Purification of Hexabenzylhexaazaisowurtzitane

Hexabenzylhexaazaisowurtzitane (HBIW) is produced by a condensation reaction of benzylamine with glyoxal in suitable organic solvents in the presence of protonic acid catalysts. Impurities have to be removed prior to the subsequent stages of the synthesis of CL-20. The effectiveness of HBIW purification by recrystallization from a variety of solvents has been studied here. This method was compared with a novel approach suggested for HBIW purification that consists of prolonged heating of the crude product in boiling methanol. This new purification method allows the product to be prepared in satisfactory purity, it is simple and easily performed on a large-scale

Application of DSC and DTA Methods for Estimation of Safety Parameters of High Energetic Materials Such as Dinitroamine Ammonium Salt

Metody DSC i DTA pozwalają przy zastosowaniu równań empirycznych wykorzystujących dane kinetyczne na zaklasyfikowanie substancji do potencjalnie niebezpiecznych lub bezpiecznych. Wykorzystanie reguły 100 oraz temperatury ADT24 pozwala określić maksymalną bezpieczną temperaturę prowadzenia procesów technologicznych. Materiały wysokoenergetyczne z punktu widzenia bezpieczeństwa można zaklasyfikować przy użyciu: potencjału Koenena, indeksu termicznego ryzyka, indeksu zagrozenia reakcją, indeksu chwilowej gęstości mocy oraz parametru zagrożenia wybuchem. Wykonano analizy DSC i DTA soli amonowej dinitroaminy (ADN), wyznaczono parametry kinetyczne i na ich podstawie oszacowano bezpieczeństwo użytkowania i warunki bezpieczne prowadzenia procesów technologicznych. Maksymalna, bezpieczna temperatura prowadzenia procesów technologicznych z wykorzystaniem ADN-u jest niższa od 351 K. Sól amonowa dinitroaminy została zaklasyfikowana do grupy związków niestabilnych, potencjalnie niebezpiecznych, zdolnych do wybuchu, do grupy związków wysokiego ryzyka. Uzyskane wysokie parametry indeksów niebezpieczeństwa wskazują na to, że ADN wymaga szczególnej ostrożności w procesach technologicznych oraz przy wykorzystywaniu w formach użytkowych.DSC and DTA methods, combined with empirical equations based on kinetic data, allow one to classify a substance as potentially harmful or safe. Utilizing the "100 degree rule" and ADT24 temperature enables one to determine the highest safe temperature at which a technological process can be carried out. High energetic materials can be classified from the safety standpoint by using: Koenen potential, Thermal risk index, Reaction hazard index, Instantaneous Power Density and Explosion Potential. DSC and DTA analysis of dinitroamine salt (ADN) were performed. On the basis of the results usage safety and safe conditions of technological process were estimated. The highest safe temperature of the technological process with using ADN is 351 K. ADN was classified to the group of the unstable compounds, potentially dangerous, able to explode and to the group of the high risk substances. The obtained high values of safety parameters indicate that ADN requires great caution when it is used in operational moulds and in technological processes

Safety of Ammonium Dinitramide Synthesis vs. Size of a Commercial Production Scale

Ammonium dinitramide (ADN) is an ecological oxidizer suggested as a substitute for ammonium chlorate(VII) in solid rocket fuels. Three ADN synthetic methods were studied in order to estimate process safety under increased production scale, viz.: from ammonia (Method I), from urea (Method II), or from potassium sulfamate (Method III). The intermediates formed in these processes were identified and their thermal stability was examined. DSC analysis showed that the intermediates in Method II are unstable, they readily decompose and pose an explosion hazard. The intermediate in Method III is more thermally stable and less hazardous than its counterparts in Method II. The most suitable methods for large-scale processes are Methods I and III. The preferred method for commercial ADN production, in terms of safety, is Method III

Pyrotechnic Torch for Burning of the Plastic Mine Casings

W badaniach testowano palnik pirotechniczny zaprojektowany i wykonany w Zakładzie Materiałów Wysokoenergetycznych Politechniki Warszawskiej, który może służyć do przepalania plastikowych obudów min. Palnik ten składał się z tekturowo-gipsowej obudowy, w której umieszczony był ładunek pirotechniczny. Ładunek pirotechniczny składał się z masy termitowej oraz masy generującej tlen. Skonstruowany palnik pirotechniczny w oparciu o zmodyfikowane masy termitowe przepalał w ciągu kilku sekund plastikowe płytki o grubości 3 mm, także te, które były umieszczone pod 5-centymetrową warstwą piasku. Najlepszy efekt uzyskano dla masy termitowej o składzie: Fe2O3 (69%); Al (23%); Viton A (8%). Zastosowanie dodatkowych ładunków generujących tlen pozwoliło efektywniej przepalać plastikowe płytki.Pyrotechnic torch designed and constructed in Division of High Energetic Materials, Warsaw University of Technology, was tested in these studies. It can be used to burning the plastic mine casings. This torch consisted of a cardboard - plaster casing in which a pyrotechnic charge was placed. The charge was composed of a termite and an oxygen-generating mass. The torch based on a modified termite mass burned in a few seconds the plastic plates with a thickness of 3 mm, even those that were placed under 5 cm sand layer. The best effect was achieved for the following mass composition: Fe2O3 (69%); Al (23%); Viton A (8%). Application of additional oxygengenerating charges allowed for more efficient burning of the plastic plate

Ecological rocket propellants with low trail level

Szybko spalające się i wysoko wydajne paliwa rakietowe najczęściej są oparte o dobrze znany utleniacz nadchloran amonu i aluminium. Zasadniczą wadą tego utleniacza jest powstawanie łatwo wykrywalnej smugi i wydzielanie dużych ilości chlorowodoru. Wykrycie trajektorii lotu pozwala z łatwością określić położenie miejsca startu rakiety. Wydzielanie dużych ilości chlorowodoru wpływa niszcząco na środowisko. Podejmowane są badania w kierunku uformowania paliwa, w ktorym utleniacz nie posiadał wymienionych wad. W Zakładzie Materiałów Wysokoenergetycznych Politechniki Warszawskiej podjęto prace mające na celu opracowania paliw niezawierających nadchloranu amonu lub w ilościach na tyle małych, aby smuga powstała w wyniku pracy silnika nie była wykrywalna na obecnym poziomie technicznego zaawansowania. Prowadzone są systematyczne prace nad otrzymaniem i zastosowaniem soli amonowej dinitroaminy jako utleniacza i lepiszcz polimerowych zawierających grupy eksplozoforowe. Wymienione składniki posiadają duże potencjalne możliwości do formowania paliw do rakiet superszybkich.The ammonium perchlorate and aluminium is a well known oxidiser commonly used for highly efficient and fast burning rocket propellants. The main disadvantage of this propellant is the easy detectable trace and great emission of hydrogen chloride what in consequence leads to detection of missile’s trajectory and its launching pad. Moreover the emission of hydrogen chloride has a very negative impact into the environment. The research works are carried out to develop a propellant without these drawbacks and in the Section of High Energetic Materials at the Warsaw’s University of Technology they focus on propellants without ammonium perchlorate or with so low amount of it to prevent the detection of a rocket motor trail by contemporary technical means. Systematic works are under way on the receiving and using of dinitroaminum ammonium salt as a oxidiser and binding polymers with explozophorous groups. The components listed above have great potential possibilities to become propellants of super fast rockets

Palladium Catalyst in the HBIW Hydrodebenzylation Reaction. Deactivation and Spent Catalyst Regeneration Procedure

The polycyclic nitramine 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12- hexaazaisowurtzitane (HNIW, CL-20) is synthesized via hydrodebenzylation of 2,4,6,8,10,12-hexabenzyl-2,4,6,8,10,12-hexaazaisowurtzitane (HBIW) over a palladium-based catalyst. This process is the key step in the synthesis of CL-20, a compound with unique energetic and explosive characteristics. The use of CL-20 is restricted at present by the high cost of the hydrodebenzylation process, during which the palladium-based catalyst becomes rapidly deactivated. The catalyst deactivation has now been shown to consist of deposition of the reaction products on the carbon support with simultaneous blocking of the active centers by these products. The HBIW decomposition products can permanently combine with palladium, thereby reducing the number of the active centers on the catalyst. Other byproducts clog the pores of the active carbon and reduce both the surface area of the active carbon and the pore volume. The reaction yield is also reduced by aggregation of palladium particles. A palladium catalyst regeneration procedure which has now been developed, consists of heating the catalyst for a specific time at 350 °C in a nitrogen and water vapour stream, and allows partial recovery of the activity of the palladium catalyst in a subsequent HBIW hydrodebenzylation reaction. The specific area and overall pore volume of the regenerated catalyst are also enhanced. The yield from the HBIW hydrodebenzylation reaction using the regenerated catalyst was ca. 42%

Application and properties of aluminum in primary and secondary explosives

Aluminum is an easily available and cheap material, which is widely used in military and civil industries, e.g. in space technology, explosion welding, mining, production of oil and natural gas, manufacture of airbags. Primary and secondary explosives containing aluminum are described in this part of the work. Aluminum is added to high explosives of different shapes and sizes. These parameters influence inter alia detonation velocity (D), explosion heat, detonation pressure, pressure impulse and thermal stability. Detonation parameters of high explosive (HE) containing aluminum have been determined for binary systems consisting of high explosive or oxidizer and aluminum, plastic bonded explosives (PBX), melt cast explosives, thermobaric explosives (TBX), ammonium nitrate fuel oil (ANFO). Aluminum causes different effects on detonation velocity and explosion heat depending on the type of high explosive in binary systems. The dependence of the aluminum content in a mixture with ammonium nitrate with detonation velocity increased for an aluminum range from 0 to 10%, changed little between 10 and 16% of aluminum added and decreased from 16 to 40% of the aluminum content. For an aluminum content higher than 40%, the detonation process was not observed. The performance of explosives can be determined by the shock wave intensity. An increase in the pressure impulse made Al particle react with gaseous products and the air behind the front of detonation wave. The addition of aluminum also influences the thermal stability of high explosive materials

Właściwości reologiczne i termiczne mieszanin polibutadienu z końcowymi grupami hydroksylowymi oraz plastyfikatora

Mixtures of hydroxyl-terminated polybutadiene (HTPB) and dioctyladipate (DOA) as a plasticizer, which after crosslinking are applied as binders in heterogeneous propellants, were studied.The influence of mixture composition on rheological and thermal properties, important from technological and utility viewpoint were specified. The temperature dependence of prepared mixtures viscosity were studied. Systems were subjected to crosslinking and values of pot life (tpl) were determined. It was stated that tpl rose with increasing plasticizer content. Differential scanning calorimetry and thermogravimetry techniques were used toanalyze thermal stability of mixtures. It was concluded that applied component scould not decompose in the temperature range of 290–350 K and studied mixtures did not cause the hazard of thermal explosion.Zbadano mieszaniny polibutadienu z końcowymi grupami hydroksylowymi (HTPB) oraz adypinianu dioktylu (DOA) jako plastyfikatora, które po usieciowaniu wykorzystywane są jako lepiszcza w heterogenicznych paliwach rakietowych. Określono wpływ składu na reologiczne i termiczne właściwości mieszanin, mające istotne znaczenie z technologicznego i użytkowego punktu widzenia. Zbadano zależność lepkości przygotowanych mieszanin od temperatury. Badane układy poddano sieciowaniu i wyznaczono wartości czasu życia technologicznego (tpl).Wykazano, że tpl wydłuża się ze wzrostem zawartości plastyfikatora. Stabilność termiczną mieszanin zbadano za pomocą różnicowej kalorymetrii skaningowej i termograwimetrii. Stwierdzono, że zastosowane składniki nie ulegają rozkładowi w temperaturze od 290 do 350 K i badane mieszaniny nie powodują zagrożenia eksplozją

Application and properties of aluminum in primary and secondary explosives

Aluminum is an easily available and cheap material, which is widely used in military and civil industries, e.g. in space technology, explosion welding, mining, production of oil and natural gas, manufacture of airbags. Primary and secondary explosives containing aluminum are described in this part of the work. Aluminum is added to high explosives of different shapes and sizes. These parameters influence inter alia detonation velocity (D), explosion heat, detonation pressure, pressure impulse and thermal stability. Detonation parameters of high explosive (HE) containing aluminum have been determined for binary systems consisting of high explosive or oxidizer and aluminum, plastic bonded explosives (PBX), melt cast explosives, thermobaric explosives (TBX), ammonium nitrate fuel oil (ANFO). Aluminum causes different effects on detonation velocity and explosion heat depending on the type of high explosive in binary systems. The dependence of the aluminum content in a mixture with ammonium nitrate with detonation velocity increased for an aluminum range from 0 to 10%, changed little between 10 and 16% of aluminum added and decreased from 16 to 40% of the aluminum content. For an aluminum content higher than 40%, the detonation process was not observed. The performance of explosives can be determined by the shock wave intensity. An increase in the pressure impulse made Al particle react with gaseous products and the air behind the front of detonation wave. The addition of aluminum also influences the thermal stability of high explosive materials