AU2017436546A1 - Methods for producing a low CO2 cement composition - Google Patents
Methods for producing a low CO2 cement composition Download PDFInfo
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- AU2017436546A1 AU2017436546A1 AU2017436546A AU2017436546A AU2017436546A1 AU 2017436546 A1 AU2017436546 A1 AU 2017436546A1 AU 2017436546 A AU2017436546 A AU 2017436546A AU 2017436546 A AU2017436546 A AU 2017436546A AU 2017436546 A1 AU2017436546 A1 AU 2017436546A1
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- Prior art keywords
- reactive powder
- accelerator
- slag
- retardant
- activator
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- 238000000034 method Methods 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- 239000004568 cement Substances 0.000 title claims abstract description 56
- 239000000843 powder Substances 0.000 claims abstract description 73
- 239000012190 activator Substances 0.000 claims abstract description 55
- 238000002156 mixing Methods 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000376 reactant Substances 0.000 claims abstract description 15
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 82
- 239000002893 slag Substances 0.000 claims description 74
- 239000011398 Portland cement Substances 0.000 claims description 51
- 239000001175 calcium sulphate Substances 0.000 claims description 35
- 235000011132 calcium sulphate Nutrition 0.000 claims description 35
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 33
- 239000010440 gypsum Substances 0.000 claims description 31
- 229910052602 gypsum Inorganic materials 0.000 claims description 31
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 20
- 235000011152 sodium sulphate Nutrition 0.000 claims description 20
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 14
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 14
- 239000000292 calcium oxide Substances 0.000 claims description 14
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 14
- 229910000831 Steel Inorganic materials 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000010959 steel Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 5
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 5
- 239000001120 potassium sulphate Substances 0.000 claims description 5
- 235000011151 potassium sulphates Nutrition 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000004281 calcium formate Substances 0.000 claims description 3
- 229940044172 calcium formate Drugs 0.000 claims description 3
- 235000019255 calcium formate Nutrition 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 235000005985 organic acids Nutrition 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 3
- 238000007792 addition Methods 0.000 description 30
- -1 gypsum Chemical compound 0.000 description 24
- 239000011230 binding agent Substances 0.000 description 13
- 229910052925 anhydrite Inorganic materials 0.000 description 12
- 239000003638 chemical reducing agent Substances 0.000 description 11
- 230000003111 delayed effect Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000007832 Na2SO4 Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920001732 Lignosulfonate Polymers 0.000 description 2
- 239000004117 Lignosulphonate Substances 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 235000012241 calcium silicate Nutrition 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 235000019357 lignosulphonate Nutrition 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920005646 polycarboxylate Polymers 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 239000011396 hydraulic cement Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/08—Slag cements
- C04B28/082—Steelmaking slags; Converter slags
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00215—Mortar or concrete mixtures defined by their oxide composition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present disclosure relates to improved methods for producing a low CO2 cement composition. Disclosed herein are methods for producing a cement composition comprising mixing reactants comprising a reactive powder, an activator, and a retardant in the presence of water, followed by the mixing of an accelerator into the reactants, and allowing the reactants to react to form the cement composition.
Description
METHODS FOR PRODUCING A LOW CO2 CEMENT COMPOSITION FIELD
The present disclosure relates to methods of producing a low CO2 cement composition.
BACKGROUND
Manufacture of portland cement contributes significantly to global CO2 emissions and is a major cost component of concrete. The manufacture and use of portland cement has been refined over time and thus there are few avenues remaining to increase efficiency and reduce carbon emissions in cement manufacture, and these are relatively expensive to implement (e.g. carbon capture and storage). Reducing the amount of portland cement used in concrete to achieve a given strength requirement is therefore highly desirable, as it will reduce carbon emissions and concrete cost.
Previous attempts to reduce carbon emissions included a ternary system of ordinary portland cement (OPC), ground granulated blast furnace slag (GGBFS) and an activator (e.g. sodium sulphate). This ternary system produced binders with superior performance to systems without activator when the mix design was optimized. See WO2011/134025. The two main binder materials - OPC and GGBFS - have different reaction potentials and therefore the required performance is usually not reached in a desirable timeframe for commercial application as the GGBFS is slower to react under normal hydration conditions. When the right concentration of sodium sulphate activator was employed, it acted on the GGBFS to increase reactivity, and overall the reaction potential of the system was significantly increased.
However, one of the drawbacks of this system is that the activator has a negative impact on the OPC, reducing its reaction potential. While overall the ternary system is superior to previous methods, ideally the activator would target the GGBFS only, resulting in still further increased performance.
The compositions and methods disclosed herein address these and other needs.
SUMMARY
Disclosed herein are improved methods for producing a low CO2 cement composition. The inventors have found that if a conventional retardant is added to a ternary cement system (ordinary portland cement (OPC), slag, and activator) followed by the delayed addition of an accelerator, the impact of the activator on the OPC is significantly reduced, leading to improved performance and compressive strength of the cement composition.
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In some aspects, disclosed herein is a method for producing a cement composition, comprising mixing reactants comprising a reactive powder, an activator, and a retardant in the presence of water, wherein the reactive powder comprises portland cement and/or portland cement clinker and slag; mixing an accelerator into the reactants, wherein the accelerator is added from 30 seconds to 60 minutes after the mixing of the reactive powder, activator, and retardant; and allowing the reactants to react to form the cement composition.
In some embodiments, the ratio of slag to portland cement and/or portland cement clinker is 1:3 to 9:1. In some embodiments, the ratio of slag to portland cement and/or portland cement clinker is 1:2 to 4:1. In some embodiments, the ratio of slag to portland cement and/or portland cement clinker is 1:2 to 2:1. In some embodiments, the ratio of slag to portland cement and/or portland cement clinker is 1:1 to 4:1.
In some embodiments, the portland cement and/or portland cement clinker is present in an amount of greater than 20 wt% and less than 65 wt% of the total amount of reactive powder. In some embodiments, the portland cement and/or portland cement clinker is present in an amount of greater than 30 wt% and less than 50 wt% of the total amount of reactive powder.
In some embodiments, the slag is present in an amount of 20 wt% to 90 wt% of the total amount of reactive powder. In some embodiments, the slag is present in an amount of 40 wt% to 80 wt% of the total amount of reactive powder. In some embodiments, the slag is present in an amount of 50 wt% to 70 wt% of the total amount of reactive powder.
In some embodiments, the slag is granulated blast furnace slag. In some embodiments, the slag is steel slag. In some embodiments, the slag is granulated blast furnace slag in combination with steel slag. In some embodiments, the steel slag constitutes greater than 0 to 30 wt% of the total amount of reactive powder. In some embodiments, the steel slag constitutes greater than 0 to 20 wt% of the total amount of reactive powder.
In some embodiments, the slag comprises CaO and SiCh, and wherein the CaO/SiCh wt ratio of the slag is in the range of 1.0 - 1.3.
In some embodiments, the activator is present in an amount of 1 - 6 wt%, based on the total amount of the cement composition. In some embodiments, the activator is present in an amount of 1.5 - 6 wt%, based on the total amount of the cement composition. In some embodiments, the activator includes sodium sulphate or potassium sulphate. In some embodiments, the activator includes sodium sulphate. In some embodiments, the activator includes potassium sulphate.
In some embodiments, the retardant is selected from a sugar, a phosphonate, organic acids or their salts, or a mixture thereof. In some embodiments, the retardant includes a sugar. In some embodiments, the retardant includes a commercially available retardant. In some
WO 2019/077390
PCT/IB2017/056456 embodiments, the retardant includes Sika Retarder N. In some embodiments, the retardant includes sodium citrate.
In some embodiments, the accelerator includes calcium nitrate, calcium chloride, calcium hydroxide, calcium oxide, or calcium formate. In some embodiments, the accelerator is the nitrate of an alkaline earth metal. In some embodiments, the accelerator is calcium nitrate.
In some embodiments, the accelerator includes a commercially available accelerator. In some embodiments, the accelerator includes Sika Rapid 4. In some embodiments, the accelerator is added in combination with sodium thiocyanate or triethanolamine.
In some embodiments, the accelerator is added 30 seconds to 60 minutes after the mixing of the reactive powder, activator, and retardant. In some embodiments, the accelerator is added 30 seconds to 30 minutes after the mixing of the reactive powder, activator, and retardant. In some embodiments, the accelerator is added 30 seconds to 20 minutes after the mixing of the reactive powder, activator, and retardant. In some embodiments, the accelerator is added 30 seconds to 10 minutes after the mixing of the reactive powder, activator, and retardant. In some embodiments, the accelerator is added 30 seconds to 3 minutes after the mixing of the reactive powder, activator, and retardant. In some embodiments, the accelerator is added 1 minute to 15 minutes after the mixing of the reactive powder, activator, and retardant. In some embodiments, the accelerator is added 1 minute to 10 minutes after the mixing of the reactive powder, activator, and retardant. In some embodiments, the accelerator is added 1 minute to 5 minutes after the mixing of the reactive powder, activator, and retardant.
In some embodiments, the reactive powder further comprises calcium sulphate, any of the hydrated forms of calcium sulphate (e.g. gypsum, hemihydrate, anhydrite), or a combination thereof. In some embodiments, the calcium sulphate, any of the hydrated forms of calcium sulphate (e.g. gypsum, hemihydrate, anhydrite), or a combination thereof is present in an amount greater than zero to 10 wt% of the total amount of reactive powder. In some embodiments, the calcium sulphate, any of the hydrated forms of calcium sulphate (e.g. gypsum, hemihydrate, anhydrite), or a combination thereof is present in an amount greater than zero to 5 wt% of the total amount of reactive powder. In some embodiments, the calcium sulphate, any of the hydrated forms of calcium sulphate (e.g. gypsum, hemihydrate, anhydrite), or a combination thereof is present in an amount of 1 - 6 wt% of the total amount of reactive powder. In some embodiments, the calcium sulphate, any of the hydrated forms of calcium sulphate (e.g. gypsum, hemihydrate, anhydrite), or a combination thereof is present in an amount of 2 - 5 wt% of the total amount of reactive powder. In some embodiments, the reactive powder further comprises gypsum.
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In some embodiments, a cement composition is prepared according to the methods disclosed herein.
In some embodiments, provided herein is a method of making concrete according to the methods disclosed herein, further comprising mixing aggregate with the reactants. In some embodiments, the aggregate is in a range of 65 - 95 wt % of the concrete. In some embodiments, the aggregate is in a range of 65 - 85 wt % of the concrete. In some embodiments, provided herein is a method of making concrete according to the methods disclosed herein, further comprising mixing sand and/or aggregate with the reactants.
DETAILED DESCRIPTION
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this disclosure belongs. The term “comprising” and variations thereof as used herein is used synonymously with the term “including” and variations thereof and are open, non-limiting terms. Although the terms “comprising” and “including” have been used herein to describe various embodiments, the terms “consisting essentially of’ and “consisting of’ can be used in place of “comprising” and “including” to provide for more specific embodiments and are also disclosed. As used in this disclosure and in the appended claims, the singular forms “a”, “an”, “the”, include plural referents unless the context clearly dictates otherwise.
In some aspects, disclosed herein is a method for producing a cement composition, comprising: mixing reactants comprising a reactive powder, an activator, and a retardant in the presence of water, wherein the reactive powder comprises portland cement and/or portland cement clinker and slag; mixing an accelerator into the reactants, wherein the accelerator is added from 30 seconds to 60 minutes after the mixing of the reactive powder, activator, and retardant; and allowing the reactants to react to form the cement composition.
In some embodiments, the ratio of slag to portland cement and/or portland cement clinker is 1:3 to 9:1. In some embodiments, the ratio of slag to portland cement and/or portland cement clinker is 1:2 to 4:1. In some embodiments, the ratio of slag to portland cement and/or portland cement clinker is 1:2 to 2:1. In some embodiments, the ratio of slag to portland cement and/or portland cement clinker is 1:1 to 4:1.
As noted above, the reactive powder includes portland cement and/or portland cement clinker. Portland cement is hydraulic cement” (cement that not only hardens by reacting with water but also forms a water-resistant product) produced by pulverizing clinkers which consist essentially of hydraulic calcium silicates, usually containing one or more of the forms of calcium sulphate as an inter-ground addition. Portland cement clinker is a hydraulic material which
WO 2019/077390
PCT/IB2017/056456 generally consists of at least two-thirds by mass of calcium silicates (3CaO.SiOz and 2CaO.SiO2), the remainder consisting of aluminum- and iron-containing clinker phases and other compounds. Tire magnesium content typically does not exceed 5.0% by mass. The major raw material for making the clinker is usually limestone (CaCOa) mixed with a second material containing clay as source of alumino-silicate; aluminium oxide and iron oxide are present as a flux and contribute little to the strength. The production of portland cement clinker is associated with high-CCh emissions. One w'ay to reduce clinker content in cement and concrete is to replace clinker with supplementary cementitious materials (SCM), for example, slag such as ground, granulated blast-furnace slag (GGBFS).
In some embodiments, the portland cement and/or portland cement clinker is present in an amount of from 20 wt% to 65 wt% of the total amount of the reactive powder. In some embodiments, the portland cement and/or portland cement clinker can be present in an amount of from 25 wt% to 55 wt%, from 30 wt% to 50 wt%, or from 35 wt% to 45 wt% (e.g., 40 wt%) of the total amount of the reactive powder.
The reactive powder also includes slag. In some embodiments, the slag is present in an amount of 20 wt% to 90 wt% of the total amount of reactive powder. In some embodiments, the amount of slag in the reactive powder is from 40 wt% to 80 wt % of the total amount of the reactive powder. For example, the amount of slag in the cement composition can be 20-90 wl%, 30-90 wt%, 40-80 wt%, 40-70 wt%, 50-70 wt%, 40-60 wt%, or 50 - 60 wt%.
In some embodiments, the slag includes blast, furnace slag, steel slag, or a mixture thereof. Blast furnace slag is a. nonmetallic product produced during the production of iron. It consists primarily of silicates, aluminosilicates, and calcium-alumina-silicates. Granulated blast furnace slag (GBFS) is the result of cooling and solidifying the molten slag by rapid water quenching to a glassy state, where little or no crystallization occurs. Tins process results in the formation of sand sized fragments. The physical structure of the granulated slag depends on the chemical composition of the slag, its temperature at the time of water quenching, and the method of production. When crushed or milled to very fine cement-sized particles, ground granulated blast furnace slag (GGBFS) has cementitious properties.
In some embodiments, the slag includes steel slag. In some embodiments, the slag is granulated blast furnace slag in combination with steel slag. In some embodiments, the steel slag greater than 0 to 30 wt% of the reactive powder. In some embodiments, the steel slag constitutes greater than 0 to 20 wt% of the reactive powder.
In some embodiments, the slag comprises CaO and S1O2. In some embodiments, the slag comprises CaO and S1O2, and wherein the CaO/SiO2 wt ratio of the slag is less than or equal to 1.3. In some embodiments, the slag comprises CaO and S1O2, and wherein the CaO/SiO2 wt ratio
WO 2019/077390
PCT/IB2017/056456 of the slag is in the range of 1.0 - 1.3. Generally, the lower the CaO/SiCh wt ratio, the lower the reactivity of the slag.
In some embodiments, the slag has an AhOs/SiO?. wt ratio of 0.3-0.5. In some embodiments, the slag has a MgO/CaO wt ratio of 0.1-0.5.
In some embodiments, the reactive powder further comprises calcium sulphate, any of the hydrated forms of calcium sulphate (e.g. gypsum, hemihydrate, anhydrite), or a combination thereof.
In some embodiments, the calcium sulphate, any of the hydrated forms of calcium sulphate (e.g. gypsum, hemihydrate, anhydrite), or a combination thereof is present in an amount greater than zero to 10 wt%. In some embodiments, the calcium sulphate, any of the hydrated forms of calcium sulphate (e.g. gypsum, hemihydrate, anhydrite), or a combination thereof is present in an amount greater than zero to 5 wt%. In some embodiments, the calcium sulphate, any of the hydrated forms of calcium sulphate (e.g. gypsum, hemihydrate, anhydrite), or a combination thereof is present in an amount of 1 - 6 wt%. In some embodiments, the calcium sulphate, any of the hydrated forms of calcium sulphate (e.g. gypsum, hemihydrate, anhydrite), or a combination thereof is present in an amount of 2 - 5 wt%. In some embodiments, the calcium sulphate, any of the hydrated forms of calcium sulphate (e.g. gypsum, hemihydrate, anhydrite), or a combination thereof is present in an amount of 1 - 3 wt%.
In some embodiments, the reactive powder further comprises gypsum. In some embodiments, the gypsum is present in an amount greater than 0 to 10 wt% based on the weight of the reactive powder. In some embodiments, the gypsum is present in an amount greater than 0 to 5 wt% based on the weight of the reactive powder. In some embodiments, the gypsum is present in an amount of 1 - 6 wt%, 2-5 wt%, or 1 - 3 wt% based on the weight of the reactive powder.
The methods disclosed herein include an activator. In some embodiments, the activator is sodium sulphate or potassium sulphate. In some embodiments, the activator is sodium sulphate. In some embodiments, the activator is potassium sulphate.
In some embodiments, the activator is present in an amount of 1.5 - 6 wt%, based on the total amount of the cement composition. In some embodiments, the activator is present in an amount of 1 - 6 wt%, based on the total amount of the cement composition. In some embodiments, the activator is present in an amount of 1 - 3 wt%, based on the total amount of the cement composition. In some embodiments, the activator is present in an amount of 0.5 - 6 wt%, based on the total amount of the cement composition. In some embodiments, the activator is present in an amount of 0.5 - 4 wt%, based on the total amount of the cement composition.
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The methods disclosed herein include a retardant. In some embodiments, the retardant is selected from a sugar, a phosphonate, organic acids or their salts, or a mixture thereof. In some embodiments, the retardant includes a sugar. In some embodiments, the retardant includes sodium citrate. In some embodiments, the retardant includes a commercially available retardant. In some embodiments, the retardant includes Sika Retarder N. Sika Retarder N is a proprietary retardant and is a liquid retardant containing selected carbohydrates. The rate of addition of Sika Retarder N is generally in the range of 200ml ± 100ml per 100kg of cementitious materials. In some embodiments, Sika Retarder N can be used to retard the setting time of the concrete to allow concreting under conditions of high ambient temperatures and placing of mass concrete. In some embodiments, Sika Retarder N can be used for pumped, pre-stressed and structural concrete. The effect of Sika Retarder N depends on a number of factors such as cement type, ambient temperature and mix design. The dosage used can be determined by site or laboratory tests with the particular concrete mix design. The Sika line of proprietary retardants and are available from Sika Australia Pty. Ltd.
In some embodiments, the retardant includes SikaTard 930 or SikaTard 990. SikaTard 930 is a proprietary liquid solution of polycarbonate acid salts. SikaTard 930 is an admixture developed for the control of cement hydration. SikaTard 930 facilitates stabilization of concrete mixes for long periods without negatively influencing their quality. The rate of addition of SikaTard 930 is generally in the range of 200ml ± 100ml per 100kg of cementitious materials. Sikatard 990 is also a proprietary liquid solution of polycarbonate acid salts. The rate of addition of SikaTard 990 is generally in the range of 250-2000 mls/100 kg of cementitious materials.
The methods disclosed herein include an accelerator such as a liquid or solid accelerator. In some embodiments, the accelerator is a liquid accelerator. In some embodiments, the accelerator includes an alkaline earth metal. In some embodiments, the accelerator includes calcium nitrate, calcium chloride, calcium hydroxide, calcium oxide, or calcium formate.
In some embodiments, the accelerator is a nitrate of an alkaline earth metal. In some embodiments, the accelerator is calcium nitrate. In some embodiments, the accelerator is added in combination with a strength accelerator. In some embodiments, the strength accelerator is added in combination with a salt of thiocyanic acid. In some embodiments, the accelerator is added in combination with sodium thiocyanate or triethanolamine.
In some embodiments, the accelerator includes a commercially available accelerator. In some embodiments, the accelerator includes Sika Rapid 4. SikaRapid-4 is a set accelerator for concrete and mortar containing added chloride (1000ml contains approximately 86g Chloride ion). Dosage is generally 400ml - 2000ml/100 kg of total cementitious material. The exact dosage rate can be determined by site trials. The Sika line of proprietary accelerators are
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PCT/IB2017/056456 available from Sika Australia Pty. Ltd, and comprise a mixture of calcium nitrate and calcium chloride.
In some embodiments, the method disclosed herein includes mixing the reactive powder, the activator, and the retardant in the presence of water, such as in a cement mixer, and then later adding the accelerant. In some embodiments, the accelerator is added 30 seconds to 60 minutes after the mixing of the reactive powder, activator, and retardant. In some embodiments, the accelerator is added 1 minute to 60 minutes after the mixing of the reactive powder, activator, and retardant. In some embodiments, the accelerator is added 30 seconds to 30 minutes after the mixing of the reactive powder, activator, and retardant. In some embodiments, the accelerator is added 30 seconds to 20 minutes after the mixing of the reactive powder, activator, and retardant. In some embodiments, the accelerator is added 1 minute to 15 minutes after the mixing of the reactive powder, activator, and retardant. In some embodiments, the accelerator is added 1 minute to 10 minutes after the mixing of the reactive powder, activator, and retardant. In some embodiments, the accelerator is added 1 minute to 5 minutes after the mixing of the reactive powder, activator, and retardant.
In some embodiments, the accelerator is added at least 30 seconds (for example, at least 30 seconds, at least 1 minute, at least 2 minutes, at least 3 minutes, at least 4 minutes, at least 5 minutes, at least 6 minutes, at least 7 minutes, at least 8 minutes, at least 9 minutes, at least 10 minutes, at least 15 minutes, at least 20 minutes, at least 25 minutes, at least 30 minutes, at least 40 minutes, at least 50 minutes) after the mixing of the reactive powder, activator, and retardant.
In some embodiments, the accelerator is added less than 60 minutes (for example, less than 60 minutes, less than 50 minutes, less than 40 minutes, less than 30 minutes, less than 25 minutes, less than 20 minutes, less than 15 minutes, less than 10 minutes, less than 5 minutes, or less than 1 minute) after the mixing of the reactive powder, activator, and retardant.
In some embodiments, the accelerator is added to the reactive powder, activator, and retardant after a suitable period of time to allow the ordinary portland cement (OPC) grains to adsorb the retardant.
In some embodiments, the addition of the retardant and the accelerator to the cement composition increases the compressive strength of the cement by at least 5% (for example, at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 100%) for a given amount of cement in comparison to a cement composition lacking the retardant and the accelerator. In some embodiments, the compressive strength can be measured according to AS1012.9:2014. This standard is used in Australia, but other national standards can be used as
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PCT/IB2017/056456 well. As a result, the use of the retardant and later added accelerator can produce concrete with much lower amounts of cement for a given strength grade.
In some embodiments, the cement composition is provided as a binder for aggregate and other materials to produce concrete. Concrete is a construction material composed of cement (commonly portland cement) as well as other cementitious or pozzolanic materials such as fly ash and slag, aggregate (generally a coarse aggregate made of crushed rocks such as limestone, or granite, plus a fine aggregate such as sand), water, and chemical admixtures. In some embodiments, the cement composition further comprises aggregate. In some embodiments, the aggregate is present in an amount of 65 - 95 wt % of the concrete.
EXAMPLES
The following examples are set forth below to illustrate the compositions, methods, and results according to the disclosed subject matter. These examples are not intended to be inclusive of all aspects of the subject matter disclosed herein, but rather to illustrate representative methods and results. These examples are not intended to exclude equivalents and variations of the present disclosure which are apparent to one skilled in the art. Parts and percentages are provided on a weight basis herein, unless indicated otherwise.
Example 1. Concrete cylinder results for low CO2 cement compositions
Concrete cylinders were prepared for testing. The process included preparing a blend of ordinary portland cement (OPC), ground granulated blast furnace slag (GGBFS), and/or activator, to form the binder mixture. Aggregate was then added to the binder mixture to prepare a concrete precursor. The retardant was added to the initial water and mixed with the binder mixture until sufficient time had passed for the retardant to be adsorbed onto the cement grains. Then, a liquid accelerator was added with the finishing water. The concrete mixture was formed into cylinders for testing. As tested herein, the cylinders are 100 mm in diameter and 200 mm high.
In this example, various ternary mixtures (OPC, GGBFS, and/or sodium sulphate) were analyzed in combination with the addition of retardants, following by the delayed addition of an accelerator. In some experiments, gypsum was optionally added to the mixtures. The gypsum added in the milling process partially dehydrates, and thus the mixture comprises calcium sulphate, any of the hydrated forms of calcium sulphate (e.g. gypsum, hemihydrate, anhydrite), or a combination thereof.
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The cement mixtures shown in Table 1 below (40% OPC with GGBFS replacement (gypsum / sodium sulphate additions)) were tested in combination with Sika Retarder N as a retardant and/or Sika Rapid 4 as a liquid accelerator.
Table 1. Concrete cylinder results at 23 “ C for 40% OPC with GGBFS replacement
1 | 2 | 3 | 4 | 5 | |
wt% | |||||
OPC | 100 | 40 | 40 | 40 | 40 |
GGBFS | 57 | 57 | 57 | 57 | |
Na2SO4 | 3 | 3 | |||
Gypsum | 3 | 3 |
mL / 100kg binder
Retarder | 200 | 200 | |||
Accelerator | 800 | 800 | |||
MPa | |||||
3 Day | 31 | 19 | 27 | 25 | 33 |
7 Day | 38 | 27 | 41 | 31 | 40 |
28 Day | 47 | 37 | 57 | 38 | 47 |
As shown in Table 1, addition of the retardant (retarder) followed by the delayed addition 10 of the accelerator resulted in significant improvements in cement compressive strength.
The cement mixtures shown in Table 2 below (50% OPC with GGBFS replacement (gypsum / sodium sulphate additions)) were next tested using the same process and were tested in combination with Sika Retarder N as a retardant and/or Sika Rapid 4 as a liquid accelerator.
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Table 2. Concrete cylinder results at 23 “ C for 50% OPC with GGBFS replacement
1 | 2 | 3 | 4 | |
wt% | ||||
OPC | 100 | 50 | 50 | 50 |
GGBFS | 47.5 | 47.5 | 47.5 | |
Na2SO4 | 2.5 | 2.5 | 1.25 |
Gypsum 1.25 mL / 100kg binder
Retarder | 100 | 100 | ||
Accelerator | 400 | 400 | ||
MPa | ||||
3 Day | 27 | 24 | 27 | 25 |
7 Day | 32 | 30 | 35 | 36 |
28 Day | 41 | 35 | 45 | 45 |
As shown in Table 2, addition of the retardant followed by the delayed addition of the 5 accelerator to the 50% OPC mix resulted in significant improvements in cement compressive strength.
The cement mixtures shown in Table 3 below (50% OPC with GGBFS replacement (gypsum / sodium sulphate additions)) were also tested using the same process in combination with Sika Retarder N as a retardant and/or Sika Rapid 4 as a liquid accelerator.
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Table 3: Concrete cylinder results at 23 “ C for 50% OPC with GGBFS replacement (retardant and/or accelerator)
1 | 2 | 3 | 4 | 5 | 6 | |
wt% | ||||||
OPC | 100 | 100 | 50 | 50 | 50 | 50 |
GGBFS | 47.5 | 47.5 | 47.5 | 47.5 | ||
Na2SO4 | 2.5 | 1.25 | 1.25 | 1.25 | ||
Gypsum | 1.25 | 1.25 | 1.25 |
mL / 100kg binder
Retarder Accelerator | 100 | 100 | 100 | 100 400 | 200 600 | |
MPa | ||||||
3 Day | 31 | 31 | 27 | 24 | 27 | 29 |
7 Day | 38 | 40 | 37 | 35 | 40 | 41 |
28 Day | 47 | 51 | 48 | 46 | 51 | 53 |
As shown in Table 3, addition of the retardant followed by the delayed addition of the accelerator to the 50% OPC mix resulted in significant improvements in cement compressive strength.
The cement mixtures shown in Table 4 below (100% OPC) were tested in combination with Sika Retarder N as a retardant and/or Sika Rapid 4 as a liquid accelerator, along with the addition of a water reducer. In the example here, the water reducer used was Sika Plastiment 10, which comprises a combination of polycarboxylate ether and lignosulphonate water reducing agents.
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Table 4. Concrete cylinder results at 23 ° C for 100% OPC
1 | 2 | 3 | 4 | 5 | 6 | |
wt% | ||||||
OPC GGBFS Na2SO4 Gypsum | 100 | 100 | 100 | 100 | 100 | 100 |
ml / 100kg binder | ||||||
Retarder | 200 | 200 | 400 | 800 | 800 | 1600 |
Accelerator | 800 | 1600 | 3200 | |||
Water reducer | y | y | y | y | y | y |
MPa | ||||||
3 Day | 31 | 35 | 39 | 35 | 48 | 41 |
7 Day | 41 | 43 | 49 | 43 | 53 | 53 |
28 Day | 53 | 53 | 61 | 54 | 64 | 64 |
As shown in Table 4, addition of the retardant followed by the delayed addition of the accelerator to the 100% OPC mix resulted in significant improvements in cement compressive 5 strength.
The cement mixtures shown in Table 5 below (50% OPC with GGBFS replacement (gypsum / sodium sulphate additions)) were also tested using a combination of Sika Retarder N as a retardant and/or Sika Rapid 4 as a liquid accelerator. The accelerator was added at various 10 time points to examine the effect on cement compressive strength and initial set time.
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Table 5. Concrete cylinder results at 23 ° C for 50% OPC with GGBFS replacement and various delay times
1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | |
wt% | |||||||||
OPC | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
GGBFS | 47.5 | 47.5 | 47.5 | 47.5 | 47.5 | 47.5 | 47.5 | 47.5 | 47.5 |
Na2SO4 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 |
Gypsum mL / 100kg binder
Retarder | 200 | 200 | 200 | 200 | 200 | 200 | 200 | 200 | 0 |
Accelerator | 0 | 800 | 800 | 800 | 800 | 800 | 800 | 800 | 800 |
Delay time (min) | 0 | 0 | 0.5 | 1 | 2 | 6 | 10 | 30 | 0 |
MPa | |||||||||
3 Day | 31 | 31 | 33 | 33 | 32 | 34 | 31 | 33 | 32 |
7 Day | 39 | 40 | 42 | 42 | 41 | 43 | 41 | 42 | 41 |
28 Day | 49 | 51 | 49 | 50 | 51 | 53 | 45 | 49 | 47 |
Initial Set (hours) | 5.3 | 4.4 | 5.6 | 5.5 | 5.6 | 5.1 | 5.3 | 3.9 | 3.2 |
10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | |
wt% | |||||||||
OPC | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
GGBFS | 47.5 | 47.5 | 47.5 | 47.5 | 47.5 | 47.5 | 47.5 | 47.5 | 47.5 |
Na2SO4 | 1.25 | 1.25 | 1.25 | 1.25 | 1.25 | 1.25 | 1.25 | 1.25 | 1.25 |
Gypsum | 1.25 | 1.25 | 1.25 | 1.25 | 1.25 | 1.25 | 1.25 | 1.25 | 1.25 |
mL / 100kg binder
Retarder | 200 | 200 | 200 | 200 | 200 | 200 | 200 | 200 | 0 |
Accelerator | 0 | 800 | 800 | 800 | 800 | 800 | 800 | 800 | 800 |
Delay time (min) | 0 | 0 | 0.5 | 1 | 2 | 6 | 10 | 30 | 0 |
MPa | |||||||||
3 Day | 29 | 32 | 31 | 31 | 32 | 32 | 32 | 30 | 27 |
7 Day | 39 | 40 | 41 | 42 | 41 | 42 | 41 | 42 | 36 |
28 Day | 50 | 53 | 54 | 55 | 53 | 54 | 51 | 51 | 49 |
Initial Set (hours) | 6.4 | 5.3 | 6.4 | 6.5 | 6.3 | 6.2 | 5.7 | 4.7 | 3.4 |
As shown in Table 5, addition of the retardant followed by the delayed addition of the accelerator to the 50% OPC mix resulted in significant improvements in cement compressive 5 strength. The initial set time decreased at the later delayed time points for accelerator addition
WO 2019/077390
PCT/IB2017/056456 (for example, at 30 minutes delay). These results demonstrate the importance of the delayed accelerator addition on strength and setting time.
The cement mixtures shown in Table 6 below (50% OPC with GGBFS replacement (sodium sulphate additions)) were also tested using the same process as above in combination 5 with Sika Retarder N as a retardant and/or Sika Rapid 4 as a liquid accelerator, along with the addition of a water reducer. In the example here, the water reducer used was Sika Plastiment 10, which comprises a combination of polycarboxylate ether and lignosulphonate water reducing agents. The accelerator was added at various time points (6 and 60 minutes) to examine the effect on cement compressive strength and initial set time.
Table 6. Concrete cylinder results at 23 ° C for 50% OPC with GGBFS replacement and water reducer
1 | 2 | 3 | 4 | ||
wt% | |||||
OPC | 50 | 50 | 50 | 50 | |
GGBFS | 47.5 | 47.5 | 47.5 | 47.5 | |
Na2SO4 | 2.5 | 2.5 | 2.5 | 2.5 |
Gypsum
mL / 100kg binder | ||||
Water Reducer | 400 | 400 | 400 | 400 |
Retarder | 200 | 400 | 200 | 400 |
Accelerator | 1600 | 1600 | ||
Delay time | ||||
(min) | 6 | 60 | ||
3 Day | 33 | 36 | ||
37 | 43 | |||
7 Day | 41 | 47 | 37 | 45 |
28 Day | 52 | 58 | 49 | 55 |
Initial Set | ||||
(hours) | 5.3 | 6.3 | 5.3 | 6.6 |
As shown in Table 6, addition of the retardant followed by the delayed addition of the accelerator to the 50% OPC mix in the presence of a water reducer resulted in significant improvements in cement compressive strength. However, the initial set time actually increased, even with the addition of the accelerator, when the water reducer was present.
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The methods of the appended claims are not limited in scope by the methods described herein, which are intended as illustrations of a few aspects of the claims and any methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the methods in addition to those shown and described herein are intended to fall 5 within the scope of the appended claims. Further, while only certain method steps disclosed herein are specifically described, other combinations of method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein; however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated.
Claims (38)
- WHAT IS CLAIMED IS:1. A method for producing a cement composition, comprising:mixing reactants comprising a reactive powder, an activator, and a retardant in the presence of water, wherein the reactive powder comprises:portland cement and/or portland cement clinker; and slag;mixing an accelerator into the reactants, wherein the accelerator is added from 30 seconds to 60 minutes after the mixing of the reactive powder, activator, and retardant; and allowing the reactants to react to form the cement composition.
- 2. The method of claim 1, wherein the weight ratio of slag to portland cement and/or portland cement clinker is in the range of 1:3 to 9:1.
- 3. The method of claim 2, wherein the ratio of slag to portland cement and/or portland cement clinker is 1:2 to 4:1.
- 4. The method of claim 1, wherein the portland cement and/or portland cement clinker is present in an amount of from 20 wt% to 65 wt% of the total amount of reactive powder.
- 5. The method of claim 4, wherein the portland cement and/or portland cement clinker is present in an amount of from 30 wt% to 50 wt% of the total amount of reactive powder.
- 6. The method of any one of claims 1 to 4, wherein the slag is present in an amount of 20 wt% to 90 wt% of the total amount of reactive powder.
- 7. The method of claim 6, wherein the slag is present in an amount of 50 wt% to 70 wt% of the total amount of reactive powder.
- 8. The method of any one of claims 1 to 7, wherein the slag is granulated blast furnace slag.
- 9. The method of any one of claims 1 to 7, wherein the slag is steel slag.
- 10. The method of any one of claims 1 to 9, wherein the slag is granulated blast furnace slag in combination with steel slag.WO 2019/077390PCT/IB2017/056456
- 11. The method of claim 9 or 10, wherein the steel slag constitutes greater than 0 to 30 wt% of the total amount of reactive powder.
- 12. The method of claim 11, wherein the steel slag constitutes greater than 0 to 20 wt% of the total amount of reactive powder.
- 13. The method of any one of claims 1 to 12, wherein the slag comprises CaO and S1O2, and wherein the CaO/SiCh wt ratio of the slag is in the range of 1.0 - 1.3.
- 14. The method of any one of claims 1 to 13, wherein the activator is present in an amount of 1 - 6 wt%, based on the total amount of the cement composition.
- 15. The method of any one of claims 1 to 14, wherein the activator is sodium sulphate or potassium sulphate.
- 16. The method of any one of claims 1 to 15, wherein the retardant is selected from a sugar, a phosphonate, organic acids or their salts, or a mixture thereof.
- 17. The method of claim 16, wherein the retardant includes a sugar.
- 18. The method of claim 16 or 17, wherein the retardant includes Sika Retarder N.
- 19. The method of any one of claims 16 to 18, wherein the retardant includes sodium citrate.
- 20. The method of any one of claims 1 to 19, wherein the accelerator includes the nitrate of an alkaline earth metal.
- 21. The method of claim 20, wherein the accelerator includes calcium nitrate.
- 22. The method of any one of claims 1 to 19, wherein the accelerator includes calcium nitrate, calcium chloride, calcium hydroxide, calcium oxide, or calcium formate.
- 23. The method of any one of claims 1 to 19, wherein the accelerator includes Sika Rapid 4.
- 24. The method of any one of claims 1 to 23, wherein the accelerator is added in combination with sodium thiocyanate or triethanolamine.WO 2019/077390PCT/IB2017/056456
- 25. The method of any one of claims 1 to 24, wherein the accelerator is added 30 seconds to 30 minutes after the mixing of the reactive powder, activator, and retardant.
- 26. The method of claim 25, wherein the accelerator is added 30 seconds to 20 minutes after the mixing of the reactive powder, activator, and retardant.
- 27. The method of claim 26, wherein the accelerator is added 1 minute to 15 minutes after the mixing of the reactive powder, activator, and retardant.
- 28. The method of claim 27, wherein the accelerator is added 1 minute to 10 minutes after the mixing of the reactive powder, activator, and retardant.
- 29. The method of claim 28, wherein the accelerator is added 1 minute to 5 minutes after the mixing of the reactive powder, activator, and retardant.
- 30. The method of any one of claims 1 to 29, wherein the reactive powder further comprises calcium sulphate, any of the hydrated forms of calcium sulphate, or a combination thereof.
- 31. The method of claim 30, wherein the calcium sulphate, any of the hydrated forms of calcium sulphate, or a combination thereof is present in an amount greater than 0 to 10 wt% of the total amount of reactive powder.
- 32. The method of claim 31, wherein the calcium sulphate, any of the hydrated forms of calcium sulphate, or a combination thereof is present in an amount greater than 0 to 5 wt% of the total amount of reactive powder.
- 33. The method of claim 30, wherein the calcium sulphate, any of the hydrated forms of calcium sulphate, or a combination thereof is present in an amount of 1 - 6 wt% of the total amount of reactive powder.
- 34. The method of claim 33, wherein the calcium sulphate, any of the hydrated forms of calcium sulphate, or a combination thereof is present in an amount of 2 - 5 wt% of the total amount of reactive powder.
- 35. The method of any one of claims 30 to 34, wherein the reactive powder comprises gypsum.WO 2019/077390PCT/IB2017/056456
- 36. A cement composition prepared according to any one of claims 1 to 35.
- 37. A method of making concrete according to any one of claims 1 to 36, further comprising mixing aggregate with the reactants.
- 38. The method of claim 37, wherein the aggregate is in a range of 65 - 95 wt % of 5 the concrete.
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