Process for the preparation of cement, mortars, concrete compositions containing a calcium carbonate-based filler treated with an ultrafine filler and a superplastifier, compositions and cement products obtained and their applications

Abstract

Process for the preparation of cement/mortar/concrete compositions or systems, (for simplicity hereafter “cement” compositions or systems or even “cements”), of a generally known type containing low or medium (standard) “filler(s)”, and/or optionally HP filler(s), as carbonate-based filler(s), namely coarse low or medium calcium carbonate(s), namely coarse marble(s); Product comprising, or consisting of, the pre-blend (A) of coarse, low or medium (or optionally HP) “calcium carbonate-based filler” pre-blended with at least an UF; Aqueous compositions (B) obtained by mixing the above pre-blend (A) of coarse filler(s) with UF(s) with an aqueous system such as mix water, aqueous mix fluid; Product (C) consisting of, or comprising, the pre-blend (A) or the compositions (B), treated or pretreated with at least one superplastifier or aqueous system containing superplastifier(s); Cement and Use of cement.

Claims

1. A process for preparing a cement composition comprising introducing during the manufacture of a cement composition as a filler a blend of a coarse calcium carbonate—comprising filler and an ultrafine filler, wherein the blend is treated with at least one treating agent comprising at least one superplastifier before being introduced into the cement composition, wherein the coarse calcium-carbonate comprising filler has a d.sub.50>6 microns, and the ultrafine filler has a d.sub.50 from 1 to 6 microns and a Blaine of greater than 1000 m.sup.2/kg, and wherein the cement composition so prepared comprises cement, said blend treated with said treating agent as a filler, optionally aggregates selected from the group consisting of sand and gravel, and optionally one or more additives.

2. The process according to claim 1, wherein the coarse calcium carbonate—comprising filler is ground natural calcium carbonate, precipitated calcium carbonate, modified calcium carbonate, or any mixture thereof.

3. The process according to claim 1, wherein the coarse calcium carbonate—comprising filler is a mixture of ground natural calcium carbonate and precipitated calcium carbonate at a ratio of 30/70 to 70/30% by dry weight.

4. The process according to claim 1, wherein the coarse calcium carbonate—comprising filler is selected from the group consisting of (i) calcium carbonate having a d.sub.50 of 7 to 9 microns and a Blaine of 462 to 690 m.sup.2/g, (ii) calcium carbonate having d.sub.50 of 10.4 to 10.8, and (iii) calcium carbonate having a d.sub.50 of 18 microns and a Blaine of about 365 m.sup.2/g.

5. The process according to claim 1, wherein the ultrafine filler has a d.sub.50 from 1 to 5 microns and a Blaine of greater than 1000 m.sup.2/kg and of less than 2000 m.sup.2/kg.

6. The process according to claim 1, wherein the ultrafine filler has a d.sub.50 from 1 to 3 microns and a Blaine of greater than 1000 m.sup.2/kg and of less than 2000 m.sup.2/kg.

7. The process according to claim 1, wherein the ultrafine filler has a d.sub.50 from 2 to 3 microns and a Blaine of greater than 1000 m.sup.2/kg and of less than 2000 m.sup.2/kg.

8. The process according to claim 1, wherein the ultrafine filler has a d.sub.50 of less than <5 microns and a Blaine of greater than 1000 m.sup.2/kg and of less than 2000 m.sup.2/kg.

9. The process according to claim 1, wherein the ultrafine filler has a d.sub.50 from 1 to 5 microns and a Blaine of greater than 1500 m.sup.2/kg.

10. The process according to claim 1, wherein the ultrafine filler is selected from the group consisting of: (i) a silica fume having a d.sub.50 of 1 to 2 microns, (ii) metakaolin having a d.sub.50 of 3 to 5 microns, (iii) metakaolin having a d.sub.50 of 3 to 6 microns, a chalk having a d.sub.50 of 1 to 5 microns, (iv) a calcite having a d.sub.50 of about 1 micron; (v) white limestone having a d.sub.50 of about 2 microns, (vi) a marble having a d.sub.50 of 1 to 6 microns, (vii) a marble having a d.sub.50 of 1 to 5 microns, (viii) ultrafine calcium carbonate having a d.sub.50 of 1-2 microns, (ix) ultrafine calcium carbonate from microcrystalline whiting having a d.sub.50 of about 2.4 micron, (x) an ultrafine siliceous product having a d.sub.50 of about 1.86 microns, (xi) modified calcium carbonate having a d.sub.50 of about 2.29 microns, and (xii) precipitated calcium carbonate having a d.sub.50 of about 1.52 microns.

11. The process according to claim 1, wherein the ultrafine filler is selected from the group consisting of: (i) ultrafine calcium carbonate having a d.sub.50 of about 2.4 microns, (ii) silica fume, (iii) metakaolin, and (iv) ultrafine calcium carbonate having a d.sub.50 of 1 to 2 microns.

12. The process according to according to 1, wherein superplastifier is a polycarboxylate, a polycarboxylate ether, or a product manufactured from sulfonated naphthalene condensate or sulfonated melamine formaldehyde.

13. The process according to claim 1, wherein the superplastifier is a polycarboxylate ether.

14. The process according to claim 1, wherein the superplastifier is present in an amount of from 0.3 to 3 kg for 100 kg of the cement composition, on a dry to dry basis.

15. The process according to claim 1, wherein the superplastifier is present in an amount of from 0.3 to 2 kg for 100 kg of the cement composition, on a dry to dry basis.

16. The process according to claim 1, wherein the superplastifier is present in an amount of from 0.8 to 1.23 kg for 100 kg of the cement composition, on a dry to dry basis.

17. The process according to claim 1, wherein the superplastifier is present in an amount of from 0.05 to 0.1% per dry weight based on the dry weight of the coarse calcium carbonate—comprising filler.

18. The process according to claim 1, wherein the at least one treating agent comprises a superplastifier only, or a superplastifier and a plasticizer.

19. The process according to claim 1, wherein the at least one treating agent comprises a superplastifier and a plasticizer in a ratio of from 95/5 to 85/15 on a dry weight basis.

20. The process according to claim 1, wherein the cement composition further comprises a fluidifier.

21. The process according to claim 20, wherein the fluidifier is a modified polycarboxylate.

22. The process according to claim 20, wherein the fluidifier is present in an amount from 3 to 4 g per dry weight of the total cement composition.

23. The process according to claim 1, wherein the cement composition comprises one or more of a setting accelerator, a setting retarder and an air entrainment agent as additives.

24. The process according to claim 1, wherein the coarse calcium carbonate—comprising filler is dry calcium carbonate, the at least one treating agent is a superplastifier, and the cement composition further comprises one or more additives, and optionally aggregates selected from the group consisting of sand and gravel.

25. The process according to claim 1, wherein the coarse calcium carbonate—comprising filler is dry calcium carbonate, the at least one treating agent is a superplastifier, and the cement composition further comprises one or more additives, water and optionally aggregates selected from the group consisting of sand and gravel.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) The FIGURE depicts the results from Example 1 with low grade CaCO.sub.3, various UF's, and various amounts of Superplastifier B.

EXAMPLES

Example 1 Betocarb™ SL+UF+Product B

(2) Enclosed is TABLE B showing the tests results.

(3) TABLE-US-00003 TABLE B C D E F G J A B Betocarb Betocarb Silica Meta- Etiquette H I Chrysoflui K L V-Fun- H2O Cement HP-OG SL fume kaolin violette Sand B Premia 196 Target Results nel (g) (g) (g) (g) (g) (g) (g) (g) (g) (% d/d) (g) (mm) (mm) (sec) standard 243 378 486 0 0 0 0 1350 0 0 3 >350 465 5 test 1a 243 378 0 486 0 0 0 1350 1.2 0.1 3 >350 425 7 1.3 0.11 435 test 1b 243 378 0 461 25 0 0 1350 1.2 0.1 3 >350 401 8 2.4 0.2 421 test 1c 243 378 0 461 0 25 0 1350 1.2 0.1 3 >350 415 8 1.6 0.13 423 test 1d 243 378 0 461 0 0 25 1350 0.6 0.05 3 >350 400 7 0.8 0.07 415 1.2 0.1 426 test 2a 243 378 0 436 50 0 0 1350 3 0.25 3 >350 423 9 test 2b 243 378 0 436 0 50 0 1350 0.8 0.07 3 >350 0 9 1.3 0.11 200 2.1 0.17 436 test 2c 243 378 0 436 0 0 50 1350 0.6 0.05 3 >350 425 6 test 3a 243 378 0 411 75 0 0 1350 3.6 0.3 3 >350 420 12 test 3b 243 378 0 411 0 75 0 1350 2.6 0.21 3 >350 415 10 2.8 0.23 420 test 3c 243 378 0 411 0 0 75 1350 0.6 0.05 3 >350 420 6

(4) Also enclosed is Table C showing a summary of the tests, and corresponding FIGURE.

(5) TABLE-US-00004 TABLE C Betocatb Betocatb SL + 5% Betocatb SL + 10% Betocatb SL + 15% Betocatb SL + 5% Trial SL alone Etiquette viol. Etiquette viol. Etiquette viol. Silica fume No Product % B mm % B mm % B mm % B mm % B mm 2412/1 Betocatb SL 0.10 425 0.10 426 0.05 425 0.05 420 0.20 421 Betocatb SL + 10% Betocatb SL + 15% Betocatb SL + 5% Betocatb SL + 10% Betocatb SL + 15% Trial Silica fume Silica fume Metakaolin Metakaolin Metakaolin No Product % B mm % B mm % B mm % B mm % B mm 2412/1 Betocatb SL 0.25 423 0.30 420 0.13 423 0.17 436 0.23 420

(6) Betocarb SL is a “low” calcium carbonate based filler (marble) (d50=11-12 microns) (Blaine surface=365 m2/g)

(7) Silica fume SF and metakaolin MK are two UFs as defined above.

(8) Pulverized metakaolin (MK) is made by thermal treatment of natural clay. The crystalline clay minerals are dehydroxylated. Metakaolin powder has the higher pozzolanic activity (756 mg CaO/g sample). The calcining temperature of clay affects the pozzolanic reactivity of the resulting product.

(9) Silica Fume (SF)

(10) Silica fume originates from the reduction of high purity quartz with coal in electric arc furnaces in the production of silicon and ferrosilicon alloys and consists of very fine spherical particles containing at least 85% by mass of amorphous silicon dioxide.

(11) EV (Etiquette Violette™) is an UF too as defined above, a very fine calcium carbonate from Omey, France, from microcrystalline Champagne Whiting.

(12) For each group of tests, the UF amount is the same, that is respectively 25, 50 and 75 g.

(13) Test 1a is a blank test (no UF)

(14) The amount of mix water remains constant in all tests, 243 g. So is the amount of sand, 1350 g, and water 243 g.

(15) The “standard” test is a comparative test with no UFs but with 486 g of BL 200 (d50=7 microns, Blaine=462 g/m2) serving as a reference for the cone diameter only (it is a low filler since it gives a poor flow and workability in the cone test).

(16) Superplastifier B belongs to the preferred family as defined above.

(17) Chrysofluid™ Premia 196 is a routine fluidifier and its amount remains constant at 3 g.

(18) Table B shows that the low Filler Betocarb HP-OG provides an excellent result of 465 mm in cone test “galette” diameter (BUT as explained above, a poor flow and visual aspect).

(19) When replacing the low filler Betocarb HP-OG with another low filler Betocarb SL at the same amount of 486 g (test 1a) one reaches 425 mm at 0.1% dry weight of superplastifier B or 435 mm at 0.11%.

(20) These Tables B and C show the synergy between the treatment with UF and that by the superplastifier B.

Example 2 Betocarb SL+UF PCC or UF MCC+B

(21) See Enclosed Table D

(22) TABLE-US-00005 TABLE D C D A B Betocarb Betocarb E F G H I Chrysofluid H2O Cement HP-OG SL PCC MCC Sand B Premia 196 Target Result V-Funnel Work 2/B (g) (g) (g) (g) (g) (g) (g) (g) (% d/d) (g) (mm) (mm) (sec) A1 243 378 486 0 0 0 1350 0 0 3 >350 465 6 A2 243 378 0 486 0 0 1350 to adjust to adjust 3 >350 435 7 A3 243 378 0 461 25 0 1350 to adjust to adjust 3 >350 422 8 A4 243 378 0 436 50 0 1350 to adjust to adjust 3 >350 426 9 A5 243 378 0 386 75 0 1350 to adjust to adjust 3 >350 420 10 A6 243 378 0 461 0 25 1350 to adjust to adjust 3 >350 400 8 A7 243 378 0 436 0 50 1350 to adjust to adjust 3 >350 410 10 A8 243 378 0 386 0 75 1350 to adjust to adjust 3 >350 385 11

(23) This test is the same as above Example 2 except that as UF one uses a precipitated calcium carbonate PCC d50=1.52 microns, known to be an UF, or a MCC which is a modified calcium carbonate (see U.S. Pat. No. 6,666,953) d50=2.29 microns.

(24) Results call for the same comments as in Example 2.

Example 3 Lavigne+Product A (Comparative Test)

(25) Enclosed is Table E

(26) TABLE-US-00006 TABLE E A B C D Reference sample 2252/1 2252/1 2252/1 2252/1 Reference Lavigne 13μ Lavigne 13μ + 0.05% A Lavigne 13μ + 0.1% A Lavigne 13μ + EV Cement 378 378 378 378 H.sub.2O 243 243 243 243 Sand 1350 1350 1350 1350 Filler St Béat St Béat St Béat St Béat/Violette CaCO.sub.3 486 486 486 436/50 % A (Sec/sec) 0 0.05 0.1 0 Test 4g Fluidifier Premia 196 4 4 4 4 Consistancy (>350 mm) 413 428 441 440 Aspect A2 A2 A2 A2 Observations Slow flow − Slow flow − Slow flow − Fluid mortar + Dilating mortar Dilating mortar Dilating mortar somewhat settles

(27) The low filler is Lavigne, a coarse carbonate, marble, d50=13 microns.

(28) The UF used to treat the above filler is Etiquette violette EV d50=2.4 microns.

(29) If we consider the lefthand column A (Lavigne Filler with no UF treatment and no treatment with a superplastifier) we can see that the diameter in the cone test is 413 mm.

(30) Despite the very good value of 413 mm for the diameter of the cone test, the slurry is flowing only slowly and is “dilating”; the overall result is therefore mitigated since the cone diameter is excellent but the flow test could be better in visual “aspect”.

(31) Another test has been performed (not shown in the Table) with 3 g of fluidifier instead of 4 g: in that case, the mortar becomes “fluid”.

(32) This means that the right optimum in this test is to use the indicated proportion of EV but between 3 and 4 g of fluidifier, −3.7 g, preferably 3.5 g.

(33) If we consider the two central columns, B and C, we can see that by treating the marble with resp. 0.005% or 0.10% Product A/dry weight of cement composition one obtains the same “low flow rate” and “dilating mortar” but with a better diameter.

(34) This shows that the treatment of the considered marble with 0.05 to 0.10% Product A improves the workability of the mortar composition, but for this marble type, not enough.

(35) Below 0.05%, no pertinent measurement of the precise % can be done in Laboratory conditions, so we can see or deduct from the table E that a treatment of this marble with about 0.03 to 0.05-0.10-0.15% Product B improves clearly the diameter but not the flow rate.

(36) If we consider now the next column D one can see that by replacing 486 g of Lavigne filler with 436 g of the same Lavigne filler but treated only with 50 g of EV according to the invention, with still 4 g of fluidifier Chrysofluid Premia 196 being present as above, the cement composition becomes fluid with a very high diameter of 440 mm (same as the 441 mm obtained with a treatment with only 1% of Product A) with the only disadvantage that it somewhat settles.

(37) Here again, an adjustment of the fluidifier at 3 g instead of 4 g renders the mortar “fluid”.

(38) So, here again, the optimum is a treatment in the presence of between 3 and 4 g of fluidifier, such as 3.4-3.7 g, preferably 3.5 g/dry weight of the total cement composition.

(39) We can conclude from this table E that the treatment with Product A superplastifier alone does not bring, for this specific marble, a solution which is entirely satisfactory. The treatment with only an UF brings a satisfactory solution at 3-3.5 g fluidifier (it is the subject matter of a pending application filed the same day as the present one).

(40) This test confirms the interest of treating the coarse filler first with an UF then treating the preblend with a superplastifier to take benefit from the synergy.

(41) Application(S)

(42) The applications are all those commonly using the above described cement, mortar, or concrete compositions or systems.

(43) Cement Products

(44) Those are the products or elements that are known to be manufactured from the above cement, mortar or concrete compositions, in the building industry or any other industry, in a well-known manner.