HYDRAULIC BINDER COMPOSITION COMPRISING BLAST FURNACE SLAG

Abstract

Disclosed is a hydraulic binder composition including: a hydraulic binder including at least one alumino-silicate compound, for example blast furnace slag, and an alkaline or sulfate activator and a maximum of 10 wt % of clinker, preferably between 0 and 10 wt % of clinker; a guanidine salt and/or a zinc salt; a polymer (P) including units of formulae (I) and (II):

##STR00001##

Claims

1. A hydraulic binder composition comprising: a hydraulic binder comprising at least one alumino-silicate compound, and an alkaline or sulphate activator and a maximum of 10% by weight of clinker, and optionally an activator; a guanidine salt and/or a zinc salt; a polymer (P) comprising units having the following formulae (I) and (II): ##STR00015## in which: R.sup.1 and R.sup.2 independently represent a hydrogen or a methyl; R.sup.3 represents a hydrogen or a group having the formula COO(M).sub.1/m, R.sup.4 represents a group having the formula (CH.sub.2).sub.p(OAlk).sub.q-R.sub.5 in which: p represents 1 or 2; q represents an integer from 3 to 300; the Alk of each OAlk unit of the group (OAlk).sub.q- independently represents a linear or branched alkylene containing from 2 to 4 carbon atoms; R.sup.5 represents OH or a linear or branched alkoxyl containing from 1 to 4 carbon atoms; R.sup.11 and R.sup.12 independently represent a hydrogen or a methyl; R.sup.13 represents a hydrogen or a group having the formula COO(M).sub.1/m; M represents H or a cation of valency m; when M represents H, m represents 1, and when M represents a cation, m is the valency of the cation M; a is a number from 0.05 to 0.25, such that (100?a) represents the molar percentage of units having the formula (I) within the polymer; and b is a number from 0.75 to 0.95, such that (100?b) represents the molar percentage of units having the formula (II) within the polymer.

2. A hydraulic composition comprising: a hydraulic binder that comprises at least one alumino-silicate compound, and an alkaline or sulphate activator, and a maximum of 10% by weight of clinker, and optionally mineral additives; water; optionally at least one aggregate; a guanidine salt and/or a zinc salt; and a polymer (P) comprising units having the following formulae (I) and (II): ##STR00016## in which: R.sup.1 and R.sup.2 independently represent a hydrogen or a methyl; R.sup.3 represents a hydrogen or a group having the formula COO(M).sub.1/m, R.sup.4 represents a group having the formula (CH.sub.2).sub.p(OAlk).sub.q-R.sup.5 in which: p represents 1 or 2; q represents an integer from 3 to 300; the Alk of each OAlk unit of the group (OAlk).sub.q- independently represents a linear or branched alkylene containing from 2 to 4 carbon atoms; R.sup.5 represents OH or a linear or branched alkoxyl containing from 1 to 4 carbon atoms; R.sup.11 and R.sup.12 independently represent a hydrogen or a methyl; R.sup.13 represents a hydrogen or a group having the formula COO(M).sub.1/m; M represents H or a cation of valency m; when M represents H, m represents 1, and when M represents a cation, m is the valency of the cation M; a is a number from 0.05 to 0.25, such that (100?a) represents the molar percentage of units having the formula (I) within the polymer; and b is a number from 0.75 to 0.95, such that (100?b) represents the molar percentage of units having the formula (II) within the polymer.

3. (canceled)

4. A process for enhancing the retention of fluidity over time of a hydraulic composition comprising a hydraulic binder that comprises at least one alumino-silicate compound, and an alkaline or sulphate activator, and a maximum of 10% by weight of clinker, water, and optionally at least one aggregate; including the adding of a guanidine salt and/or a zinc salt, and a polymer (P) comprising units having the following formulae (I) and (II): ##STR00017## in which: R.sup.1 and R.sup.2 independently represent a hydrogen or a methyl; R.sup.3 represents a hydrogen or a group having the formula COO(M).sub.1/m, R.sup.4 represents a group having the formula (CH.sub.2).sub.p(OAlk).sub.q-R.sup.5 in which: p represents 1 or 2; q represents an integer from 3 to 300; the Alk of each OAlk unit of the group (OAlk).sub.q- independently represents a linear or branched alkylene containing from 2 to 4 carbon atoms; R.sup.5 represents OH or a linear or branched alkoxyl containing from 1 to 4 carbon atoms; R.sup.11 and R.sup.12 independently represent a hydrogen or a methyl; R.sup.13 represents a hydrogen or a group having the formula COO(M).sub.1/m; M represents H or a cation of valency m; when M represents H, m represents 1, and when M represents a cation, m is the valency of the cation M; a is a number from 0.05 to 0.25, such that (100?a) represents the molar percentage of units having the formula (I) within the polymer; and b is a number from 0.75 to 0.95, such that (100?b) represents the molar percentage of units having the formula (II) within the polymer.

5. The hydraulic binder composition according to claim 1, in which the guanidine salt is selected from guanidine thiocyanate, guanidine acetate and guanidine nitrate.

6. The hydraulic binder composition according to claim 1, in which the activator is selected from a calcium activator or sulpho-calcium activator; or an alkaline salt.

7. The hydraulic binder composition according to claim 1, in which the hydraulic binder composition comprises from 75 to 99% by weight of blast furnace slag, relative to the total weight of hydraulic binder.

8. The hydraulic binder composition according to claim 1, in which the zinc salt is selected from zinc chloride and zinc nitrate.

9. The hydraulic binder composition according to claim 1, in which the units having the formula (I) of the polymer have the following formula (I): ##STR00018## in which: R.sup.2 independently represents a hydrogen or a methyl; R.sup.4 represents a group having the formula CH.sub.2(OCH.sub.2CH.sub.2).sub.qR.sup.5 in which: q represents an integer from 3 to 500; R.sup.5 represents OH or OMe, preferably OH; a is a number from 0.05 to 0.25, such that (100?a) represents the molar percentage of units having the formula (I) within the polymer; the units having the formula (II) of the polymer have the following formula (II): ##STR00019## in which: R.sup.12 represents a hydrogen or a methyl; M represents H or a cation of valency m; when M represents H, m represents 1, and when M represents a cation, m is the valency of the cation M; b is a number from 0.75 to 0.95, such that (100?b) represents the molar percentage of units having the formula (II) within the polymer.

10. The hydraulic binder composition according to claim 1, in which the amount of guanidine salt and/or zinc salt is between 0.1 and 5% by dry weight, relative to the total weight of hydraulic binder.

11. The hydraulic binder composition according to claim 1, in which the amount of polymer is between 0.1 and 3% by dry weight, relative to the total weight of hydraulic binder.

12. The hydraulic binder composition according to claim 1, comprising in addition at least one polyalkoxylated polyphosphonate based polymer.

13. The hydraulic binder composition according to claim 1, in which the alumino-silicate compound is selected from fly ash (as defined in the standard Cement NF EN 197-1 (2012) paragraph 5.2.4); metakaolins; and aluminosilicates.

14. The hydraulic binder composition according to claim 1, in which the alumino-silicate compound is a blast furnace slag.

15. The composition preparation process for preparing a hydraulic composition according to claim 4, in which the guanidine salt and/or the zinc salt is/are added to the hydraulic binder, and the polymer and the optional polyalkoxylated polyphosphonate based polymer are added to the water; or in which the guanidine salt and/or the zinc salt, the polymer, and the optional polyalkoxylated polyphosphonate based polymer are added to the hydraulic binder.

16. An admixture composition comprising: a guanidine salt and/or a zinc salt; a polymer comprising units having the following formulae (I) and (II): ##STR00020## in which: R.sup.1 and R.sup.2 independently represent a hydrogen or a methyl; R.sup.3 represents a hydrogen or a group having the formula COO(M).sub.1/m, R.sup.4 represents a group having the formula (CH.sub.2).sub.p(OAlk).sub.q-R.sup.5 in which: p represents 1 or 2; q represents an integer from 3 to 300; the Alk of each OAlk unit of the group (OAlk).sub.q- independently represents a linear or branched alkylene containing from 2 to 4 carbon atoms; R.sup.5 represents OH or a linear or branched alkoxyl containing from 1 to 4 carbon atoms; R.sup.11 and R.sup.12 independently represent a hydrogen or a methyl; R.sup.13 represents a hydrogen or a group having the formula COO(M).sub.1/m; M represents H or a cation of valency m; when M represents H, m represents 1, and when M represents a cation, m is the valency of the cation M; a is a number from 0.05 to 0.25, such that (100?a) represents the molar percentage of units having the formula (I) within the polymer; and b is a number from 0.75 to 0.95, such that (100?b) represents the molar percentage of units having the formula (II) within the polymer.

17. The hydraulic composition according to claim 2, in which the guanidine salt is selected from guanidine thiocyanate, guanidine acetate and guanidine nitrate.

18. The hydraulic composition according to claim 2, in which the zinc salt is selected from zinc chloride and zinc nitrate.

19. The hydraulic composition according to claim 2, in which the units having the formula (I) of the polymer have the following formula (I): ##STR00021## in which: R.sup.2 independently represents a hydrogen or a methyl; R.sup.4 represents a group having the formula CH.sub.2(OCH.sub.2CH.sub.2).sub.q-R.sup.5 in which: q represents an integer from 3 to 500; R.sup.5 represents OH or OMe; a is a number from 0.05 to 0.25, such that (100?a) represents the molar percentage of units having the formula (I) within the polymer; the units having the formula (II) of the polymer have the following formula (II): ##STR00022## in which: R.sup.12 represents a hydrogen or a methyl; M represents H or a cation of valency m; when M represents H, m represents 1, and when M represents a cation, m is the valency of the cation M; b is a number from 0.75 to 0.95, such that (100?b) represents the molar percentage of units having the formula (IF) within the polymer.

20. The hydraulic composition according to claim 2, in which the amount of guanidine salt and/or zinc salt is between 0.1 and 5% by dry weight, relative to the total weight of hydraulic binder.

21. The hydraulic composition according to claim 2, in which the alumino-silicate compound is a blast furnace slag.

Description

DETAILED DESCRIPTION

[0330] The present invention will now be described making use of the examples below.

Example 1

Study of the Performance of an Admixture Composition According to the Invention With Guanidine Salt

[0331] In order to evaluate the performance of a polymeric admixture and guanidine salt composition, a mortar composition was prepared.
The mortar composition is as follows

TABLE-US-00001 TABLE 1 Component Weight (g) Hydraulic binder (blast furnace slag + activator 210 (7% by weight of sodium silicate)) Palvadeau sand 0/0.315 mm 190 Tap water 84
It was prepared, making use of a KENWOOD KM01 1 CHEF TITANIUM mixer with a stainless steel bowl (4.6 litre capacity) and a metal agitation/stirring blade in the shape of a sage leaf (height 13 cm and width 13.6 cm), in the following manner: [0332] 1. The water and the admixture are weighed into the mixer bowl, and then the mixer is started at a speed of 43 revolutions per minute (rpm). [0333] 2. The timer is started and the hydraulic composition of blast furnace slag and sand is introduced into the bowl in 30 seconds. [0334] 3. The speed is increased to 96 rpm and the mixture is mixed for a period of one minute. [0335] 4. The mixer is stopped for a period of 30 seconds and any mortar composition splashed onto the walls is scraped back towards the centre with a spatula. [0336] 5. The mortar composition obtained is mixed for a period of one minute at 96 rpm.

[0337] At the end of the mixing, the mortar composition obtained, which is in the form of a paste, is poured into the cylindrical measuring cell of a Kinexus Pro rheometer (Netzsch) which is provided with a fin-type measuring geometry.

[0338] Five minutes after the start of mixing, the mortar composition is subjected to a pre-shear for one minute at a strain rate of 200 s.sup.?1. The mortar composition is subsequently subjected to a series of descending increments of strain rate, in logarithmic steps from 200 to 0.01 s.sup.?1, and the rheometer records the stress to be applied at each point. This then enables a flow curve to be generated linking the stress applied in order to obtain each strain rate value. These flow curves show a minimum stress which is interpreted as a threshold stress, that is to say a minimum stress to be applied so as to cause flow. This value varies inversely to the fluidity, which is why it is desirable for it to be reduced as much as possible.

[0339] The flow curve is then measured every 30 minutes until 120 minutes after the start of mixing in order to monitor the change in fluidity over time.

[0340] The polymer 2 (polymer according to the invention with a=0.2, q=114, R1=R3=R11=R13=H, R2=R12=CH3, M=Na) is introduced into the mortar compositions in a dosed amount of 0.5% by dry weight relative to the total weight of hydraulic binder. The proportions of salts are given in dry weight relative to the total weight of hydraulic binder. The results obtained are as follows:

TABLE-US-00002 TABLE 2 Threshold stress values (Pa) 5 30 60 90 120 min min min min min Polymer 2 4.5 51.8 95.7 Non Non measur- measur- able able Polymer 2 + 0.5% by dry 6.1 66.2 77.0 98.3 125.5 weight guanidine thiocyanate Polymer 2 + 1.0% by dry 5.0 44.7 55.9 74.0 94.2 weight guanidine thiocyanate Polymer 2 + 2.0% by dry 5.5 27.1 26.2 28.9 32.9 weight guanidine thiocyanate Polymer 2 + 1.4% by dry 13.9 101.6 114.9 136.7 167.2 weight sodium thiocyanate (equimolar 2.0% guanidine thiocyanate) Guanidine thiocyanate 2.0% 25.6 76.2 83.6 93.6 105.5 dry weight

TABLE-US-00003 TABLE 3 Threshold stress values (Pa) 5 30 60 90 120 min min min min min Polymer 2 4.5 51.8 95.7 Non Non measur- measur- able able Polymer 2 + guanidine 8.3 23.4 22.4 25.2 28.5 acetate (guanidine in isomolar amount relative to 1% by dry weight of guanidine thiocyanate) Polymer 2 + guanidine 4.3 58.3 58.3 71.2 91.0 nitrate (guanidine in isomolar amount relative to 1% by dry weight of guanidine thiocyanate) Guanidine acetate without 30.7 74.8 77.7 83.1 90.4 Polymer 2 (guanidine in isomolar amount relative to 1% by dry weight of guanidine thiocyanate)
These results clearly demonstrate the synergistic effect between the polymer of the invention and the guanidine salt such as to enhance the retention of fluidity of the hydraulic binder composition.

Example 2

Study of the Performance of an Admixture Composition According to the Invention With Zinc Salt

[0341] The evaluation of performance is carried out in the same manner as in Example 1 with the same mortar composition.

[0342] The polymer 2 (polymer according to the invention with a=0.2, q=114, R1=R3=R11=R13=H, R2=R12=CH3, M=Na) is introduced into the mortar compositions in a dosed amount of 0.5% by dry weight relative to the total weight of hydraulic binder. The proportions of salts are given in dry weight relative to the total weight of hydraulic binder.

The results are presented here below:

TABLE-US-00004 TABLE 4 Threshold stress values (Pa) 5 30 60 90 120 min min min min min Polymer 2 4.5 51.8 95.7 Non Non measur- measur- able able Polymer 2 + zinc chloride 11.7 12.4 39.7 59.9 78.9 0.5% by dry weight Polymer 2 + zinc chloride 62.5 25.6 22.3 25.0 32.3 1.0% by dry weight Polymer 2 + zinc nitrate in 11.9 8.5 28.6 46.6 64.1 isomolar amount zinc chloride 0.5% by dry weight Polymer 2 + zinc nitrate in 63.7 30.4 26.8 26.2 27.3 isomolar amount guanidine thiocyanate 2.0% by dry weight Zinc chloride 1.0% without 55.3 44.6 39.8 38.0 38.6 polymer 2 by dry weight
These results clearly demonstrate the synergistic effect between the polymer of the invention and the zinc salt such as to enhance the retention of fluidity of the hydraulic binder composition.

Example 3

Study of the Performance of an Admixture Composition According to the Invention With Zinc Salt and Guanidine Salt

[0343] The evaluation of performance is carried out in the same manner as in Example 1 with the same mortar composition.

[0344] The polymer 2 (polymer according to the invention with a=0.2, q=114, R1=R3=R11=R13=H, R2=R12=CH3, M=Na) is introduced into the mortar compositions in a dosed amount of 0.5% by dry weight relative to the total weight of hydraulic binder. The proportions of salts are given in dry weight relative to the total weight of hydraulic binder. The results are presented here below:

TABLE-US-00005 TABLE 5 Threshold stress values (Pa) 5 30 60 90 120 min min min min min Polymer 2 4.5 51.8 95.7 Non Non measur- measur- able able Polymer 2 + guanidine 5.0 44.7 55.9 74.0 94.2 thiocyanate 1% by dry weight Polymer 2 + zinc nitrate 1.5% 11.9 8.5 28.6 46.6 64.1 by dry weight Polymer 2 + guanidine 14.5 6.7 9.5 15.1 16.7 thiocyanate 1% + zinc nitrate 1.5% by dry weight
These results clearly demonstrate the synergistic effect between the polymer of the invention and the combination of a zinc salt and a guanidine salt such as to enhance the retention of fluidity of the hydraulic binder composition.