CA1182944A - Sulphur cements and concretes made therefrom - Google Patents
Sulphur cements and concretes made therefromInfo
- Publication number
- CA1182944A CA1182944A CA000251362A CA251362A CA1182944A CA 1182944 A CA1182944 A CA 1182944A CA 000251362 A CA000251362 A CA 000251362A CA 251362 A CA251362 A CA 251362A CA 1182944 A CA1182944 A CA 1182944A
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- Prior art keywords
- sulphur
- agent
- weight
- fly ash
- cement
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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
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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)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Novel sulphur cement pre-mixes and sulphur cement and concretes derived therefrom are provided. They contain in addition to the sulphur, a bonding agent which is adapted to stabilize the sulphur cement or sul-phur concrete against progressive embrittlement and mechanical failure un-der thermal or physical stress, the bonding agent being either a viscosity increasing, surface active, finely divided solid inorganic agent, of a size passing through a screen having a sieve opening of 0.147 mm and which is fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhotite, preferably being fly ash, or liquid olefinic hydrocarbon poly-mer material preferably derived from petroleum and having a non-volatile content greater than 50% by weight and a minimum Wijs iodine number of 100 cg/g either as such or in a form prereacted with sulphur, or a mixture of such inorganic particulate stabilizer and such organic stabilizer.
Novel sulphur concretes are also provided, which are made from such sulphur cement and conventional natural or manufactured aggregates. These sulphur cements do not suffer from the progressive embrittlement and mechanical failure under thermal or physical stress, of the heretofore provided con-ventional sulphur cements.
Novel sulphur cement pre-mixes and sulphur cement and concretes derived therefrom are provided. They contain in addition to the sulphur, a bonding agent which is adapted to stabilize the sulphur cement or sul-phur concrete against progressive embrittlement and mechanical failure un-der thermal or physical stress, the bonding agent being either a viscosity increasing, surface active, finely divided solid inorganic agent, of a size passing through a screen having a sieve opening of 0.147 mm and which is fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhotite, preferably being fly ash, or liquid olefinic hydrocarbon poly-mer material preferably derived from petroleum and having a non-volatile content greater than 50% by weight and a minimum Wijs iodine number of 100 cg/g either as such or in a form prereacted with sulphur, or a mixture of such inorganic particulate stabilizer and such organic stabilizer.
Novel sulphur concretes are also provided, which are made from such sulphur cement and conventional natural or manufactured aggregates. These sulphur cements do not suffer from the progressive embrittlement and mechanical failure under thermal or physical stress, of the heretofore provided con-ventional sulphur cements.
Description
This invention relates -to sulphur cenlents and concretes produced -there:Erom.
Sulphur c~m~lts have a lony history of use in specializecl aE)pli-ca-tions. T.hus, Canadian Pa-tent No. 71,686 issued -to George McKay provided a sulphur-contail~g cc ~ osition useful for sealing purposes a-t a join-t, for roofing purposes, for the forming of ornamental figures, and for the coating of the exposed surfaces of iron or steel steps, the com~osition including sulphur, brick-dust, tin, lead, bi.smuth, plaster of paris and korax.
~ lo~ver, attempts to make durable, high strength concre-te-like materials fro sulphur cements have encountered cost, durability, or other difficulties that precluded cc~nnercialization. Propo&als have been made to increase the strength oE suLphur as a bonding agent by the adcli.tion of coal, sand or pumice thereto. ~oreover pecuk~r cllarac-teris-tics were proposed to be impart~d by the addltion there-to of bi-tumens, me-talllc sulphides, and fibrous matel-ials. ~Iso United States Patent No. 3,459,717 patented ~ugust 5, 1969 b~ J.s~ Signouret, provided a sulphur-based plastic com~osition of .improved firep.roofing characteristics by the incorpora-tion, into the molten suLphur, of a dies-ter of dithiophosphoric acid and an ethylellic hydrocc~rbon.
C~ )n~ z~l tl cr~
~ major problem in the-c6nnQr~i~l~ti~n oE s~phur ce~ents has been the pro-gressive em~ittlement and subsequent cr~nbling, ul~l~r thermal stress, of ~e s~phur cement. The cause of this en~rittlement is believed to be the progressive crystallization of the initially amo.rphous suLphur. Partial inhibi-ti.on of -the crystallization has been achieved through various organic and inorgr~lic additives.
Thiokol products ~Trade Mark of Thiokol Chemical Corporation for oleiin polysulphides) have been used to stabilize the amorphous form of sul-phur in sulphur cements. mus, Canadian Patent No. 356,181 issued February 25, 1936 to W.W. Duecker, purports to provide a solution to the problem hy dissolving, in the sulphur, certain olefin pc>lysulphides or polymerization ~;~, "~, - 1 - ~
products thereof. These cements, h~wever, were not practical on a large scale due to their high cost and disagreeable odor. Dicyclopentadie~e has good stabili~ation properties and more favourable economics, but in~arts a nauseating odor to ~e sulphur cen~lt and has other shortcomings, e.g., its vapour, even at low concentrations, is highly toxic [see, for exa~ple, Kinkead et al, "The M2mm~1ian Toxicity of Dicyclopentadiene", Tbxicology and Applied Pharmacology, 20 552-561 (1971)]. ~loreover, dicyclopentadiene requires refluxing with molten sulphur to;avoid excessive loss of material in vapour ~orm.
An object of one aspect of this inveJntion is to provide a sulphur ce~nt composition which does not suffer the disadvantages of the con~osi-tions of the prior art.
An object of another aspect of this invention is to provide a more durable suiphur cement.
An object of yet another aspect of this invention is to provide a sulphur cement which can be made ~1ith off-~ade sulphur.
An object of still another aspect of this invention is to provide a sulphur cement which i.s resistant to the cor~osive influence of salts, most acids and solvents.
An object o a further aspect of this invention is to provide a sulphur cem~t which provides good the~mal insulation ~d which develops high strength without hours o cooling.
An object of yet a urther aspect of this invention is to provide sulphur concretes made with the sulphur cements, which are self-exting~is,~-ing.
By one broad aspect of this invention, a sulphur cement pre-mix composition is provided consisting essentially of (a) sulphur; (b) a .~
bonding agcnt which is adapted to stabilize thc sulphur ccment against pro-gressivc cmbrittlcment and mcchanical failure undcr thcrmaI or physical stress, the bonding agent comprising a viscosity incrcasing, surface actlve, finely divided, particulate solid inorganic agent, thc inorganic agent being of a size passing through a screen having a sieve opening of 0.005-0.147 mm, and being selected from the group consisting of tly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhotites, wherein for each 100 parts by weight of sulphur, there are 10 to 150 parts by weight of the agent, and an additive to provide fire resistance.
By another aspect, the present invention provides a sulphur cemcnt composition consisting essentially of: (a) sulphur which has bcen melted, and which con~:ains dispersed the melt (b) a bonding agent which is adapted to stabilizc thc sulphur cernent against progressive cmbrittlcmcnt and mech-anical failure under thermal or physical stress, the bonding agent comprising 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 0.005-0.147 mm, and being selccted from the group consisting of fIy ash, dolomite, pulverized limcstonc and a mixture of pyrites ard pyrrhotites, wherein for each 100 parts by weight of sulphur, therc are 10 to 150 parts by weight of the agent; (c) and an additivc to provide firc resistance.
8y a variant of these two aspects oE this invention, at least 10%
by weight of~the particuLate solid inorganic material is unfragmented fly ash, substantially all in the range of 0.005-0.147 mm; and the premix com-position is convertible into shaped hard products of high compressive strength.
By another variant thereof, the particulate inorganic agent is of a size passing through a screen having a sieve opening of 0.047 mm.
By yet another variant thereof, the particulate inorganic agent consists entirely of fly ash.
By still another variant thereoE, the additive to provide fire resistance comprises 1,5,9-cyclododecatriene.
By a still further variant thereof, the additive to provide fire resistance comprises the reaction product of diphenoxyphosphinic acid with sulphur and with ~-methyl styrene.
By another aspect of this invention, a sulphur concrete is pro-vided comprising:(A) a sulphur cement pre-mix composition consisting essen-tially 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 comprising a viscosity increasing, surface active, finely divided, particulate solid inorganic a agent, the inorganic agcnt being of a size passing through a screen having a sieve opcning of 0.005-0.147 mm, and being selected from the group con-sisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhotites, wherein for each 100 parts by weight of suLphur, there are 10 to 150 parts by weight of the agent and (c) an additive co provide fire resistance; and (B) natural or manufact-lred aggregates.
By another aspect of this invention, a sulpl--lr concrete is provided comprising:(A) a sulphur cement composition consistil-g essentially of (a) sulphur which has been melted and which concains dispers~c~ in the melt, (b) a bonding agent which is adapted to stabilize the sulphur cement against pro-gressive embrittlement and mechanical failure under thermal or physical stress, the bonding agent comprising 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 0.005-0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhoCites, wherein for each 100 parts by weight of sulphur, there are 10 to 150 parts by weight of the agent, and (c) an additive to provide fire resistance; and (B) natural or manufactured aggregates.
_ 4 -By still another aspect of this invention, a sulphur concrete product is provided, composed of (B) natural or manufactured aggregates distributed in (A) a solid matrix composecl of a sulphur composition consis-ting essentially of (a) sulphur (b) 20% to 80% by weight, based on the total composition weight, of a bonding agent which is adaptecl to stabilize the sulphur cement against progressive embrittlement and mechanical failure under thermal or physical stress, the bonding agent comprising a viscosity in-creasing9 surface active, finely divided, particulate solid inorganic agent, the inorganic agent being of a size passing through a screen having a sieve opening of 0.005-0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrr-hotites, wherein for each 100 parts by weight of sulphur, there are 10 to 150 parts by weight of the agent, and (c) an additive to provide fire resistance.
By a variant thereof, the ratio of aggregate (B) to sulphur cement (~) is 80-36:20-6~.
By another variant thereof, the additive to provide fire resistance, is e.g~ 1,5,9-cyclododecatrene or the reaction product of diphenoxyphosphinic acid with sulphur and with ~ -methyl styrene.
By a further variant thereof, the particulate, inorganic agel-t is of a size passing through a screen having a sieve opening of 0.074 mm.
By still another variant thereof, the particulate, inorganic agent consists entirely of fly ash of a size passing through a screen having a sieve opening of 0.147 mm.
By yet another variant thereof, the least 10% by weight of the particulate solid inorganic material is unfragmented fly ash substantially all in the range of 0.005-0.147 mm; and wherein the concrete is convertible into shaped hard products of high compressive strength.
- - 4a -The present invention in one of its aspects provides a sulphur cement which can be used for the manufacturc of a sulphur concrete having numerous applications in the construction ~ield. It is substantially free from the disadvantages of the proclucts describcd previously and has positive advantages, as will be described hereinafter.
The sulphur cement according to one aspect of this invention as described above employs, as the stabilizer, the particularly recited viscosity increasing, surface active; finely divided particulate inorganic stabilizer.
~! - 4b -The chcmical stabilizer used in sulphur ccment compositions dcs-cribed herein is any of the olefinic hydrocarbon polymers dcriv~cl from pct-roleum having a non-volatile c(ntcnt greater than 50% by weight and a minlmum 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 100% by weight of the total sulphur, and more especially in the proportion of 1 - 5~/u 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. Prefer-ably, the chemical is prereacted at approximately 140C. for 30 minutes with a smallcr 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 kno~n by the following Trade Marks: RP220, a product of Exxon Chemical Co.; RP020, a product of Exxon Chemical Co.; CTL~, a product of En~ay Chcmical Co.; and Escopol, a product of Esso Chemical AB (Sweden); all identifying a heat reactive ole-finic liquid hydrocarbon obtained by partial polymerization of olefins.
In order to provide a sulphur-containing cement of aspects of this invention having a worlcable consistency, it is necessary to add a finely divided, viscosity increasing material, for example, fly ash, gypsum, dolo-mite, 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 quantît:~es of ferric oxide, calcium oxide, magnesiumoxide, sodlum oxide, potassium oxide and carbon, ls partlcularly effec-tl~e ln this regard due to its small particle slze, shape and s~rface texture. It has been found to impart an extra measure of durability to the final cement, independent o~ 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 ti~es the total weight o~ the sulphur may be beneficially added.
A notable feature of the sulphur cement o~ aspects of this invention is that such sulphur cement does not require high purity sul-phur and can be made with off-grade sulphur contain:Lng hydrocarbon :impurities, blow dirt, and other ~'contaminants". The presence of hydrogen sulphide (H2S) in the sulphur has been determined to be detri-mental, but the simple process of remelting the sulphur usually reduces the concentration of this contaminant to harmless levels.
The resultîng cement of an aspect of this invention is substan-tially resistant to the corrosive in1uences of salts, most acids, and solvents. Hot oxidizing acids at high concentrations and strong concen-trated bases do attack the cement, however. The cement is essentiallyimpervious to moisture penetration. It provldes 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 sulphùr cement of one aspect of this invent;on as described above, to make strong, durable concretes of another aspect of this invention. Among the conven-tional aggregates useful herein for preparing the concrete of another aspect of this invention are sand, crushed cinders, brick dust, foundry sand, crushed quartzite gravel, crushed limestone, siliceous tailing sand, expanded shale, e~panded cla~, crushed barite, crushed brickj crushed 3~
portlancl cement concrete, and eru~hed grani-te. Preferably, the aggreyate par-ticles are of anguLar shape and of rough .s~lrface -texture as can be ob, talned by erushing. With a suffieiently fluid nLLX, or through use oE héated molds, -the rrold surfaees are reprocluced preeisely. Where sulphur is readily availahle, the cement and the concrete of aspeets of -tl~s inven-tion can ke produeed at compe-titive cos-ts. The e~npatibility of the sulphur eement 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. p~r cubic foot, to ranges between 100 Lbs. per eubic foot and 230 lbs. per eubie foot, or even as high as 530 lhs. per eubie foot. The suLphur eoncrete of an aspect of this invention ean be re.inforeed in eonventional fashion by the use of steel, a.sbestos or glass fibre, or other reinforcing.materials.
lhe sulphur concre-tes of aspects of this invention t~nd to be self-extinguishin~ with ash )ntents approaehing two~thirds the ~eight of s-LLphur and ean be made fire resistan-t, and/or to inhibit the formation of S02 when heated, by the addition of suitable additives, e.g., 1,5,9-eyelododeeatriene or the reaetion produet of dipheno~yphosphir~ie aeid with s~Lphur and v~~me-~hyl styrene The suLphwr eoneretes of anot-~her as~et o -this invellti~l derived Erom the sulphur eements of a first a~speet of this .inven~ion are not refrac-tory n~teri.als arlcl w:ill softerlc~r~:l melt if }~lted above :L~0C., altho~l~h the rate of melting is slow due to the low -thermal eon~uetivity i~ar-ted to the eonerete by the suLphur.
I'he prine.iples developed for the grading of aggregates used .in eon-ventional eoneretes are essentially unehanged for sulp.hur eoneretes of aspeets of this invention except for the much greater -tolerance of fines and silt of the sulph~r concretes. 80% of the ultirnate concre-te stren~th is de-veloped in one day; virt~ally 100% of ~he uLti~.ate strength is realized after four days.
3Q T~ese sL~Lphur eoncretes may be used as a construction rnaterial ,;~
for a wide variety of precast and poured-in-place applications such as, for example~ sidewalks, steps, parking curbs, highway medlan barriers, sewer pipe, septic tanks, pilings, eootings, fotmdations, 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 di~es, highway and railway embankments and as linings for irrigation canals, farm ponds~ etc.
The examples given below are intended only to illustrate aspects of the present invention.
Samples 1 - 7. Prereaction of the Hydrocarbon Stabilizers The hydrocarbon stabilizer (at 25C.) was added to molten sulphur (at 140C.) with vigorous stirring. Ileat was applied only to maintain a reaction temperature of 1~0 to 150C. ~t this temperature reaction titnes were in the order of 15 to 40 minutes. The progess 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 increasîng viscosity of the mixture. At sulphur-stabili~er ratios of less than 4:1 by w~ight, control o the addition rate was required to prevent ~he exothermici~y of the reactions raising temperatures abo-ve 155C., at which point hydrogen sulphide (~12S) was evolved with consequent oaming and degradation of the product~
When reactions were conducted under the above-prescr-Lbed 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 poiymers 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.
'Table 1 'RP220 RP020 CTLA Escopol Flash Point (COC) minlmum 150 138 150 125 Gravity (API) maximum 4 4.0 9.6 3 Iodine Number (lOOcg/g) minimum 200 160 255 135 Non-volatile Matter (~ by 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 23 25*
*cst/sooc .
Ta~le 2 Reaction Conditions for the Rreparation of Sulphur-con_a'ining'Polymers Stabilizer ~ Reaction Reaction Product Sample (STB? STB _ S Temp.(C)' Tlmé tMin~ Colour 1 CTLA 12.5 37.5 140 30 dark brown
Sulphur c~m~lts have a lony history of use in specializecl aE)pli-ca-tions. T.hus, Canadian Pa-tent No. 71,686 issued -to George McKay provided a sulphur-contail~g cc ~ osition useful for sealing purposes a-t a join-t, for roofing purposes, for the forming of ornamental figures, and for the coating of the exposed surfaces of iron or steel steps, the com~osition including sulphur, brick-dust, tin, lead, bi.smuth, plaster of paris and korax.
~ lo~ver, attempts to make durable, high strength concre-te-like materials fro sulphur cements have encountered cost, durability, or other difficulties that precluded cc~nnercialization. Propo&als have been made to increase the strength oE suLphur as a bonding agent by the adcli.tion of coal, sand or pumice thereto. ~oreover pecuk~r cllarac-teris-tics were proposed to be impart~d by the addltion there-to of bi-tumens, me-talllc sulphides, and fibrous matel-ials. ~Iso United States Patent No. 3,459,717 patented ~ugust 5, 1969 b~ J.s~ Signouret, provided a sulphur-based plastic com~osition of .improved firep.roofing characteristics by the incorpora-tion, into the molten suLphur, of a dies-ter of dithiophosphoric acid and an ethylellic hydrocc~rbon.
C~ )n~ z~l tl cr~
~ major problem in the-c6nnQr~i~l~ti~n oE s~phur ce~ents has been the pro-gressive em~ittlement and subsequent cr~nbling, ul~l~r thermal stress, of ~e s~phur cement. The cause of this en~rittlement is believed to be the progressive crystallization of the initially amo.rphous suLphur. Partial inhibi-ti.on of -the crystallization has been achieved through various organic and inorgr~lic additives.
Thiokol products ~Trade Mark of Thiokol Chemical Corporation for oleiin polysulphides) have been used to stabilize the amorphous form of sul-phur in sulphur cements. mus, Canadian Patent No. 356,181 issued February 25, 1936 to W.W. Duecker, purports to provide a solution to the problem hy dissolving, in the sulphur, certain olefin pc>lysulphides or polymerization ~;~, "~, - 1 - ~
products thereof. These cements, h~wever, were not practical on a large scale due to their high cost and disagreeable odor. Dicyclopentadie~e has good stabili~ation properties and more favourable economics, but in~arts a nauseating odor to ~e sulphur cen~lt and has other shortcomings, e.g., its vapour, even at low concentrations, is highly toxic [see, for exa~ple, Kinkead et al, "The M2mm~1ian Toxicity of Dicyclopentadiene", Tbxicology and Applied Pharmacology, 20 552-561 (1971)]. ~loreover, dicyclopentadiene requires refluxing with molten sulphur to;avoid excessive loss of material in vapour ~orm.
An object of one aspect of this inveJntion is to provide a sulphur ce~nt composition which does not suffer the disadvantages of the con~osi-tions of the prior art.
An object of another aspect of this invention is to provide a more durable suiphur cement.
An object of yet another aspect of this invention is to provide a sulphur cement which can be made ~1ith off-~ade sulphur.
An object of still another aspect of this invention is to provide a sulphur cement which i.s resistant to the cor~osive influence of salts, most acids and solvents.
An object o a further aspect of this invention is to provide a sulphur cem~t which provides good the~mal insulation ~d which develops high strength without hours o cooling.
An object of yet a urther aspect of this invention is to provide sulphur concretes made with the sulphur cements, which are self-exting~is,~-ing.
By one broad aspect of this invention, a sulphur cement pre-mix composition is provided consisting essentially of (a) sulphur; (b) a .~
bonding agcnt which is adapted to stabilize thc sulphur ccment against pro-gressivc cmbrittlcment and mcchanical failure undcr thcrmaI or physical stress, the bonding agent comprising a viscosity incrcasing, surface actlve, finely divided, particulate solid inorganic agent, thc inorganic agent being of a size passing through a screen having a sieve opening of 0.005-0.147 mm, and being selected from the group consisting of tly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhotites, wherein for each 100 parts by weight of sulphur, there are 10 to 150 parts by weight of the agent, and an additive to provide fire resistance.
By another aspect, the present invention provides a sulphur cemcnt composition consisting essentially of: (a) sulphur which has bcen melted, and which con~:ains dispersed the melt (b) a bonding agent which is adapted to stabilizc thc sulphur cernent against progressive cmbrittlcmcnt and mech-anical failure under thermal or physical stress, the bonding agent comprising 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 0.005-0.147 mm, and being selccted from the group consisting of fIy ash, dolomite, pulverized limcstonc and a mixture of pyrites ard pyrrhotites, wherein for each 100 parts by weight of sulphur, therc are 10 to 150 parts by weight of the agent; (c) and an additivc to provide firc resistance.
8y a variant of these two aspects oE this invention, at least 10%
by weight of~the particuLate solid inorganic material is unfragmented fly ash, substantially all in the range of 0.005-0.147 mm; and the premix com-position is convertible into shaped hard products of high compressive strength.
By another variant thereof, the particulate inorganic agent is of a size passing through a screen having a sieve opening of 0.047 mm.
By yet another variant thereof, the particulate inorganic agent consists entirely of fly ash.
By still another variant thereoE, the additive to provide fire resistance comprises 1,5,9-cyclododecatriene.
By a still further variant thereof, the additive to provide fire resistance comprises the reaction product of diphenoxyphosphinic acid with sulphur and with ~-methyl styrene.
By another aspect of this invention, a sulphur concrete is pro-vided comprising:(A) a sulphur cement pre-mix composition consisting essen-tially 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 comprising a viscosity increasing, surface active, finely divided, particulate solid inorganic a agent, the inorganic agcnt being of a size passing through a screen having a sieve opcning of 0.005-0.147 mm, and being selected from the group con-sisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhotites, wherein for each 100 parts by weight of suLphur, there are 10 to 150 parts by weight of the agent and (c) an additive co provide fire resistance; and (B) natural or manufact-lred aggregates.
By another aspect of this invention, a sulpl--lr concrete is provided comprising:(A) a sulphur cement composition consistil-g essentially of (a) sulphur which has been melted and which concains dispers~c~ in the melt, (b) a bonding agent which is adapted to stabilize the sulphur cement against pro-gressive embrittlement and mechanical failure under thermal or physical stress, the bonding agent comprising 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 0.005-0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhoCites, wherein for each 100 parts by weight of sulphur, there are 10 to 150 parts by weight of the agent, and (c) an additive to provide fire resistance; and (B) natural or manufactured aggregates.
_ 4 -By still another aspect of this invention, a sulphur concrete product is provided, composed of (B) natural or manufactured aggregates distributed in (A) a solid matrix composecl of a sulphur composition consis-ting essentially of (a) sulphur (b) 20% to 80% by weight, based on the total composition weight, of a bonding agent which is adaptecl to stabilize the sulphur cement against progressive embrittlement and mechanical failure under thermal or physical stress, the bonding agent comprising a viscosity in-creasing9 surface active, finely divided, particulate solid inorganic agent, the inorganic agent being of a size passing through a screen having a sieve opening of 0.005-0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrr-hotites, wherein for each 100 parts by weight of sulphur, there are 10 to 150 parts by weight of the agent, and (c) an additive to provide fire resistance.
By a variant thereof, the ratio of aggregate (B) to sulphur cement (~) is 80-36:20-6~.
By another variant thereof, the additive to provide fire resistance, is e.g~ 1,5,9-cyclododecatrene or the reaction product of diphenoxyphosphinic acid with sulphur and with ~ -methyl styrene.
By a further variant thereof, the particulate, inorganic agel-t is of a size passing through a screen having a sieve opening of 0.074 mm.
By still another variant thereof, the particulate, inorganic agent consists entirely of fly ash of a size passing through a screen having a sieve opening of 0.147 mm.
By yet another variant thereof, the least 10% by weight of the particulate solid inorganic material is unfragmented fly ash substantially all in the range of 0.005-0.147 mm; and wherein the concrete is convertible into shaped hard products of high compressive strength.
- - 4a -The present invention in one of its aspects provides a sulphur cement which can be used for the manufacturc of a sulphur concrete having numerous applications in the construction ~ield. It is substantially free from the disadvantages of the proclucts describcd previously and has positive advantages, as will be described hereinafter.
The sulphur cement according to one aspect of this invention as described above employs, as the stabilizer, the particularly recited viscosity increasing, surface active; finely divided particulate inorganic stabilizer.
~! - 4b -The chcmical stabilizer used in sulphur ccment compositions dcs-cribed herein is any of the olefinic hydrocarbon polymers dcriv~cl from pct-roleum having a non-volatile c(ntcnt greater than 50% by weight and a minlmum 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 100% by weight of the total sulphur, and more especially in the proportion of 1 - 5~/u 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. Prefer-ably, the chemical is prereacted at approximately 140C. for 30 minutes with a smallcr 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 kno~n by the following Trade Marks: RP220, a product of Exxon Chemical Co.; RP020, a product of Exxon Chemical Co.; CTL~, a product of En~ay Chcmical Co.; and Escopol, a product of Esso Chemical AB (Sweden); all identifying a heat reactive ole-finic liquid hydrocarbon obtained by partial polymerization of olefins.
In order to provide a sulphur-containing cement of aspects of this invention having a worlcable consistency, it is necessary to add a finely divided, viscosity increasing material, for example, fly ash, gypsum, dolo-mite, 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 quantît:~es of ferric oxide, calcium oxide, magnesiumoxide, sodlum oxide, potassium oxide and carbon, ls partlcularly effec-tl~e ln this regard due to its small particle slze, shape and s~rface texture. It has been found to impart an extra measure of durability to the final cement, independent o~ 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 ti~es the total weight o~ the sulphur may be beneficially added.
A notable feature of the sulphur cement o~ aspects of this invention is that such sulphur cement does not require high purity sul-phur and can be made with off-grade sulphur contain:Lng hydrocarbon :impurities, blow dirt, and other ~'contaminants". The presence of hydrogen sulphide (H2S) in the sulphur has been determined to be detri-mental, but the simple process of remelting the sulphur usually reduces the concentration of this contaminant to harmless levels.
The resultîng cement of an aspect of this invention is substan-tially resistant to the corrosive in1uences of salts, most acids, and solvents. Hot oxidizing acids at high concentrations and strong concen-trated bases do attack the cement, however. The cement is essentiallyimpervious to moisture penetration. It provldes 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 sulphùr cement of one aspect of this invent;on as described above, to make strong, durable concretes of another aspect of this invention. Among the conven-tional aggregates useful herein for preparing the concrete of another aspect of this invention are sand, crushed cinders, brick dust, foundry sand, crushed quartzite gravel, crushed limestone, siliceous tailing sand, expanded shale, e~panded cla~, crushed barite, crushed brickj crushed 3~
portlancl cement concrete, and eru~hed grani-te. Preferably, the aggreyate par-ticles are of anguLar shape and of rough .s~lrface -texture as can be ob, talned by erushing. With a suffieiently fluid nLLX, or through use oE héated molds, -the rrold surfaees are reprocluced preeisely. Where sulphur is readily availahle, the cement and the concrete of aspeets of -tl~s inven-tion can ke produeed at compe-titive cos-ts. The e~npatibility of the sulphur eement 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. p~r cubic foot, to ranges between 100 Lbs. per eubic foot and 230 lbs. per eubie foot, or even as high as 530 lhs. per eubie foot. The suLphur eoncrete of an aspect of this invention ean be re.inforeed in eonventional fashion by the use of steel, a.sbestos or glass fibre, or other reinforcing.materials.
lhe sulphur concre-tes of aspects of this invention t~nd to be self-extinguishin~ with ash )ntents approaehing two~thirds the ~eight of s-LLphur and ean be made fire resistan-t, and/or to inhibit the formation of S02 when heated, by the addition of suitable additives, e.g., 1,5,9-eyelododeeatriene or the reaetion produet of dipheno~yphosphir~ie aeid with s~Lphur and v~~me-~hyl styrene The suLphwr eoneretes of anot-~her as~et o -this invellti~l derived Erom the sulphur eements of a first a~speet of this .inven~ion are not refrac-tory n~teri.als arlcl w:ill softerlc~r~:l melt if }~lted above :L~0C., altho~l~h the rate of melting is slow due to the low -thermal eon~uetivity i~ar-ted to the eonerete by the suLphur.
I'he prine.iples developed for the grading of aggregates used .in eon-ventional eoneretes are essentially unehanged for sulp.hur eoneretes of aspeets of this invention except for the much greater -tolerance of fines and silt of the sulph~r concretes. 80% of the ultirnate concre-te stren~th is de-veloped in one day; virt~ally 100% of ~he uLti~.ate strength is realized after four days.
3Q T~ese sL~Lphur eoncretes may be used as a construction rnaterial ,;~
for a wide variety of precast and poured-in-place applications such as, for example~ sidewalks, steps, parking curbs, highway medlan barriers, sewer pipe, septic tanks, pilings, eootings, fotmdations, 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 di~es, highway and railway embankments and as linings for irrigation canals, farm ponds~ etc.
The examples given below are intended only to illustrate aspects of the present invention.
Samples 1 - 7. Prereaction of the Hydrocarbon Stabilizers The hydrocarbon stabilizer (at 25C.) was added to molten sulphur (at 140C.) with vigorous stirring. Ileat was applied only to maintain a reaction temperature of 1~0 to 150C. ~t this temperature reaction titnes were in the order of 15 to 40 minutes. The progess 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 increasîng viscosity of the mixture. At sulphur-stabili~er ratios of less than 4:1 by w~ight, control o the addition rate was required to prevent ~he exothermici~y of the reactions raising temperatures abo-ve 155C., at which point hydrogen sulphide (~12S) was evolved with consequent oaming and degradation of the product~
When reactions were conducted under the above-prescr-Lbed 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 poiymers 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.
'Table 1 'RP220 RP020 CTLA Escopol Flash Point (COC) minlmum 150 138 150 125 Gravity (API) maximum 4 4.0 9.6 3 Iodine Number (lOOcg/g) minimum 200 160 255 135 Non-volatile Matter (~ by 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 23 25*
*cst/sooc .
Ta~le 2 Reaction Conditions for the Rreparation of Sulphur-con_a'ining'Polymers Stabilizer ~ Reaction Reaction Product Sample (STB? STB _ S Temp.(C)' Tlmé tMin~ Colour 1 CTLA 12.5 37.5 140 30 dark brown
2 CTLA 8.3 41.7 140 40 dark brown
3 Escopol10.0 40.0 150 15 light brown
4 Escopol14.5 35.5 140 20 light brown RP220 8.3 41.7 150 15 dark brown 6 RP22012.5 37.5 140 20 dark brown 7 RP02012.5 37.5 140 15 dark brown ~ l to ~ ~ Sulphur Ce~ents and Concretes Derived I~erefrom -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 ll3 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.
Examples_ 0 to l3 A second series oE sulphur cements and sulphur co~cretes was prepared in a manner analogous to that of Examples 1 to 9 with vhe exception that raw stabilLzer ~i.e. not prereacted with sulphur) was added directly ~o the mix at ~he previous point of prereacted material addition. In order to allow complete reaction, the mixing time was increased to 20 minutes.
Examples 14 to 22 A third series of sulphur cements and sulphur concretes were prepared in a manner analogous to that of Examples 1 to 9 but ~ th the omission of the hydrocarbon stabilizer. Sulphur concretes prepared according to these mix designs would be limited to reasonably isothermal applications, such as underground or underwater structures subjected to very mild thermal cycling.
The results are summarized and tabulated below in Table 3.
-- 10 -`
r~ 3 Su~lur Concretes - Com~o.sltioll and l~ tie~
Chemical Stabi- Compres-Exam- Ag~re-- lizer 1)ensity sive*
ple gate_ Sulptlur Fly Ash ~'220 ( ~ c) Strength 1 Crushed quart~ite 71.720.4 7 4 0.502.38 7,160 ~ravel 2 Cruslled limestone 73.5 26 - 0.502.41 5~290 3 Siliceous tailings 63.534.8 - 1.72.21 5,290 sand 4 Expanded shale 38.637.6 23.2 0.591.73 4,610 Expanded clay 38.4 32.029.2 0.38 1.778,350 6 Crushed barite 78.715.0 5.9 0.38~.18 7,520 7 Crushed brick 54.5 27.317.5 0.68 2.l78,530 8 Crushed ~ortland 64.124.1 11.2 0.602.23 5,690 cement co~cre-te 9 Crushed granite 65.920.0 12.6 0.502.39 7,760 Crushed quart~ite 64.419.6 15.5 0.492.38 8,710 gravel 11 Siliceous tailings 60.930.8 7.5 0.772.23 6,530 sand 12 Expanded shale 50.026.6 22.7 0.661.70 4~740 13 Crushed barite 79.113.2 7.4 0.333.28 7,650 20 14 Crushed qu.lrt~lte 65.6L8.8 15.6 -- 2.40 9,270 ~ravel Crushed limestolle 60.821.8 17.4 - 2.32 7,730 16 Cruslled ~ranltc 66.221.2 12.6 - 2.37 8,250 17 Crushed barite 79.612.8 7.6 _ 3.25 7,570 18 Siliceous tailings 61.234.8 4.0 - 2.20 6,420 sand 19 Ex~anded shale 35.835.8 28.4 - 1.68 4,860 Expanded clay 41.0 34.025.0 - 1.799,320 21 Crushed brick 55.0 27.417.6 - 2.1810,130 22 Crushed portland 64.823.0 12.2 - 2.24 7,840 c~r?~t concrete * Mean of three (3) tests.
The components were mixed at 130C. in a heated ll3 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.
Examples_ 0 to l3 A second series oE sulphur cements and sulphur co~cretes was prepared in a manner analogous to that of Examples 1 to 9 with vhe exception that raw stabilLzer ~i.e. not prereacted with sulphur) was added directly ~o the mix at ~he previous point of prereacted material addition. In order to allow complete reaction, the mixing time was increased to 20 minutes.
Examples 14 to 22 A third series of sulphur cements and sulphur concretes were prepared in a manner analogous to that of Examples 1 to 9 but ~ th the omission of the hydrocarbon stabilizer. Sulphur concretes prepared according to these mix designs would be limited to reasonably isothermal applications, such as underground or underwater structures subjected to very mild thermal cycling.
The results are summarized and tabulated below in Table 3.
-- 10 -`
r~ 3 Su~lur Concretes - Com~o.sltioll and l~ tie~
Chemical Stabi- Compres-Exam- Ag~re-- lizer 1)ensity sive*
ple gate_ Sulptlur Fly Ash ~'220 ( ~ c) Strength 1 Crushed quart~ite 71.720.4 7 4 0.502.38 7,160 ~ravel 2 Cruslled limestone 73.5 26 - 0.502.41 5~290 3 Siliceous tailings 63.534.8 - 1.72.21 5,290 sand 4 Expanded shale 38.637.6 23.2 0.591.73 4,610 Expanded clay 38.4 32.029.2 0.38 1.778,350 6 Crushed barite 78.715.0 5.9 0.38~.18 7,520 7 Crushed brick 54.5 27.317.5 0.68 2.l78,530 8 Crushed ~ortland 64.124.1 11.2 0.602.23 5,690 cement co~cre-te 9 Crushed granite 65.920.0 12.6 0.502.39 7,760 Crushed quart~ite 64.419.6 15.5 0.492.38 8,710 gravel 11 Siliceous tailings 60.930.8 7.5 0.772.23 6,530 sand 12 Expanded shale 50.026.6 22.7 0.661.70 4~740 13 Crushed barite 79.113.2 7.4 0.333.28 7,650 20 14 Crushed qu.lrt~lte 65.6L8.8 15.6 -- 2.40 9,270 ~ravel Crushed limestolle 60.821.8 17.4 - 2.32 7,730 16 Cruslled ~ranltc 66.221.2 12.6 - 2.37 8,250 17 Crushed barite 79.612.8 7.6 _ 3.25 7,570 18 Siliceous tailings 61.234.8 4.0 - 2.20 6,420 sand 19 Ex~anded shale 35.835.8 28.4 - 1.68 4,860 Expanded clay 41.0 34.025.0 - 1.799,320 21 Crushed brick 55.0 27.417.6 - 2.1810,130 22 Crushed portland 64.823.0 12.2 - 2.24 7,840 c~r?~t concrete * Mean of three (3) tests.
Claims (21)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLlOWS:
1. A sulphur cement pre-mix composition consisting essentially of:
(a) sulphur;
(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 comprising a viscosity increasing, surface active, finely divided, particulate solid inorganic agent, said in-organic agent being of a size passing through a screen having a sieve opening of 0.005-0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhotites, wherein for each 100 parts by weight of sulphur, there are 10 to 150 parts by weight of the said agent; and (c) an additive to provide fire resistance.
(a) sulphur;
(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 comprising a viscosity increasing, surface active, finely divided, particulate solid inorganic agent, said in-organic agent being of a size passing through a screen having a sieve opening of 0.005-0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhotites, wherein for each 100 parts by weight of sulphur, there are 10 to 150 parts by weight of the said agent; and (c) an additive to provide fire resistance.
2. The sulphur cement pre-mix of claim 1 wherein at least 10% by weight of said particulate solid inorganic material is unfragmented fly ash substantially all in the range of 0.005-0.147 mm; and wherein said pre-mix composition is convertible into shaped hard products of high compressive strength.
3. The cornposition of claims 1 or 2 wherein said particulate in-organic agent is of a size passing through a screen having a sieve opening of 0.047 mm.
4. The composition of claims 1 or 2 wherein said particulate in-organicagent consists entirely of fly ash.
5. The composition of claims 1 or 2 wherein said additive to provide fire resistance comprises 1,5,9-cyclododecatriene.
6. The composition of claims 1 or 2 wherein said additive to pro-vide fire resistance comprises the reaction product of diphenoxyphosphinic acid with sulphur and with ? -methyl styrene.
7. A sulphur cement composition consisting essentially of:
(a) sulphur which has been melted, and which contains dispersed in said melt;
(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 comprising a viscosity increasing, surface active, finely divided, particulate solid inorganic agent, said in-organic agent being of a size passing through a screen having a sieve opening of 0.005-0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhotites, wherein for each 100 parts by weight of sulphur, there are 10 to 150 parts by weight of the said agent; and (c) an additive to provide fire resistance.
(a) sulphur which has been melted, and which contains dispersed in said melt;
(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 comprising a viscosity increasing, surface active, finely divided, particulate solid inorganic agent, said in-organic agent being of a size passing through a screen having a sieve opening of 0.005-0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhotites, wherein for each 100 parts by weight of sulphur, there are 10 to 150 parts by weight of the said agent; and (c) an additive to provide fire resistance.
8. The sulphur cement pre-mix of claim 7 wherein at least 10% by weight of said particulate solid inorganic material is unfragmented fly ash substantially all in the range of 0.005-0.147 mm; and wherein said pre-mix composition is convertible into shaped hard products of high compressive strength.
9. The composition of claims 7 or 8 wherein said particulate in-organic agent is of a size passing through a screen having a sieve opening of 0.047 mm.
10. The composition of claims 7 or 8 wherein said particulate in-organic agent consists entirely of fly ash.
11. The composition of claims 7 or 8 wherein said additive to provide fire resistance comprises 1,5,9-cyclododecatriene.
12. The composition of claims 7 or 8 wherein said additive to provide fire resistance comprises the reaction product of diphenoxyphosphinic acid with sulphur and with ?-methyl styrene.
13. A sulphur concrete comprising:
(A) a sulphur cement pre-mix composition consisting cssentially of:
(a) sulphur;
(b) a bonding agent which is adapted to stabilize said sul-phur cement against progressive embrittlement and mechanical failure under thermal or physical stress, said bonding agent comprising a viscosity in-creasing, surface active, finely divided, particulate solid inorganic agent, said inorganic agent being of a size passing through a screen having a sieve opening of 0.005-0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrr-hotites, wherein for each 100 parts by weight of sulphur, there are 10 to 150 parts by weight of the said agent; and (c) an additive to provide fire resistance;
and (B) natural or manufactured aggregates.
(A) a sulphur cement pre-mix composition consisting cssentially of:
(a) sulphur;
(b) a bonding agent which is adapted to stabilize said sul-phur cement against progressive embrittlement and mechanical failure under thermal or physical stress, said bonding agent comprising a viscosity in-creasing, surface active, finely divided, particulate solid inorganic agent, said inorganic agent being of a size passing through a screen having a sieve opening of 0.005-0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrr-hotites, wherein for each 100 parts by weight of sulphur, there are 10 to 150 parts by weight of the said agent; and (c) an additive to provide fire resistance;
and (B) natural or manufactured aggregates.
14. A sulphur concrete comprising:
(A) a sulphur cement composition consisting essentially of:
(a) sulphur which has been melted, and which contains dispersed in said melt;
(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 comprising a viscosity increasing, surface active, finely divided, particulate solid inorganic agent, said in-organic agent being of a size passing through a screen having a sieve opening of 0.005-0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhotites, wherein for each 100 parts by weight of sulphur, there are 10 to 150 parts by weight of the said agent;
(c) an additive to provide fire resistance;
and (B) natural or manufactured aggregates.
(A) a sulphur cement composition consisting essentially of:
(a) sulphur which has been melted, and which contains dispersed in said melt;
(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 comprising a viscosity increasing, surface active, finely divided, particulate solid inorganic agent, said in-organic agent being of a size passing through a screen having a sieve opening of 0.005-0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhotites, wherein for each 100 parts by weight of sulphur, there are 10 to 150 parts by weight of the said agent;
(c) an additive to provide fire resistance;
and (B) natural or manufactured aggregates.
15. A sulphur concrete product composed of (B) natural or manu-factured aggregate distributed in (A) a solid matrix composed of a sulphur composition consisting essentially of (a) sulphur;
(b) 20% to 80% by weight, based on the total composition weight, of 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 comprising a viscosity increasing, sur-face active, finely divided, particulate solid inorganic agent, said inor-ganic agent being of a size passing through a screen having a sieve opening of 0.005-0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhotites, wherein for each 100 parts by weight of sulphur, there are 10 to 150 parts by weight of the said agent;
(c) an additive to provide fire resistance.
(b) 20% to 80% by weight, based on the total composition weight, of 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 comprising a viscosity increasing, sur-face active, finely divided, particulate solid inorganic agent, said inor-ganic agent being of a size passing through a screen having a sieve opening of 0.005-0.147 mm, and being selected from the group consisting of fly ash, dolomite, pulverized limestone and a mixture of pyrites and pyrrhotites, wherein for each 100 parts by weight of sulphur, there are 10 to 150 parts by weight of the said agent;
(c) an additive to provide fire resistance.
16. The sulphur concrete of claims 13, 14 or 15 wherein the ratio of sulphur cement (A) to aggregate (B) is 20-64:80-36.
17. The sulphur concrete of claims 13, 14 or 15 wherein said particulate, inorganic agent is of a size passing through a screen having a sieve opening of 0.074 mm.
18. The sulphur concrete of claims 13, 14 or 15 wherein said par-ticulate, inorganic agent consists entirely of fly ash of a size passing through a screen having a sieve opening of 0.147 mm.
19. The sulphur concrete of claims 13, 14 or 15 wherein at least 10% by weight of said particulate solid inorganic material is unfragmented fly ash substantially all in the range of 0.005-0.147 mm; and wherein said concrete is convertible into shaped hard products of high compressive strength.
20. The sulphur concrete of claims 13, 14 or 15 including an ad-ditive to provide fire resistance, said additive comprising 1,5,9-cyclodode-catrene.
21. The sulphur concrete of claims 13, 14 or 15 including an ad-ditive to provide fire resistance, said additive comprising the reaction product of diphenoxyphosphinic acid with sulphur and with ? -methyl styrene.
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 (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US58173575A | 1975-05-29 | 1975-05-29 | |
| US581,735 | 1975-05-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1182944A true CA1182944A (en) | 1985-02-19 |
Family
ID=24326361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000251362A Expired CA1182944A (en) | 1975-05-29 | 1976-04-28 | Sulphur cements and concretes made therefrom |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5945627B2 (en) |
| CA (1) | CA1182944A (en) |
| FR (1) | FR2312466A1 (en) |
| MX (1) | MX143886A (en) |
| PL (1) | PL115768B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013112847A1 (en) * | 2012-01-27 | 2013-08-01 | Saudi Arabian Oil Company | Disposal of sulfur through use as sand-sulfur mortar |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1195020A (en) * | 1980-09-12 | 1985-10-08 | Robert E. Loov | Freeze/thaw durable sulphur compositions |
| JPS6046960A (en) * | 1983-08-24 | 1985-03-14 | 神戸材料株式会社 | Manufacture of sulfur concrete |
| ES2355001B1 (en) * | 2009-09-09 | 2012-01-25 | Consejo Superior De Investigaciones Científicas (Csic) | LIQUID MERCURY STABILIZATION PROCEDURE THROUGH POLYMERIC CEMENT OF SULFUR, VIA SULFURO DE MERCURIO |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3337355A (en) * | 1965-02-04 | 1967-08-22 | Southwest Patents Inc | Solid foamed sulphur and process for the manufacture thereof |
| US3674525A (en) * | 1970-02-25 | 1972-07-04 | Phillips Petroleum Co | Plasticized sulfur compositions |
| JPS5549024B2 (en) * | 1971-12-29 | 1980-12-09 | ||
| GB1398306A (en) * | 1972-05-10 | 1975-06-18 | Doulton & Co Ltd | Electrically conductive cement |
| JPS5229773B2 (en) * | 1972-10-20 | 1977-08-04 | ||
| JPS4986420A (en) * | 1972-12-23 | 1974-08-19 | ||
| JPS4990323A (en) * | 1972-12-28 | 1974-08-29 |
-
1976
- 1976-04-28 CA CA000251362A patent/CA1182944A/en not_active Expired
- 1976-05-19 JP JP51058472A patent/JPS5945627B2/en not_active Expired
- 1976-05-26 FR FR7615910A patent/FR2312466A1/en active Granted
- 1976-05-27 PL PL18989876A patent/PL115768B1/en unknown
- 1976-05-31 MX MX16486776A patent/MX143886A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013112847A1 (en) * | 2012-01-27 | 2013-08-01 | Saudi Arabian Oil Company | Disposal of sulfur through use as sand-sulfur mortar |
| US8758212B2 (en) | 2012-01-27 | 2014-06-24 | Saudi Arabian Oil Company | Disposal of sulfur through use as sand-sulfur mortar |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2312466A1 (en) | 1976-12-24 |
| JPS5945627B2 (en) | 1984-11-07 |
| PL115768B1 (en) | 1981-04-30 |
| JPS51146526A (en) | 1976-12-16 |
| MX143886A (en) | 1981-07-30 |
| FR2312466B1 (en) | 1983-01-28 |
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