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US3160537A - Heating composition - Google Patents

Heating composition Download PDF

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Publication number
US3160537A
US3160537A US144552A US14455261A US3160537A US 3160537 A US3160537 A US 3160537A US 144552 A US144552 A US 144552A US 14455261 A US14455261 A US 14455261A US 3160537 A US3160537 A US 3160537A
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US
United States
Prior art keywords
compositions
combustible
heating
burning
composition
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Expired - Lifetime
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US144552A
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Jr Thomas R Trafton
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Catalyst Research Corp
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Catalyst Research Corp
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Publication date
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Priority to US144552A priority Critical patent/US3160537A/en
Application granted granted Critical
Publication of US3160537A publication Critical patent/US3160537A/en
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Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00General methods of reducing to metals
    • C22B5/02Dry methods smelting of sulfides or formation of mattes
    • C22B5/04Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L5/00Solid fuels
    • C10L5/40Solid fuels essentially based on materials of non-mineral origin
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00General methods of reducing to metals
    • C22B5/02Dry methods smelting of sulfides or formation of mattes
    • C22B5/06Dry methods smelting of sulfides or formation of mattes by carbides or the like
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/30Fuel from waste, e.g. synthetic alcohol or diesel

Definitions

  • the combustible compositions in use generally consist of a combustible metal and an inorganic oxidizing agent, many of which react extremely rapidly and generate extremely high temperatures. For many purposes, such as heating water, the heat is generated faster than it can be transferred to the object to be heated, which results in heat waste and the possible failure of the container due to the high temperatures reached.
  • inert diluents such as powdered glass, mica or silica
  • inert diluents such as powdered glass, mica or silica
  • a finely divided oxidizable metal e.g., flaked or powdered
  • a finely divided inorganic oxidizing agent preferably in substantially stoichiometric proportions
  • finely divided crystalline lubricant such as graphite and/or molybdenum disulfide and, if desired, a finely dividedinert diluent.
  • the mixture is compressed to form an autogenous combustible consolidated body which is used to provide heat in the same general manner as similar compositions have been used heretofore.
  • the new compositions containing graphite and/or molybdenum disulfide burn at a slower rate than corresponding compositions not containing them.
  • the graphite and/ or molybdenum disulfide also function as a die lubricant, prolonging the life of dies used in the compression of the mixtures and making the consolidated body freely releasable from the dies.
  • the burning rate of any of the wide variety of heretofore known combustible compositions comprising a finely divided metal and an inorganic oxidizing agent may be modified by the addition of a minor amount of graphite and/ or molybdenum disulfide.
  • suitable metals are finely divided aluminum, zinc, nickel, antimony, zirconium, iron and their alloys, as well as various intermetallic compounds such as calcium silicide.
  • Suitable oxidizing agents include the pcrmanganates, such as potassium permanganate; the chlorates and perchlorates, such as those of the alkali and alkaline earth metals; inorganic oxide and peroxide, such as barium peroxide, iron oxide, litharge, manganese dioxide, and others; the chromates, such as barium chroma-te; as well as sulfur and other elements that will combine exothermically with metals.
  • these known compositions liberate no appreciable amount of gaseous products on burning. I have found that the new compositions of this invention do liberate a slight amount of gas on burning, so that'they should be used in vented containers or in hermetically sealed containers "having sufiicient free air space to accommodate the gas generated.
  • the heating composition can be tailored to provide at a desired rate the amount of heat required for a specific application.
  • the amount of retardation of burning rate increases with increasing amounts of lubricating additive and any amount desired may be used. Generally I prefer to use between about 0.1 and 5.0% lubricating additive; amounts smaller than 0.1% retard the burning rate only slightly, and the addition of amounts beyond 5.0% do not significantly increase the efiect of the additive.
  • the burning rate may be adjusted slightly by varying the pressure at which the mixtures are compressed; increasing the compression pressure will decrease the burning rate, although the effect is slight in comparison to the modification of burning rate obtained by using the crystalline lubricant.
  • mixtures are compressed under about 1000 to 10,000 p.s.i. pressure.
  • the new compositions are generally enclosed in a'cartridge provided with an igniting primer, in the same manner as similar previous compositions used for heating purposes.
  • the combustible composition mixture may be compressed directly in the containing cartridge or it may be separately compressed and the consolidated body then placed in the cartridge. Ignition may be accomplished 3 by use of an ordinary cartridge primer or a fuse. Ignition of some combustible compositions may require a supplementary starter charge which is easily ignited by primer or fuse; e.g., a stoichiometric mixture of electrolytic iron and manganese dioxide.
  • An autogenous combustible composition consisting 4 essentially of a compacted intimate mixture of the following finely diyide'd ingredients: about 22 to 25% aluminum, about 62 to 73% ferric oxide, 0 to about 15% inert diluent, and about 0.1 to 5.0% combustion retardant selected from the group consisting of graphite, molybdenum disulfide and mixtures thereof.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Lubricants (AREA)

Description

United States Patent 3,160,537 HEATlllG COMPOSITIGN Thomas R. Trafton, Jr., Middle River, Md., assignor to Catalyst Research Corporation, Pittsburgh, Pa, a corporation of Pennsylvania No Drawing. Filed Oct. 12, 1961, Ser. No. 144,552 1 (Jlaim. (Cl. 149-37) This invention relates to autogenous heating compositions for use in heating elements for supplying limited amounts of heat for such diverse purposes as heating canned foodstuffs, heating water, defrosting, sterilization.
Heretofore a variety of autogenous heating devices have been proposed and used for readily portable heat sources in which a combustible chemical mixture is placed within a vented or hermetically sealed container. The combustible compositions in use generally consist of a combustible metal and an inorganic oxidizing agent, many of which react extremely rapidly and generate extremely high temperatures. For many purposes, such as heating water, the heat is generated faster than it can be transferred to the object to be heated, which results in heat waste and the possible failure of the container due to the high temperatures reached. Heretofore, it has been customary to add substantial amounts of inert diluents, such as powdered glass, mica or silica, to the combustible composition which slows and cools the reaction by acting as a heat sink and by lowering the concentration of the active ingredients. The use of an inert diluent, however, requires a larger and heavier charge to provide a given amount of heat. I
It is an object of this invention to provide a heating composition having a modified burning rate. Another object is to provide a heating composition with a modified burning rate which contains a high proportion of active ingredients. Another object is to provide a heating composition compact which is freely releasable from forming dies. Other objects will be apparent from the following description and claims.
According to this invention, a finely divided oxidizable metal, e.g., flaked or powdered, and a finely divided inorganic oxidizing agent, preferably in substantially stoichiometric proportions, are mixed together with a minor proportion of finely divided crystalline lubricant such as graphite and/or molybdenum disulfide and, if desired, a finely dividedinert diluent. The mixture is compressed to form an autogenous combustible consolidated body which is used to provide heat in the same general manner as similar compositions have been used heretofore. The new compositions containing graphite and/or molybdenum disulfide burn at a slower rate than corresponding compositions not containing them. The graphite and/ or molybdenum disulfide also function as a die lubricant, prolonging the life of dies used in the compression of the mixtures and making the consolidated body freely releasable from the dies.
The burning rate of any of the wide variety of heretofore known combustible compositions comprising a finely divided metal and an inorganic oxidizing agent may be modified by the addition of a minor amount of graphite and/ or molybdenum disulfide. Examples of suitable metals are finely divided aluminum, zinc, nickel, antimony, zirconium, iron and their alloys, as well as various intermetallic compounds such as calcium silicide. Examples of the wide variety of suitable oxidizing agents include the pcrmanganates, such as potassium permanganate; the chlorates and perchlorates, such as those of the alkali and alkaline earth metals; inorganic oxide and peroxide, such as barium peroxide, iron oxide, litharge, manganese dioxide, and others; the chromates, such as barium chroma-te; as well as sulfur and other elements that will combine exothermically with metals. When proportioned ice stoichiometrically, or with an excess of the metal, these known compositions liberate no appreciable amount of gaseous products on burning. I have found that the new compositions of this invention do liberate a slight amount of gas on burning, so that'they should be used in vented containers or in hermetically sealed containers "having sufiicient free air space to accommodate the gas generated.
The following comparison of an old autogenous combustible composition with new compositions are illustrative of this invention. Stoichiometric portions of ZOO-mesh powdered aluminum and ferric oxide having an average particle size of about 2 microns were intimately mixed. Portions of the mixture were intimately mixed with 32 5-mesh silica fiour and/or similarly finely divided crystalline lubricants in the amounts set forth in Table I.
.The various mixtures were compacted into pellets under a pressure of 4900 p.s.i. The pellets were ignited on one side and the rate of travel of the burning front was measured. The burning rates for the various compositions are set forth in Table I.
Table I Percent, Component by Weight Component Ex.2 Ex.3 Ex.4 Ex.5
Aluminum Ferric Oxide Hone 9NPN!" coon-:00
Hone N92? 0001000 KIM E N??? OOOr-WO plute Molybdenum Disulfide- Burning Rate (inches/seea rate as one containing sixteen percent inert diluent.
Even slower burning rates may be achieved by using larger amounts of crystalline lubricant or by using both a crystalline lubricant and inert diluent. By proper selection of the type and amount of crystalline lubricant and, if desired, inert diluent, the heating composition can be tailored to provide at a desired rate the amount of heat required for a specific application.
The amount of retardation of burning rate increases with increasing amounts of lubricating additive and any amount desired may be used. Generally I prefer to use between about 0.1 and 5.0% lubricating additive; amounts smaller than 0.1% retard the burning rate only slightly, and the addition of amounts beyond 5.0% do not significantly increase the efiect of the additive.
As in the prior combustible compositions, the burning rate may be adjusted slightly by varying the pressure at which the mixtures are compressed; increasing the compression pressure will decrease the burning rate, although the effect is slight in comparison to the modification of burning rate obtained by using the crystalline lubricant.
Generally mixtures are compressed under about 1000 to 10,000 p.s.i. pressure.
The new compositions are generally enclosed in a'cartridge provided with an igniting primer, in the same manner as similar previous compositions used for heating purposes. The combustible composition mixture may be compressed directly in the containing cartridge or it may be separately compressed and the consolidated body then placed in the cartridge. Ignition may be accomplished 3 by use of an ordinary cartridge primer or a fuse. Ignition of some combustible compositions may require a supplementary starter charge which is easily ignited by primer or fuse; e.g., a stoichiometric mixture of electrolytic iron and manganese dioxide. According tothe provision of the patent statutes, I have explained the principle and method of operation of my invention and have illustrated what I now consider to represent its best embodiment. However, I desire to have it understood that, Within the scope of the appended claim, the inyention may be practiced otherwise than as specifically illustrated and described.
I claim: An autogenous combustible composition consisting 4 essentially of a compacted intimate mixture of the following finely diyide'd ingredients: about 22 to 25% aluminum, about 62 to 73% ferric oxide, 0 to about 15% inert diluent, and about 0.1 to 5.0% combustion retardant selected from the group consisting of graphite, molybdenum disulfide and mixtures thereof.
References Cited in the file of this patent UNITED STATES PATENTS 1,901,313 Mann Mar. 14, 1933 2,424,937 Linzell July 29, 1947 2,716,599 Heiskell Aug. 30, 1955 2,976,136 Heiskell Mar. 21, 1961
US144552A 1961-10-12 1961-10-12 Heating composition Expired - Lifetime US3160537A (en)

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3325316A (en) * 1965-03-29 1967-06-13 Gilmour C Macdonald Pyrotechnic compositions of metal matrix with oxide dispersed therein
US3344210A (en) * 1967-09-26 Method of making. solid thermite pellets
US3374127A (en) * 1965-08-13 1968-03-19 Aquitaine Petrole Compressed metal containing ternary explosive composition
US3503814A (en) * 1968-05-03 1970-03-31 Us Navy Pyrotechnic composition containing nickel and aluminum
US3515072A (en) * 1968-05-02 1970-06-02 Us Army Tracer projectile
US3634153A (en) * 1970-02-03 1972-01-11 Us Army Noncorrosive pyrotechnic composition
US3664898A (en) * 1969-08-04 1972-05-23 Us Navy Pyrotechnic composition
US3769106A (en) * 1971-09-17 1973-10-30 United Aircraft Corp Igniter composition
US3890168A (en) * 1970-09-21 1975-06-17 Harold A Shumway Exothermic welding composition
US3982929A (en) * 1973-02-09 1976-09-28 Esm, Inc. Composition for a fluidizing flux in the production of iron and steel
US4000022A (en) * 1974-10-17 1976-12-28 The United States Of America As Represented By The Secretary Of The Navy Fast-burning compositions of fluorinated polymers and metal powders
US4013061A (en) * 1975-01-29 1977-03-22 Thermology, Inc. Ignition system for chemical heaters
US4043314A (en) * 1975-04-16 1977-08-23 Thermology, Inc. Food heaters
US4055881A (en) * 1976-12-22 1977-11-01 Bate Micheal Donald Method of rebuilding an ingot mold
US4208226A (en) * 1978-05-01 1980-06-17 Cundari Sante M Energy producing waste material composition
US4216041A (en) * 1978-07-10 1980-08-05 Cundari Sante M Energy producing waste material composition and method of preparation
US4297303A (en) * 1978-05-01 1981-10-27 Deardorff Paul A Preparation and reaction of energy producing waste material composition
US4536237A (en) * 1984-01-20 1985-08-20 United States Steel Corporation Aluminothermic reduction reaction mixture
US4708913A (en) * 1981-02-02 1987-11-24 Alloy Surfaces Company, Inc. Pyrophoric process and product
US5454363A (en) * 1994-10-14 1995-10-03 Japan As Represented By Director General Of Agency Of Industrial Science And Technology High-temperature exothermic device
US5490888A (en) * 1993-12-06 1996-02-13 Erico International Corporation Mixture of reactants for use in welding
US20060236887A1 (en) * 2005-02-08 2006-10-26 John Childs Delay units and methods of making the same
US8794152B2 (en) 2010-03-09 2014-08-05 Dyno Nobel Inc. Sealer elements, detonators containing the same, and methods of making

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1901313A (en) * 1931-11-11 1933-03-14 Harry Dexter Peck Heat-producing compound
US2424937A (en) * 1943-02-22 1947-07-29 United States Gypsum Co Incendiary composition
US2716599A (en) * 1949-12-01 1955-08-30 Raymond H Heiskeil Dark burning igniter composition
US2976136A (en) * 1948-06-29 1961-03-21 Raymond H Heiskell Composition for tracer unit

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1901313A (en) * 1931-11-11 1933-03-14 Harry Dexter Peck Heat-producing compound
US2424937A (en) * 1943-02-22 1947-07-29 United States Gypsum Co Incendiary composition
US2976136A (en) * 1948-06-29 1961-03-21 Raymond H Heiskell Composition for tracer unit
US2716599A (en) * 1949-12-01 1955-08-30 Raymond H Heiskeil Dark burning igniter composition

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3344210A (en) * 1967-09-26 Method of making. solid thermite pellets
US3325316A (en) * 1965-03-29 1967-06-13 Gilmour C Macdonald Pyrotechnic compositions of metal matrix with oxide dispersed therein
US3374127A (en) * 1965-08-13 1968-03-19 Aquitaine Petrole Compressed metal containing ternary explosive composition
US3515072A (en) * 1968-05-02 1970-06-02 Us Army Tracer projectile
US3503814A (en) * 1968-05-03 1970-03-31 Us Navy Pyrotechnic composition containing nickel and aluminum
US3664898A (en) * 1969-08-04 1972-05-23 Us Navy Pyrotechnic composition
US3634153A (en) * 1970-02-03 1972-01-11 Us Army Noncorrosive pyrotechnic composition
US3890168A (en) * 1970-09-21 1975-06-17 Harold A Shumway Exothermic welding composition
US3769106A (en) * 1971-09-17 1973-10-30 United Aircraft Corp Igniter composition
US3982929A (en) * 1973-02-09 1976-09-28 Esm, Inc. Composition for a fluidizing flux in the production of iron and steel
US4000022A (en) * 1974-10-17 1976-12-28 The United States Of America As Represented By The Secretary Of The Navy Fast-burning compositions of fluorinated polymers and metal powders
US4013061A (en) * 1975-01-29 1977-03-22 Thermology, Inc. Ignition system for chemical heaters
US4043314A (en) * 1975-04-16 1977-08-23 Thermology, Inc. Food heaters
US4055881A (en) * 1976-12-22 1977-11-01 Bate Micheal Donald Method of rebuilding an ingot mold
US4208226A (en) * 1978-05-01 1980-06-17 Cundari Sante M Energy producing waste material composition
US4297303A (en) * 1978-05-01 1981-10-27 Deardorff Paul A Preparation and reaction of energy producing waste material composition
US4216041A (en) * 1978-07-10 1980-08-05 Cundari Sante M Energy producing waste material composition and method of preparation
US4708913A (en) * 1981-02-02 1987-11-24 Alloy Surfaces Company, Inc. Pyrophoric process and product
US4536237A (en) * 1984-01-20 1985-08-20 United States Steel Corporation Aluminothermic reduction reaction mixture
US5490888A (en) * 1993-12-06 1996-02-13 Erico International Corporation Mixture of reactants for use in welding
US5454363A (en) * 1994-10-14 1995-10-03 Japan As Represented By Director General Of Agency Of Industrial Science And Technology High-temperature exothermic device
US20060236887A1 (en) * 2005-02-08 2006-10-26 John Childs Delay units and methods of making the same
US7650840B2 (en) 2005-02-08 2010-01-26 Dyno Nobel Inc. Delay units and methods of making the same
US20100064924A1 (en) * 2005-02-08 2010-03-18 John Childs Delay units and methods of making the same
US8245643B2 (en) 2005-02-08 2012-08-21 Dyno Nobel Inc. Delay units and methods of making the same
US8794152B2 (en) 2010-03-09 2014-08-05 Dyno Nobel Inc. Sealer elements, detonators containing the same, and methods of making

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