Thermal polymerization of acrylamide in the solid state

The role of imperfections in thermal polymerization of acrylamide in the solid state was studied. The polymer yield and the degree of polymerization are highly dependent on the particle size and on the pressure to which the monomer is subjected prior to polymerization reaction. There is an enhancement in the rate of polymerization in air unlike in the case of radiation-induced polymerization. Thermal polymerization of acrylamide in pelletized form results in the formation of water-soluble linear polymer and water-insoluble cross-linked product with the evolution of ammonia. The activation energy (E) values obtained in the present investigation reveal that basically there are two processes taking place, one with E = 34–36 kcal/mole, corresponding to the initiation process, and the other with E = 19 ± 3 kcal/more for the propagation process.

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.

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.

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.

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.

Influence of the electric field on the low-temperature thermal decomposition of ammonium perchlorate/polystyrene propellant

An electric field (100 V/cm at 230°C and 150°C) has been applied to ammonium perchlorate (AP)/polystyrene (PS) propellant mixtures in order to understand the low temperature decomposition behavior of the propellant. The charge-carrying species is anionic in nature at 230°C, which could be ClO4−, but is cationic at 150°C, which could be either NH4+ or H+. These results are parallel to that observed for pure ammonium perchlorate (AP) pellets [1]. The burning rate (r' ) of the propellant was found to follow the same trend as that for the thermal decomposition of the propellant on application of an electric field. At 150°C Image was higher at the −ve electrode than at the +ve electrode, but at 230°C just the opposite was observed. Kinetic studies have confirmed that the decomposition of the orthorhombic AP follows two mechanism corresponding to E = 30 kcal mol−1 (180–230°C) and E = 15 kcal mol−1 (150–180°C).

Interaction of rat testis protein, TP, with nucleic acids in vitro. Fluorescence quenching, UV absorption, and thermal denaturation studies

The nucleic acid binding properties of the testis protein, TP, were studied with the help of physical techniques, namely, fluorescence quenching, UV difference absorption spectroscopy, and thermal melting. Results of quenching of tyrosine fluorescence of TP upon its binding to double-stranded and denatured rat liver nucleosome core DNA and poly(rA) suggest that the tyrosine residues of TP interact/intercalate with the bases of these nucleic acids. From the fluorescence quenching data, obtained at 50 mM NaCl concentration, the apparent association constants for binding of TP to native and denatured DNA and poly(rA) were calculated to be 4.4 X 10(3) M-1, 2.86 X 10(4) M-1, and 8.5 X 10(4) M-1, respectively. UV difference absorption spectra upon TP binding to poly(rA) and rat liver core DNA showed a TP-induced hyperchromicity at 260 nm which is suggestive of local melting of poly(rA) and DNA. The results from thermal melting studies of binding of TP to calf thymus DNA at 1 mM NaCl as well as 50 mM NaCl showed that although at 1 mM NaCl TP brings about a slight stabilization of the DNA against thermal melting, a destabilization of the DNA was observed at 50 mM NaCl. From these results it is concluded that TP, having a higher affinity for single-stranded nucleic acids, destabilizes double- stranded DNA, thus behaving like a DNA-melting protein.

Role of alloys in the thermal decomposition and combustion of ammonium perchlorate

The participation of aluminum in the decomposition reaction of ammonium perchlorate (AP) is enhanced if magnesium is added—either as a mixture of Al and Mg powders or as an alloy of Mg in Al. The differential thermal analyses of the compositions show a sensitization in the temperatures of decomposition, as well as increase in the heat of reaction. The AP-Mg and Ap-(Mg---Li) alloy pellets also show increased reactivity. The burning rates of AP-(Al-10% Mg) alloy pellets increase with increase in the alloy content, while calorimetric values peak at 40% alloy content. The combustion product gases of AP-40% (Al-10% Mg) alloy contain large quantities of hydrogen.

Kinetic studies on thermal decomposition of polystyrene peroxide

Polystyrene peroxide has been synthesized and its decomposition has been studied by thermogravimetry and differential thermal analysis. Polystyrene peroxide has been found to decompose exothermically at about 110°C. The activation energy for the decomposition was estimated to be 30 kcal/mole both by the Jacobs and Kureishy method and by fitting the α versus time curves to the first-order kinetic equation. This suggests that the rate-controlling step in the decomposition of polystyrene peroxide is cleavage of the O---O bond.

Behavior Of High-Voltage Machine Insulation System In The Presence Of Thermal And Electrical Stresses

This paper presents the results on a resin-rich machine insulation system subjected to varying stresses such as electrical (2.6 to 13.3 MV/m) and thermal (40 to 155° C) acting together. Accelerated electro-thermal aging experiments subsequently have been performed to understand the insulation degradation The interpretations are based on several measured properties like capacitance, loss tangent, ac resistance, leakage current, and partial discharge quantities. The results indicate that the changes in properties are not significant below a certain temperature for any applied stress, Beyond this temperature large variations are observed even for low electrical stresses. Electrothermal aging studies reveal that the acceleration of the insulation degradation and the ultimate time to failure depends on the relative values of temperature and voltage stresses. At lower temperatures, below critical, material characteristics of the system predominate whereas beyond this temperature, other phenomena come into play causing insulation deterioration. During aging under combined stresses, it appears that the prevailing temperature of the system has a significant role in the insulation degradation and ultimate failure.