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Vicarious amination of nitroarenes with trimethylhydrazinium iodine

Description: This paper investigated the use of 1,1,1-trimethylhydrazinium iodide as a vicarious nucleophilic substitution reagent for introducing amino groups into nitroaromatic substrates. The substrates included nitroarenes, polynitrobenzenes, picramide, TNB,TNT, and dinitropyrazole; other nitroazoles are being studied.
Date: November 10, 1995
Creator: Pagoria, P.F.; Schmidt, R.D. & Mitchell, A.R.
Partner: UNT Libraries Government Documents Department

ANFOL synthesis. [Quarterly report], April--June 1971

Description: A new method was developed for chlorination of 4,4-dinitropimelic acid with PCl{sub 5} using a Soxhlet extraction apparatus as the addition vessel. Acid used was that reclaimed from the purification of the crude acid chloride of 4,4-dinitropimelic acid supplied by LRL. Synthesis of FEFO plasticized AFNOL has been scaled up to a nominal 30-pound batch. Small batches and cure tests were run prior to the scaleup. Cure rate of the AFNOL system was followed by infrared spectrophotometry. The temperature range of 40-100 C was studied using the hot stage attachment to the infrared spectrophotometer.
Date: December 31, 1971
Creator: Quinlin, W.T.
Partner: UNT Libraries Government Documents Department

AFNOL preparation. Quarterly report, July--September, 1971

Description: A nominal 15-pound batch of FEFO plasticized AFNOL was in preparation. Both the first and second esterifications were completed. (An equipment malfunction resulted in a loss of the product and the reaction vessel). The paper describes the preparation procedures and the malfunction.
Date: December 31, 1971
Creator: Quinlin, W.T.
Partner: UNT Libraries Government Documents Department

Shock initiation of 1,3,3-trinitroazetidine (TNAZ)

Description: The shock sensitivity of the pressed solid explosive 1,3,3-trinitroazetidine (TNAZ) was determined using the embedded manganin pressure gauge technique. At an initial pressure of 1.3 GPa, pressure buildup (exothermic reaction) was observed after ten {mu}s. At 2 GPa, TNAZ reacted rapidly and transitioned to detonation in approximately 13 mm. At 3.6 GPa, detonation occurred in less than 6 mm of shock propagation. Thus, pure TNAZ is more shock sensitive than HMX-based explosives but less shock sensitive than PETN-based explosives. The shocked TNAZ exhibited little reaction directly behind the shock front, followed by an extremely rapid reaction. This reaction caused both a detonation wave and a retonation wave in the partially decomposed TNAZ. An Ignition and Growth reactive model for TNAZ was developed to help understand this complex initiation phenomenon.
Date: July 19, 1995
Creator: Simpson, R.L.; Urtiew, P.A. & Tarver, C.M.
Partner: UNT Libraries Government Documents Department

Shock initiation of an {epsilon}-CL-20-estane formulation

Description: The shock sensitivity of a pressed solid explosive formulation, LX-19, containing 95.2% by weight epsilon phase 2,4,6,8,10,12-hexanitrohexaazaisowurtzitane (HNIW) and 4.8% Estane binder, was determined using the wedge test and embedded manganin pressure gauge techniques. This formulation was shown to be slightly more sensitive than LX-14, which contains 95.5% HMX and 4.5% Estane binder. The measured pressure histories for LX-19 were very similar to those obtained using several HMX-inert binder formulations. An Ignition and Growth reactive model for LX-19 was developed which differed from those for HMX-inert binder formulations only by a 25% higher hot spot growth rate.
Date: July 19, 1995
Creator: Tarver, C.M.; Simpson, R.L. & Urtiew, P.A.
Partner: UNT Libraries Government Documents Department

Static and dynamic pressure effects on the thermolysis of nitroalkanes in solution

Description: The authors have measured the effects of static and shock-induced pressures on the decomposition rates and mechanisms of various nitroalkanes dissolved in different solvents with and without organic amine catalysts. While nitroalkanes without {alpha}-hydrogen decompose by homolysis of the C-NO{sub 2} bond over a wide range of conditions, the decomposition pathway of nitroalkanes having {alpha}-hydrogens (i.e., acidic nitroalkanes) is complicated and follows different decomposition mechanisms depending on the availability of organic base and reaction pressure. The Nef reaction is also an important reaction pathway. The five known decomposition pathways, homolysis of the C-NO{sub 2} bond, bimolecular reaction between the aci-form and aci-ion, cyclization of the aci-form, elimination of nitrous acid, and the Nef reaction, are highly dependent on the reaction conditions, such as pressure, presence of organic amines, water, alcohols, and polarity of solvent. The authors discuss the results of several tests used to support these various decomposition mechanisms.
Date: December 31, 1998
Creator: Brower, K.R.; Davis, L.L.; Naud, D.L. & Wang, J.
Partner: UNT Libraries Government Documents Department

Informal progress report of the explosives group. Quarterly progress report, September--November 1958

Description: The relatively high heats of combustion of CHN compounds containing multiple bonds has prompted an investigation of the possible use of these compounds as explosives components. Three possible systems are being considered for testing in the small scale plate push apparatus: acrylonitrile-tetranitromethane, propiolonitrile-tetranitromethane and dicyanoacetylene-tetranitromethane. Samples of propiolamide and acetylene dicarboxamide, intermediates in the synthesis of propiolonitrile and dicyanoacetylene respectively, have been prepared and their infrared spectra determined. The heats of explosion of uncased charges of bis-trinitroethylnitramine has been performed. A program to investigate some properties of high explosives at microwave frequencies is being undertaken. Heterogeneous explosives consisting of metal-loaded organic explosives were also tested. Synthesis work was performed on nitrogen-fluorine compounds, boron-hydrogen-nitrogen compounds, reaction of hexachloromelamine with chlorinetrifluoride, and nitration studies.
Date: January 7, 1959
Creator: Kury, J.
Partner: UNT Libraries Government Documents Department

Development of PEX explosives: Solid-liquid phase diagrams of energetic mixes. Quarterly report, July--September, 1971

Description: The solid-liquid phase diagrams of various binary mixtures of FEFO, BDNPA, EDNP and BDNPF are being studied. Temperatures at which a 0.025-inch probe penetrated the samples were measured. It appears that the samples had not crystallized but solidified into a glass.
Date: December 31, 1971
Creator: Faubion, B.D.
Partner: UNT Libraries Government Documents Department

Migration of PBX 9501 constituents

Description: The nominal composition of PBX is 94.9% HMX, 2.5% Estane 5703, 2.5% bis-2,2-dinitropropyl acetal/formal (nitroplasticizer, NP), and 0.1% stabilizer (diphenylamine, DPA or Irganox 1010). In addition to the stabilizer added to the PBX formulation, the NP eutectic liquid contains 0.1% of the stabilizer phenyl-beta-naphthylamine (PBNA). For PBX 9501 containing weapons, it is known that NP migrates from the charge into the shield polymer, and ethylene-vinyl acetate-vinyl alcohol terpolymer, becomes saturated over time with NP and that migration is then stopped. Experiments have been performed showing the saturation concentration of the shield material to be 8.8 weight percent. Prior to this work, analyses were performed on weapon components from a W76 unit that had been in the stockpile for 172 months. The HE, stress cushions, and shields were analyzed for NP and for possible products of NP decomposition. Although no evidence of NP decomposition was found, it was discovered that the PBX stabilizer and the HMX impurity, RDX, were also moving into the shields. This paper will summarize the analytical data obtained from a number of weapons of various ages. Quantitation of NP, DPA, Irganox, RDX, and PBNA has been performed on shields from six different W76 units.
Date: October 1, 1997
Creator: Spontarelli, T.
Partner: UNT Libraries Government Documents Department

AFNOL synthesis. Quarterly report, October--December, 1971

Description: Five batches of unplasticized AFNOL, each approximately one pound, were synthesized using 4,4-dinitropimelic acid as the starting material. Two 10 g batches were completed prior to the pound batches to assure the usability of the acid chloride. Characterization of each of the larger batches was by differential thermal analysis (DTA), infrared spectrophotometry (IR), and cure tests. Some characterization was also done on the commercial chemicals used in the synthesis.
Date: December 31, 1972
Creator: Quinlin, W.T.
Partner: UNT Libraries Government Documents Department

Sensitivity testing of liquid high explosives

Description: This article describes a test procedure for a liquid high explosive. The liquid to be tested is NTN, a mixture of nitromethane, tetranitomethane, and 1-nitropropane in 52, 33.3, and 14.7 weight per cent. The test is to study the sensitivity of the explosive to shock by firing it in projectiles from a M1A1 155mm howlitzer, with a charge such that it will not exceed 16,500 g`s acceleration.
Date: January 31, 1961
Creator: O`Connell, L.
Partner: UNT Libraries Government Documents Department

Bioreporter bacteria for landmine detection

Description: Landmines (and other UXO) gradually leak explosive chemicals into the soil at significant concentrations. Bacteria, which have adapted to scavenge low concentrations of nutrients, can detect these explosive chemicals. Uptake of these chemicals results in the triggering of specific bacterial genes. The authors have created genetically recombinant bioreporter bacteria that detect small concentrations of energetic chemicals. These bacteria are genetically engineered to produce a bioluminescent signal when they contact specific explosives. A gene for a brightly fluorescent compound can be substituted for increased sensitivity. By finding the fluorescent bacteria, you find the landmine. Detection might be accomplished using stand-off illumination of the minefield and GPS technology, which would result in greatly reduced risk to the deminers. Bioreporter technology has been proven at the laboratory scale, and will be tested under field conditions in the near future. They have created a bacterial strain that detects sub-micromolar concentrations of o- and p-nitrotoluene. Related bacterial strains were produced using standard laboratory protocols, and bioreporters of dinitrotoluene and trinitrotoluene were produced, screening for activity with the explosive compounds. Response time is dependent on the growth rate of the bacteria. Although frill signal production may require several hours, the bacteria can be applied over vast areas and scanned quickly, producing an equivalent detection speed that is very fast. This technology may be applicable to other needs, such as locating buried explosives at military and ordnance/explosive manufacturing facilities.
Date: April 1, 1998
Creator: Burlage, R.S.; Youngblood, T. & Lamothe, D.
Partner: UNT Libraries Government Documents Department

He synthesis. Quarterly report, October--December, 1971

Description: Existing supplies of bis-trinitroanisole and picryl hydrazine were used to make 2 kg of bis-hexanitrohydrazobenzene. Development of the HNAB recrystallization process was temporarily stopped due to the need to produce a supply of the intermediate products (picryl chloride and HNHB). Purchase orders for DINOL and DNPIA required for synthesis of AFNOL were awarded.
Date: December 31, 1972
Creator: Hayes, D.V. & Honea, F.I.
Partner: UNT Libraries Government Documents Department

Coupling experimental data and a prototype model to probe the physical and chemical processes of 2,4-dinitroimidazole solid-phase thermal decomposition

Description: The time-dependent, solid-phase thermal decomposition behavior of 2,4-dinitroimidazole (2,4-DNI) has been measured utilizing simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) methods. The decomposition products consist of gaseous and non-volatile polymeric products. The temporal behavior of the gas formation rates of the identified products indicate that the overall thermal decomposition process is complex. In isothermal experiments with 2,4-DNI in the solid phase, four distinguishing features are observed: (1) elevated rates of gas formation are observed during the early stages of the decomposition, which appear to be correlated to the presence of exogenous water in the sample; (2) this is followed by a period of relatively constant rates of gas formation; (3) next, the rates of gas formation accelerate, characteristic of an autocatalytic reaction; (4) finally, the 2,4-DNI is depleted and gaseous decomposition products continue to evolve at a decreasing rate. A physicochemical and mathematical model of the decomposition of 2,4-DNI has been developed and applied to the experimental results. The first generation of this model is described in this paper. Differences between the first generation of the model and the experimental data collected under different conditions suggest refinements for the next generation of the model.
Date: December 31, 1998
Creator: Behrens, R.; Minier, L. & Bulusu, S.
Partner: UNT Libraries Government Documents Department

Steady state HNG combustion modeling

Description: Two simplified modeling approaches are used to model the combustion of Hydrazinium Nitroformate (HNF, N{sub 2}H{sub 5}-C(NO{sub 2}){sub 3}). The condensed phase is treated by high activation energy asymptotics. The gas phase is treated by two limit cases: the classical high activation energy, and the recently introduced low activation energy approach. This results in simplification of the gas phase energy equation, making an (approximate) analytical solution possible. The results of both models are compared with experimental results of HNF combustion. It is shown that the low activation energy approach yields better agreement with experimental observations (e.g. regression rate and temperature sensitivity), than the high activation energy approach.
Date: April 1, 1998
Creator: Louwers, J.; Gadiot, G. M. H. J. L.; Brewster, M. Q.; Son, S. F.; Parr, T. & Hanson-Parr, D.
Partner: UNT Libraries Government Documents Department

Compatibility of EXTEX with tetryl by thermal methods. Quarterly report, July--September, 1971

Description: A progress report is given on the study of the compatibility of XTX 8003 and tetryl. The 100 C coupon test samples were discarded after 8 weeks because of excessive decomposition. There is no indication of a compatibility problem of XTX with tetryl as long as they are in a solid phase. The 80 C coupon test evaluations are continuing.
Date: December 31, 1971
Creator: Myers, L.C.
Partner: UNT Libraries Government Documents Department

Synthesis of benzotrifuroxane. Quarterly report, July--September, 1971

Description: This work is to find an improved method for the synthesis of benzotrifuroxane which could be conveniently scaled up. Three batches were made; the first following the LLL procedure, the second with modifications in the initial addition step, and the third with changes in fluid system and handling procedures going from the intermediate to the final product.
Date: December 31, 1971
Creator: Quinlin, W.T. & Hayes, D.V.
Partner: UNT Libraries Government Documents Department

Mechanistic and kinetic studies of the thermal decomposition of TNAZ and NDNAZ

Description: The authors have studied the mechanism and detailed reaction kinetics of the thermal decomposition of 1,3,3-trinitroazetidine (TNAZ), and separately, its key decomposition intermediate, 1-nitroso-3,3-dinitroacetidine (NDNAZ), using a simultaneous thermogravimetric modulated beam mass spectrometer (STMBMS). These decompositions were conducted in a sealed alumina cell with a 2.5 {micro}m orifice, at varying temperatures and at a range of isothermal temperatures (at 10 C intervals from 120--160 C for NDNAZ and 160--210 C for TNAZ). The gaseous products have been identified and their rates of formation have been measured as a function of time, temperature, and pressure. This system is complex, with TNAZ decomposing by four separate routes, one of which leads to NDNAZ, which itself decomposes by at least two distinct routes.
Date: December 31, 1998
Creator: Anderson, K.; Homsy, J.; Behrens, R. & Bulusu, S.
Partner: UNT Libraries Government Documents Department