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Summary Thermal analysis is an interesting technique to determine kinetic parameters of separate components, and also of a complete system to receive adequate information on the ageing process of pyrotechnic compositions. The investigated tracer is a tracking tracer of a Swiss missile. It is attached to a missile and produces during burning a red flame. The missile system is already in use for 15 years. Periodic inspections of the system take place every three years. These inspections, however only give information on the actual state of the tracer and not on the future state. The aim of this investigation is to predict the ageing behaviour of the tracer system to give additional information about the future use of the missile system. After two ageing profiles the tracer systems were tested on the test range at Armasuisse in Thun. The results of the testing show that an ageing period of 4 weeks at 60°C gives no changes in performance (light output and burning time). On the other side also a quite heavy ageing period of 4 weeks at 150°C was applied on tracer systems, which gives a dramatically change in burning time. The light output was even higher after this ageing profile, although the intensity changes a lot.
Abstract
Glass transition temperature of red crayfish flour (moisture 3.56%) was determined using a phase transition analyser (Wenger Technical Centre, USA). Due to the importance of physical ageing in functional properties of red crayfish flour (with 65% protein) the possible occurrence of physical ageing in dry powder of crayfish flour was studied at different temperatures below and close to the glass transition. Endothermic peaks that corresponded to relaxation enthalpy were observed for a commercial crayfish flour with 4.5% moisture. Enthalpy and peak temperature increased on storage of crayfish flour when it was held in the glassy-state at different temperatures (5, 15, 25°C).
Abstract
Thermally Stimulated Current (TSC) technique is a relaxation technique, such as DMA, but works at very low equivalent frequency (10−3–10−4Hz) and thus clearly resolves the peaks related to the molecular mobility. The effect of orientation on Polypropylene fibers, the relaxation of internal stresses on Polycarbonate disks, and the effect of aging on acrylic airplane windows have been investigated using the TSC method.
Abstract
The ageing characteristics of pyrotechnic compositions are influenced not only by temperature, but also by surrounding effects as humidity and vibrations. In this paper the thermal stability of the pyrotechnic system magnesium–sodium nitrate will be investigated. In an inert helium atmosphere two steps of mass loss, which were not completely separated from each other, were observed in the temperature range from 65 to 265C: a mass loss of about 15% between 65 and 160C and about 34% between 160 and 265C. It is assumed that these two steps are caused by different processes. The separation between the two steps was not or hardly detectable for measurements that were performed in a nitrogen atmosphere. Using MS and FTIR (mass spectrometry/Fourier transform infrared spectroscopy) the evolved gases were analysed. Only above about 170C evolving gases were detected (which means that during the first step no gases were detectable). The detected gas mainly consists of CO2, CO and N2O, with smaller amounts of NO2, NO and possibly HCN. A third step of mass loss (8–9%) was observed above 314C. The process which caused this step of mass loss is considered not to contribute significantly to the ageing of the material at much lower temperatures of maximum 80C, which is of interest in view of the use of the materials. Kinetic parameters for the processes which caused the first and the second step of mass loss were evaluated from kinetic analysis of the measured TG curves. By using these results the conversion can be predicted as a function of time and temperature. However, it must be considered that the inaccuracy of the predictions increases if the temperature for which the prediction is calculated is further away from the temperature at which the experiments were performed. This is caused by the exponential form of the kinetic equations. The calculations show that in particular the reaction which causes the first step of mass loss can run relatively quickly in the temperature range 25–80C, which could result in ageing of the material during storage at these conditions. The reaction which causes the second step of mass loss clearly runs at a much lower rate.
Summary A procedure for the extrapolation of accelerated thermo-oxidative ageing tests to lower temperatures is proposed. The procedure involves a deconvolution of the global process into high- and low-temperature components where the extrapolation to low temperatures is carried out using the low-temperature component. The method was tested on stabilized and unstabilized polyisoprene rubber and was found to produce realistic estimations of the length of the induction period of oxidation so giving a more accurate estimation of the service life. However, to obtain the low-temperature values of the adjustable kinetic parameters, very low heating rates are required (0.04 K min-1, 0.1 K min-1) making the measurement process time consuming. Using this method, more realistic estimates of the durability of a material are obtained.
Abstract
The physical ageing characteristics of glucose, fructose, and their mixtures were studied using standard differential scanning calorimetry (DSC). The inflection, onset, midpoint,half-height, and endpoint glass transition temperature (T g), fictive temperature (T f), and relaxation enthalpy ( H) were measured as a function of ageing time. The relationship between H and T f was evaluated. The time dependence of H was fit using the Cowie and Ferguson model. The ageing rate was expressed in terms of the average relaxation time (<>) and the entropy production (P). It was found that the fructose component decreased the rate of ageing of the mixtures.
the heavier chalcogen atoms (S, Se, Te), which are the main constituents of their covalent networks. However, chalcogen-rich glasses possess a pronounced physical aging effect under ambient conditions hindering their wide use for several applications
Abstract
A dredged sludge was studied to investigate the influence of ageing and of pretreatment on its drying rate, water sorption/retention, thermal mass loss, XRD and microstructure (SEM).
Ageing caused change in particle thickness and specific surface, a gradual aggregation to form units of the size 10–50 μm, formation of macropores of similar size, unhomogeneity and fissures between aggregates and “super-aggregates”. Macropores were detectable by the initial drying rate especially at 45°C. They indicated a tendency of collapsing at a lower drying rate at 30°C. This is consistent with SEM observations. With ageing the aggregates were more compact and less sensitive to drying.
The aggregated system indicated a higher initial drying rate (higher permeability), whereas stirring induced a lower drying rate, favouring the formation of compact laminar structure.
XRD peak intensity was lowered with ageing due to decrease in crystallinity (stacking faults and/or decrease in crystallite size). The content of amorphous material was lowered as well, reducing water sorption/desorption, which indicated that the specific surface is lower.
From the suitable microstructure induced by ageing some new phases may form (feldspar, zeolites), preferably in the coarser fraction of the sludge. This is disturbed by stirring which operation expels also carbonates from the particle edges and this may reduce the structural strength of the sludge. In aged bentonite suspension a similar tendency was observed of formation of specific microstructures capable of phase transformation, e.g. to feldspar.
Abstract
In the 'normal' ageing brain a decrease in the cerebral metabolic rate has been determined across many brain regions. This study determines whether age differences would affect metabolic rates in regions and different hemispheres of the brain. The regional metabolic rate of glucose (rCMRGlu) was examined in a group of 72 subjects, ages 22 to 82 years, with 36 regions of interest chosen from both hemispheres of the cortex, midbrain and cerebellum. To determine metabolic rates the in-vivo technique of positron emission tomography (PET) was employed. Three age groups were chosen to compare hemispherical differences. In both young and intermediate age groups the left hemisphere had higher rCMRGlu values than those of the right for the majority of regions with, although less pronounced in the intermediate group. Importantly, the older age group displayed little difference between hemispheres.
Summary Simulation of thermal ageing is an important part of qualification of materials designed for the use in nuclear power plants (NPP). According to standards, the simulation of long-term service thermal ageing is performed isothermally at elevated temperature using Arrhenius methodology. The samples or equipment are aged in thermal chamber, to bring them to the same state as after long-term service time. To proceed a reliable simulation, the testing parameters should be taken very carefully and the accelerator factors should not be too high. The testing temperature and time and the activation energy are the most important parameters. Determination of these factors and the limitations of their use in practice are discussed.