CA1121952A - Composition and method for preparing foams of solid liquescent materials using selected solid particulate substances - Google Patents
Composition and method for preparing foams of solid liquescent materials using selected solid particulate substancesInfo
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- CA1121952A CA1121952A CA000307960A CA307960A CA1121952A CA 1121952 A CA1121952 A CA 1121952A CA 000307960 A CA000307960 A CA 000307960A CA 307960 A CA307960 A CA 307960A CA 1121952 A CA1121952 A CA 1121952A
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- Prior art keywords
- solid
- liquescent
- solid particulate
- particulate substance
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/36—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing sulfur, sulfides or selenium
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing agents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Coke Industry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
986.012 Title: COMPOSITION AND METHOD FOR PREPARING FOAMS
OF SOLID LIQUESCENT MATERIALS USING
SELECTED SOLID PARTICULATE SUBSTANCES
Inventor: John A. Heinen ABSTRACT OF THE DISCLOSURE
Rigid forms are produced from normally solid but liquescent materials by incorporating certain selected solid particulate substances in solid liquescent material either alone or in combination with conventional blowing agents. The solid particulate substance is one which acts as a carrier for an entity which will function as a blowing agent when the material is in the liquid state but which will not be released from the solid particulate substance under normal storage conditions. The solid particulate substance does not undergo physical or chemical change itself to produce a foaming action. Properties of the foam or cellular structure produced by incorporating solid particulate substances may be varied, by utilizing various particulates, sizes, quantities and procedures, above and beyond those achieved, to impart additional characteristics such as structural strength, surface texture, color, insulative properties, skid resistance and the like. The composition and method according to the invention have particularly advantageous application in the production of sulfur foams and cellular aggregates produced by adding fluid coke or anthracite coal as the solid particulate substance to molten powdered elemental sulfur.
OF SOLID LIQUESCENT MATERIALS USING
SELECTED SOLID PARTICULATE SUBSTANCES
Inventor: John A. Heinen ABSTRACT OF THE DISCLOSURE
Rigid forms are produced from normally solid but liquescent materials by incorporating certain selected solid particulate substances in solid liquescent material either alone or in combination with conventional blowing agents. The solid particulate substance is one which acts as a carrier for an entity which will function as a blowing agent when the material is in the liquid state but which will not be released from the solid particulate substance under normal storage conditions. The solid particulate substance does not undergo physical or chemical change itself to produce a foaming action. Properties of the foam or cellular structure produced by incorporating solid particulate substances may be varied, by utilizing various particulates, sizes, quantities and procedures, above and beyond those achieved, to impart additional characteristics such as structural strength, surface texture, color, insulative properties, skid resistance and the like. The composition and method according to the invention have particularly advantageous application in the production of sulfur foams and cellular aggregates produced by adding fluid coke or anthracite coal as the solid particulate substance to molten powdered elemental sulfur.
Description
~121~52 986.012 S P E C I F I C A T I O N
BACKGROUND OF THE INVENTION
This invention relates to foams of solid liquescent materials and more particularly to a composition and method for preparing sueh foams using a solid particulate substance capable of producing a ~oaming action when incorporated in the liquescent material. _ Solid liquescent materials, that is, materials which are normally solid but which can be liquified, may have their physical properties ehanged when going from the solid to the liquid and back to the solid state. For example, the dens~ty, struetural strength and insulating effectiveness of a solid material ean be varied by expanding the material with a gas when in the liquid state to proauce a foam or cellular solid material upon hardening. For example, a teehnique for foaming sulfur has been developed by the Southwest Research Institute to produee foamed sulfur for various uses where an economical, durable, rigid foam is desired. Such sulfur foams have densities ranging from seven pounds per cubic foot to 30 pounds per cubic foot and higher jand not only can compete with plastic foams in certain applications ¦but, ~ecause of higher compressive strengths at similar thermal Iconductivity values, should find important additional uses.
~ 1.
~ Z
ll Contemplated uses for sulfur foams include use as structural elements, where good thermal insulating proper-ties are desired, and, as a consequence of high electrical resistivity and good dielectric strength, use as electrical insulation. In one commercial application of the sulfur foam developed by the Southwest Research Institute, Chevron Chemicals, Inc. is testing B Furcoat~'~ a modified sulfur foam, in the Artic as a pipeline insulation to protect the permafrost and as roadbed insulation where a one inch thick foam replaces one foot of gravel. The material is said to be foamed in place with a blowing agent~such as carbon dioxide which is mixed with the modified molten sulfur which locks in the gas as it solidifies.
Chemical or physical foaming agents, also known as blowing agents, have long been used to prepare plastic foams.
These solid, liquid or gaseous substances produce a cellular structure by gas formation in the material to be foamed either by a physical change in state or by chemical decomposition. Many such agents consequently require the presence of heat ina system to bring about a reaction or change in state or necessitate the presence of gas storage facilities for the introduction of gaseous ¦
blowing agents. The properties of typical physical and chemical foaming agents may be found in handbooks such as Modern Plastics Encyclopedia, Vol. 52, ~o. lOA, McGraw-Hill (1975), Pages 126-9.
¦Gaseous blowing agents such as carbon dioxide have been adsorbed e r~
) ~ '.
Oil the surface of activa-ted charcoal to produce plastic foams through gas release upon hea-ting (U.S. Patent 2,518,454).
Blowing agents such as carbon dioxide and refrigerants have been adsorbed on molecular sieves also. A porous particulate solid material gas carrier has been added to fluidic organic plastic material to cause expansion of the resultan-t plastic system to overcome curing shrinkage effects (U.S. Patent 3,960,785). The particula-te gas carrier, which has a highly porous structure, controllably releases entrapped gases during the plastic curing stage to provide numerous minute bubbles to offset shrinkage without essentially alerting essential physical properties of the product. Among those disclosed are fluid coke, ac-tivated alumina, activated bauxite and silica gel. Such materials have been added to various types of cementitious mixtures to successfully inhibit shrinkage. See, for example, U.S. Patent Nos. Re. 26,277; 3,503,767; 3,519,449;
3,794,504; and 3,890,157.
Urethane foams may be produced by adding fluid coke containing both gas ar.d water to a mixture of isocyanate and polyol.
The foam producing procedures described in the patents set forth above are relatively specific -to either a particular blowing agent or blowing purpose or a material to be foamed. Wi-th such specific uses general applicability of foaming techniques ~, llZ195Z
to other systems is limited and adaptation of one blow.ng agent or technique to another system cannot be made with accurate predictability. Although a foam of a chemically modified cross-linked polysulfide made from sulfur has been prepared using carbon dioxide as the blowing agent, there remains a need for a composition and method for foaming solid liquescent materials, such as elemental sulfur,by means other than the use of conventional blowing agents.
SUMMAF~Y OF THE INVENTION
.
I have discovered that rigid foams can be produced from normally solid but liquescent materials while avoiding the limitations which normally accompany the use of conventional blowing agents that rely upon a change in state or a chemical reaction to generate ~as. This is achieved, according to my invention, by incorporating certain selected solid particulate substances in the solld liquescent material either alone or in combination with conventional blowing agents. The solid particulate substance is one which acts as a carrier for an entity which will function as a blowing agent when the material is in the liquid state but which will not be released from the solid particulate substance under normal storage conditions. The solid ¦particulate substance does not undergo physical or chemical ; hange itsel to produco a loaming ac~ion ~ 52 The properties of the foam or cellular structure pro-duced by incorporating solid particulate substances may be varied, by utilizing various particulates, sizes, quantities and procedures , to a greater extent than is possible by using conventional blowing agents alone since the solid particulate substance remains in the material upon hardening and can impart properties above and beyond those achieved merely as a consequence of a foaming action. For example, certain selected particulates can also function as would conventional fillers or other additives which may be used to impart physical characteristics such as structural strength, surface texture, color, insulative properties, skid resistance and the like to the solid material At the same time, they are economical compared to conventional blowing agents.
The composition and method according to my invention have particularly advantageous application in the production of sulfur foams and cellular aggregates produced by adding fluid coke or anthracite coal as the solid particulate substance to molten powdered elemental sulfur. In addition to the incorporation of solid particulate substances, conventional blowing agents may also be utilized. The solid liquescent material is one which is solid under normal ambient conditions but may be liquified such as, most commonly, by melting or other means using heat and/or pressure or a solvent from which the material may be dried for esolidifica~ion.
_7_ .1 llZ195Z
Aecordingly, a feature of this invention is the Provision of a eomposition and method for preparing foams of solid liquescent materials using a solid particulate substance as the foaming action initiator.
A further feature of this invention is the provision of a foamed solid li~uescent material having reduced density and ineorporating a solid particulate substance not physically or ehemically eonsumed in the proeess of produeing a foaming action.
An additional feature of this invention is the provision of a composition and method for the preparation of sulrur foam, and the sulfur foam prepared thereby, utilizing various solid partieulate substanees capable of functioning as the vehicle for aehieving a foaming aetion when ineorporated in the liquescent material.
The foregoing and other features, advantages, and ob-jects of the invention will become-further apparent from the following deseription of preferred embodiments of the same.
.
DESCRIPTION OF T~E PREFERRED EMBODIMENTS
The following examples best illustrate the preferred embodiments of this invention.
llZ195Z
Fluid coke, having a particle size of 30-325 mesh, U.S. Standard Sieve size, and taken from storage under normal ambient conditions, was added to melted elemental sulfur powder obtained as "Triangle" brand from Stouffer Chemical Co. A
measured amount of sulfur was melted in an oven at 325 +F and the desi.red weight amount of fluid coke mixed in. The results, set forth in TABLE 1 which shows the constituent proportions in weight amounts, indicate that the density, in pounds per cubic foot (pcf), of the sulfur after hardening decreases as the a~ount of fluid coke increases. The density reduction is more than can be accounted for by the difference in density between the two constituents indicating that a foaming action takes place.
TABL~ 1 Run No. 1 2 3 - 4*
Sulfur 50 - 50 50 50 Fluid Coke 0 12.5 25 37.5 Density, pcf118 88.2 72 62.9 .
* reheated after mixing ~ ~ ~ t~l~ ~k llZi952 ¦~ EXAMPLE 2 The same procedure as EXAMPLE 1 was followed with the exception that the fluid coke was premixed with the sulfur and heated together with it to 325 *F. When the mixture was molten it was removed from the oven and permitted to solidify. The results, as set forth in TABLE 2, suggest that the heating of the fluid coke solid particulate additive together with the sulfur, when greater amounts are utilized, causes some loss in effective-ness of the foaming action so that the mixing procedure may be one way in which the properties of the sulfur foam may be varied.
That is, although a greater amount of solid particulate matter may be added the o~erall density can still be controlled through its apparent dependence upon the manner of mixing with the sulfur.
Run No. 5 6 7 8 Sulfur 50 50 40 50 ~luid Coke 12.5 25 30 50 ~Density, pCF 89.3 92.2 72.1 85.5 '10-. . I
!
I . I
~21~2 In this example, the same procedure as the preceding two examples was followed except that the fluid coke utilized was of a fine par-ticulate size, less than 100 mesh, and as a comparison another solid particulate material, fine anthracite coal, less than 100 mesh, was used. The results, set forth in TABLE 3, show that the use of fine solid particulate material results in a greater foaming action and reduced density compared to the larger particle size. In addition, the use of solid particulate anthraeite coal produces a sulfur foam having a~ low, or lower,a density compared to fine fluid coke indicating that a foaming action is also produced and, in the ease of addition of greater amounts of solid particulate substances, the foaming aetion appears to be more pronounced since the density i5 less than that obtained with a similar amount of fluid eoke.
Run No. 9 10 11 . 12* 13*
Sulfur 50 100 100 50 50 Fluid Coke 12~5 40 - 25 -Anthracite Coal - - 40 - 25 Density, pcf 59 61 48 55.4 58.2 * reheated for 3 minutes after mixing ~ Z
In this example, the particulate substance,fine anthracite coal and regular fluid coke,was used together with a chemical blowing agent known for use in rubbers, p-toluene sulfanyl hyrazide,obtainable as "Celogen TSH'~from Uniroyal, Inc.
The same procedure as EXAMPLE 1 was followed except that the specimens were placed back in the oven for reheating for 5 to 7 minutes after mixing. The results, set forth in TABLE 4, show that the presence of the chemical blowing agent further enhances the production of a foam to reduce the density of the product upon solidification.
Run No. 14 15 16 _ _ _ _ Sulfur 50 50 50 Anthracite Coal 25 Fluid Coke - 25 25 Cel.TSH 0.5 0 5 ~ensity, pcf 51 62.1 70.6 ~ ,.
, . : ,. . .-~.. -11~195~
~ 1' The effectiveness of other solid particulate substances was determined using the same procedure as EXAMPLE 1. The particulates were all added to sulfur in the proportions of 25 parts by weight of particulate to 100 parts by weight of sulfur.
The results for the various particulates, set forth in TABLE 5, show that the other particulates were not nearly as effective as the fluid coke and anthracite coal in reducing the density. This is both surprising and unexpected since some of these materials, known as industrial adsorbents, are taught in the prior art to be effective to foam organic plastic materials.
.' Run Particulate Density No. Substance pcf ~, . , . 17 Silica Gel 110.6 18 Clay 108 19 Gypsum 111.7 Activated Bauxite 113.8 5~21 Activated Alu-ina 123.5 ~ -13-1~
Selected particulates of those evaluated in EXAMPLE 5 were used together with the chemical blowing agent used in EXAMPLE 4 to determine whether any improvement was noted. The results, set forth in TABLE 6, show a reduction in density which is apparently due primarily to the blowing agent alone. A dense, non-adsorbent particulate, Ottawa sand, was also used for further comparison.
.
Run No. 22 23 24 Sulfur 50 5Q 50 Particulate Silica Gel Activated Bauxite Ottawa Sanc Amount 20 25 . 35 Cel. TSH 0.5 0.5 0 5 Density, pcf 93 62.6 126.7 . .
llZ195Z
EXAMæLE 7 . I
In order to determine whether or not the foaming action of the fluid coke was due to the presence- within the fluid coke pores, or upon its surface,of moisture which was vaporized, due to the heat of melting of the sulfur, to produce gaseous steam for foaming, a series of runs was used comparing the fluid coke obtained from storage under normal ambient conditions , i,e~
ordinary room temperature and humidity, versus fluid coke material dried at 250F. The results, set forth in T~BLE 7, show that the use of the dried material result~d - in only a small in~rease in density so that the ~oaming action must be due to reasons other than merely moisture content. A conventional blowing agent was also used together with the dried fluid coke with the results again indicating that drying of the fluid coke does result in some loss of blowing foaming action.
Run No. 25 26 - 27 28 _ _ _ _ I
. .
Sulfur 50 50 50 50 Fluid Coke - 25 - 25 Fluid Coke (dried) 25 _ 25 _ ; Cel. TSH - - 0,5 0 5 Density, pcf ~6.9 7~.7 80.~ 71.8 ~ ~1211 95~2 A further solid particulate substance, calcium carbide, was incorporated into molten sulfur alone and together with other substances to determine whether a foaming action would be obtained. As seen in TAsLE 8, calcium carbide was ineffective in producing any sort of foaming action by itself. However, in combination with other materials which may introduce water or moisture as a foaming material into the system, a foaming action and decrease in density was obtained. In the run incorporating gypsum, No. 32, water as bound in the gypsum was added to the mixture and the mixture reheated after all constituents mixed together.
Run No 29 30 31 32 Sulfur 50 50 50 50 Calcium Carbide 0.5 0.5 0 5 0 5 Fluid Coke - 30 - -Cl2y - - 10 Gypsum - - - 10 Density, pcf no foam 52.3 69.3 49 .
-l6- ~
11~195Z
Lightweight cellular aggregate par-ticles were produced , by mixing the solid particulate substance in molten sulfur in accordance with the procedure of EXAMPLE 1 with the exception that the resulting mixture was poured into cold water for solid-ification, An aggregate material of low density was producedhaving the properties shown in TABLE 9 when using fine and regular size fluid coke.
Run No. 33 34 35 .
Sulfur 50 5~ 50 Fluid Coke - 25 37.5 Fluid Coke (fine) 12.5 _ _ Density, pcf 88 92 86 llZ195;:
While the foregoing examples show the advantageous aspects of my invention particularly as applied to the solid liquescent material sulfur using various solid particulate substances, particularly fluid coke and anthracite coal, other materials can be used. For example paraffin wax was premixed with sulfur, melted and fluid coke added in the proportions of 50 parts by weight sulfur, 10 parts by weight wax and 25 parts by weight fluid coke to obtain a foam having a density of 78 pounds per cubic foot. Also, a combination of walnut shells and ammonium carbonate produced foaming in sulfur. Other solid~
liquescent materials,such as metal systems,and solid particulate substances,which can act as vehicles for carrying a foaming action into such systems;may be utilized. The essential criteria in such system is that mixing be obtained and foaming action produced at the temperatures involved.
While my invention is particularly suitable to the use of solid particulate substances which carry a foaming action into the solid liquescent material for reducing density, syntactic foams may also be produced using sulfur as a binder. For example, preformed bubbles, rather than bubbles formed through the foaming action of a particulate, can be used. For example, sulfur was melted and to it was~ added Grade 200 "Q-Cel" glass beads, ob-tained from Philadelphia Quartz Co., in the proportions of 53 parts sulfur and 10 parts and 7.5 parts Q-Cel respectively to ~ 52 produce syntactic foams having a densi-ty o 53.6 pounds per cubic foot and 56.~ pounds per cubic foot, respectively.
The results which have been obtained are surprising and unexpected in that certain selected solid particulate substances added to the solid but liquescent materials can result in foams which provide reduced density to the solid material upon hardening and solidification. Not all solid particulate sub-stances function successfully and some of those which one would expect to function, such as so-called industrial adsorbents, do so only in a limited manner with surprising and unexpected e-n-hancement being obtained using solid particulate substances such as fluid coke and anthracite coal with elemental sulfur. Also, a plurality of foaming actions can be obtained through use together with conventional blowing agents. Thus, there has b~en disclosed a composition and method for preparing foams from solid liquescent materials through the addition thereto of solid particulate substances as well as the foam prepared therby.
.,
BACKGROUND OF THE INVENTION
This invention relates to foams of solid liquescent materials and more particularly to a composition and method for preparing sueh foams using a solid particulate substance capable of producing a ~oaming action when incorporated in the liquescent material. _ Solid liquescent materials, that is, materials which are normally solid but which can be liquified, may have their physical properties ehanged when going from the solid to the liquid and back to the solid state. For example, the dens~ty, struetural strength and insulating effectiveness of a solid material ean be varied by expanding the material with a gas when in the liquid state to proauce a foam or cellular solid material upon hardening. For example, a teehnique for foaming sulfur has been developed by the Southwest Research Institute to produee foamed sulfur for various uses where an economical, durable, rigid foam is desired. Such sulfur foams have densities ranging from seven pounds per cubic foot to 30 pounds per cubic foot and higher jand not only can compete with plastic foams in certain applications ¦but, ~ecause of higher compressive strengths at similar thermal Iconductivity values, should find important additional uses.
~ 1.
~ Z
ll Contemplated uses for sulfur foams include use as structural elements, where good thermal insulating proper-ties are desired, and, as a consequence of high electrical resistivity and good dielectric strength, use as electrical insulation. In one commercial application of the sulfur foam developed by the Southwest Research Institute, Chevron Chemicals, Inc. is testing B Furcoat~'~ a modified sulfur foam, in the Artic as a pipeline insulation to protect the permafrost and as roadbed insulation where a one inch thick foam replaces one foot of gravel. The material is said to be foamed in place with a blowing agent~such as carbon dioxide which is mixed with the modified molten sulfur which locks in the gas as it solidifies.
Chemical or physical foaming agents, also known as blowing agents, have long been used to prepare plastic foams.
These solid, liquid or gaseous substances produce a cellular structure by gas formation in the material to be foamed either by a physical change in state or by chemical decomposition. Many such agents consequently require the presence of heat ina system to bring about a reaction or change in state or necessitate the presence of gas storage facilities for the introduction of gaseous ¦
blowing agents. The properties of typical physical and chemical foaming agents may be found in handbooks such as Modern Plastics Encyclopedia, Vol. 52, ~o. lOA, McGraw-Hill (1975), Pages 126-9.
¦Gaseous blowing agents such as carbon dioxide have been adsorbed e r~
) ~ '.
Oil the surface of activa-ted charcoal to produce plastic foams through gas release upon hea-ting (U.S. Patent 2,518,454).
Blowing agents such as carbon dioxide and refrigerants have been adsorbed on molecular sieves also. A porous particulate solid material gas carrier has been added to fluidic organic plastic material to cause expansion of the resultan-t plastic system to overcome curing shrinkage effects (U.S. Patent 3,960,785). The particula-te gas carrier, which has a highly porous structure, controllably releases entrapped gases during the plastic curing stage to provide numerous minute bubbles to offset shrinkage without essentially alerting essential physical properties of the product. Among those disclosed are fluid coke, ac-tivated alumina, activated bauxite and silica gel. Such materials have been added to various types of cementitious mixtures to successfully inhibit shrinkage. See, for example, U.S. Patent Nos. Re. 26,277; 3,503,767; 3,519,449;
3,794,504; and 3,890,157.
Urethane foams may be produced by adding fluid coke containing both gas ar.d water to a mixture of isocyanate and polyol.
The foam producing procedures described in the patents set forth above are relatively specific -to either a particular blowing agent or blowing purpose or a material to be foamed. Wi-th such specific uses general applicability of foaming techniques ~, llZ195Z
to other systems is limited and adaptation of one blow.ng agent or technique to another system cannot be made with accurate predictability. Although a foam of a chemically modified cross-linked polysulfide made from sulfur has been prepared using carbon dioxide as the blowing agent, there remains a need for a composition and method for foaming solid liquescent materials, such as elemental sulfur,by means other than the use of conventional blowing agents.
SUMMAF~Y OF THE INVENTION
.
I have discovered that rigid foams can be produced from normally solid but liquescent materials while avoiding the limitations which normally accompany the use of conventional blowing agents that rely upon a change in state or a chemical reaction to generate ~as. This is achieved, according to my invention, by incorporating certain selected solid particulate substances in the solld liquescent material either alone or in combination with conventional blowing agents. The solid particulate substance is one which acts as a carrier for an entity which will function as a blowing agent when the material is in the liquid state but which will not be released from the solid particulate substance under normal storage conditions. The solid ¦particulate substance does not undergo physical or chemical ; hange itsel to produco a loaming ac~ion ~ 52 The properties of the foam or cellular structure pro-duced by incorporating solid particulate substances may be varied, by utilizing various particulates, sizes, quantities and procedures , to a greater extent than is possible by using conventional blowing agents alone since the solid particulate substance remains in the material upon hardening and can impart properties above and beyond those achieved merely as a consequence of a foaming action. For example, certain selected particulates can also function as would conventional fillers or other additives which may be used to impart physical characteristics such as structural strength, surface texture, color, insulative properties, skid resistance and the like to the solid material At the same time, they are economical compared to conventional blowing agents.
The composition and method according to my invention have particularly advantageous application in the production of sulfur foams and cellular aggregates produced by adding fluid coke or anthracite coal as the solid particulate substance to molten powdered elemental sulfur. In addition to the incorporation of solid particulate substances, conventional blowing agents may also be utilized. The solid liquescent material is one which is solid under normal ambient conditions but may be liquified such as, most commonly, by melting or other means using heat and/or pressure or a solvent from which the material may be dried for esolidifica~ion.
_7_ .1 llZ195Z
Aecordingly, a feature of this invention is the Provision of a eomposition and method for preparing foams of solid liquescent materials using a solid particulate substance as the foaming action initiator.
A further feature of this invention is the provision of a foamed solid li~uescent material having reduced density and ineorporating a solid particulate substance not physically or ehemically eonsumed in the proeess of produeing a foaming action.
An additional feature of this invention is the provision of a composition and method for the preparation of sulrur foam, and the sulfur foam prepared thereby, utilizing various solid partieulate substanees capable of functioning as the vehicle for aehieving a foaming aetion when ineorporated in the liquescent material.
The foregoing and other features, advantages, and ob-jects of the invention will become-further apparent from the following deseription of preferred embodiments of the same.
.
DESCRIPTION OF T~E PREFERRED EMBODIMENTS
The following examples best illustrate the preferred embodiments of this invention.
llZ195Z
Fluid coke, having a particle size of 30-325 mesh, U.S. Standard Sieve size, and taken from storage under normal ambient conditions, was added to melted elemental sulfur powder obtained as "Triangle" brand from Stouffer Chemical Co. A
measured amount of sulfur was melted in an oven at 325 +F and the desi.red weight amount of fluid coke mixed in. The results, set forth in TABLE 1 which shows the constituent proportions in weight amounts, indicate that the density, in pounds per cubic foot (pcf), of the sulfur after hardening decreases as the a~ount of fluid coke increases. The density reduction is more than can be accounted for by the difference in density between the two constituents indicating that a foaming action takes place.
TABL~ 1 Run No. 1 2 3 - 4*
Sulfur 50 - 50 50 50 Fluid Coke 0 12.5 25 37.5 Density, pcf118 88.2 72 62.9 .
* reheated after mixing ~ ~ ~ t~l~ ~k llZi952 ¦~ EXAMPLE 2 The same procedure as EXAMPLE 1 was followed with the exception that the fluid coke was premixed with the sulfur and heated together with it to 325 *F. When the mixture was molten it was removed from the oven and permitted to solidify. The results, as set forth in TABLE 2, suggest that the heating of the fluid coke solid particulate additive together with the sulfur, when greater amounts are utilized, causes some loss in effective-ness of the foaming action so that the mixing procedure may be one way in which the properties of the sulfur foam may be varied.
That is, although a greater amount of solid particulate matter may be added the o~erall density can still be controlled through its apparent dependence upon the manner of mixing with the sulfur.
Run No. 5 6 7 8 Sulfur 50 50 40 50 ~luid Coke 12.5 25 30 50 ~Density, pCF 89.3 92.2 72.1 85.5 '10-. . I
!
I . I
~21~2 In this example, the same procedure as the preceding two examples was followed except that the fluid coke utilized was of a fine par-ticulate size, less than 100 mesh, and as a comparison another solid particulate material, fine anthracite coal, less than 100 mesh, was used. The results, set forth in TABLE 3, show that the use of fine solid particulate material results in a greater foaming action and reduced density compared to the larger particle size. In addition, the use of solid particulate anthraeite coal produces a sulfur foam having a~ low, or lower,a density compared to fine fluid coke indicating that a foaming action is also produced and, in the ease of addition of greater amounts of solid particulate substances, the foaming aetion appears to be more pronounced since the density i5 less than that obtained with a similar amount of fluid eoke.
Run No. 9 10 11 . 12* 13*
Sulfur 50 100 100 50 50 Fluid Coke 12~5 40 - 25 -Anthracite Coal - - 40 - 25 Density, pcf 59 61 48 55.4 58.2 * reheated for 3 minutes after mixing ~ Z
In this example, the particulate substance,fine anthracite coal and regular fluid coke,was used together with a chemical blowing agent known for use in rubbers, p-toluene sulfanyl hyrazide,obtainable as "Celogen TSH'~from Uniroyal, Inc.
The same procedure as EXAMPLE 1 was followed except that the specimens were placed back in the oven for reheating for 5 to 7 minutes after mixing. The results, set forth in TABLE 4, show that the presence of the chemical blowing agent further enhances the production of a foam to reduce the density of the product upon solidification.
Run No. 14 15 16 _ _ _ _ Sulfur 50 50 50 Anthracite Coal 25 Fluid Coke - 25 25 Cel.TSH 0.5 0 5 ~ensity, pcf 51 62.1 70.6 ~ ,.
, . : ,. . .-~.. -11~195~
~ 1' The effectiveness of other solid particulate substances was determined using the same procedure as EXAMPLE 1. The particulates were all added to sulfur in the proportions of 25 parts by weight of particulate to 100 parts by weight of sulfur.
The results for the various particulates, set forth in TABLE 5, show that the other particulates were not nearly as effective as the fluid coke and anthracite coal in reducing the density. This is both surprising and unexpected since some of these materials, known as industrial adsorbents, are taught in the prior art to be effective to foam organic plastic materials.
.' Run Particulate Density No. Substance pcf ~, . , . 17 Silica Gel 110.6 18 Clay 108 19 Gypsum 111.7 Activated Bauxite 113.8 5~21 Activated Alu-ina 123.5 ~ -13-1~
Selected particulates of those evaluated in EXAMPLE 5 were used together with the chemical blowing agent used in EXAMPLE 4 to determine whether any improvement was noted. The results, set forth in TABLE 6, show a reduction in density which is apparently due primarily to the blowing agent alone. A dense, non-adsorbent particulate, Ottawa sand, was also used for further comparison.
.
Run No. 22 23 24 Sulfur 50 5Q 50 Particulate Silica Gel Activated Bauxite Ottawa Sanc Amount 20 25 . 35 Cel. TSH 0.5 0.5 0 5 Density, pcf 93 62.6 126.7 . .
llZ195Z
EXAMæLE 7 . I
In order to determine whether or not the foaming action of the fluid coke was due to the presence- within the fluid coke pores, or upon its surface,of moisture which was vaporized, due to the heat of melting of the sulfur, to produce gaseous steam for foaming, a series of runs was used comparing the fluid coke obtained from storage under normal ambient conditions , i,e~
ordinary room temperature and humidity, versus fluid coke material dried at 250F. The results, set forth in T~BLE 7, show that the use of the dried material result~d - in only a small in~rease in density so that the ~oaming action must be due to reasons other than merely moisture content. A conventional blowing agent was also used together with the dried fluid coke with the results again indicating that drying of the fluid coke does result in some loss of blowing foaming action.
Run No. 25 26 - 27 28 _ _ _ _ I
. .
Sulfur 50 50 50 50 Fluid Coke - 25 - 25 Fluid Coke (dried) 25 _ 25 _ ; Cel. TSH - - 0,5 0 5 Density, pcf ~6.9 7~.7 80.~ 71.8 ~ ~1211 95~2 A further solid particulate substance, calcium carbide, was incorporated into molten sulfur alone and together with other substances to determine whether a foaming action would be obtained. As seen in TAsLE 8, calcium carbide was ineffective in producing any sort of foaming action by itself. However, in combination with other materials which may introduce water or moisture as a foaming material into the system, a foaming action and decrease in density was obtained. In the run incorporating gypsum, No. 32, water as bound in the gypsum was added to the mixture and the mixture reheated after all constituents mixed together.
Run No 29 30 31 32 Sulfur 50 50 50 50 Calcium Carbide 0.5 0.5 0 5 0 5 Fluid Coke - 30 - -Cl2y - - 10 Gypsum - - - 10 Density, pcf no foam 52.3 69.3 49 .
-l6- ~
11~195Z
Lightweight cellular aggregate par-ticles were produced , by mixing the solid particulate substance in molten sulfur in accordance with the procedure of EXAMPLE 1 with the exception that the resulting mixture was poured into cold water for solid-ification, An aggregate material of low density was producedhaving the properties shown in TABLE 9 when using fine and regular size fluid coke.
Run No. 33 34 35 .
Sulfur 50 5~ 50 Fluid Coke - 25 37.5 Fluid Coke (fine) 12.5 _ _ Density, pcf 88 92 86 llZ195;:
While the foregoing examples show the advantageous aspects of my invention particularly as applied to the solid liquescent material sulfur using various solid particulate substances, particularly fluid coke and anthracite coal, other materials can be used. For example paraffin wax was premixed with sulfur, melted and fluid coke added in the proportions of 50 parts by weight sulfur, 10 parts by weight wax and 25 parts by weight fluid coke to obtain a foam having a density of 78 pounds per cubic foot. Also, a combination of walnut shells and ammonium carbonate produced foaming in sulfur. Other solid~
liquescent materials,such as metal systems,and solid particulate substances,which can act as vehicles for carrying a foaming action into such systems;may be utilized. The essential criteria in such system is that mixing be obtained and foaming action produced at the temperatures involved.
While my invention is particularly suitable to the use of solid particulate substances which carry a foaming action into the solid liquescent material for reducing density, syntactic foams may also be produced using sulfur as a binder. For example, preformed bubbles, rather than bubbles formed through the foaming action of a particulate, can be used. For example, sulfur was melted and to it was~ added Grade 200 "Q-Cel" glass beads, ob-tained from Philadelphia Quartz Co., in the proportions of 53 parts sulfur and 10 parts and 7.5 parts Q-Cel respectively to ~ 52 produce syntactic foams having a densi-ty o 53.6 pounds per cubic foot and 56.~ pounds per cubic foot, respectively.
The results which have been obtained are surprising and unexpected in that certain selected solid particulate substances added to the solid but liquescent materials can result in foams which provide reduced density to the solid material upon hardening and solidification. Not all solid particulate sub-stances function successfully and some of those which one would expect to function, such as so-called industrial adsorbents, do so only in a limited manner with surprising and unexpected e-n-hancement being obtained using solid particulate substances such as fluid coke and anthracite coal with elemental sulfur. Also, a plurality of foaming actions can be obtained through use together with conventional blowing agents. Thus, there has b~en disclosed a composition and method for preparing foams from solid liquescent materials through the addition thereto of solid particulate substances as well as the foam prepared therby.
.,
Claims (23)
1. In a method for preparing foams of solid liquescent materials including the steps of liquefying the solid material, incorporating a substance in the liquefied material capable of foaming the material, causing the liquefied material to foam by expansion in the liquid state and allowing the material to harden in the expanded state to produce a solid foam, the improvement comprising selecting as the substance a solid particulate substance which acts as a carrier for an entity which is capable of being released and functioning as blowing agent for producing a foaming action in the liquefied material without the solid particulate substance carrier under-going physical or chemical change itself to produce such action but which entity will not be released from the solid particulate substance carrier under normal ambient storage conditions in which the liquescent material is solid and in-corporating the solid particulate substance in the solid liquescent material in an amount effective to cause the material to expand when in the liquid state.
2. A method for preparing foams of solid liquescent materials as claimed in Claim 1 wherein the solid particulate substance is incorporated in the solid liquescent material after the solid liquescent material has been liquefied.
3. A method for preparing foams of solid liquescent materials as claimed in Claim 1 further including the step of mixing the solid liquescent material and the solid particulate substance together in the solid state.
4. A method for preparing foams of solid liquescent materials as claimed in Claim 1 wherein the solid particulate substance is one selected from the group consisting of fluid coke and anthracite coal.
5. A method for preparing foams of solid liquescent materials as claimed in Claim 4 wherein the solid liquescent material is sulfur.
6. A method for preparing foams of solid liquescent materials as claimed in Claim 1 wherein the solid particulate substance is of a size finer than 100 mesh.
7. A method for preparing foams of solid liquescent materials as claimed in Claim 1 further including the step of incorporating in the material a conventional blowing agent which expands the material by undergoing a chemical reaction or change of state to produce a gas.
8. A method for preparing foams of solid liquescent materials as claimed in Claim 1 wherein the solid particulate substance is one which produces a foaming action through the release of gas under the conditions of incorporation in the liquefied material.
9. A method for preparing foams of solid liquescent materials as claimed in Claim 1 wherein the solid particulate substance is one which produces a foaming action through the release of a chemical blowing agent under the conditions of incorporation in the liquefied material.
10. A method for preparing foams of solid liquescent materials as claimed in Claim 1 wherein the solid particulate substance is one which produces a foaming action through the release of both gas and a chemical blowing agent under the conditions of incorporation in the liquefied material.
11. A method for preparing foams of solid liquescent materials as claimed in Claim 1 wherein the solid liquescent material is liquefied by heating to melting.
12. A rigid sulfur foam comprising sulfur and a solid particulate substance selected from the group consisting of fluid coke and anthracite coal, said foam having a reduced density in relation to the density of a mixture of said fluid coke and anthracite coal in the absence of said foam.
13. A rigid sulfur foam as claimed in Claim 12 having a density, in pounds per cubic feet, of less than 90.
14. A rigid sulfur foam as claimed in Claim 12 wherein the amount of solid particulate substance, based on total weight of sulfur and solid particulate substance, is greater than 20 percent by weight.
15. A rigid sulfur foam as claimed in Claim 12 where the solid particulate substance has a particle size finer than 100 mesh.
16. A composition for producing a foam of solid liquescent materials comprising solid liquescent material and a solid particulate substance, the solid particulate substance being one which is capable of producing a foaming action by expanding the solid liquescent material when in a liquid state without undergoing physical or chemical change itself to produce such action, the solid particulate substance being present in an amount effective to expand the liquid liquescent material to produce a rigid foam when solidified.
17. A composition for producing a foam of solid liquescent material as claimed in Claim 16 wherein the solid particulate substance is one selected from the group consisting of fluid coke and anthracite coal.
18. A composition for producing a foam of solid liquescent material as claimed in Claim 17 wherein the solid liquescent material is sulfur.
19. A composition for producing a foam of solid liquescent material as claimed in Claim 16 wherein the solid particulate substance is of a size finer than 100 mesh.
20. A composition for producing a foam of solid liquescent material as claimed in Claim 16 further comprising a conventional blowing agent which expands the material by undergoing a chemical reaction or change of state to produce a gas.
21. A composition for producing a foam of solid liquescent material as claimed in Claim 16 wherein the solid particulate substance is one which produces a foaming action through the release of gas under the conditions of incorporation in the liquefied material.
22. A composition for producing a foam of solid liquescent material as claimed in Claim 16 wherein the solid particulate substance is one which produces a foaming action through the release of a chemical blowing agent under the conditions of incorporation in the liquefied material.
23. A composition for producing a foam of solid liquescent material as claimed in Claim 16 wherein the solid particulate substance is one which produces a foaming action through the release of both gas and a chemical blowing agent under the conditions of incorporation in the liquefied material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US82023577A | 1977-07-29 | 1977-07-29 | |
| US820,235 | 1992-01-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1121952A true CA1121952A (en) | 1982-04-20 |
Family
ID=25230263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000307960A Expired CA1121952A (en) | 1977-07-29 | 1978-07-24 | Composition and method for preparing foams of solid liquescent materials using selected solid particulate substances |
Country Status (4)
| Country | Link |
|---|---|
| CA (1) | CA1121952A (en) |
| DE (1) | DE2833142A1 (en) |
| FR (1) | FR2398707A1 (en) |
| GB (1) | GB2002727B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1195020A (en) * | 1980-09-12 | 1985-10-08 | Robert E. Loov | Freeze/thaw durable sulphur compositions |
| US4426456A (en) | 1980-09-12 | 1984-01-17 | Sulphur Development Institute Of Canada (Sudic) | Freeze/thaw durable sulphur compositions |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2518454A (en) * | 1944-11-14 | 1950-08-15 | Myron A Elliott | Manufacture of water sealed cable and construction thereof |
| US3300296A (en) * | 1963-07-31 | 1967-01-24 | American Can Co | Method of producing a lightweight foamed metal |
| US3337355A (en) * | 1965-02-04 | 1967-08-22 | Southwest Patents Inc | Solid foamed sulphur and process for the manufacture thereof |
| US3960785A (en) * | 1972-03-13 | 1976-06-01 | Construction Products Research, Inc. | Composition and method for inhibiting curing shrinkage in organic plastic systems |
| FR2196370B1 (en) * | 1972-08-17 | 1976-11-12 | Chevron Res |
-
1978
- 1978-07-24 CA CA000307960A patent/CA1121952A/en not_active Expired
- 1978-07-28 GB GB7831552A patent/GB2002727B/en not_active Expired
- 1978-07-28 FR FR7822507A patent/FR2398707A1/en active Granted
- 1978-07-28 DE DE19782833142 patent/DE2833142A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| DE2833142A1 (en) | 1979-02-08 |
| FR2398707B3 (en) | 1981-04-30 |
| GB2002727A (en) | 1979-02-28 |
| GB2002727B (en) | 1982-06-16 |
| FR2398707A1 (en) | 1979-02-23 |
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