The oxidation of Al alloys containing 0.3-4.5 wt% Mg in an atmosphere with a very low oxygen partial pressure (< 0.5 ppm, to depict the atmosphere within a double oxide film defect) was studied using differential scanning calorimetry and scanning electron microscopy. The results showed that a newly formed Al2O3 layer held in an Al-Mg melt first transformed to MgAl2O4 spinel and then to MgO. This mechanism was the same for all the Al alloys containing 0.3-4.5 wt% Mg, but the kinetics of the transformations were different and depended on the Mg content of the melt. The results also suggest that the two layers of a double oxide film defect that is held in an Al melt containing 0.3-4.5 wt% Mg can heal (i.e. bond to each other) if held in the liquid metal for a long enough period of time.
The catalytic effect of ferrocyanide salts of d-metals on the thermo-oxidative degradation of lignocellulose-inorganic sorbents derived from apricot seed shells was investigated by differential thermal analysis. A comparative analysis of the thermal characteristics of the apricot seed shells and the lignocellulose matrix obtained from the shells by alkali-acid pretreatment was performed. It was shown that acid-alkali pretreatment of the apricot seed shells increases the thermal stability of the lignocellulosic material, due to the removal of low molecular weight carbohydrates and other components. The thermal degradation process of the lignocellulose-inorganic samples containing different ferrocyanides occurred at lower temperatures than the initial lignocellulose matrix, indicating the catalytic activity of modifiers. It was demonstrated that for the sorbents containing mixed salts of potassium cobalt and potassium nickel ferrocyanide, thermal destruction ends at temperatures that are 60 A degrees C lower than those for the initial lignocellulose matrix. The obtained results also show that the thermal destruction of composite lignocellulose-inorganic sorbents can be a suitable method for their disposal.
Thermal behavior and chemical properties of selected raw and NaOH-pretreated rice husk varieties were investigated. NaOH-pretreatment process involved soaking 5 g rice husk samples in 40 mL of 2%w/v NaOH, shaking (400 rpm) and heating (50 °C) for 3 h. NaOH-pretreated samples were water-washed, oven-dried, and milled for use in the determination of their thermal behavior and surface functional groups. Alkaline wash-water was also analyzed for sugar components. Thermal decomposition temperatures, degradation rates, and the subsequent mass losses varied from one rice husk variety to another. These thermal properties increased after NaOH-pretreatment of the rice husk varieties, reducing their char yields (17.1–20.4% db). These changes mainly had to do with the lignin, hemicellulose, and ash removal from the rice husk varieties, as confirmed by their FTIR analysis, as well as by the sugar composition analysis of their alkaline wash-water. Consequently, the FTIR spectra differed between the raw and NaOH-pretreated rice husk varieties.
Thin films of 3,4-epoxycyclohexyhnethyl 3',4'-epoxycyclohexane carboxylate were UV irradiated (1.1 J cm(-2)) under isothermal conditions ranging from 0 to 50degreesC. Under these conditions the polymerization advanced quickly but only to a conversion level of less than 10% before the reaction rate slowed by more than an order of magnitude. This drop off in rate was not caused by the glass transition temperature, T-g, reaching or exceeding the reaction temperature, T-rxn, since the epoxide's T-g remained at least 40degreesC below T-rxn. Raising the sample temperature above 60degreesC caused a sharp increase in the conversion level. At 100degreesC conversion exceeds 80% and the ultimate T-g approaches 190degreesC. The addition of 10 mass% 1,6-hexanediol, HD, to the epoxy caused the conversion at room temperature to quintuple over the level obtained without the alcohol present. The heat liberated from this alcohol epoxy blend during cure on a UV conveyor belt system caused the sample's temperature to increase by about 100degreesC above ambient whereas the epoxy alone under these conditions only experienced a modest temperature rise of about 26degreesC. If the amount of HD in the blend is increased above 10% the heat of reaction at 23degreesC decreases due to HD being trapped in a nonreactive crystalline phase. Boosting reaction temperatures above 50degreesC melts the HD crystals and yields significantly improved conversion ratios. As the level of alcohol blended with the epoxy is raised its ultimate T-g is lowered and when the concentration of alcohol in the blend nears 30 mass% T-g drops below room temperature.
Complex-shaped lamellar graphite iron castings are susceptible to casting defects related to the volume change during solidification. The formations of these recurring defects are caused by the flow of the liquid in the intradendritic area, between the austenite dendrite arms, and in the extradendritic area between the austenite grains. The conditions for the liquid flow, in turn, are determined by the solidification behavior. The present study suggests a new measurement method and a novel calculation algorithm to determine the pressure of the extradendritic liquid during solidification. The method involves a spherical sample suspended in a measurement device, where the temperature and the volume changes are measured during solidification. The calculation algorithm is based on the numerical interpretation of the Clausius-Clapeyron equation where the temperature variation, the volume change and the released latent heat are processed to determine the local pressure of the extradendritic liquid area during solidification.
The mechanism and kinetics of thermal degradation of materials developed from cellulose fiber and synergetic fire retardant or expandable graphite have been investigated using thermogravimetric analysis. The model-free methods such as Kissinger–Akahira–Sunose (KAS), Friedman, and Flynn–Wall–Ozawa (FWO) were applied to measure apparent activation energy (Ea).The increased Ea indicated a greater thermal stability because of the formation of a thermally stable char, and the decreased Ea after the increasing region related to the catalytic reaction of the fire retardants, which revealed that the pyrolysis of fire retardant-containing cellulosic materials through more complex and multi-step kinetics. The Friedman method can be considered as the best method to evaluate the Ea of fire-retarded cellulose thermal insulation compared with the KAS and two methods. A master-plots method such as the Criado method was used to determine the possible degradation mechanisms. The degradation of cellulose thermal insulation without a fire retardant is governed by a D3 diffusion process when the conversion value is below 0.6, but the materials containing synergetic fire retardant and expandable graphite fire retardant may have a complicated reaction mechanism that fits several proposed theoretical models in different conversion ranges. Gases released during the thermal degradation were identified by pyrolysis–gas chromatography/mass spectrometry. Fire retardants could catalyze the dehydration of cellulosic thermal insulating materials at a lower temperature and facilitate the generation of furfural and levoglucosenone, thus promoting the formation of char. These results provide useful information to understand the pyrolysis and fire retardancy mechanism of fire-retarded cellulose thermal insulation.