CA1097917A - Thermogenic compositions - Google Patents
Thermogenic compositionsInfo
- Publication number
- CA1097917A CA1097917A CA273,505A CA273505A CA1097917A CA 1097917 A CA1097917 A CA 1097917A CA 273505 A CA273505 A CA 273505A CA 1097917 A CA1097917 A CA 1097917A
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- Prior art keywords
- thermogenic
- composition
- heat
- compound
- air
- Prior art date
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/015—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone
- A61L9/02—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air by heating or combustion
- A61L9/03—Apparatus therefor
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24V—COLLECTION, PRODUCTION OR USE OF HEAT NOT OTHERWISE PROVIDED FOR
- F24V30/00—Apparatus or devices using heat produced by exothermal chemical reactions other than combustion
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Epidemiology (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Thermotherapy And Cooling Therapy Devices (AREA)
Abstract
THERMOGENIC COMPOSITIONS
Abstract of the disclosure:
A thermogenic composition comprising (1) at least one compound such as an alkali metal sulphide, polysulphide, hydrosulphide, hydrate thereof or mixture thereof, (2) at least one catalytically functional compound such as carbonaceous material or iron carbide and, if desired, (3) at least one filler such as natural or synthetic staple fibers or aluminum oxide.
Abstract of the disclosure:
A thermogenic composition comprising (1) at least one compound such as an alkali metal sulphide, polysulphide, hydrosulphide, hydrate thereof or mixture thereof, (2) at least one catalytically functional compound such as carbonaceous material or iron carbide and, if desired, (3) at least one filler such as natural or synthetic staple fibers or aluminum oxide.
Description
~L~97~
This invention relates to a novel thermogenic com-position and more particularly to a thermogenic compositionthat generates a large amount of heat merely through contact with air without addition of water.
There have heretofore been ~nown numbers of thermoge-nic compositions which use the thermogenic chemical phenomena as heat sources, for example:
(1) ~ composition of powder of iron, aluminum or the like and an inorganic oxidizing catalyst such as an iron sulphate, copper sulphate or iron chloride. The composition generates heat by adding water thereto and coming in contact with oxygen.
This invention relates to a novel thermogenic com-position and more particularly to a thermogenic compositionthat generates a large amount of heat merely through contact with air without addition of water.
There have heretofore been ~nown numbers of thermoge-nic compositions which use the thermogenic chemical phenomena as heat sources, for example:
(1) ~ composition of powder of iron, aluminum or the like and an inorganic oxidizing catalyst such as an iron sulphate, copper sulphate or iron chloride. The composition generates heat by adding water thereto and coming in contact with oxygen.
(2) A composition the main component of which is an inorganic oxide such as calcium oxide that ~ields a large amount of heat by reacting with or dissolving in water. For generation of heat it requires pouring of water thereinto from outside.
(3) A composition made up of sodium or potassium hydroxide and a sulphate containing water of crystallization.
It generates heat when the two components are brought into contact.
Of the above-mentioned compositions, those (1) and (2) are capable ~f generating satisfactory amounts of heat, but their use re~uires addition of large quantities of water from outside. This inconvenience largely limits the modes and scope of their practical applications.
The composition (3), on the other hand, has the advantage of requirin~ for heat generation the mere contact of the two components without water added from outside. But the heat, yenerated by dissolution and neutralization,is small in amount, bringing about a temperature not higher than about 60C.
Another disadvantage of the composition (3) is that the use of .~j ,,, .~ .
~7~
strong alkali powder as its component raises problem as to safety and storage.
The novel therrnogenic composition of the present invention is free from the above-mentioned defects and inconve-niences of conventional ones. The characteristics o-f the novel composltion are set forth as follows:
(1) With no water fed from outside at all, but merely by bringing it into contact with oxygen in the air, this compo-sition exhibits a higher thermogenic performance than the conventional ones. The highest temperature attainable and the duration of heat generation of the composition can be easil~
regulated by varying the degree of contact thereof with the air (oxygen), the weight ratio of the components thereof, and the like.
(2) The heating can be easily stopped or resumed by contact or non-contact with the air. The composition, unlike the conventional ones, does not require repeated addition of water thereto ~or sustained generation of heat, nor has it the defect that once the heating starts it cannot be stopped when desired, (3) Since no water is used, the composition, during its exothermic reaction, does not evolve steam which might scald human bodies. The reaction does not yield a toxic gas, either. The composition is, therefore, a very safe one.
It generates heat when the two components are brought into contact.
Of the above-mentioned compositions, those (1) and (2) are capable ~f generating satisfactory amounts of heat, but their use re~uires addition of large quantities of water from outside. This inconvenience largely limits the modes and scope of their practical applications.
The composition (3), on the other hand, has the advantage of requirin~ for heat generation the mere contact of the two components without water added from outside. But the heat, yenerated by dissolution and neutralization,is small in amount, bringing about a temperature not higher than about 60C.
Another disadvantage of the composition (3) is that the use of .~j ,,, .~ .
~7~
strong alkali powder as its component raises problem as to safety and storage.
The novel therrnogenic composition of the present invention is free from the above-mentioned defects and inconve-niences of conventional ones. The characteristics o-f the novel composltion are set forth as follows:
(1) With no water fed from outside at all, but merely by bringing it into contact with oxygen in the air, this compo-sition exhibits a higher thermogenic performance than the conventional ones. The highest temperature attainable and the duration of heat generation of the composition can be easil~
regulated by varying the degree of contact thereof with the air (oxygen), the weight ratio of the components thereof, and the like.
(2) The heating can be easily stopped or resumed by contact or non-contact with the air. The composition, unlike the conventional ones, does not require repeated addition of water thereto ~or sustained generation of heat, nor has it the defect that once the heating starts it cannot be stopped when desired, (3) Since no water is used, the composition, during its exothermic reaction, does not evolve steam which might scald human bodies. The reaction does not yield a toxic gas, either. The composition is, therefore, a very safe one.
(4) The composition can be sup~lied in compact form, e.g., in sheet form, since its reaction does not require water addition and a small quantity of the composition is sufficient to yield a large amount of heat. Because of these advantages the composition have a wider range of applications than the conventional ones.
The composition of the present invention will be detailed hereinbelow:
~9~g~
Alkali metal sulphides, polysulphides or hydrates thereof, or hydrosulphides (hereinafter called A component) used in the preparation of the composition of this invention include alkali metal sulphides, polysulphides, hydrosulphides and hydrates thereof in powder form, the alkali metal being Li, Na, K, Rb, Cs or the like. These alkali metal compolmds may be used singly or jointly as the A component. of the alkali metals used in the preparation of the compounds, Na and K are preferred with Na being more preferred. These alkali metal compounds are thermally stable in the air and generate no heat for themsel~es.
They yield heat, however, when mixed with a carbonaceous material ~her~inafter called s component) such as carbon black and exposed to the air.
The B component is at least one compound ~elected from (1) carbonaceous materials, (2) iron carbide, ~3) activated clay, (4) iron, nickel and cobalt sulphates and hydrates thereof,
The composition of the present invention will be detailed hereinbelow:
~9~g~
Alkali metal sulphides, polysulphides or hydrates thereof, or hydrosulphides (hereinafter called A component) used in the preparation of the composition of this invention include alkali metal sulphides, polysulphides, hydrosulphides and hydrates thereof in powder form, the alkali metal being Li, Na, K, Rb, Cs or the like. These alkali metal compolmds may be used singly or jointly as the A component. of the alkali metals used in the preparation of the compounds, Na and K are preferred with Na being more preferred. These alkali metal compounds are thermally stable in the air and generate no heat for themsel~es.
They yield heat, however, when mixed with a carbonaceous material ~her~inafter called s component) such as carbon black and exposed to the air.
The B component is at least one compound ~elected from (1) carbonaceous materials, (2) iron carbide, ~3) activated clay, (4) iron, nickel and cobalt sulphates and hydrates thereof,
(5) derivatives of sulphonated anthraquinone, and the like. With respectts thermogenic capability, carbonaceous materials and iron ~carbide in combination are the most recommendable.
The invention relates to a thermsgenic composition comprising (A) at least sne compound selected frsm the group consisting of alkali metal sulphides, polysulphides, hydro-sulphides, hydrates th'ereof and mixtures thereof and (B) at least one compound serving catalytically for the generation of heat of the compound (A), said compound (s) being a member - sèlected from t~e group consisting of (1) carbonaceous material, (2~ iron carbide, (3) activated clay, (4) at least one member selected from the group consisting of iron, nickel and cobalt sulphates and hydrates thereof and (5) at least one anthraquinonesulfonate derivative.
'7 The carbonaceous materials are carbon black, active carbon, wood charcoal, coal, coke, pitch, asphalt, soot and the like. Particularly desirable are highly surface active matexials such as carbon black, active carbon and wood charcoal. Such a substance adhering to a carrier may also be used as the s compo-nent.
Iron carbide may be produced by the method previously developed by the same inventors of this composition as described in Japanese Patent Applications No. 728~9/73, No. 118644/74, No~
10 22272/74 (corresponding to Japanese Patent Application Laying-Open Gazettes Nos. 22000/75, 45700/76 and 116397/75, respective-ly), etc. It is obtained by thermal decomposition o~ Prussian blue in an inert or non-oxidizing atmosphere.
-3a-~, ~
The B components used herein also include active clay, iron, nickel and cobalt sulphates and hydrates thereof, and potassium salt or other derivatives of anthraquinone sulpho-nate. Any one of these can be used singly or in combination with one or more of the other B components previously named.
The A and B components in powder form may be of various diameters. In general, the smaller the diameter, the better thermogenic effect is obtained.
In the invention particle sizes of 10 mesh or finer may be employed, but larger sizes may be used too. A minute arnount of water may be present in the A and B components.
The heat generating mechanism of the thermogenic composition of this invention is not clearly known as yet. It -is assumed, howe~er, that the heat produced by, as the heat source, the oxidation of the A component with oxygen in the air and that the reaction is catalyzed by the ~ component. This assumption is supported by the facts that the A component does not generate heat unless it is mixed with the B component, that a large quantity of sulphuric acid radical is detected in the analysis of the thermog^enic reaction products. The yield of heat or calorific value (cal/g) of the thermoyenic co~position of this invention, therefore, is variable according to the A and B components, as the heat sources,and the desired yield of heat, that is, calorific value is obtainable by regulating the mixing ratio of the A and B components. In this case, however, it is preferable that the A component is kept within the range of 10 -90% by weight. If the ratio is less than 10%, the yield of heat is insufficient and if the ratio exceeds 90%, the thermogenic efficiency falls owing to the insufficient contact with the B component.
The velocity and duration of thermogenic reaction can be controlled as desired by changing the area of contact ~7~7 with air, more specifically, by changiny the particle sizes of the A and B components, the quantity of air flow, the kind and quantity of the filler, etc.
The fillers (hereinafter called C component) function as a heat buffer to inhibit a sudden change in temperature due to heat ~eneration and radiation and also as a heat preserver to retain heat, in addition, the fillers may preferably be porous, permeable to the air, and small in specific gravity.
They include natural fibers in staple form such as wooa dust, cotton linter and cellulose, synthetic fibers in staple form such as polyester staple fibers; waste of foamed synthetic resins such as foamed polystyrene and polyurethane,-and other materials such as silica powder, porous silica gel, Glauber's salt (sodium sulphat~), bariurn sulphate, iron o~ides and aluminum o~ide. The weight ratio of the C component/A and B
components may range from 0/100 to 90/lO,preferably from 20~80 to 70/30-Since the thermogenic composition of this inventioncontains not only the A component but also the B component which is assumed to catalyze the thermogenic reaction of the A com-ponent, the control of heat generation will be easy as compared with the other types of composition wherein only the ~ components is contained even if the filler be not used. As a result, the control of heat and the preservation thereof are possible by using a less quantity of the cornposition of the present invention.
The thermogenic composition of this inven-tion gererates heat of about 100 - 1,100 cal/g in the air, with the highest attainable temperature of above 200C. For comparison, the conventional iron powder-iron sulphate-water cornposition yields heat of about 20 cal/g with the highest attainable temperature of below 100C.
~397~
Of the oxygen sources, air is the most convenient and inexpensive. Other materials to serve the purpose includ~
pure oxygen and substances that release oxygen by chemical reactions.
The thermogenic composition of this invention rnay take various forms of marketable finished goods. In general, it may be vacuum-packed or packed with an inert gas like nitrogen or argon in a bag or vessel made of a material impermeable to air like aluminum foil, a metal vessel or plastic film so that at the time of use the package may be opened to contact the compostion with air. Or the A and B components may-be separately placed in an air-permeable material and at the time -of use they are mixed for heat generation.
The velocity and duration of the thermogenic reaction may be controlled by varying the area of contact with oxygen and other means, that is, varying the weight ratio of the A and B components, diameters of their particles, flow rate of oxygen, - kind or quantity of the filler, etc.
The rate of air (oxygen) supply may be controlled by one of the following methods or a combination of some of them:
(1) The thermogenic composition is placed in a container made of air-impermeable material. The container has one or more air inlet holes on the outside wall. The speed of the air supply is controlled by varying the diameter or the number of the holes.
(2) T~e thermogenic composition is placed in a container made of an air-permeable material and the speed of air supply is controlled by varying the air permeability of the container.
(3) The thermogenic composition is placed in the inner container made of an air-permeable material. The inner container is placed in the outer container made of material
The invention relates to a thermsgenic composition comprising (A) at least sne compound selected frsm the group consisting of alkali metal sulphides, polysulphides, hydro-sulphides, hydrates th'ereof and mixtures thereof and (B) at least one compound serving catalytically for the generation of heat of the compound (A), said compound (s) being a member - sèlected from t~e group consisting of (1) carbonaceous material, (2~ iron carbide, (3) activated clay, (4) at least one member selected from the group consisting of iron, nickel and cobalt sulphates and hydrates thereof and (5) at least one anthraquinonesulfonate derivative.
'7 The carbonaceous materials are carbon black, active carbon, wood charcoal, coal, coke, pitch, asphalt, soot and the like. Particularly desirable are highly surface active matexials such as carbon black, active carbon and wood charcoal. Such a substance adhering to a carrier may also be used as the s compo-nent.
Iron carbide may be produced by the method previously developed by the same inventors of this composition as described in Japanese Patent Applications No. 728~9/73, No. 118644/74, No~
10 22272/74 (corresponding to Japanese Patent Application Laying-Open Gazettes Nos. 22000/75, 45700/76 and 116397/75, respective-ly), etc. It is obtained by thermal decomposition o~ Prussian blue in an inert or non-oxidizing atmosphere.
-3a-~, ~
The B components used herein also include active clay, iron, nickel and cobalt sulphates and hydrates thereof, and potassium salt or other derivatives of anthraquinone sulpho-nate. Any one of these can be used singly or in combination with one or more of the other B components previously named.
The A and B components in powder form may be of various diameters. In general, the smaller the diameter, the better thermogenic effect is obtained.
In the invention particle sizes of 10 mesh or finer may be employed, but larger sizes may be used too. A minute arnount of water may be present in the A and B components.
The heat generating mechanism of the thermogenic composition of this invention is not clearly known as yet. It -is assumed, howe~er, that the heat produced by, as the heat source, the oxidation of the A component with oxygen in the air and that the reaction is catalyzed by the ~ component. This assumption is supported by the facts that the A component does not generate heat unless it is mixed with the B component, that a large quantity of sulphuric acid radical is detected in the analysis of the thermog^enic reaction products. The yield of heat or calorific value (cal/g) of the thermoyenic co~position of this invention, therefore, is variable according to the A and B components, as the heat sources,and the desired yield of heat, that is, calorific value is obtainable by regulating the mixing ratio of the A and B components. In this case, however, it is preferable that the A component is kept within the range of 10 -90% by weight. If the ratio is less than 10%, the yield of heat is insufficient and if the ratio exceeds 90%, the thermogenic efficiency falls owing to the insufficient contact with the B component.
The velocity and duration of thermogenic reaction can be controlled as desired by changing the area of contact ~7~7 with air, more specifically, by changiny the particle sizes of the A and B components, the quantity of air flow, the kind and quantity of the filler, etc.
The fillers (hereinafter called C component) function as a heat buffer to inhibit a sudden change in temperature due to heat ~eneration and radiation and also as a heat preserver to retain heat, in addition, the fillers may preferably be porous, permeable to the air, and small in specific gravity.
They include natural fibers in staple form such as wooa dust, cotton linter and cellulose, synthetic fibers in staple form such as polyester staple fibers; waste of foamed synthetic resins such as foamed polystyrene and polyurethane,-and other materials such as silica powder, porous silica gel, Glauber's salt (sodium sulphat~), bariurn sulphate, iron o~ides and aluminum o~ide. The weight ratio of the C component/A and B
components may range from 0/100 to 90/lO,preferably from 20~80 to 70/30-Since the thermogenic composition of this inventioncontains not only the A component but also the B component which is assumed to catalyze the thermogenic reaction of the A com-ponent, the control of heat generation will be easy as compared with the other types of composition wherein only the ~ components is contained even if the filler be not used. As a result, the control of heat and the preservation thereof are possible by using a less quantity of the cornposition of the present invention.
The thermogenic composition of this inven-tion gererates heat of about 100 - 1,100 cal/g in the air, with the highest attainable temperature of above 200C. For comparison, the conventional iron powder-iron sulphate-water cornposition yields heat of about 20 cal/g with the highest attainable temperature of below 100C.
~397~
Of the oxygen sources, air is the most convenient and inexpensive. Other materials to serve the purpose includ~
pure oxygen and substances that release oxygen by chemical reactions.
The thermogenic composition of this invention rnay take various forms of marketable finished goods. In general, it may be vacuum-packed or packed with an inert gas like nitrogen or argon in a bag or vessel made of a material impermeable to air like aluminum foil, a metal vessel or plastic film so that at the time of use the package may be opened to contact the compostion with air. Or the A and B components may-be separately placed in an air-permeable material and at the time -of use they are mixed for heat generation.
The velocity and duration of the thermogenic reaction may be controlled by varying the area of contact with oxygen and other means, that is, varying the weight ratio of the A and B components, diameters of their particles, flow rate of oxygen, - kind or quantity of the filler, etc.
The rate of air (oxygen) supply may be controlled by one of the following methods or a combination of some of them:
(1) The thermogenic composition is placed in a container made of air-impermeable material. The container has one or more air inlet holes on the outside wall. The speed of the air supply is controlled by varying the diameter or the number of the holes.
(2) T~e thermogenic composition is placed in a container made of an air-permeable material and the speed of air supply is controlled by varying the air permeability of the container.
(3) The thermogenic composition is placed in the inner container made of an air-permeable material. The inner container is placed in the outer container made of material
-6-impermeable to air. The outer container has an air inlet opening and the speed of air supply is controlled by varying the greatness of the opening.
As an example of the method (1), which uses the container of air-impermeable material such as plastic film or metal foil, 10 -- 20g of the thermogenic composition are placed in a bag measuring ~cm x 12cm which has 20 - ~0 holes of 2.5mm diameter each. By varying the n~nber of holes it is possible to control the temperature and the duration of heating at desired levels between 50 and 65C and between 1 and 2.5 hours, respectively.
Similar controls of the temperature and the duration of heating may also be attained ~y using paper, cloth, or their resin-treated products as the material of the container according to the degrees of their air-permeabilityO
In the case of the method (3), which uses theinner and outer containers, the air inlet opening of the outer container may have the device to open or close the hole or change the opening space so that the temperature of heating as to change the temperature or to suspend the heating midway.
The thermogenic composition in sheet form may be used in a stationary state or in a moving state as in the case it is attached to a human body. Though the air inlet hole has the same opening space there is a difference in the speed of air supply between the two cases causing a difference in temperature attainable by thermogenic reaction.
The thermogenic composition of the present invention makes it possible for users to gain the desired temperature or change the temperature when desired by regulating the air 3t7~
supply according to the purpose and mode of it,s use.
The proper material of the container to hold the thermogenic composition may be selected from a wide range of materials including natural fibers, synthetic fibers, paper, plastic films, and metal foils. Composite materials made up of some of these materials may ~e used, too. Particularly, it i desirable that the material be made partly or wholly made up of a substance having a high thermal conductivity.
The sheet containing the thermogenic composition of this invention, though its thickness may be as small as 2mm to 5mm, is capable of sufficiently heating other objects since the composition genérates a large amount of heat. The ; use of a higly thermoconductive substance as sheet material may eliminate local variation of heating though the thermogenic composition may be divided into sections with some spaces between them.
The thermogenic composition of this invention generates heat merely by contacting with air without need of water addition. For generation of heat it is necessary, therefore, that its container admits air for supply of oxygen. Since the composition needs no water addition, it may be placed in a thin sheet consisting of small compartments.
To make the container permeable to air this invention uses as its material a film or foil with tiny holes, cloth, net, etc.
The material may be selected in consideration o~ the degree of its air permeability to obtain the desired temperature and duration of the heat generation.
In this invention the compartments to contain the thermo~enic composition are 1 to 5cm square each. The compartments may be separated by air-permeable wal]s or may be independent completely. In the case of independent com-partments, fairly large spaces may b0 placed between corn-partments or between groups of compartments so that the spaces may be used for cutting the sheet or connect separate sheets into desired shapes including non-flat and solid shapes. This way the sheets may be used in belly warmers, shoulder warmers and other articles that warm wide areas of contact.
In order to retain the encased thermogenic composition in its place without undesirable displacement, ensure a uniform gerleration of heat and a soft structure as the case for the composition, the case of support for the composition may be made of a hair-planted cloth, pile cloth, reticulate sheet, tubular material or it may be screen printed to form -thereon compartments defined by relieved lines produced by the printing.
Materials of good thermal conductivity are used for manufacture of the whole or part o~ the container of support. These materials include metal foil, film or sheet laminated with metal or coated with metal deposited in vapour phase, metal thread sheet or net, and cloth or sheet incorporated with metal granules or powder of metal or other substances.
The thermogenic composition of this invention itself may also be pressed in sheet or pellet form so that it may not be scattered away when part of its covering is opened to contact it with oxygen in the air.
Examples of encased therrnogenic cornposition embodying this invention are given in the following diagrammatic drawings. Or course, practical applications of this invention are not lirnited to these examples.
... .. . ... . ..
As an example of the method (1), which uses the container of air-impermeable material such as plastic film or metal foil, 10 -- 20g of the thermogenic composition are placed in a bag measuring ~cm x 12cm which has 20 - ~0 holes of 2.5mm diameter each. By varying the n~nber of holes it is possible to control the temperature and the duration of heating at desired levels between 50 and 65C and between 1 and 2.5 hours, respectively.
Similar controls of the temperature and the duration of heating may also be attained ~y using paper, cloth, or their resin-treated products as the material of the container according to the degrees of their air-permeabilityO
In the case of the method (3), which uses theinner and outer containers, the air inlet opening of the outer container may have the device to open or close the hole or change the opening space so that the temperature of heating as to change the temperature or to suspend the heating midway.
The thermogenic composition in sheet form may be used in a stationary state or in a moving state as in the case it is attached to a human body. Though the air inlet hole has the same opening space there is a difference in the speed of air supply between the two cases causing a difference in temperature attainable by thermogenic reaction.
The thermogenic composition of the present invention makes it possible for users to gain the desired temperature or change the temperature when desired by regulating the air 3t7~
supply according to the purpose and mode of it,s use.
The proper material of the container to hold the thermogenic composition may be selected from a wide range of materials including natural fibers, synthetic fibers, paper, plastic films, and metal foils. Composite materials made up of some of these materials may ~e used, too. Particularly, it i desirable that the material be made partly or wholly made up of a substance having a high thermal conductivity.
The sheet containing the thermogenic composition of this invention, though its thickness may be as small as 2mm to 5mm, is capable of sufficiently heating other objects since the composition genérates a large amount of heat. The ; use of a higly thermoconductive substance as sheet material may eliminate local variation of heating though the thermogenic composition may be divided into sections with some spaces between them.
The thermogenic composition of this invention generates heat merely by contacting with air without need of water addition. For generation of heat it is necessary, therefore, that its container admits air for supply of oxygen. Since the composition needs no water addition, it may be placed in a thin sheet consisting of small compartments.
To make the container permeable to air this invention uses as its material a film or foil with tiny holes, cloth, net, etc.
The material may be selected in consideration o~ the degree of its air permeability to obtain the desired temperature and duration of the heat generation.
In this invention the compartments to contain the thermo~enic composition are 1 to 5cm square each. The compartments may be separated by air-permeable wal]s or may be independent completely. In the case of independent com-partments, fairly large spaces may b0 placed between corn-partments or between groups of compartments so that the spaces may be used for cutting the sheet or connect separate sheets into desired shapes including non-flat and solid shapes. This way the sheets may be used in belly warmers, shoulder warmers and other articles that warm wide areas of contact.
In order to retain the encased thermogenic composition in its place without undesirable displacement, ensure a uniform gerleration of heat and a soft structure as the case for the composition, the case of support for the composition may be made of a hair-planted cloth, pile cloth, reticulate sheet, tubular material or it may be screen printed to form -thereon compartments defined by relieved lines produced by the printing.
Materials of good thermal conductivity are used for manufacture of the whole or part o~ the container of support. These materials include metal foil, film or sheet laminated with metal or coated with metal deposited in vapour phase, metal thread sheet or net, and cloth or sheet incorporated with metal granules or powder of metal or other substances.
The thermogenic composition of this invention itself may also be pressed in sheet or pellet form so that it may not be scattered away when part of its covering is opened to contact it with oxygen in the air.
Examples of encased therrnogenic cornposition embodying this invention are given in the following diagrammatic drawings. Or course, practical applications of this invention are not lirnited to these examples.
... .. . ... . ..
7~7 Each drawing is a diagrarnmatic cross-sectional view illustrating a specific encased thermogenic composition ernbodying the present i~vention and the manner of i~5 use.
~ Fig. 1 shows an encased thermogenic composition which is filled between the inner and outer walis of the receptacle or case, the thermogenic composition being designated at 1, Fig. 2 presents a variation of the case in which the thermogenic composition 1 is packed between the douhle bottom walls, Fig. 3 shows another variation of the encased thermogenic composition of Fig. 1, in which variation a heat conductive oxygen-impermeable coat 3 enclosing the composition 1 is fitted to a lid 2, Fig. 4 shows a thermogenic composition 1 enclosed in a rod-like case 3 and the encased composition body 4a partly inserted into a container 5a for heating the contents 6 therein;
Fig. 5 shows an encased thermogenic composition body 4b in whcih a container 5b is placed for heating saXe (Japanese rice wine), coffee, milk or the like therein, Fig. 6 shows another variation of the encased composition body 4b of Fig. 5, in which variation a container Sb is surrounded with the encased composition body 4c in flexible sheet form for heating the contents in the container: and Figs~7 and 8 show encased thermogenic composition bodies'4d and 4e which may removably be contacted closely with containers 5c and 5d, respectively. If the containers 5c and 5d are disposable ones in Figs. 7 and 8, the encased .~
~7~7 thermogenic compositions 4d and ~e may of course be fitted to the containers, respectively.
In order to allow the encased`t~ermogenic composition to generate heat, the composition may only be contacted with oxygen gas, usually air, as previously mentioned. Thie is achieved by perforating the oxygen gas-impermeable case with something like a needle, by peeling off from the case at least one oxygen gas-impermeable cover film sealably covering at least one perforation of opening previously provided on the case, by using a so-called - easy opening mechanism such as pull-tab, by using a screw-type perforating mechanism or by other suitable means.
The encased thermogenic compositions may be surrounded with known thermal insulating materials and they may also be closely contacted with bodies to be heated by the use of an adhesive~therebetween.
Since the thermogenic compositions of this invention can have a calorific power of at least 1,000 cal/g as previously mentioned, it is possible to produce encased thermogenic compositions having a composition suitable for their u~se and being capable of controllably generating heat.
The encased thermogenic composition may characteristically be used for heating ready-to-cook foods such as retortable pouch, canne~ and bottled foods, and noodle, for heating coffee, sake, milk, diet ~or patients, field rations and the like, for thawing frozen foods, for warming window glass to prevent ~reezing and frosting of moisture thereon in frigid zones, for pocket heaters and warmed wet dressing as a heat source, for thermally volatilizing insecticides, fungicides, perfumes and the like, 7~7 for heating plastics for welding; for hot-melt adhesives as a heat source, -for warming battery-powered communications and the like, for heating to evolve gases; for warming shoes, gloves and the like; for substituting for portable fuel;
and for warming mats and the like.
This invention will be better understood by the following Examples wherein all parts are by weight unless otherwise specified.
EX~MPLE 1 . . . _ Sodium sulphide pentahydrate having a particle size of about lOO~m and powdered activated carbon having a - particle size of not greater than l~m, the total amount ofjthese two ingredients being lg, were mixed togetherl in the weight ratios shown in the following Table thereby to obtain thermogenic compositions. Each of the thermogenic compositions so obtained was enclosed or encased in a 50-ml glass ampoule in a nitrogen atmosphere, thoroughly mixed and then exposed to the air by opening the ampoule thereby to obtain a calori-fic value shown in the following Table 1.
T~BLE 1 Sodium sulphide Calorific value Activated carbon pentahydrate(cal/g) 1 Part(s) 9 parts 110 2 " 8 " 295 4 " 6 " 230 6 " 4 " 100 The measurement of calorific value of each thermogenic composition encased in the glass ampoule was ef-fected by placing the encased composition in the sample room of an adiabetic calorimeter immersed in a thermostatic tank, break-ing the glass ampoule and then measuring a rise in temperature _; -12-.. . .
7~7 of the water in the calorimeter while passing dry air at a predetermined flow rate and a predetermined temperature for contact with the composition, from which temperature rise the calorific value of the ~hermogenic composition was calculated.
The procedure of Example 1 was followed except thàt carbon black of 16 ,um in particle size for paints (produced lmder the trademark of No. 999 by Columbian Carbon Co., Ltd.) and sodlum polysulphide having passed through a 20 mesh screen (produced by Yoneyama Pharmaceutical Industria~ Co.,.Ltd~) were substituted for the activated carbon black and the sodium sulphide as shown in the following Table 2, thereby to find the calorific value of each thermo-genic composition as shown in Table 2.
Calorific value Carbon black Sodium poly ulphide ~ /8 1 Part~s) 9 Parts 250 4 " 6 " 1,200 6 " 4 " 200
~ Fig. 1 shows an encased thermogenic composition which is filled between the inner and outer walis of the receptacle or case, the thermogenic composition being designated at 1, Fig. 2 presents a variation of the case in which the thermogenic composition 1 is packed between the douhle bottom walls, Fig. 3 shows another variation of the encased thermogenic composition of Fig. 1, in which variation a heat conductive oxygen-impermeable coat 3 enclosing the composition 1 is fitted to a lid 2, Fig. 4 shows a thermogenic composition 1 enclosed in a rod-like case 3 and the encased composition body 4a partly inserted into a container 5a for heating the contents 6 therein;
Fig. 5 shows an encased thermogenic composition body 4b in whcih a container 5b is placed for heating saXe (Japanese rice wine), coffee, milk or the like therein, Fig. 6 shows another variation of the encased composition body 4b of Fig. 5, in which variation a container Sb is surrounded with the encased composition body 4c in flexible sheet form for heating the contents in the container: and Figs~7 and 8 show encased thermogenic composition bodies'4d and 4e which may removably be contacted closely with containers 5c and 5d, respectively. If the containers 5c and 5d are disposable ones in Figs. 7 and 8, the encased .~
~7~7 thermogenic compositions 4d and ~e may of course be fitted to the containers, respectively.
In order to allow the encased`t~ermogenic composition to generate heat, the composition may only be contacted with oxygen gas, usually air, as previously mentioned. Thie is achieved by perforating the oxygen gas-impermeable case with something like a needle, by peeling off from the case at least one oxygen gas-impermeable cover film sealably covering at least one perforation of opening previously provided on the case, by using a so-called - easy opening mechanism such as pull-tab, by using a screw-type perforating mechanism or by other suitable means.
The encased thermogenic compositions may be surrounded with known thermal insulating materials and they may also be closely contacted with bodies to be heated by the use of an adhesive~therebetween.
Since the thermogenic compositions of this invention can have a calorific power of at least 1,000 cal/g as previously mentioned, it is possible to produce encased thermogenic compositions having a composition suitable for their u~se and being capable of controllably generating heat.
The encased thermogenic composition may characteristically be used for heating ready-to-cook foods such as retortable pouch, canne~ and bottled foods, and noodle, for heating coffee, sake, milk, diet ~or patients, field rations and the like, for thawing frozen foods, for warming window glass to prevent ~reezing and frosting of moisture thereon in frigid zones, for pocket heaters and warmed wet dressing as a heat source, for thermally volatilizing insecticides, fungicides, perfumes and the like, 7~7 for heating plastics for welding; for hot-melt adhesives as a heat source, -for warming battery-powered communications and the like, for heating to evolve gases; for warming shoes, gloves and the like; for substituting for portable fuel;
and for warming mats and the like.
This invention will be better understood by the following Examples wherein all parts are by weight unless otherwise specified.
EX~MPLE 1 . . . _ Sodium sulphide pentahydrate having a particle size of about lOO~m and powdered activated carbon having a - particle size of not greater than l~m, the total amount ofjthese two ingredients being lg, were mixed togetherl in the weight ratios shown in the following Table thereby to obtain thermogenic compositions. Each of the thermogenic compositions so obtained was enclosed or encased in a 50-ml glass ampoule in a nitrogen atmosphere, thoroughly mixed and then exposed to the air by opening the ampoule thereby to obtain a calori-fic value shown in the following Table 1.
T~BLE 1 Sodium sulphide Calorific value Activated carbon pentahydrate(cal/g) 1 Part(s) 9 parts 110 2 " 8 " 295 4 " 6 " 230 6 " 4 " 100 The measurement of calorific value of each thermogenic composition encased in the glass ampoule was ef-fected by placing the encased composition in the sample room of an adiabetic calorimeter immersed in a thermostatic tank, break-ing the glass ampoule and then measuring a rise in temperature _; -12-.. . .
7~7 of the water in the calorimeter while passing dry air at a predetermined flow rate and a predetermined temperature for contact with the composition, from which temperature rise the calorific value of the ~hermogenic composition was calculated.
The procedure of Example 1 was followed except thàt carbon black of 16 ,um in particle size for paints (produced lmder the trademark of No. 999 by Columbian Carbon Co., Ltd.) and sodlum polysulphide having passed through a 20 mesh screen (produced by Yoneyama Pharmaceutical Industria~ Co.,.Ltd~) were substituted for the activated carbon black and the sodium sulphide as shown in the following Table 2, thereby to find the calorific value of each thermo-genic composition as shown in Table 2.
Calorific value Carbon black Sodium poly ulphide ~ /8 1 Part~s) 9 Parts 250 4 " 6 " 1,200 6 " 4 " 200
8 " 2 " 500 The procedure of Example 1 was followed, but substituting powdered graphite having passed though a 48 mesh screen and potassium sulphide pentahydrate having passed through a 20 mesh screen for the activated carbon and the sodium sulphide, as shown in the following Table 3, thereby to find the calorific value of each thermogenic compositi.on as shown in Table 3.
;~
Potassium ~ulphideCalorific value Graphite ~ ~entahydrate _ _(cal/q) - 1 Part(s) ~ 9 Parts 100 4 " ~ " 210 6 " 4 " 320 8 " 2 " 250 The procedure of Example 1 was followed except that powdered iron carbide having an about 10-,um particle size was substituted for the activated carbon as shown in the following Table 4, thereby to find the calorific value of each thermogenic composition as shown in Table 4.
Sodium sulphideCalorific value Iron carbide pentahydrate (cal/~) _
;~
Potassium ~ulphideCalorific value Graphite ~ ~entahydrate _ _(cal/q) - 1 Part(s) ~ 9 Parts 100 4 " ~ " 210 6 " 4 " 320 8 " 2 " 250 The procedure of Example 1 was followed except that powdered iron carbide having an about 10-,um particle size was substituted for the activated carbon as shown in the following Table 4, thereby to find the calorific value of each thermogenic composition as shown in Table 4.
Sodium sulphideCalorific value Iron carbide pentahydrate (cal/~) _
9 Parts 1 Part(s) 110 8 " 2 " 230 6 " 4 " 295 4 " 6 " 100 EX~MPLE S
The procedure of Example 1 was repeated except that powdered iron carbide having passe~ through an about
The procedure of Example 1 was repeated except that powdered iron carbide having passe~ through an about
10 ~m mesh screen and sodium sulphide anhydrate haviny passed thrcugh a 48 mesh screen as shown in the following Table 5, thereby to find the calorific value of each thermogenic composition as shown in Table 5.
.~ .
37~!~7 Sodium sulphide Calorific value Iron carbide anhydrate_ (cal/ql_ 9 Parts 1 Part~s) 185 8 " 2 " 495 6 " 4 " 525 4 " 6 " 280 ~'XAMPLE 6 . . _ Following the procedure of Example 1, but substituting powdered iron carbide having an about 10-ym particle size and potassium sulphide pentahydrate having passed through a 20 mesh screen, there was obtained the calorific value of each thermogenic composition as indicated in Table 6.
Potassium sulphide Calorific value Iron carbide pentadehydrate _(cal 9 Parts 1 Part(s) 100 8 " 2 " 210 6 " 3 " 320 ~ " 4 " 250 Following the procedure of Example 1, but substituting powdered iron carbide having an about 10-~m particle size and sodium polysulphide having passed through a 20 me,sh screen as shown in Table 7, there was obtained the calorific value of each thermogenic compos.ition as shown in Table 7.
,. ~
~97~7 _ Calorific value Iron carbide Sodiwm ~olvsul~hide (cal/q) 9 Parts l Part(s3 250 8 " 2 " 500 6 " 4 " l,200 4 " 6 " 200 Comparative exarnple There were prepared a thermogenic composition of this invention having the following composition and a conventional thermogenic composition having the following compositionO For comparison, the novel and conventional thermogenic compositions were tested for calorif1c value with the result being shown in the following Table~
TABLE
__ Conventional the_moqenic Novel ther_oqenic Composition (5g) Composition (5g~
Powdered iron 3g Iron carbide 3g Ferric sulphatelg Sodium sulphide pentahydrate 2g 20 Water lg Calorific value 20 cal/g Calorific value 230 cal/g From this Table it is seen that the therrnogenic composition of this invention exhibited remarkably high calorific value and excellent perfomances as compared with the conventional one.
. . . _ Following the procedure of Example 1, but substituting sodiwn sulphide pentahydra-te having a particle size of about lO0 ~n, powdered activated carbon having particle sizes of not greater than l ~m and iron carbide having a particle size of about 10 ~m as shown in the following Table 8, there were obtained thermogenic compositions 37~7 which were then tested for their calorific value. The composition and calorific value of each thermogenic composi-tion are indicated in Table 80 TAsLE 8 Activated Sodium sulphide Calorific carbon Iron carbide pentahydratevalue (cal/q) 2 Parts 3 Part(s) 5 Parts 220 2 " 4 " 4 " 205 3 " 1 " 6 " 240 3 ~ 2 " 5 " 250 3 " 3 " 4 " 215 4 " l " 5 " 270 4 " 2 " 4 " 230 " 1 " 4 " 230 EX~MPLE 9 Carbon black for paints, having a particle size of 16 ~m (produced under the Trademark of No. 999 hy Columbian Carbon Co., Ltd.), iron carbide having a particle size of about lO ym and sodium polysulphide having passed through a 20 mesh screen, were mixed together in the ratios shown in the following Table 9 in the same manner as in Example 1 thereby to obtain thermogenic compositions which were then measured for calorific value. The results are shown in Table 9 TAsLE_9 Sodi.um Calorific Carbon black _ron carbide polysulphide value (cal/q) 2 Parts 3 Part(s) 5 Parts 895 3 " l " 6 " 960 30 3 " 2 " 5 " 1,000 4 " 1 " 5 " 1,080 4 " 2 " 4 " 930 " l " 4 " 905 .~
~75~L7 Powdered graphite having passed through a 48 mesh screen, iron carbide having a particle size of about 10 ~n and potassium sulphide pentahydrate having passed through a 20 mesh screen, were mixed together thereby to obtain thermogenic compositions which were measured for calorific value with the results being shown in the following Table 10.
TAsLE 10 Potassium Calorific sulphide value Graph teI~on carbide pentahYdrate (cal/~) _ 2 Parts3 Part(s) 5 Parts 160 3 " 1 " 6 " -185 3 " 2 " 5 " 190 4 " 1 " 5 " 210 4 " 2 " 4 " 175 " 1 " 4 " 180 -EXAMæLE 11 Carbon black having a particle size of 16 ym (produced under the trademark of Mitsubishi Carbon Black No. 900 by Mitsubishi Kasei Co., Ltd.) and sodium hydrosulphide dihydrate having passed through a 20 mesh screen, were mixed together to form thermogenic compositions which were then measured for calorific value in the same manner as in Example 1. The result~ are shown in the following Table 11.
Sodium hyclrosulphicle Calorific value Carbon black dihydrate _ _ _ (cal/~_ 9 Parts 1 Part(s) 75 7.5 " 2.5 " ~72 6 " ~ ' 645 " 5 " 521 4 " 6 " 183 ~.
~g~ L7 . _ Five parts of sodium sulphide pentahydrate having a particle size of about 100 ~m, 1 part of carbon black having a particle size of 16 ~m (produced under the trade-mark of Mitsubishi Carbon slack No. 900 by Mitsubishi Kasei Co., Ltd.), 1 part of iron carbide having a particle size of about 10 ,um, 2 parts of powdered microcrystalline cellulose having a particle size of about 40 ~um (produced under the trademark of Avicel PH 101 by Asahi Kasei Kogyo Co., Ltd.) and 1 part of anhydrous sodium carbonate having passed through a 48 mesh screen, were mixed together to produce a thermogenic composition which was then measured for calorific value in the same manner as in Example 1. The calorific value obtained was 290 cal/g.
.
Thermogenic compositions were prepared by mixing together sodium sulphide pentahydrate having a particle size of about 100 ~m, carbon black having a particle size of about 16 ,um (produced under the trademark of Mitsubishi Carbon Black No. 900 by Mitsubishi Kasei Co., Ltd.), iron carbide having a particle size of about 10 ~m and, as a temperature buffer agent, celite (made mainly of diatomaceous earth~ having a particle size of about 100 ~m, in the various ratios shown in the following Table 13.
Each o-f the thermogenic compositions so prepared was charged in a cloth-made bag or case, 80mm wide and 120mm long, and the whole mass was put in a polyester film made case which was then so perforaked to provide holes of 2.5mm in diameter for vent as indicated in the following Table 13, thereby to test the thermogenic composition for '7~7 its maximal temperature (C) attainable and duration (min.) of heat generation ak not lower than 40C. The results are shown in Table 13~
~ ~ .
, ~
'7~L7 ._ C o o '- o o IY~ ~ _ __ N _ ~ . I Ll) d' Lr) "., ~ ~ Ln ~9 ~ U~
_ _E~. _ _ ._ _ I
~ O In Ll~ O O
U~ .~ Ct) ~ ~1 r-l ,_1 . ____ __ a) ~ ~ ~ t~ Oo co ~ ~ U~ U~ U~ L~
4~ _ _~ _ . ___ .~ O O O ~0 0 ~ o~ _ ~
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~3 ~ o ~, U
.,1 r~ ~ ~ ~ ~ ~
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~ ~ U~ - o _ __ o o ~ ~ o o ~ :n r~
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_ __ ~ I ~ L~ ~ I_ X _____ ~j ~7g~7 E~AMPLE 18 . _ Fifty-eight (58) parts of sodium sulphide pentahydrate having a particle size of about 100 ~m, 12 parts of carbon blac~ having a particle size of 16 ~um (produced under the trademark of Mitsubishi Carbon black No. 900), 6 parts of iron carbide having a particle size of about 10 ~m and 23 parts of celite having a particle size of about 100 ~m, were mixed together to produce a thermogenic composition.
r~WO to four grams (2 - 4g) of the thermogenic composition so produced were placed in each compartment, 4cm x 4cm, provided with 3 to 6 vents of 2.5mm in -diameter of two cases consisting of many ~uch compartments.
One of the cases was a control made of polyester film and the other is made of a laminate of a polyester film with a - 15 ym thick aluminum foil. The polyester film case was identical with the laminate case in size and number of compartments.
The polyester film-encased thermogenic composition genexated heat at an average temperature of 52 55C with a difference of +4 - 5C between the local temperatures , while the aluminum laminate-encased one generated heat at an average temperature of 50 - 52C with a difference of +1 -2C between the local temperatures, this indicating that the latter composition could be a thermogenic sheet generating heat at a uniform temperature due to the high heat conductivity of the aluminum.
~ he thic~ness of the thermogenic sheet varies depending on the composition and amount of the thermogenic composition encased in the compartment, and it may usually be in the ~ange of 2 - 20mm.
.~ .
37~!~7 Sodium sulphide Calorific value Iron carbide anhydrate_ (cal/ql_ 9 Parts 1 Part~s) 185 8 " 2 " 495 6 " 4 " 525 4 " 6 " 280 ~'XAMPLE 6 . . _ Following the procedure of Example 1, but substituting powdered iron carbide having an about 10-ym particle size and potassium sulphide pentahydrate having passed through a 20 mesh screen, there was obtained the calorific value of each thermogenic composition as indicated in Table 6.
Potassium sulphide Calorific value Iron carbide pentadehydrate _(cal 9 Parts 1 Part(s) 100 8 " 2 " 210 6 " 3 " 320 ~ " 4 " 250 Following the procedure of Example 1, but substituting powdered iron carbide having an about 10-~m particle size and sodium polysulphide having passed through a 20 me,sh screen as shown in Table 7, there was obtained the calorific value of each thermogenic compos.ition as shown in Table 7.
,. ~
~97~7 _ Calorific value Iron carbide Sodiwm ~olvsul~hide (cal/q) 9 Parts l Part(s3 250 8 " 2 " 500 6 " 4 " l,200 4 " 6 " 200 Comparative exarnple There were prepared a thermogenic composition of this invention having the following composition and a conventional thermogenic composition having the following compositionO For comparison, the novel and conventional thermogenic compositions were tested for calorif1c value with the result being shown in the following Table~
TABLE
__ Conventional the_moqenic Novel ther_oqenic Composition (5g) Composition (5g~
Powdered iron 3g Iron carbide 3g Ferric sulphatelg Sodium sulphide pentahydrate 2g 20 Water lg Calorific value 20 cal/g Calorific value 230 cal/g From this Table it is seen that the therrnogenic composition of this invention exhibited remarkably high calorific value and excellent perfomances as compared with the conventional one.
. . . _ Following the procedure of Example 1, but substituting sodiwn sulphide pentahydra-te having a particle size of about lO0 ~n, powdered activated carbon having particle sizes of not greater than l ~m and iron carbide having a particle size of about 10 ~m as shown in the following Table 8, there were obtained thermogenic compositions 37~7 which were then tested for their calorific value. The composition and calorific value of each thermogenic composi-tion are indicated in Table 80 TAsLE 8 Activated Sodium sulphide Calorific carbon Iron carbide pentahydratevalue (cal/q) 2 Parts 3 Part(s) 5 Parts 220 2 " 4 " 4 " 205 3 " 1 " 6 " 240 3 ~ 2 " 5 " 250 3 " 3 " 4 " 215 4 " l " 5 " 270 4 " 2 " 4 " 230 " 1 " 4 " 230 EX~MPLE 9 Carbon black for paints, having a particle size of 16 ~m (produced under the Trademark of No. 999 hy Columbian Carbon Co., Ltd.), iron carbide having a particle size of about lO ym and sodium polysulphide having passed through a 20 mesh screen, were mixed together in the ratios shown in the following Table 9 in the same manner as in Example 1 thereby to obtain thermogenic compositions which were then measured for calorific value. The results are shown in Table 9 TAsLE_9 Sodi.um Calorific Carbon black _ron carbide polysulphide value (cal/q) 2 Parts 3 Part(s) 5 Parts 895 3 " l " 6 " 960 30 3 " 2 " 5 " 1,000 4 " 1 " 5 " 1,080 4 " 2 " 4 " 930 " l " 4 " 905 .~
~75~L7 Powdered graphite having passed through a 48 mesh screen, iron carbide having a particle size of about 10 ~n and potassium sulphide pentahydrate having passed through a 20 mesh screen, were mixed together thereby to obtain thermogenic compositions which were measured for calorific value with the results being shown in the following Table 10.
TAsLE 10 Potassium Calorific sulphide value Graph teI~on carbide pentahYdrate (cal/~) _ 2 Parts3 Part(s) 5 Parts 160 3 " 1 " 6 " -185 3 " 2 " 5 " 190 4 " 1 " 5 " 210 4 " 2 " 4 " 175 " 1 " 4 " 180 -EXAMæLE 11 Carbon black having a particle size of 16 ym (produced under the trademark of Mitsubishi Carbon Black No. 900 by Mitsubishi Kasei Co., Ltd.) and sodium hydrosulphide dihydrate having passed through a 20 mesh screen, were mixed together to form thermogenic compositions which were then measured for calorific value in the same manner as in Example 1. The result~ are shown in the following Table 11.
Sodium hyclrosulphicle Calorific value Carbon black dihydrate _ _ _ (cal/~_ 9 Parts 1 Part(s) 75 7.5 " 2.5 " ~72 6 " ~ ' 645 " 5 " 521 4 " 6 " 183 ~.
~g~ L7 . _ Five parts of sodium sulphide pentahydrate having a particle size of about 100 ~m, 1 part of carbon black having a particle size of 16 ~m (produced under the trade-mark of Mitsubishi Carbon slack No. 900 by Mitsubishi Kasei Co., Ltd.), 1 part of iron carbide having a particle size of about 10 ,um, 2 parts of powdered microcrystalline cellulose having a particle size of about 40 ~um (produced under the trademark of Avicel PH 101 by Asahi Kasei Kogyo Co., Ltd.) and 1 part of anhydrous sodium carbonate having passed through a 48 mesh screen, were mixed together to produce a thermogenic composition which was then measured for calorific value in the same manner as in Example 1. The calorific value obtained was 290 cal/g.
.
Thermogenic compositions were prepared by mixing together sodium sulphide pentahydrate having a particle size of about 100 ~m, carbon black having a particle size of about 16 ,um (produced under the trademark of Mitsubishi Carbon Black No. 900 by Mitsubishi Kasei Co., Ltd.), iron carbide having a particle size of about 10 ~m and, as a temperature buffer agent, celite (made mainly of diatomaceous earth~ having a particle size of about 100 ~m, in the various ratios shown in the following Table 13.
Each o-f the thermogenic compositions so prepared was charged in a cloth-made bag or case, 80mm wide and 120mm long, and the whole mass was put in a polyester film made case which was then so perforaked to provide holes of 2.5mm in diameter for vent as indicated in the following Table 13, thereby to test the thermogenic composition for '7~7 its maximal temperature (C) attainable and duration (min.) of heat generation ak not lower than 40C. The results are shown in Table 13~
~ ~ .
, ~
'7~L7 ._ C o o '- o o IY~ ~ _ __ N _ ~ . I Ll) d' Lr) "., ~ ~ Ln ~9 ~ U~
_ _E~. _ _ ._ _ I
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U~ .~ Ct) ~ ~1 r-l ,_1 . ____ __ a) ~ ~ ~ t~ Oo co ~ ~ U~ U~ U~ L~
4~ _ _~ _ . ___ .~ O O O ~0 0 ~ o~ _ ~
~ a) o ~ o E~ ~ Ln L~ In __ _ _ ~ ~ ~.3 ~o ~ ~ ~o ~
~3 ~ o ~, U
.,1 r~ ~ ~ ~ ~ ~
~o _ _ L~ I
o ~ _ o~
~rl S~ ~ ~ ~ ~ ~ ~
~ ~ ~ ~ ~1 ~ ~1 ~
~ ~ U~ - o _ __ o o ~ ~ o o ~ :n r~
O t~ ~ ~ InLr~ In U~
_ __ ~ I ~ L~ ~ I_ X _____ ~j ~7g~7 E~AMPLE 18 . _ Fifty-eight (58) parts of sodium sulphide pentahydrate having a particle size of about 100 ~m, 12 parts of carbon blac~ having a particle size of 16 ~um (produced under the trademark of Mitsubishi Carbon black No. 900), 6 parts of iron carbide having a particle size of about 10 ~m and 23 parts of celite having a particle size of about 100 ~m, were mixed together to produce a thermogenic composition.
r~WO to four grams (2 - 4g) of the thermogenic composition so produced were placed in each compartment, 4cm x 4cm, provided with 3 to 6 vents of 2.5mm in -diameter of two cases consisting of many ~uch compartments.
One of the cases was a control made of polyester film and the other is made of a laminate of a polyester film with a - 15 ym thick aluminum foil. The polyester film case was identical with the laminate case in size and number of compartments.
The polyester film-encased thermogenic composition genexated heat at an average temperature of 52 55C with a difference of +4 - 5C between the local temperatures , while the aluminum laminate-encased one generated heat at an average temperature of 50 - 52C with a difference of +1 -2C between the local temperatures, this indicating that the latter composition could be a thermogenic sheet generating heat at a uniform temperature due to the high heat conductivity of the aluminum.
~ he thic~ness of the thermogenic sheet varies depending on the composition and amount of the thermogenic composition encased in the compartment, and it may usually be in the ~ange of 2 - 20mm.
Claims (5)
1. A thermogenic composition comprising (Al at least one compound selected from the group consisting of alkali metal sulphides, polysulphides, hydrosulphides, hydrates thereof and mixtures thereof and (B) at least one compound serving catalytically for the generation of heat of the compound (A), said compound B being a member selected from the group consisting of (1) carbonaceous material, (2) iron carbide,(3) activated clay, (4) at least one member selected from the group consisting of iron, nickel and cobalt sulphates and hydrates thereof and (5) at least one anthra-quinonesulfonate derivative.
2. A thermogenic composition according to claim 1, further comprising a filler (C).
3. A thermogenic composition according to claim 2, wherein the filler (C) is selected from the group consisting of natural and synthetic staple fibers, waste of foamed synthetic resins, silica powder, porous silica gel, Glauber's salt, barium sulphate, iron oxides and aluminum oxide.
4. A thermogenic composition according to claim 1, wherein the compound (A) is present in an amount of 10-90%
by weight of the composition.
by weight of the composition.
5. A thermogenic composition according to claim 2 or claim 3 9 wherein the compound (A) is present in an amount of 10-90% by weight of the total of the compounds (A) and (B), and the filler (C) is present in a ratio by weight of from 0/100 to 90/10 between the filler (C) and the total of the compounds (A) and (B).
Applications Claiming Priority (14)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24699/76 | 1976-03-09 | ||
| JP2470076A JPS52108383A (en) | 1976-03-09 | 1976-03-09 | Exothermic composition |
| JP24700/76 | 1976-03-09 | ||
| JP2469976A JPS52108382A (en) | 1976-03-09 | 1976-03-09 | Exothermic composition |
| JP40867/76 | 1976-04-13 | ||
| JP4086776A JPS52123985A (en) | 1976-04-13 | 1976-04-13 | Exothermic composition |
| JP6929876A JPS52153254A (en) | 1976-06-15 | 1976-06-15 | Heating sheet |
| JP69297/76 | 1976-06-15 | ||
| JP6929776A JPS52153255A (en) | 1976-06-15 | 1976-06-15 | Heating sheet |
| JP69298/76 | 1976-06-15 | ||
| JP8605176A JPS5312532A (en) | 1976-07-21 | 1976-07-21 | Heating structure |
| JP86051/76 | 1976-07-21 | ||
| JP14712476A JPS5371691A (en) | 1976-12-09 | 1976-12-09 | Heat generating agent composition |
| JP147124/76 | 1976-12-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1097917A true CA1097917A (en) | 1981-03-24 |
Family
ID=27564042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA273,505A Expired CA1097917A (en) | 1976-03-09 | 1977-03-08 | Thermogenic compositions |
Country Status (8)
| Country | Link |
|---|---|
| BE (1) | BE852293A (en) |
| CA (1) | CA1097917A (en) |
| CH (1) | CH601458A5 (en) |
| DE (1) | DE2710287C3 (en) |
| FR (1) | FR2343802A1 (en) |
| GB (1) | GB1557416A (en) |
| IT (1) | IT1076886B (en) |
| NL (1) | NL182835C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1100866A (en) * | 1977-06-10 | 1981-05-12 | Keisuke Kaiho | Thermally diffusible composites |
| JPS5543132A (en) * | 1978-09-21 | 1980-03-26 | Toyo Ink Mfg Co Ltd | Heat-evolving composition |
| US4309980A (en) * | 1980-03-07 | 1982-01-12 | Thermal Energy Storage, Inc. | Closed vaporization heat transfer system |
| US5040552A (en) * | 1988-12-08 | 1991-08-20 | Philip Morris Incorporated | Metal carbide heat source |
| WO1991007996A1 (en) * | 1989-12-04 | 1991-06-13 | The Clorox Company | Fragrance device and method, chemically or mechanically activated |
| EP1205192A1 (en) * | 2000-11-07 | 2002-05-15 | The Procter & Gamble Company | Efficient self-heating device for dispensing volatile materials |
| AU2002230463A1 (en) * | 2000-11-07 | 2002-05-21 | The Procter And Gamble Company | Controllably activatable self-heating devices for dispensing volatile materials |
| EP1205195A1 (en) * | 2000-11-07 | 2002-05-15 | The Procter & Gamble Company | Controllably activatable self- heating devices for dispensing volatile materials |
| EP1205194A1 (en) * | 2000-11-07 | 2002-05-15 | The Procter & Gamble Company | Self-heating device for prolonged dispensing of volatilized materials |
| EP1205193A1 (en) * | 2000-11-07 | 2002-05-15 | The Procter & Gamble Company | Easily activatable self-heating device for dispensing volatile materials |
| DE102018209566A1 (en) * | 2018-06-14 | 2019-12-19 | BSH Hausgeräte GmbH | Method for operating a cooking device and cooking device |
-
1977
- 1977-02-28 GB GB8364/77A patent/GB1557416A/en not_active Expired
- 1977-03-07 FR FR7706608A patent/FR2343802A1/en active Granted
- 1977-03-08 NL NLAANVRAGE7702483,A patent/NL182835C/en not_active IP Right Cessation
- 1977-03-08 CA CA273,505A patent/CA1097917A/en not_active Expired
- 1977-03-08 CH CH285977A patent/CH601458A5/xx not_active IP Right Cessation
- 1977-03-09 IT IT21094/77A patent/IT1076886B/en active
- 1977-03-09 BE BE6045915A patent/BE852293A/en not_active IP Right Cessation
- 1977-03-09 DE DE2710287A patent/DE2710287C3/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| IT1076886B (en) | 1985-04-27 |
| FR2343802B1 (en) | 1980-02-15 |
| CH601458A5 (en) | 1978-07-14 |
| BE852293A (en) | 1977-07-01 |
| GB1557416A (en) | 1979-12-12 |
| NL182835C (en) | 1988-05-16 |
| NL182835B (en) | 1987-12-16 |
| DE2710287A1 (en) | 1977-09-15 |
| DE2710287C3 (en) | 1980-10-02 |
| DE2710287B2 (en) | 1980-01-31 |
| NL7702483A (en) | 1977-09-13 |
| FR2343802A1 (en) | 1977-10-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |