CA2157059A1 - Environmentally neutral reformulation of military explosives and propellants - Google Patents

Abstract

Polymer and wax bound military explosives and propellants are removed from a rocket casing, warhead or the like. Included with the explosive or propellant are materials added to improve brisance, resiliency, etc. of the explosive material and adventitious materials such as glue. The polymer and wax bound military explosive is oxygen balanced with an oxidizing agent in the form that it is removed from the casing, etc. and provided as an explosive, for example, for use as a powerful blasting agent.

Description

7 ~
O. rlhl~ ~ALLY NEUTRAL KhrU~crlU~ATION OF
MILITARY EXPLOSIVES AND PROPELLANTS
Backgrol]nd of the Invention 1. Field of the Invention The present invention relates to reformulating polymer or wax bound military explosives and propellants into a useful form.

2. Brief Description of the Prior Art A number of explosive ~ _ ~c used in military explosives and propellants possess properties that are not desired in military warheads and in other military applications. To improve their properties, highly brisant explosives are often embedded in or coated with a curable plastic material or with a 15 wax. When the explosive or propellant i5 coated with a wax the process is called phlegmati~ation. Other materials such as rubber can be added to impart specified r~-hAnil-~l properties like elasticity. The term plastic includes gelatinized liquid nitrocompounds of plasticine-like consistency.
Waste military explosives and propellants are a growing ~icp~c~l problem as a result of world demilitarization. In the past, they have been ~ rQc~ of by deep sea burial, open burning, open detonation or incineration.
For example, rocket motors have been dumped into the ocean off the continental shelf where the high specific gravity of the solid propellant causes the motors to sink rapidly. The rate at which the propellant leaches out under oceanic conditions is 30 unknown, as are the likely products of hydrolysis. The environmental impact of deep sea burial and the cumulative effect of dumping large tonnages of explosives and propellants is theref ore unknown .

2~ ~7~9 ' In open burning, loose explosive or propellant materials or a complete rocket motor, for example, i8 placed on the ground or in a tray or pit which may be lined with a concrete pad. An explosive train leading to the material i5 used to initiate 5 burning. The burning explosive or propellant creates a large updraft dispersing a plume of combustion products into the ai ~ 'ere.
The combustion products of open detonation are similar to 10 those produced during open burning. Incineration is cleaner but requires special incinerators and safety considerations since explosives and propellants can burn with intense heat and some can explode. Emissions of HCl, N0x and HCN and particulates such as aluminum oxides, requires expensive air pollution control devices.
15 The combustion products may be highly corrosive, thus affecting capital and maintenance costs.
other ~1;CPOCA1 methods for destroying explosives or propellants include converting them into a less noxious form 20 through chemical conversion, biodegradation, electrorhPm;~Al oxidation, supercritical oxidation and so forth. All of these tl;RrOSAl methods involve high investment costs and/or may result in the same or different regulatory or environmental problems as deep sea burial, open burning, etc. In addition, destruction of the 25 explosive or propellant (including conversion into a less noxious form for ~ PO~A1 ) is contrary to the Resource Conservation and Recovery Act (RCRA).
Reclamation of the explosives or propellants as opposed 30 to destroying them is in compliance with RCRA but reclamation requires the identification of a solvent which will dissolve the explosive or propellant out of the materials that are added to improve its properties. When the explosive or propellant is polymer bound, reclamation may not be possible when the polymer is 35 too highly cross-linked.

2ls7as~
.
One such reclamation method uses waterjets to wash out the explosive or propellant from the warhead or the like. The washed out material is passed over a vibrating screen which separates solids and liquids. Solid materials are placed in 5 containers such as f iber drums and ~ pos~ of by open burning .
~he solvent is recirculated until the re~l A;- ' explosive or propellant reaches a level at which the solvent is discharged into an open evapuL ation basin or treated in some other way ( i . e ., crystallization, etc.). In addition to the r~clAi~^1 material, the 10 above reclamation process results an explosive-contaminated binder and an explosive-contaminated solvent, giving rise to a host of other ~l;cposAl problems. Moreover, there i6 no guarantee that the r~c~ A;r?d material will requalify to meet military specifications and in some case6 it has no other legitimate customer.
There is a need for a process where the military explosive or propellant could be used without reclaiming it from the materials added to improve its properties. One proposed process uses military explosives or propellants as an extender in 20 commercial explosives. In an oxygen-balanced explosive, the amount of oxygen present is ~ust sufficient to oxidize all carbon to Co2 and all ~IydL-~y~ll to H20 and any metals to their oxides with a minimum production of toxic NOx, Co and HCN. If there is insufficient oxygen to do this, the oxygen balance is negative.
25 ExcessiVe amounts of oxygen should be avoided because the amount of energy liberated is greatest at a slightly negative oxygen balance with explosives, for example, containing only C, H, N and O. Most military explosives and propellants, however, are oxygen deficient so that the full energetic potential of the material is not 30 achieved when a military explosive or propellant is used as an extender. In addition, the mixture gives rise to toxic fumes such as Cû, NOx and HCN when it is detonated and any chlorine in the explosiVe or propellant may end up in the form of chlorinated dibenzo~ Y;nc or dibenzofurans.

. ` 2~70~9 SummarY of the Invçntion In view of the above, it is an object of the present invention to provide an environmentally neutral process for reformulating military explosives and propellants into a useful 5 form for which there is a ready market. It is another object to provide a method for reformulating military polymer bound explosives and solid rocket propellants in a form which does not waste the energetic potential of the explosive or propellant and which minimizes the production of toxic fumes. Other objects and 10 features of the invention will be in part apparent and in part pointed out hereinafter.
A process for reformulating explosives and propellants in accordance with the present invention and the products thereof 15 includes the steps of selecting an oxygen def icient polymer or wax bound military explosive or propellant and detPnmin;n~ its empirical formula. An oxidizing agent is then selected and the amount of the oxidizing agent necessary to oxygen balance the explosive is determined. That amount of oxidizing agent is added 20 to the explosive whereby the energetic potential of the explosive is maximized and the production of toxic fumes minimized when the reformulated explosive is detonated. Gas and heat modifying agents such as urea may be added to modify the explosive power. Mixtures of eYplosives and propellants reformulated in accordance with the 25 present invention may be used to modify the power or the sensitivity of the reformulated mixture to initiation.
The invention summarized above comprises the processes and products hereinafter described, the scope of the invention 30 being indicated in the subjoined claims.
Det~ i 1 ed Description of the Invention Explosives are materials that, when properly initiated, undergo very rapid self-propagating decomposition or reaction of 35 ingredients, with the consequent formation of more stable materials 21~7~59 (mostly gaseous) and the liberation of considerable heat. The products of explosion occupy a much greater volume than that of the explosive material. Fur~h~ e, the liberated heat expands the gaseous products, thereby developing a high pressure that can be 5 applied to doing work. The work done (or energy liberated~ depends primarily on the amount of heat given off during the explosion and quantity of gases generated.
Explosives may consist of a single explosive chemical 10 compound, a formulation of such compounds, or a formulation of one or more explosive compounds with nonexplosive material. Each explosive product has unique and important individual characteristics that determine its potential usefulness to specific applications. These include sensitivity, strength, power, 15 brisance, stability, hygroscopicity, volatility, reactivity and toxicity .
Industrial Ex~losives Industrial explosives compose a large group of explosive 20 compositions designed to perform mechanical work such as quarrying, ore dislodgement, ditching and excavation with a low expenditure of time and money. They are categorized as either high explosives or blasting agents; the principal distinction being their sensitivity to initiation. High explosives are cap-sensitive (i.e., can be 25 detonated with a No. 8 blasting cap), but blasting agents cannot, and therefore require a primer for initiation.
Industrial high explosives include dynamites, cap-sensitive water gels and emulsion slurries, cast primers and 30 boosters. "Permissible" explosives are grades of high explosives tested by the U. 5 . Bureau of Mines and approved by the Mine Safety and E~ealth Administration for use, in a prescribed manner, in Und~I~L-JUlld coal mines where the presence of flammable gases and dust makes other explosives hazardous.

0~9 Blasting agents are insensitive to commercial detonators or blasting caps. Most blasting agents are essentially mixtures of ammonium nitrate (AN) plus a fuel. Free-flowing mixtures of AN
(usually in the form of low-density prills) and fuel oil called 5 ANF0 and bulk-mixed water gels and emulsion slurries are used extensively. AN blasting agents dominate the industrial market.
MilitarY Exl~losives Military explosives include propellants and high 10 explosives. Propellants are explosive materials formulated in a manner permitting the generation of large volumes of hot gas at highly controlled predetPrm;nPd rates. The major use of propellants is for launching projectiles from guns, rockets and missile systems. There are composite propellants, double-base 15 propellants and composite modified double-base propellants.
Composite propellants consist primarily of a binder material such as polybutadiene and a finely ground solid fuel (such as aluminum) and an oxidizer (such a6 ammonium perchlorate).
20 Double-base propellants consist primarily of stabilized nitrocellulose (NC) and nitroglycerine (NG). Composite modified double-base propellants use a double-base propellant for a binder, with the solid f illers commonly found in composite propellants .
A number of binder materials are used in the manufacture of composite propellants. Among these are asphalt, polysulfides, polystyrene-polyester and polyurethanes. Propellants of recent development are prP~ ;n~ntly products of the polybutadiene family such as carboxy-terminated polybutadiene, hydroxy-terminated 3 0 polybutadiene and carboxy-terminated polybutadiene-acrylonitrile .
In composite propellants, the binder also serves as a fuel so that the addition of a separate fuel is not always necessary. While the addition of metallic fuels to the propellant significantly increase6 the energy of the propellant, it also produces primary 35 ~moke in the form ~f metal oxides. The most commonly added metal 2~7059 is aluminum, but magnesium, beryllium and other metals have been tried. The commonly used r~ l; 7Pr (which makes up the preponderance of the weight of the propellant) is ammonium perchlorate. other oxidizers which have been used include ammonium 5 nitrate, potas6ium nitrate and potassium perchlorate.
Double-base propellants contain nitrocellulose of various nitration levels, nitroglycerine and a stabilizer. Various inert plasticizers are added to modify either the flame temperature or 10 the physical properties of the propellant.
Composite modified double-base propellants classically have contained nitrocellulose, nitroglycerine, aluminum, ammonium perchlorate and the explosive 1,3,5,7-tetranitro-1,3,5,7-15 tetraazacyclooctane (HMX) which serves as a fuel, energy source andgas-producing additive.
Military high explosives include binary 2, 4, 6-trinitrotoluene (TNT)-based formulations, TNT-based aluminized 20 explosives and plastic-bonded explosives. Binary TNT-based formulations are made by adding a higher melting explosive ,_ ^nt to liquefied TNT. The most widely used binary explosive, Composition B, is made by adding 1,3,5-trinitro-hexahydro-s-triazine (RDX) to TNT. Other ~- IFuull ls may be added to decrease 25 sensitivity and to increase the mechanical strength of the cast.
Composition B ~or slightly modified formulations) is used in loading pro~ectile and warheads and as the starting material for making ~ m;n; 7ed explosives. other binary military explosive mixtures include the octols (HMX + TNT), cyclotols (RDX + TNT), 30 pentolites (pentaerythritol tetranitrate ~PETN) + TNT), tetrytols (tetryl + TNT), amatols (ammonium nitrate + TNT) and picratols (ammonium picrate + TNT).
TNT-based aluminized explosives are made by the addition 35 of screened, finely divided aluminum particles to a melted, binary 2i~7~59 TNT-based slurry, such as Composition 8 (RDX + TNT). A
desensitizer and calcium chloride may be added to the mixture. The incorporation of All7m;ml7~ increases the bla5t effect of explosives.
Typical TNT-based all~ ;n;~d explosives are the tritonals (TNT +
5 Al), ; 1~: (TNT + AN + Al) and the torpexes and IBXs (TNT + RDX
+ Al).
If an explosive ~ 7nr7 is too sensitive in its pure crystalline state to permit press loading, or it lacks the required 10 mechanical propertie5 in its compressed state for subsequent use, it may be coated with polymeric materials or waxes to form molding powders. These molding powders are known as plastic-bonded explosives tPBX). Thorough and uniform coating of the explosive crystals is required for desensitization. They are generally 15 prepared with 80-95% RDX or .~Y~.
Reformulation of Pro~ellant5 and Hi~h '~Ynlosives As discussed above, the di5posal of military explosives and propellants is a growing problem. The Resources Conservation 2 0 and Recovery Act (RCRA) places a premium on waste management p_o~r al~.~ that recover and use portions (preferably all) of a waste stream. Processes which do not meet the RCP~A criteria are not favored by the U. S. Environmental Protection Agency (EPA) .
The avoidance of toxic fumes or fume5 that can give a secondary explo5ion is not of high importance in the case of military explosives and propellants so that most are oxygen deficient. one reason behind this is that the power benefit of having an oxygen balance may not outweigh the added energy 3 0 requirement of getting the charge to a target . Sensitivity and formulation problems may be other reasons since, inter alia, military propellants and high explosives must be transported safely and stored in rP~';n~s~ sometimes for long periods of time.

2~57~59 .
In accordance with the present invention, an oxygen deficient military explosive or propellant is selected for reformulation as a bla6ting agent or the like. The explosive or propellant is cut, ground or otherwise divided into small particles 5 for example with a high pressure waterjet. Suitable materials for reformulation include but are not limited to oxygen deficient polymer bound explosives, oxygen deficient polymer and wax bound propellants, oxygen deficient nitrocellulose bound propellants and mixtures thereof.
Some examples of polymer bound explosives tPBX) not treated in the examples, include, PBX-9010 (90% RDX, 10% Kel-F), PBX-9011 t90% HMX, 10% estane), PBX-9404-03 (94% HMX, 3% NC and 3%
chloroethylphosphate), PBX-9205 (92% RDX, 6% polystyrene, 2%
15 ethylhexylphthalate), PBX-9501 (92% HMX, 2.5% dinil Lu~Luuy acrylate-fumarate and 2.5% estane), PBXN-l (68% RDX, 20% aluminum, 12% nylon) and PBXN-2 (95% HMX and 5% nylon). All of these can be pressed to fill a desired volume. The explosive PBXN-201 (83% RDX, 12% Viton and 5% Teflon) can be extruded while the explosiveiPBXN-20 102 (59% E~MX, 23% aluminum and 18% Laminac) can be cast. Theexplosive PBXC-303 (80% PETN and 20% Sylgard 183) can be injection molded. The explosives, Composition C (88.3% RDX and 11.7% non-explosive plasticizer), Composition C-2 (80% RDX and 20% explosive plasticizer), Composition C-3 (78% RDX and 22% explosive 25 plasticizer) and Composition C-4 (90% RDX and 10% polyisobutylene) are some other examples of military explosives generally classified as plastic explosives.
Alternatively pure explosive compounds may be 30 phlegmatized by adding a phlegmatizer, particularly wax. This is specially true with the very brisant explosives, RDX, E~MX and PETN.
The addition of a phlegmatizer has the benef it of permitting the safe compression of the resulting mixture to maximize density and hence more closely approach the maximum power per unit volume 35 available fro~ the explosive. If the explosives were compressed ~t ~7~59 without the presence of a phlegmatizing agent, there would be considerable danger of initiation a5 a consequence of the friction sensitivity of these materials. The added wax serves the dual role of lubricant and binder. Some examples include Compositions A, A-2 5 and A-3, which are based on RDX and differ by the various kinds of wax they contain. Compositions B and B-2 are castable mixtures of RDX and TNT ln the proportion 60:40 and some of these are also formulated with waxes.
The empirical formula of the selected explosive or propellant is de~orminod and its oXXgen deficiency calculated.
The empirical formula includes the explosive material and any materials added to improve or alter its properties as well as any adventitious organic materials (such as glue which is recovered 15 with the explosive or propellant from a rocket casing, warhead, etc . ) . An r)~ ; 7 i n~ agent is selected, its empirical f ormula detorm;nocl and the amount of oxidizing agent needed to bring the explosive or propellant to near or substantial oxygen balance calculated .
Suitable oxidizing agents include salts of oxy-acids such as nitric acid, chloric acid, bromic acid and perchloric acid. The most common salts are those derived from lithium, sodium, potassium, magnesium and calcium. In the case of perchloric acid 25 and nitric acid, the related ammonium salts can also be employed.
On the basis of cost, ammonium nitrate is preferred but ~ m perchlorate, calcium nitrate, calcium nitrate tetrahydrate, calcium perchlorate, lithium nitrate, lithium perchlorate, magnesium nitrate, r~~nes;l]m perchlorate, potassium nitrate, potassium 30 perchlorate, sodium nitrate, sodium perchlorate and so forth can also be used. The oxidizing agent is preferably provided in finely divided form, for example, as small prills, fine crystals or powders of 8 mesh or f iner .
.

1- 2i~7~59 The oxidizing agent is mixed with the explosive and the mixture provided in an acceptable form such as a flowable mixture or as a gel or slurry. In some cases, a gas forming material such as urea may be added to increase the volume of gases produced and 5 work obtained when the oxygen b ~ ncPd mixture is detonated.
Other materials such as ammonium oxalate, oxamic acid, oxamide, methyl urea, urea-formaldehyde resins, nitroguanidine, nitrourea, urea nitrate and nitric acid may be added in place of or in conjunction with urea for the purpose of modifying the explosive 10 power by regulating the amount of heat and gas liberated. Mixtures of reformulated military explosives or propellants ~such as PBXN-4 oxygen b~l;9nc~d with AN and PBXN-4 oxygen b~l~ncPd with sodium perchlorate (SP) ) may also be used to modify the explosive power by regulating the amount of heat and gas liberated and/or modifying 15 the sensitivity of the reformulated explosive to initiation.
In general, most military propellants and high explosives reformulated in accordance with the present invention liberate more energy than commonly used AN blasting agents on a comparable weight 20 basis. This makes possible the use of smaller holes and expanded blast hole patterns thus reducing drilling costs (on a per-yard-of-rock basis), leading to a ready market for the reformulated material .
The following examples illustrate the invention.
il:k le 1 The theoretical explosive potential of several military explosives were screened based on their chemical composition and 30 density (rho in g/cc) using a Hess Law treatment of the heat of explosion (Q in cal/g mole) and an estimation of the detonation pressure (PD in Kbar) and detonation velocity (VD in km/sec) employing the method of Kamlett and Jacobs (M. J. Kamlett and S . J.
Jacobs, J. Chem, Phvs., 48, 23 (1968) ) . The power factor (PF) was 35 determined by multiplying VD by PD and by 10-Z and normalized ~1~7~59 .
against the power ~actor ~or ANF0 ~NPF)- ANF0 is an industrial explosive containing 94 . 596 by weight ammonium nitrate and 5 . 5% by weight fuel oil. The results for PBXN-101, PBXN-105, PBXN-106, PBXN-3, PBXN-4, PBXN-5, PBXN-6 and AFX-108 are reported in Table I
5 below.
TABLE I
Formulation 1~D YD O Rho PF NPF
10PBXN-101 328 8.67 654 1.76 2.84 0.23 PBXN-105 280 7.81 1769 2.01 2.19 0.24 PBXN-106 286 8 .17 1136 1. 69 2 . 34 0 . 26 PBXN--3 260 7.86 740 1.69 2.04 0.28 PBXN-4 206 7 459 1. 7 1. 44 0 . 33 20PBXN--5 398 9.25 1138 1.95 3.68 0.19 PBXN--6 340 8 . 75 1144 1. 82 2 . 98 0 . 22 AFX-108 259 7 . 77 1119 1. 70 2 . 01 0 . 26 PBXN-101 is 82% by weight H~X and 18% by weight polystyrene and has an elemental composition on a lOOg basis of approximatelY C2.sz8H3.628NZ.199IZ.199-PBXN-105 is approximately 26% by weight aluminum, 50% by weight ammonium perchlorate, 6.5% by weight bis-(2,2-diniLL~,~ru~yl)acetal (bis-DNPA), 6.5~6 by weight bis-(2,2-diniL~ JLC)~l') formal (bix-DNPF), 396 by weight PEG, 7% by weight RDX
and 1% by weight TDI. PEG is polyethylene glycol and TDI is 21~70~9 toluene diisocyanate. PBXN-105 has an elemental composition on a O0g basis of approximatelY C0 62H2.73Ho ssz.30Al0.96Cl0.42 PBXN-106 is 9 . 3% by weight bis-DNPA, 9 . 3% by weight bis-5 DNPF and 75% by weight RDX with the balance being a polyurethanebinder formed from TDI, PEG and 1,l-tris(~lydLuxy tllyl)propane and has an elemental composition on a lOOg basis of approximately PBXN-3 is approximately 86~6 by weight HMX and 14% by weight nylon ( i . e ., ZYTELtm or ELVAMIDEtm) . It has an elemental composition on a lOOg basis of approximately C2 ooH3 68N2 4s2 4s PBXN-4 is 54% by weight DATB and 6% by weight nylon 15 (i . e., ZYTELtm) and has an elemental composition on a lOOg basis of approximately C2 64H3 29Nl 992.37 DATB is 1, 3-diamino-2, 4, 6-trinitrobenz ene .
PBXN-5 is 5% by weight copolymer of vinylidene fluoride 20 and hexafluoI-J~L~J~ylene and 95% by weight HMX and has an elemental composition on a lOOg basis of approximatelY C1 z3H2.672Nz s78o2~578Fo.174~
PBXN-6 is 5% by weight copolymer of vinylidene fluoride and hexafluoropropylene and 95% by weight RDX and has an elemental 25 composition on a lOOg basis of approximately C1 23H2 672Nz 57s2 57sFo 174 AFX-108 is 82~ by weight RDX, 5% by weight isodecylpelargonate with the balance being a polyurethane binder and small quantities of stabilizerS. It has an elemental 30 composition on a lOOg basis of approximate C2 1OH3 8sN2 2s2 48 Exam~le 2 To obtain the maximum amount of energy available from an explosive, it is n~PC~ry to obtain oxygen balance The military ~1~7~59 explo6ives in Example 1 are oxygen deficient on a lOOg basis as shown in Table II.
Table II
5 Fol~mulation OxY~en Def iciency PBXN-101 4 . 66 gram atoms PBXN-105 2 . 45 PBXN-106 2 . 70 PBXN--3 4 . 66 15PBXN--4 4 . 55 PBXN-5 1. 13 PBXN--6 1.13 The theoretical explosive potential of bringing the explosives to oxygen balance by adding the amount of oxygen shown in Table II as ammonium nitrate was then det~rm;n~d. The results are given in Table III.
Table III
Formulation PBX Basç AN ~D ~4 0 Rho PF PFN
WED-88 PBXN-101 373 323 8.53 1001 1.8 2.76 4.96 WED--90 PBXN-105 196 350 8 . 74 1322 1. 88 3 . 06 5 . 75 WED--91 PBXN--106 216 399 9.57 1742 1.69 3.82 6.46 35WED-71 PBXN--3 373 311 8.45 1039 1.75 2.63 4.60 -~1~7059 .
WED--72 PBXN--4 364 319 8.45 981 1.79 2.71 4.84 WED--73 PBXN-5 123.5 339 8.74 1151 1.81 2.96 5.36 5 WED-74 PBXN--6 123.5 321 8.58 1153 1.75 2.75 4.82 Exam,ole 3 DATB can be recovered from PBXN-4 by solvent trituration.
The theoretical explosive potential of DATB when it is oxygen 10 balanced with several different oxidizers is given in Table IV.
Table IV
Formulation Q~i ~; 7çr Amount I~D YD !2 Rhp PF PFN
WED-100 AN 214 315 8.51 1131 1.75 2.68 4.69 15 WED--101 AP1 125 . 7 410 9 . 46 1435 1. 9 3 . 88 7 . 37 WED--102 Hp2 177.2 420 9.57 1559 1.9 4.02 7.64 WED--103 LIN3 133.9 451 9.59 835 2.15 4.33 9.30 In the above table, AP1 i8 ammonium perchlorate, Hp2 is hydrazinium perchlorate and LIN3 is lithium nitrate.
Exam~le 4 Packing density inf luences both detonation velocity and ~SLULe:. The theoretical impact of packing density for PBXN-101 brought to oxygen balance with AN is shown in Table V below.
Table V
3 0 rho ~D ~D PF
0.90 5.54 81 0.45 1 . 00 6 . 04 100 0 . 58 1.10 6.20 120 0.75 1.20 6.54 143 0.94 1.30 6.87 168 1.15 2~70S9 1.40 7.20 195 1.40 1 . 50 7 . 53 224 1 . 69 1 . 60 7 . 86 255 2 . oo 1.70 8.20 288 2.36 5 1.80 8.53 323 2.75 F~r~mrle 5 Samples of formulations based upon the polymer bound explosives PBXN-3, PBXN-4, PBXN-101, PBXN-105 and AFX-108 and the 10 1.1 solid rocket propellants DDP, VTQ-3 and VTG-5A were oxyyen b~1 Inl Ptl and packaged in sticks having lengths varying from 7 . 00 to 17.25 inches and diameters from 1.4687 inches to 2.25 inches and detonated. All sticks detonated. Details are given in Table 6 below.
DDP is a composite double base alllmini~ecl Class 1.1 military solid rocket propellant containing ammonium perchlorate and having the approximate 100 g empirical formula C1 KHz 39N1 502 06Alo 78Clo 17 and is approximately 3 . 88 gram atoms of 20 oxygen deficient per 100 grams of propellant.
VTQ-3 is a Class 1.1 solid military rocket propellant containing nitroglycerin, ammonium perchlorate and aluminum plus various other C~mrnn~nts. It has an approximate 100 gram empirical 25 formula of C1 07E~2 ~sN1 s2o2 78A10 59clo 07 and is approximately 2.32 gram atoms of oxygen deficient per loO grams of propellant. VTQ-3 is a classified propellant, hence the empirical formula and oxygen def iciency is very approximate .
VTG-5A is a Class 1.1 complex military solid rocket propellant containing nitroglycerin, aluminum and ammonium perchlorate and is approximately 1. 64 gram atoms of oxygen deficient per 100 grams of propellant and with an approximate 100 gram empirical formula of Co.98H2.00N1 49o2.36Alo.72clo o8s 2157~59 Table 6 ~i~ Militarv Base Q~idizer Weiqht Lenqth Rho PBXN-4 SP 442.94g 13.31in 1.06 5 2 AFX-108 AN 373 . 56 13 . 25 0 . 897 3 PBXN--4 SP/AN 448 . 90 13 . 34 1. 07 4 PBXN--101 AN 516.12 14.16 1.16 5 PBXN-101 AN/Urea/AN 491.48 12.39 1.11 6 PBXN-101 AN 445 . 78 13 . 02 1. 09 10 7 PBXN-4 SP 513.3i 12.92 1.26 8 PBXN--4 AN 298 . 65 8 . 25 1.15 9 PBXN--101 AN 209 . 00 7 . 00 o . 95 10 PBXN-105 AN/Urea/AN 436.52 13.38 1.04 11 PBXN--101 AN 467 . 44 14 . 56 1. 02 1512 PBXN-101 AN 443 .16 14 . 22 0 . 99 13 DDP AN 402 . 00 14 . 25 1. 02 14 VTQ--3 AN 365 . 00 12 . 75 1. 03 15 PBXN--4 AN/SP 382 . 00 14 . 5 0 . 95 16 VTG--5A AN 422.00 14.5 1.05 2017 AFX--108 AN 358 . 00 13 . 25 0 . 97 18 PBXN--4 AN 347 . 00 13 . 5 0 . 93 19 PBXN--4 SP 402.00 13.25 1.09 20 PBXN-101 AN/Urea 348.60 14.00 0.90 21 DDP AN 307.00 11.5 0.96 2522 PBXN-105 AN/Urea 431. 00 15 . 0 1. 04 23 AFX--108 AN 334 . 00 12 . 25 0 . 98 24 PBXN--3 AN 362.2 14.25 0.92 25 PBXN-3 AN 394 . 81 13 . 75 0 . 90 26 PBXN--3 AN 339.50 13.50 0.91 3027 Mixture 504 . 00 17 . 25 0 . 95 Sticks 1-12 had a cross section of 10. 93 cm2 and a it -tF~r of 1 15/32 inch. The oxidizer was in the form of powder.
sticks 13-26 had a cro~s 6ection of 12.37 cm2 and a diameter of 1 35 9/16 inch. The oxidizer was in the form of prills. All sticks ~705~
with the exception of stick 9 were f illed under a packing thrust of 400 pound6. Stick 9 was filled under a thrust of 450 pounds. All polymer bound explosives were ground f ine with the exception of PBXN-105 which was coarse. All 1.1 rocket propellants were coarse.

Each stick was outfitted with a 7g PENTOLITE stinger (a 50:50 pourable mixture of TNT and PETN with a density of 1.65 g/cm3 and a detonation rate of 7400 m/sec) and a No. 8 blasting cap.
Exam~le 6 Samples of formulations based on the polymer explosives PBXN-101 and PBXN-4 were oxygen balanced and packaged in sticks.
The sticks were provided with a 7g PENTOLITE stinger and a No. 8 blasting cap. The sticks were detonated and the velocity of 15 detonation measured with point ionization probes attached to a VOD
meter. The results are reported in Table 7 below.
Table 7 Stick ~_ PBX Base ~Y; ~ er Weiqht Lenqth Rho 20 1 200J~ PBXN-101 AN 433g 34 . 6 cm O . 99 4 2 300# PBXN--4 SP 519 33.6 1.15 3.78 3 150# PBXN--4 SP 519 33 . 6 1.15 3 . 49 5 loose PBXN-101 AN 105 10 . 2 0 . 95 2 . 42 6 loose PBXN-101 AN 408 39.4 0.95 5.79 25 7 loose PBXN-101 AN 409 39.4 0.95 5.10 As various changes could be made in the above-described methods and products without departing from the scope of the inventiOn, it is intended that all matter contained in the above 30 description or shown in the accompanying drawing shall be int~r ~ d as illustrative and not in a limiting sense.

Claims (12)

1. A process for reformulating a military explosive or propellant which comprises the steps of:
(a) selecting an oxygen deficient polymer or wax bound military explosive or propellant;
(b) determining the empirical formula of the explosive or propellant;
(c) selecting an oxidizing agent;
(d) determining the amount of oxidizing agent necessary to oxygen balance the explosive or propellant; and, (e) adding the amount of oxidizing agent determined in step (d) to the explosive or propellant whereby the energetic potential of the explosive or propellant is maximized and the production of toxic fumes minimized when the reformulated mixture is detonated.

2. The process of claim 1 wherein the military explosive or propellant includes a member selected from the group consisting of RDX, HMX, PETN and mixtures thereof.

3, The process of claim 2 wherein the oxidizer is a metal or ammonium salt of an oxy-acid selected from the group consisting of nitric acid, chloric acid, bromic acid, perchloric acid and mixtures thereof.

4. The process of claim 1 wherein a gas forming material is added with the oxidizing agent to modify the explosive power of the reformulated mixture by regulating the amount of heat and gas liberated.

5. A process for reformulating a military explosive or propellant which comprises the steps of:
(a) selecting an oxygen deficient polymer or wax bound military explosive or propellant containing an explosive member selected from the group consisting of RDX, HMX, PETN and mixtures thereof;
(b) determining the empirical formula of the explosive or propellant including the polymer or wax;
(c) selecting an oxidizing agent which is a metal or ammonium salt of an oxy-acid selected from the group consisting of nitric acid, chloric acid, bromic acid, perchloric acid and mixtures thereof;
(d) determining the amount of oxidizing agent necessary to oxygen balance the explosive or propellant; and, (e) adding the amount of oxidizing agent determined in step (d) to the explosive or propellant whereby the energetic potential of the explosive or propellant is maximized and the production of toxic fumes minimized when the reformulated mixture is detonated.

6. The process of claim 5 wherein a gas forming material is added with the oxidizing agent to modify the explosive power of the reformulated mixture by regulating the amount of heat and gas liberated.

7. The process of claim 6 wherein the gas forming material is selected from the group consisting of urea, ammonium oxalate, oxamic acid, oxamide, methyl urea, urea-formaldehyde resins, nitroguanidine, nitrourea, urea nitrate, nitric acid and mixtures thereof.

8. The process of claim 5 wherein the military explosive or propellant is provided in a finely divided form.

9. The process of claim 5 wherein the oxidizer is provided in a finely divided form.

10. The process of claim 5 wherein the military explosive or propellant is oxygen balanced with at least two different oxidizing agents to modify the explosive power of the reformulated mixture.

11. The process of claim 5 wherein at least two different military explosives or propellants are selected.

12. The process of claim 5 wherein adventitious materials present in the military explosive or propellant serve as fuel when the reformulated mixture is detonated.