Investigation on the Reaction of Powdered Tin as a Metallic Fuel with Some Pyrotechnic Oxidizers

Thermogravimetry (TG), differential thermal analysis (DTA), and differential scanning calorimetry (DSC) have been used to examine the thermal behavior of Sn+KClO₃, Sn+KNO₃, and Sn+KClO₄ pyrotechnic systems and the results were compared with thermal characteristics of individual constituents. TG curves for tin powder, heated alone in air, showed a relatively slow oxidation above 570 °C. From thermal results the decomposition temperatures of KClO₃, KClO₄, and KNO₃, in nitrogen atmosphere, were measured at 472, 592 and 700 °C, respectively. For the Sn+KNO₃ pyrotechnic system, the tin oxidation was completed within the range of 480 to 500 °C. Replacing KNO₃ with KClO₄ led to an increase of thermal stability of the pyrotechnic mixture. Among above‐mentioned pyrotechnic mixtures, Sn+KClO₃ has the lowest ignition temperature at about 390 °C. The apparent activation energy (E), ΔG^#, ΔH^# and ΔS^# of the combustion processes were obtained from the DSC experiments. Based on these kinetic data and ignition temperatures, the relative reactivity of these mixtures was found to obey in the following order: Sn+KClO₃>Sn+KNO₃>Sn+KClO₄.     

Phase and crystallization behavior of solution-blended poly(ether ether ketone) and poly(ether imide)

Results on solution-blended poly(ether ether ketone) (PEEK) and poly(ether imide) (PEI) blends are reported. Dichloroacetic acid was used as the cosolvent for blending. PEEK and PEI are confirmed to be miscible in the melt. The glass transition, T_g, behavior obeys the simple Fox equation or the Gordon-Taylor equation with the adjustable coefficient k = 0.86. This agrees with prior data on melt-blended PEEK/PEI blends. The T_g width of the amorphous PEEK/PEI blends was found to be broader than that of the pure components. The maximum broadening is about 10°C. The specific volume of the amorphous PEEK/PEI blends shows a slight negative deviation from linearity, indicating favorable interaction between PEEK and PEI. The spherulitic growth and resultant blend morphology at 270°C were studied by a cross-polarized optical microscope. The radial growth rate of PEEK spherulites formed from the miscible melt at 270°C decreases from 3.04 μm/min for PEEK/PEI 90/10 blend to 0.77 μm/min for PEEK/PEI 70/30 blend. The decrease in crystalization rate of PEEK from PEEK/PEI blends is attributable to the increase in blend T_g. A linear growth was observed for PEEK spherulites formed from miscible melt at 270°C in the early growth stage. The spherulitic growth deviated from linearity in the late stage of growth. PEEK spherulites formed from the miscible PEEK/PEI melt at 270°C are essentially volume-filling. The branches of the spherulites become more clear for PEEK spherulites formed from the blend than that formed from pure PEEK melt.     

Effect of moisture on the oxidation behavior of ZrB2

Oxidation studies of ZrB₂ were performed under wet air and dry air conditions at 1200°C, 1400°C, and 1500°C for 1, 4, and 10 h. Compared to dry air, the presence of water vapor was found to enhance the oxidation kinetics by a factor of 7 to 30, depending on the temperature. Thermodynamic calculations suggested that water vapor promoted the formation of additional volatile species such as boric acid (HBO₂), in addition to boria (B₂O₃) produced in dry air, which increased the evaporation rate of B₂O₃. Compared to dry air, the presence of water vapor leads to more rapid evaporation of boria and the transition from parabolic oxidation kinetic behavior (ie, rate controlled by diffusion through boria) to linear (ie, underlying ZrB₂ is directly exposed to the oxidizing environment) at shorter times and lower temperatures.     

Low-temperature air oxidation of caking coals. 1. Effect on subsequent reactivity of chars produced

The effect of preoxidation of two highly caking coals in the temperature range 120–250 °C on weight loss during pyrolysis in a N₂ atmosphere up to 1000 °C and reactivity of the resultant chars in 0.1 MPa air at 470 °C has been investigated. Preoxidation markedly enhances char reactivity (by a factor of up to 40); the effect on char reactivity is more pronounced for lower levels of preoxidation. For a given level of preoxidation, the oxidation temperature and the presence of water vapour in the air used during preoxidation have essentially no effect on weight loss during pyrolysis and char reactivity. An increase in particle size of the caking coals reduces the rate of preoxidation as well as subsequent char reactivity. Preoxidation of caking coals sharply increases the surface area of the chars produced. Compared to heat treatment in a N₂ atmosphere, pyrolysis in H₂ of either the as-received or preoxidized coal results in a further increase in weight loss and a decrease in subsequent char reactivity.     

Thermal behavior of transparent poly(etheretherketone)(PEEK) film

The thermal behavior of poly(etheretherketone)(PEEK) film heated in an open differential scanning calorimetry (DSC) pan at 20°C/min is distorted by relaxation of the strained film. PEEK film in a closed pan or quenched PEEK in open or closed pans shows a glass-transition temperature (T_g) around 144°C, cold crystallization (～22 J/g) at 177°C, melt-temperature (T_m) peaking at 335–340°C, with an enthalpy of fusion of 32–34 J/g, and recrystallization on cooling at 285°C, with a crystallization exotherm of about 40 J/g. The enthalpy of fusion decreases with increasing heating rate from 2–100°C/min and approaches the enthalpy of cold crystallization. With increasing heating rate, further crystallization of PEEK during the DSC scan is suppressed. With increasing cooling rate, PEEK melt crystallizes at larger supercoolings to a lesser extent. Crystallization on cooling the melt was more complete than cold crystallization and annealing on heating.     

Aging of Pyrotechnik Compositions. The investigation of chemical changes by IR spectroscopy and x-ray diffraction

The aging of tracers, containing different amounts of Mg, Sr(NO₃)₂, KClO₄, Al-Mg alloy and organic binder, was conducted under the conditions of 50.0% and 98.5% relative humidities at 75 °C, and of 98.5% relative humidity at 25 °C. IR spectroscopy and X-ray diffraction were used for investigation of chemical changes. At the lower humidity no detectable changes were observed. Tracer of metauoxidant ratio >1 exhibits decreased stability, changing significantly under the conditions of higher humidity, even at room temperature. In the reaction sequence of aging process (Mg(OH)₂) and SrCO₃ are formed, with concomitant decrease in Mg and Sr(NO₃)₂ content. Alloy changes only slightly, and the content of KClO₄ and binder remains unchanged. Interaction between metal and nitrate is considered to be essential in the process of chemical aging.     

Reactive synthesis for porous TiVAlC ceramics by TiH2,V,Al and graphite powders

Using the mixed powder of TiH₂, graphite, aluminum and vanadium as starting materials, porous TiVAlC ceramics were fabricated by the reactive synthesis technology at 1300 °C. The chemical steadiness of porous TiVAlC along with the effects of sintering temperature on the viscous permeability coefficient, strength, porosity, pore size and volume expansion rate of the porous TiVAlC were explored, and the mechanism of pore formation was also revealed. The preparation process includes five steps as follows: (i) the complete decomposition of stearic acid at 500 °C; (ii) the pyrolysis of TiH₂ at 700 °C, converting TiH₂ into hydrogen and titanium (iii) The solid-liquid chemical reaction of solid vanadium, titanium and molten aluminum at 700 °C, converting the mixture into V–Al and Ti–Al compounds; (iv) At 900–1100 °C, Surplus V and Ti interact with graphite to synthesize carbides of TiVC₂, VC, and TiC; (v) Reactive synthesized carbides (TiVC₂, VC, and TiC), Ti₂AlC, V–Al and Ti–Al compounds that yield porous TiVAlC at 1300 °C.     

Functional and chemical characterization of the aging process of an igniter

The igniter consisting of 34% Mg, 60% KNO₃, 3% KClO₄ and 3% organic binder was subjected to accelerated aging under the conditions of 85% relative humidity at 65°C, 75°C and 85°C, and at 75°C with 92% relative humidity. Chemical aging was followed through formation of Mg(OH)₂ and KNO₂. Functional characterization was accomplished in a device constructed to enable simultaneous determination of the heat of combustion and pressure-time recording of the combustion process of both fresh and aged samples. The maximum acceptable deterioration occured at different times depending upon the conditions. The acceleration factor for every 10°C at 85% relative humidity is on average 2.8, leading to a prediction of shelf life of not more than 4 years at 25°C. At the time when burning characteristics were significantly changed, the mixture suffered only slight chemical changes, with only about 1% Mg(OH)₂ and 0.5% KNO₂ being formed. Thus, no chemical changes should be tolerated in such formulations.     

Enthalpies of pyrolysis and oxidation of Athabasca oil sands

Thermal degradation of Athabasca oil sands, bitumen, and its fractions have been investigated in N₂and in air, at 25–600 °C and at pressures up to 6.9 MPa, using thermogravimetry (TG) and high pressure differential scanning calorimetry (PDSC). These conditions are likely to occur during in-situ recovery of bitumen by underground combustion processes. Two regions of weight loss are detected using both gases. The endothermic low temperature volatilization reactions (150–400 °C) absorbed +26 mJ mg^?1 for oil sand to +2319 mJ mg^?1 for medium oil. The heats of reaction for high-temperature cracking and volatilization reactions (400–550 °C) were similar. The heats of reaction for the low-temperature oxidation reactions (150–375 °C) were ?405 mJ mg^?1 for oil sand to ?30200mJ mg^?1 for medium oil. Values for the high-temperature oxidation reactions (400–550 °C) were slightly higher. Increasing the pressure of nitrogen and air caused an increase in the endothermicity and exothermicity of the respective reactions.     

Combustion synthesis of titanium aluminides via co-reduction of oxides

In this study, Ti-50Al and Ti-48Al-2Cr powders were produced via reduction of TiO₂/Al₂O₃ and TiO₂/Al₂O₃/Cr₂O₃ mixtures with Ca. Upon addition of KClO₄ to the above mixtures, a combustion synthesis process was initiated in the systems. In the presence of KClO₄, the reduction temperature decreased from 1000 to 550°C.      

High performance polymer composites on PEEK reinforced with aluminum oxide

A study on high performance poly(ether‐ether‐ketone) (PEEK) composites prepared by incorporating aluminum oxide (Al₂O₃), 0 to 50 wt % by hot compaction at 15 MPa and 350°C was described. Density, thermogravimetric analysis/differential scanning calorimetry, and scanning electron microscopy (SEM) were employed to evaluate their density, thermal stability, crystallinity, and morphology. Experimental density was found higher than theoretical density, which indicates that composite samples are sound. It was found that the addition of micron sized (< 15 μm) Al₂O₃ increased the peak crystallization temperature by 12°C when compared with neat PEEK with insignificant increase in melting temperature. Half‐time of crystallization is reduced from 2.05 min for the neat PEEK to 1.08 min for PEEK incorporated with 30 wt % Al₂O₃ because of the strong nucleation effect of Al₂O₃. The thermal stability of composites in air atmosphere was increased by 26°C. However, thermal stability in nitrogen atmosphere decreases at lower concentration of Al₂O₃ but increases above 20 wt % of Al₂O₃. Uniform dispersion of Al₂O₃ particles was observed in PEEK polymer matrix by SEM. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4623–4631, 2006     

Catalytic Oxidation of CO Over Synthesized Nickel Ferrite Nanoparticles from Fly Ash

Catalytic oxidation of carbon monoxide (CO) gas over nanosized nickel ferrites prepared from fly ash has been investigated. X-ray diffraction analyses showed that pure crystalline nickel ferrite, NiFe₂O₄, phase can be obtained by thermal treatment of the precursors at temperature >800 °C for 120 min in the studied pH range, from 7 (neutral) to 12 (highly alkaline). In the temperature range 500 ≤ T ≤ 800 °C, impure low crystalline NiFe₂O₄ phase formed. The main impurities are FeO (OH) and Fe₂O₃ · H₂O phases. Higher magnetization (32 emu/g) is obtained for a precursor precipitated at pH 10 and thermally treated at 1,200 °C for 120 min. The catalytic oxidation of CO over nanocrystalline NiFe₂O₄ powders was studied using quadrupole mass gas analyzer system. The main parameters as crystal size, surface area and firing temperature are used to clarify the efficiency of using NiFe₂O₄ powders in catalytic oxidation of CO. It was found that the efficiency of catalytic oxidation decreased by increasing firing temperature and crystallite size of the samples. The lower crystal size (2–8.5 nm), the higher surface area (25–55 m²/g) and the presence of impurities FeO(OH) phase enhanced CO adsorption and consequently its oxidation.     

Fabrication and oxidation behavior of Al4SiC4 powders

Al₄SiC₄ powders with high purity were synthesized by heating the powder mixture of aluminum (Al), silicon (Si), and carbon (C) at 1800°C in argon. The microstructure is characterized as platelike single grain. Both the nonisothermal and isothermal oxidation behavior of Al₄SiC₄ was investigated at 800°C‐1500°C in air by means of thermogravimetry method. It is demonstrated that Al₄SiC₄ powder possesses good oxidation resistance up to 1200°C and is almost completely oxidized at 1400°C. At 800°C‐1100°C, the oxide scales consist of an Al₂O₃ outer layer and a transition layer. Al₄SiC₄ remains the main phase. At 1200°C, some spallation resulting from the increment of Al₂O₃ and the mismatch of thermal expansion coefficient between different product layers can be observed. Above 1300°C, the oxide layer is composed of two part, i.e., large‐scale Al₂O₃ crystals (outer layer) and mullite with less amount of SiO₂ (inner layer). The oxidation behavior changes due to the different oxide products. For the reaction kinetics, a new kind of real physical picture model is adopted and obtains a good agreement with the experimental data. The apparent activation energy is calculated to be 176.9 kJ/mol (800°C‐1100°C) and 267.1 kJ/mol (1300°C‐1400°C).     

A process for production of titanium aluminide: Reaction mechanism

A new combustion synthesis process for production of TiAl from TiO₂, Al, Ca and KClO₄ has been developed. In a closed reaction vessel, this process gets started at about 505°C with the reaction between Ca and KClO₄ yielding CaO and KCl. Subsequent two-stage reaction between TiO₂ and Al leads to formation of titanium aluminides and α-Al₂O₃. Then the reaction between α-Al₂O₃ and CaO results in formation of CaAl₄O₇ (grossite). The overall reaction scheme can be represented as 6TiO₂ + 22Al + 4KClO₄ + 4Ca = 6TiAl + 4CaAl₄O₇ + 4KCl. The temperature reached in the process (1950°C) is high enough for the melting of TiAl and CaAl₄O₇ and evaporation of KCl.      

Mechanical,Thermal, and Oxidation Properties of Refractory Hafnium and zirconium Compounds

The thermal conductivity, thermal expansion, Youngs Modulus, flexural strength, and brittle–plastic deformation transition temperature were determined for HfB₂, HfC_0·98, HfC_0·67, and HfN_0·92 ceramics. The oxidation resistance of ceramics in the ZrB₂–ZrC–SiC system was characterized as a function of composition and processing technique. The thermal conductivity of HfB₂ exceeded that of the other materials by a factor of 5 at room temperature and by a factor of 2·5 at 820°C. The transition temperature of HfC exhibited a strong stoichiometry dependence, decreasing from 2200°C for HfC_0·98 to 1100°C for HfC_0·67 ceramics. The transition temperature of HfB₂ was 1100°C. The ZrB₂/ZrC/SiC ceramics were prepared from mixtures of Zr (or ZrC), SiB₄, and C using displacement reactions. The ceramics with ZrB₂ as a predominant phase had high oxidation resistance up to 1500°C compared to pure ZrB₂ and ZrC ceramics. The ceramics with ZrB₂/SiC molar ratio of 2 (25 vol% SiC), containing little or no ZrC, were the most oxidation resistant.     

Thermal stability of polypyrroles

The effect of dopants and level of doping on the thermal stability of polypyrrole at 90, 120 and 150°C in dry air and nitrogen was investigated by monitoring the decay of conductivity. Polymers doped with aromatic anions (p-toluene sulphonate and p-chlorobenzene sulphonate) exhibit better stability than polymers doped with an aliphatic anion (dodecyl sulphate). The conductivity decay appears to follow diffusion controlled kinetics. After an initial decrease in conductivity, polypyrrole doped with p-toluene sulphonate anion maintains a constant conductivity at 150°C in air for at least 4 weeks. Dedoping results in materials of lower conductivity but greater thermal stability. Differential scanning calorimetry (DSC) and thermogravimetry (TG) were found to be useful techniques to characterize and investigate thermal stability. Oxidation of polypyrrole films, monitored by DSC, shows diffusion controlled kinetics. Although both oxidation and conductivity decay show typical diffusion kinetics, oxidation is a necessary but not sufficient condition for the decay.     

Preparation and characterization of sulfated zirconia catalysts obtained via various procedures

Sulfated zirconia catalysts were prepared in two ways: (i) using colloidal sol–gel technique, when the peptization of Zr(OH)₄ precipitated with ammonia from a solution of ZrOCl₂ was carried out with H₂SO₄ or with a solution of CH₃COOH and H₂SO₄, respectively, and by (ii) impregnation of Zr(OH)₄. Impregnation was carried out using Zr(OH)₄ as such or using precipitated Zr(OH)₄ previously heated in suspension at 90°C under reflux and strong stirring. Samples obtained following the above procedures were activated by heating in Ar or air at 550°C or 650°C. Sample characterization was carried out using chemical analysis, N₂ adsorption–desorption techniques, titration with propylamine in the presence of Hammet indicators, XRD, Raman spectroscopy, pyridine and CD₃CN-FTIR and XPS. In the samples obtained via colloidal sol–gel technique the amount of retained sulfur was high and mono and polynucleate sulfate species as well as supported H₂SO₄ were found to coexist. In such conditions, both Lewis and Brønsted acid sites were identified and a large dispersion of acid strength was determined. Samples obtained via impregnation contained only a small amount of sulfur compared with those obtained via colloidal sol–gel technique. In this case only mono and dinucleate sulfate species were found, and the acid strength exhibited a rather sharp distribution. It was also found that in that case Lewis acid sites predominate. Activation in air exhibited a positive effect upon the increase of the acidity, irrespective of the preparation variant, its presence “catalyzing” the nucleation of the superficial sulfate groups.     

Catalytic dry oxidation of aniline,benzene, and pyridine adsorbed on a CuO doped activated carbon

Adsorption of aniline, benzene and pyridine from water on a copper oxide doped activated carbon (CuO/AC) at 30 °C and oxidation behavior of the adsorbed pollutants over CuO/AC in a temperature range up to 500 °C are investigated in TG and tubular-reactor/MS systems. Results show that the AC has little activity towards oxidation of the pollutants and CuO is the active oxidation site. Oxidation of aniline occurs at 231–349 °C and yields mainly CO₂, H₂O and N₂. Oxidation of pyridine occurs at a narrower temperature range, 255–309 °C, after a significant amount of desorption starting at 150 °C. Benzene desorbs at temperatures as low as 105 °C and shows no sign of oxidation. The result suggests that adsorption-catalytic dry oxidation is suitable only for the strongly adsorbed pollutants. Oxidation temperatures of CuO/AC for organic pollutants are higher than 200 °C and pollutants desorbing easily at temperatures below 200 °C cannot be treated by the method. This work was presented at the 7 ^th China-Korea Workshop on Clean Energy Technology held at Taiyuan, Shanxi, China, June 26–28, 2008.     

Effect of Nb–Al–SiC elements combined with pre-oxidation treatment on the pesting resistance of MoSi2

Nb, Al, SiC elements were introduced into the matrix to improve the pest phenomenon of the MoSi₂ composites. The results showed that although the oxidation rate of the composite decreased, the pest phenomena eventually occurred at the oxidation temperature of 500 °C and 750 °C. And after 120 h of oxidation, the bending strength of the composite decreased dramatically from 472 MPa to 258 MPa (500 °C) and 225 MPa (750 °C). In order to solve this problem, pre-oxidation has been adopted. During pre-oxidation at 1200 °C via exposure to air, a dense fibrous layer was in-situ formed, which had excellent adhesion to the matrix. The substrate which adjoins the interface of the oxide layer and matrix was oxidized into nano-sized grains. This layer and the nano-sized substrate played important roles in eliminating the pest phenomenon of the MoSi₂ composite.     

Oxidation behaviors of (Ti1-xNbx)C ceramic solid solutions

(Ti_1-xNb_x)C (x=0, 0.2, 0.5 and 0.8) ceramic solid solutions were prepared by spark plasma sintering and their oxidation behaviours were investigated at 1000 °C in air. The niobium content was found to exhibit a remarkable influence on the oxidation resistance of (Ti_1-xNb_x)C solid solutions. An optimization of oxidation resistance was achieved in (Ti_0.8Nb_0.2)C. After oxidation at 1000 °C for 4 h, the oxidation layer thickness of (Ti_0.8Nb_0.2)C is less than 1/4 of the oxidation layer thickness of monolithic TiC. The higher oxidation resistance can be ascribed to the presence of Nb-doped rutile TiO₂ phase in the oxidation layer of (Ti_0.8Nb_0.2)C. The (Ti,Nb)O₂ phase suppressed the abnormal grain growth and the formation of cracks in the oxide layer, more importantly, it could effectively sluggish the outward diffusion of titanium during oxidation.