New initiators for the ring-opening thermal polymerization of hexachlorocyclotriphosphazene: synthesis of linear poly(dichlorophosphazene) in high yields

Ring-opening thermal polymerization of hexachlorocyclotriphosphazene (N3P3C&h)a s been investigated at 250 "C and at 1.333-Pa pressure using chlorocyclotriphosphazenes N3P3C15(N=PPh3) and N3P3Cl,.,(NMe2), (n = 2-4), salt hydrates, triphenylphosphine, and benzoic acid as initiators. The linear poly (dich1orophosphazene) products are phenoxylated, and the phenoxy polymers are characterized by gel permeation chromatography and dilute solution viscometry. Among the various initiators investigated, CaS04.2H20b rings about a high conversion (>60%) of N3P3C&to the linear [NPC12], polymer which possesses a high molecular weight (>5 X lo6). The rationale for the choice of the initiators and possible mechanism(s) of polymerization is discussed. Several mixed substituent polymers, [NP(OPh),(OC6H4Me-p)2,1, and [NP(OPh),(OCHzCF3)2,]nh, ave been prepared and their thermal properties evaluated.

Thermal requirements, field mortality and population phenology modelling of Paropsis atomaria Olivier, an emergent pest in subtropical hardwood plantations

Paropsis atomaria is a recently emerged pest of eucalypt plantations in subtropical Australia. Its broad host range of at least 20 eucalypt species and wide geographical distribution provides it the potential to become a serious forestry pest both within Australia and, if accidentally introduced, overseas. Although populations of P. atomaria are genetically similar throughout its range, population dynamics differ between regions. Here, we determine temperature-dependent developmental requirements using beetles sourced from temperate and subtropical zones by calculating lower temperature thresholds, temperature-induced mortality, and day-degree requirements. We combine these data with field mortality estimates of immature life stages to produce a cohort-based model, ParopSys, using DYMEX™ that accurately predicts the timing, duration, and relative abundance of life stages in the field and number of generations in a spring–autumn (September–May) field season. Voltinism was identified as a seasonally plastic trait dependent upon environmental conditions, with two generations observed and predicted in the Australian Capital Territory, and up to four in Queensland. Lower temperature thresholds for development ranged between 4 and 9 °C, and overall development rates did not differ according to beetle origin. Total immature development time (egg–adult) was approximately 769.2 ± S.E. 127.8 DD above a lower temperature threshold of 6.4 ± S.E. 2.6 °C. ParopSys provides a basic tool enabling forest managers to use the number of generations and seasonal fluctuations in abundance of damaging life stages to estimate the pest risk of P. atomaria prior to plantation establishment, and predict the occurrence and duration of damaging life stages in the field. Additionally, by using local climatic data the pest potential of P. atomaria can be estimated to predict the risk of it establishing if accidentally introduced overseas. Improvements to ParopSys’ capability and complexity can be made as more biological data become available.

Evaluation Of Diffusion-Coefficient And Ionic Mobility In (Nh4)4fe(Cn)6.1.5 H2o

The diffusion coefficient, D, and the ionic mobility, μ, in the protonic conductor ammonium ferrocyanide hydrate have been determined by the isothermal transient ionic current method. D is also determined from the time dependence of the build up of potential across the samples and theretical expressions describing this build up in terms of double exponential dependence on time are obtained. The values obtained are D=3.875×10−11m2s−1 and μ=1.65×10−9 m2V−1s−1.

Diffusion Parameters in the Nb-Mo System: Revisited

The variation of the interdiffusion coefficient with the change in composition in the Nb-Mo system is determined in the temperature range of 1800 °C to 1900 °C. It was found that the activation energy has a minimum at around 45 at. pct Nb. The values of the pre-exponential factor and the activation energy for diffusion are compared with the data available in the literature. Further, the impurity diffusion coefficients of Nb in Mo and Mo in Nb are calculated.

Pulsed laser surface treatment of magnesium alloy: Correlation between thermal model and experimental observations

The effect of deposition of Al +Al2O3 on MRI 153 M Mg alloy processed using a pulsed Nd:YAG laser is presented in this study. A composite coating with metallurgical joint to the substrate was formed. The microstructure and phase constituents were characterized and correlated with the thermal predictions. The laser scan speed had an effect on the average melt depth and the amount of retained and/or reconstituted alumina in the final coating. The coating consisted of alumina particles and highly refined dendrites formed due to the extremely high cooling rates (of the order of 10(8) K/s). The microhardness of the coating was higher and several fold improvement of wear resistance compared to the substrate was observed for the coatings. These microstructural features and physical properties were correlated with the effects predicted by a thermal model.

Mossbauer Effect Study of the Thermal Decomposition in Hydrogen of Homogeneously Mixed Ferrous Nickel Oxalates with Different Iron to Nickel Ratios

Mossbauer effect and X-ray measurements are carried out on product samples of the thermogravimetric analysis (TGA) and isothermal decomposition in hydrogen of homogeneously mixed ferrous nickel oxalates with different iron to nickel ratios. The formation of Fe-Ni alloy is obtained at considerably lower temperatures (z 300 "C) in each case. The Fe-Ni alloys obtained shift from iron-rich to nickel-rich composition as the nickel ratio in the mixed metal oxalates is increased. The formation of Pe-Ni Invar from mixed metal oxalate with Fe:Ni = 1:l is indicated in the early stages but not from those with Fe:Ni = 2: 1 or 64:36. An Produktproben von homogen verteilten Eisen-Nickeloxalaten mit unterschiedlichem Eisen- Nickel-Verhaltnis nach thermogravimetrischer Analyse (TGA) und isothermem Zerfall in Wasserstoff werden Mollbauereffekt- und Rontgenmessnngen durchgefuhrt. In allen Fiillen wird die Bildung der Fe-Ni-Legierung bei betriichtlich niedrigeren Temperaturen (= 300 "C) erhalten. Die erhaltenen Fe-Ni-Legierungen verschieben sich von der eisenreichen zur nickelreichen Zusrtmmensetzung, wenn das Nickelverhaltnis in dem BIetall-Mischoxalat erhoht wird. Die Bildung der Fe-Ni-lnvar-Legierung aus dem Metall-Mischoxalat mit Fe:Ni = 1 : 1 wird in fruhen Zustanden beobachtet, iedoch nicht aus Oxalaten mit Fe:Ni = 2:1 oder 64:36.

An Exact Analysis of Unsteady Convective Diffusion in an Annular Pipe

An exact solution to the unsteady convective diffusion equation for the dispersion of a solute in a fully developed laminar flow in an annular pipe is obtained. Generalized dispersion model which is valid for all time after the injection of solute in the flow is used to evaluate the dispersion coefficients as functions of time. It is observed that the axial dispersion decreases with an increase in the radius of the inner cylinder.

Swarm intelligence-based solver for parameter estimation of laboratory through-diffusion transport of contaminants

Theoretical approaches are of fundamental importance to predict the potential impact of waste disposal facilities on ground water contamination. Appropriate design parameters are generally estimated be fitting theoretical models to data gathered from field monitoring or laboratory experiments. Transient through-diffusion tests are generally conducted in the laboratory to estimate the mass transport parameters of the proposed barrier material. Thes parameters are usually estimated either by approximate eye-fitting calibration or by combining the solution of the direct problem with any available gradient-based techniques. In this work, an automated, gradient-free solver is developed to estimate the mass transport parameters of a transient through-diffusion model. The proposed inverse model uses a particle swarm optimization (PSO) algorithm that is based on the social behavior of animals searching for food sources. The finite difference numerical solution of the forward model is integrated with the PSO algorithm to solve the inverse problem of parameter estimation. The working principle of the new solver is demonstrated and mass transport parameters are estimated from laboratory through-diffusion experimental data. An inverse model based on the standard gradient-based technique is formulated to compare with the proposed solver. A detailed comparative study is carried out between conventional methods and the proposed solver. The present automated technique is found to be very efficient and robust. The mass transport parameters are obtained with great precision.

Thermal decomposition of hydrazinium hydrogen oxalate and dihydrazinium oxalate

Thermal decompositions of hydrazinium hydrogen oxalate (HHOX) and dihydrazinium oxalate (DOX) have been studied. DOX on heating is converted into HHOX and thereafter both follow the same pattern of decomposition.

Thermal decomposition of hydrazinium aluminium sulfate hydrate and hydrazinate

Abstract is not available.

Exact calculations of survival probability for diffusion on growing lines, disks, and spheres: The role of dimension

Unlike standard applications of transport theory, the transport of molecules and cells during embryonic development often takes place within growing multidimensional tissues. In this work, we consider a model of diffusion on uniformly growing lines, disks, and spheres. An exact solution of the partial differential equation governing the diffusion of a population of individuals on the growing domain is derived. Using this solution, we study the survival probability, S(t). For the standard nongrowing case with an absorbing boundary, we observe that S(t) decays to zero in the long time limit. In contrast, when the domain grows linearly or exponentially with time, we show that S(t) decays to a constant, positive value, indicating that a proportion of the diffusing substance remains on the growing domain indefinitely. Comparing S(t) for diffusion on lines, disks, and spheres indicates that there are minimal differences in S(t) in the limit of zero growth and minimal differences in S(t) in the limit of fast growth. In contrast, for intermediate growth rates, we observe modest differences in S(t) between different geometries. These differences can be quantified by evaluating the exact expressions derived and presented here.

Internal nitride formation during gas-phase thermal nitridation of titanium

Titanium nitride surface layers were prepared by gas-phase thermal nitridation of pure titanium in an ammonia atmosphere at 1373 K for different times. In addition to the surface nitride layer, nitride/hydride formation was observed in the bulk of the specimen. The cross-section of the specimen was characterized by various techniques such as optical microscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy, secondary ion mass spectrometry and nanomechanical testing, and the mechanism of formation of these phases is discussed.

Nucleation parameters for polymer crystallization from non-isothermal thermal analysis

Differential scanning calorimetry (DSC) has been used to obtain kinetic and nucleation parameters for polymer crystallization under a non-isothermal mode of operation. The available isothermal nucleation growth-rate equation has been modified for non-isothermal kinetic analysis. The values of the nucleation constant (K g ) and surface free energies (sgr, sgr e ) have been obtained for i-polybutene-1, i-polypropylene, poly(L-lactic acid), and polyoxymethylene and are compared with those obtained from isothermal kinetic analysis; a good agreement in both is seen.

Defect Sensitization of Combustion and Thermal Decomposition of Ammonium Perchlorate: Effect of Pelletizing Pressure and Dwell Time

A systematic study was undertaken on the combustion and thermal decomposition of pelletized Ammonium Perchlorate (AP) to investigate the effects of pelletizing pressure and dwell time. At constant pressure, increasing the dwell time results in an increase in the burning rate up to a maximum and thereafter decreases it. The dwell time required for the pellets to have maximum burning rate is a function of pressure. The maximum burning rate is the same for all the pressures used and is also unaffected by increasing, to the range 90-250 μ, the particle size of AP used. In order to explain the occurrence of a maximum in burning rate, pellets were examined for their thermal sensitivities, physical nature and the changes occurring during pelletization with dwell time and pressure. The variations are argued in terms of increasing density, formation of defects such as dislocations leading to an increase in the number of reactive sites, followed by their partial annihilation at longer dwell times due to flow of material during pelletization.