Classifications

• • C—CHEMISTRY; METALLURGY
  • C06—EXPLOSIVES; MATCHES
  • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
  • C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
• • C—CHEMISTRY; METALLURGY
  • C06—EXPLOSIVES; MATCHES
  • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
  • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
  • C06B21/0091—Elimination of undesirable or temporary components of an intermediate or finished product, e.g. making porous or low density products, purifying, stabilising, drying; Deactivating; Reclaiming
• • C—CHEMISTRY; METALLURGY
  • C06—EXPLOSIVES; MATCHES
  • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
  • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L7/00—Fuels produced by solidifying fluid fuels
  • C10L7/02—Fuels produced by solidifying fluid fuels liquid fuels
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L7/00—Fuels produced by solidifying fluid fuels
  • C10L7/02—Fuels produced by solidifying fluid fuels liquid fuels
  • C10L7/04—Fuels produced by solidifying fluid fuels liquid fuels alcohol
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1608—Well defined compounds, e.g. hexane, benzene
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
  • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
  • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic

Definitions

• the invention relates to a fuel component for an explosive according to the preamble of claim 14, and a method for its preparation according to claim 1.
• the invention relates to an explosive having an oxidizing agent and a fuel component according to claim 15, an explosive device according to claim 17 and an explosion process according to claim 19.
• explosive substances are solid, liquid and gaseous substances or mixtures in a metastable state which are capable of rapid chemical reaction without the addition of additional reactants.
• fabrics that are not made for the purpose of blasting and shooting such as Fertilizers, gas-binder of the foam and plastics industry or various catalysts.
• Explosives are a subset of the explosive substances and are solid, liquid and gelatinous substances and mixtures of substances which are produced for the purpose of blasting or blowing, see eg Köhler, J. and Meyer R. in "explosives", VCH Verlagsgesellschaft mbH Weinheim 1995 ,
• the triggering of an explosive reaction can be carried out by mechanical stress (impact), friction, thermal action or by detonation impact.
• reaction partners are usually in bound form, e.g. the oxygen as nitrate or as nitro group.
• a disadvantage compared with the liquid-oxygen explosive developed and to be used according to the invention is that part of the chemical-exothermic reaction energy has to be expended on all conventional explosives in order to obtain the actual Reactants "fuel” and / or “oxidizing agent” to dissolve out of their chemical attachment bonds. This is the specific exothermic energy release compared to liquid-oxygen explosives.
• Another disadvantage is that environmentally harmful substances arise or remain both by the reaction products themselves or by unexploded explosives.
• a use according to the invention of classical explosives for rock erosion, similar to that practiced by Louie in 1973 with C4 explosive, s. in Willliam C. Mauer, "Advanced Drilling Techniques", Petroleum Publishing Co., 1421 S. Sheridan, PO BOX 1260, Tulsa, OK 74101, is also opposed to the current legislation regarding explosives (storage, transportation, and stockpile of a machine system with explosives), environmental protection, and the risk of terrorist abuse.
• Explosives satisfying such requirements include, for example, nitrogen-free oxidants, sodium perchlorates or special water-gel emulsion explosives, or else peroxide and liquid oxygen-based explosives; like in US 5,920,030 is disclosed.
• liquid-air or liquid-oxygen explosives have been known for about 100 years various explosives. These are produced by impregnating fuels such as wood or cork flour, peat, carbene and other substances in liquid oxygen.
• fuels such as wood or cork flour, peat, carbene and other substances in liquid oxygen.
• the first systematic scientific work in this field was carried out by the Kaiser Wilhelm Institute in Berlin in the 1920s: see eg Journal of Applied Chemistry, Volume 37, pp. 973-992 of December 11, 1924 No. 50 , In the course of this work substances such as carbene, carbon black, cork, peat and wood flour, cellulose and coal dust were investigated.
• a disadvantage of the previously known liquid oxygen explosives is that these explosives can not be used according to the invention because, on the one hand, they react detonatively only with sufficient attenuation and, on the other hand, they have too low a detonation rate. If, for rock excavation, explosive charges in e.g. iron shell would have to be used, then this would correspond to a use of military splinter grenades, which is no longer civil licensing. Furthermore, the spoil volume to be removed from the working face would be loaded with steel splinters, and not least the economic efficiency of such a method would be low.
• WO 92/07808 describes a cryogenic fuel, which can be used for the application of propulsion systems for supersonic missiles under and over water as well as explosives.
• various auxiliary equipment is used to produce the flammable or explosive mixture and for the controlled initiation of the combustion or explosion reaction.
• the main fuel component here is liquid hydrogen in a form or in the form of mixtures with solids and additionally with the addition of methane, ethane, acetylene and others.
• LOX oxygen
• air, fluorine or other oxidizing substances can be used.
• the invention has for its object to provide a highly reactive fuel component, for a strong, undiluted detonatable explosive as well as a cost efficient method for producing the same, wherein the fuel component safe to handle and the explosive in absence of detonation has good environmental compatibility.
• the invention solves the problem by a fuel component for an explosive having the features of claim 14 and by a method for its production with the features of claim 1.
• Advantageous embodiments of the invention are set forth in the dependent claims.
• the restructuring according to the invention in particular volume expansion, creates a volume-expanded structure of the basic fuel component.
• the molecules of the fuel component are initially molecularly structured and in bulk form in solid form.
• This macromolecular assembly assumes a packing density under normal gravity conditions, which does not leave enough space for the uptake of oxidants in the packing volume or for substances to be sorbed because the molecules of the basic fuel component are freely movable and compact.
• volume-expanded structure in order to create a space inside the fuel volume up to the molecular dimensions in space for the inclusion or storage of additional fuel components in the form of hydrocarbons and oxidants, the molecular arrangement of the fuel base component by admixing a liquid Alcohol in such a slightly bonded or crosslinked state, the inhomogeneities and cavities on a microscopic scale, hereinafter referred to as volume-expanded structure exist and arise.
• volume-expanded structure as volume adaptation in the fuel is expedient in order to set or maintain in the finished liquid-oxygen explosive mixture a volumetric proportion required between the components fuel and oxidant for the rapid and explosive reaction.
• a volume expansion is preferably set.
• volume reduction or the constant of the averaged volume possible. For example, if the fuel occupies only 15% to 20% of the total volume that it structurally spans, and the remainder is filled by the oxidant, then due to the low fuel density, an explosive reaction reaction initiated locally in the mixture could cause it to go out or slow to progress come through the mixture.
• volume structuring or adaptation by an absolute volume fraction reduction of the fuel component, for example, according to the same process path. Also, such volume fraction reduction falls under the process of creating a volume-expanded structure. Inside the fuel volume inhomogeneous and anisotropically distributed microstructured areas are generated and fixed.
• the fuel base component After mixing the fuel base component with a liquid alcohol and subsequent desorption of the alcohol from the fuel component, a loose volume-expanded structure of the bulk macromolecule remains. By adding a liquid alcohol and desorbing it, the ensemble of the fuel base component is placed in a collective volume expanded state characterized by the additional intermolecular distances and spaces created between the macromolecules of the fuel base component.
• a comparable spatial targeted networking can also be achieved by measures such as dissolving, heating, irradiation and gluing.
• the bulk-like molecular structure of the basic fuel component which prior to the alcohol treatment tends to occupy the highest possible packing density, is now mixed or "crunched" to a lower integral density, so that, despite the existing macromolecular structuring, a sufficiently large, homogeneously distributed volume of free space spans into the bulk material package becomes.
• the mixing in of the alcohol ensures that the molecules of the basic fuel component are partially deformed chemically and mainly by physical interactions and also partially crosslinked. After expulsion of the alcohol from the mixture, the resulting loose structure of the macromolecular bulk material dressing remains.
• the type and amount of the added alcohol and the mechanical mixing process determine the degree of collective volume expansion or density reduction in the molecular ensemble.
• the volume expanded fuel base component is mixed with a combustible low molecular weight hydrocarbon to form a conditioned fuel component.
• the desorption and thus the cleaning of the boundary regions of such reaction-inhibiting substances can be carried out, for example, by vacuum, the influence of temperature, irradiation or with the aid of cleaning agents, which are subsequently expelled themselves.
• the desorption of molecules deposited in the fuel base component results in the formation of a kind of radical or defect at the energetic level of the physical bond which seeks to sorb and absorb moisture, carbon dioxide and other substances from the atmosphere sorptively.
• another advantageous process step of preparing the fuel component for rapid reactivity is that only combustible hydrocarbon molecules of low to medium carbon number per molecule, preferably from C 1 to C 10 , are resorbed into the purified fuel molecular composite.
• fast reaction-promoting substances are specifically deposited in the basic fuel component. That can also be catalysts.
• the ready-conditioned fuel component is not hazardous in itself, does not belong to the explosives and, since the sorbed and stored hydrocarbons are hardly volatile, it is strictly classified as hazardous in the sense of combustible dusts.
• a spray-dried emulsion polymer or condensate is used as the fuel base component.
• a spray-dried emulsion polymer or condensate is used as the fuel base component.
• Such a polymer is relatively simple and inexpensive to produce and has an extremely high specific surface area, which causes a very high reactivity of the fuel.
• fuel base component preference is given to using polymers from the class of the methacrylates, preferably methyl methacrylate or ethyl methacrylate or mixtures thereof.
• any other hydrocarbon-based molecules can also be used as the basic fuel component if they are present under normal thermal conditions as a molecular-structured solid.
• the conditioning step of volumetrically converting the fuel base component for the increased storage capacity for oxidizing agent is carried out with methanol or ethanol or a mixture of these two substances. But also propanol and butanol are suitable.
• methane or ethane or a mixture thereof is used as the combustible low molecular weight hydrocarbon.
• other lower carbon number alkanes for example propane, butane or pentane or mixtures thereof or chemical derivatives based on their basic molecule or carbon atom number.
• the combustible low molecular weight hydrocarbon is added together with a liquid hydrocarbon.
• the purified during the desorption phase fuel can sorb low molecular weight volatile hydrocarbons such as methane or ethane, only in the trace range and keep stored for long enough. Is in the course of ventilation with methane gas pressure equalization completely on the ambient pressure carried out, then it comes naturally after removal of the fuel from the plant for the evaporation of non-sorbed methane.
• the last pressure equalization phase can be carried out by injection with higher, but under atmospheric atmospheric conditions easily volatile, hydrocarbons.
• hydrocarbons liquid butane, pentane, hexane or higher and similar hydrocarbons may be added to the fuel component explicitly. However, only a maximum so much that the bulk solid or solid state of the fuel is not affected in total.
• Particularly effective additives are petan, hexane and iso-octane.
• conditioning procedures or their individual partial steps imply sufficient freedom in the fuel component to be able to set desired ignition sensitivities and detonative reaction rates of the reaction rates for a mixture with an oxidizing agent.
• the basic fuel component is mixed before or during mixing with the alcohol with a further additional fuel base component in the form of a molecularly dispersed organic solid.
• This additive fuel base component extends the property spectrum of the fuel and the ability to tailor the appropriate ignitability and detonative conversion rates to the particular application.
• Particularly suitable auxiliary fuel base components are pulverulent fuel components, such as, for example, melamine, solid alcohols or balsa wood powder.
• the mixture is irradiated with microwaves before completion.
• the volume-expanding state generated by the abovementioned conditioning procedures is fixed in the substance micro- and macroscopically as a self-supporting molding. It can form a stable coating on the surface, which can be caused by polymerization.
• the desorption is carried out by means of vacuum drying, desorption or freeze drying. These procedures ensure fast and efficient expulsion of alcohol and other undesirable substances.
• the desorption phase can also be achieved by the action of elevated temperature or by irradiation, for example with microwaves.
• the invention also provides a fuel component for an explosive according to claim 14 comprising a volume expanded molecular disperse hydrocarbon prepared by the aforementioned method.
• Another aspect of the invention relates to an explosive having an oxidizing agent and the fuel component of the invention.
• Halogens in particular fluorine, interhalogen compounds, halogen oxygen compounds and all oxygen modifications are particularly suitable as oxidizing agents.
• Particularly suitable is an explosive in which the oxidizing agent comprises liquid oxygen.
• Such a mixture of the fuel component according to the invention and liquid oxygen a so-called LOX-Ex mixture, apart from the reaction-related splitting of the hydrocarbon and oxygen molecules into atomic Modification only from exothermic reaction partners. All components of the mixture are immediately available after reaction initiation via the rapid complete energetic reaction and not only by parallel running, for example, endothermic, secondary reactions of metastable accumulation states chemically trigger or release.
• the explosive according to the invention can be classified in the series of the strongest existing explosives.
• liquid oxygen explosive As a fuel component of the liquid oxygen explosive are special poly- and macromolecular hydrocarbon molecules in the state of condensed matter molecularly individually, but still like a bulk material, which are conditioned by conditioning in a state so that after their mixing with liquid oxygen, the fuel components find their oxidant directly adjacent to each other , This ensures that even the local entry of impact or impact energy into the volume of the mixture triggers a detonative reaction reaction with a sufficiently high reaction rate.
• the total volume of the liquid oxygen explosive mixture is recorded. Due to the fact that the fuel components and their oxidant partners are arranged directly next to one another, a chemically high reactive energy density and, after ignition, a high detonative reaction or reaction rate in the mixture is achieved.
• the liquid oxygen explosive consists of components which, taken by themselves, are not explosives and do not contain any chemically energetic fiber, such as chemical oxidant carriers.
• the chain of the aforementioned preparatory operations of the fuel component causes the microstructured and nanostructured macromolecular assembly to sufficiently expand in volume.
• a reaction-related optimal volumetric proportion relation between fuel and oxidant is given.
• the fuel and oxidant partners in the mixing phase are spatially distributed so that the potential partners in the explosive mixture are present next to each other, or are held in a stable mixed state reactive as long as sufficient cryogenic liquid oxygen is present and penetrates the fuel volume.
• the explosive according to the invention is characterized by a number of advantageous properties.
• a high detonative reaction or conversion rate of the entire LOX Ex volume The triggering of the entire detonation reaction can be triggered by shock, Impact, friction or pressure from a small volume range of the LOX-Ex-charge made out.
• the LOX-Ex mixture contains no fiber and thus has a high chemical reactive energy density.
• the explosive has a high rock erosion capacity.
• the cost of an explosive is mass-related in the size range of the cost of fuel oil, the fuel and the liquid oxygen by themselves are not explosives and do not require explosive-specific safety precautions until they are mixed to LOX-Ex. For the raw materials of the LOX-Ex-mixture, the Dangerous Goods Ordinance applies at best.
• the fuel, the liquid oxygen and the finished LOX-Ex mixture and the explosive reaction products or the remaining after a misfire residues are not harmful to the environment.
• Produced but unleacted LOX-Ex mixture decays relatively quickly by evaporation of the cryogenic liquid oxygen in the non-explosive state and is therefore harmless. Also does not occur a flame ignition of a free LOX Ex mixture.
• the mixture then burns explosively, such as black powder.
• the detonative surge of a reacting LOX-Ex mixture initiates the detonative response of a spatially adjacent positioned LOX-Ex mass.
• the merging of the fuel with the liquid oxygen to the LOX-Ex mixture can be done manually or automatically.
• the invention also provides an explosive device with the explosive according to the invention.
• the LOX-Ex mixture can easily be filled into capsules made of different materials, in particular readily biodegradable, such as cardboard. Or the LOX-Ex mixture is produced directly with a capsule as skin from the own fuel component, so that LOX-Ex capsules are available.
• the LOX-Ex capsules are pneumatic, blowpipe-type, acceleratable and fire-resistant to a target area while retaining explosive properties.
• the necessary ignition pulse can be applied, for example, by means of an explicit detonator detonator, by enclosing the LOX-Ex mixture in a pressure vessel and subsequent pressure increase, or by collision of the LOX-Ex capsule with an obstacle.
• the detonating ignition is also with a mechanical passive and non-reactive ignition device explicitly located in the LOX-Ex mixture triggered.
• a mechanical passive and non-reactive ignition device explicitly located in the LOX-Ex mixture triggered.
• Such an ignition device consists in the simplest case of one or more suitably placed in the charge metallic or mineral solids. These bodies remain in their resting position during the acceleration of the capsule, and at the moment of the impact of the LOX-Ex capsule on an obstacle, according to their own inertia, the bodies move on in the LOX-Ex mixture.
• a traffic jam shock wave with reaction-triggering strength and rubbing effect builds up in front of such a body.
• such an embedded body strikes like a pestle on an embedded obstacle in the capsule according to the hammer-anvil principle and initiates a pressure surge or a compression impact effect, whereby the entire chemical reaction is triggered detonatively.
• the LOX Ex charge is designed as a shaped charge, then a suitable Zünding at the moment of impact of the capsule is also possible that such an inertial body or plunger inside the charge against the mechanically stabilized tip of the cone material or its axial extension into the capsule interior beats and there ignites the LOX-Ex mixture.
• a dynamic Trägheitsverdämmung is provided in the explosive device.
• the effect of the dynamic inertia detunification comes about at the moment the capsule serves and detonates.
• the rear part of the capsule is formed as a sluggish solid mass, which opposes a propagation resistance due to their inertia-inertia to their own destruction of the backward detonation effect of the capsule and thus enhances the destructive forward action.
• the inertial mass may be concrete, for example. Due to its mass inertia, this concrete body generates a dynamic damming that does not allow the detonation pressure to escape completely unhindered into the free space behind.
• the explosive device according to the invention is particularly suitable for use in an automated rock erosion process.
• the LOX Ex charge is preferably geometrically formed as a hollow charge.
• an explosion method having the features of claim 19 is proposed.
• a fuel component according to the invention is mixed immediately before an explosion with an oxidizing agent to form an explosive.
• the individual components can be stored protected over a longer period of time and also transported separately, whereby the security risk can be significantly reduced.
• the reactivity of the two components, in particular immediately after mixing is also markedly increased in comparison with a point in time after prolonged storage, so that an enhanced detonation effect can also be achieved.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Crystallography & Structural Chemistry (AREA)
• Solid Fuels And Fuel-Associated Substances (AREA)
• Liquid Carbonaceous Fuels (AREA)

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Citations (6)

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• 2007
  • 2007-05-10 EP EP07009414A patent/EP1992675A1/fr not_active Withdrawn
• 2008
  • 2008-05-06 CA CA2630748A patent/CA2630748C/fr not_active Expired - Fee Related
  • 2008-05-07 US US12/149,754 patent/US8236113B2/en not_active Expired - Fee Related

Patent Citations (6)

Non-Patent Citations (3)

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