Thermal decomposition of methylammonium perchlorate

The thermal decomposition of methylammonium perchlorate (MAP) has been studied under isothermal and non-isothermal conditions. Differential thermal analysis of MAP showed, in addition to the exotherm due to decomposition, another exotherm at 408° which was observed for the first time. Chemical analysis and the infrared spectrum of the residue left behind after the decomposition proved it to contain NH4ClO4. The results have been explained on the basis of a methyl group transfer in addition to proton transfer in the decomposition process.

Thermal decomposition of sodium azide

The thermal decomposition of sodium azide has been investigated in the temperature range 240–365°C. Three values for the activation energy, 37.0, 59.0 and 14 kcal mol−1 have been obtained depending on the temperature range of study. The mechanism of decomposition seems to involve excited azide ions (through internal conversion) and excitations. The activation energy of 14 kcal mol−1 appears to be associated with the promotion of electron in the presence of sodium metal.

Thermal degradation of polystyrene

The importance of the study of thermal degradation of polymeric fuels arises from their role in the combustion of solid propellants. Estimation of the condensed-phase heat release during combustion can be facilitated by the knowledge of the enthalpy change associated with the polymer degradation process. Differential scanning calorimetry has been used to obtain enthalpy data. Kinetic studies on the polymeric degradation process have been carried out with the following objectives. The literature values of activation energies are quite diverse and differ from author to author. The present study has tried to locate possible reasons for the divergence in the reported activation energy values. A value of 30 kcal has been obtained and found to be independent of the technique employed. The present data on the kinetics support to chain-end initiation and unzipping process. The activation energies are further found to be independent of the atmosphere in which the degradation of polymer fuel is carried out. The degradation in air, N2, and O2 all yield a value of 30 kcal/mole for the activation energies.

Thermal decomposition of titanyl oxalates-I : Barium titanyl oxalate

Thermal decomposition of barium titanyl oxalate tetrahydrate (BTO) has been investigated employing TGA, DTG and DTA techniques and gas and chemical analysis. The decomposition proceeds through five steps and is not affected much by the surrounding gas atmosphere. The first step which is the dehydration of the tetrahydrate is followed by a low-temperature decomposition of the oxalate groups. In the temperature range 190–250°C half a mole of carbon monoxide is evolved with the formation of a transient intermediate containing both oxalate and carbonate groups. The oxalate groups are completely destroyed in the range 250–450°C, resulting in the formation of a carbonate which retains free carbon dioxide in the matrix. The trapped carbon dioxide is released in the temperature range of 460–600°C. The final decomposition of the carbonate takes place between 600–750°C and yields barium titanate. The i.r. spectra, surface area measurements and X-ray, powder diffraction data support entrapment of carbon dioxide in the matrix.

Negative differential resistance in GaN nanocrystals above room temperature

Negative differential resistance (NDR) has been observed for the first time above room temperature in gallium nitride nanocrystals synthesized by a simple chemical route. Current-voltage characteristics have been used to investigate this effect through a metal-semiconductor-metal (M-S-M) configuration on SiO2. The NDR effect is reversible and reproducible through many cycles. The threshold voltage is similar to 7 V above room temperature.

Combustion and thermal decomposition characteristics of composite solid propellants

The role of thermal decomposition of the binder and the oxidiser in the thermal decomposition, ageing and combustion of composite solid-propellants has been investigated. The present study shows that the burning rate and ageing of polystyrene and ammonium perchlorate propellant are related to the thermal decomposition of the propellant itself and ammonium perchlorate.

Normalization and Charter 77 : Violence, Commitment and Resistance in Czechoslovakia

In Czechoslovakia, the occupation of 1968 denoted the beginning of normalization , a political and societal stagnation that lasted two decades. Dissident initiative Charter 77 emerged in 1977, demanding that the leaders of the country respect human rights. The Helsinki process provided a macro-level framework that influenced opposition and dissident activities throughout Eastern Europe. The study contributes a focused empirical analysis of the period of normalization and the dissident movement Charter 77. Dissent in general is seen as an existential attitude; it can be encapsulated as a morally rationalized critical stance as derived from shared experience or interpretation of injustice, which serves as a basis for a shared collective identity comprising oppositional consciousness as one unifying factor. The study suggests that normalization can be understood as a fundamentally violent process and discusses the structural and cultural manifestations of violence with relation to Charter 77. In general, the aim of the system was to passivize the society to such an extent that it would not constitute a potential threat to the hegemonic rule of the regime. Normalization caused societal stagnation and apoliticization, but it also benefited those who accepted the new political reality. The study, however, questions the image of Czechoslovakia s allegedly highly repressive rule by showing that there was also quite considerable tolerance of Charter 77 and consideration before severe repression was brought to bear against dissidents. Furthermore, the study provides understanding of the motives and impetuses behind dissent, the strategic shifts in Charter 77 activities, and the changes in the regime s policies toward Charter 77. The study also adds new perspective on the common image of Charter 77 as a non political initiative and suggests that Charter 77 was, in fact, a political entity, an actively political one in the latter half of the 1980s. Charter 77 was a de facto hybrid of a traditional dissident initiative and an oppositional actor. Charter 77 adopted a two-dimension approach: firstly, it still emphasized its role as a citizens initiative supporting human rights, but, secondly, at the same time, it was a directly political actor supporting and furthering the development of political opposition against the ruling power.

Thermal decomposition of hydrazinium monoperchlorate in the molten state

The thermal decomposition of hydrazinium monoperchlorate (HP-1) in the molten state has been investigated using differential thermal analysis, thermogravimetric analysis, a constant volume manometric technique and mass-spectrometry. The stoichiometry of the reaction can be represented by the equation: 20 N2H5C1O4 13 NH4C1O4 + 3.5 Cl2 + 2 O2 + 13 N2 + 0.5 N2O + 0.5 H2 + + 23.5 H2O The data seem to indicate that the mechanism, which involves an associated complex, remains unchanged from 140 to 190°. Consequently, impurities capable of forming associated complexes with the hydrazinium or the perchlorate ion desensitize the thermal decomposition of HP-1, the extent of desensitization being determined by the size, the charge and the concentration of the impurity.

Thermal expansion and a new phase transition in pyroelectric LiKSO4

Single crystal macroscopic thermal expansion coefficient measurements have been made on uniaxial lithium potassium sulphate crystal both along and normal to the six fold axis, employing Fizeau’s interferometer method. Measurements were made in the range of −120°C to 500°C. The results show that lithium potassium sulphate exhibits two major anomalies in its expansion coefficients around −95°C and 422°C respectively, the one at −95°C has been observed for the first time. The nature of dimensional changes of the crystal at the upper and lower transition points are opposite in nature. The crystal shows considerable lattice anisotropy. Megaw’s tilt concept has been invoked to explain the relative magnitudes of expansion coefficients alonga andc directions. Structural features responsible for the absence of ferroelectricity in this crystal have been pointed out.

Ignition and thermal behaviour of solid hydrazones

Abstract is not available.

Sublimation and thermal decomposition of ammonium perchlorate

Abstract is not available.

Effect of manganese dioxide on the thermal decomposition of ammonium perchlorate

Thermal decomposition of powdered ammonium perchlorate, catalysed by manganese dioxide (MnO2), has been studied in the low concentration ranges of the catalyst. MnO2 sensitises the thermal decomposition of ammonium perchlorate. The activation energy estimations of catalysed ammonium perchlorate show that the value is about 30 kcal/mol throughout the low and the high temperature regions whereas uncatalysed ammonium perchlorate gives two activation energies, 20 kcal/mol in the low temperature region (280-320°C) and 60 kcal/mol in the higher temperature region (350-390°C). This behaviour has been explained on the basis of an electron transfer process. The effectiveness of MnO2 in the thermal decomposition further increases on pre-heating the sample at 50°C for two weeks; manganese ions enter the ammonium perchlorate lattice during the process of pre-heating.

Effect of Molecular Weight on the Thermal and Impact Sensitivity of Polymers in Propellants

Abstract is not available.

Environmental effects of thermal and radioactive discharges from nuclear power plants in the boreal brackish-water conditions of the northern Baltic Sea

During recent decades, thermal and radioactive discharges from nuclear power plants into the aquatic environment have become the subject of lively debate as an ecological concern. The target of this thesis was to summarize the large quantity of results obtained in extensive monitoring programmes and studies carried out in recipient sea areas off the Finnish nuclear power plants at Loviisa and Olkiluoto during more than four decades. The Loviisa NPP is located on the coast of the Gulf of Finland and Olkiluoto NPP on that of the Bothnian Sea. The state of the Gulf of Finland is clearly more eutrophic; the nutrient concentrations in the surface water are about 1½ 2 times higher at Loviisa than at Olkiluoto, and the total phosphorus concentrations still increased in both areas (even doubled at Loviisa) between the early 1970s and 2000. Thus, it is a challenge to distinguish the local effects of thermal discharges from the general eutrophication process of the Gulf of Finland. The salinity is generally low in the brackish-water conditions of the northern Baltic Sea, being however about 1 higher at Olkiluoto than at Loviisa (the salinity of surface water varying at the latter from near to 0 in early spring to 4 6 in late autumn). Thus, many marine and fresh-water organisms live in the Loviisa area close to their limit of existence, which makes the biota sensitive to any additional stress. The characteristics of the discharge areas of the two sites differ from each other in many respects: the discharge area at Loviisa is a semi-enclosed bay in the inner archipelago, where the exchange of water is limited, while the discharge area at Olkiluoto is more open, and the exchange of water with the open Bothnian Sea is more effective. The effects of the cooling water discharged from the power plants on the temperatures in the sea were most obvious in winter. The formation of a permanent ice cover in the discharge areas has been delayed in early winter, and the break-up of the ice occurs earlier in spring. The prolonging of the growing season and the disturbance of the overwintering time, in conditions where the biota has adjusted to a distinct rest period in winter, have been the most significant biological effects of the thermal pollution. The soft-bottom macrofauna at Loviisa has deteriorated to the point of almost total extinction at many sampling stations during the past 40 years. A similar decline has been reported for the whole eastern Gulf of Finland. However, the local eutrophication process seems to have contributed into the decline of the zoobenthos in the discharge area at Loviisa. Thermal discharges have increased the production of organic matter, which again has led to more organic bottom deposits. These have in turn increased the tendency of the isolated deeps to a depletion of oxygen, and this has further caused strong remobilization of phosphorus from the bottom sediments. Phytoplankton primary production and primary production capacity doubled in the whole area between the late 1960s and the late 1990s, but started to decrease a little at the beginning of this century. The focus of the production shifted from spring to mid- and late summer. The general rise in the level of primary production was mainly due to the increase in nutrient concentrations over the whole Gulf of Finland, but the thermal discharge contributed to a stronger increase of production in the discharge area compared to that in the intake area. The eutrophication of littoral vegetation in the discharge area has been the most obvious, unambiguous and significant biological effect of the heated water. Myriophyllum spicatum, Potamogeton perfoliatus and Potamogeton pectinatus, and vigorous growths of numerous filamentous algae as their epiphytes have strongly increased in the vicinity of the cooling water outlet, where they have formed dense populations in the littoral zone in late summer. However, the strongest increase of phytobenthos has extended only to a distance of about 1 km from the outlet, i.e., the changes in vegetation have been largest in those areas that remain ice-free in winter. Similar trends were also discernible at Olkiluoto, but to a clearly smaller extent, which was due to the definitely weaker level of background eutrophy and nutrient concentrations in the Bothnian Sea, and the differing local hydrographical and biological factors prevailing in the Olkiluoto area. The level of primary production has also increased at Olkiluoto, but has remained at a clearly lower level than at Loviisa. In spite of the analogous changes observed in the macrozoobenthos, the benthic fauna has remained strong and diversified in the Olkiluoto area. Small amounts of local discharge nuclides were regularly detected in environmental samples taken from the discharge areas: tritium in seawater samples, and activation products, such as 60Co, 58Co, 54Mn, 110mAg, 51Cr, in suspended particulate matter, bottom sediments and in several indicator organisms (e.g., periphyton and Fucus vesiculosus) that effectively accumulate radioactive substances from the medium. The tritium discharges and the consequent detection frequency and concentrations of tritium in seawater were higher at Loviisa, but the concentrations of the activation products were higher at Olkiluoto, where traces of local discharge nuclides were also observed over a clearly wider area, due to the better exchange of water than at Loviisa, where local discharge nuclides were only detected outside Hästholmsfjärden Bay quite rarely and in smaller amounts. At the farthest, an insignificant trace amount (0.2 Bq kg-1 d.w.) of 60Co originating from Olkiluoto was detected in Fucus at a distance of 137 km from the power plant. Discharge nuclides from the local nuclear power plants were almost exclusively detected at the lower trophic levels of the ecosystems. Traces of local discharge nuclides were very seldom detected in fish, and even then only in very low quantities. As a consequence of the reduced discharges, the concentrations of local discharge nuclides in the environment have decreased noticeably in recent years at both Loviisa and Olkiluoto. Although the concentrations in environmental samples, and above all, the discharge data, are presented as seemingly large numbers, the radiation doses caused by them to the population and to the biota are very low, practically insignificant. The effects of the thermal discharges have been more significant, at least to the wildlife in the discharge areas of the cooling water, although the area of impact has been relatively small. The results show that the nutrient level and the exchange of water in the discharge area of a nuclear power plant are of crucial importance.