Metallic Crystalline Oxidizers

Flaws in the anodic oxide film are usually the primary source of electronic conduction. These flaws are either stmctural or chemical in nature. The stmctural flaws include thermal crystalline oxide, nitrides, carbides, inclusion of foreign phases, and oxide recrystaUi2ed by an appHed electric field. The roughness of the tantalum surface affects the electronic conduction and should be classified as a stmctural flaw (58) the correlation between electronic conduction and roughness, however, was not observed (59). Chemical impurities arise from metals alloyed with the tantalum, inclusions in the oxide of material from the formation electrolyte, and impurities on the surface of the tantalum substrate that are incorporated in the oxide during formation. 

Cobalt(II) chloride hexahydrate [7791-13-1], C0CI2 6H20 is a deep red monoclinic crystalline material that deflquesces. It is prepared by reaction of hydrochloric acid with the metal, simple oxide, mixed valence oxides, carbonate, or hydroxide. A high purity cobalt chloride has also been prepared electrolyticaHy (4). The chloride is very soluble in water and alcohols. The dehydration of the hexahydrate occurs stepwise ... 

Conversely, if the pressure of O2 above a crystalline oxide is decreased below the equilibrium value appropriate for the stoichiometric composition, oxygen boils out of the lattice leaving supernumerary metal atoms or lower-valent ions in interstitial positions, e.g. ... 

There have been many instances of examination of the effect of additive product on the initiation of nucleation and growth processes. In early work on the dehydration of crystalline hydrates, reaction was initiated on all surfaces by rubbing with the anhydrous material [400]. An interesting application of the opposite effect was used by Franklin and Flanagan [62] to inhibit reaction at selected crystal faces of uranyl nitrate hexa-hydrate by coating with an impermeable material. In other reactions, the product does not so readily interact with reactant surfaces, e.g. nickel metal (having oxidized boundaries) does not detectably catalyze the decomposition of nickel formate [222],... 

Ammonium dinitramide (ADN) is a crystalline oxidizer with the formula NH4N(N02)2, that is, it is composed ofionicaUy bonded ammonium cations, NH4, and dinitramide anions, N(N02)2- Though ADN is crystalline and has a high oxygen content, similar to AP and KP, it has no halogen or metal atoms within its structure. ADN is used as an oxidizer in smokeless composite propellants, similar to AN and HNF. It melts at about 364 K, accompanied by the latent heat of fusion. 

The chosen combinations of these chemicals and metals depend on the requirements of the specific application. Gasless combustion prevents pressure increase in a closed combustion chamber. Some combinations of metal particles and metal oxide particles or of metal particles and crystalline oxidizers are chosen as chemical ingredients of gasless pyrolants. On the other hand, hydrocarbon polymers are used to obtain combustion products of low molecular mass, such as H2O, CO, CO2, and H2. High pressure is thus obtained by the combustion of hydrocarbon polymers. Table 10.6 shows the chemical ingredients used to formulate various types of pyrolants. 

Vinylidene fluoride hexafluoropropene polymer (Vt) Metal particles + crystalline oxidizers... 

Table 10.7 shows the physicochemical properties of the crystalHne materials used as oxidizers. Potassium and sodium are combined with nitrate or perchlorate to form stabilized crystalline oxidizers. Metal oxides are formed as their combustion products. On the other hand, ammonium ions are combined with nitrate or perchlorate to form stabilized crystalline oxidizers such as NH4NO3 and NH4CIO4 without metal atoms. When these oxidizers are decomposed, no solid products are formed. As discussed in Section 10.1.1, for the oxidizers used for propulsion, such as in propellants for rockets and guns, the molecular mass of the combustion products needs to be as low as possible. 

Hydrocarbon polymers (HCP) are used not only as fuel components but also as binders of crystalline oxidizers and metal powders in the formulation of pyrolants, similar to composite propellants and plastic-bonded explosives. There are many types of HCP, the physicochemical properties of which are dependent on their molecular structures. The viscosity, molecular mass, and functionality of the poly-... 

Real ignition processes are rather complicated and heterogeneous because igniters contain various types of metal particles and crystalline oxidizer particles. The metal particles are oxidized by the gaseous oxidizer fragments and produce high-... 

The key to the successful application of high performance, pourable nitrocellulose plastisols lies in a reasonably priced, high quality source of fine-particle, at least partially colloided, spheroidal nitrocellulose. Here we are speaking of particles much finer than the well-known ball powder, produced by the Olin Mathieson Chemical Co. for small arms for over 30 years (7). Actually, particles on the order of 5-50/x diameter appear to be required to assure a reasonable continuum of uniformly plasticized nitrocellulose binder in a propellant containing 45% or more of combined crystalline oxidizer and powdered metal fuel. Such a continuum of binder is necessary to assure acceptable mechanical properties and reproducible burning characteristics of the finished propellant. Preincorporation of a certain content of the water-insoluble solids within the nitrocellulose microspheres is an effective means of helping to assure this continuum of binder and alleviates the requirements for extremely small ball size. The use of a total of 45% or more of crystalline oxidizer and (generally) metal fuel is essential if the propellant is to be competitive with other modern propellants now in service. 

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