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US-12617724-B2 - Hydraulic binder composition comprising blast furnace slag

US12617724B2US 12617724 B2US12617724 B2US 12617724B2US-12617724-B2

Abstract

A hydraulic binder composition comprising: 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; and a polymer.

Inventors

  • Pascal Boustingorry
  • Laurent Bonafous

Assignees

  • CHRYSO

Dates

Publication Date
20260505
Application Date
20220125
Priority Date
20210125

Claims (20)

  1. 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): in which: R 1 and R 2 independently represent a hydrogen or a methyl; R 3 represents a hydrogen or a group having the formula —COO(M) 1/m ; R 4 represents a group having the formula —(CH 2 ) p —(OAlk) q -R 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 —(OAIk) q - independently represents a linear or branched alkylene containing from 2 to 4 carbon atoms; R 5 represents —OH or a linear or branched alkoxyl containing from 1 to 4 carbon atoms; R 11 and R 12 independently represent a hydrogen or a methyl; R 13 represents a hydrogen or a group having the formula —COO(M) 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. 2 . The hydraulic binder composition according to claim 1 , in which the guanidine salt is selected from guanidine thiocyanate, guanidine acetate and guanidine nitrate.
  3. 3 . 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.
  4. 4 . 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.
  5. 5 . The hydraulic binder composition according to claim 1 , in which the zinc salt is selected from zinc chloride and zinc nitrate.
  6. 6 . The hydraulic binder composition according to claim 1 , in which the units having the formula (I) of the polymer have the following formula (I′): in which: R 2 independently represents a hydrogen or a methyl; R′ 4 represents a group having the formula —CH 2 —(O—CH 2 —CH 2 ) q -R 5 in which: q represents an integer from 3 to 500; R 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′): in which: R 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.
  7. 7 . 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.
  8. 8 . 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.
  9. 9 . The hydraulic binder composition according to claim 1 , comprising in addition at least one polyalkoxylated polyphosphonate based polymer.
  10. 10 . The hydraulic binder composition according to claim 1 , in which the alumino-silicate compound is selected from fly ash; metakaolins; and aluminosilicates.
  11. 11 . The hydraulic binder composition according to claim 1 , in which the alumino-silicate compound is a blast furnace slag.
  12. 12 . 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): in which: R 1 and R 2 independently represent a hydrogen or a methyl; R 3 represents a hydrogen or a group having the formula —COO(M) 1/m ; R 4 represents a group having the formula —(CH 2 ) p —(OAlk) q -R 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 —(OAIk) q - independently represents a linear or branched alkylene containing from 2 to 4 carbon atoms; R 5 represents —OH or a linear or branched alkoxyl containing from 1 to 4 carbon atoms; R 11 and R 12 independently represent a hydrogen or a methyl; R 13 represents a hydrogen or a group having the formula —COO(M) 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.
  13. 13 . The hydraulic composition according to claim 12 , in which the guanidine salt is selected from guanidine thiocyanate, guanidine acetate and guanidine nitrate.
  14. 14 . The hydraulic composition according to claim 12 , in which the zinc salt is selected from zinc chloride and zinc nitrate.
  15. 15 . The hydraulic composition according to claim 12 , in which the units having the formula (I) of the polymer have the following formula (I′): in which: R 2 independently represents a hydrogen or a methyl; R′ 4 represents a group having the formula —CH 2 —(O—CH 2 —CH 2 ) q -R 5 in which: q represents an integer from 3 to 500; R 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′): in which: R 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.
  16. 16 . The hydraulic composition according to claim 12 , 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.
  17. 17 . The hydraulic composition according to claim 12 , in which the alumino-silicate compound is a blast furnace slag.
  18. 18 . 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): in which: R 1 and R 2 independently represent a hydrogen or a methyl; R 3 represents a hydrogen or a group having the formula —COO(M) 1/m ; R 4 represents a group having the formula —(CH 2 ) p —(OAlk) q -R 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 —(OAIk) q - independently represents a linear or branched alkylene containing from 2 to 4 carbon atoms; R 5 represents —OH or a linear or branched alkoxyl containing from 1 to 4 carbon atoms; R 11 and R 12 independently represent a hydrogen or a methyl; R 13 represents a hydrogen or a group having the formula —COO(M) 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.
  19. 19 . The process according to claim 18 , in which the guanidine salt and/or the zinc salt is/are added to the hydraulic binder, and the polymer is added to the water; or in which the guanidine salt and/or the zinc salt, and the polymer are added to the hydraulic binder.
  20. 20 . An admixture composition comprising: a guanidine salt and/or a zinc salt; a polymer comprising units having the following formulae (I) and (II): in which: R 1 and R 2 independently represent a hydrogen or a methyl; R 3 represents a hydrogen or a group having the formula —COO(M) 1/m ; R 4 represents a group having the formula —(CH 2 ) p —(OAlk) q -R 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 —(OAIk) q - independently represents a linear or branched alkylene containing from 2 to 4 carbon atoms; R 5 represents —OH or a linear or branched alkoxyl containing from 1 to 4 carbon atoms; R 11 and R 12 independently represent a hydrogen or a methyl; R 13 represents a hydrogen or a group having the formula —COO(M) 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.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application is the US national stage of PCT/EP2022/051622, filed Jan. 25, 2022, which claims the priority of FR Patent Application No. 2100670, filed Jan. 25, 2021. The entire contents of each foregoing application are incorporated herein by reference. BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a hydraulic binder composition comprising at least one alumino-silicate compound, and an alkaline or sulphate activator, and a reduced quantity of clinker, and to the retention of workability of the hydraulic composition obtained, in particular by the adding of water to the hydraulic binder composition. Description of the Related Art Common cementitious compositions comprise a variable, sometimes high proportion of clinker. For example, a cementitious composition according to the standard NF EN 197-1 of 2012 comprises from 5 to 95% by weight of clinker. However, the manufacture of clinker requires the use of powerful kilns, thus resulting in the emission of large quantities of carbon dioxide. The extraction of raw materials is also a source for discharging carbon dioxide emissions. It is therefore sought to lower the clinker content of cementitious compositions in order to reduce the carbon impact thereof, while however maintaining the mechanical and rheological properties thereof. To this end, new hydraulic binder compositions have been developed in which the amount of clinker is reduced. Cementitious compositions in which the hydraulic binder is a blast furnace slag have been previously disclosed, these compositions are generally activated. However, there is a very rapid drop in the workability of these compositions, which is to say that they go from a fluid to an almost solid state in less than 30 minutes. From a rheological standpoint, threshold stresses of 1 to 10 Pa are typically observed five minutes after mixing, with the values increasing to 50 to 100 Pa between 30 and 60 minutes after mixing. There is therefore an interest in providing a solution which makes it possible to enhance the fluidity of compositions that comprise at least one alumino-silicate compound, for example blast furnace slag, and an alkaline or sulphate activator. SUMMARY OF THE INVENTION One objective of the present invention is to provide a composition comprising at least one alumino-silicate compound, for example blast furnace slag, and an alkaline or sulphate activator which makes it possible to obtain a hydraulic composition that exhibits enhanced retention of fluidity. Another object of the present invention is to provide such a composition that serves to enable fluidity to be retained for a period of 1 hour or 1 hour and 30 minutes. Other additional objectives will also become apparent upon reading the description of the invention which follows. All of these objectives are achieved in the present application which relates to a hydraulic binder composition (HBC) comprising: a hydraulic binder that comprises at least one alumino-silicate compound, for example blast furnace slag, and an alkaline or sulphate activator and a maximum of 10% by weight of clinker, preferably from 0 to 10% by weight of clinker;a guanidine salt and/or a zinc salt;a polymer (P) comprising units having the following formulae (I) and (II): in which: R1 and R2 independently represent a hydrogen or a methyl;R3 represents a hydrogen or a group having the formula —COO(M)1/m;R4 represents a group having the formula —(CH2)p—(OAlk)q-R5 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)q- independently represents a linear or branched alkylene containing from 2 to 4 carbon atoms;R5 represents —OH or a linear or branched alkoxyl containing from 1 to 4 carbon atoms;R11 and R12 independently represent a hydrogen or a methyl;R13 represents a hydrogen or a group having the formula —COO(M)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, andb 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. In an advantageous manner the inventors have shown that the adding of guanidine salt and/or zinc salt, and polymer (P) according to the invention provides the means for enhancing the retention of fluidity (also referred to as retention of workability) over time, of a hydraulic composition prepared from the hydraulic binder composition (HBC), in particular by adding at least water, as compared to a composition that does not contain any guanidine salt, zinc salt and polymer (P) according to the invention. In the context of the present invention, the enhancement in the retention of workability, as measured, for example, by the ev