CEMENTITIOUS COMPOSITION

Abstract

The present application relates to a cementitious composition suitable to be applied to an object via a nozzle. The composition comprises a) 15-90% by weight of a cementitious binder, b) 0.02-3% by weight of an ettringite formation controller, c) 0.15-10% by weight of a magnesium salt accelerator and d) 0.02-2% by weight of a polyhydroxy compound A, and/or salts or esters thereof, wherein the polyhydroxy compound A is selected from polyalcohols with a carbon to oxygen ratio of C/O?1 and mixtures 0 thereof, based on the total dry weight of the composition. Further a process for applying the composition onto a surface and a hardened structure obtained by the process is disclosed.

Claims

1.-15. (canceled)

16. A composition suitable to be applied to an object via a nozzle comprising, based on the total dry weight of the composition, a) 15-90% by weight of a cementitious binder; b) 0.02-3% by weight of an ettringite formation controller comprising (i) a glyoxylic acid condensate and/or a glyoxylic acid adduct and/or glyoxylic acid; c) 0.15-10% by weight of a magnesium salt accelerator; d) 0.02-2% by weight of a polyhydroxy compound A and/or salts or esters thereof, wherein the polyhydroxy compound A is selected from polyalcohols with a carbon to oxygen ratio of C/O?1 and mixtures thereof.

17. The composition according to claim 16, wherein the glyoxylic acid condensate is an amine-glyoxylic acid condensate, a melamine-glyoxylic acid condensate, a urea-glyoxylic acid condensate, a melamine-urea-glyoxylic acid condensate and/or a polyacrylamide-glyoxylic acid condensate and/or their salts.

18. The composition according to claim 16, wherein the glyoxylic acid adduct is a bisulfite adduct of glyoxylic acid or a salt or a mixed salt thereof, wherein the bisulfite adduct has the general formula (I) ##STR00022## wherein X is in each case independently selected from H or a cation equivalent K.sub.a, wherein K is an alkali metal, alkaline earth metal, zinc, iron, aluminum, ammonium, or a phosphonium cation, and wherein a is 1/n, wherein n is the valence of the cation.

19. The composition according to claim 16, wherein the ettringite formation controller additionally comprises (ii) a carbonate source.

20. The composition according to claim 19, wherein the inorganic carbonate is selected from sodium carbonate, lithium carbonate; and the organic carbonate is selected from ethylene carbonate and propylene carbonate.

21. The composition according to claim 16, wherein the ettringite formation controller additionally comprises (iii) a component selected from polycarboxylic acids or salts thereof whose milliequivalent number of carboxyl groups is 5.00 meq/g or higher, assuming all the carboxyl groups to be in unneutralized form; and ?-hydroxy carboxylic acids or salts thereof.

22. The composition according to claim 16, wherein the cementitious binder is selected from Portland cement, gypsum, calcium aluminate cement and/or sulfoaluminate cement.

23. The composition according to claim 16, wherein the composition additionally comprises a latent hydraulic binder or a pozzolanic binder, or mixtures thereof.

24. The composition according to claim 16, wherein the polyhydroxy compound A is selected from sugar alcohols and their condensation products, alkanolamines and their condensation products, carbohydrates, pentaerythritol, trimethylolpropane, and mixtures thereof.

25. The composition according to claim 16, additionally comprising a dispersant, 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, sulfonated melamine-formaldehyde condensates, lignosulfonates, sulfonated ketone-formaldehyde condensates, sulfonated naphthalene-formaldehyde condensates, phosphonate containing dispersants, phosphate containing dispersants, and mixtures thereof.

26. The composition according to claim 16, wherein the composition comprises less than 0.1% by weight of an alkali-free, aluminum-based accelerator based on the total dry weight of the composition.

27. The composition according claim 16, wherein the composition does not comprise an alkali-free, aluminum-based accelerator.

28. The composition according to claim 16, wherein the magnesium salt accelerator is selected from magnesium salts with a solubility of more than 100 g/liter at 20? C.

29. A process comprising providing a composition comprising a) 15-90 by weight of a cementitious binder; b) 0.02 3% by weight of an ettringite formation controller comprising (i) a glyoxylic acid condensate and/or a glyoxylic acid adduct and/or glyoxylic acid; d) 0.02-2% by weight of a polyhydroxy compound A and/or salts or esters thereof, wherein the polyhydroxy compound A is selected from polyalcohols with a carbon to oxygen ratio of C/O?1 and mixtures thereof, admixing an c) 0.15-10% by weight of a magnesium salt accelerator; and applying the composition onto a surface to obtain a structure and allowing the structure to harden; wherein the % by weight are based on the total dry weight of the composition.

30. A hardened structure obtained by the process according to claim 29.

Description

EXAMPLES

A.) Materials

[0232] Binder: OPC CEM I Bernburg 42.5 R and calcium sulfate anhydride CAB 30 from Knauf.

[0233] Plasticiziser: Melflux 6680 L, available from BASF Construction Additives GmbH, a polycarboxylate ether (PCE) based plasticizers was used.

[0234] As accelerators were used: [0235] Aluminium sulfate octadecahydrate from Sigma Aldrich (reference) [0236] MasterRoc SA 160 from BASF Construction Solutions GmbH. MasterRoc SA 160 is an aqueous suspension type alkali-free accelerator based on aluminum sulfate with solid content in the range of 50?4%. (reference) [0237] Magnesium sulfate hydrate from Riedel-de-Haen (invention) [0238] HyCon? S 3200 F is a calcium silicate hydrate hardening accelerator in powder form from BASF Construction Additives GmbH

[0239] The retarder mixture contains: [0240] a) Glyoxylic acid urea condensate [0241] b) Sodium gluconate [0242] c) Glycerol from Sigma-Aldrich and triethanolamine from Sigma-Aldrich as polyolcomponent [0243] d) Sodium bicarbonate from Sigma-Aldrich

TABLE-US-00001 Content as solid in wt.-% VZ F4 VZ F35 VZ F42 A Glyoxylic acid urea condensate 20.1 29.7 14.93 B Sodium gluconate 6.71 9.90 4.98 C Glycerol from Sigma-Aldrich 32.2 0 49.75 and triethanolamine from Sigma-Aldrich ratio 2:1 D Sodium bicarbonate from 40.9 60.4 30.35 Sigma-Aldrich 1.5 wt.-%.sup.1 1.01 wt.-%.sup.1 2.0 wt.-%.sup.1 VZ F4 VZ F35 VZ F42 Glyoxylic acid urea condensate 0.30.sup.1 0.30.sup.1 0.30.sup.1 Sodium gluconate 0.10.sup.1 0.10.sup.1 0.10.sup.1 Glycerol from Sigma-Aldrich 0.48.sup.1 0.00 1.00.sup.1 and triethanolamine from Sigma-Aldrich ratio 2:1 Sodium bicarbonate from 0.61.sup.1 0.61.sup.1 0.61.sup.1 Sigma-Aldrich .sup.1wt.-% of the sum of solid of active components relative to the weight of binder (cement plus anhydride)

[0244] The glyoxylic acid urea condensate was synthesized as follows: Glyoxylic acid (1.2 g of glyoxylic acid, 50 wt.-% solution in water) was charged into a reaction vessel and aqueous potassium hydroxide (40 wt.-%) was added until a pH value of 5 was reached. 1 g of urea was added and the mixture was heated to 80? C. The thus obtained glyoxylic acid urea condensate (M.sub.n=950 g/mol) is an aqueous solution with a solids content of 49.3%.

B. Analytical Methods

[0245] Gel Permeation Chromatography (GPC)

[0246] Column combination: OH-Pak SB-G, OH-Pak SB 804 HQ and OH-Pak SB 802.5 HQ by Shodex, Japan; eluent: 80 vol.-% aqueous solution of HCO.sub.2NH.sub.4 (0.05 mol/1) and 20 vol.-% Methanol; injection volume 100 ?l; flow rate 0.5 ml/min. The molecular weight calibration was performed with poly(acrylate) standards for the RI detector, purchased from PSS Polymer Standards Service, Germany.

C. Application Test

[0247] The compounded mortar had a sand/binder ratio of s/b=2.2. The sand was a mixture of 70% norm sand and 30% quartz sand. The water/binder weight ratio was 0.42. The amounts of additives are listed in table 1, 2 and 3.

[0248] The mortar was prepared in a 5 L RILEM mixer. The mixer was charged with the binder cement and gypsum anhydride. The plasticizer and the ettringite formation controlling agent are added to the mixing water. The mixing procedure are shown in the table.

TABLE-US-00002 Time in Mixing seconds Speed Note 0 I Addition mixing water to binder, start slow mixing 30 I Sand is added to the paste 60 II Fast mixing 90 0 Stop mixing 180 II Start mixing 240 0 End of mixing

[0249] For the mortar tests with setting accelerators, the accelerator was mixed with RILEM mixer in the mortar for ten seconds with mixing speed 1. The accelerator was added to the fresh mortar after the time shown in table 1 and 2. After the ten seconds consecutive mixing, the final mortar is filled into 4?4?16 cm prism molds, densified at a vibrating table for 1 minute, sealed and stored at 20? C. and 50% relative humidity. The initial setting was determined with a Vicat apparatus according to DIN EN 196-3. The strength was measured according to DIN EN 196-1.

TABLE-US-00003 TABLE 1 Mortar Mix Component M1 M2 M3 M4 Cement [g] 832.82 832.82 832.82 832.82 Gypsum anhydride [g] 43.43 43.43 43.43 43.43 Norm sand [g] (DIN EN 196-1) 1350 1350 1350 1350 Quartz sand 0.1-0.3 mm [g] 567.87 567.87 567.87 567.87 Melflux 6680L Plasticizer [wt-%].sup.1 0.04 0.04 0.04 0.04 MasterRoc SA 160 2.5 Accelerator [wt.-%].sup.2 Al.sub.2(SO.sub.4).sub.3*18H.sub.2O [wt.-%].sup.2 2.5 MgSO.sub.4 Hydrate Accelerator [wt.-%].sup.2 VZ F35 1.01 1.01 1.01 Ettringite formation controller [wt.-%].sup.2 Time Accelerator added after 0 30 30 30 Mortar mixing [min.] Water [g] (total amount) 368.03 368.03 368.03 368.03 .sup.1wt.-% of the sum of solid of active components relative to the weight of cement (bwoc) .sup.2wt.-% of the sum of solid of active components relative to the weight of binder (cement plus anhydride)

TABLE-US-00004 TABLE 2 Mortar Mix Component M5 M6 M7 M8 M9 M10 M11 M12 M13 Cement [g] 832.82 832.82 832.82 832.82 832.82 832.82 832.82 832.82 832.82 Gypsum 43.43 43.43 43.43 43.43 43.43 43.43 43.43 43.43 43.43 anhydride [g] Norm sand [g] 1350 1350 1350 1350 1350 1350 1350 1350 1350 (DIN EN 196-1) Quartz sand 567.87 567.87 567.87 567.87 567.87 567.87 567.87 567.87 567.87 0.1-0.3 mm [g] Melflux 6680L 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 Plasticizer in wt.-%.sup.1 MgSO.sub.4 Hydrate 2.5 2.5.sup.3 2.5 2.5 2.5 2.5.sup.3 3.4 2.85 2.5 Accelerator [wt.-%].sup.2 VZ F4 1.5 1.5 1.5 1.5 1.5 1.5 Ettringite for- mation controller [wt.-%].sup.2 VZ F35 1.01 1.01 Ettringite for- mation controller [wt.-%].sup.2 VZ F42 2.0 Ettringite for- mation controller [wt.-%].sup.2 Time added 30 30 30 60 90 30 30 30 30 Accelerator after Mortar mixing [min.] Water [g] 368.03 368.03 368.03 368.03 368.03 368.03 368.03 368.03 368.03 (total amount) .sup.1wt.-% of the sum of solid of active components relative to the weight of cement (bwoc) .sup.2wt.-% of the sum of solid of active components relative to the weight of binder (cement plus anhydride) .sup.3Accelerator added as solution with a solid content of 30%

TABLE-US-00005 TABLE 3 Mortar Mix Component M14 M15 M16 M17 Cement [g] 832.82 832.82 832.82 832.83 Gypsum 43.43 43.43 43.43 43.43 anhydride [g] Norm sand [g] 1350 1350 1350 1350 (DIN EN 196-1) Quartz sand 567.87 567.87 567.87 567.87 0.1-0.3 mm [g] Melflux 6680L 0.04 0.04 0.04 0.04 Plasticizer in wt.-%.sup.1 Ca(OH).sub.2 2.23 2.5 4.26 5 [wt.-%].sup.2 HyCon? S 3200 F 0.27 0.54 [wt.-%].sup.2 VZ F4 1.5 1.5 1.5 1.5 Ettringite formation controller [wt.-%].sup.2 Time added 30 30 30 30 Accelerator after Mortar mixing [min.] Water [g] 368.03 368.03 368.03 368.03 (total amount) .sup.1wt.-% of the sum of solid of active components relative to the weight of cement (bwoc) .sup.2wt.-% of the sum of solid of active components relative to the weight of binder (cement plus anhydride)

TABLE-US-00006 TABLE 4 M7 M8 M9 M10 M1 M2 M3 M4 M5 M6 (inv) (inv.) (inv.) (inv.) Vicat 164 380 +12.sup.1 +7.sup.1 +14.sup.1 +24.sup.1 +14.sup.1 +16.sup.1 +14.sup.1 +13.sup.1 needle Begin [min.] Vicat 272 440 +17.sup.1 +14.sup.1 +23.sup.1 +30.sup.1 +18.sup.1 +20.sup.1 +18.sup.1 +16.sup.1 needle End [min.] Strength n.M. n.M n.M. n.M. n.M n.M. 4.1 3.3 2.7 5.0 after 2 h [N/mm.sup.2] Strength n.M. n.M n.M. n.M. n.M n.M. 6.45 7.1 7.1 8 after 6 h [N/mm.sup.2] Strength 15.0 1.67 6.75 17.8 2.2 2.4 6.95 8.81 8.5 9.4 after 24 h [N/mm.sup.2] M11 M12 M13 (inv.) (inv.) (inv.) M14 M15 M16 M17 Vicat +9.sup.1 +12.sup.1 +8.sup.1 +56.sup.1 +86.sup.1 +30.sup.1 +40.sup.1 needle Begin [min.] Vicat +14.sup.1 +16.sup.1 +11.sup.1 +68.sup.1 +106.sup.1 +39.sup.1 +44.sup.1 needle End [min.] Strength 3.2 4.1 5.9 4.6 0 4.7 4.5 after 2 h [N/mm.sup.2] Strength 5.1 6.6 8.9 6.7 6.7 6.3 6.8 after 6 h [N/mm.sup.2] Strength 7.7 7.7 10.2 9.5 9.1 9.1 9.2 after 24 h [N/mm.sup.2] n.M.: not measured, to weak inv.: according to the invention .sup.1Setting time after accelerator is added