © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1649–1661, 1997     

Methods for the determination of cyclopropenoid fatty acids. IV. Application of the step-wise HBr titration method to the analysis of refined and crude cottonseed oils

A method is described for the determination of cyclopropenoid fatty acids in refined and crude cottonseed oils to within 0.01%. It is based upon a stepwise hydrogen bromide titration at 3C and 55C after removal of interfering substances by adsorption on activated alumina. Highly oxidized cottonseed oils first must be converted to methyl esters. Presented at AOCS Meeting in Minneapolis, 1963. So. Utiliz. Res. and Dev. Div., ARS, USDA.     

Studies on the preparation and properties of conductive polymers. IV. Novel method to prepare metallized plastics from metal chelates of polymides–imides

A new type of polyamide–imides (PAI) was synthesized by direct polycondensation. A series of polyamide–imide metal chelate films was prepared by the transition-metal salts (AgNO₃, CuCl₂, and CoCl₂) mixed with the polyamide–imides in NMP solution. These polyamide–imide metal chelate films were reduced by various reducing agents, and the reduced films exhibited low surface resistivity around 10⁰?10¹ Ω/cm². The surfaces of these conductive films were proved to be metallized by means of X-ray analysis. The metal adhered on the film was believed to be responsible for the improvement of electrical conductivity. The effects of kinds and concentrations of metal salts, kinds and concentrations of reducing agents, and reduction time on the conductivity of metallized films were investigated. The IR spectra and SEM observations of unreduced and reduced polymer chelate films were also studied.     

A novel mathematical procedure to evaluate the effects of surface topography on the interfacial state of stress. Part II. Verification of the method for scarf interfaces

A mathematical procedure was developed to utilize the complementary energy method, by minimization, in order to obtain an approximate analytical solution to the 3D stress distributions in bonded interfaces of dissimilar materials. The stress solutions obtained predict the stress jumps at the interfaces, which cannot be captured by the current FEA methods. As a novel method, the penalty function is used to enforce the displacement boundary conditions at the interfaces. Furthermore, the mathematical procedure developed enables the integration of different interfacial topographies into the solution procedure. In order to incorporate the effects of surface topography, the interface is expressed as a general surface in Cartesian coordinates, i.e. F(x, y, z) = 0. In this paper, the scarf interface problem, i.e. y = x/2 surface is considered for verification of the method by comparison with finite element analysis (FEA) results. Comparison of the results reveals our new mathematical procedure to be a promising and efficient method for optimizing interface topographies.     

Part IV: Dynamic evolution of the particle size distribution in particulate processes. A comparative study between Monte Carlo and the generalized method of moments

The present work provides a comparative study on the numerical solution of the dynamic population balance equation (PBE) for batch particulate processes undergoing simultaneous particle aggregation, growth and nucleation. The general PBE was numerically solved using three different techniques namely, the Galerkin on finite elements method (GFEM), the generalized method of moments (GMOM) and the stochastic Monte Carlo (MC) method. Numerical simulations were carried out over a wide range of variation of particle aggregation and growth rate models. The performance of the selected techniques was assessed in terms of their numerical accuracy and computational requirements. The numerical results revealed that, in general, the GFEM provides more accurate predictions of the particle size distribution (PSD) than the other two methods, however, at the expense of more computational effort and time. On the other hand, the GMOM yields very accurate predictions of selected moments of the distribution and has minimal computational requirements. However, its main disadvantage is related to its inherent difficulty in reconstructing the original distribution using a finite set of calculated moments. Finally, stochastic MC simulations can provide very accurate predictions of both PSD and its corresponding moments while the MC computational requirements are, in general, lower than those required for the GFEM.     

Solvent effects in the oxidation of sulphur compounds. Anionic oxidation of high molecular weight thiols and disulphides to sulphonate salts

The base-catalysed oxidation of high molecular-weight aliphatic thiols and disulphides to sulphonate salts by molecular oxygen has been studied from 23.5° to 80°. The preferred solvent was hexamethylphosphoramide. Generally, yields and selectivities of the sulphonate salts varied from 95 to 99% at 80°. Potassium and sodium hydroxides were equally effective as the base catalysts. Other solvents and bases were explored and factors which control selectivity to the final product determined. The reactions are believed to involve sulphenate ions produced by attack of hydroxide ion on the disulphide linkage. Such species are unstable and may be oxidised directly by oxygen or disproportionate to sulphonate ions and disulphides.     

A rigorous method to evaluate the consistency of experimental data in phase equilibria. Application to VLE and VLLE

This work forms part of a broader study that describes a methodology to validate experimental data of phase equilibria for multicomponent systems from a thermodynamic‐mathematical perspective. The goal of this article is to present and justify this method and to study its application to vapor–liquid equilibria (VLE) and vapor–liquid–liquid equilibria (VLLE), obtained under isobaric/isothermal conditions. A procedure based on the Gibbs‐Duhem equation is established which presents two independent calculation paths for its resolution: (a) an integral method and (b) a differential method. Functions are generated for both cases that establish the verification or consistency of data, δψ for the integral test and δζ for the differential approach, which are statistically evaluated by their corresponding average values [ , ], and the standard deviations [ , ]. The evaluation of these parameters for application to real cases is carried out using a set of hypothetical systems (with data generated artificially), for which the values are adequately changed to determine their influence on the method. In this way, the requirements of the proposed method for the data are evaluated and their behavior in response to any disruption in the canonical variables (p,T, phase compositions). The conditions for thermodynamic consistency of data are: , , , and . In systems with VLLE, in addition to the previous criteria, must occur that: and . The new proposed method has been tested with a set of 300 experimental binary systems, biphasic and triphasic, obtained from published bibliography, and the results are compared with those of other tests commonly used for testing thermodynamic consistency. The results show that the greater rigor of the proposed method is mainly due to the simultaneous verification of various independent variables. As a result, the conditions for the new test are verified for fewer systems than using other tests mentioned in the literature (i.e., Fredenslund‐test and direct of Van Ness). Its unique application is sufficient to ensure the consistency of experimental data, without using other tests. © 2017 American Institute of Chemical Engineers AIChE J, 2017     

A novel mathematical procedure to evaluate the effects of surface topography on the interfacial state of stress. Part I: Verification of the method for flat surfaces

A mathematical procedure is developed to utilize the complementary energy method, by minimization, in order to obtain an approximate analytical solution to the 3D stress distributions in bonded interfaces of dissimilar materials. The stress solutions obtained predict the stress jumps at the interfaces, which cannot be captured by current FEA methods. As a novel method, the penalty function is used to enforce the displacement boundary conditions at the interfaces. Furthermore, the mathematical procedure developed enables the integration of different interfacial topographies into the solution procedure. In order to incorporate the effects of surface topography, the interface is expressed as a general surface in Cartesian coordinates, i.e. F (x, y, z) = 0. In this paper, the flat interface problem, i.e. y = 0 surface is considered for verification of the method by comparison with the FEA method. A comparison of the results reveals our new mathematical procedure to be a promising and efficient method for optimizing interface topographies.     

Volatilisation and catalytic effects of alkali and alkaline earth metallic species during the pyrolysis and gasification of Victorian brown coal. Part III. The importance of the interactions between volatiles and char at high temperature

A novel two-stage fluidised-bed/fixed-bed reactor was designed to investigate the effects of volatile-char interactions on the volatilisation of alkali and alkaline earth metallic (AAEM) species during the pyrolysis of Victorian brown coal at 900 °C. With the two-stage reactor configuration, the AAEM-free volatiles generated from the pyrolysis of the H-form coal in the fluidised bed came into direct contact with the char from NaCl-loaded or Na-form coals in the fixed bed. The results indicated that the interactions between the volatiles, especially free radicals in the volatiles, and the char particles enhanced the volatilisation of Na from the char drastically. However, such radical-char interactions resulted in little volatilisation of Mg and Ca, indicating the importance of valence of the AAEM species. The degree of the volatile-char interactions was also related to the ageing of the char and the chemical form of AAEM species in the coal substrate. The volatiles interacted more strongly with the nascent char than the aged char, indicating that the AAEM species existed in the aged char in more stable forms than in the nascent char.     

Development and validation of an HPLC method for the quantification of vitamin A in human milk. Its application to a rural population in Argentina

A methodology for the quantification of vitamin A in human milk was developed and validated. Vitamin A levels were assessed in 223 samples corresponding to the 5th, 6th and 7th postpartum months, obtained in the province of Santiago del Estero, Argentina. The samples (500 microL) were saponified with potassium hydroxide/ethanol, extracted with hexane, evaporated to dryness and reconstituted with methanol. A column RP-C18, a mobile phase methanol/water (91:9 v/v) and a fluorescence detector (lambda excitation 330 nm and lambda emition 470 nm) were used for the separation and quantification of vitamin A. The analytical parameters of linearity (r2: 0.9995), detection (0.010 microg/mL) and quantification (0.025 microg/mL) limits, precision of the method (relative standard deviation, RSD = 9.0% within a day and RSD = 8.9% among days) and accuracy (recovery = 83.8%) demonstrate that the developed method allows the quantification of vitamin A in an efficient way. The mean values + standard deviation (SD) obtained for the analyzed samples were 0.60 +/- 0.32; 0.65 +/- 0.33 and 0.61 +/- 0.26 microg/ mL for the 5th, 6th and 7th postpartum months, respectively. There were no significant differences among the three months studied and the values found were similar to those in the literature. Considering the whole population under study, 19.3% showed vitamin A levels less than 0.40 microg/mL, which represents a risk to the children in this group since at least 0.50 microg/mL are necessary to meet the infant daily needs.