Synthesis and characterization of 3,6-bis(1H-1,2,3,4-tetrazol-5-ylamino)-1,2,4,5-tetrazine (BTATz): novel high-nitrogen content insensitive high energy material.

This paper reports the synthesis, characterization and thermolysis studies of 3,6-bis(1H-1,2,3,4-tetrazol-5-ylamino)-1,2,4,5-tetrazine (BTATz) and 3-(1H-1,2,3,4-tetrazol-5-ylamino)-6-(3,5-dimethyl-pyrazol-1-yl)-s-tetrazine monohydrate (TADPTz). The synthesized BTATz and TADPTz have been characterized by spectroscopic techniques and the data obtained confirm their structure. TGA and DSC results suggested that BTATz decomposes in the range 265-350 degrees C and TADPTz in the range 245-275 degrees C respectively. The calculated energy of activation of BTATz and TADPTz is 212.69 and 257.29kJ/mol respectively. The experimentally determined DeltaH(f) value matches with theoretically computed heat of explosion. The computed volume of gases indicates that they can find application in gas generating compositions.

Environmentally compatible next generation green energetic materials (GEMs).

This paper briefly reviews the literature work reported on the environmentally compatible green energetic materials (GEMs) for defence and space applications. Currently, great emphasis is laid in the field of high-energy materials (HEMs) to increase the environmental stewardship along with the deliverance of improved performance. This emphasis is especially strong in the areas of energetic materials, weapon development, processing, and disposal operations. Therefore, efforts are on to develop energetic materials systems under the broad concept of green energetic materials (GEMs) in different schools all over the globe. The GEMs program initiated globally by different schools addresses these challenges and establishes the framework for advances in energetic materials processing and production that promote compliance with environmental regulations. This review also briefs the principles of green chemistry pertaining to HEMs, followed by the work carried out globally on environmentally compatible green energetic materials and allied ingredients.

Computer code to predict the heat of explosion of high energy materials.

The computational approach to the thermochemical changes involved in the process of explosion of a high energy materials (HEMs) vis-à-vis its molecular structure aids a HEMs chemist/engineers to predict the important thermodynamic parameters such as heat of explosion of the HEMs. Such a computer-aided design will be useful in predicting the performance of a given HEM as well as in conceiving futuristic high energy molecules that have significant potential in the field of explosives and propellants. The software code viz., LOTUSES developed by authors predicts various characteristics of HEMs such as explosion products including balanced explosion reactions, density of HEMs, velocity of detonation, CJ pressure, etc. The new computational approach described in this paper allows the prediction of heat of explosion (DeltaH(e)) without any experimental data for different HEMs, which are comparable with experimental results reported in literature. The new algorithm which does not require any complex input parameter is incorporated in LOTUSES (version 1.5) and the results are presented in this paper. The linear regression analysis of all data point yields the correlation coefficient R(2)=0.9721 with a linear equation y=0.9262x+101.45. The correlation coefficient value 0.9721 reveals that the computed values are in good agreement with experimental values and useful for rapid hazard assessment of energetic materials.

Electro-analysis of energetic materials.

Cyclic voltammetric studies of triaminoguanidine nitrate (TAGN), 3,3'-hydrazino bis(bis[6,6'-(3,5-dimethylpyrazol-lyl])-1,2,4,5-tetrazine (HBPT), 4,6-dinitrobenzofuroxan (DNBF) and 3,3'-diamino-4,4'-azoxyfurazan (DAAF) were carried out at different pH conditions in 50% aqueous acetonitrile using glassy carbon electrode. Optimum pH was selected for individual compounds. Influence of scan rate and concentration on the voltammetric response were studied in optimum pH. The number of electron transferred was determined by controlled potential coulometry. All compounds undergo diffusion controlled electrochemical reaction. Based on cyclic voltammetric results, differential pulse and square wave voltammetric methods have been developed for the analytical determination. Instrumental parameters such as initial scan potential, amplitude, pulse increment, pulse period, pulse width and frequency were studied. Optimum experimental conditions for each compound were obtained. After fixing optimum conditions, the effect of concentration was studied and calibration plot was arrived. These plots can be used to determine the traces of the above said four energetic materials.

Study on ultrasound assisted precipitation of CL-20 and its effect on morphology and sensitivity.

Applying ultrasound to crystallizing systems offers significant advantages for modifying and improving the processes as well as quality of products. This paper reports on ultrasound assisted reprecipitation of CL-20 to obtain fine particles as well as to achieve desired morphology, which will improve insensitivity characteristics. In this study, CL-20 has been reprecipitated by sonication process and has been characterized by DSC, SEM and particle size analysis. The results are compared with control CL-20 sample (unsonicated). SEM photographs revealed that sonication process offer uniform crystalline morphology without any agglomeration. The particle size of sonicated CL-20 sample obtained is around 5+/-1 microm with a narrow particle size distribution. The DSC thermogram of sonicated and unsonicated sample is identical. CL-20 samples were subjected to impact and friction sensitivity experiments, the results indicate the sensitivity characteristics reduced considerably. Ultrasonic assisted crystallization technique reduces the time of reprecipitation considerably with an enhanced recovery of CL-20 with a very narrow particle size distribution.

Synthesis, characterization and thermolysis studies on new derivatives of 2,4,5-trinitroimidazoles: potential insensitive high energy materials.

This paper reports the synthesis of three new derivatives of 2,4,5-trinitroimidazole namely, 1-methyl-2,4,5-trinitroimidazole (III), 1-carboethoxy-2,4,5-trinitroimidazole (V) and 1-picryl-2,4,5-trinitroimidazole (VII). The title compounds (III) and (V) were synthesized by the nitration of 1-methyl-/1-carboethoxy-(2,4,5-triiodoimidazole) (II and IV) with fuming nitric acid at 0 degrees C and (VII) was synthesized by condensation of 2,4,5-triiodoimidazole (I) with picryl chloride to obtain 1-picryl-2,4,5-triiodoimidazole (VI) followed by its nitration with fuming nitric acid at 0 degrees C. The synthesized compounds have been characterized by elemental analysis, spectral and thermal techniques. The thermolysis studies using TG-DTA revealed exothermic decomposition of the nitroimidazoles (III, V and VII) with T(max) in the temperature range of 196-225 degrees C. The energy of activation obtained for these compounds was in the range 150-170 kJ/mol. The sensitivity data obtained for the newly synthesized compounds (III, V and VII) indicated their safe nature towards external stimuli (h(50%)>100 cm; friction>36 kg) and could be potential candidates for low vulnerable applications in the futuristic systems. The theoretically predicted performance parameters suggest that 1-methyl-2,4,5-trinitroimidazole (III), exhibits higher velocity of detonation (VOD: 8.8 km/s) compared to compounds V and VII (VOD: 7.6 and 8.41 km/s, respectively).

Preparation and thermal studies on tetranitrodibenzo tetraazapentalene (TACOT): a thermally stable high explosive.

Thermally stable high explosive, tetranitro-2,3,5,6-dibenzo-1,3a,4,6a-tetraazapentalene (TACOT) was synthesized and characterized during this work. Thermo analytical techniques (TG and DSC) were applied to study the thermal decomposition behaviour of TACOT in comparison with benchmark thermally stable high explosive 1,3,5-triamino-2,4,6-trinitrobenzene (TATB). Kinetic parameters such as reaction order, activation energy and pre-exponential factors were computed from the thermal data. The activation energy for TACOT (292 kJ/mol) was found 1.5 times to that of TATB (200 kJ/mol), which can account for its higher thermal stability and can be attributed to pentalene moiety in the former.

Synthesis, characterization and thermolysis studies on triazole and tetrazole based high nitrogen content high energy materials.

This paper reports the synthesis, characterisation and thermolysis studies of hydrazinium azotetrazolate (HAZ) and 1,1'-dinitro-3,3'-azo-1,2,4-triazole (N-DNAT). TGA and DSC results suggested that HAZ decomposes in the range of 150-180 degrees C and N-DNAT in the range of 160-170 degrees C, respectively. The pattern of decomposition of HAZ dihydrate and N-DNAT has been predicted with the help of pyrolysis GC/MS technique and a probable decomposition mechanism has been proposed. The theoretically predicted performance data suggests the potential nature of HAZ and N-DNAT for their use in propellant/explosive as well as in gas generator formulations.

Computer code for the optimization of performance parameters of mixed explosive formulations.

LOTUSES is a novel computer code, which has been developed for the prediction of various thermodynamic properties such as heat of formation, heat of explosion, volume of explosion gaseous products and other related performance parameters. In this paper, we report LOTUSES (Version 1.4) code which has been utilized for the optimization of various high explosives in different combinations to obtain maximum possible velocity of detonation. LOTUSES (Version 1.4) code will vary the composition of mixed explosives automatically in the range of 1-100% and computes the oxygen balance as well as the velocity of detonation for various compositions in preset steps. Further, the code suggests the compositions for which least oxygen balance and the higher velocity of detonation could be achieved. Presently, the code can be applied for two component explosive compositions. The code has been validated with well-known explosives like, TNT, HNS, HNF, TATB, RDX, HMX, AN, DNA, CL-20 and TNAZ in different combinations. The new algorithm incorporated in LOTUSES (Version 1.4) enhances the efficiency and makes it a more powerful tool for the scientists/researches working in the field of high energy materials/hazardous materials.

Prediction of heat of formation and related parameters of high energy materials.

Heat of formation is one of the most important parameters in the performance prediction of explosive and propellant formulations and their individual ingredients. This paper reports the development of user-friendly computer code for the prediction of heat of formation based on two approaches. In first methodology, the logic of Benson's Group additivity method and in the second method, the logic of Pedley method was used for predicting the heats of formation of high energy materials (HEMs). The predicted heats of formation by Benson method for various classes of high energy materials gave deviation in the range of 2-10%, whereas nearly 10-15% deviation was observed using Pedley methodology in comparison to experimental values. The linear regression coefficient values (R(2)) of 0.9947 and 0.9637 are obtained for heat of formation values predicted by this code using methodologies I and II, respectively. The newly developed code LOTUSES (version 1.3) has been validated by calculating the heats of formation of standard explosives such as TNT, pentaerythritol tetranitrate (PETN), RDX, HMX, etc., To the best of our knowledge, no such code is reported in literature which can predict heats of formation values integrated with performance parameters of HEMs belonging to all categories of organic compounds viz. aliphatic, aromatic and heterocyclic materials. The code can also be used to obtain parameters such as velocity of detonation, C-J pressure, volume of explosion products, power index, temperature of explosion and oxygen balance of HEMs. The code has been developed in Visual Basic having enhanced Windows environment. This software namely LOTUSES 1.3 is an updated version of the earlier ones namely LOTUSES 1.1 and 1.2 which do not cater for the calculation of heat of formation and temperature of explosion of HEMs. LOTUSES 1.3 is, therefore, a totally integrated software for computing most of the vital parameters of HEMs requiring mainly the molecular structural information of an explosive under consideration.

Establishment of process technology for the manufacture of dinitrogen pentoxide and its utility for the synthesis of most powerful explosive of today--CL-20.

This paper reviews the recent work done on the synthesis as well as characterization of dinitrogen pentoxide (DNPO). The physico-chemical characteristics of DNPO are also discussed. The review brings out the key aspects of N2O5 technology with relevance to realize modern and novel HEMs. The paper also includes the aspects related with establishing the synthesis facility of dinitrogen pentoxide at HEMRL by gas phase interaction of N2O4 with O3. The process parameters for the synthesis of N2O5 at 50 g/batch have been optimized. The synthesized dinitrogen pentoxide has been characterized by UV [204, 213, 258 nm (pi-->pi*) 378 and 384 nm (n-->pi*)] and IR (1428, 1266, 1249, 1206, 1044, 822, 750, 546 and 454 cm(-1)) spectroscopy. The DSC clearly showed the sublimation of N2O5 at 32 degrees C. The nitration studies on 2,6,8,12-tetraacetylhexaaza tetracyclo[5,5,0,0(3,11)0(5,9)]dodecane (TAIW) proved its viability in 2,4,6,8,10,12-hexanitro-2,4,6,8(10,12))-hexaazatetracyclo [5,5,0,0(3,11)0(5,9)]dodecane (CL-20) synthesis. The synthesized CL-20 and its precursors have also been subjected to hyphenated TG-FTIR studies to understand decomposition pattern.

Synthesis, characterization and thermal studies on furazan- and tetrazine-based high energy materials.

This paper reports the synthesis of high energy materials (HEMs) viz. 3,3'-diamino-4,4'-azoxyfurazan (DAAF), 3,3s'-azobis(6-amino-1,2,4,5-tetrazine) [DAAT] and 1,4-dihydrazino tetrazine (DHTz). The products obtained were characterized by IR, 1H NMR, 13C NMR and mass spectra. Thermolysis of these compounds carried out by applying TG-DTA and DSC techniques indicated that the thermal stability of DAAF and DAAT was in the temperature range of 230-250 degrees C, whereas that of DHTz was up to approximately 140 degrees C. TG-FTIR of gaseous products of these compounds suggests the evolution of NH2CN/NH3 and HCN as major decomposition products. The impact and friction sensitivity data revealed that DAAF is insensitive to mechanical stimuli whereas DAAT and DHTz are vulnerable to impact stimuli. The cyclic voltammetric studies brought out that, DAAF, DAAT and DHTz are electroactive compounds and thereby can be detected at even low concentration at pH 7 and 13. The theoretical predictions of explosive power of DAAF, DAAT and DHTz alone and their combinations with well-known insensitive high explosives using Becker-Kistiakowsky Wilson (BKW) code as well as that of propellants based on them by NASA-CEC-71 suggest their potential in specific systems.

Computer simulation for prediction of performance and thermodynamic parameters of high energy materials.

A new code viz., Linear Output Thermodynamic User-friendly Software for Energetic Systems (LOTUSES) developed during this work predicts the theoretical performance parameters such as density, detonation factor, velocity of detonation, detonation pressure and thermodynamic properties such as heat of detonation, heat of explosion, volume of explosion gaseous products. The same code also assists in the prediction of possible explosive decomposition products after explosion and power index. The developed code has been validated by calculating the parameters of standard explosives such as TNT, PETN, RDX, and HMX. Theoretically predicated parameters are accurate to the order of +/-5% deviation. To the best of our knowledge, no such code is reported in literature which can predict a wide range of characteristics of known/unknown explosives with minimum input parameters. The code can be used to obtain thermochemical and performance parameters of high energy materials (HEMs) with reasonable accuracy. The code has been developed in Visual Basic having enhanced windows environment, and thereby advantages over the conventional codes, written in Fortran. The theoretically predicted HEMs performance can be directly printed as well as stored in text (.txt) or HTML (.htm) or Microsoft Word (.doc) or Adobe Acrobat (.pdf) format in the hard disk. The output can also be copied into the Random Access Memory as clipboard text which can be imported/pasted in other software as in the case of other codes.

Agricultural solid waste for the removal of organics: adsorption of phenol from water and wastewater by palm seed coat activated carbon.

Adsorption studies for phenol removal from aqueous solution on activated palm seed coat carbon (PSCC) were carried out under varying experimental conditions of contact time, phenol concentration, adsorbent dose and pH. Adsorption equilibrium was reached within 3 h for phenolic concentrations 10-60 mg l(-1). Kinetics of adsorption obeyed a first order rate equation. The percent removal remained constant over the pH range 4-9 for a phenolic concentration of 25 mg (l-1). The equilibrium data could be described well by the Freundlich isotherm equation. The adsorption of phenol on PSCC follows the film diffusion process. A comparative study with a commercial activated carbon showed that PSCC is two times more effective than commercial activated carbon. The studies showed that the palm seed coat carbon can be used as an efficient adsorbent material for the removal of phenolics from water and wastewater.

Removal of phenol from aqueous solution and resin manufacturing industry wastewater using an agricultural waste: rubber seed coat.

Activated carbon prepared from rubber seed coat (RSCC), an agricultural waste by-product, has been used for the adsorption of phenol from aqueous solution. In this work, adsorption of phenol on rubber seed coat activated carbon has been studied by using batch and column studies. The equilibrium adsorption level was determined to be a function of the solution pH, adsorbent dosage and contact time. The equilibrium adsorption capacity of rubber seed coat activated carbon for phenol removal was obtained by using linear Freundlich isotherm. The adsorption of phenol on rubber seed coat activated carbon follows first order reversible kinetics. The suitability of RSCC for treating phenol based resin manufacturing industry wastewater was also tested. A comparative study with a commercial activated carbon (CAC) showed that RSCC is 2.25 times more efficient compared to CAC based on column adsorption study for phenolic wastewater treatment.

Lipid peroxidation in the rat uterus during deciduoma induced cell differentiation.

The influence of deciduoma-induced differentiation on the lipid peroxidation in the rat uterus was investigated. The wet weight of uterus and its protein content increased during deciduoma progression. Content of the thiobarbituric acid reactive substances (TBARS) as well as lipid peroxidation induced by ascorbate and cumene hydroperoxide showed significant decreases during deciduoma growth. Restoration of normalcy was observed during regression. The activity of superoxide dismutase, an inhibitor of lipid peroxidation showed an opposite pattern namely increase during deciduoma development and decline during the regressive phase. We conclude that cell differentiation during deciduoma induction is accompanied by a temporary and reversible decrease in the peroxidative potential of the rat uterus.

Effect of cycloheximide on deciduoma morphogenesis and implantation in rats.

Intraperitoneal administration of cycloheximide (1 mg/kg body weight) to rats immediately after an artificial deciduoma induction inhibits the development of decidual tissue. Besides inhibiting the differentiation of stromal to decidual cells, wet weight and levels of uterine protein and RNA are low following the antibiotic treatment. Injection of the drug (1 mg/kg body weight) into pregnant rats, either on the eve of Day 4 or in the morning of Day 5 of pregnancy, does not prevent implantation but interferes with the growth of embryos.

Effect of whole-body x-irradiation on the morphogenesis of rat deciduoma.

Exposure of rats to whole-body X-irradiation (600 R) within 30 minutes of artificial induction of deciduoma resulted in impaired growth of deciduoma involving both endometrium and myometrium. Protein synthesis in endometrium was low 2 days after X-irradiation when compared with unirradiated controls. In addition, levels of RNA and DNA were low in the endometrium of irradiated rats. Development of metrial gland was inhibited in the irradiated rats. The number and morphology of antimesometrial and mesometrial decidual cells were altered in the irradiated animals. Endometrial and myometrial soluble proteins of irradiated rats resolved into fewer bands than those of unirradiated animals.

Protein anabolism in endometrium and myometrium during the growth of induced deciduoma in rats.

Protein anabolism in the endometrium and myometrium was studied during the growth of induced deciduoma in terms of incorporation of [14C]-leucine into proteins. The data show that the specific activity of the proteins was highest 2 days after decidualisation. Protein synthesis in the endometrium studied on that day as a function of time after injection of the labelled amino acid showed a steady increase during the first 2 h. Cycloheximide (2 mg/kg b.wt) administration produced nearly 95% inhibition of protein synthesis in endometrium as well as in myometrium.