CA1187908A

CA1187908A - Additive for hydraulic cement mixes

Info

Publication number: CA1187908A
Application number: CA000411226A
Authority: CA
Inventors: Philip A. Rosskopf
Original assignee: Individual
Current assignee: MBT Holding AG
Priority date: 1981-09-14
Filing date: 1982-09-10
Publication date: 1985-05-28
Also published as: AR227750A1; DE3268563D1; FI831620L; NZ201882A; US4373956A; WO1983001061A1; DK215183D0; JPS623792B2; EP0077129B1; KR890002885B1; AU8957782A; KR840001527A; FI69825C; EP0077129A1; DK215183A; JPS5879853A; FI69825B; BR8207857A; MX157328A; PT75539B

Abstract

ADDITIVE FOR HYDRAULIC CEMENT MIXES

Abstract of the Disclosure A hydraulic cement mix including hydraulic cement, aggregate, sufficient water to effect hydraulic setting of the cement, and an additive comprising a mixture of an alkali or alkaline earth or ammonium salt of thiocyanic acid, such as sodium, potassium, lithium, calcium or magnesium thiocyanate, and an alkanolamine, such as tri-ethanolamine, the additive being present in an amount sufficient to increase rate of hardening, and the compressive strength of the hardened mix. Generally, the additive is present in a total amount of up to about 2.5% by weight based upon the weight of the cement, usually in an amount of between about 0.05% and about 2.55% by weight based upon the weight of the cement, preferably in an amount in the range of about 0.4% to about 0.6% by weight.

Description

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ADDITIVE FOR HYDRAULIC CEMENT MIXES

~ackground of the Invention This invention relates to additive compositions, otherwise krown as admixtures, for incorporation in hydraulic cer~nt mixes, for example, hydraulic cement concretes, mortars, and grouts, neat cement mixes, concrete block mixes, and dry mixes for making such concretes, mortars, and grouts, especially to accelerate their rate of hardening and set-ting.
A variety of techniques have been employed -to accelerate the hard~
ening of hydraulic cement mixes. These techniques are employed because of circumstances or conditions that render unduly extended the time re-quired for hardening of such mixes in given applications. The rate of hydration of portland cement is very dependent upon -temperature, for example, so that concrete containing it will often harden at a slower rate than desired during the winter season unless provisions are taken to accelerate the hardening process. Among the various -techni4ues em-ployed for this purpose are the increasing of the propor-tion o-f portland cenlent in the mix; the use of the most rapid setting type of cement available; the heating of the water and other components of the concrete;
and the use of chemical admixtures that act, catalytically or otherwise, j to increase the rate at which the concrete hardens.
A number of chemical agents that serve to accelerate the rate of hardening of concrete are known in the art. Calcium chloride in par-ticular is well known as an effective and economic accelerator. In use, however, this additive is known to have certain disadvantages, principally its tendency under certain circumstances to promote cor-rosion of metal embedded in, or in contact with, the calcium chloride-containing concrete. Other agents9 such as alkanolamines, urea, sodium thiosulfa-te, low molecular weight aldehydes and their polymers, salts of nitrous and nitric acid, and calcium formate, do not promote corro-sion of metal~ but have a less pronounced effect in accelerating the rate or hardening of concrete, and aldehydes are kno~n to evolve fun,es which have oeen considered objectionable.

~ r ~' ' There is a continuing need in the art, thereFore, ~or improved set accelerating agents. In particular, there is a need for new se-t accelerating agents capable of rapidly accelerating the rate of se-t of portland cement mixes, which do not promo-te corrosion of metal em-bedded, or in contact with, the calcium chloride-con-taining concrete~
In addition, of course, there is a continuing desire in the art for admixtures capable of permitting other advantages, suGh as reduction of the water content of the mix and improved compressive strength oF
the hardened concrete.
Another use for accelerators is to over~ome re~ardation caused by strength enhancing admixtures. Many admixtures employed to achieve improved compressive strength are known to act also as set retarders, arld such admixtures slow the chemical process of hydration so that the concrete remains plastic and workable for a longer time than con-cre-te without such a retarder. ~hile admixtures having set retarding and compressive strength improving properties are useful per se, fre-quently there are instances where improved compressive strength is desired but any significant retarding of the rate of hardening of the cement or concrete mix would be undesirable. In such an instance, it is desirable to overcome the undesirable retarding eFfect, by using accelerators that overcome the retarding tendency.
Thus a need exists for additive compositions, or admixtures, for incorporation in hydraulic cement mixes, which additives will provide improved compressive strength and/or accelera-ted rate of hardening and setting for the resulting cement products, while not causing ad-verse effects on the hydraulic mixes, such as unduly entraining air, or producing undesirable fumes or corrosive ef-fects, or decreased strength at later ages.

Summary of the Invention _ The present invention is an additive composition or admixture For incorporation in hydraulic cement mixes, such as concretes, mortars, and grouts, neat cement mixes, nonplastic cement mixes, and dry mixes for making concretes, mortars, and grouts and thus the improved cement mixes and process for incorporating the additive composition~

For the purposes of this invention, the terrn "hydraulic cement"
is intended to mean and to include all cementitious compositions ca-pable of being set and hardened by the action of water, such as portiand cements, sulphate resisting cerrents, blast-furnace cements, pozzolanic cements, and high-alumina cements, since the additive composition or admixture of the present invention can be incorporated into all hy~
draulic cement mixes. But the preferred use of the present composition or admixture is in portland cerr~nt mixes. Also for -the purposes of this invention, ~he term "portland cernent" is intended to include all cementitious compositions which have a high content of tricalcium silicate and thus are portland cement or are chemically similar or analogous to and thus portland type cement, the specification For which is set Forth in American Society for Testing Materials specification (ASTM) C 150-80. This would include cements, in which flyash, such as frcm steam or power ger,erating stations, limestone, poz~olana slag, such as from blast furnaces, or mixtures of these, are incorporated and are considered portland cements, or portland blended cements such as those in ASTM C-595-79.
Broadly, the invention comprises a hydraulic cement mix includ-2n ing hydraulic cement, aggregate, sufficient water to effect hydraulic setting of the cement, and an additive comprising a mixture of an alkali or alkaline earth or ammonium salt of thiocyanic acid and an alkanolamine, the additive being present in an amount sufficient to increase rate of hardening, the workability and the compressive strength of the hardened mix. The additive is preferably selected from the group comprising sodium, potassium, lithium, calcium, mag-nesium or ammonium thiocyanate, in combination with triethanolamine, and is present in a total amount of up to about 2.5% by weight based upon the weight of the cement, generally in an amount of between about 0.1% and about 2~55~o by weight based upon the weigllt of the cement, preferably in an amount in the range of about 0O4% to about 0.6% by weight. Use of the additive is beneficial to -the engineer-ing properties of hydraulic cement mixes in that it results in pro-ducts having an accelerated rate of hardening and setting over similar mixes prepared without the additive, without causing the cor-rosion problems present with chloride accelerators, such as calcium chlorideO Further, use of this aclditive in portland cements ~ithin the preferred ranges generally results in an increase in the com-pressive strength of the hardened hydraulic cement mixes.
It is therefore an object of the present invention to provide improved hydraulic cement mixesO
It i 5 another object of this invention to provide improved hy-draulic cement mixes, such as portland cement mixes, including con-crete, mortar and grout mixes, neat cement mixes9 nonplastic cement 1n mixes, and dry mixes9 which include an additive composition or ad-mixture which will advantageously accelerate the ra-te of hardening and setting of the cement mix and/or increase the early compressive strength.

De_ailed Description of the Invention_ _ The a'lkali and alkaline earth salts of thiocyanic acid having the following general formula:
R(SCN)X
wherein R represents an alkali or alkaline earth metal, such as sodium, potassium, lithium, calcium or magnesium, or ammonium and X
is 1 depending upon whether R is an alkali metal or ammonium, and X
is 2 when R is an alkaline earth metal. Thiocyanate salts are also variously known as sulfocyanate, sulfocyanide, rhodanate! and rhodanide salts. Thiocyanate salts are commercially available pro-ducts and have known utility in t'he dyeing and printing and textiles industries, as well as a solvent for cellulose and polyacrylate.
Alkanolamine is the generic name for a group of compoun ~ in which nitrogen is attached directly to the carbon of an alkyl alcohol.
Ethanolamine, diethanolamine and triethanolamine~ alone and in various blends, are well known examples of alkanolamines. For the purpose of this app'lication, the term alkanolamine is intended to mean one of the alkanolamines per se as well as a blend alkanolamine. Triethano-~' lamine, also known as tri-(2-hydroxyethyl) amine and by the formula (HOCH2CH2)3N is a commercial1y available product and has known utility in detergents and as a cem~nt accelerator.
In the practice of the present invention~ the thiocyanate salt ard alkanolamine are used in combination and are incorporated in hy-draulic cement mixes, such as portland cement concretes and mortars, high alumina cement concretes and mortars, and dry rnixes for makirg such concretes and mortars in amounts sufficient to accelerate the rate of hardening and setting of the hydraulic cenmer,t mi~. Broadly, the combination will be incorporated in the cement mix in total amount of up to about 2.55% by weight based upon the weigh-t of the cement, usually within the range of 0.1% to 2.55% by weight. Preferably the thiocyanate salt is present in an amount of between 0.1% and 2.5%
by weight, based upon the ~eight of the cement, with the alkanolamine being present in ar, amount of between O~OOl~o and 0.05% by weight, based upon the weight of the cement. A fur-ther preferred amount of thiocyanate salt is 0~257D to 1.5% by weight, based upon the weight of the cement~ and a further preferred amount of alkanolamine is about 0.01% to 0.04% by weight, based upon the weight of the cenlent.
The additive of the present invention is incorporated into hydraulic cement mixes preferably by adding it to a portion of the mix water used for mixing of the hydraulic cement and aggregate. But, the additive could be incorporated in any other convenient manner, in-cluding adding it to the dry mix before the water is incorporated therein.
The term aggregate is intended to include both fine aggregate, such dS sand, and coarse aggregate, such as crushed stone or gravel, as is common in the art. In general for mortars, the aggregate may be sand or other fine aggregate meeting the requirements of ASTM
standard C-33-80. The precise size, purity, quality, and quantity, or ranges thereof, of the fine and coarse aggregates will vary de-pending upon the desired use and properties of the mortar or con-crete. For most common uses, although not limited -thereto, the size of the fine aggregate will be within the broad range of about +4 mesh to -100 mesh U.S. Standard Sieve (ASTM C-11-70), while the size of the coarse aggregate will be within the broad range of 3 inches (7.6 cm) to 4 mesh. The coarse aggregate will usually be of mineral .

origin, such ~s gravel or crushed rock~ but it may in some cases con-sis~ at least partially of graded n~tallic material such as iror, chips, or manufac-tured aygregate, such as slag.
Further in general for dry mortar mixes, the proporti~n of fine aggregate to cement will be in the range of about 25% to about 75% by weisht based upon the weight of the cement mix, depending upon the nature of the aggregate and the desired properties and use oF the mix.
For both the mortars and cements, the amount o~ ~-ater employed generally should be enough to effect hydraulic setting of the c~,lent present in the mix and to provide suitable workability~ This may broadly range from about 20% to 60% by weight of the cement in the mix ~or the mort~rs an~ ~bout 25% to 70,, by weight of the ce~ent ir~ th~
mix tor the concretes. The precise amounts of water will depend upon the end use of the cement mix, as well as the aggregate and other ad-mixtures present in the mix.
For purposes of illustrating the advantageous results obtainable by the practice of the present invention, plain cement mixes were pre-pared and compared with similar mixes in which various thiocyanate salts and triethanolamine, both alone and tosether, were incorporated in varying dosages. The same type and brand of c~ment was used in each mix, and the proportion and kind of aggregate employed were su~-stantially the same. A sufficient amount o~ water was added to each mix to effect hydraulic setting of the cement m;x and to produce cement mixes of essentially the same consistency. The tes-ts ~rom which the results were derived were those commonly employed and s~an-dardized in the ASTM standards for testing cement andlor concrete mixes, including ASTM standards C-39-72 (197~)~ C-143-78~ C-231-78, C-403-~7~ In addition and Eor the purpose of further illustratin~
the invention, comparisons were ~ade with calci~m chloride ~CaC12)~
which is known and commercially availa~le as an acceleratlng admixture and calcium ll$nosulfonate, which is a known, retarding, water reducing adm~gture.
The results shown in Tables I through IV illustrate generally the use of the admixture in accordance with the present inven-tion in two Type I portland cement mixes ~where the cements ~Rre fro~ two ~.

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different manufacturers) to form concretes. For con~enience, the tests were run as a series of tests wherein, by comparison to a plain (no admixture) concrete mix, the dosages were varied~ and com-parisons were made with known prior art accelerators and a retarding, strength enhancing admixture. The fine aggregate to coarse aggregate ratio was between 0.46 and 0.49, the amount of cement was 420 lbs. per cubic yard (249 kg~ per cubic meter) of concrete and the consistencies of the concretes (measured as "slump" in accordance with ASTM C-143-78) were such that they had slumps of 5 inches + 1/2 inch (12.7 cm. ~ 1.3 cm.).
All of the testing in Tables I, III, and IV was done at 70F ~ 2F
(21C ~ 1C) while that in Table II was done at 50F + 2F (10C ~ 1C).
All of the data shown is the average result of two tests.
In each series the rate of set is shown relative to the plain mix in that series, or the first plain mix when there is more than one.
The actual rate of set of the plain mix is shown parenthetically. Where two plain mixes are done~ the second serves to confirm the first plain mix. In the tables, TEA is an exemplary commercially available alka-nolamine, namely triethanolarnine, NaSCN is an exemplary thiocyanate, specifically sodium thiocyanate, CaLS is a commercially available cal-cium lignosulfonate, which is a known water reducing9 strength enhancing admixture having set retarding properties, and Na2S203 is sodium thio-sulfate which is a known "non~chloride" accelerator.
As can be seen from Table I, the use of the admixture in accordance with the present invention, namely the combination of a thiocyanate ~ salt and an alkanolamine, produces an accelerated rate of set and an - increased one day strength gain, versus each component alone. Further, the combination can produce approximately the same acceleration of the rate of setting and hardening and early (one day~ compressive strength as did calcium chloride at a dosage of 1% by weight based upon the weight of cement9 when compared to plain concrete, in which no additiYe was employed. This is especially brought out in Table I, Series C, which was at 70F ~ 2F (21C ~ 1C) and Table II which was done at 50F ~ 2F (10C ~ 1C). During colder weather, the rate of set is usually longer and the need for an accelerator is greater. When the admixture of the present invention is used with a se-t retarding, strength enhancing admixture such as calcium lignosulfona-te as shown in Table III, the set retarding feature can be overcome with-out detrimentally affecting the hydraulic strength of the concrete.
The tests shown in Table IV show the thiocyanate salt component in combination with known prior art accelerators and the results are not nearly as beneficial as are achieved with the combination of thiocyanate salt and alkanolamine that is taught by the present i nventi onO
It is within the scope of the invention to incorpora-te9 in the cement mixes prepared as herein provided, other additives known in the art for the express purpose for which they are normally employed.
Such other additives may, for example, be air-entraining agents, air-detraining agents, pozzolanic materials, flyash, coloring agents, water repellants, strength enhancing admixtures and -the like~ The accelerators of the present invention may also be employed in con-junction with a combination of such cement additives to produce desired changes in the physical properties of the concrete being produced.

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It is also within the scope of the invention to employ the ad-mixture of the present invention together with known set retarders, such as lignosulfonates, sugars, glucosacchardes, and the like, or combinations thereof to obtain improvement in the compressive strength of the hardened mix, but with less retarding effect than would result from such set retarders. The accelerators of the present invention and said known set retarders can also be employed together with con-ventional set accelerators as mentioned above to achieve a desired combination of benefits.
While the invenbion has been described with reference to cer-tain preferred embodiments thereof, those skilled in the art will appreciate that various changes and modifications and substitutions can be made without departing from the spirit of -the invention. It is intended, therefore, that the invention will be limited only by the scope of the claims which follow.

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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A hydraulic cement mix comprising a hydraulic cement, aggre-gate in an amount of up to 80% by weight based upon the total weight of said cement mix, sufficient water to effect hydraulic setting of the cement and an additive comprising a mixture of an alkali and/or alkaline earth or ammonium salt of thiocyanic acid in an amount of between 0.05% and 2.5% by weight based upon the weight of the cement and an alkanolamine, in an amount of between 0.001% and 0.05% by weight based upon the weight of the cement whereby the rate of har-dening of said cement mix is accelerated and the early compressive strength of the hardened mix is increased.

2. A hydraulic cement mix in accordance with Claim 1, wherein said hydraulic cement comprises portland cement.

3. A hydraulic cement mix in accordance with Claim 1, wherein said salt of thiocyanate is present in an amount of between 0.5%
and 1.5% by weight based upon the weight of the cement and said alkanolamine is present in an amount of between 0.01% and 0.04% by weight based upon the weight of the cement.

4. A hydraulic cement mix in accordance with Claim 1, wherein said salt of thiocyanic acid is sodium thiocyanate.

5. A hydraulic cement mix in accordance with Claim 1, wherein said salt of thiocyanic acid is potassium thiocyanate.

6. A hydraulic cement mix in accordance with Claim 1, wherein said salt of thiocyanic acid is calcium thiocyanate.

7. A hydraulic cement mix in accordance with Claim 1, wherein said salt of thiocyanic acid is magnesium thiocyanate.

8. A hydraulic cement mix in accordance with Claim 1, wherein said aggregate is present in an amount of from 20% to 80% by weight.

9. A hydraulic cement mix in accordance with Claim 1, wherein said alkanolamine comprises triethanolamine.

10. A process for accelerating the hardening of hydraulic cement mixes which include hydraulic cement aggregate in an amount of up to 80% by weight based upon the total weight of said cement mix, and sufficient water to effect hydraulic setting of the cement comprising incorporating an additive comprising a mixture of an alkali, alkaline earth or ammonium salt of thiocyanic acid in an amount of between 0.05% and 2.5% by weight based upon the weight of the cement and an alkanolamine, in an amount between 0.001% and 0.05% by weight based upon the weight of the cement, whereby the rate of hardening or said cement mix is accelerated and the early compressive strength of the hardened mix is increased.

11. A process in accordance with Claim 10, wherein said hydraulic cement comprises portland cement.

12. A process in accordance with Claim 10, wherein said salt of thiocyanate is present in an amount of between 0.05% and 0.5% by weight based upon the weight of the cement and said alkanolamine is present in an amount of between 0.01% and 0.04% by weight based upon the weight of the cement.

13. A process in accordance with Claim 10, wherein said salt of thiocyanic acid is sodium thiocyanate.

14. A process in accordance with Claim 10, wherein said salt of thiocyanic acid is potassium thiocyanate.

15. A process in accordance with Claim 10, wherein said salt of thiocyanic acid is calcium thiocyanate.

16. A process in accordance with Claim 10, wherein said salt of thiocyanic acid is magnesium thiocyanate.

17. A process in accordance with Claim 10, wherein said aggre-gate is present in an amount of from 20% to 80% by weight.

18. A process in accordance with Claim 10, wherein said alka-nolamine comprises triethanolamine.