CA1227505A - Admixture for hydraulic cement compositions - Google Patents
Admixture for hydraulic cement compositionsInfo
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- CA1227505A CA1227505A CA000477803A CA477803A CA1227505A CA 1227505 A CA1227505 A CA 1227505A CA 000477803 A CA000477803 A CA 000477803A CA 477803 A CA477803 A CA 477803A CA 1227505 A CA1227505 A CA 1227505A
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Abstract
ABSTRACT
Admixture compositions for hydraulic cement compositions are disclosed which comprise a borate ester of a polyhydroxy compound and a hydraulic cement water-reducing agent. The inventive admixtures provide increased slump retention in hydraulic cement compositions while causing only a relatively minimal increase in the initial and final setting times of the cement mix.
Admixture compositions for hydraulic cement compositions are disclosed which comprise a borate ester of a polyhydroxy compound and a hydraulic cement water-reducing agent. The inventive admixtures provide increased slump retention in hydraulic cement compositions while causing only a relatively minimal increase in the initial and final setting times of the cement mix.
Description
~2~S~ 6925-292 ADMIXTURE FOR HYDRAULIC CEMENT COMPOSITIONS
. . .
BACKGROUND OF THE INVENTION
This invention relates to admixtures for hydraulic cement compositions and more particularly to water-reducing admixtures which provide improved slump retention in hydraulic cement compositions with relatively minimal increases in initial and final setting times.
The use of various water-reducing admixtures in hy-draulic cement compositions, e.g., mortars, grouts, and concrete, is well known. These admixtures allow the use of lesser amounts of water to achieve a desired plasticity or workability. The admixture also provides higher compressive strengths in the cement composition after setting, due either to the use of less water in the mix or to a more complete dispersion oE the cement particles in the plastic cement mix by the admixture.
A major problem associated with the use of conventional water-reducing admixtures is that the length of time during which the admixture is able to maintain a desired high level of plasticity or workability in the cement mix is relatively short, lastlng an average of 25 to 45 minutes after addition of the admixture. In most job situations, this generally requires that the admixture be added just prior to placement, i.e., at the job site, thus requiring the equipping of delivery trucks with specially designed dispensing equipment. In addition to the expense associated with the installation and maintenance of this equipment, its use can be problemmatic where local work specifications or conditions prohibit on site addition of admixtures. In addition, the relatively short duration of ~Z2~0~ 6925-292 increased plasticity limits the amount of time the applicator has to place and work the mixture. This can be a particularly troublesome constraint under difficult placement or job conditions.
la I
~sè 2764 ~Z2750~i The problem of a relatively short duration of increased plastlcity can sornetimes be lessened by a high dosage of the water-reduclng admixture. However, this tends to provide too fluid a mix immediately following addition and generally results in excessive set retardation.
This latter disadvantage, in turn, can delay strength gain in the cement mix after setting.
The plasticity of a hydraulic cement mixture is normally evaluated by slump measurement, e.g., in accordance with ASTM C143. The slump is measured by filling a truncated cone with the mixture, removing the cone, and measuring the drop Tn l1elght of the unsupported mlxture. As a measure of the decrease in plasticity of the mixture over time, slump measurements are made on the aglng mlxture at spaced time intervals. The decreasing plastlcity is thus quantified as the decrease In slump with tlme. A lesser decrease in slump with time i.e,, Increased slump retention, Indlcates a greater abllity on the part of a water-reducing admlxture to impart increased plastlcity to the cement mixture for a longer duratlon.
SUMMARY_OF THE INVENTION
The present invention is directed toward novel water-reducing admixture compositions for hydraulic cement materials which can provide levels of water reduction which are at least as great as those provided by conventional water-reducing agents and, in additlon, provide substantially increased levels of slump retention. A particular Case !764 12~505 advantage of the inventive admixtures is that they can be formulated to provide significant and substantlal Increases in slump retentlon ~tth only relativeiy minimal increases in the initial and final settlng tlmes of the cementitious mix. The admlxture composltTons of thls Invention are blends or mixtures which comprlse a hydraulic cement water-reducing agent and a borate ester of a polyhydroxy compound. By the term "polyhydroxy compound" is meant a dioi or a polyhydric compound, i.e., one which contains more than two hydroxy groups. The polyhydroxy compound can be an aromatic compound, such as a catechol, or an aliphatic compound, with the latter being preferred from the standpoint of attaining lower levels of set retardation. Most preferably, the polyhydroxy compound is an allphatlc polyhydrlc carboxyllc acld, e.g., a glyconlc acld.
The admixture compositlon can comprlse tile1 borate ester com,oonent lS in combination with a single water-reduclng agent or, preferably, In combination with two or more water-reduclnq agents. Preferred water-reducing agents for use In the inventive admixtures are aromatic sulfonic acid-aldehyde condensate salts and lignosulfonic acid salts.
Most preferably, both of these preferred water-reducing agents are present in the admixture together with the borate ester.
The relative quantity of each of the admixture components can vary over a wide range such that a variety of admixture formulations can be provided to meet different requirements of slump retention or set retardation. This flexibility in formulating the admixture can also be used to compensate for variations in reactivity of different cements Cud se 2 7 6 4 ~;LZZ75( ~5 to the admixture. This flexibility is significantiy increased by the use of two or more different water-reducing agents in the admlxture, inasmuch as the ratio of the water-reducing agents to each other, as well as to the borate ester, can be adjusted. Thus, a wider variety of formulations, with a correspondingly broader range of properties in hydraulic cement mixes, can be provided.
The admixture blends of this invention can be provided and used as neat formulations in the form of a dry powder or, preferably, as aqueous-based solutions, i.e., the admixture components can be dissolved in an aqueous-based solvent.
The present invention is further directed to hydraulic cement compositions comprising the admixture components.
DETA!LED DESCRIPTION OF THE INVENTION
As used hereln, the term hydraulic cement composition is intended to refer to any composition containing a hydraulic cement binder, e.g., an ASTM Type 1, Il, 111, IV, or V Portland cement, inclusive of both dry cement compositions and wet cement slurries or pastes. Included within the term are concretes, grouts, mortars, cement pastes, and the like. The admixtures of this invention are particularly useful in Portland cement concretes, and especially in larger scale Portland cement concrete preparations where the concrete is prepared at a mixing plant and transported to the Job site.
As indicated above, the admixtures of this invention provide a longer slump life, i.e., increased slump retention, in hydraulic cement compositions. For many larger scale applications using :;. , #I .,,.,~
Case 2764 Z~S~5 Portland cement concrete, the increased slump retention permits addition of the admixture to the concrete at the mixing plant, rather than at the job site. This option can be advantageous where local work specifications or conditions prohibit on site addition of admixtures.
Moreover, it facilitates mixing during transportation to the job site and provides greater flexibility in terms of the time alloweci for pouring, placing, and working the concrete at the job site. i-lowever, since the admixtures can be formulated to provide the increased slump retention while causing only a relatively minimal increase in the initiai setting time, (as compared, for example, to the initlal setting time obtained with a conventional water-reducing agent) the cement mix will generally thereafter set up in sufficient time to permit the applicator to gain access onto the concrete and finish it within the time constraints of the average work day, An additional unexpected advantage provided by the inventive admixtures is the generally excellent finishing characteristics imparted to hydraulic cement compositions, whereby the composition assumes a smooth, creamy consistency, for an extended duration, without stickiness, and thus can be surface finished easily and with highly satisfactory results.
The borate esters used in the admixtures of this invention are believed to provide the improved finishing characteristics and slump retention which have been observed in hydraulic cement compositions containing the admixtures. These borate esters are cyclic esters which are believed to involve complexation or bonding of a boron moiety to t Yo hydroxyl groups within an esterifying polyhydroxy compound so as to form a cyclic structure. As noted previousiy, the esterifying polyhydroxy compound is preferably aliphatic. Tha aliphatic compound can be, for example, an aliphatic diol, e.g. ethylene glycol, 1,2-propanediol, or 1,3-propanediol; an aliphatic polyhydric alcohol, ; I: ':$`
a se 2 7 6 4 7S~lIS
e.g., glycerol, glucose, or mannose; an aliphatic diol carboxylic acid e.g., 2,3-dihydroxypropionic acid or tartaric acid; or, preferab,ly, an aliphatic polyhydric carboxylic acid, e.g., glucaric acid The preferred aliphatic polyhydric carboxylic acids for use herein are the glyconic acids, particularly gluconic acid and glucoheptonlc acid. The stereospecificity of the polyhydroxy esterifying compound must, of course, be such as to permit formation of the cyclic borate ester. The stereospecific molecular requirements relating to borate ester formation are well known. An early study of this subject is provided by J. i30eseken, Advances in Carbohydrate Chemistry, 4, 189-210 (1949).
The borate esters generally used herein are belleved to be mono-esters involving the complexation or bondlng of one molecule of esterifying compound to one boron moiety, with the thlrd valence positlon of the boron moiety occupled by a hydroxyl group. This hydroxyl group may be neutrallzed wlth a cation as discussed here7nafter, Preparation of the mono-ester is normally facllitated by reacting approximately equimolar amounts of boron and the esterifying compound.
i-lowever, the mono-ester may also be prepared using a molar excess of the esterifying compound, as may prove necessary where stereospecific or steric factors hamper the reaction of the esterifylng compound with the boron moiety. Conversely, where the esterifylng compound is readily reacted with the boron moiety, bis esters may be formed using a molar excess of the esterifying compound and the present invention broadly comtemplates the use of bis borate esters as well.
,. I ''I' ' Ca ye 2 7 6 4 ~2~75~
The borate esters may be used in the free acid form, I . e. with an -OH group on the boron and ~COOH group on an esterifying carboxylic acid compound. However, the salt form of the ester can provide less set retardation in concrete formulations and is thus generally preferred for use herein. Where the esterifying polyhydroxy compound is a pclyhydroxy alcohol, the salt form incorporates a cation which displaces the hydrogen of the remaining hydroxyl group on the boron moiety.
Where the esterifying polyhydroxy compound is a polyhydroxy carboxylic acid, this salt form incorporates a cation associated with the carboxyl group(s) of the esterifying compound and, optionally, a cation which displaces the hydrogen of the remaining hydroxyl group on the boron moiety. The cation can be an alkali metal, e.g., sodium or potassium, or an alkaline earth metal, e.g., calclum or magnesium.
Preferably, however, the catlon is ammonium: alkylammonium, e.g., triethylammonium; alkanolammonlum, e.g. dlethanolammonium, triethanolammonium, or mixtures of the same. Utillzation of alkanolammonlum borate ester salts in particular has been found to result in admixtures which provide lesser increases In initial and final setting tlmes as compared, for example, to similar admixtures comprising alkaline earth ester salts. A particularly preferred cationic grouping is that provided by neutralization of the borate ester with a mixture of monoethanolamine, diethanolamine and triethanolamine.
The borate esters can be prepared by known methods. Thus, boric acid can be reacted with the esterifying compound in an aqueous medium, using mild heating to facilitate completion of the reaction.
Case 2764 ~2~'7SOS
Where the esterifying compound is not readily reactive with borlc acid it may prove desirable to employ an anhydrous polar reaction solvent, e.g., tetrahydrofuran, or hlgher reaction temperatures in order to promote ester formation. An esterifying carboxylic acid may be reacted in its salt form, e.CJ., calcium gluconate may be reacted with boric acid to provide the correspondingly neutralized calclum borogluconate. A
precursor to the carboxylic acid esterifying compound, e.g. a precursor lactone, may also be utilized as an esterifying reagent.
The esters may also be prepared by reaction of a borate salt such as zinc borate or calcium borate wlth the esterJfying compound, e.g., as described in U. S. Patent No. 3,053,674.
After formation of the ester, a base may be added to the reaction solution to neutralize the ester or as desired for cation exchange.
However, the pH of the solution should be maintained at less than pH
10-11, and preferably less than about pH 8, In order to provlde a stable solution which can be stored for extended periods.
Any of the known hydraulic cement water-reducing agents, can be used in the Inventive admixtures. It Is preferred to use as the water-reducing agent component elther an aromatic sulfonlc ? acid-aldehyde condensate salt or a lignosulfonic acid salt. Most preferably, the admixture comprises both of these preferred water-reducing agents. The aromatic sulfonic acid-aldehyde condensate salt which can be used in the present admixtures can be any such polymeric condensate which meets the ASTM C494 standard for a Type A or Type F water-reducer. SUCh condensates and their use as dispersants or water-reducers in hydraulic cements are disclosed, for example, in U. S. Patent Nos, 2,141 ,569; 2,690,975; 3,359,225;
3,582,375 4,125,410; 4,391,645; and 4,424,074.
Case 2764 5 Exemplary aromatic moieties which can be present in the condensate polymer are phenyl, tolyl, xylyl, benzoic acid, phthalic acid, phenol, melamine, diphenyl, naphthalene, methylnaphthalene or anthracene moieties. The condensate polymer may contain a slngle aromatic moiety or two or more different aromatic moieties in the polymer chain.
The aldehyde used in preparation of the condensate is an alkylaldehyde~ e.g. acetaldehyde, or preferably formaldehyde. The formaldehyde condensates are particularly well known water-reducing agents and are generally preferred from an availability, cost, and performance standpoint .
The condensates can be prepared by reaction of an aromatic sulfonic acid with an aldehyde to form a condensation polymer, followed by neutralization with a basic material, e.g., sodium hydroxide, or they can be prepared by condensation of an aromatic compound with the aldehyde followed by sulfonation of the condensation product and neutralization of the sulfonated material. Processes for preparing the condensates are disclosed in U. S. Patent Nos. 2,141,589; 3,0~57,243;
3,193,575; 3,277,162; and 4,125,410, The condensates used on the present admixture are in the sait
. . .
BACKGROUND OF THE INVENTION
This invention relates to admixtures for hydraulic cement compositions and more particularly to water-reducing admixtures which provide improved slump retention in hydraulic cement compositions with relatively minimal increases in initial and final setting times.
The use of various water-reducing admixtures in hy-draulic cement compositions, e.g., mortars, grouts, and concrete, is well known. These admixtures allow the use of lesser amounts of water to achieve a desired plasticity or workability. The admixture also provides higher compressive strengths in the cement composition after setting, due either to the use of less water in the mix or to a more complete dispersion oE the cement particles in the plastic cement mix by the admixture.
A major problem associated with the use of conventional water-reducing admixtures is that the length of time during which the admixture is able to maintain a desired high level of plasticity or workability in the cement mix is relatively short, lastlng an average of 25 to 45 minutes after addition of the admixture. In most job situations, this generally requires that the admixture be added just prior to placement, i.e., at the job site, thus requiring the equipping of delivery trucks with specially designed dispensing equipment. In addition to the expense associated with the installation and maintenance of this equipment, its use can be problemmatic where local work specifications or conditions prohibit on site addition of admixtures. In addition, the relatively short duration of ~Z2~0~ 6925-292 increased plasticity limits the amount of time the applicator has to place and work the mixture. This can be a particularly troublesome constraint under difficult placement or job conditions.
la I
~sè 2764 ~Z2750~i The problem of a relatively short duration of increased plastlcity can sornetimes be lessened by a high dosage of the water-reduclng admixture. However, this tends to provide too fluid a mix immediately following addition and generally results in excessive set retardation.
This latter disadvantage, in turn, can delay strength gain in the cement mix after setting.
The plasticity of a hydraulic cement mixture is normally evaluated by slump measurement, e.g., in accordance with ASTM C143. The slump is measured by filling a truncated cone with the mixture, removing the cone, and measuring the drop Tn l1elght of the unsupported mlxture. As a measure of the decrease in plasticity of the mixture over time, slump measurements are made on the aglng mlxture at spaced time intervals. The decreasing plastlcity is thus quantified as the decrease In slump with tlme. A lesser decrease in slump with time i.e,, Increased slump retention, Indlcates a greater abllity on the part of a water-reducing admlxture to impart increased plastlcity to the cement mixture for a longer duratlon.
SUMMARY_OF THE INVENTION
The present invention is directed toward novel water-reducing admixture compositions for hydraulic cement materials which can provide levels of water reduction which are at least as great as those provided by conventional water-reducing agents and, in additlon, provide substantially increased levels of slump retention. A particular Case !764 12~505 advantage of the inventive admixtures is that they can be formulated to provide significant and substantlal Increases in slump retentlon ~tth only relativeiy minimal increases in the initial and final settlng tlmes of the cementitious mix. The admlxture composltTons of thls Invention are blends or mixtures which comprlse a hydraulic cement water-reducing agent and a borate ester of a polyhydroxy compound. By the term "polyhydroxy compound" is meant a dioi or a polyhydric compound, i.e., one which contains more than two hydroxy groups. The polyhydroxy compound can be an aromatic compound, such as a catechol, or an aliphatic compound, with the latter being preferred from the standpoint of attaining lower levels of set retardation. Most preferably, the polyhydroxy compound is an allphatlc polyhydrlc carboxyllc acld, e.g., a glyconlc acld.
The admixture compositlon can comprlse tile1 borate ester com,oonent lS in combination with a single water-reduclng agent or, preferably, In combination with two or more water-reduclnq agents. Preferred water-reducing agents for use In the inventive admixtures are aromatic sulfonic acid-aldehyde condensate salts and lignosulfonic acid salts.
Most preferably, both of these preferred water-reducing agents are present in the admixture together with the borate ester.
The relative quantity of each of the admixture components can vary over a wide range such that a variety of admixture formulations can be provided to meet different requirements of slump retention or set retardation. This flexibility in formulating the admixture can also be used to compensate for variations in reactivity of different cements Cud se 2 7 6 4 ~;LZZ75( ~5 to the admixture. This flexibility is significantiy increased by the use of two or more different water-reducing agents in the admlxture, inasmuch as the ratio of the water-reducing agents to each other, as well as to the borate ester, can be adjusted. Thus, a wider variety of formulations, with a correspondingly broader range of properties in hydraulic cement mixes, can be provided.
The admixture blends of this invention can be provided and used as neat formulations in the form of a dry powder or, preferably, as aqueous-based solutions, i.e., the admixture components can be dissolved in an aqueous-based solvent.
The present invention is further directed to hydraulic cement compositions comprising the admixture components.
DETA!LED DESCRIPTION OF THE INVENTION
As used hereln, the term hydraulic cement composition is intended to refer to any composition containing a hydraulic cement binder, e.g., an ASTM Type 1, Il, 111, IV, or V Portland cement, inclusive of both dry cement compositions and wet cement slurries or pastes. Included within the term are concretes, grouts, mortars, cement pastes, and the like. The admixtures of this invention are particularly useful in Portland cement concretes, and especially in larger scale Portland cement concrete preparations where the concrete is prepared at a mixing plant and transported to the Job site.
As indicated above, the admixtures of this invention provide a longer slump life, i.e., increased slump retention, in hydraulic cement compositions. For many larger scale applications using :;. , #I .,,.,~
Case 2764 Z~S~5 Portland cement concrete, the increased slump retention permits addition of the admixture to the concrete at the mixing plant, rather than at the job site. This option can be advantageous where local work specifications or conditions prohibit on site addition of admixtures.
Moreover, it facilitates mixing during transportation to the job site and provides greater flexibility in terms of the time alloweci for pouring, placing, and working the concrete at the job site. i-lowever, since the admixtures can be formulated to provide the increased slump retention while causing only a relatively minimal increase in the initiai setting time, (as compared, for example, to the initlal setting time obtained with a conventional water-reducing agent) the cement mix will generally thereafter set up in sufficient time to permit the applicator to gain access onto the concrete and finish it within the time constraints of the average work day, An additional unexpected advantage provided by the inventive admixtures is the generally excellent finishing characteristics imparted to hydraulic cement compositions, whereby the composition assumes a smooth, creamy consistency, for an extended duration, without stickiness, and thus can be surface finished easily and with highly satisfactory results.
The borate esters used in the admixtures of this invention are believed to provide the improved finishing characteristics and slump retention which have been observed in hydraulic cement compositions containing the admixtures. These borate esters are cyclic esters which are believed to involve complexation or bonding of a boron moiety to t Yo hydroxyl groups within an esterifying polyhydroxy compound so as to form a cyclic structure. As noted previousiy, the esterifying polyhydroxy compound is preferably aliphatic. Tha aliphatic compound can be, for example, an aliphatic diol, e.g. ethylene glycol, 1,2-propanediol, or 1,3-propanediol; an aliphatic polyhydric alcohol, ; I: ':$`
a se 2 7 6 4 7S~lIS
e.g., glycerol, glucose, or mannose; an aliphatic diol carboxylic acid e.g., 2,3-dihydroxypropionic acid or tartaric acid; or, preferab,ly, an aliphatic polyhydric carboxylic acid, e.g., glucaric acid The preferred aliphatic polyhydric carboxylic acids for use herein are the glyconic acids, particularly gluconic acid and glucoheptonlc acid. The stereospecificity of the polyhydroxy esterifying compound must, of course, be such as to permit formation of the cyclic borate ester. The stereospecific molecular requirements relating to borate ester formation are well known. An early study of this subject is provided by J. i30eseken, Advances in Carbohydrate Chemistry, 4, 189-210 (1949).
The borate esters generally used herein are belleved to be mono-esters involving the complexation or bondlng of one molecule of esterifying compound to one boron moiety, with the thlrd valence positlon of the boron moiety occupled by a hydroxyl group. This hydroxyl group may be neutrallzed wlth a cation as discussed here7nafter, Preparation of the mono-ester is normally facllitated by reacting approximately equimolar amounts of boron and the esterifying compound.
i-lowever, the mono-ester may also be prepared using a molar excess of the esterifying compound, as may prove necessary where stereospecific or steric factors hamper the reaction of the esterifylng compound with the boron moiety. Conversely, where the esterifylng compound is readily reacted with the boron moiety, bis esters may be formed using a molar excess of the esterifying compound and the present invention broadly comtemplates the use of bis borate esters as well.
,. I ''I' ' Ca ye 2 7 6 4 ~2~75~
The borate esters may be used in the free acid form, I . e. with an -OH group on the boron and ~COOH group on an esterifying carboxylic acid compound. However, the salt form of the ester can provide less set retardation in concrete formulations and is thus generally preferred for use herein. Where the esterifying polyhydroxy compound is a pclyhydroxy alcohol, the salt form incorporates a cation which displaces the hydrogen of the remaining hydroxyl group on the boron moiety.
Where the esterifying polyhydroxy compound is a polyhydroxy carboxylic acid, this salt form incorporates a cation associated with the carboxyl group(s) of the esterifying compound and, optionally, a cation which displaces the hydrogen of the remaining hydroxyl group on the boron moiety. The cation can be an alkali metal, e.g., sodium or potassium, or an alkaline earth metal, e.g., calclum or magnesium.
Preferably, however, the catlon is ammonium: alkylammonium, e.g., triethylammonium; alkanolammonlum, e.g. dlethanolammonium, triethanolammonium, or mixtures of the same. Utillzation of alkanolammonlum borate ester salts in particular has been found to result in admixtures which provide lesser increases In initial and final setting tlmes as compared, for example, to similar admixtures comprising alkaline earth ester salts. A particularly preferred cationic grouping is that provided by neutralization of the borate ester with a mixture of monoethanolamine, diethanolamine and triethanolamine.
The borate esters can be prepared by known methods. Thus, boric acid can be reacted with the esterifying compound in an aqueous medium, using mild heating to facilitate completion of the reaction.
Case 2764 ~2~'7SOS
Where the esterifying compound is not readily reactive with borlc acid it may prove desirable to employ an anhydrous polar reaction solvent, e.g., tetrahydrofuran, or hlgher reaction temperatures in order to promote ester formation. An esterifying carboxylic acid may be reacted in its salt form, e.CJ., calcium gluconate may be reacted with boric acid to provide the correspondingly neutralized calclum borogluconate. A
precursor to the carboxylic acid esterifying compound, e.g. a precursor lactone, may also be utilized as an esterifying reagent.
The esters may also be prepared by reaction of a borate salt such as zinc borate or calcium borate wlth the esterJfying compound, e.g., as described in U. S. Patent No. 3,053,674.
After formation of the ester, a base may be added to the reaction solution to neutralize the ester or as desired for cation exchange.
However, the pH of the solution should be maintained at less than pH
10-11, and preferably less than about pH 8, In order to provlde a stable solution which can be stored for extended periods.
Any of the known hydraulic cement water-reducing agents, can be used in the Inventive admixtures. It Is preferred to use as the water-reducing agent component elther an aromatic sulfonlc ? acid-aldehyde condensate salt or a lignosulfonic acid salt. Most preferably, the admixture comprises both of these preferred water-reducing agents. The aromatic sulfonic acid-aldehyde condensate salt which can be used in the present admixtures can be any such polymeric condensate which meets the ASTM C494 standard for a Type A or Type F water-reducer. SUCh condensates and their use as dispersants or water-reducers in hydraulic cements are disclosed, for example, in U. S. Patent Nos, 2,141 ,569; 2,690,975; 3,359,225;
3,582,375 4,125,410; 4,391,645; and 4,424,074.
Case 2764 5 Exemplary aromatic moieties which can be present in the condensate polymer are phenyl, tolyl, xylyl, benzoic acid, phthalic acid, phenol, melamine, diphenyl, naphthalene, methylnaphthalene or anthracene moieties. The condensate polymer may contain a slngle aromatic moiety or two or more different aromatic moieties in the polymer chain.
The aldehyde used in preparation of the condensate is an alkylaldehyde~ e.g. acetaldehyde, or preferably formaldehyde. The formaldehyde condensates are particularly well known water-reducing agents and are generally preferred from an availability, cost, and performance standpoint .
The condensates can be prepared by reaction of an aromatic sulfonic acid with an aldehyde to form a condensation polymer, followed by neutralization with a basic material, e.g., sodium hydroxide, or they can be prepared by condensation of an aromatic compound with the aldehyde followed by sulfonation of the condensation product and neutralization of the sulfonated material. Processes for preparing the condensates are disclosed in U. S. Patent Nos. 2,141,589; 3,0~57,243;
3,193,575; 3,277,162; and 4,125,410, The condensates used on the present admixture are in the sait
2~ form, so as to possess desired water solubility, and can comprise, as the salt forming cation, sodium, potassium, calcium, zinc, aluminum, magnesium, manganese, ferrous, ferric, or ammonium cations.
Alkylammonium or alkanolammonium cations can also be used such as methylammonium, dimethylammonium, ethanolammonium or diethanolammonium cations.
Naphthalenesulfonic acid-formaldehyde condensate salt is the preferred condensate polymer for use in the admixture of this invention. A commercial naphthaienesulfonic acid-formaldehyde condensate which has been found particularly useful in the inventive _, J .~ 0 Case 2764 admixtures is that sold under the trademark "WRI)A-l9" by W. R. Grace Co., Cambridge, Massachusetts.
With respect to the the use of a lignosulfonate component In the present admixtures, lignosulfonates, as a class, are well known materials which have been used as water-reducing agents, plasticizers, and set-retarding agents in Portland cement compositions.
Lignosulfonates are commonly obtained as water-soluble salt derivatTves of conventional sulfite wood-pulping processes. These derivatives may be subsequently treated to provide "desugarized" lignosulfonates and these desugarized materials are preferred for use herein. The lignosulfonate used herein can be a salt of any alkali metal such as sodium or potassium or any alkaline earth metal such as caicium or magnesium.
As previously indicated, the relative quantlty of each admixture component can be varied as approprlate to meet different requirements of slump retention or set retardation or to compensate for variations in reactivity of different cements to the admixture. Accordingly, any ratio of the aforementioned components can be employed, as necessary for particular applications. In general, it is preferred to employ less than about 30% by weight of the borate ester component, based on the total weight of admixture components, in order to minimize any set retardation imparted by the admixture.
The set retardation encountered by use of the present admixtures can be modulated by adlustment in the relative proportion of the borate ester in the admixture, with a lower proportion generally resulting in a iesser degree of set retardation by use and adjustment of the relative proportion of a set retarding water-reducing agent, e.g., lignosulfonate by use of differently neutralized borate esters, with i Ca se 2 7 6 4 ~Z~
ammonium, alkylammonium, anci alkanolammonium neutralized borate esters tending to provide lesser degrees of set retardation than alkali metal and alkaline earth metal neutralized borate esters; and by adjustment of the concentration or "dosage" of the admixture in the cementitious mix.
The initial slump and the slump retention obtained by use of the present admixtures can be modulated by adjustment in the relative proportion of the borate ester, with a higher proportion generally providing a higher initial slump and increased slump retention; and by adjustment of the dosage of admixture in the cementitious mix.
For most applications, it will be desired to obtain a maximal increase in slump retention with minimal set retardatlon. Any of the above methods of modulating set retardation and slump retention may be used, either individually or in combination, to obtain the desired performarlce, In general, optimal combinations of slump retention and set retardation are most readily obtained utilizing the preferred admixtures of this invention comprising both the naphthalene sulfonic acid-formaldehyde condensate polymer salt and lignosulfonic acld salt.
Most preferably, from the standpoint of minimizing set retardation, - these preferred admixtures should comprise as the borate ester component an ammonium, alkylammonium, or alkanolammonium neutralized bo ra te este r .
Although it is generally preferred to formulate the admixture so as to provide minimal set retardation, for some applications, such as hot weather applications, a greater degree of set retardation may be desired and adjustments can be made in the admixture formulation or dosage, as described above, in order to meet this need.
A particularly preferred admixture of this invention comprises about 30 to 90 percent b`y weight of an aromatic sulfonic acid-aldehyde condensate, about 15 to 70 percent by weight of a lignosulfonic acid salt, and about 1 to 15 percent by weight of borate ester, where the .~ . .. i Case 2764 12~7~;0~i percentage is of the total weight of the three components. A more preferred admixture formulation comprises about 50 to 70 percent by weight of the condensate, about 25 to 45 percent by weight of the lignosulfonate, and about 3 to 10 percent by weight of the borate ester. In general, it is desirable to employ less than about 10 percent by weight of the borate estsr in the admixture compositions containing both the condensate and lignosulfonic acid salt in order to provide desirably low levels of set retardation, although higher proportions of the borate ester may be employed where the admixture Is to be used at a low concentration In the cementitious mix.
The admixture can be provided as a dry powder mixture of the aforementloned components but preferably, for purposes of easy dispensing into cement formulations, Is provlded In an aqueous solution, generally at a concentratlon of 30 to 50 percent by weight of the admixture, based on the total weight of the solution, The admixture can be dissolved in water at these concentratlon levels at a pH ranging between about 3 to 10 to provlde a stable, homogeneous solution.
The admixtures of this Invention can be used as either low range water-reducing agents, as defined by ASTM C494, Type A, or as high range water-reducers, defined by ASTM C494, Type F or Type G . I n general, the functioning of the admixture as a low range or high range water-reducer is dependent on the dosage level, although performance in this regard may also be dependent on the particular admixture formulation and hydraulic cement type. As a general guide for Portland 2i cement concretes, the admixture will function as a low range water-reducer at dosage levels of less than about 0 . 20% solids of the admixture, based on the weight of Portland cement binder in the concrete, and as a high range water-reducer at dosage levels .. :
Ca se 2 7 6 4 3L~2~5~5 above about 0.20%, similarly based. It is generally preferred to employ the admixture as a high range water-reducer in Portland cement concretes utilizing dosage levels in the range of about 0,20% to 0.50%.
At these levels, the admixtures have been found to provide initial slumps in the desired range of approximately 8 to 10 inches (ASTM
C143) and improved slump retention (as quantified in the following Examples), while retarding initial setting times by approximately 112 hour to 2 hours as compared to the initial setting tlme of the same concrete containing comparable dosages of conventlonal water-reducing agents. Accordlngly, a high slump concrete is provided which retains its slump for !onger durations but is generally capable of setting and being surface finished within the tlme constrlctlons of a typical work day .
The admlxture may be added to the dry cementitious mixture or to the wet cement slurry. In general, the admlxture wlll be added In its dry powder form to a dry cementltious mix while an aqueous solution of the admlxture is used in the case of additlon to a wet cement slurry.
While the admixture may be dissolved in the mix water used to prepare the cement slurry, it preferably is added as a separate solution following preparation of the slurry. After addition, sufficient mixing should be provided to assure a substantially uniform distribution of the admixture throughout the cement composition.
Consistent with the foregoing, the present invention is further directed toward hydraulic cement compositions comprising a hydraulic cement binder and the admixture components of this invention. The total arnount of the admixture components in the cement compositions is preferably about 0.0S% to 0.50% by weight, based on the weight of hydraulic cement binder. The cement composition can be in an essentially dry, free-flowing powder form or a wet slurry form. The cement composition can be formed by individual addition of ~LZ;~
each of the admixture components to the hydraulic cement binder or by addition the multicomponent admixture, either in dry form, or, preferably, in solution. The preferred hydraulic cement binder is Portland cement and the inventive cement compositions may comprise additional materials such as fine or course aggregate or additional admixture materials. Consistent with the foregoing, in Portland cement concretes the admixture components, in total, will generally be present in a weight concentration of about 0.05% to about 0.20%, based on the weight of Portland cement binder, where performance of the admixture as a low range water-reducer is desired and in a weight concen-tration of about 0.20% to about 0.50%, where performance as a high range water-reducer is desired.
The admixtures of this invention can be prepared by mixing the respective components in dry form or, preferably, by blending aqueous solutions of the respective components followed by adjustment O:e the blended solution to a desired con-centration by water addition.
The following Examples are given to further describe and illustrate the present invention. The following Examples are illustrative only and are not intended to limit the present invention in any sense. All parts and percentages are by weight unless otherwise indicated.
Preparation of calcium borogluconate solution:
860.5 grams of calcium gluconate minohydrate and 244 grams o e technical grade boric acid were added to 1100 grams of water at room temperature. The resultant mixture was stirred and warmed to a temperature of about 50C until a dark brown solution was obtained. The solution was allowed to cool to ~2%7~ 6925-292 room temperature. The solution can be used as is or the water can be evaporated to provide the calcium borogluconate as a brownish solid.
Preparation of calcium borogluconate solution:
28 grams of calcium oxide were added to water to form a thick slurry. This slurry was slowly added with stirring to 392 grams of a 50% aqueous solution of technical grade gluconic acid. After all of the slurry was added the resultant mixture was cooled and 61.8 grams of technical grade boric acid added. The mixture was stirred until a dark brown solution was obtained and then adjusted by water addition to provide a 40% solids solution.
EXAMPLE _ Preparation of sodium boroglucoheptonate solution:
123.7 grams of technical grade boric acid were added slowly to 1417 grams of a 35% aqueous solution of technical grade sodium glucoheptonate. The mixture was stirred at room temperature until a dark brown solution was obtained.
-Preparation of triethanolammonium borogluconate solution:
35.6 grams of gluconolactone and 12.2 grams of technical grade boric acid were added to 50 ml. of water at room temperature. The resultant mixture was stirred and heated at about 50C. for about 4 hours and the water allowed to evaporate I.
~L2;~7~s to reduce the mixture volume to about 45 ml. The mixture was then cooled to room temperature and 28 grams of triethanolamine were added with stirring.
2584 grams of a 35% solids aqueous solution of technical grade sodium glucoheptonate were adjusted to about pH 6 by addition of 20.5 grams of an 88~ formic acid solution.
226 grams of technical grade boric acid were then added to the pH adjusted solution and the resultant mixture stirred overnight at room temperature. 476 grams of a mixture of monoethanolamine, diethanolamine, and triethanolamine were then added with stir-ring, bringing the pH of the resultant solution to pH I. The alkanol amine mixture was reported by the supplier to contain 0-15% monoethanolamine, 13-~5~ diethanolamine, 55-76% triethanol-amine, and 0-5~ of other materials.
The borate ester prepared in this Example is herein-after referred to as sodium-mixed alkanolamine boroglucohepton-ate and is believed to comprise a mixture of both the sodium and alkanolamine borate ester salts.
Preparation of mixed alkanolamine borogluconate solution:
500 grams of gluconolactone and 173.6 grams of technical grade boric acid were added to 500 ml. of water and the resultant mixture stirred and warmed until a dark brown solution was obtained. The solution was cooled to room temperature and 418 grams of the alkanolamine mixture of Example 5 were added with cooling. The resultant solution was diluted ~227S~
with water to a total weight of 1980.4 grams to provide a 50%
solids solution of the mixed alkanolamine borogluconate.
16a Case 2764 ~;~27$~
The following admixtures were prepared by blending a 40% soiids aqueous solution of naphthalene sulfonic acid-formaldehyde condensate salt ("WRDA-lg", available from W, R, Grace Co., Cambridge, Massachusetts), a 50sg solids aqueous solution of sodium lignosulfonate, and an aqueous solution of a borate ester, as indicated below. The weight ratios given below are solids weight ratios of the condensate:
lignosulfonate: borate ester. The resultant blends were adjusted to a concentration of 40% solids by addition of water to provide a final admixture solution, Admixture Weight Ratio Borate Ester ___ _. _ A 65:25:10 Mixed alkanolamine borogluconate (Example 6) B 65: 25: 10 Calcium borogluconate C 65:30:5 Mixed alkanolamine borogluconate (Example 6) D 65: 30: 5 Sodium-mixed alkanolamine boroglucoheptonate (Example 5) E 65: 30: 5 Calcium borogiuconate F 65:30:7 Mixed alkanolamine borogluconate (Example 6) G 65:30:7 Triethanolammonium borogluconate (Example 4) H 15:80:5 Mixed alkanolamine borogluconate (Example 6) :; 17 ~L2~751[1S
Case 2764 Admixtures A and B were added to individual batches of a Type l l Portland cement concrete slurry which had been prepared with a water/cement ratio of 0.49 and mixed for about 11 minutes prior to addition of the admixture. The amount of admixture added to the cement in this and the following Examples is given in terms of the total weight of solid admixture components expressed as a percentage of the weight of Portland cement binder present in the concrete formulation, hereinafter termed "percent solîds on solids" (% s/s). In this Example, each of the admixture solutions was added to the individual concrete batches in an amount sufficient to provide an admixture concentration of 0,40% s/s.
The concrete of this Example and the concretes of the following Exampies 9-13 were prepared at a cement factor of 611 Ibs/yd.
To provide a reference sample, an individual portion of the concrete was also admixed with WRDA-19 alone at a concentration of O . 40% s/s . This commerciai matertal has been widely used as a high range water-reducer.
Slump measurements were carried out on the concrete before and after addition of the admixtures in accordance with ASTM C143. The measured slumps are presented in Table i. The times given in Table i and in the following Examples are the times at which slump measurements were made and denote the total mixing time of the concrete. As noted above, the admixtures were added at about 11 minutes into the mix cycle.
~275~5 Case 2764 Table I
Admixture Slump (inches) 9 Min15 Min 30 Min . 45 Min . 60 Min .
Reference 4.2510.00 8.25 5.25 3.25 S A 4.0010.50 8.75 7.25 4.50 B 4.2510.25 8.75 7.50 5.50 The results presented in Table I indicate approximately equal initial ( l 5 Mln . ) slumps among the three samples and substantlally improved slurnp retention in the samples containlng the admixtures of this inventlon, The concretes of this Example and of the foliowlng Examples were also measured for alr content (ASTM C231), Inltlal and final setting times (ASTM C403), and compressive strength (ASTM C192) at 1, 7, and 28 days (average of two cylinders). These measurements on the concretes of this Example are presented in Table l l .
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Alkylammonium or alkanolammonium cations can also be used such as methylammonium, dimethylammonium, ethanolammonium or diethanolammonium cations.
Naphthalenesulfonic acid-formaldehyde condensate salt is the preferred condensate polymer for use in the admixture of this invention. A commercial naphthaienesulfonic acid-formaldehyde condensate which has been found particularly useful in the inventive _, J .~ 0 Case 2764 admixtures is that sold under the trademark "WRI)A-l9" by W. R. Grace Co., Cambridge, Massachusetts.
With respect to the the use of a lignosulfonate component In the present admixtures, lignosulfonates, as a class, are well known materials which have been used as water-reducing agents, plasticizers, and set-retarding agents in Portland cement compositions.
Lignosulfonates are commonly obtained as water-soluble salt derivatTves of conventional sulfite wood-pulping processes. These derivatives may be subsequently treated to provide "desugarized" lignosulfonates and these desugarized materials are preferred for use herein. The lignosulfonate used herein can be a salt of any alkali metal such as sodium or potassium or any alkaline earth metal such as caicium or magnesium.
As previously indicated, the relative quantlty of each admixture component can be varied as approprlate to meet different requirements of slump retention or set retardation or to compensate for variations in reactivity of different cements to the admixture. Accordingly, any ratio of the aforementioned components can be employed, as necessary for particular applications. In general, it is preferred to employ less than about 30% by weight of the borate ester component, based on the total weight of admixture components, in order to minimize any set retardation imparted by the admixture.
The set retardation encountered by use of the present admixtures can be modulated by adlustment in the relative proportion of the borate ester in the admixture, with a lower proportion generally resulting in a iesser degree of set retardation by use and adjustment of the relative proportion of a set retarding water-reducing agent, e.g., lignosulfonate by use of differently neutralized borate esters, with i Ca se 2 7 6 4 ~Z~
ammonium, alkylammonium, anci alkanolammonium neutralized borate esters tending to provide lesser degrees of set retardation than alkali metal and alkaline earth metal neutralized borate esters; and by adjustment of the concentration or "dosage" of the admixture in the cementitious mix.
The initial slump and the slump retention obtained by use of the present admixtures can be modulated by adjustment in the relative proportion of the borate ester, with a higher proportion generally providing a higher initial slump and increased slump retention; and by adjustment of the dosage of admixture in the cementitious mix.
For most applications, it will be desired to obtain a maximal increase in slump retention with minimal set retardatlon. Any of the above methods of modulating set retardation and slump retention may be used, either individually or in combination, to obtain the desired performarlce, In general, optimal combinations of slump retention and set retardation are most readily obtained utilizing the preferred admixtures of this invention comprising both the naphthalene sulfonic acid-formaldehyde condensate polymer salt and lignosulfonic acld salt.
Most preferably, from the standpoint of minimizing set retardation, - these preferred admixtures should comprise as the borate ester component an ammonium, alkylammonium, or alkanolammonium neutralized bo ra te este r .
Although it is generally preferred to formulate the admixture so as to provide minimal set retardation, for some applications, such as hot weather applications, a greater degree of set retardation may be desired and adjustments can be made in the admixture formulation or dosage, as described above, in order to meet this need.
A particularly preferred admixture of this invention comprises about 30 to 90 percent b`y weight of an aromatic sulfonic acid-aldehyde condensate, about 15 to 70 percent by weight of a lignosulfonic acid salt, and about 1 to 15 percent by weight of borate ester, where the .~ . .. i Case 2764 12~7~;0~i percentage is of the total weight of the three components. A more preferred admixture formulation comprises about 50 to 70 percent by weight of the condensate, about 25 to 45 percent by weight of the lignosulfonate, and about 3 to 10 percent by weight of the borate ester. In general, it is desirable to employ less than about 10 percent by weight of the borate estsr in the admixture compositions containing both the condensate and lignosulfonic acid salt in order to provide desirably low levels of set retardation, although higher proportions of the borate ester may be employed where the admixture Is to be used at a low concentration In the cementitious mix.
The admixture can be provided as a dry powder mixture of the aforementloned components but preferably, for purposes of easy dispensing into cement formulations, Is provlded In an aqueous solution, generally at a concentratlon of 30 to 50 percent by weight of the admixture, based on the total weight of the solution, The admixture can be dissolved in water at these concentratlon levels at a pH ranging between about 3 to 10 to provlde a stable, homogeneous solution.
The admixtures of this Invention can be used as either low range water-reducing agents, as defined by ASTM C494, Type A, or as high range water-reducers, defined by ASTM C494, Type F or Type G . I n general, the functioning of the admixture as a low range or high range water-reducer is dependent on the dosage level, although performance in this regard may also be dependent on the particular admixture formulation and hydraulic cement type. As a general guide for Portland 2i cement concretes, the admixture will function as a low range water-reducer at dosage levels of less than about 0 . 20% solids of the admixture, based on the weight of Portland cement binder in the concrete, and as a high range water-reducer at dosage levels .. :
Ca se 2 7 6 4 3L~2~5~5 above about 0.20%, similarly based. It is generally preferred to employ the admixture as a high range water-reducer in Portland cement concretes utilizing dosage levels in the range of about 0,20% to 0.50%.
At these levels, the admixtures have been found to provide initial slumps in the desired range of approximately 8 to 10 inches (ASTM
C143) and improved slump retention (as quantified in the following Examples), while retarding initial setting times by approximately 112 hour to 2 hours as compared to the initial setting tlme of the same concrete containing comparable dosages of conventlonal water-reducing agents. Accordlngly, a high slump concrete is provided which retains its slump for !onger durations but is generally capable of setting and being surface finished within the tlme constrlctlons of a typical work day .
The admlxture may be added to the dry cementitious mixture or to the wet cement slurry. In general, the admlxture wlll be added In its dry powder form to a dry cementltious mix while an aqueous solution of the admlxture is used in the case of additlon to a wet cement slurry.
While the admixture may be dissolved in the mix water used to prepare the cement slurry, it preferably is added as a separate solution following preparation of the slurry. After addition, sufficient mixing should be provided to assure a substantially uniform distribution of the admixture throughout the cement composition.
Consistent with the foregoing, the present invention is further directed toward hydraulic cement compositions comprising a hydraulic cement binder and the admixture components of this invention. The total arnount of the admixture components in the cement compositions is preferably about 0.0S% to 0.50% by weight, based on the weight of hydraulic cement binder. The cement composition can be in an essentially dry, free-flowing powder form or a wet slurry form. The cement composition can be formed by individual addition of ~LZ;~
each of the admixture components to the hydraulic cement binder or by addition the multicomponent admixture, either in dry form, or, preferably, in solution. The preferred hydraulic cement binder is Portland cement and the inventive cement compositions may comprise additional materials such as fine or course aggregate or additional admixture materials. Consistent with the foregoing, in Portland cement concretes the admixture components, in total, will generally be present in a weight concentration of about 0.05% to about 0.20%, based on the weight of Portland cement binder, where performance of the admixture as a low range water-reducer is desired and in a weight concen-tration of about 0.20% to about 0.50%, where performance as a high range water-reducer is desired.
The admixtures of this invention can be prepared by mixing the respective components in dry form or, preferably, by blending aqueous solutions of the respective components followed by adjustment O:e the blended solution to a desired con-centration by water addition.
The following Examples are given to further describe and illustrate the present invention. The following Examples are illustrative only and are not intended to limit the present invention in any sense. All parts and percentages are by weight unless otherwise indicated.
Preparation of calcium borogluconate solution:
860.5 grams of calcium gluconate minohydrate and 244 grams o e technical grade boric acid were added to 1100 grams of water at room temperature. The resultant mixture was stirred and warmed to a temperature of about 50C until a dark brown solution was obtained. The solution was allowed to cool to ~2%7~ 6925-292 room temperature. The solution can be used as is or the water can be evaporated to provide the calcium borogluconate as a brownish solid.
Preparation of calcium borogluconate solution:
28 grams of calcium oxide were added to water to form a thick slurry. This slurry was slowly added with stirring to 392 grams of a 50% aqueous solution of technical grade gluconic acid. After all of the slurry was added the resultant mixture was cooled and 61.8 grams of technical grade boric acid added. The mixture was stirred until a dark brown solution was obtained and then adjusted by water addition to provide a 40% solids solution.
EXAMPLE _ Preparation of sodium boroglucoheptonate solution:
123.7 grams of technical grade boric acid were added slowly to 1417 grams of a 35% aqueous solution of technical grade sodium glucoheptonate. The mixture was stirred at room temperature until a dark brown solution was obtained.
-Preparation of triethanolammonium borogluconate solution:
35.6 grams of gluconolactone and 12.2 grams of technical grade boric acid were added to 50 ml. of water at room temperature. The resultant mixture was stirred and heated at about 50C. for about 4 hours and the water allowed to evaporate I.
~L2;~7~s to reduce the mixture volume to about 45 ml. The mixture was then cooled to room temperature and 28 grams of triethanolamine were added with stirring.
2584 grams of a 35% solids aqueous solution of technical grade sodium glucoheptonate were adjusted to about pH 6 by addition of 20.5 grams of an 88~ formic acid solution.
226 grams of technical grade boric acid were then added to the pH adjusted solution and the resultant mixture stirred overnight at room temperature. 476 grams of a mixture of monoethanolamine, diethanolamine, and triethanolamine were then added with stir-ring, bringing the pH of the resultant solution to pH I. The alkanol amine mixture was reported by the supplier to contain 0-15% monoethanolamine, 13-~5~ diethanolamine, 55-76% triethanol-amine, and 0-5~ of other materials.
The borate ester prepared in this Example is herein-after referred to as sodium-mixed alkanolamine boroglucohepton-ate and is believed to comprise a mixture of both the sodium and alkanolamine borate ester salts.
Preparation of mixed alkanolamine borogluconate solution:
500 grams of gluconolactone and 173.6 grams of technical grade boric acid were added to 500 ml. of water and the resultant mixture stirred and warmed until a dark brown solution was obtained. The solution was cooled to room temperature and 418 grams of the alkanolamine mixture of Example 5 were added with cooling. The resultant solution was diluted ~227S~
with water to a total weight of 1980.4 grams to provide a 50%
solids solution of the mixed alkanolamine borogluconate.
16a Case 2764 ~;~27$~
The following admixtures were prepared by blending a 40% soiids aqueous solution of naphthalene sulfonic acid-formaldehyde condensate salt ("WRDA-lg", available from W, R, Grace Co., Cambridge, Massachusetts), a 50sg solids aqueous solution of sodium lignosulfonate, and an aqueous solution of a borate ester, as indicated below. The weight ratios given below are solids weight ratios of the condensate:
lignosulfonate: borate ester. The resultant blends were adjusted to a concentration of 40% solids by addition of water to provide a final admixture solution, Admixture Weight Ratio Borate Ester ___ _. _ A 65:25:10 Mixed alkanolamine borogluconate (Example 6) B 65: 25: 10 Calcium borogluconate C 65:30:5 Mixed alkanolamine borogluconate (Example 6) D 65: 30: 5 Sodium-mixed alkanolamine boroglucoheptonate (Example 5) E 65: 30: 5 Calcium borogiuconate F 65:30:7 Mixed alkanolamine borogluconate (Example 6) G 65:30:7 Triethanolammonium borogluconate (Example 4) H 15:80:5 Mixed alkanolamine borogluconate (Example 6) :; 17 ~L2~751[1S
Case 2764 Admixtures A and B were added to individual batches of a Type l l Portland cement concrete slurry which had been prepared with a water/cement ratio of 0.49 and mixed for about 11 minutes prior to addition of the admixture. The amount of admixture added to the cement in this and the following Examples is given in terms of the total weight of solid admixture components expressed as a percentage of the weight of Portland cement binder present in the concrete formulation, hereinafter termed "percent solîds on solids" (% s/s). In this Example, each of the admixture solutions was added to the individual concrete batches in an amount sufficient to provide an admixture concentration of 0,40% s/s.
The concrete of this Example and the concretes of the following Exampies 9-13 were prepared at a cement factor of 611 Ibs/yd.
To provide a reference sample, an individual portion of the concrete was also admixed with WRDA-19 alone at a concentration of O . 40% s/s . This commerciai matertal has been widely used as a high range water-reducer.
Slump measurements were carried out on the concrete before and after addition of the admixtures in accordance with ASTM C143. The measured slumps are presented in Table i. The times given in Table i and in the following Examples are the times at which slump measurements were made and denote the total mixing time of the concrete. As noted above, the admixtures were added at about 11 minutes into the mix cycle.
~275~5 Case 2764 Table I
Admixture Slump (inches) 9 Min15 Min 30 Min . 45 Min . 60 Min .
Reference 4.2510.00 8.25 5.25 3.25 S A 4.0010.50 8.75 7.25 4.50 B 4.2510.25 8.75 7.50 5.50 The results presented in Table I indicate approximately equal initial ( l 5 Mln . ) slumps among the three samples and substantlally improved slurnp retention in the samples containlng the admixtures of this inventlon, The concretes of this Example and of the foliowlng Examples were also measured for alr content (ASTM C231), Inltlal and final setting times (ASTM C403), and compressive strength (ASTM C192) at 1, 7, and 28 days (average of two cylinders). These measurements on the concretes of this Example are presented in Table l l .
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Case 2764 Table l l indicates the generally observed result of lesser increases in setting time where the borate ester is neutralized with an alkanolamine (Admixture A) rather than an alkaline earth metal (Adrnixture B).
Admixture solutions A and C were added to individual batches of a Type l / l l Portland cement concrete slurry in amounts sufficient to provide admixture solids concentrations of 0.40~ s/s, 0.33% s/s, and 0.25% s/s. The concrete was prepared wlth a water/cement ratio of 0.48 and the admixtures were added at 11 minutes as in Example 8.
Reference samples were prepared ivy addition of WRDA-19 alone at the three different concentratlon levels. Measurements were taken as in Example 8 and are presented in Tables l l l and IV.
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Case 2764 ~22~7~iO~
Table l l l Admixture Slump (inches) Admixture Concentration (%s/s? 9 Min,~15 Min. 30 Min. 45 Min, 60 Min.
Reference 0.40 3.00 9.75 8.00 6.00 3.50 A 0.40 2.75 9.50 7.00 5.75 4.25 C 0.40 3.25 9.50 .50 7.00 5.00 Reference 0.33 2.25 9.75 6.00 3.75 2.50 A 0.33 3.50 9.75 6.50 5.00 4.00 C 0.33 2.50 9,00 7,75 4,50 3.50 Reference 0.25 3.25 8.25 4.50 3.50 3.00 A 0.25 3,75 8.25 6.00 4.75 3.50 C 0.25 3.00 8.00 6`.00 3.50 3.50 ~2~iiOSi _~ us o f ._ us :r o cn Ln ,>~_ CO Us Q C f ED . o `1 co (I J to Of I` CO . l . O
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XE $ a) 6 ( ) 6 , Us f " 23 ~2Z7505 Case 2764 The results presented in Tables lll and IV indicate increased slump - retention over the reference at all admixture concentration levels.
Compressive strengths and air content are close to those of the reference samples at all admixture concentration levels. The increases in initial and final setting times resulting from use of the admixtures decreases with decreasing concentration, with the setting time with Admixture A at 0.25% s/s being about equal to that of the reference.
Admixtures solutions C and D were each added to batches of two concretes which respectively contained Type 1/11 and Type 11 Portland cement binders, respectively designated as Concretes I and 11.
Admixture concentration was 0.33% s/s for all batches and the admixtures were added at 11 minutes into the mix cycle. The concretes were each prepared at a water/cement ratio of 0.57.
For comparison, reference sarnples were prepared as in Examples 8 and 9 (WRDA-19 alone) at an admlxture concentration of 0.33% s/s ("Reference l In addition, a second reference ("Reference 2") was prepared in which WRDA-19 was acided at 11 minutes into the mix cycle to Concretes I and 11 which contained 0.1~ s/s of a commercial low range water-reducer sold under the ye "Hycol" by W. R .
Grace Co. The combined concentration of the water-reducers was thus 0. 43% s/s.
Slurnp measurements were conducted as in Examples 8 and 9 and are presented in Table V.
I.
C a s e 2764 3L2Z7~;0~ 1 Table V
Slump ( inches) ConcreteAdmixture 9 Min .15 Min . 30 Min, 45 Min . 60 Min .
-- j Reference 1 2.258.50 5.50 3.25 2.25 I Reference 2 5.7510.00 7.75 4.75 4.25 C 3.509.50 8.00 6.25 4.50 D 3.509.75 8.00 6.25 4.50 I lReference 1 2.005.50 3.50 2.50 2.50 IlReference 2 2.508.00 3.50 2.75 2.50 ll C 1.757.50 3.50 2.75 2.00 I l D 2.256.75 4.25 3.25 2.75 The results of Table V Indicate Improved slump retention over Reference I in both concretes by both admlxtures. The slump retention provided by both admixtures is comparable to or better than that provided by Reference 2 notwithstanding the higher total concentration of water-reducers in Reference 2, with this result being more pronounced in Concrete 1.
The air content, setting times, and compressive strengths of the concretes were measured as in Example 8 and are provided in Table Vl.
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.
I, Case 2764 7505 Example l l Admixtures E, F, and G werè added to concrete batches at a concentration of 0.40% s/s at 11 minutes into the mix cycle. The concrete was prepared using the Type i / l l Portland cement binder of Example 9 at a water/cement ratio of about 0.48. Slump retention measurements are presented in Table Vi I .
Table Vl l Slump tinches) Admixture 9 min . l S min . 30 min . 45 min . 60 min, __ _ E 3.00 lO,00 8,50 7,00 5.25 F 3.50 10.25 8,50 6.75 4.75 G 3.50 9.75 8.75 7.75 5.00 leasurement of air content, setting times, and compressive strengths are given in Table Vl l l .
I! ,;
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C) s Case 2764 As shown in Tahle Vl l l, setting times are less using the mixed alkanolamine borogluconate (Admixture F) rather than calcium borogluconate (Admixture E), notwithstanding the higher dosage of the borogluconate component in Admixture F. Admixture F also provides lower setting times than Admixture G, which is consistent with a generally observed trend of lower setting times using a borate ester neutralized with the alkanolamine mixture, as opposed to a borate ester neutralized solely with triethanolamine. However, the setting times provided with Admixture C are still approximately equal to those provided with Admixture E, notwithstanding a higher dosage of the borogluconate component.
Example 1 2 In order to demonstrate a water-reducing capability at low dosage, admixtures C and H were each added to concrete slurry batches in concentrations of 0,10% s/s and 0,16% s/s. The admixtures were added with the mix water used to prepare the slurries and slump measurements were taken at 9 minutes into the mix cycle. The concrete was prepared using the Type l / l l Portland cement binder of Example 9 at a water/cement ratio of about 0.49.
The experimental concretes were compared against a batch with no admixture added ("Blank")and a batch to which were added the same dosages of the commercial low range water-reducing agent "Hycol". The 9 minute slumps and results of similar measurements as in the above Examples are provided in Table I X .
27~
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_ L C
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s Case 2764 As shown by Table IX, significant water reduction was provided by both Admixtures C and H. The increases in setting time over the blank sample were least with Admixture C and greatest with the Hycol samples.
Examp!e 13 Two 40% solids admixture solutions of this invention were prepared by blending lNRDA-19 and an aqueous solution of calcium borogluconate at WRDA-19: calcium borogluconate solids weight ratios of 50:50 and 75: 25 and adjusting the final concentration with water. These admixtures were added to concrete batches at 11 minutes into the mix cycle at a dosage of 0.2~ s/s and compared against a reference concrete dosed with 0.2~ s/s WRDA-19 alone. The concretes were prepared using the Type l l Portland cement binder of Example 8 at a water/cement ratio of 0.51. Slump retention measurements and air content, setting times, and compressive strengths are provided in Tables X and X 1.
Table X
S!ump (inches Admixture 9 min .15 min . 30 min .45 min .60 min .
Reference 3.00 6.25 4.00 3.00 2.25 75:25 2.508.50 5.()0 4.00 3.00 50:50 4.00 8.00 5.25 4.00 2,75 ~2~
n 1 ._ or f ._ L
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Case 2764 The results provided in the above Examples should be taken as exemplifying the performance which can be obtained employing the admixtures of this invention. As previously indicated, the admixture performance will vary as a function of admixture composition and the 5 variables associated with formulation of the cementitious mix such as cement type and source, water/cement ratio, and aggregate size and amount .
Case 2764 Table l l indicates the generally observed result of lesser increases in setting time where the borate ester is neutralized with an alkanolamine (Admixture A) rather than an alkaline earth metal (Adrnixture B).
Admixture solutions A and C were added to individual batches of a Type l / l l Portland cement concrete slurry in amounts sufficient to provide admixture solids concentrations of 0.40~ s/s, 0.33% s/s, and 0.25% s/s. The concrete was prepared wlth a water/cement ratio of 0.48 and the admixtures were added at 11 minutes as in Example 8.
Reference samples were prepared ivy addition of WRDA-19 alone at the three different concentratlon levels. Measurements were taken as in Example 8 and are presented in Tables l l l and IV.
.. .,.
Case 2764 ~22~7~iO~
Table l l l Admixture Slump (inches) Admixture Concentration (%s/s? 9 Min,~15 Min. 30 Min. 45 Min, 60 Min.
Reference 0.40 3.00 9.75 8.00 6.00 3.50 A 0.40 2.75 9.50 7.00 5.75 4.25 C 0.40 3.25 9.50 .50 7.00 5.00 Reference 0.33 2.25 9.75 6.00 3.75 2.50 A 0.33 3.50 9.75 6.50 5.00 4.00 C 0.33 2.50 9,00 7,75 4,50 3.50 Reference 0.25 3.25 8.25 4.50 3.50 3.00 A 0.25 3,75 8.25 6.00 4.75 3.50 C 0.25 3.00 8.00 6`.00 3.50 3.50 ~2~iiOSi _~ us o f ._ us :r o cn Ln ,>~_ CO Us Q C f ED . o `1 co (I J to Of I` CO . l . O
O O
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(us our =r . .-~ Us o - O ' ' Us n w ,_ > _ - oO~ J
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OOO COO OOO
o O C
XE $ a) 6 ( ) 6 , Us f " 23 ~2Z7505 Case 2764 The results presented in Tables lll and IV indicate increased slump - retention over the reference at all admixture concentration levels.
Compressive strengths and air content are close to those of the reference samples at all admixture concentration levels. The increases in initial and final setting times resulting from use of the admixtures decreases with decreasing concentration, with the setting time with Admixture A at 0.25% s/s being about equal to that of the reference.
Admixtures solutions C and D were each added to batches of two concretes which respectively contained Type 1/11 and Type 11 Portland cement binders, respectively designated as Concretes I and 11.
Admixture concentration was 0.33% s/s for all batches and the admixtures were added at 11 minutes into the mix cycle. The concretes were each prepared at a water/cement ratio of 0.57.
For comparison, reference sarnples were prepared as in Examples 8 and 9 (WRDA-19 alone) at an admlxture concentration of 0.33% s/s ("Reference l In addition, a second reference ("Reference 2") was prepared in which WRDA-19 was acided at 11 minutes into the mix cycle to Concretes I and 11 which contained 0.1~ s/s of a commercial low range water-reducer sold under the ye "Hycol" by W. R .
Grace Co. The combined concentration of the water-reducers was thus 0. 43% s/s.
Slurnp measurements were conducted as in Examples 8 and 9 and are presented in Table V.
I.
C a s e 2764 3L2Z7~;0~ 1 Table V
Slump ( inches) ConcreteAdmixture 9 Min .15 Min . 30 Min, 45 Min . 60 Min .
-- j Reference 1 2.258.50 5.50 3.25 2.25 I Reference 2 5.7510.00 7.75 4.75 4.25 C 3.509.50 8.00 6.25 4.50 D 3.509.75 8.00 6.25 4.50 I lReference 1 2.005.50 3.50 2.50 2.50 IlReference 2 2.508.00 3.50 2.75 2.50 ll C 1.757.50 3.50 2.75 2.00 I l D 2.256.75 4.25 3.25 2.75 The results of Table V Indicate Improved slump retention over Reference I in both concretes by both admlxtures. The slump retention provided by both admixtures is comparable to or better than that provided by Reference 2 notwithstanding the higher total concentration of water-reducers in Reference 2, with this result being more pronounced in Concrete 1.
The air content, setting times, and compressive strengths of the concretes were measured as in Example 8 and are provided in Table Vl.
:; ''A!S.' A ,;
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.
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.
I, Case 2764 7505 Example l l Admixtures E, F, and G werè added to concrete batches at a concentration of 0.40% s/s at 11 minutes into the mix cycle. The concrete was prepared using the Type i / l l Portland cement binder of Example 9 at a water/cement ratio of about 0.48. Slump retention measurements are presented in Table Vi I .
Table Vl l Slump tinches) Admixture 9 min . l S min . 30 min . 45 min . 60 min, __ _ E 3.00 lO,00 8,50 7,00 5.25 F 3.50 10.25 8,50 6.75 4.75 G 3.50 9.75 8.75 7.75 5.00 leasurement of air content, setting times, and compressive strengths are given in Table Vl l l .
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E LLI u. E
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C) s Case 2764 As shown in Tahle Vl l l, setting times are less using the mixed alkanolamine borogluconate (Admixture F) rather than calcium borogluconate (Admixture E), notwithstanding the higher dosage of the borogluconate component in Admixture F. Admixture F also provides lower setting times than Admixture G, which is consistent with a generally observed trend of lower setting times using a borate ester neutralized with the alkanolamine mixture, as opposed to a borate ester neutralized solely with triethanolamine. However, the setting times provided with Admixture C are still approximately equal to those provided with Admixture E, notwithstanding a higher dosage of the borogluconate component.
Example 1 2 In order to demonstrate a water-reducing capability at low dosage, admixtures C and H were each added to concrete slurry batches in concentrations of 0,10% s/s and 0,16% s/s. The admixtures were added with the mix water used to prepare the slurries and slump measurements were taken at 9 minutes into the mix cycle. The concrete was prepared using the Type l / l l Portland cement binder of Example 9 at a water/cement ratio of about 0.49.
The experimental concretes were compared against a batch with no admixture added ("Blank")and a batch to which were added the same dosages of the commercial low range water-reducing agent "Hycol". The 9 minute slumps and results of similar measurements as in the above Examples are provided in Table I X .
27~
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'-- 1--X
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c ._ Q~l E o o us us o Ln o U o o r. on o V)_ J us J us --I
_ L C
X I o O o O O o O o O O
U
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s Case 2764 As shown by Table IX, significant water reduction was provided by both Admixtures C and H. The increases in setting time over the blank sample were least with Admixture C and greatest with the Hycol samples.
Examp!e 13 Two 40% solids admixture solutions of this invention were prepared by blending lNRDA-19 and an aqueous solution of calcium borogluconate at WRDA-19: calcium borogluconate solids weight ratios of 50:50 and 75: 25 and adjusting the final concentration with water. These admixtures were added to concrete batches at 11 minutes into the mix cycle at a dosage of 0.2~ s/s and compared against a reference concrete dosed with 0.2~ s/s WRDA-19 alone. The concretes were prepared using the Type l l Portland cement binder of Example 8 at a water/cement ratio of 0.51. Slump retention measurements and air content, setting times, and compressive strengths are provided in Tables X and X 1.
Table X
S!ump (inches Admixture 9 min .15 min . 30 min .45 min .60 min .
Reference 3.00 6.25 4.00 3.00 2.25 75:25 2.508.50 5.()0 4.00 3.00 50:50 4.00 8.00 5.25 4.00 2,75 ~2~
n 1 ._ or f ._ L
C
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CO
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, _ Ln f .
.
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Case 2764 The results provided in the above Examples should be taken as exemplifying the performance which can be obtained employing the admixtures of this invention. As previously indicated, the admixture performance will vary as a function of admixture composition and the 5 variables associated with formulation of the cementitious mix such as cement type and source, water/cement ratio, and aggregate size and amount .
Claims (34)
1. A hydraulic cement water-reducing admixture composition comprising a hydraulic cement water-reducing agent and a borate ester of a polyhydroxy compound.
2. A composition of claim 1 wherein said polyhydroxy compound is an aliphatic diol, an aliphatic polyhydric alcohol, an aliphatic diol carboxylic acid, or an aliphatic polyhydric carboxylic acid.
3. A composition of claim 1 wherein said polyhydroxy compound is an aliphatic polyhydric carboxylic acid.
4. A composition of claim 3 wherein said polyhydroxy compound is a glyconic acid.
5. A composition of claim 4 wherein said glyconic acid is gluconic acid or glucoheptonic acid.
6. A composition of claim 1 wherein said borate ester is in a salt form.
7. A composition, of claim 6 wherein said borate ester comprises an alkali metal cation, alkaline earth metal cation, ammonium cation, alkylammonium cation, or alkanolammonium cation.
8. A composition of claim 1 wherein said hydraulic cement water-reducing agent comprises a salt of an aromatic sulfonic acid-aldehyde condensate polymer or a lignosulfonic acid salt.
9. A composition of claim 1 comprising, as the water-reducing agent component, at least two different hydraulic cement water-reducing agents.
10. A composition of claim 9 comprising a salt of an aromatic sulfonic acid-aldehyde condensate polymer and a lignosulfonic acid salt.
11. A composition of claim 1 wherein said water-reducing agent comprises a salt of a naphthalenesulfonic acid-formaldehyde condensate polymer .
12. A composition of claim 1 comprising less than about 30% by weight of said borate ester, based on the total weight of the admixture.
13. A hydraulic cement water-reducing admixture composition comprising a salt of a naphthalenesulfonic acid-formaldehyde condensate polymer, a lignosulfonic acid salt, and a borate ester of a glyconic acid.
14. A composition of claim 13 wherein said glyconic acid is glucoheptonic acid or gluconic acid.
15. A composition of claim 14 wherein said borate ester is a borate ester salt and comprises an ammonium, alkylammonium, or alkanolammonium cation.
16. A composition of claim 15 wherein said borate ester salt comprises a mixture of alkanolammonium cations.
17. A composition of claim 15 wherein said borate ester salt comprises an alkali metal cation and an alkanolammonium cation.
18. A composition of claim 13 comprising less than about 10 percent by weight of said borate ester, based on the total weight of said condensate polymer, lignosulfonic acid salt, and borate ester.
19. A composition of claim 13 comprising about 30 to 90 percent by weight of said condensate polymer, about 15 to 69 percent by weight of said lignosulfonic acid salt, and about 1 to 15 percent by weight of said borate ester, based on the total weight of said condensate polymer, lignosulfonic acid salt, and borate ester.
20. A composition of claim 19 comprising about 50 to 70 percent by weight of said condensate polymer, about 25 to 45 percent by weight of said lignosulfonic acid salt, and about 3 to 10 percent by weight of said borate ester.
21. An aqueous solution of the admixture composition of claim 13.
22. A solution of claim 21 comprising about 30 to 50 percent by weight of said admixture composition and having a pH between about 3 to 10.
23. A hydraulic cement composition comprising a hydraulic cement binder, a hydraulic cement water-reducing agent, and a borate ester of a polyhydroxy compound.
24. A cement composition of claim 23 wherein the total amount of said water reducing agent and said borate ester is about 0.05% to 0.50%
by weight, based on the weight of said hydraulic cement binder.
by weight, based on the weight of said hydraulic cement binder.
25. A cement composition of claim 23 wherein said hydraulic cement binder is Portland cement.
26. A cement composition of claim 23 wherein said water-reducing agent comprises a salt of an aromatic sulfonic acid-aldehyde condensate polymer or a lignosulfonic acid salt.
27. A cement composition of claim 26 wherein said water-reducing agent comprises said condensate polymer and said lignosulfonic acid salt.
28. A cement composition of claim 23 wherein said polyhydroxy compound is a glyconic acid.
29. A cement composition of claim 23 comprising a Portland cement binder, a salt of a naphthalene sulfonic acid-formaldehyde condensate polymer, a lignosulfonic acid salt, and a salt of a borate ester of a glyconic acid.
30. A cement composition of claim 29 wherein the total amount of said condensate polymer, lignosulfonic acid salt, and borate ester is about 0.2% to about 0.5% by weight, based on the weight of said Portland cement binder.
31. A hydraulic cement water-reducing admixture composition comprising a hydraulic cement water-reducing agent and the product obtained by reacting boric acid with a polyhydroxy compound in an aqueous medium.
32. A composition of claim 31 wherein said polyhydroxy compound is a salt of a glyconic acid.
33. A hydraulic cement water-reducing admixture composition comprising a hydraulic cement water-reducing agent and the product obtained by reacting a borate salt with a polyhydroxy compound in an aqueous medium.
34. A composition of claim 33 wherein said polyhydroxy compound is a glyconic acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US59506784A | 1984-03-29 | 1984-03-29 | |
| US595,067 | 1984-03-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1227505A true CA1227505A (en) | 1987-09-29 |
Family
ID=24381583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000477803A Expired CA1227505A (en) | 1984-03-29 | 1985-03-28 | Admixture for hydraulic cement compositions |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA1227505A (en) |
| PH (1) | PH22199A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130000904A1 (en) * | 2011-06-29 | 2013-01-03 | William Chrys Scoggins | Cement Retarder and Method of Using the Same |
-
1985
- 1985-03-28 CA CA000477803A patent/CA1227505A/en not_active Expired
-
1986
- 1986-08-22 PH PH34178A patent/PH22199A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130000904A1 (en) * | 2011-06-29 | 2013-01-03 | William Chrys Scoggins | Cement Retarder and Method of Using the Same |
| US9410072B2 (en) * | 2011-06-29 | 2016-08-09 | Baker Hughes Incorporated | Cement retarder and method of using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| PH22199A (en) | 1988-06-28 |
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