Compositions and methods of making gelling binders

Abstract

The present disclosure describes compositions of cementitious materials and methods of making the same. The cementitious material may be a chemically activated concrete material utilizing industrial by-products and / or natural materials, which may provide an environmentally friendly substitute for Portland cement and other traditional cement materials. The cementitious material can replace Portland cement or be added to Portland cement to form a building material.

Description

Cross-references to related applications

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 453,437, filed March 20, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0002] This disclosure relates to compositions of chemically activated cementitious materials and methods for manufacturing the same. Background Technology

[0003] Cementitious materials are a key component of building materials and other industries. One of the most common cementitious materials is Portland cement. Despite its widespread use, Portland cement presents environmental problems, including greenhouse gas emissions and the significant energy demands of its production process. Therefore, there is a need for cementitious materials with a smaller environmental footprint.

[0004] One such material is chemically activated cementitious materials, which can be considered an alternative to Portland cement. Chemically activated cementitious materials may contain industrial byproducts or natural materials containing aluminosilicates, such as slag, fly ash, ash from wastes, clay, natural pozzolans, granite, basalt, or zeolite, and represent an opportunity to develop green building materials. Ideally, the alternative should offer strength and durability comparable to Portland cement, while requiring lower energy costs. However, currently available chemically activated materials suffer from poor processability and limited strength. Therefore, it is advantageous and necessary to develop compositions of chemically activated cementitious materials with improved strength, durability, and other desired properties. Summary of the Invention

[0005] In some aspects, the technology described herein relates to a cementing material comprising: one or more chemical activators and industrial by-products or natural materials, wherein the activators include one or more of potassium silicate, potassium carbonate, potassium phosphate, potassium bicarbonate, potassium nitrate, potassium hydroxide, potassium oxide, potassium sulfate, sodium silicate, sodium carbonate, sodium phosphate, sodium bicarbonate, sodium nitrate, sodium hydroxide, sodium oxide, sodium sulfate, calcium nitrate, calcium silicate, calcium hydroxide, calcium oxide, calcium aluminate, calcium sulfate, calcium aluminosilicate, hydrated calcium silicate, hydrated calcium aluminosilicate, or combinations thereof, and wherein the industrial by-products or natural materials include ferrous slag, non-ferrous slag, converter steel slag, air-cooled slag, Solvay phosphorus slag, bauxites slag / residue, zinc slag, lead slag, and electric arc furnace (EAF) slag. (EAF) slag), granulated blast furnace slag, ladle slag, copper slag, mine tailings, zeolite, clay, volcanic lava, volcanic tuff, metakaolin, calcined shale, silica fume gauze, biomass ash, halloysite, calcined clay, basalt, granite, pumice, natural volcanic ash, bottom ash, fly ash, cement kiln dust, fine waste glass powder from waste glass, mining waste (e.g., Belterra clay), finely ground waste concrete powder from construction and demolition waste. powder), or rubble, and EAF dust and lime kiln dust, municipal solid waste incineration ash, limestone, marble, gabbro, or any combination thereof.

[0006] In some respects, the technology described herein relates to a cementing material that further comprises one or more of sand, gravel, pH adjusting additives, curing enhancers, agglomeration reducers, retarders, strength enhancers, corrosion inhibitors, shrinkage reducers, crack reducers, viscosity reducers, superplasticizers, air-entraining agents, or combinations thereof.

[0007] In some respects, the techniques described herein relate to a gelling material containing less than about 30 wt.% of a chemical activator.

[0008] In some respects, the techniques described herein relate to a gelling material containing less than about 15 wt.% of a chemical activator.

[0009] In some respects, the techniques described herein relate to a gelling material containing less than about 10 wt.% of a chemical activator.

[0010] In some respects, the techniques described herein relate to a gelling material containing less than about 5 wt.% of a chemical activator.

[0011] In some aspects, the technology described herein relates to a method for manufacturing a cementitious material, comprising: combining a chemical activator with industrial by-products and / or natural materials with water to form a cementitious material, wherein the activator comprises potassium silicate, potassium carbonate, potassium phosphate, potassium bicarbonate, potassium nitrate, potassium hydroxide, potassium oxide, potassium sulfate, sodium silicate, sodium carbonate, sodium phosphate, sodium bicarbonate, sodium nitrate, sodium hydroxide, sodium oxide, sodium sulfate, calcium nitrate, calcium silicate, calcium hydroxide, calcium oxide, calcium aluminate, calcium sulfate, calcium aluminosilicate, hydrated calcium silicate, hydrated calcium aluminosilicate, or combinations thereof, and wherein the industrial by-products or natural materials comprise iron slag, non-iron slag, converter steel slag, air-cooled slag, and thallium slag. Phosphorus slag, bauxite slag or bauxite residue, zinc slag, lead slag, electric arc furnace (EAF) slag, granulated blast furnace slag, ladle slag, copper slag, mine tailings, zeolite, clay, volcanic lava, volcanic tuff, metakaolin, calcined shale, silica fume, biomass ash, halloysite, calcined clay, basalt, granite, pumice, natural volcanic ash, bottom ash, fly ash, cement kiln dust, fine waste glass powder from waste glass, mining waste (e.g., Beltera clay), finely ground waste concrete powder or crushed stone from construction and demolition waste, as well as EAF dust and lime kiln dust, municipal solid waste incineration ash, limestone, marble, gabbro, or any combination thereof.

[0012] In some respects, the techniques described herein relate to a method in which the chemical activator and the industrial byproducts and / or natural materials are mixed prior to being combined with water.

[0013] In some respects, the techniques described herein relate to a method in which the chemical activator and the industrial byproducts and / or natural materials are mixed in a grinding mill.

[0014] In some respects, the techniques described herein relate to a method in which the chemical activator is first dissolved in water before being combined with the industrial byproducts and / or natural materials.

[0015] In some respects, the technology described herein relates to a method that further includes adding one or more of sand, gravel, pH-adjusting additives, curing enhancers, agglomeration reducers, retarders, strength enhancers, corrosion inhibitors, shrinkage reducers, crack reducers, viscosity reducers, superplasticizers, air-entraining agents, or combinations thereof to the chemical activator and the industrial by-products and / or natural materials.

[0016] In some aspects, the technology described herein relates to a cementing material comprising: a chemical activator including one or more of potassium silicate, potassium carbonate, potassium phosphate, potassium bicarbonate, potassium nitrate, potassium hydroxide, potassium oxide, potassium sulfate, sodium silicate, sodium carbonate, sodium phosphate, sodium bicarbonate, sodium nitrate, sodium hydroxide, sodium oxide, sodium sulfate, calcium nitrate, calcium silicate, calcium hydroxide, calcium oxide, calcium aluminate, calcium sulfate, calcium aluminosilicate, hydrated calcium silicate, and hydrated calcium aluminosilicate; and industrial by-products and / or natural materials including iron slag, non-iron slag, converter steel slag, air-cooled slag, Solvay phosphate slag, bauxite slag / residue, zinc slag, lead slag, electric arc furnace (EAF) slag, granulated blast furnace slag, ladle slag, copper slag, mine tailings, zeolite, clay, volcanic lava, volcanic tuff, metakaolin, calcined shale, and silica fume. The following are included in the list of solid waste materials: gaize, biomass ash, halloysite, calcined clay, basalt, granite, pumice, natural volcanic ash, bottom ash, fly ash, cement kiln dust, fine waste glass powder from waste glass, mining waste (e.g., Beltera clay), finely ground waste concrete powder or gravel from construction and demolition waste, and EAF dust and lime kiln dust, or municipal solid waste incineration ash.

[0017] In some respects, the technology described herein relates to a cementing material that further comprises one or more of sand, gravel, pH adjusting additives, curing enhancers, agglomeration reducers, retarders, strength enhancers, corrosion inhibitors, shrinkage reducers, crack reducers, viscosity reducers, superplasticizers, air-entraining agents, or combinations thereof.

[0018] In some respects, the techniques described herein relate to a gelling material containing less than about 30 wt.% of a chemical activator.

[0019] In some respects, the techniques described herein relate to a gelling material containing less than about 15 wt.% of a chemical activator.

[0020] In some respects, the techniques described herein relate to a gelling material containing less than about 10 wt.% of a chemical activator.

[0021] In some respects, the techniques described herein relate to a gelling material containing less than about 5 wt.% of a chemical activator.

[0022] In some respects, the technology described herein relates to a gelling material that further comprises a pigment admixture in an amount of about 0.1 wt.% to about 3 wt.% of the gelling material, wherein the pigment admixture comprises one or more of red iron oxide, black iron oxide, chromium oxide, and cobalt oxide.

[0023] In some respects, the technology described herein relates to a cementitious material that further comprises an admixture in an amount of about 0.5% to about 5% of the cementitious material, and wherein said admixture includes a pH adjusting admixture, a curing enhancer, an agglomeration reducer, a retarder, a strength enhancer, a corrosion inhibitor, a shrinkage reducer, a crack reducer, a viscosity reducer, a superplasticizer, an air entrainer, or a combination thereof.

[0024] In some respects, the technology described herein relates to a gelling material having a compressive strength of at least 1000 psi after curing.

[0025] In some respects, the technology described herein relates to a cementitious material that is capable of curing at a temperature of at least about 23°C for cast-in-place or precast applications.

[0026] In some aspects, the technology described herein relates to a method of manufacturing a gelling material, comprising: contacting an industrial by-product and / or natural material with one or more chemical activators or water; mixing the industrial by-product and / or natural material with one or more of the chemical activators or water to form a gelling material, wherein the chemical activator comprises one or more of potassium silicate, potassium carbonate, potassium phosphate, potassium bicarbonate, potassium nitrate, potassium hydroxide, potassium oxide, potassium sulfate, sodium silicate, sodium carbonate, sodium phosphate, sodium bicarbonate, sodium nitrate, sodium hydroxide, sodium oxide, sodium sulfate, calcium nitrate, calcium silicate, calcium hydroxide, calcium oxide, calcium aluminate, calcium sulfate, calcium aluminosilicate, hydrated calcium silicate, and hydrated calcium aluminosilicate, and wherein the industrial by-product and / or natural material is mixed with one or more of the chemical activators or water to form a gelling material. By-products or natural materials include iron slag, non-iron slag, converter steel slag, air-cooled slag, Solvay phosphorus slag, bauxite slag / residue, zinc slag, lead slag, electric arc furnace (EAF) slag, granulated blast furnace slag, ladle slag, copper slag, mine tailings, zeolite, clay, volcanic lava, volcanic tuff, metakaolin, calcined shale, silica fume, biomass ash, halloysite, calcined clay, basalt, granite, pumice, natural volcanic ash, bottom ash, fly ash, cement kiln dust, fine waste glass powder from waste glass, mining waste (e.g., Beltera clay), finely ground waste concrete powder or crushed stone from construction and demolition waste, and one or more of EAF dust and lime kiln dust, or municipal solid waste incineration ash.

[0027] In some respects, the techniques described herein relate to a method in which both water and a chemical activator are mixed with the industrial by-product and / or the natural material, and the chemical activator is mixed with the industrial by-product and / or the natural material prior to the water being mixed with the industrial by-product and / or the natural material.

[0028] In some respects, the techniques described herein relate to a method in which the mixing is performed using a grinding mill.

[0029] In some respects, the techniques described herein relate to a method in which the chemical activator is dissolved in water before being mixed with the industrial byproducts and / or natural materials.

[0030] In some respects, the techniques described herein relate to a method that further includes grinding one or more of the industrial by-products and / or natural materials and the chemical activators.

[0031] In some respects, the techniques described herein relate to a method in which the grinding is performed for up to 50 hours.

[0032] In some respects, the technology described herein relates to a method that further includes mixing one or more of sand, gravel, pH-adjusting additives, curing enhancers, agglomeration reducers, retarders, strength enhancers, corrosion inhibitors, shrinkage reducers, crack reducers, viscosity reducers, superplasticizers, and air-entraining agents with the chemical activator and the industrial by-products and / or natural materials.

[0033] In some respects, the techniques described herein relate to a method in which the mixing involves mixing less than about 30 wt.% of a chemical activator.

[0034] In some respects, the techniques described herein relate to a method in which the mixing involves mixing less than about 15 wt.% of a chemical activator.

[0035] In some respects, the techniques described herein relate to a method in which the mixing involves mixing less than about 5 wt.% of a chemical activator.

[0036] In some respects, the techniques described herein relate to a method that further includes curing the cementitious material by contacting it with moisture.

[0037] In some respects, the techniques described herein relate to a method in which the gelling material is cured at a temperature above 0 °C.

[0038] In some respects, the techniques described herein relate to a method in which the chemical activators are mixed in an amount of at least 0.5 wt.%.

[0039] In some respects, the technology described herein relates to a method that further includes curing the cementitious material at a temperature of at least about 23 °C to form a product for cast-in-place or precast applications.

[0040] In some respects, the technology described herein relates to a composite material comprising the cementitious material and one or more aggregates. Detailed Implementation

[0041] This disclosure describes cementitious materials comprising at least one chemical activator and industrial by-products and / or natural materials, and methods for their manufacture. The compositions of this invention may, in some respects, offer improved performance relative to conventional Portland cement, while requiring less energy to produce, thus reducing environmental costs. This disclosure also describes methods and compositions for improving various properties of chemically activated materials. The activated material compositions of the present invention may include iron slag, non-iron slag, converter steel slag, air-cooled slag, Solvay phosphate slag, bauxite slag / residue, zinc slag, lead slag, electric arc furnace (EAF) slag, granulated blast furnace slag, ladle slag, copper slag, mine tailings, zeolite, clay, volcanic lava, volcanic tuff, metakaolin, calcined shale, silica fume, biomass ash, halloysite, calcined clay, basalt, granite, pumice, natural volcanic ash, bottom ash, fly ash, cement kiln dust, fine waste glass powder from waste glass, mining waste (e.g., Belterra clay), finely ground waste concrete powder or crushed stone from construction and demolition waste, as well as EAF dust and lime kiln dust, municipal solid waste incineration ash, limestone, marble, gabbro, or combinations thereof. This disclosure may include milling, which can improve strength and other properties. The cementing materials of this disclosure may also be referred to as binders, chemically activated binders, chemically activated cementing materials, etc.

[0042] In some embodiments, a gelling material is provided, comprising a chemical activator and industrial byproducts and / or natural materials. The gelling material may be a chemically activated gelling binder. The activator is not limited and may include one or more of potassium silicate, potassium carbonate, potassium phosphate, potassium bicarbonate, potassium nitrate, potassium hydroxide, potassium oxide, potassium sulfate, sodium silicate, sodium carbonate, sodium phosphate, sodium bicarbonate, sodium nitrate, sodium hydroxide, sodium oxide, sodium sulfate, calcium nitrate, calcium silicate, calcium hydroxide, calcium oxide, calcium aluminate, calcium sulfate, calcium aluminosilicate, hydrated calcium silicate, hydrated calcium aluminosilicate, or combinations thereof. In some embodiments, the industrial by-products and / or natural materials include iron slag, non-iron slag, converter steel slag, air-cooled slag, Solvay phosphate slag, bauxite slag / residue, zinc slag, lead slag, electric arc furnace (EAF) slag, granulated blast furnace slag, ladle slag, copper slag, mine tailings, zeolite, clay, volcanic lava, volcanic tuff, metakaolin, calcined shale, silica fume, biomass ash, halloysite, calcined clay, basalt, granite, pumice, natural volcanic ash, bottom ash, fly ash, cement kiln dust, fine waste glass powder from waste glass, mining waste (e.g., Belterra clay), finely ground waste concrete powder or crushed stone from construction and demolition waste, and one or more of EAF dust and lime kiln dust, municipal solid waste incineration ash, limestone, marble, gabbro, or combinations thereof, as well as various chemical activators as described above and admixtures for activation, enhancing strength and durability, reducing water content, controlling color, and improving other properties.

[0043] In some aspects, the gelling material comprises the industrial by-products and / or natural materials, two or more chemical activators, and additives for activation, enhancing strength and durability, reducing water content, controlling color, and improving other properties. In some embodiments, the chemically activated gelling binder comprises the industrial by-products and / or natural materials, two or more chemical activators, and additives, subjected to milling for a certain period of time to achieve mechanochemical activation, enhance strength and durability, control color, increase the surface area for effective reaction, and thereby improve other properties.

[0044] In some embodiments, the gelling material of this disclosure is in slurry form, such as an adhesive slurry, wherein the components described herein are mixed with water. The chemically activated gelling adhesives described herein are mixed with water in some embodiments and can cure at room temperature.

[0045] In some embodiments, the gelling material of this disclosure is in slurry form, such as an adhesive slurry, wherein the components described herein are mixed with water. The chemically activated gelling binders described herein are mixed with water in some embodiments and can be cured under high temperature, humid conditions, high pressure, or combinations thereof to manufacture preformed products. The chemically activated gelling binders described herein, in some embodiments, solidify at high temperature within hours, making them ready for demolding.

[0046] In some implementations, for prefabricated products, the curing temperature can be from about 15 °C to about 100 °C, and the curing time can be from about 1 hour to about 24 hours.

[0047] In some embodiments, the cementitious material further comprises sand, gravel, pH adjusting additives, curing enhancers, agglomeration reducers, retarders, strength enhancers, corrosion inhibitors, shrinkage reducers, crack reducers, viscosity reducers, superplasticizers, air-entraining agents, or combinations thereof. Other additives familiar to those skilled in the art may also be included.

[0048] In some embodiments, the gelling material described herein includes a chemical activator, which may comprise various and / or multiple components as described above. The chemical activator may be present in an amount from about 1 wt.% to about 30 wt.% of the mixture, and may be selected from one or more of the aforementioned chemical activators. In some embodiments, the gelling material contains less than about 15 wt.% of a chemical activator or a combination thereof, such as about 30 wt.%, about 29 wt.%, about 28 wt.%, about 27 wt.%, about 26 wt.%, about 25 wt.%, about 24 wt.%, about 23 wt.%, about 22 wt.%, about 21 wt.%, about 20 wt.%, about 19 wt.%, about 18 wt.%, about 17 wt.%, about 16 wt.%, about 15 wt.%, about 14 wt.%, about 13 wt.%, about 12 wt.%, about 11 wt.%, about 10 wt.%, about 9 wt.%, about 8 wt.%, about 7 wt.%, about 6 wt.%, about 5 wt.%, about 4 wt.%, about 3 wt.%, about 2 wt.%, about 1 wt.%, about 0.5 wt.%, or any range or value contained therein. In some embodiments, the remaining weight percentage of the gelling material is industrial by-products and / or natural materials, as well as other additives described herein. In some embodiments, the gelling material comprises at least 80 wt.% or more of industrial by-products and / or natural materials, with the remainder (about 20 wt.% or less) being activators and / or additives. In some embodiments, the gelling material comprises pigments, which are present in an amount of about 0.1 to 10 wt.% of the binder in some embodiments, and may include iron oxide, cobalt oxide, or chromium oxide pigments. In some embodiments, the gelling material may include pH-adjusting additives, curing enhancers, agglomeration reducers, retarders, strength enhancers, corrosion inhibitors, shrinkage reducers, crack reducers, viscosity reducers, air entertainers, plasticizers, and superplasticizers, one or more of which are present in an amount of about 0.1 wt.% to about 5 wt.% of the binder.

[0049] A method for manufacturing a gelling material is provided, comprising combining a chemical activator and an industrial byproduct or natural material with water. In some embodiments, the activator may include one or more of potassium silicate, potassium carbonate, potassium phosphate, potassium bicarbonate, potassium nitrate, potassium hydroxide, potassium oxide, potassium sulfate, sodium silicate, sodium carbonate, sodium phosphate, sodium bicarbonate, sodium nitrate, sodium hydroxide, sodium oxide, sodium sulfate, calcium nitrate, calcium silicate, calcium hydroxide, calcium oxide, calcium aluminate, calcium sulfate, calcium aluminosilicate, hydrated calcium silicate, hydrated calcium aluminosilicate, or combinations thereof. In some embodiments, the industrial by-products and / or natural materials include iron slag, non-iron slag, converter steel slag, air-cooled slag, Solvay phosphate slag, bauxite slag / residue, zinc slag, lead slag, electric arc furnace (EAF) slag, granulated blast furnace slag, ladle slag, copper slag, mine tailings, zeolite, clay, volcanic lava, volcanic tuff, metakaolin, calcined shale, silica fume, biomass ash, halloysite, calcined clay, basalt, granite, pumice, natural volcanic ash, bottom ash, fly ash, cement kiln dust, fine waste glass powder from waste glass, mining waste (e.g., Beltera clay), finely ground waste concrete powder or crushed stone from construction and demolition waste, and one or more of EAF dust and lime kiln dust, municipal solid waste incineration ash, limestone, marble, gabbro, or combinations thereof. There are no particular limitations on the source and specific composition of the industrial by-products and / or natural materials. Combinations of chemical activators and industrial byproducts and / or natural materials with water can form binder slurries and lead to the activation of industrial byproducts and / or natural materials.

[0050] In some embodiments, the chemical activator and the industrial by-product and / or natural material are mixed before being combined with water. In some embodiments, the chemical activator and the industrial by-product and / or natural material may be mixed in a grinder or ball mill such that they are dry-mixed. It is not desirable to be bound by theory, but mixing the chemical activator and the industrial by-product and / or natural material may result in the mechanochemical activation of the industrial by-product, followed by the addition of water to form a binder slurry. In some embodiments, the chemical activator mixture is milled for about 0.1 to about 10 hours, about 1 to about 10 hours, about 1 to about 20 hours, about 1 to about 40 hours, about 1 to about 50 hours, and about 1 to about 100 hours.

[0051] In some embodiments, the chemical activator is dissolved in water and then combined with the industrial by-product and / or natural materials, wherein the water is hot water in some embodiments. The chemical activator dissolved in water can then be combined with the industrial by-product and / or natural materials.

[0052] In some embodiments, the cementitious materials described herein and manufactured by the methods described herein are used directly as cementitious materials in any manner familiar to those skilled in the art, such as for forming concrete. In other embodiments, the cementitious materials of this disclosure are combined with Portland cement or other cementitious materials prior to use. The cementitious materials described in any of the embodiments herein can be used in cast-in-place or precast building applications.

[0053] In some embodiments, the cementitious material provides improved performance relative to Portland cement. Improved performance is not limited and may refer to increased strength, increased durability, reduced water content, lower or reduced heat of hydration, color control, or combinations thereof. The cementitious material disclosed herein may be more environmentally friendly and less expensive than conventional Portland cement.

[0054] This document provides chemically activated material compositions, such as chemically activated gelling materials and chemically activated gelling binders, comprising one or more additives. Methods for preparing chemically activated materials containing one or more additives are also disclosed. Without being bound by theory, the chemical activators and additives described herein activate reactions and improve one or more properties of the chemically activated binders. Milling for different durations can also improve one or more properties of the chemically activated materials. In one embodiment, the size of the chemical activator or additive can be coarse, fine, or ultrafine.

[0055] In some embodiments, a chemically activated gelling binder material is provided, comprising a base material, such as an industrial byproduct and / or a natural material, activated with one or more chemical activators, wherein the activators may include potassium silicate, potassium carbonate, potassium phosphate, potassium bicarbonate, potassium nitrate, potassium hydroxide, potassium oxide, potassium sulfate, sodium silicate, sodium carbonate, sodium phosphate, sodium bicarbonate, sodium nitrate, sodium hydroxide, sodium oxide, sodium sulfate, calcium nitrate, calcium silicate, calcium hydroxide, calcium oxide, calcium aluminate, calcium sulfate, calcium aluminosilicate, hydrated calcium silicate, hydrated calcium aluminosilicate, or combinations thereof; and a combination of one or more admixtures, said admixtures including pigment admixtures, pH adjusting admixtures, curing enhancers, agglomeration reducers, retarders, strength enhancers, corrosion inhibitors, shrinkage reducers, crack reducers, viscosity reducers, air-entraining agents, water-reducing admixtures, plasticizers, and superplasticizers, or combinations thereof.

[0056] The chemically activated gelling binder materials disclosed herein may comprise industrial by-products and / or natural materials with an average particle size of about 1 μm to about 10 μm, about 1 μm to about 20 μm, about 1 μm to about 50 μm, about 1 μm to about 100 μm, about 1 μm to about 150 μm, or about 1 μm to about 200 μm. The admixtures described herein may have an average particle size of about 1 μm to about 10 μm, about 1 μm to about 20 μm, about 1 μm to about 50 μm, about 1 μm to about 100 μm, about 1 μm to about 150 μm, and about 1 μm to about 200 μm. The admixtures are mixed with the materials in a solid or semi-solid, semi-dissolved or completely dissolved form in water.

[0057] In some embodiments, the chemically activated gelling adhesive material comprises one or a combination of two or more chemical activators, which may include compounds such as potassium silicate, potassium carbonate, potassium phosphate, potassium bicarbonate, potassium nitrate, potassium hydroxide, potassium oxide, potassium sulfate, sodium silicate, sodium carbonate, sodium phosphate, sodium bicarbonate, sodium nitrate, sodium hydroxide, sodium oxide, sodium sulfate, calcium nitrate, calcium silicate, calcium hydroxide, calcium oxide, calcium aluminate, calcium sulfate, calcium aluminosilicate, hydrated calcium silicate, hydrated calcium aluminosilicate, or combinations thereof.

[0058] In some embodiments, the mass ratio of the base material (e.g., slag or any industrial by-products and / or natural materials described herein) to the chemical activator is greater than 4.0, for example, from about 5 to about 99. In some embodiments, this ratio is about from 5 to 99. In some embodiments, this ratio is about from 5 to 50. In some embodiments, this ratio is from 5 to 10.

[0059] In some embodiments, the mass ratio of one chemical activator to another is greater than 1, for example, from about 1 to 20. In some embodiments, the ratio is about from 1 to 10. In some embodiments, the ratio is about from 1 to 5. In some embodiments, the ratio is about from 1 to 4.5. In some embodiments, the ratio is about from 1 to 3.5. In some embodiments, the ratio is about from 1 to 2.5. In some embodiments, the ratio is about from 1 to 2. In some embodiments, the ratio is about from 1 to 1.5. In some embodiments, the ratio is about from 1 to 1.25. In some embodiments, the ratio is about from 1 to 1.

[0060] In one embodiment, the chemically activated material comprises an additive, which is one or more pigments uniformly or non-uniformly dispersed in a binder matrix. The pigment can be any suitable metal oxide salt pigment, such as iron oxide red, iron oxide black, chromium oxide, and cobalt oxide. The pigment can be any color, including black, gray, white, blue, green, red, yellow, and brown.

[0061] In some embodiments, the mass ratio of the chemical activator to the pigment additive is greater than 1, for example, from about 1 to 2. In some embodiments, the ratio is from about 1 to 5. In some embodiments, the ratio is from about 1 to 10. In some embodiments, the ratio is from about 1 to 20.

[0062] In some embodiments, the chemically activated gelling adhesive material may include a curing enhancer additive in an amount of about 0.1 wt.% to about 5 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 4 wt.%. In some embodiments, the amount is about 0.1% to about 3%. In some embodiments, the amount is about 0.1% to about 3%. In some embodiments, the amount is about 0.1% to about 2%. In some embodiments, the amount is about 0.1% to about 1%. In some embodiments, the amount is about 0.1% to about 0.5%.

[0063] In some embodiments, the chemically activated gelling binder material may include an agglomeration-reducing admixture in an amount of about 0.1 wt.% to about 5 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 4 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 3 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 3 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 2 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 1 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 0.5 wt.%.

[0064] In some embodiments, the chemically activated gelling binder material may include a strength-enhancing admixture in an amount of about 0.1 wt.% to about 5 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 4 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 3 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 3 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 2 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 1 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 0.5 wt.%.

[0065] In some embodiments, the chemically activated gelling binder material may include a retarder admixture in an amount of about 0.1 wt.% to about 5 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 4 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 3 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 3 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 2 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 1 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 0.5 wt.%.

[0066] In some embodiments, the chemically activated gelling binder material may include a shrinkage-reducing admixture in an amount of about 0.1 wt.% to about 5 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 4 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 3 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 3 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 2 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 1 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 0.5 wt.%.

[0067] In some embodiments, the chemically activated cementitious binder material may comprise a crack-reducing admixture in an amount of about 0.1 wt.% to about 5 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 4 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 3 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 3 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 2 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 1 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 0.5 wt.%.

[0068] In some embodiments, the chemically activated gelling binder material may include a viscosity-reducing additive in an amount of about 0.1 wt.% to about 5 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 4 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 3 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 3 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 2 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 1 wt.%. In some embodiments, the amount is about 0.1 wt.% to about 0.5 wt.%.

[0069] In some embodiments, the chemically activated gelling binder material may include water-reducing admixtures (plasticizers and superplasticizers). The efficiency of the plasticizers and superplasticizers can be evaluated based on their water-reducing capacity in the binder mixture while maintaining the same consistency.

[0070] In some embodiments, the chemically activated gelling binder material comprises at least 0.5 wt.% of one or more of the chemical activators. In some embodiments, the activated gelling binder material comprises pigment additives in an amount from about 0.1 wt.% to about 3 wt.% of the activated material, wherein the pigment additives include iron oxide red, iron oxide black, chromium oxide, and cobalt oxide.

[0071] In some embodiments, the base material is pre-mixed in water and then added to and mixed with the one or more chemical activators, or the one or more chemical activators are pre-mixed in water and then added to and mixed with the base material, or the one or more chemical activators are added together with the base material and then mixed with water.

[0072] In some implementations, one or more base materials, one or more chemical activators, or a combination thereof are ground.

[0073] In some embodiments, the grinding time of the mixture is approximately 0-5 hours. In some embodiments, the grinding time of the mixture is approximately 0-10 hours. In some embodiments, the grinding time of the mixture is approximately 0-20 hours. In some embodiments, the grinding time of the mixture is approximately 0-30 hours. In some embodiments, the grinding time of the mixture is approximately 0-40 hours. In some embodiments, the grinding time of the mixture is approximately 0-50 hours.

[0074] Any suitable aggregate can be used to form composite materials from the chemically activated cementitious binder material, such as building sand or gravel, dark rock, industrial waste, and other types of fillers. The average particle size of the aggregate can range from about 0.1 to about 30 mm. In some embodiments, the average particle size of the aggregate can range from about 0.1 to about 15 mm, or from about 0.1 mm to about 10 mm, or from about 0.1 mm to about 5 mm, or from about 0.1 to about 1 mm.

[0075] This document provides methods for improving one or more properties of chemically activated cementitious binder materials, including by adding various chemical activators and / or admixtures to the binder composition, and / or by grinding the chemically activated cementitious binder mixture. In some embodiments, adding a chemical activator to the base material (e.g., any industrial by-products and / or natural materials described herein) includes adding a solid chemical activator. In some embodiments, adding a chemical activator to the base material includes adding a liquid chemical activator. In some embodiments, adding a chemical activator to the base material includes adding a mixture of solid and liquid chemical activators. In some embodiments, adding an admixture to the base material includes adding a solid admixture. In some embodiments, adding an admixture to the base material includes adding a liquid admixture. In some embodiments, adding an admixture to the base material includes adding a mixture of liquid and solid admixtures. In some embodiments, the base material (such as industrial by-products and / or natural materials), the chemical activator, and the admixture mixture may all be ground. The methods provided herein may include a curing step to form a concrete product. In some embodiments, the chemically activated cementitious binder material has a compressive strength of at least 1000 psi after curing. In some embodiments, the chemically activated gelling adhesive material can be cured at temperatures above about 0 °C. In some embodiments, the chemically activated gelling adhesive material can be cured under normal or humid conditions, room temperature or high temperature, or a combination thereof.

[0076] In some embodiments, when more than one chemical activator is added, the activators can be added in any order. In some embodiments, two or more chemical activators can be added together as a mixture.

[0077] This article provides methods for improving one or more strength properties of chemically activated cementitious binder materials (relative to conventional materials) by adding chemical activators and / or admixtures and / or grinding. Examples of strength properties that can be improved include compressive strength, torsional strength, splitting tensile strength, tensile strength, flexural strength, and combinations thereof.

[0078] This article provides methods for controlling the color of concrete products by adding different admixtures. In some examples, pigment admixtures described in this article are added.

[0079] In some embodiments, activation of the base material (industrial byproducts and / or natural materials) described herein may result in the formation of one or more geopolymer phases, such as hydrated calcium (aluminum) silicate (CASH), hydrated sodium (aluminum) silicate (NASH), or hydrated calcium silicate (CSH), carbonates, or combinations thereof.

[0080] The embodiments described herein can be combined in any way to form new implementations.

[0081] This disclosure is not limited to the specific systems, devices, and methods described, as these are subject to change. The terminology used in the description is for the purpose of describing a particular version or embodiment only and is not intended to limit the scope.

[0082] As used herein, unless the context clearly specifies otherwise, the singular forms “a,” “an,” and “the” include plural references. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Nothing in this disclosure should be construed as an admission that the embodiments described herein are not authorized to exist prior to this disclosure by virtue of a prior invention. As used herein, the term “comprising” means “including, but not limited to,” “including.”

[0083] As used herein, the term “about” means plus or minus 10% of the value used. For example, “about 50%” means in the range of 45-55%. The ranges disclosed herein include both upper and lower limits.

[0084] As used herein, the terms “gelling material,” “chemically activated gelling material,” “chemically activated admixture,” “chemically activated material,” “chemically activated gelling binder,” etc., may be used to refer to the compositions or precursors described herein.

[0085] As used herein, the terms “basic material,” “industrial byproduct,” “natural material,” “slag,” etc., refer to the same general starting material activated by the chemical activators described herein.

[0086] This disclosure should not be limited to the specific embodiments described herein, which are intended to illustrate various aspects. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and apparatuses within the scope of this disclosure, other than those listed herein, will be apparent to those skilled in the art from the foregoing description. Such modifications and variations are intended to fall within the scope of the appended claims. This disclosure should be limited only by the terms of the appended claims and the full scope of their equivalents. It should be understood that this disclosure is not limited to specific methods, reagents, compounds, compositions, or biological systems, which are of course subject to variation. It should also be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0087] Regarding the use of any substantially plural and / or singular terms in this document, those skilled in the art may appropriately convert from plural to singular and / or from singular to plural depending on the context and / or application. For clarity, various permutations and combinations of singular / plural forms may be explicitly listed herein.

[0088] Those skilled in the art will understand that, generally, the terms used herein, particularly in the appended claims (e.g., the body of the appended claims), are generally intended to be “open” terms (e.g., the term “comprising” should be interpreted as “including but not limited to,” the term “having” should be interpreted as “having at least,” the term “including” should be interpreted as “comprising but not limited to,” etc.). While various compositions, methods, and apparatuses are described according to “comprising” various components or steps (interpreted as meaning “including but not limited to”), compositions, methods, and apparatuses may also be “consistently composed of various components and steps” or “comprises various components and steps,” and such terms should be interpreted to define a substantially closed group of members. Those skilled in the art will further understand that if there is an intention to introduce a particular number of claim statements, such intention will be explicitly stated in the claims, and without such statements, such intention does not exist. For example, to aid understanding, the appended claims may contain the use of introductory phrases “at least one” and “one or more” to introduce the claim statement. However, the use of such phrases should not be construed as implying that a claim statement introduced by the indefinite article “a (a)” or “an” limits any particular claim containing such an introductory claim statement to an embodiment containing only one such statement, even when the same claim includes the introductory phrases “one or more” or “at least one” and indefinite articles such as “a (a)” or “an” (e.g., “a (a)” and / or “an” should be interpreted as meaning “at least one” or “one or more”); the same applies to the use of definite articles to introduce the claim statement.

[0089] Furthermore, even when a specific number of introduced claim statements are explicitly stated, those skilled in the art will recognize that such statements should be interpreted as referring to at least the stated number (e.g., a bare statement of "two statements" without other modifiers means at least two statements, or two or more statements). Additionally, in cases where the convention of "at least one of A, B, and C" is used, such a structure is generally intended to be understood by those skilled in the art (e.g., "a system having at least one of A, B, and C" will include, but is not limited to, systems having only A, only B, only C, both A and B, both A and C, both B and C, and / or both A, B, and C). In cases where the convention of "at least one of A, B, or C" is used, such a structure is generally intended to be understood by those skilled in the art (e.g., "a system having at least one of A, B, or C" will include, but is not limited to, systems having only A, only B, only C, both A and B, both A and C, both B and C, and / or both A, B, and C). Those skilled in the art will further understand that virtually any extractive word and / or phrase presenting two or more alternative terms, whether in the specification, claims, or drawings, should be understood to include the possibility of including one, any, or both terms. For example, the phrase “A or B” will be understood to include the possibility of including “A” or “B” or “A and B”.

[0090] Furthermore, where features or aspects of this disclosure are described in terms of the Markush group, those skilled in the art will recognize that this disclosure also describes any individual member or subgroup of the Markush group.

[0091] As those skilled in the art will understand, for any and all purposes, such as in providing a written description, all scopes disclosed herein also include any and all possible subscopes and combinations thereof. Any listed scope can be readily considered adequately descriptive and capable of being decomposed into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each scope discussed herein can be readily decomposed into lower thirds, middle thirds, and upper thirds, etc. As those skilled in the art will also understand, all language such as “up to,” “at least,” etc., includes the stated numbers and refers to scopes that can subsequently be decomposed into subscopes as described above. Finally, as those skilled in the art will understand, a scope includes each individual member. Thus, for example, a group having 1-3 compounds means a group having 1, 2, or 3 compounds.

[0092] The various and other features and functions disclosed above, or their alternatives, can be combined into many other different systems or applications. Those skilled in the art may subsequently make various substitutions, modifications, variations, or improvements that are not currently foreseeable or anticipated, all of which are intended to be included within the disclosed embodiments.

Claims

1. A cementitious material comprising: Chemical activators, including one or more of potassium silicate, potassium carbonate, potassium phosphate, potassium bicarbonate, potassium nitrate, potassium hydroxide, potassium oxide, potassium sulfate, sodium silicate, sodium carbonate, sodium phosphate, sodium bicarbonate, sodium nitrate, sodium hydroxide, sodium oxide, sodium sulfate, calcium nitrate, calcium silicate, calcium hydroxide, calcium oxide, calcium aluminate, calcium sulfate, calcium aluminosilicate, hydrated calcium silicate, and hydrated calcium aluminosilicate; and Industrial by-products and / or natural materials, including iron slag, non-iron slag, converter steel slag, air-cooled slag, Solvay phosphorus slag, bauxite slag / residue, zinc slag, lead slag, electric arc furnace (EAF) slag, granulated blast furnace slag, ladle slag, copper slag, mine tailings, zeolite, clay, volcanic lava, volcanic tuff, metakaolin, calcined shale, silica fume, biomass ash, halloysite, calcined clay, basalt, granite, pumice, natural volcanic ash, bottom ash, fly ash, cement kiln dust, fine waste glass powder from waste glass, mining waste (e.g., Beltera clay), finely ground waste concrete powder or crushed stone from construction and demolition waste, and one or more of EAF dust and lime kiln dust, or municipal solid waste incineration ash.

2. The cementitious material according to claim 1, further comprising one or more of the following: sand, gravel, pH adjusting additive, curing enhancer, agglomeration reducer, retarder, strength enhancer, corrosion inhibitor, shrinkage reducer, crack reducer, viscosity reducer, superplasticizer, air entrainer, or combinations thereof.

3. The cementitious material according to claim 1, wherein the cementitious material contains less than about 30 wt.% of the chemical activator.

4. The gelling material according to claim 1, wherein the gelling material contains less than about 15 wt.% of the chemical activator.

5. The gelling material according to claim 1, wherein the gelling material contains less than about 10 wt.% of the chemical activator.

6. The gelling material according to claim 1, wherein the gelling material contains less than about 5 wt.% of the chemical activator.

7. The cementitious material according to claim 1, further comprising a pigment additive in an amount of about 0.1 wt.% to about 3 wt.% of the cementitious material, wherein the pigment additive comprises one or more of iron oxide red, iron oxide black, chromium oxide and cobalt oxide.

8. The cementitious material according to claim 1, further comprising an admixture in an amount of about 0.5% to about 5% of the cementitious material, wherein the admixture comprises a pH adjusting admixture, a curing enhancer, an agglomeration reducer, a retarder, a strength enhancer, a corrosion inhibitor, a shrinkage reducer, a crack reducer, a viscosity reducer, a superplasticizer, an air entrainer, or a combination thereof.

9. The cementitious material of claim 1, wherein the cementitious material has a compressive strength of at least 1000 psi after curing.

10. The cementitious material of claim 1, wherein the cementitious material is capable of curing at a temperature of at least about 23°C for cast-in-place or precast applications.

11. A method for manufacturing a cementitious material, comprising: Contacting industrial byproducts and / or natural materials with one or more chemical activators or water, The industrial byproducts and / or natural materials are mixed with one or more of the chemical activators or the water to form a gelling material. The chemical activator mentioned herein includes one or more of the following: potassium silicate, potassium carbonate, potassium phosphate, potassium bicarbonate, potassium nitrate, potassium hydroxide, potassium oxide, potassium sulfate, sodium silicate, sodium carbonate, sodium phosphate, sodium bicarbonate, sodium nitrate, sodium hydroxide, sodium oxide, sodium sulfate, calcium nitrate, calcium silicate, calcium hydroxide, calcium oxide, calcium aluminate, calcium sulfate, calcium aluminosilicate, hydrated calcium silicate, and hydrated calcium aluminosilicate. The industrial by-products or natural materials mentioned therein include iron slag, non-iron slag, converter steel slag, air-cooled slag, Solvay phosphorus slag, bauxite slag / residue, zinc slag, lead slag, electric arc furnace (EAF) slag, granulated blast furnace slag, ladle slag, copper slag, mine tailings, zeolite, clay, volcanic lava, volcanic tuff, metakaolin, calcined shale, silica fume, biomass ash, halloysite, calcined clay, basalt, granite, pumice, natural volcanic ash, bottom ash, fly ash, cement kiln dust, fine waste glass powder from waste glass, mining waste (e.g., Beltera clay), finely ground waste concrete powder or crushed stone from construction and demolition waste, and one or more of EAF dust and lime kiln dust, or municipal solid waste incineration ash.

12. The method of claim 11, wherein both water and the chemical activator are mixed with the industrial by-product and / or the natural material, and the chemical activator is mixed with the industrial by-product and / or the natural material prior to the water being mixed with the industrial by-product and / or the natural material.

13. The method of claim 12, wherein the mixing is performed using a grinding mill.

14. The method of claim 11, wherein the chemical activator is dissolved in water before being mixed with the industrial by-product and / or natural material.

15. The method of claim 11, further comprising grinding one or more of the industrial by-products and / or natural materials and the chemical activator.

16. The method of claim 15, wherein the grinding is performed for a maximum of 50 hours.

17. The method of claim 11, further comprising mixing one or more of sand, gravel, pH adjusting additive, curing enhancer, agglomeration reducer, retarder, strength enhancer, corrosion inhibitor, shrinkage reducer, crack reducer, viscosity reducer, superplasticizer, and air-entraining agent with the chemical activator and the industrial by-product and / or natural material.

18. The method of claim 11, wherein the mixing is mixing less than about 30 wt.% of a chemical activator.

19. The method of claim 11, wherein the mixing is mixing less than about 15 wt.% of a chemical activator.

20. The method of claim 11, wherein the mixing is mixing less than about 5 wt.% of a chemical activator.

21. The method of claim 11, further comprising curing the cementitious material by contacting it with moisture.

22. The method of claim 21, wherein the gelling material is cured at a temperature above 0 °C.

23. The method of claim 11, wherein the chemical activator is mixed in an amount of at least 0.5 wt.%.

24. The method of claim 11, further comprising curing the cementitious material at a temperature of at least about 23 °C to form a product for cast-in-place or precast applications.

25. A composite material comprising the cementitious material according to any one of claims 1-10 and one or more aggregates.