Ternary hydraulic binder composition

Abstract

A ternary hydraulic binder composition including the mineralogical compound C.sub.4A.sub.3$ (ye'elimite) and a member selected from the group consisting of gypsum, calcium sulfate hemihydrate, anhydrite and mixtures thereof (collectively named C$H.sub.x with x being a rational number from 0 to 2), and optionally C.sub.2S (belite), including an added content of the mineralogical compound C.sub.12A.sub.7 (dodecacalcium heptaaluminate). Moreover, it suggests a process for the manufacture thereof, a process for the manufacture of a construction chemical composition including water, and the use of the ternary composition in construction chemical compositions including knifing fillers, screeds, and repair mortars, tile adhesives, tiling grouts, plasters, base coats and sealings.

Claims

1. A method for accelerating the setting and hardening, improving the hydration performance, or reducing the shrinkage of a binder composition comprising: 24-64% b.wt. of a mineralogical compound C.sub.4A.sub.3$, 6-40% b.wt. of C$H.sub.x, wherein C$H.sub.x is a member selected from the group consisting of gypsum, calcium sulfate hemihydrate, anhydrite and mixtures thereof and wherein x being a rational number from 0 to 2, 0-5% b.wt. of a mineralogical compound C.sub.12A.sub.7, and optionally C.sub.2S, the method comprising incorporating an additional amount of 0.2-20% b.wt. of the mineralogical compound C.sub.12A.sub.7 into the binder composition.

2. The method of claim 1, wherein the mineralogical compound C.sub.12A.sub.7 improves the hydration performance of the binder composition.

3. The method of claim 1, wherein the mineralogical compound C.sub.12A.sub.7 reduces the shrinkage of the binder composition.

4. The method of claim 1, wherein the mineralogical compound C.sub.12A.sub.7 accelerates the setting and hardening of the binder composition.

5. The method of claim 1, wherein the binder composition is present in the form of a CSA cement.

Description

(1) In the drawings

(2) FIG. 1 shows the shrinkage of self-levelling compositions at room temperature,

(3) FIG. 2 shows the shrinkage of self-levelling compositions at +5 C.

GENERAL METHOD

(4) Water and powder temperatures are adjusted to 23 C.1 C. In a polyethylene bucket with an electric drill as a stirrer, 1 kg of the sample and water are mixed until homogeneous and free of lumps (about one minute). Smaller batches may also be mixed in a kitchen bowl with an electric kitchen mixer.

Method A

(5) A spatula is dipped into the mixed composition and pulled out at intervals of 5 minutes. The drops falling from the spatula fall back into the composition. If the drops are completely immersed in the surface of the composition, the composition can still be used. The end of the processing time is reached when a convex meniscus is formed on the surface of the composition by the falling drop. Method E is similar, but the consistency of the composition is here judged by an experienced worker.

Method B

(6) A spreading table is leveled. A test ring is placed in the middle of the spreading table. A sufficient amount of a self-leveling composition is poured into the test ring at 23 C.1 C. After e.g. 1, 10 or 15 minutes, the ring is quickly pulled upwards perpendicular to spreading table. The slump (i.e. the diameter of the slump) is measured twice after exactly one minute at right angles to one other. The average value is noted as the slump [cm].

Method D

(7) Adhesive tensile strengths and sag resistance [mm] are measured according to DIN EN 12004-2:2017-05.

Example 1

(8) TABLE-US-00003 Self-Levelling Composition Reference 1 Rp. 2 Quartz sand (0.1-0.3 mm) 37.80 37.80 Fine filler 36.75 33.75 Ye'elimite-rich clinker 17.60 17.60 Calcium sulfate 4.40 4.40 C.sub.12A.sub.7 3.00 Redispersible polymer powder 3.00 3.00 Li.sub.2CO.sub.3 0.02 0.02 Retarder 0.08 0.08 Further additives 0.35 0.35 Methods Water [g/kg] 260.0 260.0 Method A Processing time [min] 37 24 Vicat Setting time start-end [min] (23/50) 64-84 46-62 (~DIN EN 13409) Setting time start-end [min] (5/90) 150-195 95-120 Method B Slump [cm] 15 15 (~DIN EN 12706) ~DIN EN ISO 2431 Flow time [s] 23 24 DIN EN 13892-2 Compressive strength/bending ten- 3.6/16.3 4.3/18.7 sile strength 24 h [N/mm.sup.2] (23/50) Compressive strength/bending ten- 5.2/20.2 7.2/31.3 sile strength 28 d [N/mm.sup.2] (23/50) Compressive strength/bending ten- 6.0/22.3 6.1/25.8 sile strength 28 d [N/mm.sup.2] (5/90) Graf-Kaufmann Shrinkage 28 d [mm/m] (23/50) 0.7 0.5 (~DIN EN 13872) Shrinkage 28 d [mm/m] (5/90) 1.1 0.7

(9) When using C.sub.12A.sub.7 as an additive, the setting is accelerated in normal climates and at low temperatures, and the shrinkage is minimized. Also compressive strengths and bending tensile strengths are improved. The drawings FIG. 1 and FIG. 2 show much improved shrinkage values.

Example 2

(10) TABLE-US-00004 Self-Levelling Composition Reference 2 Rp. 3 Rp. 4 Rp. 5 Rp. 6 Quartz sand (0.1-0.3 mm) 37.80 37.80 37.80 37.80 37.80 Fine filler 25.77 20.77 25.77 25.77 25.77 Ye'elimite-rich clinker 20.80 20.80 20.40 16.80 12.80 Calcium sulfate 12.70 12.70 12.60 11.70 10.70 C.sub.12A.sub.7 5.00 0.50 5.00 10.00 Redispersible polymer powder 2.50 2.50 2.50 2.50 2.50 Li.sub.2CO.sub.3 Retarder 0.08 0.08 0.08 0.08 0.08 Further additives 0.35 0.35 0.35 0.35 0.35 Methods Water [g/kg] 260.0 260.0 260.0 260.0 260.0 Method A Processing time [min] 47 28 45 33 34 Vicat Setting time start-end [min] (23/50) 64-94 43-55 62-76 50-72 51-77 (~DIN EN 13409) Method B Slump [cm] 15 15 15 15 15 (~DIN EN 12706) ~DIN EN ISO 2431 Flow time [s] 22 18 21 20 19 DIN EN 13892-2 Compressive strength/bending tensile 2.0/6.5 2.1/13.5 1.9/6.9 2.3/9.6 1.9/8.1 strength 4 h [N/mm.sup.2] (23/50) Compressive strength/bending tensile 3.9/17.6 5.8/29.2 3.8/21.4 4.4/22.8 4.7/23.4 strength 24 h [N/mm.sup.2] (23/50) Compressive strength/bending tensile 8.2/36.5 9.4/49.6 9.5/40.5 8.9/44.2 6.2/47.9 strength 28 d [N/mm.sup.2] (23/50) Graf-Kaufmann Shrinkage 28 d [mm/m] (23/50) 0.7 0.6 0.7 0.4 0.4 (~DIN EN 13872) Using C.sub.12A.sub.7 as an additive results in higher (early) strengths, and the setting is accelerated. Shrinkage as well as expansion tend to be lower. The more C.sub.12A.sub.7 used, the higher the (early) strengths. However, an amount of 10% adversely affects the 4 h strengths and the shrinkage or expansion behavior, however the (early) strength and the setting are still good.

Example 3

(11) TABLE-US-00005 Tile Adhesive Composition Reference 3 Rp. 7 Rp. 8 Rp. 9 Quartz sand (0.1-0.3 mm) 63.64 63.14 59.64 53.64 Ye'elimite-rich clinker 24.00 24.00 24.00 24.00 Calcium sulfate 6.00 6.00 6.00 6.00 C.sub.12A.sub.7 0.50 4.00 10.00 Pozzolane 2.44 2.44 2.44 2.44 Redispersible polymer powder 2.50 2.50 2.50 2.50 Li.sub.2CO.sub.3 0.05 0.05 0.05 0.05 Retarder 0.18 0.18 0.18 0.18 Further additives 1.19 1.19 1.19 1.19 Methods Water [g/kg] 260.0 260.0 260.0 260.0 Method D Sag resistance [mm] 1 1 1 1 Method E Processing time [min] 60 60 45 30 Vicat Setting time start-end [min] (23/50) 90-110 75-90 50-65 30-50 Vicat Setting time start-end [min] (5/90) 150-195 120-160 60-105 30-45 DIN EN 12004- Adhesive tensile strength 3 h 0.9 1.0 1.3 1.0 1: 2017-05 [N/mm.sup.2] (23/50) Adhesive tensile strength 6 h 1.4 1.4 1.6 1.5 [N/mm.sup.2] (23/50) Adhesive tensile strength 28 d 2.3 2.2 2.5 2.5 [N/mm.sup.2] (23/50) Adhesive tensile strength 28 d, 1.1 1.0 1.1 1.0 wet [N/mm.sup.2] (23/50) Adhesive tensile strength 28 d, 1.9 2.3 2.1 1.8 warm [N/mm.sup.2] (23/50) Adhesive tensile strength 28 d, 0.5 0.7 0.0 0.0 open time (E) [N/mm2] (23/50) Graf-Kaufmann Shrinkage 28 d [mm/m] (23/50) 1.0 0.7 0.7

(12) Using C.sub.12A.sub.7 as an additive results in higher (early) strengths, setting is accelerated and shrinkage is reduced. The more C.sub.12A.sub.7 is used, the higher the (early) strengths. However, a quantity of 10% adversely affects the (early) strengths.

Example 4

(13) TABLE-US-00006 Tile Adhesive Composition Reference 4 Rp. 10 Reference 5 Rp. 11 Quartz sand (0.1-0.3mm) 59.64 59.64 59.60 59.58 Ye'elimite-rich clinker 27.20 24.00 27.20 24.00 (~50% ye'elimite) Calcium sulfate 6.80 6.00 6.80 6.00 C.sub.12A.sub.7 4.00 4.00 Pozzolane 2.44 2.44 2.44 2.44 Redispersible polym. powd. 2.50 2.50 2.50 2.50 Li.sub.2CO.sub.3 0.05 0.05 0.05 0.05 Retarder 0.18 0.18 0.22 0.24 Further additives 1.19 1.19 1.19 1.19 Methods Water [g/kg] 260.0 260.0 260.0 260.0 Method D Sag resistance [mm] 0 1 0 0 Method E Processing time [min] 45 45 60 55 Vicat Setting time start-end 50-75 50-65 65-95 60-85 [min] (23/50) Vicat Setting time start-end 115-170 60-105 125-170 105-135 [min] (5/90) DIN EN 12004- Adhesive tensile strength 6 h 1.5 1.6 1.4 1.6 1: 2017-05 [N/mm.sup.2] (23/50) Adhesive tensile strength 28 d 2.2 2.5 2.4 2.3 [N/mm.sup.2] (23/50) Adhesive tensile strength 28 d, 0.9 1.1 1.0 1.0 wet [N/mm.sup.2] (23/50) Adhesive tensile strength 28 d, 1.3 2.1 1.1 1.4 warm [N/mm.sup.2] (23/50) Graf-Kaufmann Shrinkage 28 d [mm/m] (23/50) 0.7 0.7 Shrinkage 28 d [mm/m] (5/90) 0.6 0.2

(14) When using C.sub.12A.sub.7 as an additive, higher (early) strengths result, the setting is accelerated in normal climates and at low temperatures, and the shrinkage or expansion behavior minimized.

Example 5

(15) TABLE-US-00007 Tile Adhesive Composition Reference 5 Rp. 12 Quartz sand (0.1-0.3 mm) 54.60 63.14 Ye'elimite-rich clinker 24.00 Calcium sulfate 6.00 C.sub.12A.sub.7 0.50 Calcium aluminate (CA) 7.90 Portland cement 30.30 Pozzolane 2.44 2.44 Redispersible polymer powder 3.0 2.5 Li.sub.2CO.sub.3 0.25 0.05 Retarder 0.16 0.18 Further additives 1.35 1.19 Methods Water [g/kg] 270.0 260.0 Method D Sag resistance [mm] 0 1 Method E Processing time [min] 55 60 Vicat Setting time start-end [min] (23/50) 65-85 75-90 Vicat Setting time start-end [min] (5/90) 195-330 120-160 DIN EN 12004- Adhesive tensile strength 6 h 0.4 1.4 1: 2017-05 [N/mm.sup.2] (23/50) Adhesive tensile strength 28 d 1.3 2.2 [N/mm.sup.2] (23/50) Adhesive tensile strength 28 d, 0.7 1.0 wet [N/mm.sup.2] (23/50) Adhesive tensile strength 28 d, 1.4 2.3 warm [N/mm.sup.2] (23/50) Graf-Kaufmann Shrinkage 28 d [mm/m] (23/50) 4.6 0.7

(16) When using C.sub.12A.sub.7 as an additive, faster setting times at 5 C. and higher early strengths are obtained in CSA cement instead of OPC while using much lower amounts of binders and lithium salts.