CA1086884A - Stabilized sulphur cements and concretes - Google Patents
Stabilized sulphur cements and concretesInfo
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- CA1086884A CA1086884A CA332,505A CA332505A CA1086884A CA 1086884 A CA1086884 A CA 1086884A CA 332505 A CA332505 A CA 332505A CA 1086884 A CA1086884 A CA 1086884A
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Abstract
ABSTRACT OF THE DISCLOSURE
Novel sulphur cement pre-mixes and sulphur cement and concretes derived therefrom are provided herein. They contain, in addition to the sulphur, a bonding agent which is adapted to stabilize the sulphur cement or sulphur concrete against pro-gressive embrittlement and mechanical failure under thermal or physical stress, the bonding agent being selected from the group consisting of (i) up to 10% by weight of the total amount of sulphur, of a liquid organic agent adapted to stabilize said sulphur cement against progressive embrittlement and subsequent crumbling under thermal stress, said agent comprising an olefinic hydrocarbon polymer material, and having a non-volatile content greater than 50% by weight and a minimum Wijs iodine number of 100 cg/g, such polymer material being capable of reacting with sulphur to form a sulphur-containing polymer and being present in the sulphur cement as said sulphur-containing polymer; and (ii) a mixture of up to 10% by weight of the total amount of sulphur, of said liquid organic agent (i) and, for each 100 parts by weight of sulphur, from 10 to 150 parts by weight of a viscosity increasing, surface active, finely divided, particulate solid inorganic agent, said inorganic agent being of a size passing through a screen having a sieve opening of 0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulver-ized limestone and a mixture of pyrites and pyrrhctites. Novel sulphur concretes are also provided, which are made from sulphur cement and conventional natural or manufactured aggregates.
These sulphur cements do not suffer from the progressive embrit-tlement and mechanical failure under thermal or physical stress, of the hertofore provided conventional sulphur cements or sulphur concretes.
Novel sulphur cement pre-mixes and sulphur cement and concretes derived therefrom are provided herein. They contain, in addition to the sulphur, a bonding agent which is adapted to stabilize the sulphur cement or sulphur concrete against pro-gressive embrittlement and mechanical failure under thermal or physical stress, the bonding agent being selected from the group consisting of (i) up to 10% by weight of the total amount of sulphur, of a liquid organic agent adapted to stabilize said sulphur cement against progressive embrittlement and subsequent crumbling under thermal stress, said agent comprising an olefinic hydrocarbon polymer material, and having a non-volatile content greater than 50% by weight and a minimum Wijs iodine number of 100 cg/g, such polymer material being capable of reacting with sulphur to form a sulphur-containing polymer and being present in the sulphur cement as said sulphur-containing polymer; and (ii) a mixture of up to 10% by weight of the total amount of sulphur, of said liquid organic agent (i) and, for each 100 parts by weight of sulphur, from 10 to 150 parts by weight of a viscosity increasing, surface active, finely divided, particulate solid inorganic agent, said inorganic agent being of a size passing through a screen having a sieve opening of 0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulver-ized limestone and a mixture of pyrites and pyrrhctites. Novel sulphur concretes are also provided, which are made from sulphur cement and conventional natural or manufactured aggregates.
These sulphur cements do not suffer from the progressive embrit-tlement and mechanical failure under thermal or physical stress, of the hertofore provided conventional sulphur cements or sulphur concretes.
Description
This invention relates to sulphur cements and concretes pro-duced therefrom.
This application is a division of application Serial No.
251,362 filed April 28, 1976.
Sulphur cements have a long history of use in specialized appli-cations. Thus, Canadian Patent No. 71,636 issued to George McKay pro-vided a sulphur-containing composition useful for sealing purposes at a joint, for roofing purposes, for the forming of ornamental figures, and for the coating of the exposed surfaces of iron or steel steps, the com-position including sulphur, brick-dust, tin, lead, bismuth, plaster of paris and borax.
However, attempts to make durable, high strength concrete-like materials from sulphur cements have encountered cost, durability, or other difficulties that precluded commercialization. Proposals have been made to increase the strength of sulphur as a bonding agent by the addi-tion of coal, sand or pumice thereto. Moreover, peculiar characteristics were proposed to be imparted by the addition thereto of bitumens, metallic sulphides, and fibrous materials. Also, United States Patent j No. 3,459,717 patented August 5, 1969 by J.B. Signouret, provided a ~0 sulphur-based plastic composition of improved fireproofing characteristics by the incorporation, into the molten sulphur, of a diester of dithio-phosphoric acid and an ethylenic hydrocarbon. A major problem in the commercialization of sulphur cements has been the progressive embrittle-ment and subsequent crumbling, under thermal stress, of the sulphur cement. The cause of this embrittlement is believed to be the progressive crystallization of the initially amorphous sulphur. Partial inhibition of the crystallization has been achieved through various organic and inorganic additives.
Thiokol (Trade Mark of Thiokol Chemical Corporation for olefin polysulphide products) have been used to stabilize the amorphous form of ~L
., 1 q~
, ~ : ' sulphur in sulphur cements. Thtl8, Canadian Patent No. 356,181 lssued February 25, l936 to W.W. Vuecker, purports to provide a solution to the problem by dissolving, in the sulphur, certain olefin polysulphides or polymerization products thereof. These cements, however, were not practical on a large scale due to their high cost and disagreeable odor.
Dicyclopentadiene has good stabilization properties and more favourable economics, but imparts a nauseating odor to the sulphur cement and has other shortcomings, e.g., its vapour, even at low concentrations, is highly toxic [see, for example, Kinkead et al, "The Mammalian Toxicity of Dicyclopentadiene", Toxicology and Applied Pharmacology, 20 552-561 (1971)]. Moreover, dicyclopentadiene requires refluxing with molten sulphur to avoid excessive loss of material in vapour form.
An object of one aspect of this invention now provided by the present divisional application is to provide a sulphur cement composition which does not suffer the disadvantages of the compositions of the prior art.
An object of another aspect of this invention now provided by the present divisional application is to provide a more durable sulphur cement.
An object of yet another aspect of this invention now provided by the present divisional application is to provide a sulphur cement which can be made with off-grade sulphur.
An object of still another aspect of this invention now pro-vided by the present divisional application is to provide a sulphur cement which is resistant to the corrosive influence of salts, most acids and solvents.
An object of a further aspect of this invention now provided by the present divisional application is to provide a sulphur cement which provides good thermal insulation and which develops high strength without hours of cooling.
. -- 2 --' ' - ~
~136884 ., An ob~ect of yet a further aspect of this invention now pro-vided by the present divisional application i9 to provide sulphur con-cretes made with the sulphur cements, which are self-extlnguishing.
By one broad aspect of this invention now provided by the present divisional application, a sulphur cement pre-mix composition i8 provided comprising: (a) sulphur and (b) a bonding agent which is adapted to stabilize the sulphur cement against progressive embrittlement and mechanical failure under thermal or physical stress, the bonding agent being selected from the group consisting of: (i) up to 10% by weight of the total amount of sulphur, of a liquid organic agent adapted to stabilize the sulphur cement against progressive embrittlement and subsequent crumbling under thermal stress, the agent comprising an olefinic hydrocarbon polymer material, and having a non-volatile content greater than 50% by weight and a minimum Wijs iodine number of 100 cg/g, such polymer material being capable of reaÇtin~ with sulphur to form a sulphur-containing polymer and being present ~n the su~p~hur cement as the sulphur-containing polymer; and (ii) a mixture of up to 10% by weight of the total amount of sulphur, of the liquid organic agent (i) and, for each 100 parts by weight of sulphur, from 10 to 150 parts by weight of a viscosity increasing, surface active, finely divided, particulate solid in-organic agent, the inorganic agent being of a size passing through a screen having a sieve opening of 0.147 mm, and being selected from the group con-: sisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhotites.
By another aspect, the present invention now provided by the pre-sent divisional application provides a sulphur cement composition consisting essentially of: (a) sulphur which has been melted to ~ontain dispersed therein (b) a bonding agent which is adapted to stabilize the sulphur cement against progressive embrittlement and mechanical ~ailire under thermal or physical stress, the bonding agent being se.lected from the group consisting _ 3 _ :.
-, :
... :
10~16884 (i) up to 10% by weight of tlle total amount of suLpimr, of a liquid or-g~nic agent comprising an olefinic hydrocarbon polymer material having a non-volatile content greater than 50~ by weight and a minimum Wi~5 iodine number of 100 cg/g. such polymer material being capable of reacting with sulphur to form a sulphur-containing polymer and being present in the sul-phur cement as the sulphur-containing polymer; and (li) a mixture of up to 10% by weight of the total amount of sulphur, of the liquid organic~agent (i) and, for each 100 parts by weight of sulphur, from 10 to 150 parts by weight of and a viscosity increasing, surface active, finely divided, parti-culate solid inorganic agent, the inorganic agent being of a size passingthrough a screen having a sieve opening of 0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulvçrized limestone and a mixture of pyrites and pyrrhotites.
By one variant, the bonding agent may consist essentially of (i), or it may consist essentially of the mixture defined as (ii).
By another variant, the bonding agent consists essentially of the olefinic hydrocarbon polymer material, which polymer material is in the form of a pre-reacted sulphur-containing polymer provided by reacting the olefinic liquid hydrocarbon polymer with a smaller proportion of sulphur than is required in the final sulphur cement.
By variations thereof, the ratio of the sulphur to the liquid organic agent may be 2.45:1 or greater, or the amount of liquid organic agent may be 1 to 5% by weight of the total sulphur.
By another variant, the bonding agent consists essentially of the olefinic liquid hydrocarbon polymer material, the polymer material being in the form of a pre-reacted sulphur-containing polymer provided by reacting the heat reactive olefinic liquid hydrocarbon polymer with a smaller proportion of sulphur than is required in the final sulphur cement, and wherein the liquid organic agent is present in an amount of 1 to 5% by weight of the total amount of sulphur.
By a variation thereof, the bonding agent comprises a mixture ~ --. . : . :
~: ' ' ~688~
of such organic material and fly ash of a size passing through a screen having a sieve opening of 0.147 mm.
By still another variation, the bonding agent comprises a mix-ture of the olefinic liquid hydrocarbon polymer material which i9 in the form of a pre-reacted sulphur-containing polymer provided by reacting the heat reactive olefinic liquid hydrocarbon polymer with a smaller propor-tiOII of sulphur than is required in the final sulphur cement and fly ash of a size passing through a screen having a sieve opening of 0.147 mm.
By yet a further variant, the composition includes an additive to provide fire resistance, e.g., 1,5,9-cyclododecatriene, or the reac-tion product of diphenoxyphosphinic acid with sulphur and with ~-methyl styrene.
By another aspect of this invention now provided by the present divisional application, a sulphur concrete is provided comprising (A) a sulphur cement pre-mix composition consisting essentially of (a) sulphur and (b) a bonding agent which is adapted to stabilize the sulphur cement against progressive embrittlement and mechanical failure under thermal or physical stress, the bonding agent being selected from the group consis-ting of (i) up to 10% by weight of the total amount of sulphur, of a liquid organic agent, the agent comprising an olefinic hydrocarbon poly-mer material having a non-volatile content greater than 50~ by weight and a minimum Wijs iodine number of 100-cg/g, such polymer material being ; capable of reacting with sulphur to form a sulphur-containing polymer and being present in the sulphur cement as the sulphur-containing polymer; and (ii) a mixture of up to 10% by weight of the total amount of sulphur, of the liquid organic agent (i) and, for each 100 parts by weight of sulphur, from 10 to 150 parts by weight of and ~ viscosity increasing, surface active, - finely divided, particulate solid inorganic agent, the inorganic agent being of a size passing through a screen having a sieve opening of 0.147 mm, and being selected from the group consisting of fly ash, dolomite, .
A - 5 _ .... . .
, ~ .
- pulverized limestone ant a mixture of pyrites and pyrrhotites; and (B) natural or manufactured aggregates.
By another aspect of this invention now provided by the present divisional application, a sulphur concrete is provi.ded comprising (A) a sulphur cement composition consisting essentially of: (a) sulphur which has been melted to contain dispersed therein (b) a bonding agent which is adapte~ to stabilize the sulphur cement against progressive embrittle-ment and mechanical failure under thermal or physical stress, the bonding agent being selected from the group consisting of ti) up to 10% by weight of the total amount.of sulphur, of a liquid organic agent, the agent comprising an olefinic hydrocarbon polymer material and having a non-volatile content greater than 50% by weight and a minimum Wijs iodine number of 100 cg/g, such polymer material being capable of reacting with sulpjur to form a sulphur-containing polymer and being present in the sulphur cement as the sulphur-containing polymer; and (ii) a mixture of up to 10% by weight of the tot~l amount of sulphur, of the liquid organ-ic agent (i) and, for each 100 parts by weight of sulphur, from 10 to 150 parts by weight of and a viscosity increasing, surface active, finely . _ , . _ . . . .
divided, particulate solid inorganic agent, the inorganic agent being of a size passing through a screen having a sieve opening of 0.147 mm, and being selected from the group consisting of fly ash, dolomite, pul-verized limestone and a mixture of pyrites and pyrrhotites; and (B) natural or manufactured aggregates. -By a variant thereof, the ratio of aggregate (B) to sulphur cement (A) is 80-36:20-64.
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.
868~4 The sulphur cement or sulphur-cement pre-mix forming an essen-tial element of the sulphur concrete of this aspect of this invention now provided by the present divisional appllcation may be any one of the variants and variations heretofore described.
The present invention now provided by the pre~ent divisional application in one of its aspects provides a sulphur cement which can be used for the manufacture of sulphur concrete having numerous applications r~
A 6 a -~ . ~ ., .
- 1~86884 in the construction field. It is substantlally free from the disadvan-tages of the products described previously and has positive advantages, as will be described hereinafter.
The sulphur cement according to one aspect of this invention now provided by the present divisional application employs, as the stabil-izer, the particularly recited olefinic liquid hydrocarbon stabilizer, e.g., the heat reactive polymer derived from petroleum, as hereinabove more particularly described. The proportions of the chemical stabilizer may be varied depending upon the end use of the cement.
The chemical stabilizer used in the compositions of aspects of this invention now provided by the present divisional application is any of the olefinic hydrocarbon polymers derived from petroleum having a non-volatile content greater than 50% by weight and a minimum Wijs iodine number of 100 cg/g capable of reacting with sulphur to form a sulphur-containing polymer. Typically, the chemical stabilizer is used in amounts up to 10% by weight of the total sulphur, and more especially in the pro-portion of l - 5% of the total sulphur by weight. The amount of such chemical stabilizer required depends upon the end use of the cement and the properties desired.
The chemical stabilizer can be incorporated into the final cement mix by several reaction routes within the ambit of this invention.
Preferably, the chemical is pre-reacted at approximately 140C. for 30 minutes with a smaller proportion of sulphur than is required in the final mix. The resulting concentrate can then be either stored for future use or dissolved in the residual sulphur (liquefied) required for the final mix at the mixing temperature.
While any chemical stabilizer having the above properties may be used, typical such chemical stabilizers are those known by the following Trade Marks: RP220, a product of Exxon Chemical Co.; RP020, a product of Exxon Chemical Co.; CTLA, a product of Enjay Chemical Co.;
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, ~0~688~
and ESCOPOL, a product o Esso Chemical AB (Sweden); all identifying a heat reactive olefinic liquid hydrocarbon obtained by partial polymeriza-tion of olefins.
In order to provide a sulphur-containing cement of aspects of this invention now provided by the present divisional application having a workable consistency, it is necessary to add to the liquid organic stabilizer, a finely divided, viscosity increasing material, for example, fly ash, gypsum, dolomite, pulverized limestone, a mixture of pyrites and pyrrhotites, or rock dust of a size up to minus 100 mesh, but preferably of a size of minus 200 mesh. Fly ash from the burning of hydrocarbon fossil fuels and generally in the form of tiny hollow spheres called cenospheres and consisting of major amounts of silicon oxide and aluminum oxide, with smaller quantities of ferric oxide, calcium oxide, magnesium oxide, sodium oxide, po$assium oxide and carbon, is particularly effec-tive in this regard due to its small particle size, shape and surface texture. It has been found to impart an extra measure of durability to the final cement, independent of its source, and serves the dual func-tion of viscosity increaser and sulphur cement stabilizer. Depending upon the degree of fineness of the fly ash and the consistency desired, an amount up to one and one-half times the total weight of the sulphur may be beneficially added.
A notable feature of the sulphur cement of aspects of this invention now provided by the present divisional application is that such sulphur cement does not require high purity sulphur and can be made with off-grade sulphur containing hydrocarbon impurities, blow dirt, and other "contaminants". The presence of hydrogen sulphide (H2S) in the sulphur has been determined to be detrimental, but the simple process of remelting the sulphur usually reduces the concentration of this contaminant to harmless levels.
The resulting cement of an aspect of this invention now provided ~ .. .. . .. , ~ :~. ~ .
~. . .
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~0~3~884 by the present divisional application is substantially resistant to the corrosive influences of salts, most acids, and solvents. Hot oxidizing acids at high concentrations and strong concentrated bases do attack the cement, however. The cement is essentially impervious to moisture penetration. It provides good thermal insulation, is used hot with no water, and develops high strength within hours of cooling. Thus, sulphur concrete pouring can take place in winter without the usual freezing problems of conventional portland cement concretes, which require the presence of water for setting.
A wide range of aggregates can be used with the sulphur cement of one aspect of this invention now provided by the present divisional application as described above, to make strong, durable concretes of another aspect of this invention now provided by the present ~ivisional application. Among the conventional aggregates useful herein for pre-paring the concrete of another aspect of this invention now provided by the present divisional application are sand, crushed cinder~, brick dust, foundry sand, crushed quart~ite gravel, crushed limestone, siliceous tailing sand, expanded shale, expanded clay, crushed barite, crushed brick, crushed portland cement concrete, and crushed granite. Preferably, the aggregate particles are of angular shape and of rough surface texture as can be obtained by crushing. With a sufficiently fluid mix, or through use of heated molds, the mold surfaces are reproduced precisely.
Where sulphur is readily available, the cement and the concrete of aspects of this invention now provided by the present divisional applica-tion can be produced at competitive costs. The compatibility of the sulphur cement of aspects of this invention now provided by the present divisional application with aggregates of wide ranging densities permits the design of concretes having very wide ranges of densities ranging, for example, as low as 10 lbs. per cubic foot, to ranges between 100 lbs. per cubic foot and 230 lbs. per cubic foot, or even as high as 500 lbs. per ,- : , 10~6884 cubic foo~. The sulphur concrete of an aspect of this lnvention now pro-vided by the present divisional application can be reinforced in conven-tional fashion by the use of steel, asbestos or glass fibre, or other reinforcing materials.
The sulphur concretes of aspects of this inven~ion now provided by the present divisional application tend to be self-extinguishing with ash contents approaching two-thirds the weight of sulphur and can be made fire resistant, and/or to inhibit the formation of S02 when heated, by the addition of suitable additives, e.g., 1,5,9-cyclododecatriene or the reaction product of diphenoxyphosphinic acid with sulphur and t~-methyl styrene.
The sulphur concretes of another aspect of this invention now provided by the present divisional application derived from the sulphur cements of a first aspect of this int~ention now provided by the present divisional application are not refractory materials and will soften and melt if heated above 120C., although the rate of melting is slow due to the low thermal conductivity imparted to the concrete by the sulphur.
`~ The principles developed for the grading of aggregates used in conventional concretes are essentially unchanged for sulphur concretes ~0 of aspects of this invention now provided by the present divisional application except for the much greater tolerance of fines and silt of the sulphur concretes. 80% of the ultimate concrete strength is developed in one day; virtually 100% of the ultimate strength is realized after four days.
These sulphur concretes may be used as a construction material for a wide variety of precast and poured-in-place applications, e.g., sidewalks, steps 9 parking curbs, highwary median barriers, sewer pipe, septic tanks, pilings, footings, foundations, pavements, industrial tanks, ponds, swimming pools, etc. The hot sulphur concrete mix may also be pumped and sprayed for waterproof and erosion proof coatings on earth-fill . ~
:- . ' ' . :
1~6884 dikes, highway and railway embankments and as linings for irrigation canals, farm ponds, etc.
The examples given below are lntended only to lllustrate aspects of the present invention now provided by the present divisional applica-tion.
The hydrocarbon stabilizer (at 25C.) was added to molten sulphur (at 140C.) with vigorous stirring. Heat was applied only to maintain a reaction temperature of 140 to 150C. At this temperature reaction times were in the order of 15 to 40 minutes. The progress of the reaction could be monitored by the degree of homogeneity of the mix, by careful observation of the temperature of the reaction mixture, or by observation of the increasing viscosity of the mixture. At sulphur-stabilizer ratios of less than 4:1 by weight, control of the addition rate was required to prevent the exothermicity of the reactions raising temperatures above 155C., at which point hydrogen sulphide (H2S~ was evolved with consequent foaming and degradation of the product.
When reactions were conducted under the above-prescribed con-ditions, the product was a sulphur-containing polymer which, on cooling, possessed glass-like properties which were retained indefinitely.
The properties of the olefinic hydrocarbon polymers used for illustrative purposes herein are given in Table 1. Reaction conditions for the preparation of seven sulphur-containing polymers are contained in Table 2.
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- Table 1 RP220 RP020CTLA Escopol Flash Point (COC) minimum 150 13R 150 125 Gravity (API) maximum 4 4.0 9.6 3 Iodine Number (lOOcg~g) minimum 200 160 255 135 Non-volatile Matter (X b~ weight) 80 70 83 75 (3 hrs. @ 105C) minimum Density (15.6C.) gm/cc 1.05 1.04 1.00 1.03 Viscosity (cst/100C) maximum 25 26 28 25*
*cst/50C.
Table 2 Reaction Conditions for the Preparation_of Sulphur-containing Polymers Stabillzer Weight (K~) Reaction Reaction Product Sample (STB)STB S ''Temp.(C)' Time (Min) Colour 1 CTLA 12.5 37.5 140 30 dark brown
This application is a division of application Serial No.
251,362 filed April 28, 1976.
Sulphur cements have a long history of use in specialized appli-cations. Thus, Canadian Patent No. 71,636 issued to George McKay pro-vided a sulphur-containing composition useful for sealing purposes at a joint, for roofing purposes, for the forming of ornamental figures, and for the coating of the exposed surfaces of iron or steel steps, the com-position including sulphur, brick-dust, tin, lead, bismuth, plaster of paris and borax.
However, attempts to make durable, high strength concrete-like materials from sulphur cements have encountered cost, durability, or other difficulties that precluded commercialization. Proposals have been made to increase the strength of sulphur as a bonding agent by the addi-tion of coal, sand or pumice thereto. Moreover, peculiar characteristics were proposed to be imparted by the addition thereto of bitumens, metallic sulphides, and fibrous materials. Also, United States Patent j No. 3,459,717 patented August 5, 1969 by J.B. Signouret, provided a ~0 sulphur-based plastic composition of improved fireproofing characteristics by the incorporation, into the molten sulphur, of a diester of dithio-phosphoric acid and an ethylenic hydrocarbon. A major problem in the commercialization of sulphur cements has been the progressive embrittle-ment and subsequent crumbling, under thermal stress, of the sulphur cement. The cause of this embrittlement is believed to be the progressive crystallization of the initially amorphous sulphur. Partial inhibition of the crystallization has been achieved through various organic and inorganic additives.
Thiokol (Trade Mark of Thiokol Chemical Corporation for olefin polysulphide products) have been used to stabilize the amorphous form of ~L
., 1 q~
, ~ : ' sulphur in sulphur cements. Thtl8, Canadian Patent No. 356,181 lssued February 25, l936 to W.W. Vuecker, purports to provide a solution to the problem by dissolving, in the sulphur, certain olefin polysulphides or polymerization products thereof. These cements, however, were not practical on a large scale due to their high cost and disagreeable odor.
Dicyclopentadiene has good stabilization properties and more favourable economics, but imparts a nauseating odor to the sulphur cement and has other shortcomings, e.g., its vapour, even at low concentrations, is highly toxic [see, for example, Kinkead et al, "The Mammalian Toxicity of Dicyclopentadiene", Toxicology and Applied Pharmacology, 20 552-561 (1971)]. Moreover, dicyclopentadiene requires refluxing with molten sulphur to avoid excessive loss of material in vapour form.
An object of one aspect of this invention now provided by the present divisional application is to provide a sulphur cement composition which does not suffer the disadvantages of the compositions of the prior art.
An object of another aspect of this invention now provided by the present divisional application is to provide a more durable sulphur cement.
An object of yet another aspect of this invention now provided by the present divisional application is to provide a sulphur cement which can be made with off-grade sulphur.
An object of still another aspect of this invention now pro-vided by the present divisional application is to provide a sulphur cement which is resistant to the corrosive influence of salts, most acids and solvents.
An object of a further aspect of this invention now provided by the present divisional application is to provide a sulphur cement which provides good thermal insulation and which develops high strength without hours of cooling.
. -- 2 --' ' - ~
~136884 ., An ob~ect of yet a further aspect of this invention now pro-vided by the present divisional application i9 to provide sulphur con-cretes made with the sulphur cements, which are self-extlnguishing.
By one broad aspect of this invention now provided by the present divisional application, a sulphur cement pre-mix composition i8 provided comprising: (a) sulphur and (b) a bonding agent which is adapted to stabilize the sulphur cement against progressive embrittlement and mechanical failure under thermal or physical stress, the bonding agent being selected from the group consisting of: (i) up to 10% by weight of the total amount of sulphur, of a liquid organic agent adapted to stabilize the sulphur cement against progressive embrittlement and subsequent crumbling under thermal stress, the agent comprising an olefinic hydrocarbon polymer material, and having a non-volatile content greater than 50% by weight and a minimum Wijs iodine number of 100 cg/g, such polymer material being capable of reaÇtin~ with sulphur to form a sulphur-containing polymer and being present ~n the su~p~hur cement as the sulphur-containing polymer; and (ii) a mixture of up to 10% by weight of the total amount of sulphur, of the liquid organic agent (i) and, for each 100 parts by weight of sulphur, from 10 to 150 parts by weight of a viscosity increasing, surface active, finely divided, particulate solid in-organic agent, the inorganic agent being of a size passing through a screen having a sieve opening of 0.147 mm, and being selected from the group con-: sisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhotites.
By another aspect, the present invention now provided by the pre-sent divisional application provides a sulphur cement composition consisting essentially of: (a) sulphur which has been melted to ~ontain dispersed therein (b) a bonding agent which is adapted to stabilize the sulphur cement against progressive embrittlement and mechanical ~ailire under thermal or physical stress, the bonding agent being se.lected from the group consisting _ 3 _ :.
-, :
... :
10~16884 (i) up to 10% by weight of tlle total amount of suLpimr, of a liquid or-g~nic agent comprising an olefinic hydrocarbon polymer material having a non-volatile content greater than 50~ by weight and a minimum Wi~5 iodine number of 100 cg/g. such polymer material being capable of reacting with sulphur to form a sulphur-containing polymer and being present in the sul-phur cement as the sulphur-containing polymer; and (li) a mixture of up to 10% by weight of the total amount of sulphur, of the liquid organic~agent (i) and, for each 100 parts by weight of sulphur, from 10 to 150 parts by weight of and a viscosity increasing, surface active, finely divided, parti-culate solid inorganic agent, the inorganic agent being of a size passingthrough a screen having a sieve opening of 0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulvçrized limestone and a mixture of pyrites and pyrrhotites.
By one variant, the bonding agent may consist essentially of (i), or it may consist essentially of the mixture defined as (ii).
By another variant, the bonding agent consists essentially of the olefinic hydrocarbon polymer material, which polymer material is in the form of a pre-reacted sulphur-containing polymer provided by reacting the olefinic liquid hydrocarbon polymer with a smaller proportion of sulphur than is required in the final sulphur cement.
By variations thereof, the ratio of the sulphur to the liquid organic agent may be 2.45:1 or greater, or the amount of liquid organic agent may be 1 to 5% by weight of the total sulphur.
By another variant, the bonding agent consists essentially of the olefinic liquid hydrocarbon polymer material, the polymer material being in the form of a pre-reacted sulphur-containing polymer provided by reacting the heat reactive olefinic liquid hydrocarbon polymer with a smaller proportion of sulphur than is required in the final sulphur cement, and wherein the liquid organic agent is present in an amount of 1 to 5% by weight of the total amount of sulphur.
By a variation thereof, the bonding agent comprises a mixture ~ --. . : . :
~: ' ' ~688~
of such organic material and fly ash of a size passing through a screen having a sieve opening of 0.147 mm.
By still another variation, the bonding agent comprises a mix-ture of the olefinic liquid hydrocarbon polymer material which i9 in the form of a pre-reacted sulphur-containing polymer provided by reacting the heat reactive olefinic liquid hydrocarbon polymer with a smaller propor-tiOII of sulphur than is required in the final sulphur cement and fly ash of a size passing through a screen having a sieve opening of 0.147 mm.
By yet a further variant, the composition includes an additive to provide fire resistance, e.g., 1,5,9-cyclododecatriene, or the reac-tion product of diphenoxyphosphinic acid with sulphur and with ~-methyl styrene.
By another aspect of this invention now provided by the present divisional application, a sulphur concrete is provided comprising (A) a sulphur cement pre-mix composition consisting essentially of (a) sulphur and (b) a bonding agent which is adapted to stabilize the sulphur cement against progressive embrittlement and mechanical failure under thermal or physical stress, the bonding agent being selected from the group consis-ting of (i) up to 10% by weight of the total amount of sulphur, of a liquid organic agent, the agent comprising an olefinic hydrocarbon poly-mer material having a non-volatile content greater than 50~ by weight and a minimum Wijs iodine number of 100-cg/g, such polymer material being ; capable of reacting with sulphur to form a sulphur-containing polymer and being present in the sulphur cement as the sulphur-containing polymer; and (ii) a mixture of up to 10% by weight of the total amount of sulphur, of the liquid organic agent (i) and, for each 100 parts by weight of sulphur, from 10 to 150 parts by weight of and ~ viscosity increasing, surface active, - finely divided, particulate solid inorganic agent, the inorganic agent being of a size passing through a screen having a sieve opening of 0.147 mm, and being selected from the group consisting of fly ash, dolomite, .
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- pulverized limestone ant a mixture of pyrites and pyrrhotites; and (B) natural or manufactured aggregates.
By another aspect of this invention now provided by the present divisional application, a sulphur concrete is provi.ded comprising (A) a sulphur cement composition consisting essentially of: (a) sulphur which has been melted to contain dispersed therein (b) a bonding agent which is adapte~ to stabilize the sulphur cement against progressive embrittle-ment and mechanical failure under thermal or physical stress, the bonding agent being selected from the group consisting of ti) up to 10% by weight of the total amount.of sulphur, of a liquid organic agent, the agent comprising an olefinic hydrocarbon polymer material and having a non-volatile content greater than 50% by weight and a minimum Wijs iodine number of 100 cg/g, such polymer material being capable of reacting with sulpjur to form a sulphur-containing polymer and being present in the sulphur cement as the sulphur-containing polymer; and (ii) a mixture of up to 10% by weight of the tot~l amount of sulphur, of the liquid organ-ic agent (i) and, for each 100 parts by weight of sulphur, from 10 to 150 parts by weight of and a viscosity increasing, surface active, finely . _ , . _ . . . .
divided, particulate solid inorganic agent, the inorganic agent being of a size passing through a screen having a sieve opening of 0.147 mm, and being selected from the group consisting of fly ash, dolomite, pul-verized limestone and a mixture of pyrites and pyrrhotites; and (B) natural or manufactured aggregates. -By a variant thereof, the ratio of aggregate (B) to sulphur cement (A) is 80-36:20-64.
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868~4 The sulphur cement or sulphur-cement pre-mix forming an essen-tial element of the sulphur concrete of this aspect of this invention now provided by the present divisional appllcation may be any one of the variants and variations heretofore described.
The present invention now provided by the pre~ent divisional application in one of its aspects provides a sulphur cement which can be used for the manufacture of sulphur concrete having numerous applications r~
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- 1~86884 in the construction field. It is substantlally free from the disadvan-tages of the products described previously and has positive advantages, as will be described hereinafter.
The sulphur cement according to one aspect of this invention now provided by the present divisional application employs, as the stabil-izer, the particularly recited olefinic liquid hydrocarbon stabilizer, e.g., the heat reactive polymer derived from petroleum, as hereinabove more particularly described. The proportions of the chemical stabilizer may be varied depending upon the end use of the cement.
The chemical stabilizer used in the compositions of aspects of this invention now provided by the present divisional application is any of the olefinic hydrocarbon polymers derived from petroleum having a non-volatile content greater than 50% by weight and a minimum Wijs iodine number of 100 cg/g capable of reacting with sulphur to form a sulphur-containing polymer. Typically, the chemical stabilizer is used in amounts up to 10% by weight of the total sulphur, and more especially in the pro-portion of l - 5% of the total sulphur by weight. The amount of such chemical stabilizer required depends upon the end use of the cement and the properties desired.
The chemical stabilizer can be incorporated into the final cement mix by several reaction routes within the ambit of this invention.
Preferably, the chemical is pre-reacted at approximately 140C. for 30 minutes with a smaller proportion of sulphur than is required in the final mix. The resulting concentrate can then be either stored for future use or dissolved in the residual sulphur (liquefied) required for the final mix at the mixing temperature.
While any chemical stabilizer having the above properties may be used, typical such chemical stabilizers are those known by the following Trade Marks: RP220, a product of Exxon Chemical Co.; RP020, a product of Exxon Chemical Co.; CTLA, a product of Enjay Chemical Co.;
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and ESCOPOL, a product o Esso Chemical AB (Sweden); all identifying a heat reactive olefinic liquid hydrocarbon obtained by partial polymeriza-tion of olefins.
In order to provide a sulphur-containing cement of aspects of this invention now provided by the present divisional application having a workable consistency, it is necessary to add to the liquid organic stabilizer, a finely divided, viscosity increasing material, for example, fly ash, gypsum, dolomite, pulverized limestone, a mixture of pyrites and pyrrhotites, or rock dust of a size up to minus 100 mesh, but preferably of a size of minus 200 mesh. Fly ash from the burning of hydrocarbon fossil fuels and generally in the form of tiny hollow spheres called cenospheres and consisting of major amounts of silicon oxide and aluminum oxide, with smaller quantities of ferric oxide, calcium oxide, magnesium oxide, sodium oxide, po$assium oxide and carbon, is particularly effec-tive in this regard due to its small particle size, shape and surface texture. It has been found to impart an extra measure of durability to the final cement, independent of its source, and serves the dual func-tion of viscosity increaser and sulphur cement stabilizer. Depending upon the degree of fineness of the fly ash and the consistency desired, an amount up to one and one-half times the total weight of the sulphur may be beneficially added.
A notable feature of the sulphur cement of aspects of this invention now provided by the present divisional application is that such sulphur cement does not require high purity sulphur and can be made with off-grade sulphur containing hydrocarbon impurities, blow dirt, and other "contaminants". The presence of hydrogen sulphide (H2S) in the sulphur has been determined to be detrimental, but the simple process of remelting the sulphur usually reduces the concentration of this contaminant to harmless levels.
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~0~3~884 by the present divisional application is substantially resistant to the corrosive influences of salts, most acids, and solvents. Hot oxidizing acids at high concentrations and strong concentrated bases do attack the cement, however. The cement is essentially impervious to moisture penetration. It provides good thermal insulation, is used hot with no water, and develops high strength within hours of cooling. Thus, sulphur concrete pouring can take place in winter without the usual freezing problems of conventional portland cement concretes, which require the presence of water for setting.
A wide range of aggregates can be used with the sulphur cement of one aspect of this invention now provided by the present divisional application as described above, to make strong, durable concretes of another aspect of this invention now provided by the present ~ivisional application. Among the conventional aggregates useful herein for pre-paring the concrete of another aspect of this invention now provided by the present divisional application are sand, crushed cinder~, brick dust, foundry sand, crushed quart~ite gravel, crushed limestone, siliceous tailing sand, expanded shale, expanded clay, crushed barite, crushed brick, crushed portland cement concrete, and crushed granite. Preferably, the aggregate particles are of angular shape and of rough surface texture as can be obtained by crushing. With a sufficiently fluid mix, or through use of heated molds, the mold surfaces are reproduced precisely.
Where sulphur is readily available, the cement and the concrete of aspects of this invention now provided by the present divisional applica-tion can be produced at competitive costs. The compatibility of the sulphur cement of aspects of this invention now provided by the present divisional application with aggregates of wide ranging densities permits the design of concretes having very wide ranges of densities ranging, for example, as low as 10 lbs. per cubic foot, to ranges between 100 lbs. per cubic foot and 230 lbs. per cubic foot, or even as high as 500 lbs. per ,- : , 10~6884 cubic foo~. The sulphur concrete of an aspect of this lnvention now pro-vided by the present divisional application can be reinforced in conven-tional fashion by the use of steel, asbestos or glass fibre, or other reinforcing materials.
The sulphur concretes of aspects of this inven~ion now provided by the present divisional application tend to be self-extinguishing with ash contents approaching two-thirds the weight of sulphur and can be made fire resistant, and/or to inhibit the formation of S02 when heated, by the addition of suitable additives, e.g., 1,5,9-cyclododecatriene or the reaction product of diphenoxyphosphinic acid with sulphur and t~-methyl styrene.
The sulphur concretes of another aspect of this invention now provided by the present divisional application derived from the sulphur cements of a first aspect of this int~ention now provided by the present divisional application are not refractory materials and will soften and melt if heated above 120C., although the rate of melting is slow due to the low thermal conductivity imparted to the concrete by the sulphur.
`~ The principles developed for the grading of aggregates used in conventional concretes are essentially unchanged for sulphur concretes ~0 of aspects of this invention now provided by the present divisional application except for the much greater tolerance of fines and silt of the sulphur concretes. 80% of the ultimate concrete strength is developed in one day; virtually 100% of the ultimate strength is realized after four days.
These sulphur concretes may be used as a construction material for a wide variety of precast and poured-in-place applications, e.g., sidewalks, steps 9 parking curbs, highwary median barriers, sewer pipe, septic tanks, pilings, footings, foundations, pavements, industrial tanks, ponds, swimming pools, etc. The hot sulphur concrete mix may also be pumped and sprayed for waterproof and erosion proof coatings on earth-fill . ~
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1~6884 dikes, highway and railway embankments and as linings for irrigation canals, farm ponds, etc.
The examples given below are lntended only to lllustrate aspects of the present invention now provided by the present divisional applica-tion.
The hydrocarbon stabilizer (at 25C.) was added to molten sulphur (at 140C.) with vigorous stirring. Heat was applied only to maintain a reaction temperature of 140 to 150C. At this temperature reaction times were in the order of 15 to 40 minutes. The progress of the reaction could be monitored by the degree of homogeneity of the mix, by careful observation of the temperature of the reaction mixture, or by observation of the increasing viscosity of the mixture. At sulphur-stabilizer ratios of less than 4:1 by weight, control of the addition rate was required to prevent the exothermicity of the reactions raising temperatures above 155C., at which point hydrogen sulphide (H2S~ was evolved with consequent foaming and degradation of the product.
When reactions were conducted under the above-prescribed con-ditions, the product was a sulphur-containing polymer which, on cooling, possessed glass-like properties which were retained indefinitely.
The properties of the olefinic hydrocarbon polymers used for illustrative purposes herein are given in Table 1. Reaction conditions for the preparation of seven sulphur-containing polymers are contained in Table 2.
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- Table 1 RP220 RP020CTLA Escopol Flash Point (COC) minimum 150 13R 150 125 Gravity (API) maximum 4 4.0 9.6 3 Iodine Number (lOOcg~g) minimum 200 160 255 135 Non-volatile Matter (X b~ weight) 80 70 83 75 (3 hrs. @ 105C) minimum Density (15.6C.) gm/cc 1.05 1.04 1.00 1.03 Viscosity (cst/100C) maximum 25 26 28 25*
*cst/50C.
Table 2 Reaction Conditions for the Preparation_of Sulphur-containing Polymers Stabillzer Weight (K~) Reaction Reaction Product Sample (STB)STB S ''Temp.(C)' Time (Min) Colour 1 CTLA 12.5 37.5 140 30 dark brown
2 CTLA 8.3 41.7 140 40 dark brown
3 Escopol 10.0 40.0 150 15 light brown
4 Escopol 14.5 35.5 140 20 light brown RP220 8.3 41.7 150 15 dark brown 6 RP220 12.5 37.5 140 20 dark brown 7 RP020 12.5 37.5 140 15 dark brown Examples'l to 9 - Sulphur Cements and Concretes Derived Therefrom A first series of sulphur cements, Examples 1 through 9, were prepared by addition of: the required sulphur (less than contained in the prereacted material), the prereacted material, and lastly, fly ash to achieve the desired consistency of the sulphur cement'. Then the aggregate was added to provide the sulphur concrete.
The components were mixed at 130C. in a heated 1/3 cubic foot concrete mixer for 15 minutes before pouring into molds. Compaction was obtained through vibration or tapping of the molds. For simplicity of representation, all the examples are chosen using RP220 as the hydrocar-~` bon stabilizer.
1~86884 Examples 10 to 13 A second series of sulphur cements and sulphur concretes was prepared in a manner analogous to that of Examples 1 to 9 with the exception that raw stabilizer (i.e. not pre-reacted with sulphur) was added directly to the mix at the previous point of pre-reacted material addition. In order to allow completç reaction, the mixing time was increased to 20 minutes.
The results are summarized and tabulated below in Table 3.
Table 3 Sulphur Concretes - Composition and Properties Chemical Stabi- Compres-Exam- Aggre-lizer Density sive*
ple gateSulphur Fly Ash RP220 (g/cc) Strength 1 Crushed quartzite 71.720.4 7.4 0.50 2.38 7,160 gravel 2 Crushed limestone 73.526 - 0.50 2.41 5,290 3 Siliceous tailings 63.534.8 - 1.7 2.21 5,290 sand 4 Expanded shale 38.6 37.623.2 0.59 1.73 4,610 Expanded clay 38.4 32.029.2 0.38 1.77 8,350 6 Crushed barite 78.7 15.05.9 0.38 3.18 7,520 7 Crushed brick 54.5 27.317.5 0.68 2.17 8,530 8 Crushed portland 64.124.1 11.2 0.60 2.23 5,690 cement concrete 9 Crushed granite 65.920.0 12.6 0.50 2.39 7,760 Crushed quartzite 64.419.6 15.5 0.49 2.38 8,710 gravel 11 Siliceous tailings 60.930.8 7.5 0.77 2.23 6,530 sand 12 Expanded shale 50.0 26.622.7 0.66 1.70 4,740 13 Crushed barite 79.1 13.27.4 0.33 3.28 7,650 * Mean of three (3) tests.
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The components were mixed at 130C. in a heated 1/3 cubic foot concrete mixer for 15 minutes before pouring into molds. Compaction was obtained through vibration or tapping of the molds. For simplicity of representation, all the examples are chosen using RP220 as the hydrocar-~` bon stabilizer.
1~86884 Examples 10 to 13 A second series of sulphur cements and sulphur concretes was prepared in a manner analogous to that of Examples 1 to 9 with the exception that raw stabilizer (i.e. not pre-reacted with sulphur) was added directly to the mix at the previous point of pre-reacted material addition. In order to allow completç reaction, the mixing time was increased to 20 minutes.
The results are summarized and tabulated below in Table 3.
Table 3 Sulphur Concretes - Composition and Properties Chemical Stabi- Compres-Exam- Aggre-lizer Density sive*
ple gateSulphur Fly Ash RP220 (g/cc) Strength 1 Crushed quartzite 71.720.4 7.4 0.50 2.38 7,160 gravel 2 Crushed limestone 73.526 - 0.50 2.41 5,290 3 Siliceous tailings 63.534.8 - 1.7 2.21 5,290 sand 4 Expanded shale 38.6 37.623.2 0.59 1.73 4,610 Expanded clay 38.4 32.029.2 0.38 1.77 8,350 6 Crushed barite 78.7 15.05.9 0.38 3.18 7,520 7 Crushed brick 54.5 27.317.5 0.68 2.17 8,530 8 Crushed portland 64.124.1 11.2 0.60 2.23 5,690 cement concrete 9 Crushed granite 65.920.0 12.6 0.50 2.39 7,760 Crushed quartzite 64.419.6 15.5 0.49 2.38 8,710 gravel 11 Siliceous tailings 60.930.8 7.5 0.77 2.23 6,530 sand 12 Expanded shale 50.0 26.622.7 0.66 1.70 4,740 13 Crushed barite 79.1 13.27.4 0.33 3.28 7,650 * Mean of three (3) tests.
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Claims (24)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A sulphur cement pre-mix composition consisting essentially of:
(a) sulphur and (b) a bonding agent which is adapted to stabilize said sulphur cement against progressive embrittlement and mechanical failure under thermal or physical stress, said bonding agent being selected from the group consist-ing of (i) up to 10% by weight of the total amount of sulphur, of a liquid organic agent adapted to stabilize said sulphur ce-ment against progressive embrittlement and subsequent crumbling under thermal stress, said agent comprising an olefinic hydrocarbon polymer material, and having a non-volatile content greater than 50% by weight and a minimum Wijs iodine number of 100 cg/g, such polymer material being capable of reacting with sulphur to form a sulphur-contain-ing polymer and being present in the sulphur cement as said sulphur-containing polymer;
and (ii) a mixture of up to 10% by weight of the total amount of sulphur, of said liquid organic agent (i) and, for each 100 parts by weight of sulphur, from 10 to 150 parts by weight of a viscosity increasing, surface active, finely divided, particulate solid inorganic agent, said inorganic agent being of a size passing through a screen having a sieve opening of 0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulverized lime-stone and a mixture of pyrites and pyrrhotites.
(a) sulphur and (b) a bonding agent which is adapted to stabilize said sulphur cement against progressive embrittlement and mechanical failure under thermal or physical stress, said bonding agent being selected from the group consist-ing of (i) up to 10% by weight of the total amount of sulphur, of a liquid organic agent adapted to stabilize said sulphur ce-ment against progressive embrittlement and subsequent crumbling under thermal stress, said agent comprising an olefinic hydrocarbon polymer material, and having a non-volatile content greater than 50% by weight and a minimum Wijs iodine number of 100 cg/g, such polymer material being capable of reacting with sulphur to form a sulphur-contain-ing polymer and being present in the sulphur cement as said sulphur-containing polymer;
and (ii) a mixture of up to 10% by weight of the total amount of sulphur, of said liquid organic agent (i) and, for each 100 parts by weight of sulphur, from 10 to 150 parts by weight of a viscosity increasing, surface active, finely divided, particulate solid inorganic agent, said inorganic agent being of a size passing through a screen having a sieve opening of 0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulverized lime-stone and a mixture of pyrites and pyrrhotites.
2. A sulphur cement composition consisting essentially of:
(a) sulphur which has been melted to contain dispersed therein (b) a bonding agent which is adapted to stabilize said sulphur cement against progressive embrittlement and mechanical failure under thermal or physical stress, said bonding agent being selected from the group consist-ing of (i) up to 10% by weight of the total amount of sulphur, of a liquid organic agent comprising an olefinic hydrocarbon polymer material having a non-volatile content greater than 50% by weight and a minimum Wijs iodine number of 100 cs/g, such polymer material being capable of reacting with sul-phur to form a sulphur-containing polymer and being present in the sulphur cement as said sulphur-containing polymer;
and (ii) a mixture of up to 10% by weight of the total amount of sul-phur, of said liquid organic agent (i) and, for each 100 parts by weight of sulphur, from 10 to 150 parts by weight of a viscosity increasing, surface active, finely divided, particulate solid inorganic agent, said inorganic agent being of a size passing through a screen having a sieve opening of 0.147 mm, and being selected from the group con-sisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhotites.
(a) sulphur which has been melted to contain dispersed therein (b) a bonding agent which is adapted to stabilize said sulphur cement against progressive embrittlement and mechanical failure under thermal or physical stress, said bonding agent being selected from the group consist-ing of (i) up to 10% by weight of the total amount of sulphur, of a liquid organic agent comprising an olefinic hydrocarbon polymer material having a non-volatile content greater than 50% by weight and a minimum Wijs iodine number of 100 cs/g, such polymer material being capable of reacting with sul-phur to form a sulphur-containing polymer and being present in the sulphur cement as said sulphur-containing polymer;
and (ii) a mixture of up to 10% by weight of the total amount of sul-phur, of said liquid organic agent (i) and, for each 100 parts by weight of sulphur, from 10 to 150 parts by weight of a viscosity increasing, surface active, finely divided, particulate solid inorganic agent, said inorganic agent being of a size passing through a screen having a sieve opening of 0.147 mm, and being selected from the group con-sisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhotites.
3. The composition of claims 1 or 2 wherein said bonding agent consists essentially of said liquid organic agent (i).
4. The composition of claims 1 or 2 wherein said bonding agent comprises said mixture (ii).
5. The composition of claims 1 or 2 wherein said bonding agent con-sists essentially of said olefinic liquid hydrocarbon polymer material, said polymer material being in the form of a pre-reacted sulphur-containing polymer provided by reacting said olefinic liquid hydrocarbon polymer with a smaller proportion of sulphur than is required in the final sulphur cement.
6. The composition of claims 1 or 2 wherein said liquid organic agent is present in an amount of 1 to 5% by weight of the total amount of sul-phur.
7. The composition of claims 1 or 2 wherein the ratio of sulphur to liquid organic agent is 2.45:1 or greater.
8. The composition of claims 1 or 2 wherein said bonding agent con-sists essentially of said olefinic liquid hydrocarbon polymer material, said polymer material being in the form of a pre-reacted sulphur-containing polymer provided by reacting said heat reactive olefinic liquid hydrocarbon polymer with a smaller proportion of sulphur than is required in the final sulphur cement, and wherein said liquid organic agent is present in an amount of 1 to 5% by weight of the total amount of sulphur.
9. The composition of claims 1 or 2 wherein said bonding agent com-prises a mixture of said olefinic hydrocarbon material and fly ash of a size passing through a screen having a sieve opening of 0.147 mm.
10. The composition of claims 1 or 2 wherein said bonding agent com-prises a mixture of said olefinic liquid hydrocarbon polymer material which is in the form of a pre-reacted sulphur-containing polymer provided by reacting said heat reactive olefinic liquid hydrocarbon polymer with a smaller propor-tion of sulphur than is required in the final sulphur cement,and fly ash of a size passing through a screen having a sieve opening of 0.147 mm.
11. The composition of claims 1 or 2 including an additive to provide fire resistance.
12. The composition of claims 1 or 2 including an additive to provide fire resistance, wherein said additive is 1,5,9-cyclododecatriene.
13. The composition of claims 1 or 2 including an additive to provide fire resistance, wherein said additive is the reaction product of diphenoxy-phosphinic acid with sulphur and with .alpha. -methyl styrene.
14. A sulphur concrete comprising (A) a sulphur cement pre-mix composition consisting essentially of:
(a) sulphur and (b) a bonding agent which is adapted to stabilize said sulphur cement against progressive embrittlement and mechanical fail-ure under thermal or physical stress, said bonding agent being selected from the group consisting of (i) up to 10% by weight of the total amount of sulphur, of a liquid organic agent, said agent comprising an olefinic hydrocarbon polymer material having a non-volatile con-tent greater than 50% by weight and a minimum Wijs iodine number of 100 cg/g, such polymer material being capable of reacting with sulphur to form a sulphur-containing polymer and being present in the sulphur cement as said sulphur-containing polymer;
and (ii) a mixture of up to 10% by weight of the total amount of sulphur, of said liquid organic agent (i) and, for each 100 parts by weight of sulphur, from 10 to 150 parts by weight of a viscosity increasing, surface ac-tive, finely divided, particulate solid inorganic a-gent, said inorganic agent being of a size passing through a screen having à sieve opening of 0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhotites;
and (B) natural or manufactured aggregates.
(a) sulphur and (b) a bonding agent which is adapted to stabilize said sulphur cement against progressive embrittlement and mechanical fail-ure under thermal or physical stress, said bonding agent being selected from the group consisting of (i) up to 10% by weight of the total amount of sulphur, of a liquid organic agent, said agent comprising an olefinic hydrocarbon polymer material having a non-volatile con-tent greater than 50% by weight and a minimum Wijs iodine number of 100 cg/g, such polymer material being capable of reacting with sulphur to form a sulphur-containing polymer and being present in the sulphur cement as said sulphur-containing polymer;
and (ii) a mixture of up to 10% by weight of the total amount of sulphur, of said liquid organic agent (i) and, for each 100 parts by weight of sulphur, from 10 to 150 parts by weight of a viscosity increasing, surface ac-tive, finely divided, particulate solid inorganic a-gent, said inorganic agent being of a size passing through a screen having à sieve opening of 0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhotites;
and (B) natural or manufactured aggregates.
15. A sulphur concrete comprising (A) a sulphur cement composition consisting essentially of:
(a) sulphur which has been melted to contain dispersed therein (b) a bonding agent which is adapted to stabilize said sulphur cement against progressive embrittlement and mechanical fail-ure under thermal or physical stress, said bonding agent being selected from the group consisting of (i) up to 10% by weight of the total amount of sulphur, of a liquid organic agent, said agent comprising an olefin-ic hydrocarbon polymer material and having a non-vola-tile content greater than 50% by weight and a minimum Wi~s iodine number of 100 cg/g, such polymer material being capable of reacting with sulphur to form a sul-phur-containing polymer and being present in the sulphur cement as said sulphur-containing polymer:
and (il) a mixture of up to 10% by weight of the total amount of sulphur, of said liquid organic agent (i) and, for each 100 parts by weight of sulphur, from 10 to 150 parts by weight of a viscosity increasing, surface active, finely divided, particulate solid inorganic agent, said inorganic agent being of a size passing through a screen having a sieve opening of 0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhotites;
and (B) natural or manufactured aggregates.
(a) sulphur which has been melted to contain dispersed therein (b) a bonding agent which is adapted to stabilize said sulphur cement against progressive embrittlement and mechanical fail-ure under thermal or physical stress, said bonding agent being selected from the group consisting of (i) up to 10% by weight of the total amount of sulphur, of a liquid organic agent, said agent comprising an olefin-ic hydrocarbon polymer material and having a non-vola-tile content greater than 50% by weight and a minimum Wi~s iodine number of 100 cg/g, such polymer material being capable of reacting with sulphur to form a sul-phur-containing polymer and being present in the sulphur cement as said sulphur-containing polymer:
and (il) a mixture of up to 10% by weight of the total amount of sulphur, of said liquid organic agent (i) and, for each 100 parts by weight of sulphur, from 10 to 150 parts by weight of a viscosity increasing, surface active, finely divided, particulate solid inorganic agent, said inorganic agent being of a size passing through a screen having a sieve opening of 0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhotites;
and (B) natural or manufactured aggregates.
16. The sulphur concrete of claims 14 or 15 wherein the ratio of sul-phur cement (A) to aggregate (B) is 20-64:80-36.
17. The sulphur concrete of claims 14 or 15 wherein said bonding agent consists essentially of said olefinic liquid hydrocarbon polymer mater-ial.
18. The sulphur concrete of claims 14 or 15 wherein said bonding agent consists essentially of said olefinic liquid hydrocarbon polymer mater-ial, said polymer being in the form of a pre-reacted sulphur containing poly-mer provided by reacting said olefinic liquid hydrocarbon polymer with a smal-ler proportion of sulphur than is required in the final composition.
19. The sulphur concrete of claims 14 or 15 wherein said bonding agent consists essentially of said mixture (ii).
20. The sulphur concrete of claims 14 or 15 wherein said bonding agent comprises a mixture of said olefinic liquid hydrocarbon polymer material and fly ash of a size passing through a screen having a sieve opening of 0.147 mm.
21. The sulphur concrete of claims 14 or 15 wherein said bonding agent comprises a mixture of said olefinic liquid hydrocarbon polymer material, said polymer material being in the form of a pre-reacted sulphur containing polymer provided by reacting said olefinic liquid hydrocarbon polymer with a smaller proportion of sulphur than is required in the final composition, and fly ash of a size passing through a screen having a sieve opening of 0.147 mm.
22. The sulphur concrete of claims 14 or 15 including an additive to provide fire resistance.
23. The sulphur concrete of claims 14 or 15 including an additive to provide fire resistance, said additive comprising the reaction product of diphenoxyphosphinic acid with sulphur and with .alpha. -methyl styrene.
24. The sulphur concrete of claims 14 or 15 including an additive to provide fire resistance, said additive comprising 1,5,9-cyclododecatriene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA332,505A CA1086884A (en) | 1975-05-29 | 1979-07-25 | Stabilized sulphur cements and concretes |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US58173575A | 1975-05-29 | 1975-05-29 | |
| US581,735 | 1975-05-29 | ||
| CA000251362A CA1182944A (en) | 1975-05-29 | 1976-04-28 | Sulphur cements and concretes made therefrom |
| CA332,505A CA1086884A (en) | 1975-05-29 | 1979-07-25 | Stabilized sulphur cements and concretes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1086884A true CA1086884A (en) | 1980-09-30 |
Family
ID=27164442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA332,505A Expired CA1086884A (en) | 1975-05-29 | 1979-07-25 | Stabilized sulphur cements and concretes |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1086884A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010085165A1 (en) * | 2009-01-26 | 2010-07-29 | Brookhaven Science Associates, Llc | Stabilized sulfur binding using activated fillers |
-
1979
- 1979-07-25 CA CA332,505A patent/CA1086884A/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010085165A1 (en) * | 2009-01-26 | 2010-07-29 | Brookhaven Science Associates, Llc | Stabilized sulfur binding using activated fillers |
| KR101536692B1 (en) * | 2009-01-26 | 2015-07-14 | 브룩하벤 싸이언스 어쏘씨에이츠 엘엘씨 | Stabilized sulfur binding using activated fillers |
| US9085488B2 (en) | 2009-01-26 | 2015-07-21 | Brookhaven Science Associates, Llc | Stabilized sulfur binding using activated fillers |
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