Hydration control mixture for mortar and cement compositions

Abstract

The present invention relates to a mixture comprising at least one compound comprising an -hydroxy-carboxylic unit, -hydroxy-sulfonic acid unit or -carbonyl-carboxylic unit and at least one water-soluble organic carbonate. The mixture is useful as a hydration control agent in construction chemical compositions comprising an inorganic binder.

Claims

1. A construction chemical composition, comprising: a) a mixture comprising A) at least one compound of formula I: ##STR00019## wherein R1 is OH; R2 is H, OH, C.sub.1-C.sub.6 alkoxy, SO.sub.2, X-SO.sub.3X, OSO.sub.3X, PO.sub.3X.sub.2, COOX, OPO.sub.3X.sub.2, ZCOOX or CH(OH)SO.sub.3X; R3 is H, C.sub.1-C.sub.6 alkyl which may be substituted by 1 or 2 OH or C.sub.1-C.sub.6 alkoxy; m is 0 or 1; or R1 and R2 taken together with the carbon atom to which they are attached form a carbonyl group provided m is 0; R4 is COOY or SO.sub.3X; X is selected from H or a cation equivalent K.sub.a wherein K is selected from an alkali metal, alkaline earth metal, zinc, iron, ammonium or phosphonium cation and a is l/n wherein n is the valency of the cation; Y=is selected from X, C.sub.1-C.sub.6 alkyl or phenyl; and Z is CH.sub.2 or CH(OH), and B) at least one water-soluble organic carbonate; and b) at least one inorganic binder selected from the group consisting of calcium sulfate hemihydrate, anhydrite, and aluminate-containing cements, wherein a content of a) is 0.01 wt % to 5.0 wt % by weight of b).

2. The construction chemical composition of claim 1, wherein m is 0 and R2 is OH.

3. The construction chemical composition of claim 1, wherein R2 is COOX.

4. The construction chemical composition of claim 1, wherein R3 is H.

5. The construction chemical composition of claim 1, wherein R4 is COOX.

6. The construction chemical composition of claim 1, wherein a) m is 0, R2 is SO.sub.3X and R4 is COOX; b) m is 0, R2 is COOX and R4 is COOX; c) m is 0, R2 is ZCOOX and Z is CH.sub.2 and R4 is COOX; d) m is 0, R2 is ZCOOX and Z is CH(OH) and R4 is COOX; e) m is 0; R1 and R2 taken together with the carbon atom to which they are attached form a carbonyl group and R4 is COOX; f) m is 0; R1 and R2 taken together with the carbon atom to which they are attached form a carbonyl group and R4 is SO.sub.3X; or g) m is 0; R2 is CH(OH)SO.sub.3X, and R4 is SO.sub.3X.

7. The construction chemical composition of claim 6, wherein in and R2 are as defined in a) to g) and R3 is H.

8. The construction chemical composition of claim 1, wherein Y is X.

9. The construction chemical composition of claim 1, wherein the water-soluble carbonate is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, trimethylene carbonate, glycerol carbonate, dimethyl carbonate, and di(hydroxyethyl)carbonate.

10. The construction chemical composition of claim 9, wherein the water-soluble carbonate is ethylene carbonate, propylene carbonate or a mixture thereof.

11. The construction chemical composition of claim 1, wherein a weight ratio of component A) to component B) is in the range from 100:1 to 1:100.

12. The construction chemical composition of claim 1, additionally comprising at least one additive.

13. The construction chemical composition of claim 12, wherein the additive is at least one selected from the group consisting of inorganic carbonates, alkali metal sulfates, latent hydraulic binders, dispersants, and fillers.

14. The construction chemical composition of claim 13, wherein the additive is at least one inorganic carbonate.

15. The construction chemical composition of claim 14, wherein the inorganic carbonate is at least one selected from the group consisting of sodium carbonate, potassium carbonate, lithium carbonate, magnesium carbonate, calcium carbonate, and calcium-magnesium carbonate.

16. The construction chemical composition of claim 13, wherein the additive is at least one polymeric dispersant.

17. The construction chemical composition of claim 16, wherein the dispersant is a sulfonic acid and/or sulfonate group containing dispersant selected from the group consisting of lignosulfonates, melamine formaldehyde sulfonate condensates, -naphthalene sulfonic acid condensates, sulfonated ketone-formaldehyde-condensates, and copolymers comprising sulfa group containing units and/or sulfonate group-containing units and carboxylic acid and/or carboxylate group-containing units.

18. The construction chemical composition of claim 1, wherein the aluminate-containing cement is at least one selected from the group consisting of CEM cement and aluminate cement.

19. The construction chemical composition of claim 18, wherein the aluminate-containing cement is CEM cement.

20. The construction chemical composition of claim 18, wherein the aluminate-containing cement is a mixture of CEM cement and alumni, to cement or a mixture of CEM cement, high alumina cement and sulfoaluminate cement.

21. The construction chemical composition of claim 18, additionally comprising a calcium sulfate.

22. The construction chemical composition of claim 12, wherein the additive is at least one selected from the group consisting of inorganic carbonates, alkali metal sulfates, latent hydraulic binders, dispersants, hardening accelerators, fillers, essentially aluminate-free cement, and aggregates.

23. A method, comprising employing the construction chemical composition according to claim 1 as a retarder for aluminate-containing building material formulations and/or for producing building products.

Description

EXAMPLE 1

(1) Mortar Mix

(2) For application tests a dry mortar was mixed based on the components summarized in Table 4:

(3) TABLE-US-00005 TABLE 4 Mortar mix Type Component Weight (g) Binder Cement A 492.75 Binder Fondu 54.75 Binder -hemihydrate 21.90 Filler Quartz sand (0.1-0.3 mm) 652.13 Filler Limestone powder 300.00 Water 300.00

(4) The additives according to the invention or for comparative purposes were added to the mortar mix given in Table 4. The additives were dissolved in the batching water before mixing the mortar.

(5) The mixing was done according to following procedure: 1. Water (contains additives depending on the example) is added to the mixing vessel 2. Dry component is added to the water 3. Mixer (Toni Technik) is started and initial stirring is carried out for 1 min at mixing power 2 4. Stop mixing for 30 s 5. Start mixer again for 1 min at mixing power 2 6. Total stirring time: 2 min

(6) For characterization of the mortars different parameters were determined: 1. The setting time was determined according to the standard DIN EN 196-3. Begin of setting and final setting was determined with a 300 g needle (0.5 mm.sup.2) at 23 C./50% relative humidity. 2. Compressive strength after 24 h: Fresh mortar is filled into a polystyrene form to produce 4416 cm mortar prisms. The form is covered for 24 h and is stored at 23 C./50% relative humidity. After 24 h the compressive strength is measured on the prisms. 3. Surface hardness: Surface hardness is determined by Shore D measurement at 4 h, 5 h, and 6 h after mixing the dry components with water. The measurements are performed on samples which have a thickness of 5 mm and which were filled into a form directly after mixing. 4. For flowable mortar the initial flow of the mortar after mixing and the flow 10 min after mixing is determined according to DIN EN 12706. For determination of the flow after 10 min the mortar is filled into the cone directly after mixing. The mortar is not homogenized before determination of the flow value after 10 min.

(7) 1.1 Mortar with Non Flowable Properties

(8) The formulation of table 4 was modified by addition of a mixture according to the invention by weight of the sum of dry components in table 4. For the dosage of component a) and the ethylene carbonate the inventive mixture 6 was the starting point. The dosage of component a1 and ethylene carbonate was chosen to achieve an initial setting after 30 min5 min. This behavior is achieved at a dosage of 0.1 wt.-% for component a1 and ethylene carbonate. For comparison this dosage was chosen for mixtures 1 to 6 and 32 to 33. For mixture 30 and 31, the dosage of tartaric acid (component a3) was reduced by 50% compared to component a1 due to the known high efficiency of tartaric acid. The results are given in table 6.

(9) Composition 1 is the blank mortar formulation from table 4 without any further additive. The strength after 24 hours achieves the target value but the initial setting occurs after 148 min which is later as the target. Additionally the Shore D values are smaller as required.

(10) Compositions 2 and 3 represent a mortar formulation which contains only one component of the mixture according to the invention (ethylene carbonate or glyoxylic acid derivate). The different properties are close to the value of example 1.

(11) Compositions 4, 30, 32 and 33 are comparative experiments with the state of the art accelerators tartaric acid and citric acid.

(12) TABLE-US-00006 TABLE 5 Addition of additives to the mortar formulation given in table 4 (values are given in wt.-% by weight of the sum of dry components in the mortar mix according to table 4) Component Component Component Citric Ethylene a1 a2 a3 acid carbonate Composition Type (%) (%) (%) (%) (%) 1 Ref 0 0 2 Ref 0.1 0 3 Ref 0 0.1 30 Ref 0 0 0.05 0 31 Inv 0 0 0.05 0.1 4 Ref 0 0.1 0 32 Ref 0.1 0 33 Ref 0.1 0.1 6 Inv 0.1 0.1 7 Inv 0.2 0.2 8 Inv 0.1 0.2 9 Inv 0.2 0.1 10 Inv 0.075 0.1 11 Inv 0.15 0.2 Ref: Reference example Inv: Example according to the invention

(13) TABLE-US-00007 TABLE 6 Result for non flowable mortar test based on mortar formulations given in table 5: Initial Final Setting 24 h Shore Shore Shore Compo- Setting Setting Time CS D D D sition Type (min) (min) (min) (MPa) 4 h 5 h 6 h 1 Ref 148 174 26 23.5 11 17 25 2 Ref 157 182 25 22.4 11 25 28 3 Ref 117 152 35 22.3 14 27 28 30 Ref 20 36 16 20.5 20 22 24 31 Inv 51 69 18 17.0 33 35 42 4 Ref 69 77 8 5.61 26 34 36 32 Ref 29 40 11 4.9 23 29 32 33 Inv 122 148 26 12.7 20 25 32 6 Inv 28 37 9 22.3 22 27 30 7 Inv 106 126 20 22.5 15 21 32 8 Inv 28 38 10 20.5 28 32 37 9 Inv 39 52 13 20.6 32 36 40 10 Inv 18 27 9 21.1 28 33 37 11 Inv 42 57 15 23.4 36 38 42 CS: Compressive strength

(14) A comparison of Compositions 2, 3 and 6 shows that the composition 6 of the invention provides a significantly reduced but sufficient open time and a significantly reduced setting time. Further, it provides a shorter strength development as can be seen from the Shore D values.

(15) A comparison of Compositions 33 and 6 shows that the composition 6 of the invention provides a significantly reduced but sufficient open time and a significantly reduced setting time. Further, it provides a significantly increased 24 h compressive strength.

(16) A comparison of compositions 4 and 31 shows that the beginning of setting is comparable. However, development of strength is increased when using the inventive hydration control mixture comprising component a1 and b) ethylene carbonate.

(17) 1.2 Mortar with Flowable Properties:

(18) The formulation of table 4 was modified by addition of a mixture according to the invention. The aim was to provide a mortar which shows an initial setting after 40 min to 140 min and a compressive strength of >15 MPa after 24 hours. Further, a shore D value of >25 should be achieved after 6 hours. In addition, the flowable mortar should achieve an initial flow of >10 cm and the flow after 10 min should be also >10 cm. The final formulations with addition of retarder and plasticizer are summarized in table 7. The results are given in table 8.

(19) The compositions according to the invention fulfill the requirements.

(20) TABLE-US-00008 TABLE 7 Formulations for flowable mortar (values are given in wt.-% by weight of the sum of dry components in the mortar mix according to table 4) Component Component Ethylene a1 a2 carbonate Disper- Disper- Disper- Composition Type (%) (%) (%) sant 1 sant 2 sant 3 12 Ref 0.1 0 0.05 13 Ref 0.2 0 0.05 14 Ref 0 0.1 0.05 15 Ref 0 0.2 0.05 16 Ref 0 0 0.05 17 Inv 0.1 0.1 0.05 18 Inv 0.1 0.2 0.05 19 Inv 0.2 0.1 0.05 20 Inv 0.075 0.1 0.05 21 Inv 0.15 0.2 0.05 24 Inv 0.1 0.1 0.11 25 Inv 0.1 0.1 0.16 26 Inv 0.1 0.1 0.23 23 Ref 0.05

(21) TABLE-US-00009 TABLE 8 Result for flowable mortar test based on mortar formulations given in table 4: Initial flow F.sub.i Flow after after 10 Flow Initial mixing min F.sub.10 F.sub.10-F.sub.i Setting Final Set- Setting 24 h CS Shore Shore Shore Composition Type (cm) (cm) (cm) (min) ting (min) Time (min) (MPa) D 4 h D 5 h D 6 h 12 Ref 10 5 5 40 50 10 25.1 19 21 24 13 Ref 17.7 5 12.7 28 37 9 24.1 24 28 33 14 Ref 7.5 5 2.5 52 65 13 25.2 18 20 24 15 Ref 6.7 5 1.7 39 50 11 24.9 25 29 34 16 Ref 6.9 5 1.9 176 200 24 24.9 10 15 24 17 Inv 15.2 13.1 2.1 51 67 16 22.2 25 30 34 18 Inv 13 10.4 2.6 112 135 23 18.4 12 20 28 19 Inv 13.5 12.7 0.8 82 115 33 17.6 18 26 36 20 Inv 17.6 16.0 1.6 62 79 17 18.2 28 33 35 21 Inv 18.7 16.4 2.3 136 169 33 17.0 12 30 38 24 Inv 10.3 9.0 1.3 43 58 15 18.4 22 30 35 25 Inv 12.4 11.6 0.8 50 64 14 19.4 23 28 32 26 Inv 15.3 16.6 1.3 57 72 15 20 22 27 32 23 Ref 6.1 5.0 1.1 172 192 20 22.3 8 13 18

EXAMPLE 2

Self Leveling Underlayment (SLU)

(22) The mixtures according to the invention were used for a composition of a self leveling underlayment (SLU). The compositions of the different mortars are summarized in table 9:

(23) TABLE-US-00010 TABLE 9 Mortar composition for a SLU composition (values are given in wt.-% by weight of the sum of mortar components). Composition SLU1 SLU2 SLU3 Type Inv Ref Inv Component (%) (%) (%) Cement A 31.59 31.59 31.59 Fondu 3.51 3.51 3.51 -hemihydrate 1.40 1.40 1.40 Limestone powder 19.23 19.23 19.23 Quartz sand H33 41.91 41.98 41.91 Latex Powder 2.00 2.00 2.00 Dispersant 1 0.045 0.045 0.045 Ethylene carbonate 0.086 0.086 Component a1 0.086 0.086 Component a3 (tartaric acid) 0.100 Dispersant 4 0.040 0.040 Dispersant 5 0.040 Diutan Gum 0.040 0.040 0.040 Defoamer 0.064 0.064 0.064 Sum mortar components 100.00 100.00 100.00 Water 20.00 20.00 20.00

(24) The water content relates to the total sum of mortar components given in table 9.

(25) The dry compositions given in table 9 were mixed with the amount of water (given in table 9) according to EN 1937 (mixing procedure with waiting time).

(26) TABLE-US-00011 Mixing procedure: (Mortar mixer according EN196-1) Time after start Duration Description 000 000-020 20 s Addition of powder and dispersants to the water 020-120 60 s Stirring (140 U/min) 120-140 20 s Clean mixer and bowl 140-240 60 s Stirring (285 U/min) 240-740 300 s Ripening time 740-755 15 s Stirring (285 U/min)

(27) TABLE-US-00012 TABLE 10 Results of mortar testing of compositions from table 9 Composition SLU1 SLU2 SLU3 Test method Unit Inv Ref Inv Flow after (according DIN EN 12706) 8 min cm 16.1 15.9 16.2 15 min cm 15.9 15.3 16.1 30 min cm 13.0 13.7 14.0 45 min cm 7.2 7.0 10.4 60 min cm 3.0 3.0 3.0 Setting (according to DIN EN 196-3) Initial Setting min 111 114 100 Final Setting min 142 152 131 Shore D (according to DIN 53505) 3 h 13 8 18 4 h 19 16 22 5 h 20 20 26 6 h 21 23 30 7 h 26 26 36 8 h 27 29 36 Compressive strength after (according to DIN EN 196-1) 1 d MPa 10.9 4.1 10.4 2 d MPa 19.9 11.0 19.3 7 d MPa 38.1 31.1 37.3 28 d MPa 41.8 32.7 43.4

(28) SLU2 is a comparative example with tartaric acid as prior art retarder. The dosage of the hydration control mixture according to the invention comprising component a1 and ethylene carbonate in the example SLU1 was adapted to achieve an initial setting which is comparable to SLU2. Whereas the Shore D development is comparable in SLU1 and SLU2 the strength after 24 h and 48 h is very different between SLU 1 and SLU2: In SLU1 the compressive strength after 24 h and 48 h with the hydration control mixture according to the invention is much higher compared to SLU2.

(29) Compositions SLU4 to SLU11

(30) These examples were designed to show the synergistic effect of the mixture of the invention and the surprising advantage of the compositions of the invention over the prior art composition known from WO 00/14026 A2 and EP 650 940 A1. The constituents of the tested compositions are given in table 11 and the test results are given in table 12.

(31) TABLE-US-00013 TABLE 11 Dry mortar formulations for SLU Composition SLU4 SLU5 SLU6 SLU4 R SLU5R SLU6R SLU11 Type Inv Inv Ref Ref Ref Ref Ref Component (%) (%) (%) (%) (%) (%) (%) Cement A 31.59 31.59 31.59 31.59 31.59 31.59 31.59 Fondu (HAC) 3.51 3.51 3.51 3.51 3.51 3.51 3.51 -hemihydrate 1.4 1.4 1.4 1.4 1.4 1.4 1.4 Limestone powder 19.23 19.23 19.23 19.23 19.23 19.23 19.23 Quartz sand H33 41.91 41.98 41.91 41.98 41.91 41.98 41.98 Latex Powder 2 2 2 2 2 2 2 Dispersant 1 0.027 0.027 0.027 0.027 0.027 0.027 0.027 Ethylene 0.025 0.025 0.025 carbonate Sodium Carbonate 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Component a1 0.08 0.08 Lithium Carbonate Citric Acid 0.14 0.14 Component a3 0.041 0.041 (tartaric acid) Dispersant 4 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Diutan Gum 0.04 0.04 0.04 0.04 0.04 0.04 0.04 Defoamer (Vinapor 0.064 0.064 0.064 0.064 0.064 0.064 0.064 DF9010) Sum mortar 100 100 100 100 100 100 100 components Water 20 20 20 20 20 20 20

(32) TABLE-US-00014 TABLE 12 Results of mortar testing of compositions from table 11 Composition SLU4 SLU5 SLU6 SLU4 R SLU5 R SLU6 R SLU11 Test method Unit Inv Inv Ref Ref Ref Ref Ref Flow after (according to DIN EN 12706) 8 min cm 15.8 15.9 15 15.8 14.8 14.3 8 15 min cm 15.9 15.8 15.2 15.2 11.2 6.5 5.2 30 min cm 15.6 15.8 15.3 13 3.1 45 min cm 15.4 15.5 14.4 10.5 60 min cm 14.3 7.2 6.4 Setting (according to DIN EN 196-3) Initial Setting min 143 118 136 113 112 88 91 Final Setting min 163 140 169 141 122 134 176 Shore D (according to DIN 53505) 3 h 10 13 11 13 14 10 0 4 h 15 19 15 17 22 14 10 5 h 21 26 19 23 27 18 13 6 h 28 30 24 25 29 22 16 7 h 32 34 26 27 31 24 21 Compressive strength after (according to DIN EN 196-1) 1 d MPa 7.5 8 3.7 10.3 9.2 2.8 13.1 2 d MPa 15.3 16.1 10.4 n.d. n.d. n.d. n.d. 7 d MPa 30.9 31.6 31.6 n.d. n.d. n.d. n.d. 28 d MPa 42.8 44.2 41.2 n.d. n.d. n.d. n.d. n.d. = not determined

(33) TABLE-US-00015 TABLE 13 Dry mortar formulations for SLU Composition SLU7 SLU8 SLU9 SLU10 Type Inv Ref Ref Ref Component (%) (%) (%) (%) Cement A 31.59 31.59 31.59 31.59 Fondu (HAC) 3.51 3.51 3.51 3.51 -hemihydrate 1.4 1.4 1.4 1.4 Limestone powder 19.23 19.23 19.23 19.23 Quartz sand H33 41.98 41.91 41.98 41.98 Latex Powder 2 2 2 2 Dispersant 1 0.027 0.027 0.027 0.027 Ethylene carbonate 0.025 Sodium Carbonate 0.1 0.1 Component a1 0.08 0.1 0.15 Lithium Carbonate 0.1 0.1 Citric Acid Component a3 (tartaric acid) Dispersant 4 0.05 0.05 0.05 0.05 Diutan Gum 0.04 0.04 0.04 0.04 Defoamer (Vinapor DF9010) 0.064 0.064 0.064 0.064 Sum mortar components 100 100 100 100 Water 20 20 20 20

(34) TABLE-US-00016 TABLE 14 Results of mortar testing of compositions from table 13 Composition SLU7 SLU8 SLU9 SLU10 Test method Unit Inv Ref Ref Ref Flow after (according to DIN EN 12706) 8 min cm 15.8 7.8 15.9 15 15 min cm 15.8 6.1 15.6 13.7 30 min cm 15.7 3.7 13.5 5.2 45 min cm 14.7 0 11.5 0 60 min cm 11.8 0 8.8 0 Setting (according to DIN EN 196-3) Initial Setting min 140 158 132 57 Final Setting min 172 296 152 67 Shore D (according to DIN 53505) 3 h 10 0 0 18 4 h 17 0 15 24 5 h 28 0 21 27 6 h 37 11 27 29 7 h 44 17 29 31 Compressive strength after (according to DIN EN 196-1) 1 d MPa 8.3 11.3 9.3 8.6

(35) Compositions SLU 4R to 6R are the corresponding references to compositions SLU 4 to 6 without use of ethylene carbonate. Without ethylene carbonate the compositions show insufficient flow behavior over time; without ethylene carbonate in the compositions the time until the flow is sufficient is strongly reduced at similar early strength development (measured by Shore D).

(36) Compositions SLU 4 to 6 are a comparison of mixtures according to the invention (SLU 4, 5) with a prior art mixture. As can be seen, the mixtures of the invention provide surprising advantages with regard to flow and 1 d and 2 d compressive strength.

EXAMPLE 3

(37) 3.1 CR0 to CR6: Pure Portland Cement Based Cementitious Formulation for Render

(38) The following mortar compositions were used for the experiment which is reflecting a formulation of a sag resistant mortar for wall application (for example a cementitious render). They are given in table 15, the results are given in table 16.

(39) TABLE-US-00017 TABLE 15 Mortar Composition (values in wt.-% by weight of the sum of moartar components) Composition CR0 CR1 CR2 CR3 CR4 CR5 CR6 Type Ref Inv Inv Inv Ref Ref Ref Components Cement B 20.00 20.00 20.00 20.00 20.00 20.00 20.00 Quartz sand 0.3-1.0 mm 69.90 69.70 69.60 69.50 69.875 69.85 69.82 Limestone Powder 10.00 10.00 10.00 10.00 10.00 10.00 10.00 Cellulose Ether 0.07 0.07 0.07 0.07 0.07 0.07 0.07 Foaming agent 0.03 0.03 0.03 0.03 0.03 0.03 0.03 Ethylene Carbonate 0.10 0.15 0.20 Component a1 0.10 0.15 0.20 Component a3 (tartaric 0.025 0.05 0.08 acid) Sum mortar component 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Water 15.5 15.5 15.5 15.5 15.5 15.5 15.5

(40) The water content relates to the total sum of all mortar components given in table 13.

(41) The mortar was mixed in a Rilem Mixer (Toni Technik) at mixer speed 65 rpm for 60 s. The setting time was determined at 23 C. by Vicat cone (weight 100 g) and the strength development was measured by an ultrasonic measuring device. The results are summarized in table 14.

(42) TABLE-US-00018 TABLE 16 Results of mortar test Composition CR0 CR1 CR2 CR3 CR4 CR5 CR6 Type Ref Inv Inv Inv Ref Ref Ref Initial Setting 302 378 123 188 22 63 354 (min) Final Setting 425 577 133 211 27 73 419 (min) Time of reaching defined ultrasonic velocity (h) Velocity 200 m/s 4.1 0.9 1.8 3.0 0.2 0.9 4.9 Velocity 500 m/s 6.7 12..0 2.1 3.4 0.6 1.0 5.9 Velocity 1200 11.8 19.1 19.8 23.0 n.d. n.d. n.d. m/s n.d.not achieved on 24 h

(43) The results show that the inventive mixtures lead to a long open time (CR1 and CR3) but the final strength formation can nevertheless be achieved whereas in the retarded system with tartaric acid (CR4-CR6) the final strength (ultrasonic speed at 1200 m/s) is not achieved within 24 hours. The ultrasonic velocity reflects the formation of strength. The velocity increases if water is resorbed in the system under formation of hydrate phases. In comparable mortars the ultrasonic velocity correlates with strength, that means if a special ultrasonic velocity is achieved in different mixtures the strength in both mixtures at this time is comparable. The method of ultrasonic measurement is described in DIN EN 12504-4.

(44) 3.2 CR7 to CR13: Render Mortar Systems

(45) The composition of the render systems is given in table 17. The dosage was adapted to achieve an initial stiffening time (100 g cone) of 60 min10 min according to DIN EN 13279-2.

(46) TABLE-US-00019 TABLE 17 Mortar Composition (values in wt.-% by weight of the sum of mortar components) Composition CR7 CR8 CR9 CR10 CR11 CR12 CR13 Type Ref. Inv Ref Ref Inv Ref Ref Components Cement B 20.00 20.00 20.00 20.00 20.00 20.00 20.00 Quartz sand 0.3-1.0 mm 69.92 69.86 69.91 69.91 69.90 69.89 69.90 Limestone Powder 10.00 10.00 10.00 10.00 10.00 10.00 10.00 Cellulose Ether 0.07 0.07 0.07 0.07 0.07 0.07 0.07 Foaming agent 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Ethylene Carbonate 0.17 0.17 0.17 0.17 Component a1 0.17 Component a3 (tartaric 0.07 0.07 acid) Citric Acid 0.11 0.11 Sum mortar 100.00 100.00 100.00 100.00 100.00 100.00 100.00 component Water 15.5 15.5 15.5 15.5 15.5 15.5 15.5

(47) CR8 is a system according to the invention. CR9 and CR10 are presenting comparative compositions showing the influence of fruit acids (tartaric acid and citric acid) on the system without addition of organic carbonate. The addition of the fruit acids was adapted on the performance to achieve an initial setting time of about 60 min. CR11 is an inventive composition showing the use of tartaric acid in combination with ethylene carbonate whereas CR12 is a comparative example with citric acid in place of component a1.

(48) Example CR13 shows the impact of ethylene carbonate alone.

(49) TABLE-US-00020 TABLE 18 Results of mortar test Experiment CR7 CR8 CR9 CR10 CR11 CR12 CR13 Type Ref. Inv Ref Ref Inv Ref Ref Initial Setting 234 74 61 71 57 205 215 (min) Final Setting 474 154 168 141 144 288 487 (min) Compressive strength (in MPa) After 24 h 1.7 2.1 <d.l. <d.l. <d.l. n.m. 1.7 Cumulated heat of hydration after 24 h HoH (J/g mortar) 30.4 23.8 8.8 9.1 13.6 18.9 28.4 <d.l.below detection limit (prisms are available but strength below detection limit n.m.not measureable (prism was too soft for measurement or was broken before measurement)

(50) CR9 and CR10 shows no strength formation after 24 h at the same setting behavior like inventive composition CR8 and the cumulated heat of hydration (which represents strength formation) is much lower compared to CR8.

(51) The combination of tartaric or citric acid with ethylene carbonate (CR11 and CR12) shows only in the case of CR11 a good setting behavior. CR12 is retarded too much resulting in a very low 24 h strength while heat of hydration is increased compared to inventive example CR11. Examples CR8 and CR11 show the surprisingly superior performance of the compositions of the invention over CR12 containing citric acid in place of component a1. This indicates that citric acid is disadvantageous in combination with organic carbonate. CR13 is a comparative example showing only the influence of ethylene carbonate: The 24 h strength is increased compared to the inventive examples but the setting behavior is much more different. The setting behavior is comparable to the mortar without additives (CR7) and hence does not fulfill the target of the invention.

EXAMPLE 4

Mortar with White Portland Cement

(52) An OPC based mortar was produced and investigated with a base composition according to following table 19.

(53) TABLE-US-00021 TABLE 19 Dyckerhoff White Cem I 42.5 R 400 Quartz sand 0.3-1.0 mm 500 Limestone Powder 100 Water 200

(54) The amount of quartz sand was reduced by the weight of the additives used in the different formulations. Values in table 18 are wt.-% by weight of sum of dry components (OPC+Quartz sand+Limestone powder+additives). The results are given in table 20.

(55) TABLE-US-00022 TABLE 20 Composition N3.1 N3.3 N3.4 N3.5 N3.9 N3.10 N3.8 N3.6 N3.7 Ref Comp Comp Comp Comp Comp Comp Comp Comp component a1 Ethylene carbonate Component a3 (tartaric 0.12 acid) Citric acid 0.16 CSA (Belith CS 10) 0.5 1 2 HAC (Kerneos Fondu) 0.5 1 2 Initial Set (300 g needle) 133 70 75 128 108 81 130 129 117 Final Set (300 g needle) 160 108 88 152 131 98 157 148 137 Compressive Strength 15.1 2.4 1.9 17.2 18.0 19.6 16.7 17.2 17.9 (6 h) Compressive Strength 22.3 16.8 28.2 25.6 28.1 30.0 25.5 29.1 27.5 (24 h) Composition N3.2 N3.11 N3.12 N3.13 N3.14 N3.15 N3.16 Inv Inv Inv Inv Inv Inv Inv Component a1 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Ethylene carbonate 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Component a3 (tartaric acid) Citric acid CSA (Belith CS 10) 0.5 1 2 HAC (Kerneos Fondu) 0.5 1 2 Initial Set (300 g needle) 59 60 55 48 63 59 56 Final Set (300 g needle) 68 67 61 54 67 64 62 Compressive Strength 12.7 15.2 16.0 18.6 13.6 15.5 16.7 (6 h) Compressive Strength 20.5 22.3 21.9 22.1 20.0 21.8 20.3 (24 h) CSA: calcium sulfoaluminate cement HAC: high alumina cement

(56) N3.1 to N3.4 show mortar without additional aluminate source (CSA). In N3.3 and N3.4 dosage of tartaric or citric acid was adapted to achieve an initial setting (300 g needle) after 60 min15 min. In comparison to inventive example N3.2 at comparable initial setting time the 6 h strength is reduced significantly.

(57) Examples N3.5, N3.9 and N3.10 are comparative examples for the addition of CSA cement to the mortar in different amounts. The addition of CSA cement reduces the setting time to earlier times compared to the reference N3.1. With the addition of component a1 and ethylene carbonate (N3.11 to N3.13) the initial setting can be further reduced to the target of 60 min15 min due to the controlled retardation of the initial aluminate reaction resulting from OPC and CSA. This control of setting time has an acceptable minor impact in 6 h compressive strength (is reduced only by 2 MPa). Additionally, the 6 h strength compared to the reference (mortar without additional aluminate source) is not negatively influenced. The 24 h strength is in the range of that one of the reference but the setting profile was changed in accordance with the goal of the invention.

(58) A comparable behavior is observed with HAC as additional aluminate source (comparative examples N3.6 to N3.8; inventive examples N3.14 to N3.16)

EXAMPLE 5

Repair Mortar

(59) Following example reflects a repair mortar formulation with flowable properties for floor application. The mortar should contain a good flow behavior over time (constant flow for one hour), fast setting after latest 2 hours and sufficient strength development (>10 MPa after 24 h). Inventive experiment RM2 shows sufficient slump flow over time compared to RM3 and increased compressive strength after 24 h compared to RM3. RM2 shows a wanted balanced hardening profile which enables good workability time (flow), fast setting and high early compressive strength after 24 h.

(60) Mixing Procedure of Mortar (According to DIN EN 196-1):

(61) TABLE-US-00023 Time after start Duration Description 000 000-020 20 s Addition of powder and additives to the water 020-220 120 s Stirring (140 U/min) 220-320 60 s Clean mixer and bowl 320-520 120 s Stirring (140 U/min)

(62) TABLE-US-00024 TABLE 21 Mortar Composition (values in wt.-% by weight of the sum of mortar components) Composition RM1 RM2 RM3 Type Ref. Inv Comp Components Cement B 30.0 30.0 30.0 GGBFS 3.5 3.5 3.5 Quartz sand 0.3-1.0 mm 53.1 69.9 69.9 Limestone Powder 13.0 13.0 13.0 Starvis S 5514 F 0.20 0.20 0.20 Dispersant 5 0.10 0.10 0.10 Defaomer Vinapor DF 9010 0.05 0.05 0.05 Starvis 3040 F 0.05 0.05 0.05 Propylene Carbonate 0.2 Component a1 0.2 Citric Acid 0.2 Sum mortar component 100.00 100.00 100.00 Water 17.0 17.0 17.0 Results of mortar tests Slump Flow(*.sup.1) (cm) after 5 min 16.9 28.4 24.8 15 min 14.0 27.8 19.2 30 min 12.0 29.2 11.1 45 min 11.3 27.8 10.4 60 min 10.8 25.2 10.0 75 min 10.6 22.0 10.0 90 min 10.5 18.0 10.0 Setting according to DIN EN 196-3 Initial Setting 100 g needle (min) 213 95 37 Final Setting 300 g needle (min) 316 100 51 Final Setting 1000 g needle (min) 422 103 53 Compressive strength after 24 h 17.9 13.4 3.9 according to DIN EN 196-1 (MPa) (*.sup.1)Slump flow was determined according to DIN EN 1015-3 with the Hagermann cone. The mortar was remixed for 10 s before measurement of flow.