Admixture for hydraulic cement

• US RE35,194 E
• Filed: 01/12/1994
• Issued: 04/02/1996
• Est. Priority Date: 04/11/1983
• Status: Expired due to Term

• Current Assignee: MBT Holding AG
• Original Assignee: Sandoz Inc. (Novartis Ag)
• Inventors: Gerber, Arthur H.
• Primary Examiner(s): MARCANTONI, PAUL D
• Application Number:
  US08/180,357
• Time in Patent Office: 811 Days
• Field of Search: 106/724, 106/696, 106/725, 106/727, 106/802, 106/819, 106/823, 524/5
• US Class Current: 106/696
• CPC Class Codes: C04B 28/02 containing hydraulic cements other than calcium sulfates

Abstract

The present invention is a specific combination of components having unique properties both in composition and benefits. Such a combination has been found in alkali or alkaline earth metal nitrates, alkanolamines and alkali or alkaline earth metal thiocyanates. In such combinations it has also been found that alkaline and alkali earth thiosulfates and chlorides below the concentration level where corrosion is promoted may advantageously be substituted for all or part of the thiocyanates and that diethanolamine, N,N-di(hydroxyethyl)glycine (bicine) and N,N-di(hydroxyethyl)-β-aminopropionic acid (DAPA) and certain alkanolamines and alkanolamino acids and derivatives may advantageously be substituted for all or part of the triethanolamine.

Claims

1. A hydraulic cement mix comprising hydraulic cement, aggregate, sufficient water to effect hydraulic setting of the cement, and an admixture comprising a composition or a mixture of compositions selected from the group consisting of alkali, ammonium and alkaline earth salts of thiocyanic acid, and water soluble thiosulfates;

a composition or a mixture of compositions selected from the group . .comprising.!. .Iadd.consisting of .Iaddend.alkanolamine; and

. .related water soluble alkanolamines and.!. alkanolamino acids; and

a composition or a mixture of compositions selected from the group . .comprising.!. .Iadd.consisting of .Iaddend.alkali and alkaline earth salts of nitric acid;

said additive being present in an amount sufficient to accelerate the rate of hardening of said hydraulic cement mix and to increase its compressive strength after hardening.

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 salts of thiocyanic acid are sodium, potassium, ammonium and calcium thiocyanate;

said soluble thiosulfates are sodium, potassium, ammonium, calcium and magnesium thiosulfates;

said alkanolamines are diethanolamine and triethanolamine;

said alkanolamino acids are bicine and di(hydroxyethyl)-β

-propionic acid;

a said related soluble alkanolamine is tetra(hydroxyethyl)ethylenediamine; and

said salts of nitric acid are sodium, potassium, calcium, magnesium and ammonium nitrates..!. . .4. A hydraulic cement mix in accordance with claim 1 wherein said salt of thiocyanic acid is present in an amount from about 0.01% to about 2.50% based on the weight of the cement;

said alkanolamine is present in an amount from 0.005% to about 0.08% based on the weight of the cement;

said salt of nitric acid is present in an amount from about 0.05% to about 2.00% based on the weight of the cement;

said alkanolamino acid is present from about 0.005% to 0.10% based on weight of cement; and

said thiosulfate salt is present in an amount from about 0.05%

3. to about 2.00% based on weight of cement..!. 5. A hydraulic cement mix in accordance with claim 1 wherein said salt of thiocyanic acid is present in an amount from about 0.025% to about 0.50%;

said alkanolamine from about 0.005% to about 0.02%; and

said salt of nitric acid from about 0.10% to

4. about 1.00%, based on the weight of the cement. 6. A hydraulic cement mix in accordance with claim 1 wherein said salt of thiocyanic acid is sodium

5. thiocyanate. 7. A hydraulic cement mix in accordance with claim 1 wherein

6. said salt of nitric acid is sodium nitrate. 8. A hydraulic cement mix in accordance with claim 1 wherein said salt of nitric acid is calcium

7. nitrate. 9. A hydraulic cement mix in accordance with claim 1 wherein said salt of nitric acid is a mixture of sodium nitrate and calcium nitrate.

8. A hydraulic cement mix in accordance with claim 1 wherein said salt of

9. nitric acid is a mixture of magnesium nitrate and calcium nitrate. 11. A hydraulic cement mix in accordance with claim 1 wherein said alkanolamine

10. is triethanolamine. 12. A hydraulic cement mix in accordance with claim 1

11. wherein said alkanolamine is diethanolamine. 13. A hydraulic cement mix in accordance with claim 1 wherein said thiosulfate salt is sodium

12. thiosulfate. 14. A hydraulic cement mix in accordance with claim 1 wherein

13. said thiosulfate salt is calcium thiosulfate. 15. A hydraulic cement mix in accordance with claim 1 wherein said . .water soluble.!. alkanolamino

14. acid is bicine. 16. A hydraulic mix in accordance with claim 1 wherein said . .water soluble.!. alkanolamino acid is

15. di(hydroxyethyl)-β

-aminopropionic acid. 17. A hydraulic mix in accordance with claim 1 wherein said . .water soluble.!. alkanolamino acid

16. is di(hydroxyethyl)-β

-amino-α

-methylpropionic acid. 18. A hydraulic mix in accordance with claim 1 wherein said alkanolamino acid is

17. N,N-di(hydroxyethyl)aminomethyl succinic acid. 19. A hydraulic cement mix in accordance with claim 1 wherein said . .water soluble.!. alkanolamine

24. nitrate. 27. A process in accordance with claim . .17.!. .Iadd.20 .Iaddend.wherein the nitrate is a mixture of sodium nitrate and calcium

25. nitrate. 28. A process in accordance with claim . .17.!. .Iadd.20 .Iaddend.wherein the nitrate is a mixture of magnesium nitrate and calcium

26. nitrate. 29. A process in accordance with claim . .17.!. .Iadd.20

27. Iaddend.wherein said thiosulfate salt is sodium thiosulfate. 30. A process in accordance with claim . .17.!. .Iadd.20 .Iaddend.wherein said

28. thiosulfate salt is calcium thiosulfate. 31. A process in accordance with claim . .17.!. .Iadd.20 .Iaddend.wherein said water soluble . .of.!.

29. alkanolamino acid is bicine. 32. A process in accordance with claim . .17.!. .Iadd.20 .Iaddend.wherein said water soluble alkanolamino acid is

30. di(hydroxyethyl)-β

-aminopropionic acid. 33. A process in accordance with claim . .17.!. .Iadd.20 .Iaddend.wherein said . .water soluble.!.

31. alkanolamine is tetra(hydroxyethyl)ethylenediamine. .Iadd.34. A hydraulic cement mix in accordance with claim 1 wherein

said composition or mixture of compositions selected from the group consisting of alkali, ammonium and alkaline earth salts of thiocyanic acid and water soluble thiosulfates is present in an amount from about 0.01% to about 0.50% based on the weight of the cement;

said composition or mixture of compositions selected from the group consisting of alkanolamine and alkanolamino acids is present in an amount from about 0.005% to about 0.10% based on the weight of the cement, with the proviso that alkanolamines, when present, are present in an amount from about 0.005% to about 0.08% based on the weight of the cement; and

said composition or mixture of compositions selected from the group consisting of alkali and alkaline earth salts of nitric acid is present in an amount from about 0.05% to about 2.00% based on the weight of the cement. .Iaddend. .Iadd.35. A hydraulic cement mix in accordance with claim 34 wherein thiocyanate is present in an amount from about 0.01% to about 0.50% based on the weight of the cement, and wherein alkanolamine is present in an amount from about 0.005% to about 0.08% based on the weight of the cement. .Iaddend. .Iadd.36. A process in accordance with claim 20 wherein

said composition selected from the group consisting of ammonium, alkali, and alkaline earth salts of thiocyanic acid, and mixtures thereof, and water soluble thiosulfates that may be substituted for the thiocyanates is present in an amount from about 0.0% to about 0.50% based on the weight of the cement;

said alkanolamine and water soluble alkanolamino acids substituted for the alkanolamine are present in an amount from about 0.005% to about 0.10% based on the weight of the cement, with the proviso that alkanolamine, when present, is present in an amount from about 0.005% to about 0.08% based on the weight of the cement; and

said composition selected from the group consisting of ammonium, alkali, and alkaline earth salts of nitric acid, and mixtures thereof is present in an amount from about 0.05% to about 2.00% based on the weight of the cement. .Iaddend. .Iadd.37. A process in accordance with claim 36 wherein thiocyanate is present in an amount from about 0.01% to about 0.50% based on the weight of the cement, and wherein alkanolamine is present in an amount from about 0.005% to about 0.08% based on the weight of the cement. .Iaddend. .Iadd.38. A hydraulic cement mix comprising hydraulic cement, aggregate, sufficient water to effect hydraulic setting of the cement, and an admixture comprising;

a) composition or a mixture of compositions selected from the group consisting of alkali, ammonium and alkaline earth salts of thiocyanic acid, and water soluble thiosulfates, wherein said salts of thiocyanic acid are sodium, potassium, ammonium and calcium thiocyanate; and

said soluble thiosulfates are sodium, potassium, ammonium, calcium and magnesium thiosulfates;

b) a composition or a mixture of compositions selected from the group consisting of alkanolamine and alkanolamino acids, wherein said alkanolamines are diethanolamine, triethanolamine or tetra(hydroxyethyl)ethylenediamine; and

said alkanolamino acids are bicine and N,N-di(hydroxyethyl)-β

- aminopropionic acid; and

c) a composition or a mixture of compositions selected from the group consisting of alkali, ammonium and alkaline earth salts of nitric acid, wherein said salts of nitric acid are sodium, potassium, calcium, magnesium and ammonium nitrates;

said admixture being present in an amount sufficient to accelerate the rate of hardening of said hydraulic cement mix and to increase its compressive strength after hardening. .Iaddend.

18. is tetra(hydroxyethyl)ethylenediamine. 20. A process for accelerating the hardening of hydraulic cement mixes which includes sequentially adding hydraulic cement, aggregate in an amount up to 80% by weight based on total weight of said cement mix, and sufficient water to effect hydraulic setting of the cement, comprising incorporating an admixture comprising mixtures of

(a) a composition selected from the group . .comprising.!. .Iadd.consisting of .Iaddend.ammonium, alkali, and alkaline earth salts of thiocyanic acid, and mixtures thereof;

and water soluble thiosulfates that may be substituted in whole or in part for the thiocyanates; and

(b) an alkanolamine; and

water soluble alkanolamino acids, substituted in whole or part for the alkanolamine;

(c) a composition selected from the group . .comprising.!. .Iadd.consisting of .Iaddend.ammonium, alkali, and alkaline earth salts of nitric acid, and mixtures thereof;

said additive being incorporated in an amount sufficient to accelerate the rate of hardening of said hydraulic cement mix and to increase its

20. cement..!. 23. A process in accordance with claim 20 wherein the

19. compressive strength after hardening. 21. A process in accordance with claim 20, wherein said hydraulic cement comprises portland cement. . .22. A process in accordance with claim 20, wherein the thiocyanate is present in an amount from about 0.01% to about 0.50%;

the alkanolamine is present in an amount from about 0.005% to about 0.08%; and

the nitrate is present in an amount from about 0.05% to about 2.00% based on the weight of the cement in the mix;

said soluble alkanolamino acid is present from about 0.005 to 0.10% based on weight of cement; and

said thiosulfate salt is present in an amount from about 0.05% to about 2.00% based on weight of

23. accordance with claim 20 wherein the nitrate is sodium nitrate. 26. A process in accordance with claim 20 wherein the nitrate is calcium

21. thiocyanate is sodium thiocyanate. 24. A process in accordance with claim

22. 20 wherein the alkanolamine is triethanolamine. 25. A process in