Hydraulic binder composition comprising blast furnace slag
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.
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 . The hydraulic binder composition according to claim 1 , in which the guanidine salt is selected from guanidine thiocyanate, guanidine acetate and guanidine nitrate.
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 . 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 . The hydraulic binder composition according to claim 1 , in which the zinc salt is selected from zinc chloride and zinc nitrate.
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 . 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 . 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 . The hydraulic binder composition according to claim 1 , comprising in addition at least one polyalkoxylated polyphosphonate based polymer.
10 . The hydraulic binder composition according to claim 1 , in which the alumino-silicate compound is selected from fly ash; metakaolins; and aluminosilicates.
11 . The hydraulic binder composition according to claim 1 , in which the alumino-silicate compound is a blast furnace slag.
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 . The hydraulic composition according to claim 12 , in which the guanidine salt is selected from guanidine thiocyanate, guanidine acetate and guanidine nitrate.
14 . The hydraulic composition according to claim 12 , in which the zinc salt is selected from zinc chloride and zinc nitrate.
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 . 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 . The hydraulic composition according to claim 12 , in which the alumino-silicate compound is a blast furnace slag.
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 . 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 . 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.