CONSTRUCTION COMPOSITION

Abstract

A construction composition comprises a) a cementitious binder comprising one or more calcium silicate mineral phases and one or more calcium aluminate mineral phases; b) optionally, an extraneous aluminate source; c) a sulfate source; d) an ettringite formation controller comprising (i) glyoxylic acid, a glyoxylic acid salt and/or a glyoxylic acid derivative; and (ii) at least one of a borate source and a carbonate source, wherein the carbonate source is selected from inorganic carbonates having an aqueous solubility of 0.1 g.Math.L.sup.−1 or more, organic carbonates, and mixtures thereof; and e) a polyol in an amount of 0.2 to 2.5 wt.-%, relative to the amount of cementitious binder a). The composition contains 0.05 to 0.2 mol of total available aluminate, calculated as Al(OH).sub.4.sup.−, from the calcium aluminate mineral phases plus the optional extraneous aluminate source, per 100 g of cementitious binder a); and the molar ratio of total available aluminate to sulfate is 0.4 to 2.0. The construction composition exhibits high early strength and sufficient open time. The advantageous effects are readily achievable for a variety of cements with varying elemental compositions.

Claims

1. A construction composition comprising a) a cementitious binder comprising one or more calcium silicate mineral phases and one or more calcium aluminate mineral phases; b) optionally, an extraneous aluminate source; c) a sulfate source; d) an ettringite formation controller comprising (i) glyoxylic acid, a glyoxylic acid salt and/or a glyoxylic acid derivative; and (ii) at least one of a borate source and a carbonate source, wherein the carbonate source is selected from inorganic carbonates having an aqueous solubility of 0.1 g.Math.L.sup.−1 or more at 25° C., organic carbonates, and mixtures thereof; and e) a polyol in an amount of 0.2 to 2.5 wt.-%, relative to the amount of cementitious binder a); wherein the composition contains 0.05 to 0.2 mol of total available aluminate, calculated as Al(OH).sub.4.sup.−, from the calcium aluminate mineral phases plus the optional extraneous aluminate source, per 100 g of cementitious binder a); and the molar ratio of total available aluminate to sulfate is 0.4 to 2.0.

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 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 composition additionally comprises f) at least one of a latent hydraulic binder, a pozzolanic binder and a filler material.

6. The composition according to claim 1, wherein the extraneous aluminate source b) is selected from non-calciferous aluminate sources, and calciferous aluminate sources .

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

8. The composition according to claim 1, wherein the amount of polyol e) is 0.2 to 1 wt.-%, relative to the amount of cementitious binder a), if the Blaine surface area of the cementitious binder a) is 1500 to 4000 cm.sup.2/g, and the amount of polyol e) is 1 to 2.5 wt.-%, relative to the amount of cementitious binder a), if the Blaine surface area is more than 4000 cm.sup.2/g.

9. 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.sub.2 aqueous solution, is titrated with a 0.5 mol/L CaCl.sub.2 aqueous solution at 20° C., inhibits precipitation of calcium aluminate up to a calcium concentration of 75 ppm.

10. The composition according to claim 9, 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): ##STR00020## wherein X is ##STR00021## wherein R is —CH.sub.2OH, —NH.sub.2, n is an integer from 1 to 4, m is an integer from 1 to 8.

11. The composition according to claim 1, wherein the glyoxylic acid derivative is a glyoxylic acid polymer.

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

13. The composition according to claim 1, wherein the ettringite formation controller additionally comprises (iii) a polycarboxylic acid or a salt thereof whose milliequivalent number of carboxyl groups is 3.0 meq/g or higher, assuming all the carboxyl groups to be in unneutralized form.

14. The composition according to claim 13, wherein the polycarboxylic acid is selected from phosphonoalkyl carboxylic acids, amino carboxylic acids, and polymeric carboxylic acids.

15. The composition according to claim 1, wherein the ettringite formation controller additionally comprises (iv) a α-hydroxy monocarboxylic acid or a salt thereof.

16. The composition according to claim 1, additionally comprising a dispersant selected from 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, such as Al.sup.3+, Fe.sup.3+ or Fe.sup.2+, 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, lignosulfonates, sulfonated ketone-formaldehyde condensates, sulfonated naphthalene-formaldehyde condensates, phosphonate containing dispersants, phosphate containing dispersants, and mixtures thereof.

17. The composition according to claim 1, wherein the construction composition comprises less than 5 wt.-% of cementitious hydration products, relative to the total weight of the construction composition.

18. The construction composition according to claim 1, in freshly mixed form, wherein the ratio of water to cementitious binder a) is in the range of 0.2 to 0.7.

Description

METHODS

Testing Procedure—Open Time

[0237] Open time was determined with a Vicat needle according to DIN EN 480.

Calcium Aluminate Precipitation Test

[0238] For the calcium aluminate precipitation test, an automated titration module (Titrando 905, available from Metrohm) equipped with a high performance pH-electrode (iUnitrode with Pt 1000, available from Metrohm) and a photosensor (Spectrosense 610 nm, available from Metrohm) was used. First, a solution of 400 mL of a 1 wt.-% aqueous solution of a polyol to be investigated and 20 mL of a 1 mol/L NaOH aqueous solution was equilibrated for 2 min under stirring in the automated titration module. Then, 50 mL of a 25 mmol/L NaAlO.sub.2 aqueous solution was added thereto, followed by equilibration for another 2 min, obtaining an essentially clear test solution. In a next step, the test solution is titrated with a 0.5 mol/L CaCl.sub.2 aqueous solution which is dosed with a constant rate of 2 mL/min. During the whole experiment, the temperature is hold constant at 20° C. The elapsed time to a turbidity inflection is recorded. To this end, the photo current signal in mV is plotted against the time of dosage of the CaCl.sub.2 aqueous solution. From the diagram, the onset point is determined as the intersection of the baseline tangent with a tangent to the curve after the inflection of the curve.

[0239] The invention is illustrated by the following examples. All wt.-% are understood as % bwoc, i.e., as relative to the mass of cementitious binder a). Various mortar mixes were prepared, adjusted to the same slump and their early strength development was measured. The basic recipe is as follows, to which further ingredients were added as described in detail below.

TABLE-US-00001 Material Amount [kg/m.sup.3] Cementitious binder 542 Limestone powder 68 Anhydrite (CAB 30) 54 Water 209 Quartz sand (0.1-0.3 mm) 155 Quartz sand (0.3-1 mm) 118 Natural sand (0-4 mm) 977 Crushed stones (2-5 mm) 279

[0240] Throughout examples 1 to 39, retarder 7 of WO 2019/077050 was used as glyoxylic acid urea polycondensate (GA UC).

[0241] In examples 40 to 45, the glyoxylic acid bisulfite adduct (GA BA) was used, the production of which is described in WO 2017/212045, additive 1.

Mixing Procedure

[0242] The crushed stones were dried in an oven at 70° C. for 50 h. Sands were dried in an oven at 140° C. for 68 h. Afterwards, the crushed stones and sands were stored at 20° C. for at least 2 d at 65% relative humidity. A glyoxylic acid urea polycondensate, sodium gluconate, NaHCO.sub.3 and a polycarboxylate based superplasticizer (Master Suna SBS 8000, available from Master Builders Solutions Deutschland GmbH) were added to the total amount of mixing water, to obtain a liquid aqueous component. Subsequently, crushed stones, sands, cementitious binder, anhydrite (CAB 30, available from Lanxess) and limestone were added to a 5 L Hobbart mixer. The liquid aqueous component was added thereto and the mixture was stirred for 2 min at level 1 (107 rpm) and for further 2 min at level 2 (198 rpm) to obtain an aqueous construction composition.

Testing Procedure—Mini-Slump

[0243] The used procedure is analogous to DIN EN 12350-2, with the modification that a mini-slump cone (height: 15 cm, bottom width: 10 cm, top width: 5 cm) was used instead of a conventional Abrams cone. 2 L of the aqueous construction composition were filled into the mini-slump cone. The cone was filled completely immediately after mixing. Afterwards, the cone was placed on a flat surface, and lifted, and the slump of the mortar mix was measured. The slump of all mixes was adjusted to 11 cm by adjusting the dosage of the superplasticizer to allow for comparability. The dosage of the superplasticizer was in the range of 0.11 to 0.22 wt.-% (dosage calculated as active substance).

Testing Procedure—Early Strength Development

[0244] The adjusted mortar mixes were each filled into mortar steel prisms (16/4/4 cm), and after 3 h at a temperature of 20 ° C. and relative humidity of 65%, a hardened mortar prism was obtained.

[0245] The hardened mortar prism was demolded and compressive strength was measured according to DIN EN 196-1.

Reference Example: Calcium Aluminate Precipitation-Inhibiting Properties of Polyols

[0246] Various polyols were assed for their precipitation-properties in the calcium aluminate precipitation test. The results are shown in the table that follows. For the control, 400 mL of bidestilled water was used instead of 400 mL of a 1 wt.-% aqueous solution of a polyol. The titration endpoint, expressed as the maximum calcium concentration (as Ca.sup.2+) before the onset of turbidity, is calculated from the elapsed time to the onset point. FIG. 1 shows a plot of the photo current signal in mV against the time of dosage of CaCl2. Curve a) of FIG. 1 shows the results in the absence of a polyol (“blank”). Curve b) of FIG. 1 shows the results for addition of 1% of triethanolamine. For curve b), a first tangent 1, referred to as “baseline tangent”, and a second tangent 2 are shown. From the baseline tangent 1 and the second tangent 2, the onset point in s may be determined as the intersection of the baseline tangent 1 with the second tangent 2.

TABLE-US-00002 control (without ethylene triethanol- Polyol polyol) glycol glycerol amine erythrit Onset point [s] 42 42 64 500 686 Ca endpoint 59 59 93 682 924 [ppm]

Preparation and Evaluation of Construction Compositions

[0247] Examples 1 to 15 (table 1) illustrate the impact of the total amount of available aluminate, i.e. available aluminate from the cementitious binder and the optionally present extraneous aluminate source, as well as the impact of glycerol, on early strength development. For examples 1 to 15, the following specifications apply: [0248] ratio of water to cementitious binder=0.37 [0249] NaHCO.sub.3=0.37 wt.-% [0250] sodium gluconate=0.077 wt.-% [0251] glyoxylic acid urea polycondensate=0.4 wt.-% (calculated as active substance) [0252] anhydrite=10 wt.-%

[0253] The amount of available aluminate in the cementitious binder was determined by Rietveld refinement of an X-ray diffraction (XRD) powder pattern. Only the mineral phases C3A and C4AF were assessed.

TABLE-US-00003 TABLE 1 total mol Al(OH).sub.4— per ratio of compressive cementitious 100 g of cementitious Al(OH).sub.4— glycerol strength after # binder binder to (SO.sub.4).sup.2— [wt.-%] 3 h [MPa]  1 Colacem Gubbio 0.076 0.77 0.5 4 CEM | 2.5 R  2 Colacem Gubbio 0.076 0.77 1.5 16 CEM | 52.5 R  3 Couvrot 0.084 0.84 0.5 5 CEM | 52.5 R  4 Couvrot 0.084 0.84 1.0 0 20 CEM | 52.5 R  5 Mergelstetten 0.088 0.87 0.5 10 CEM | 42.5 N  6 .sup.[1] Mergelstetten 0.088 0.87 0.5 11 CEM | 42.5 N  7 Karlstadt 0.092 0.80 0.5 19 CEM | 42.5 R  8* Gaurain 0.064 0.70 0 0 CEM | 52.5 R  9 Gaurain 0.064 0.70 0.5 2 CEM | 52.5 R 10 Gaurain 0.064 0.70 1.0 5 CEM | 52.5 R 11 Gaurain 0.083 .sup.[2] 0.91 1.0 7 CEM | 52.5 R 12 Gaurain 0.102 .sup.[3] 1.12 1.0 15 CEM | 52.5 R 13 Gaurain 0.102 .sup.[3] 1.12 1.5 21 CEM | 52.5 R 14 Aalborg White 0.060 .sup.[4] 0.62 1.5 5 CEM | 52.5 R 15* Aalborg White 0.022 0.23 1.5 0 CEM | 52.5 R *comparative example .sup.[1] The composition of example 6 did not comprise sodium gluconate. .sup.[2] = 0.064 mol aluminate/100 g cementitious binder + 0.019 mol additional aluminate/100 g cementitious binder from extraneous 1.5 wt.-% Al(OH).sub.3 .sup.[3] = 0.064 mol aluminate/100 g cementitious binder + 0.038 mol additional aluminate/100 g cementitious binder from extraneous 3.0 wt.-% Al(OH).sub.3 .sup.[4] = 0.022 mol aluminate/100 g cementitious binder + 0.038 mol additional aluminate/100 g cementitious binder from extraneous 3.0 wt.-% Al(OH).sub.3

[0254] Examples 16 to 26 (table 2) illustrate the impact of the molar ratio of total available aluminate to sulfate on early strength development. For examples 16 to 26, the following specifications apply: [0255] ratio of water to cementitious binder=0.37 [0256] NaHCO.sub.3=0.37 wt.-% [0257] sodium gluconate=0.077 wt.-% [0258] glyoxylic acid urea polycondensate=0.4 wt.-% (calculated as active substance) [0259] glycerol=0.5 wt.-%

TABLE-US-00004 TABLE 2 total mol Al(OH).sub.4— per ratio of compressive compressive 100 g of Al(OH).sub.4— open strength strength cementitious cementitious anhydrite to time after 3 h after 24 h # binder binder [wt.-%] (SO.sub.4).sup.2— [min] [Mpa] [Mpa] 16 Mergelstetten 0.088 5.0 1.11 n.d. 6 n.d. CEM | 42.5 N 17 Mergelstetten 0.088 10.0 0.76 n.d. 9 n.d. CEM | 42.5 N 18 Mergelstetten 0.088 12.5 0.66 n.d. 12 n.d. CEM | 42,5 N 19 Mergelstetten 0.088 15.0 0.58 n.d. 12 n.d. CEM | 42.5 N 20 Mergelstetten 0.088 20.0 0.46 n.d. 10 n.d. CEM | 42.5 N 21 Karlstadt 0.092 5.0 1.16 55 12 24 CEM | 42.5 R 22 Karlstadt 0.092 10.0 0.80 50 19 29 CEM | 42.5 R 23 Karlstadt 0.092 12.5 0.69 50 20 36 CEM | 42.5 R 24 Karlstadt 0.092 15.0 0.61 45 17 36 CEM | 42.5 R 25 Karlstadt 0.092 20.0 0.50 40 13 28 CEM | 42.5 R 26 Karlstadt 0.130 .sup.[1] 20.0 0.69 n.d. 21 (after 1 n.d. CEM | 42.5 R h) 26 (after 3 h) * n.d. = not determined .sup.[1] = 0.092 mol aluminate/100 g cementitious binder + 0.038 mol additional aluminate/100 g cementitious binder from extraneous 3.0 wt.-% Al(OH).sub.3

[0260] Examples 27 to 30 (table 3) illustrate the impact of the ratio of water to cementitious binder on early strength development. For examples 27 to 30, the following specifications apply: [0261] NaHCO.sub.3=0.37 wt.-% [0262] sodium gluconate=0.077 wt.-% [0263] glyoxylic acid urea polycondensate=0.4 wt.-% (calculated as active substance) [0264] glycerol=2.0 wt.-% [0265] anhydrite=10 wt.-%

TABLE-US-00005 TABLE 3 total mol Al(OH).sub.4.sup.− per 100 g of ratio of water compressive cementitious cementitious to cementitious strength after # binder binder binder 3 h [Mpa] 27 Couvrot CEM | 52.5 R 0.085 0.37 20 28 Couvrot CEM | 52.5 R 0.085 0.30 33 29 Gaurain CEM | 52.5 R 0.064 0.37 9 30 Gaurain CEM | 52.5 R 0.064 0.30 22

[0266] The open time for mortar mixes 1 to 30 was in each case at least 20 min. The open time may be further adjusted by incorporation of an α-hydroxy monocarboxylic acid salt, as is evident from the comparison of example 5 (open time 60 min) and example 6 (open time 30 min).

[0267] For examples 31 to 37 (table 4), the following specifications apply: [0268] anhydrite (CAB 30)=15 wt.-% [0269] Al(OH).sub.4.sup.−/(SO.sub.4).sup.2−ratio=0.61 [0270] ratio of water to cementitious binder=0.37 [0271] glyoxylic acid urea polycondensate=0.5 wt.-% (calculated as active substance) [0272] Na.sub.2CO.sub.3=0.90 wt.-%

TABLE-US-00006 TABLE 4 open compressive compressive cementitious dosage time strength after strength after # binder polyol [wt.-%] [min] 3 h [MPa] 24 h [MPa] 31 Karlstadt — — 60 3 n.d.* CEM | 42.5 R 32 Karlstadt sucrose 0.3 60 8 10 CEM | 42.5 R 33 Karlstadt sucrose 0.9 30 12 n.d. CEM | 42.5 R  34* Karlstadt ethylene 0.5 100 4  7 CEM | 42.5 R glycol 35 Karlstadt triethanol- 0.5 65 16 20 CEM | 42.5 R amine 36 Karlstadt glycerol 0.5 70 15 22 CEM | 42.5 R 37 Karlstadt erythrit 0.5 65 20 26 CEM | 42.5 R n.d. = not determined *comparative example

[0273] Examples 38 to 45 (table 5) illustrate the impact of the carbonate source and the glyoxylic acid bisulfite adduct on early strength development. For examples 38 to 45, the following specifications apply: [0274] ratio of water to cementitious binder=0.37 [0275] ettringite formation controller=0.4 wt.-%, calculated as active substance [0276] sodium gluconate=0.077 wt.-% [0277] glycerol=0.5 wt.-%

TABLE-US-00007 TABLE 5 total mol Al(OH).sub.4— per ratio of ettringite dosage compressive compressive 100 g of Al(OH).sub.4— formation dosage carbonate of d) open strength strength cementitious cementitious anhydrite to controller of d) (i) source d) (ii) time after 3 h after 24 h # binder binder [wt.-%] (SO.sub.4).sup.2— d) (i) [wt.-%] (ii) [wt.-%] [min] [MPa] [MPa] 38* Karlstadt 0.092 15.0 0.61 GA UC 0.4 — — 10 10 22 CEM | 42.5 R 39  Karlstadt 0.092 15.0 0.61 GA UC 0.4 propylene 0.37 95 15 23 CEM | 42.5 R carbonate 40  Karlstadt 0.092 5.0 1.16 GA BA 0.4 NaHCO.sub.3 0.37 25 11 19 CEM | 42.5 R 41  Karlstadt 0.092 10.0 0.80 GA BA 0.4 NaHCO.sub.3 0.37 20 16 28 CEM | 42.5 R 42  Karlstadt 0.092 15.0 0.61 GA BA 0.4 NaHCO.sub.3 0.37 20 13 22 CEM | 42.5 R 43  Karlstadt 0.092 5.0 1.16 GA BA + 0.36 + NaHCO.sub.3 0.37 25 11 18 CEM | 42.5 R CA .sup.[1] 0.04 44  Karlstadt 0.092 10.0 0.80 GA BA + 0.36 + NaHCO.sub.3 0.37 20 15 30 CEM | 42.5 R CA .sup.[1] 0.04 45  Karlstadt 0.092 15.0 0.61 GA BA + 0.36 + NaHCO.sub.3 0.37 15 17 24 CEM | 42.5 R CA .sup.[1] 0.04 .sup.[1] CA = citric acid