Keto-RDX was obtained by one-step method with a certain amount of RDX as by-product.The effects of various parameters on high yield were studied.A simple analytical method was also introduced to determine simultaneous...Keto-RDX was obtained by one-step method with a certain amount of RDX as by-product.The effects of various parameters on high yield were studied.A simple analytical method was also introduced to determine simultaneously Keto-RDX/RDX mole ratio.Some important theoretical characterizations of Keto-RDX such as detonation performance at maximum nominal density and shock sensitivity were determined by new methods and compared with RDX.展开更多
The hexanitrostilben(HNS) is a thermally stable explosive that can be prepared from hexanitrobibenzyl(HNBB).Therefore,the investigation of thermal stability of HNBB can be important in the yield of preparation of HNS....The hexanitrostilben(HNS) is a thermally stable explosive that can be prepared from hexanitrobibenzyl(HNBB).Therefore,the investigation of thermal stability of HNBB can be important in the yield of preparation of HNS.The decomposition kinetic of HNBB and HNS are studied by non-isothermal gravimetric method.The TG/DTG curves in non-isothermal method are obtained in range of 25℃-400℃at heating rates of 3℃/min,5℃/min,8℃/min,10℃/min and 12℃/min.The data of weighttemperature are used for calculation of activation energy(E_a) of thermal decomposition reactions by methods of Ozawa,Kissinger,Ozawa-Flynn-Wall(OFW) and Kissinger-Akahira-Sunose(KAS) as modelfree methods and Strink's equation as model-fitting method.The compensation effect is used for prediction of mechanism and determination of pre-exponential factor(InA) of the decomposition reaction.A reduction 60 kj/mol for the average of activation energy of thermal decomposition reaction of HNBB is obtained versus HNS.This result shows the lower thermal stability of HNBB in comparison to HNS,The Avrami equation(A_(3/2)) with function f(α)=3/2(1-α)[-In(1-α)]^(1/3) indicates the predicted mechanism for thermal decomposition reaction both explosives.展开更多
Many of the physical and functional properties of RDX and HMX explosives are related to the crystalline structure of these materials. Crystalline defects affect the quality of the explosives. Therefore, in order to en...Many of the physical and functional properties of RDX and HMX explosives are related to the crystalline structure of these materials. Crystalline defects affect the quality of the explosives. Therefore, in order to enhance the quality of these materials, it is necessary to form crystals with the lowest defects. In this research, we report the optimization of recrystallization process of RDX and HMX by statistical techniques. The solvent/anti-solvent procedure was used for recrystallization of HMX and RDX particles. The four parameters of i) ratio of anti-solvent to solvent, ii) ratio of solute to solvent, iii) aging time, and iv)cooling rate of mixture, were optimized by Taguchi analysis design. Taguchi L16 orthogonal array was used with sixteen rows corresponding to the number of tests in four columns at four levels. The apparent density of recrystallized of RDX and HMX particles was considered as the quality characteristic with the concept of "the larger-the-better". The obtained graphs showed that the studied parameters were optimized in ratio 1:1 for anti-solvent to solvent, ratio 0.1 g,m L^(-1) for solute to solvent, aging time of 2 h and cooling rate of 1℃,min^(-1). Also, the correlation between the investigated parameters and apparent density of crystals were studied by multiple linear regressions(MLR) method for obtaining a model of prediction of apparent density. The P-values were indicated that in confidence level of 95%, the null hypothesis is rejected and a meaningful addition is observed in the proposed model.展开更多
The kintic and activation energy of mass loss of two grades of melted TNT explosive, grade A and grade B, with freezing points of 80.57 and 78.15 ℃, respectively, were studied by isothermal and nonisothermal gravimet...The kintic and activation energy of mass loss of two grades of melted TNT explosive, grade A and grade B, with freezing points of 80.57 and 78.15 ℃, respectively, were studied by isothermal and nonisothermal gravimetric methods. In isothermal method, the mass loss of samples in containers of glass and aluminum was followed in temperatures of 80, 90 and 100 ℃. The kinetic of the mass loss of the samples in the aluminum container was higher than the kinetic of it in the glass container that can be related to the effects of heat transfer and catalytic of aluminm metal. Also, the presence of impurities in grade B was due to increasing of kinetic of mass loss of it versus grade A. The non-isothermal curves were obtained in range of 30-330 ℃ at heating rates of 10,15 and 20 ℃·min^(-1).The TG/DTG data were used for determination of activation energy(E_a) of mass loss of TNT samples upon degradation by using Ozawa, Kissinger, Ozawa-Flynn-Wall(OFW) and Kissinger-Akahira-Sunose(KAS) methods as model free methods. The activation energies of grades of A and B of TNT was obtained 99-120 and 66-70 kJ mol^(-1)respectively. The lower values of activation energy of the degradation reaction of grade B confirm the effect of impurities in the kinetics of mass loss of this grade.展开更多
A new modified carbon paste electrode based on cyclam as a modifier was prepared for the determination of Co(Ⅱ) ions. The proposed electrode shows a Nernstian slope 28.4 mV per decade over a wide concentration range ...A new modified carbon paste electrode based on cyclam as a modifier was prepared for the determination of Co(Ⅱ) ions. The proposed electrode shows a Nernstian slope 28.4 mV per decade over a wide concentration range 5.0×10 -6_1.0×10 -1 mol/L of Co 2+ ions with detection limit 2.5×10 -6 mol/L. The sensor exhibits good selectivities for Co 2+ over a wide variety of other cations. It can be used as an indicator electrode in potentiometric titration of cobalt(Ⅱ) ions as well as in direct determination of cobalt(Ⅱ) ions in wastewater of acidic cobalt electroplating bath. The electrode shows Nernestian behavior in a solution of 25% ethanol.展开更多
The unfavorable growth and agglomeration of micro-particles of RDX explosive was almost observed in manufacture process. For preventing of growth of micro-particles and agglomeration in anti-solvent crystallization pr...The unfavorable growth and agglomeration of micro-particles of RDX explosive was almost observed in manufacture process. For preventing of growth of micro-particles and agglomeration in anti-solvent crystallization process, the effect of additives glucose, sucrose and poly ethylene glycol-2000 and wetting solvent of isopropyl alcohol were studied. Taguchi experimental design was used for optimization of the operating conditions. The type of additive, the amount of additive(%wt.), solvent of wetting and wetting time were selected for optimization of the conditions. By using 4 factor and 3 levels, 27 experiments were conducted(L27). Results showed that in the presence of 2 %wt. of sucrose additive and isopropyl alcohol solvent, the agglomerations of particles were decreased so that a decrease 30-50% in the average of particles size was seen. Addition additives were effective in storage container and for reduce the agglomeration of particles during storage. Also, the agglomeration rate of particles was reduced over time at optimized conditions. Imaging optical microscopy, scanning electron microscopy(SEM), and particle size analyzer(PSA) methods were used for particles size analyzing as a response in statistical optimization and quality control of the final product. The sensitivity to some mechanical and shock stimuli on the RDX in presence of sucrose additive was tested and the obtained results showed the insignificant effect of additive on the safety properties of pure RDX.展开更多
An electrochemical approach to fabricate a nanostructured Fe/Pt-Fe catalyst through electrodeposition followed by galvanic replacement is presented. An Fe/Pt-Fe nanostructured electrode was prepared by deposition of F...An electrochemical approach to fabricate a nanostructured Fe/Pt-Fe catalyst through electrodeposition followed by galvanic replacement is presented. An Fe/Pt-Fe nanostructured electrode was prepared by deposition of Fe-Zn onto a Fe electrode surface, followed by replacement of the Zn by Pt at open-circuit potential in a Pt-containing alkaline solution. Scanning electron microscopy and energy-dispersive X-ray techniques reveal that the Fe/Pt-Fe electrode is porous and contains Pt. The electrocatalytic activity of the Fe/Pt-Fe electrode for oxidation of methanol was examined by cyclic voltammetry and chronoamperometry. The electrooxidation current on the Fe/Pt-Fe catalyst is much higher than that on flat Pt and smooth Fe catalysts. The onset potential and peak potential on the Fe/Pt-Fe catalyst are more negative than those on flat Pt and smooth Fe electrodes for methanol electrooxidation. All results show that this nanostructured Fe/Pt-Fe electrode is very attractive for integrated fuel cell applications in alkaline media.展开更多
In this study, an organic electrolyte solution based on zinc acetate/diethylene glycol(ZA/DEG) is introduced for the selective purification of cyclotetramethylene tetranitramine(HMX) high explosive from its identical ...In this study, an organic electrolyte solution based on zinc acetate/diethylene glycol(ZA/DEG) is introduced for the selective purification of cyclotetramethylene tetranitramine(HMX) high explosive from its identical homologue cyclotrimethylene trinitramine(RDX). The dielectric constant of various organic solutions were investigated through Electrochemical Impedance Spectroscopy(EIS) in the range of 1.0 Hz—30 MHz. and some quantum-chemical descriptors of RDX and HMX dissolutions in the ZA cosolvent were analyzed using Density Functional Theory(DFT). The results show dielectric constant and solubility of RDX is higher than that of HMX, and by increasing of ZA concentration in DEG solvent, the values of dielectric constants were enhanced. Furthermore, the presence of ZA cosolvent on the solubility of two explosives was statistically investigated by Central Composite Design(CCD) of experiment, and some solubility parameters including activity coefficient, dissolving enthalpy, and mixing enthalpies were determined. The experimental results indicate that the weight ratio of RDX to HMX solubility in the proposed organic electrolyte changes up to 30 times, which provides a selective and sequential separation method to separate two materials with similar chemical properties with a separation efficiency>98% and HMX purity> 99.8%. The X-Ray Diffraction(XRD) analysis, High-Performance Liquid Chromatography(HPLC), Laser-Induced Breakdown Spectroscopy(LIBS), and Fourier Transform Infrared Spectroscopy(FT-IR) approves the acceptable quality of the separated materials. The proposed method makes the efficient and safe purification of high-quality HMX for application in oil and gas well perforating gun charges, using a nonvolatile and inflammable organic electrolyte.展开更多
The photostabilies of hexanitrostillbene(HNS)were studied at 1%wt.of photostabilizers.The photostabilizers of Chiguard BP-12(UV-531),ADK STAB LA-326(UV-326),ADK STAB LA-32(UV-P),Irganox 1010 and Everstab LS944 were us...The photostabilies of hexanitrostillbene(HNS)were studied at 1%wt.of photostabilizers.The photostabilizers of Chiguard BP-12(UV-531),ADK STAB LA-326(UV-326),ADK STAB LA-32(UV-P),Irganox 1010 and Everstab LS944 were used in this study.A photoreactor including a 30 W monochromatic UV lamp was used for investigation of photodegradations of solid HNS.The changes in surface area of HNS peak in HPLC chromatogram at time intervals of 2,4,6 and 8 h were used for calculation of kinetic rate constants of photodegradation process.The compound of UV-P photostabilizer was found to have the greatest effect on enhancing photostability for HNS among the investigated photostabilizers.The kinetic rate constants were obtained 6.2×10^(-2) and 4.1×10^(-2)h^(-1),respectively,for photodegradation process of HNS in absence and in presence of UV-P.展开更多
文摘Keto-RDX was obtained by one-step method with a certain amount of RDX as by-product.The effects of various parameters on high yield were studied.A simple analytical method was also introduced to determine simultaneously Keto-RDX/RDX mole ratio.Some important theoretical characterizations of Keto-RDX such as detonation performance at maximum nominal density and shock sensitivity were determined by new methods and compared with RDX.
基金the research committee of Malek-ashtar University of Technology(MUT)for supporting this work。
文摘The hexanitrostilben(HNS) is a thermally stable explosive that can be prepared from hexanitrobibenzyl(HNBB).Therefore,the investigation of thermal stability of HNBB can be important in the yield of preparation of HNS.The decomposition kinetic of HNBB and HNS are studied by non-isothermal gravimetric method.The TG/DTG curves in non-isothermal method are obtained in range of 25℃-400℃at heating rates of 3℃/min,5℃/min,8℃/min,10℃/min and 12℃/min.The data of weighttemperature are used for calculation of activation energy(E_a) of thermal decomposition reactions by methods of Ozawa,Kissinger,Ozawa-Flynn-Wall(OFW) and Kissinger-Akahira-Sunose(KAS) as modelfree methods and Strink's equation as model-fitting method.The compensation effect is used for prediction of mechanism and determination of pre-exponential factor(InA) of the decomposition reaction.A reduction 60 kj/mol for the average of activation energy of thermal decomposition reaction of HNBB is obtained versus HNS.This result shows the lower thermal stability of HNBB in comparison to HNS,The Avrami equation(A_(3/2)) with function f(α)=3/2(1-α)[-In(1-α)]^(1/3) indicates the predicted mechanism for thermal decomposition reaction both explosives.
文摘Many of the physical and functional properties of RDX and HMX explosives are related to the crystalline structure of these materials. Crystalline defects affect the quality of the explosives. Therefore, in order to enhance the quality of these materials, it is necessary to form crystals with the lowest defects. In this research, we report the optimization of recrystallization process of RDX and HMX by statistical techniques. The solvent/anti-solvent procedure was used for recrystallization of HMX and RDX particles. The four parameters of i) ratio of anti-solvent to solvent, ii) ratio of solute to solvent, iii) aging time, and iv)cooling rate of mixture, were optimized by Taguchi analysis design. Taguchi L16 orthogonal array was used with sixteen rows corresponding to the number of tests in four columns at four levels. The apparent density of recrystallized of RDX and HMX particles was considered as the quality characteristic with the concept of "the larger-the-better". The obtained graphs showed that the studied parameters were optimized in ratio 1:1 for anti-solvent to solvent, ratio 0.1 g,m L^(-1) for solute to solvent, aging time of 2 h and cooling rate of 1℃,min^(-1). Also, the correlation between the investigated parameters and apparent density of crystals were studied by multiple linear regressions(MLR) method for obtaining a model of prediction of apparent density. The P-values were indicated that in confidence level of 95%, the null hypothesis is rejected and a meaningful addition is observed in the proposed model.
基金the research committee of Malek-ashtar University of Technology(MUT)
文摘The kintic and activation energy of mass loss of two grades of melted TNT explosive, grade A and grade B, with freezing points of 80.57 and 78.15 ℃, respectively, were studied by isothermal and nonisothermal gravimetric methods. In isothermal method, the mass loss of samples in containers of glass and aluminum was followed in temperatures of 80, 90 and 100 ℃. The kinetic of the mass loss of the samples in the aluminum container was higher than the kinetic of it in the glass container that can be related to the effects of heat transfer and catalytic of aluminm metal. Also, the presence of impurities in grade B was due to increasing of kinetic of mass loss of it versus grade A. The non-isothermal curves were obtained in range of 30-330 ℃ at heating rates of 10,15 and 20 ℃·min^(-1).The TG/DTG data were used for determination of activation energy(E_a) of mass loss of TNT samples upon degradation by using Ozawa, Kissinger, Ozawa-Flynn-Wall(OFW) and Kissinger-Akahira-Sunose(KAS) methods as model free methods. The activation energies of grades of A and B of TNT was obtained 99-120 and 66-70 kJ mol^(-1)respectively. The lower values of activation energy of the degradation reaction of grade B confirm the effect of impurities in the kinetics of mass loss of this grade.
文摘A new modified carbon paste electrode based on cyclam as a modifier was prepared for the determination of Co(Ⅱ) ions. The proposed electrode shows a Nernstian slope 28.4 mV per decade over a wide concentration range 5.0×10 -6_1.0×10 -1 mol/L of Co 2+ ions with detection limit 2.5×10 -6 mol/L. The sensor exhibits good selectivities for Co 2+ over a wide variety of other cations. It can be used as an indicator electrode in potentiometric titration of cobalt(Ⅱ) ions as well as in direct determination of cobalt(Ⅱ) ions in wastewater of acidic cobalt electroplating bath. The electrode shows Nernestian behavior in a solution of 25% ethanol.
基金the research committee of Malek-ashtar University of Technology (MUT) for supporting this work
文摘The unfavorable growth and agglomeration of micro-particles of RDX explosive was almost observed in manufacture process. For preventing of growth of micro-particles and agglomeration in anti-solvent crystallization process, the effect of additives glucose, sucrose and poly ethylene glycol-2000 and wetting solvent of isopropyl alcohol were studied. Taguchi experimental design was used for optimization of the operating conditions. The type of additive, the amount of additive(%wt.), solvent of wetting and wetting time were selected for optimization of the conditions. By using 4 factor and 3 levels, 27 experiments were conducted(L27). Results showed that in the presence of 2 %wt. of sucrose additive and isopropyl alcohol solvent, the agglomerations of particles were decreased so that a decrease 30-50% in the average of particles size was seen. Addition additives were effective in storage container and for reduce the agglomeration of particles during storage. Also, the agglomeration rate of particles was reduced over time at optimized conditions. Imaging optical microscopy, scanning electron microscopy(SEM), and particle size analyzer(PSA) methods were used for particles size analyzing as a response in statistical optimization and quality control of the final product. The sensitivity to some mechanical and shock stimuli on the RDX in presence of sucrose additive was tested and the obtained results showed the insignificant effect of additive on the safety properties of pure RDX.
基金supported by the Iranian Nanotechnology Society and the Office of the Vice-chancellor in Charge of Research at Malek-Ashtar University of Technology
文摘An electrochemical approach to fabricate a nanostructured Fe/Pt-Fe catalyst through electrodeposition followed by galvanic replacement is presented. An Fe/Pt-Fe nanostructured electrode was prepared by deposition of Fe-Zn onto a Fe electrode surface, followed by replacement of the Zn by Pt at open-circuit potential in a Pt-containing alkaline solution. Scanning electron microscopy and energy-dispersive X-ray techniques reveal that the Fe/Pt-Fe electrode is porous and contains Pt. The electrocatalytic activity of the Fe/Pt-Fe electrode for oxidation of methanol was examined by cyclic voltammetry and chronoamperometry. The electrooxidation current on the Fe/Pt-Fe catalyst is much higher than that on flat Pt and smooth Fe catalysts. The onset potential and peak potential on the Fe/Pt-Fe catalyst are more negative than those on flat Pt and smooth Fe electrodes for methanol electrooxidation. All results show that this nanostructured Fe/Pt-Fe electrode is very attractive for integrated fuel cell applications in alkaline media.
基金financial support of this work by Malek-ashtar University of Technology (I.R. Iran)。
文摘In this study, an organic electrolyte solution based on zinc acetate/diethylene glycol(ZA/DEG) is introduced for the selective purification of cyclotetramethylene tetranitramine(HMX) high explosive from its identical homologue cyclotrimethylene trinitramine(RDX). The dielectric constant of various organic solutions were investigated through Electrochemical Impedance Spectroscopy(EIS) in the range of 1.0 Hz—30 MHz. and some quantum-chemical descriptors of RDX and HMX dissolutions in the ZA cosolvent were analyzed using Density Functional Theory(DFT). The results show dielectric constant and solubility of RDX is higher than that of HMX, and by increasing of ZA concentration in DEG solvent, the values of dielectric constants were enhanced. Furthermore, the presence of ZA cosolvent on the solubility of two explosives was statistically investigated by Central Composite Design(CCD) of experiment, and some solubility parameters including activity coefficient, dissolving enthalpy, and mixing enthalpies were determined. The experimental results indicate that the weight ratio of RDX to HMX solubility in the proposed organic electrolyte changes up to 30 times, which provides a selective and sequential separation method to separate two materials with similar chemical properties with a separation efficiency>98% and HMX purity> 99.8%. The X-Ray Diffraction(XRD) analysis, High-Performance Liquid Chromatography(HPLC), Laser-Induced Breakdown Spectroscopy(LIBS), and Fourier Transform Infrared Spectroscopy(FT-IR) approves the acceptable quality of the separated materials. The proposed method makes the efficient and safe purification of high-quality HMX for application in oil and gas well perforating gun charges, using a nonvolatile and inflammable organic electrolyte.
文摘The photostabilies of hexanitrostillbene(HNS)were studied at 1%wt.of photostabilizers.The photostabilizers of Chiguard BP-12(UV-531),ADK STAB LA-326(UV-326),ADK STAB LA-32(UV-P),Irganox 1010 and Everstab LS944 were used in this study.A photoreactor including a 30 W monochromatic UV lamp was used for investigation of photodegradations of solid HNS.The changes in surface area of HNS peak in HPLC chromatogram at time intervals of 2,4,6 and 8 h were used for calculation of kinetic rate constants of photodegradation process.The compound of UV-P photostabilizer was found to have the greatest effect on enhancing photostability for HNS among the investigated photostabilizers.The kinetic rate constants were obtained 6.2×10^(-2) and 4.1×10^(-2)h^(-1),respectively,for photodegradation process of HNS in absence and in presence of UV-P.
