Limestone calcined clay cement (LC3) construction composition

Patent metadata

Field	Value
Publication number	US-11939273-B2
Application number	US-202118023055-A
Country	US
Kind code	B2
Filing date	Aug 25, 2021
Priority date	Aug 26, 2020
Publication date	Mar 26, 2024
Grant date	Mar 26, 2024

Abstract

A limestone calcined clay cement construction composition comprises a) a cementitious binder comprising one or more calcium silicate mineral phases and one or more calcium aluminate mineral phases, and having a Blaine surface area of at least 3800 cm 2 /g; b) a supplementary cementitious material having a Dv90 of less than 200 μm comprising (b-1) a calcined clay material and (b-2) a carbonate rock powder in a weight ratio of (b-1) to (b-2) in the range of 0.5 to 2; c) optionally, an extraneous aluminate source; d) a sulfate source; and e) a polyol. The composition contains a controlled amount of available aluminate, calculated as Al(OH) 4 − , from the calcium aluminate mineral phases plus the optional extraneous aluminate source; and the molar ratio of total available aluminate to sulfate is 0.4 to 2.0. The construction composition further comprises f) an ettringite formation controller. The limestone calcined clay cement construction composition is a reduced carbon footprint composition and exhibits high early strength, high final strength, sufficient open time and high durability.

First claim

The invention claimed is:

1. A limestone calcined clay cement construction composition comprising
a) a cementitious binder comprising one or more calcium silicate mineral phases and one or more calcium aluminate mineral phases, and having a Blaine surface area of at least 3800 cm 2 /g, in an amount of 180 to 400 kg per m 3 of the limestone calcined clay cement construction composition;
b) a supplementary cementitious material having a Dv90 of less than 200 μm, in a total amount of 50 to 100 parts by weight, relative to 100 parts by weight of the cementitious binder a), the supplementary cementitious material comprising (b-1) a calcined clay material and (b-2) a carbonate rock powder in a weight ratio of (b-1) to (b-2) in the range of 0.5 to 2;
c) optionally, an extraneous aluminate source;
d) a sulfate source; and
e) a polyol in an amount of 0.3 to 2.5 wt.-%, relative to the amount of the cementitious binder a);
wherein the composition contains available aluminate, calculated as Al(OH) 4 − , from the calcium aluminate mineral phases plus the optional extraneous aluminate source, per 100 g of the cementitious binder a), in a total amount of
at least 0.08 mol, if the amount of said cementitious binder a) is in the range of 180 to less than 220 kg per m 3 of the limestone calcined clay cement composition,
at least 0.06 mol, if the amount of the cementitious binder a) is in the range of 220 to less than 280 kg per m 3 of the limestone calcined clay cement composition, and
at least 0.05 mol, if the amount of the cementitious binder a) is 280 kg or more per m 3 of the limestone calcined clay cement composition;
and the molar ratio of total available aluminate to sulfate is 0.4 to 2.0;
the limestone calcined clay cement construction composition further comprising
f) an ettringite formation controller comprising (i) at least one of glyoxylic acid, a glyoxylic acid salt or a glyoxylic acid derivative; and (ii) at least one of (ii-a) a borate source and (ii-b) a carbonate source, wherein the carbonate source is selected from inorganic carbonates having an aqueous solubility of 0.1 g·L −1 or more at 25° C., organic carbonates, and mixtures thereof; and
g) a co-retarder selected from (g-1) α-hydroxy monocarboxylic acids and salts thereof, (g-2) phosphonic acids and salts thereof, (g-3) polycarboxylic acids and salts thereof, and mixtures thereof.

2. The composition according to claim 1 , wherein the calcium silicate mineral phases and calcium aluminate mineral phases constitute at least 90 wt.-% of the cementitious binder a), and wherein the calcium silicate mineral phases constitute at least 60 wt. % of the cementitious binder a).

3. The composition according to claim 1 , wherein the calcium aluminate mineral phases are selected from C3A, C4AF, and C12A7.

4. The composition according to claim 1 , wherein the cementitious binder a) is Portland cement.

5. The composition according to claim 1 , wherein the calcined clay material has a Ca(OH) 2 consumption according to the Chapelle test of at least 200 mg per 1 g of calcined clay material.

6. The composition according to claim 1 , wherein the carbonate rock powder is selected from limestone, dolomite and mixtures thereof.

7. The composition according to claim 1 , further comprising an inorganic pigment.

8. The composition according to claim 1 , wherein the supplementary cementitious material b) has a Dv90 of less than 150 μm.

9. The composition according to claim 1 , wherein the extraneous aluminate source c) is selected from non-calciferous aluminate sources, calciferous aluminate sources, sulfoaluminate cement or synthetic calcium aluminate mineral phases.

10. The composition according to claim 1 , wherein the sulfate source d) is a calcium sulfate source.

11. The composition according to claim 1 , wherein the cementitious binder a) has a Blaine surface area of at least 4500 cm 2 /g.

12. The composition according to claim 1 , wherein the polyol, in a calcium aluminate precipitation test in which a test solution, obtained by supplementing 400 mL of a 1 wt.-% aqueous solution of the polyol with 20 mL of a 1 mol/L NaOH aqueous solution and 50 mL of a 25 mmol/L NaAlO 2 aqueous solution, is titrated with a 0.5 mol/L CaCl 2 ) aqueous solution at 20° C., inhibits precipitation of calcium aluminate up to a calcium concentration of 75 ppm.

13. The composition according to claim 12 , wherein the polyol is selected from monosaccharides, oligosaccharides, water-soluble polysaccharides, compounds of general formula (P-I) or dimers or trimers of compounds of general formula (P-I):

wherein X is

wherein
R is —CH 2 OH, —NH 2 ,
n is an integer from 1 to 4,
m is an integer from 1 to 8.

14. The composition according to claim 1 , wherein the glyoxylic acid derivative is a melamine-glyoxylic acid condensate, a urea-glyoxylic acid condensate, a melamine-urea-glyoxylic acid condensate and/or a polyacrylamide-glyoxylic acid condensate.

15. The composition according to claim 1 , wherein the glyoxylic acid, glyoxylic acid salt and/or glyoxylic acid derivative (i) is present in a total amount of 0.2 to 2 wt.-% relative to the amount of the cementitious binder a).

16. The composition according to claim 1 , wherein the inorganic carbonate is selected from potassium carbonate, sodium carbonate, sodium bicarbonate, lithium carbonate and magnesium carbonate; and the organic carbonate is selected from ethylene carbonate, propylene carbonate and glycerol carbonate.

17. The composition according to claim 1 , wherein the carbonate source (ii-b) is present in an amount of 0.3 to 1 wt.-% relative to the amount of the cementitious binder a).

18. The composition according to claim 1 , wherein the α-hydroxy monocarboxylic acid salt is sodium gluconate.

19. The composition according to claim 1 , wherein the polycarboxylic acid or a salt thereof (g-3) has a milliequivalent number of carboxyl groups of 3.0 meq/g or higher assuming all the carboxyl groups to be in unneutralized form.

20. The composition according to claim 1 , wherein the polycarboxylic acid is selected from phosphonoalkyl carboxylic acids, amino carboxylic acids, and polymeric carboxylic acids.

21. The composition according to claim 1 , wherein the composition additionally comprises
h) at least one aggregate.

22. The composition according to claim 1 , additionally comprising a dispersant.

23. The composition according to claim 22 , wherein the dispersant is selected from the group of
comb polymers having a carbon-containing backbone to which are attached pendant cement-anchoring groups and polyether side chains,
non-ionic comb polymers having a carbon-containing backbone to which are attached pendant hydrolysable groups and polyether side chains, the hydrolysable groups upon hydrolysis releasing cement-anchoring groups,
colloidally disperse preparations of polyvalent metal cations, and a polymeric dispersant which comprises anionic and/or anionogenic groups and polyether side chains, and the polyvalent metal cation is present in a superstoichiometric quantity, calculated as cation equivalents, based on the sum of the anionic and anionogenic groups of the polymeric dispersant,
sulfonated melamine-formaldehyde condensates,
l

Assignees

• Construction Research & Technology Gmbh
• Construction Res &Technology Gmbh

Inventors

• Bandiera Massimo
• Schwesig Peter
• Sachsenhauser Bernhard
• Dhers Sebastien

Classifications

• C04B22/10

  containing carbon in the anion, e.g. carbonates · CPC title

• C04B7/02 Primary

  Portland cement · CPC title

• C04B22/143

  Calcium-sulfate · CPC title

• C04B24/02

  Alcohols; Phenols; Ethers · CPC title

• C04B24/04

  Carboxylic acids; Salts, anhydrides or esters thereof · CPC title