WO2015103107A1 - Revêtements anticorrosifs, procédés et leurs utilisations - Google Patents

Revêtements anticorrosifs, procédés et leurs utilisations Download PDF

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Publication number
WO2015103107A1
WO2015103107A1 PCT/US2014/072494 US2014072494W WO2015103107A1 WO 2015103107 A1 WO2015103107 A1 WO 2015103107A1 US 2014072494 W US2014072494 W US 2014072494W WO 2015103107 A1 WO2015103107 A1 WO 2015103107A1
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Prior art keywords
μιη
anticorrosive coating
article
iron
metal
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PCT/US2014/072494
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English (en)
Inventor
Jitendra JAIN
Vahit Atakan
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Solidia Technologies, Inc.
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Publication of WO2015103107A1 publication Critical patent/WO2015103107A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1055—Coating or impregnating with inorganic materials
    • C04B20/107—Acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/02—Pretreatment of the fibres or filaments
    • C22C47/04—Pretreatment of the fibres or filaments by coating, e.g. with a protective or activated covering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising
    • C23C8/16—Oxidising using oxygen-containing compounds, e.g. water, carbon dioxide
    • C23C8/18—Oxidising of ferrous surfaces

Definitions

  • This invention generally relates to anticorrosive coatings for metal surfaces and processes and uses thereof. More particularly, the invention relates to formation of anticorrosive coatings on iron or steel surfaces, such as on embedded iron or steel reinforcement components in composite materials and on surfaces of iron or steel piles and vessels.
  • the unique siderite coating possesses excellent anticorrosive properties, can be formed alongside curing of the bulk composite material, and can significantly improve the service life of coated objects.
  • Precast concrete objects such as pre-stressed concrete girders, beams and railway ties, are elongated beams typically with plain carbon steel as reinforcement.
  • cast-in-place concretes such as bridge deck slabs and pavements are often reinforced with steel.
  • reinforcing bars are common steel bars or meshes of steel wires regularly used as tension devices in reinforced concrete and reinforced masonry structures to strengthen as well as to hold the concrete in compression.
  • the common rebar is made of unfinished tempered steel, making it susceptible to rusting.
  • the concrete cover typically provides a pH value higher than 12, helping the rebar avoid or slow the corrosion process.
  • too little concrete cover or loss of coverage over time can compromise this guard through carbonation from the surface and salt penetration.
  • the high pH of the concrete may protect reinforcing steel from corroding
  • the concrete is affected by chloride penetration from salts during winter season or carbonation reaction with atmospheric carbon dioxide (C0 2 ), which reduces the pH of concrete. This breaks the passivation layer on the rebar leading to corrosion of steel.
  • C0 2 atmospheric carbon dioxide
  • novel composite material that exhibit excellent performance characteristics, including toughness, flexibility, abrasion resistance and durability, which match or exceed that of conventional concrete.
  • the novel composite material can be readily produced from widely available, low cost raw materials by a process suitable for large-scale production with reduced equipment need, improved energy consumption, and more desirable carbon footprint.
  • the raw materials include inexpensive calcium silicate materials, for example, ground wollastonite. Carbon dioxide is consumed in the production as a reactive species and ends up sequestered in the final product. (See, e.g., U.S. Patent No. 8,114,367; U.S. Pub. Nos.
  • the invention is based in part on the unexpected discovery of novel coating methods to protect iron or steel surfaces against corrosion.
  • the methods of the invention can be used in a wide range of applications, for example, to protect iron or steel reinforcement components embedded in composite materials as well as steel surfaces of oil and gas pipelines and vessels.
  • the unconventional process is inexpensive and with desirable carbon footprint.
  • the formed coating exhibits strong bonding to both iron or steel reinforcement components and to the composite material they are embedded in.
  • the anticorrosive coating of the invention can be readily produced from widely available, low cost raw materials by a process suitable for large-scale processing with lower energy consumption.
  • the necessary conditions are aqueous environment with saturated carbon dioxide.
  • the anticorrosive coating of the invention may be used to protect metal objects. It may also be used to protect metal objects embedded in a composite material.
  • the anticorrosive coating may be formed during the carbonation curing of a composite material containing inexpensive calcium silicate and aggregates (e.g., filler materials such as trap rock, sand, perlite or vermiculite).
  • a fluid component is provided as a reaction medium, comprising liquid water and/or water vapor, and a reagent, comprising carbon dioxide (C0 2 ), which is consumed in the production as a reactive species and ends up sequestered in the final product.
  • additives can be used to improve mixture consistency and flow and to fine-tune the physical appearance and mechanical properties of the resulting composite material.
  • additives may include chemical admixtures, rheology modifying admixtures, and pigments.
  • Additive materials may also include natural, synthetic or recycled materials, as well as additives to the fluid component, such as a water-soluble dispersant.
  • the invention generally relates to a process for forming an anticorrosive coating on a metal surface.
  • the process includes contacting the metal surface with an aqueous atmosphere of C0 2 and water vapor at a temperature and for a time period sufficient to form an anticorrosive coating on the metal surface.
  • the invention generally relates to a process for passivating iron or steel reinforcement wires or bars for corrosion resistance.
  • the process includes contacting the iron or steel reinforcement wires, cables or bars with an aqueous suspension of particulate calcium silicate under an atmosphere of C0 2 and water vapor at a pH from about 3.5 to about 14 to form an anticorrosive coating of iron carbonate covering the surface of iron or steel reinforcement wires, cables or bars.
  • the step of contacting the iron or steel surface with an aqueous suspension of particulate calcium silicate is conducted at a temperature in the range from about 10°C to about 150°C, for a time period from about 1 hour to about 150 hours, and under an atmosphere of water and C0 2 having a pressure in the range from ambient atmospheric pressure to about 150 psi above ambient and having a C0 2 concentration ranging from about 10% to about 99%.
  • the particulate calcium silicate having a median particle size in the range from about 500 nm to about 100 ⁇ .
  • the invention generally relates to an article of manufacture having a body prepared from a composite material.
  • the body is embedded with one or more
  • the composite material includes: a plurality of bonding elements, wherein each bonding element comprises: a core comprising primarily calcium silicate, a silica-rich first or inner layer, and a calcium carbonate-rich second or outer layer, and filler particles comprising coarse filler particles and/or fine filler particles, wherein the plurality of bonding elements and the plurality of filler particles together form one or more bonding matrices and the bonding elements and the filler particles are substantially evenly dispersed therein and bonded together.
  • the invention generally relates to an article of manufacture comprising a metal surface coated with an anticorrosive coating comprising metal carbonate.
  • the invention generally relates to an article of manufacture having a body prepared from Portland cement, the body being embedded with one or more
  • each of the one or more reinforcement metal wires, cables or bars is coated with an anticorrosive coating comprising metal carbonate.
  • FIG. 1 is a pressure -temperature phase diagram showing the phases present in the reversible reaction CaC0 3 +Si0 2 ⁇ CaSi0 3 (calcium silicate) + C0 2 .
  • FIG. 2 is a pressure -temperature phase diagram showing the phases present in the reversible reaction 3CaC0 3 + 2CaSi0 3 ⁇ 2Ca 2 Si0 4 CaC0 3 + C0 2 .
  • FIG. 3 is a phase diagram of the CaO-Si0 2 -C0 2 system at a pressure of 1 kilobar.
  • FIG. 4 is a pressure -temperature phase diagram showing the phases present in the reversible reaction MgO + C0 2 ⁇ MgC0 3 .
  • FIG. 5 is a pressure -temperature phase diagram showing the equilibrium curves for the reversible reaction MgO + C0 2 ⁇ MgC0 3 as a function of the proportion of C0 2 in an inert gas.
  • FIG. 6 is a temperature-composition phase diagram that illustrates the stability regions for various phases in the CaC0 3 -MgC0 3 system.
  • FIG. 7 is a tetrahedron diagram illustrating the phase relationships among the compounds CaO, MgO, Si0 2 and C0 2 , and showing the C0 2 deficient region below the Cc-Di- Wo and the Cc-Wo-Mo planes (shaded), where Cc denotes calcite, Wo denotes Wollastonite, Ak denotes Akermanite, Di denotes diopside, and Mo denotes monticellite (CaMgSi0 4 ). [0027] FIG.
  • FIG. 8 is a pressure -temperature phase diagram illustrating the phase relationships among the compounds CaO, MgO, Si0 2 and C0 2 , with univariant curves emanating from the quaternary invariant point involving the phases calcite (Cc), diopside (Di), forsterite (Fo), monticellite (Mo), Akermanite (Ak), and C0 2 .
  • the inset is the phase diagram for the three compound systems of CaC0 3 , MgO and Si0 2 .
  • FIG. 9 is a schematic diagram of a C0 2 composite material curing chamber that provides humidification according to principles of the invention.
  • FIG. 10 is a schematic diagram of a curing chamber with multiple methods of humidity control as well as ability to control and replenish C0 2 using constant flow or pressure regulation and that can control the temperature according to principles of the invention.
  • FIGs. ll(a)-ll(c) are schematic illustrations of cross-sections of bonding elements according to exemplary embodiments of the present invention, including three exemplary core morphologies: (a) fibrous, (b) elliptical, and (c) equiaxed.
  • FIGs. 12(a)-12(f) are schematic illustrations of side view and cross section views of composite materials according to exemplary embodiments of the present invention, illustrating (a) ID oriented fiber-shaped bonding elements in a dilute bonding matrix (bonding elements are not touching), (b) 2D oriented platelet shaped bonding elements in a dilute bonding matrix (bonding elements are not touching), (c) 3D oriented platelet shaped bonding elements in a dilute bonding matrix (bonding elements are not touching), and (d) randomly oriented platelet shaped bonding elements in a dilute bonding matrix (bonding elements are not touching), wherein the composite materials includes the bonding matrix and filler components such as polymers, metals, inorganic particles, aggregates etc., (e) a concentrated bonding matrix (with a volume fraction sufficient to establish a percolation network) of bonding elements where the matrix is 3D oriented, and (f) a concentrated bonding matrix (with a volume fraction sufficient to establish a percolation network)
  • FIG. 13 is a schematic illustration of an exemplary system for forming anticorrosive coating on embedded rebar.
  • FIG. 14 shows an exemplary micrograph showing anticorrosive coating on embedded rebar during carbonation curing of composite material at 60°C.
  • FIG. 15 shows an exemplary EDX analysis for the coating formed on embedded rebar during carbonation curing of composite material at 60°C.
  • FIG. 16 shows an exemplary micrograph showing anticorrosive coating on embedded rebar during carbonation curing of composite material at 90°C.
  • FIG. 17 shows an exemplary EDX analysis for the coating formed on embedded rebar during carbonation curing of composite material at 90°C.
  • FIG. 18 shows an exemplary X- Ray diffraction pattern for an exemplary coating formed on plain carbon steel.
  • FIG. 19 shows XRD pattern for ductile cast iron exposed to 1M sodium bicarbonate solution for 24 hours at 90°C.
  • FIG. 20 shows Scanning electron micrograph for ductile cast iron exposed to 1M sodium bicarbonate solution for 24 hours at 90°C.
  • the invention provides novel anticorrosive methods for the protection of iron or steel surfaces against corrosion.
  • the methods are suitable for forming a protective coating on various iron or steel objects (e.g., reinforcement components embedded in composite materials as well as steel surfaces of oil and gas pipelines and vessels).
  • the unconventional approach disclosed herein is easy and inexpensive to apply and greatly helps with service life of the underlining iron or steel components.
  • novel, reinforced objects can be readily produced from widely available, low cost raw materials by a process suitable for large-scale production with improved energy
  • the production method of the invention consumes large quantities of C0 2 resulting in a C0 2 sequestrated product thereby making it carbon-neutral and environmentally friendly.
  • the anticorrosive coating can be formed on plain carbon steel embedded in the composite material during curing of the composite material without the need for a
  • novel objects manufactured from the composite material embedded with iron or steel reinforcement components with anticorrosive coating exhibit excellent physical and performance characteristics matching or exceeding existing precast and cast-in-place objects made from conventional concrete. These novel objects also possess excellent durability and performance characteristics, including toughness, flexibility, abrasion resistance, and chemical resistance.
  • iron refers to the metal iron in solid state in any size, shape, weight or environment of presence.
  • steel refers to an alloy of iron and a small amount of carbon, in solid state in any size, shape, weight or environment of presence.
  • Additional elements may also present in steel, for example, small to trace amounts of
  • manganese, phosphorus, sulfur, silicon, oxygen, nitrogen and aluminum examples include ductile cast iron and examples of steel include plain carbon steel.
  • the reinforced objects of the invention can be used in a wide range of applications such as building and construction components including, for example, hollow core slabs, railroad ties, wall panels, floor panels, roof panels, bridges, frames, pathways, Jersey barriers, linings, foundations, blocks, beams, pipes, culverts utility vaults, septic tanks, and storm drains.
  • building and construction components including, for example, hollow core slabs, railroad ties, wall panels, floor panels, roof panels, bridges, frames, pathways, Jersey barriers, linings, foundations, blocks, beams, pipes, culverts utility vaults, septic tanks, and storm drains.
  • the one or more reinforcement elements may be bars, wires or cables or combinations thereof.
  • the one or more reinforcement bars are made of iron, steel, polymeric materials, glass, or a combination thereof. In certain preferred embodiments, the one or more reinforcement bars are made of iron, steel, polymeric materials, glass, or a combination thereof. In certain preferred
  • the one or more reinforcement elements are pre-stressed.
  • Reinforcement elements may be solid bars, wires or cables.
  • the reinforcement elements may take any suitable physical dimensions, for examples, as a solid bar having a cross section from about 1 ⁇ 4 inch to 3 inches in diameter and up to about 40 feet or more in length, as a flexible cable with a cross section from about 1 ⁇ 4 inch to 4 inches in diameter and up to about 100 feet or more in length.
  • a cable may be a plurality of wires or filaments bundled together.
  • the reinforcement elements may be made with materials of desired characteristics, for example, iron, steel, polymeric materials, glass, or a combination thereof.
  • the reinforcement elements are steel bars.
  • the reinforcement elements are steel cables.
  • the reinforcement elements are steel wires.
  • a key feature of the anticorrosive approach of the invention is that the coating can be readily formed on embedded reinforcement components directly during the curing process of the underlining object. There is no pre-treatment or post-reaction. There is also no requirement of additional agents or ingredients in addition to the raw materials used to form the bulk of the underling objects. [0047] In regard to protecting non-embedded components such as iron or steel pipes or vessels, the invention provides a process for directly forming an anticorrosive coating on the surfaces of the pipes and vessels using inexpensive materials and simple processes. The thickness of the coatings may be controlled to meet specific needs depending on the application.
  • the invention generally relates to a process for forming an anticorrosive coating on a metal surface.
  • the process includes contacting the metal surface with an aqueous atmosphere of C0 2 and water vapor at a temperature and for a time period sufficient to form an anticorrosive coating on the metal surface.
  • the metal surface is a surface of a metal selected from iron and steel.
  • the object is selected from iron or steel bars, wires, cables, shards, filaments, tubings, pipes, containers, vessels and equipment.
  • the aqueous suspension of particulate calcium silicate under an atmosphere of C0 2 and water vapor is characterized by a pH value between about 3.5 to about 14 (e.g., between about 4.0 to about 13.0, between about 4.0 to about 12.0, between about 4.0 to about 11.0, between about 4.0 to about 10.0, between about 5.0 to about 14.0, between about 5.0 to about 13.0, between about 5.0 to about 12.0, between about 5.0 to about 11.0, between about 6.0 to about 14.0, between about 6.0 to about 13.0, between about 6.0 to about 12.0, between about 6.0 to about 11.0, between about 7.0 to about 14.0, between about 7.0 to about 13.0, between about 7.0 to about 12.0, between about 7.0 to about 11.0, between about 7.0 to about 10.0, between about 7.0 to about 9.0, between about 7.0 to about 8.0, between about 8.0 to about 12.9, between about 9.0 to about 12.9, between about 10.0 to about 12.9, between about
  • the anticorrosive coating comprises metal carbonate, e.g., iron carbonate (FeC0 3 , also referred to as siderite).
  • metal carbonate e.g., iron carbonate (FeC0 3 , also referred to as siderite).
  • FeC0 3 iron carbonate
  • siderite iron carbonate
  • anticorrosive coating consists essentially of iron carbonate.
  • the anticorrosive coating may be generated in an environment comprising C0 2 and having an appropriate pH without calcium silicate.
  • the anticorrosive coating has a thickness in the range from about 1 ⁇ to about 50 ⁇ (e.g., from about 1 ⁇ to about 40 ⁇ , from about 1 ⁇ to about 30 ⁇ , from about 1 ⁇ to about 20 ⁇ , from about 5 ⁇ to about 50 ⁇ , from about 10 ⁇ to about 50 ⁇ , from about 20 ⁇ to about 50 ⁇ , from about 30 ⁇ to about 50 ⁇ , from about 5 ⁇ to about 40 ⁇ , from about 10 ⁇ to about 40 ⁇ , from about 10 ⁇ to about 30 ⁇ , from about 20 ⁇ to about 30 ⁇ ).
  • the anticorrosive coating has a surface coverage of about 90% or greater (e.g., about 95% or greater, about 97% or greater, about 98% or greater, about 99% or greater).
  • the anticorrosive coating has a porosity of about 2.5 x 10 ⁇ 2 or less (e.g., about 2.0 x 10 "2 or less, about 1.5 x 10 "2 or less, about 1.0 x 10 "2 or less, about 5.0 x 10 " 4 or less).
  • the invention generally relates to a process for passivating iron or steel reinforcement wires or bars for corrosion resistance.
  • the process includes contacting the iron or steel reinforcement wires, cables or bars with an aqueous suspension of particulate calcium silicate under an atmosphere of C0 2 and water vapor at a pH from about 3.5 to about 14 to form an anticorrosive coating of iron carbonate covering the surface of iron or steel reinforcement wires, cables or bars.
  • the step of contacting the iron or steel surface with an aqueous suspension of particulate calcium silicate is conducted at a temperature in the range from about 10°C to about 150°C, for a time period from about 1 hour to about 150 hours, and under an atmosphere of water and C0 2 having a pressure in the range from ambient atmospheric pressure to about 150 psi above ambient and having a C0 2 concentration ranging from about 10% to about 99%.
  • the particulate calcium silicate having a median particle size in the range from about 500 nm to about 100 ⁇ .
  • any suitable calcium silicate may be used as a precursor for the bonding elements.
  • the term "calcium silicate” refers to naturally-occurring minerals or synthetic materials that are comprised of one or more of a group of calcium-silicon-containing compounds including CaSi0 3 (also known as “wollastonite” and pseudo-wollastonite, and sometimes formulated as CaO Si0 2 ), Ca 3 Si 2 0 7 (also known as Rankinite and sometimes formulated as 3CaO2Si0 2 ), Ca 2 Si0 4 (also known as "Belite” and sometimes formulated as 2CaO Si0 2 ), Ca 3 SiC"5 (also known as "Alite” and sometimes formulated as 3CaOSi0 2 ), which material may include one or more other metal ions and oxides (e.g., aluminum, magnesium, iron or manganese oxides), or blends thereof, or may include an amount of magnesium silicate in naturally- occurring or synthetic form(s) ranging from trace amount (1
  • magnesium silicate refers to naturally-occurring minerals or synthetic materials that are comprised of one or more of a groups of magnesium-silicon-containing compounds including, for example, Mg 2 SiO 4 (also known as “Fosterite”) and Mg 3 Si 4 O 1 o(OH) 2 (also known as "Talc”), which material may include one or more other metal ions and oxides (e.g., calcium, aluminum, iron or manganese oxides), or blends thereof, or may include an amount of calcium silicate in naturally-occurring or synthetic form(s) ranging from trace amount (1%) to about 50%) or more by weight.
  • Mg 2 SiO 4 also known as "Fosterite”
  • Mg 3 Si 4 O 1 o(OH) 2 also known as "Talc”
  • the pH value is between about 3.5 to about 14 (e.g., between about 3.5 to about 12.0, between about 3.5 to about 1 1.0, between about 3.5 to about 10.0, between about 3.5 to about 9.0, between about 3.5 to about 8.0, between about 5.0 to about 14, between about 6.0 to about 14, between about 7.0 to about 14, between about 8.0 to about 14, between about 9.0 to about 14, between about 10.0 to about 14, between about 1 1.0 to about 14).
  • the temperature is in the range from about 10°C to about 150°C (e.g., from about 10°C to about 130°C, from about 10°C to about 120°C, from about 10°C to about 1 10°C, from about 20°C to about 130°C, from about 20°C to about 120°C, from about 20°C to about 1 10°C, from about 50°C to about 120°C, from about 50°C to about 1 10°C, from about 50°C to about 100°C, from about 50°C to about 90°C, from about 50°C to about 80°C, from about 50°C to about 70°C, from about 60°C to about 120°C, from about 70°C to about 120°C, from about 80°C to about 120°C, from about 90°C to about 120°C, from about 70°C to about 100°C).
  • 10°C to about 150°C e.g., from about 10°C to about 130°C, from about 10°C to about 120°C, from about 10°
  • Curing time may be adjusted according to the desired end product, for example, 1 hour to about 150 hours (e.g., for about 1 hour to about 120 hours, for about 1 hour to about 100 hours, for about 1 hour to about 90 hours, for about 1 hour to about 70 hours, for about 1 hour to about 60 hours, for about 6 hours to about 120 hours, for about 6 hours to about 100 hours, for about 6 hours to about 80 hours, for about 6 hours to about 70 hours, for about 6 hours to about 60 hours, for about 10 hours to about 80 hours, for about 10 hours to about 70 hours, for about 10 hours to about 60 hours, for about 15 hours to about 120 hours, for about 15 hours to about 100 hours, for about 15 hours to about 80 hours, for about 15 hours to about 60 hours, for about 15 hours to about 50 hours, for about 20 hours) under an atmosphere of water and C0 2 . It is noted that, depending on the application, certain shortened or lengthened curing duration may be employed, for example, from about 1 , 3, 5, 7 days to as long as 15, 20 or 28 days,
  • the atmosphere of water and C0 2 has a pressure in the range from ambient atmospheric pressure to about 40 psi above ambient and having a C0 2 concentration ranging from about 50% to about 95% (e.g., from about 60% to about 95%, from about 70% to about 95%, from about 80% to about 95%, from about 90% to about 95%, from about 50%) to about 90%>, from about 50%> to about 80%>, from about 50%> to about 70%>, from about 50% to about 60%).
  • a pressure in the range from ambient atmospheric pressure to about 40 psi above ambient and having a C0 2 concentration ranging from about 50% to about 95% (e.g., from about 60% to about 95%, from about 70% to about 95%, from about 80% to about 95%, from about 90% to about 95%, from about 50%) to about 90%>, from about 50%> to about 80%>, from about 50%> to about 70%>, from about 50% to about 60%).
  • the invention generally relates to an article prepared by a process according to the invention.
  • Such articles includes, for example, hollow core slabs, solid slabs, aerated structures, railroad ties, wall panels, floor panels, roof panels, bridges, frames, pathways, Jersey barriers, linings, foundations, blocks, beams, pipes, culverts utility vaults, septic tanks, and storm drains.
  • the article can be manufactured to any suitable sizes, dimensions and weights.
  • the invention generally relates to an article of manufacture having a body prepared from a composite material.
  • the body is embedded with one or more reinforcement metal wires, cables or bars.
  • Each of the one or more reinforcement metal wires, cables or bars is coated with an anticorrosive coating.
  • the composite material includes: a plurality of bonding elements, wherein each bonding element comprises: a core comprising primarily calcium silicate, a silica-rich first or inner layer, and a calcium carbonate-rich second or outer layer, and filler particles comprising coarse filler particles and/or fine filler particles, wherein the plurality of bonding elements and the plurality of filler particles together form one or more bonding matrices and the bonding elements and the filler particles are substantially evenly dispersed therein and bonded together.
  • the metal surface is a surface of a metal selected from iron and steel.
  • the object is selected from bars, wires, cables, shards, filaments, tubings, pipes, containers, vessels and equipment.
  • the anticorrosive coating exhibits strong bonding to both the metal (e.g., iron or steel) reinforcement components and to the cured composite material they are embedded in.
  • the anticorrosive coating has a thickness in the range from about 1 ⁇ to about 50 ⁇ (e.g., from about 1 ⁇ to about 40 ⁇ , from about 1 ⁇ to about 30 ⁇ , from about 1 ⁇ to about 20 ⁇ , from about 1 ⁇ to about 10 ⁇ , from about 5 ⁇ to about 50 ⁇ , from about 10 ⁇ to about 50 ⁇ , from about 20 ⁇ to about 50 ⁇ , from about 30 ⁇ to about 50 ⁇ , from about 5 ⁇ to about 40 ⁇ , from about 10 ⁇ to about 40 ⁇ , from about 10 ⁇ to about 30 ⁇ , from about 20 ⁇ to about 30 ⁇ ).
  • a thickness in the range from about 1 ⁇ to about 50 ⁇ e.g., from about 1 ⁇ to about 40 ⁇ , from about 1 ⁇ to about 30 ⁇ , from about 1 ⁇ to about 20 ⁇ , from about 1 ⁇ to about 10 ⁇ , from about 5 ⁇ to about 50 ⁇ , from about 10 ⁇ to about 50 ⁇ , from about 20
  • the anticorrosive coating has a surface coverage of about 90% or greater (e.g., about 95% or greater, about 97% or greater, about 98% or greater, about 99% or greater). In certain embodiments, the anticorrosive coating has a porosity of about 2.5 x 10 ⁇ 2 or less (e.g., about 2.0 x 10 ⁇ 2 or less, about 1.5 x 10 "2 or less, about 1.0 x 10 "2 or less, about 5.0 x 10 "4 or less).
  • the plurality of bonding elements may have any suitable median particle size and size distribution dependent on the desired composite material.
  • the plurality of bonding elements have a median particle size in the range of about 500 nm to about 100 ⁇ (e.g., about 500 nm to about 80 ⁇ , about 500 nm to about 60 ⁇ , about 500 nm to about 50 ⁇ , about 500 nm to about 40 ⁇ , about 500 nm to about 30 ⁇ , about 500 nm to about 20 ⁇ , about 500 nm to about 10 ⁇ , about 1 ⁇ to about 90 ⁇ , about 1 ⁇ to about 80 ⁇ , about 1 ⁇ to about 70 ⁇ , about 1 ⁇ to about 60 ⁇ , about 5 ⁇ to about 90 ⁇ , about 5 ⁇ to about 80 ⁇ , about 5 ⁇ to about 70 ⁇ , about 5 ⁇ to about 60 ⁇ , about 5 ⁇ to about 50 ⁇ , about 5 ⁇ to about 40 ⁇ , about 10 ⁇ to about 80 ⁇ , about 10 ⁇ to about 100
  • the plurality of bonding elements are chemically transformed from ground calcium silicate and the filler particles are lime particles. In certain preferred embodiments, the plurality of bonding elements are chemically transformed from a precursor calcium silicate comprising one or more of aluminum, magnesium and iron. In certain preferred embodiments, wherein the plurality of bonding elements are chemically transformed from a precursor calcium silicate other than ground calcium silicate (e.g., ground Wollastonite).
  • ground calcium silicate e.g., ground Wollastonite
  • the plurality of bonding elements are prepared by chemical transformation from ground calcium silicate by reacting it with C0 2 via a controlled hydrothermal liquid phase sintering (HLPS) process.
  • the plurality of bonding elements are prepared by chemical transformation from the precursor calcium silicate other than ground calcium silicate (e.g., ground Wollastonite) by reacting it with C0 2 via a controlled HLPS process.
  • the invention generally relates to an article of manufacture comprising a metal surface coated with an anticorrosive coating comprising metal carbonate.
  • the invention generally relates to an article of manufacture having a body prepared from Portland cement, the body being embedded with one or more
  • each of the one or more reinforcement metal wires, cables or bars is coated with an anticorrosive coating comprising metal carbonate.
  • the metal is iron or steel and the anticorrosive coating consists essentially of iron carbonate.
  • the article may be any object, e.g., selected from metal bars, wires, shards, filaments, tubings, pipes, containers, vessels and equipment.
  • Chemical admixtures may include plasticizers, retarders, accelerators, dispersants and other rheology-modifying agents. Certain commercially available chemical admixtures such as GleniumTM 7500 by BASF ® Chemicals and AcumerTM by Dow Chemical Company may also be included.
  • one or more pigments may be evenly dispersed or substantially unevenly dispersed in the bonding matrices, depending on the desired composite material.
  • the pigment may be any suitable pigment including, for example, oxides of various metals (e.g., black iron oxide, cobalt oxide and chromium oxide).
  • the pigment may be of any color or colors, for example, selected from black, white, blue, gray, pink, green, red, yellow and brown.
  • the pigment may be present in any suitable amount depending on the desired composite material, for example in an amount ranging from about 0.0% to about 10% by weight (e.g., about 0.0% to about 8%, about 0.0% to about 6%, about 0.0% to about 5%, about 0.0% to about 4%, about 0.0% to about 3%, about 0.0% to about 2%, about 0.0% to about 1%, about 0.0% to about 0.5%, about 0.0% to about 0.3%, about 0.0% to about 2%, about 0.0% to about 0.1%).
  • about 0.0% to about 10% by weight e.g., about 0.0% to about 8%, about 0.0% to about 6%, about 0.0% to about 5%, about 0.0% to about 4%, about 0.0% to about 3%, about 0.0% to about 2%, about 0.0% to about 1%, about 0.0% to about 0.5%, about 0.0% to about 0.3%, about 0.0% to about 2%, about 0.0% to about 0.1%).
  • the relative humidity environment of the curing process may be adjusted to fit the desired outcome, for example, ranging from about 10%> to about 98%> (e.g., from about 20%> to about 98%, from about 30% to about 98%, from about 50% to about 98%, from about 80% to about 98%, from about 90% to about 98%, from about 10% to about 90%, from about 10% to about 70%), from about 10%> to about 50%>, from about 10%> to about 40%>, from about 10%> to about 30%, from about 10% to about 20%) and with a C0 2 pressure ranging from about ambient atmospheric pressure to about 100 psi above ambient atmospheric pressure (e.g., from about ambient atmospheric pressure to about 90 psi above ambient, from about ambient atmospheric pressure to about 80 psi above ambient, from about ambient atmospheric pressure to about 70 psi above ambient, from about ambient atmospheric pressure to about 60 psi above ambient, from about 20 above ambient to about 100 psi above ambient, from about 30 above ambient to about 100 psi above ambient), and having
  • the materials used are ground calcium silicate.
  • the ground calcium silicate may have a median particle size from about 1 ⁇ to about 100 ⁇ (e.g., about 1 ⁇ to about 80 ⁇ , about 1 ⁇ to about 60 ⁇ , about 1 ⁇ to about 50 ⁇ , about 1 ⁇ to about 40 ⁇ , about 1 ⁇ to about 30 ⁇ , about 1 ⁇ to about 20 ⁇ , about 1 ⁇ to about 10 ⁇ , about 5 ⁇ to about 90 ⁇ , about 5 ⁇ to about 80 ⁇ , about 5 ⁇ to about 70 ⁇ , about 5 ⁇ to about 60 ⁇ , about 5 ⁇ to about 50 ⁇ , about 5 ⁇ to about 40 ⁇ , about 10 ⁇ to about 80 ⁇ , about 10 ⁇ to about 70 ⁇ , about 10 ⁇ to about 60 ⁇ , about 10 ⁇ to about 50 ⁇ , about 10 ⁇ to about 40 ⁇ , about 10 ⁇ to about 30 ⁇ , about 10 ⁇ to about 20 ⁇ , about 1 ⁇ , 10 ⁇ , 15 ⁇ , 20 ⁇ , 25 ⁇ , 30 ⁇ , about
  • the particulate composition comprises about 10 wt.% to about 95 wt.% of ground calcium silicate materials ⁇ e.g., about 20 wt.%> to about 95 wt.%>, about 30 wt.
  • various combinations of curing conditions may be devised to achieve the desired production process, including varied reaction temperatures, pressures and lengths of reaction.
  • water in liquid form along with C0 2 gas is delivered to an article that has been pre-dried in a drying oven and the curing process is conducted at about 90°C and about 20 psig ⁇ i.e., 20 psi above ambient pressure) for about 48 hours.
  • water is present in the precursor material ⁇ e.g., as residual water from prior mixing step) and C0 2 gas is delivered to an article and the curing process is performed at about 60°C and 0 psig (at ambient atmospheric pressure) for about 19 hours.
  • water is delivered to an article in vapor form along with C0 2 and the curing process is performed at about 90°C and 20 psig (20 psi above ambient atmospheric pressure) for about 19 hours.
  • the properties, production time and scale of the article can be fine tuned based on the disclosures herein, for example, by adjusting curing techniques ⁇ e.g., C0 2 delivery, system pressure and temperature) as well as mixture proportions and constituents.
  • This invention provides apparatus and methods used to manufacture novel composite materials that are cured predominantly by a C0 2 consumption reaction.
  • the materials exhibit useful properties and can be readily produced from widely available, low cost precursor materials by a process suitable for large-scale production with minimal environmental impact.
  • the precursor materials include inexpensive and abundant calcium silicate rich compositions, fine particles and coarse particles.
  • the fine and coarse particles may be comprised of ground limestone or other calcium carbonate based materials, ground quartz or other Si0 2 based materials, sand and crushed rock.
  • the fine and coarse particles may also be comprised of crushed minerals such as granite, mica and feldspar.
  • Other process components include water and C0 2 .
  • Various additives can be used to modify and fine-tune the physical appearance and/or mechanical properties of the resulting composite material, such as additives selected from one or more of pigments (e.g., black iron oxide, cobalt oxide and chromium oxide), colored glass and/or colored quartz. Additives regarding water usage reduction and changes in rheology can also be used.
  • any suitable calcium silicate composition may be used as a precursor for the bonding elements.
  • the term "calcium silicate composition” generally refers to naturally- occurring minerals or synthetic materials that are comprised of one or more of a group of calcium silicate phases including CS (wollastonite or pseudowollastonite, and sometimes formulated CaSi0 3 or CaOSi0 2 ), C3S2 (rankinite, and sometimes formulated as Ca 3 Si 2 0 7 or 3CaO2Si0 2 ), C2S (belite , P-Ca 2 Si0 4 or larnite, P-Ca 2 Si0 4 or bredigite, a-Ca 2 Si0 4 or ⁇ - Ca 2 Si0 4 , and sometimes formulated as Ca 2 Si0 4 or 2CaO Si0 2 ), a calcium-silicate based amorphous phase, each of which material may include one or more other metal ions and oxides (e.g., aluminum, magnesium, iron or manganese
  • Calcium silicate compositions may contain amorphous (non-crystalline) calcium silicate phases in addition to the crystalline phases described above.
  • the amorphous phase may additionally incorporate Al, Fe and Mg ions and other impurity ions present in the raw materials.
  • the calcium silicate compositions may also include small quantities of residual CaO (lime) and Si0 2 (silica).
  • the calcium silicate composition may also include small quantities of C3S (alite, Ca 3 Si0 5 ).
  • the calcium silicate compositions may also include quantities of inert phases such as melilite type minerals (melilite or gehlenite or akermanite) with the general formula
  • the calcium silicate composition is comprised only of amorphous phases.
  • the calcium silicate comprises only of crystalline phases.
  • some of the calcium silicate composition exists in an amorphous phase and some exists in a crystalline phase.
  • the calcium silicate compositions of the invention do not hydrate.
  • minor amounts of hydratable calcium silicate phases e.g., C2S, C3S and CaO
  • C2S exhibits slow kinitecs of hydration when exposed to water and is quickly converted to CaC0 3 during C0 2 curing processes.
  • C3S and CaO hydrate quickly upon exposure to water and thus should be limited to ⁇ 5% by mass.
  • the molar ratio of elemental Ca to elemental Si of the calcium silicate composition is from about 0.80 to about 1.20. In certain preferred embodiments, the molar ratio of Ca to Si of the composition is from about 0.85 to about 1.15. In certain preferred embodiments, the molar ratio of Ca to Si of the composition is from about 0.90 to about 1.10. In certain preferred embodiments, the molar ratio of Ca to Si of the composition is from about 0.95 to about 1.05. In certain preferred embodiments, the molar ratio of Ca to Si of the composition is from about 0.98 to about 1.02. In certain preferred embodiments, the molar ratio of Ca to Si of the composition is from about 0.99 to about 1.01.
  • the metal oxides of Al, Fe and Mg contained within the calcium silicate composition are generally controlled to be less than about 30%.
  • the composition has about 20% or less of metal oxides of Al, Fe and Mg by total oxide mass.
  • the composition has about 15% or less of metal oxides of Al, Fe and Mg by total oxide mass.
  • the composition has about 12% or less of metal oxides of Al, Fe and Mg by total oxide mass.
  • the composition has about 10% or less of metal oxides of Al, Fe and Mg by total oxide mass.
  • the composition has about 5% or less of metal oxides of Al, Fe and Mg by total oxide mass.
  • Each of these calcium silicate phases is suitable for carbonation with C0 2 .
  • the discrete calcium silicate phases that are suitable for carbonation will be referred to as reactive phases.
  • the various reactive phases may account for any suitable portions of the overall reactive phases.
  • the reactive phases of CS are present at about 10 to about 60 wt%> (e.g., about 15 wt%> to about 60 wt%>, about 20 wt%> to about 60 wt%>, about 25 wt% to about 60 wt%, about 30 wt% to about 60 wt%, about 35 wt% to about 60 wt%, about 40 wt% to about 60 wt%, about 10 wt% to about 50 wt%, about 10 wt% to about 40 wt%, about 10 wt% to about 30 wt%, about 10 wt% to about 25 wt%, about 10 wt% to about 20 wt%); C3S2 in about 5 to 50 wt% (e.g., about 10 wt% to 50 wt%, about 15 wt% to 50 wt%, about
  • the reactive phases comprise a calcium-silicate based amorphous phase, for example, at about 40% or more (e.g., about 45% or more, about 50%> or more, about 55% or more, about 60% or more, about 65 % or more, about 70% or more, about 75%) or more, about 80%> or more, about 85% or more, about 90%> or more, about 95% or more) by mass of the total phases.
  • the amorphous phase may additionally incorporate impurity ions present in the raw materials.
  • the calcium silicate compositions of the invention are suitable for carbonation with C0 2 .
  • the composition of calcium silicate is suitable for carbonation with C0 2 at a temperature of about 30 °C to about 90 °C to form CaC0 3 with mass gain of about 20% or more.
  • the mass gain reflects the net sequestration of C0 2 in the carbonated products.
  • the composition is suitable for carbonation with C0 2 at a temperature of about 30 °C to about 90 °C (e.g., about 40 °C to about 90 °C, about 50 °C to about 90 °C, about 60 °C to about 90 °C, about 30 °C to about 80 °C, about 30 °C to about 70 °C, about 30 °C to about 60 °C, about 40 °C to about 80 °C, about 40 °C to about 70 °C, about 40 °C to about 60 °C) to form CaC0 3 with mass gain of 10%> or more (e.g., 15% or more, 20%> or more, 25% or more, 30%) or more).
  • Precursor calcium silicate compositions are typically used in powder form having a mean particle size (d50) of about 8 ⁇ to about 25 ⁇ , with 10%> of particles (dlO) sized below about 0.1 ⁇ to about 3 ⁇ , and 90% of particles (d90) sized above about 35 ⁇ to about 100 ⁇ .
  • the ratio of d90 : dlO is selected to allow improved powder flow or decreased water demand for casting.
  • the ratio of d50 : dlO is selected to allow improved reactivity, improved packing, or decreased water demand for casting.
  • the ratio of d90 : d50 is selected to allow improved the reactivity, improved packing, or decreased water demand for casting.
  • filler particles may be used, for example, calcium oxide-containing or silica-containing materials.
  • Exemplary filler particles include lime, quartz (including sand), wollastonite, xonotlite, burned oil shale, fly - or volcanic-ash, stack dust from kilns, ground clay, pumice dust.
  • Materials such as industrial waste materials (e.g., fly ash, slag, silica fume) may also be used as fillers.
  • light-weight aggregates such as perlite or vermiculite may also be used as fillers.
  • filler particles are made from a calcium oxide -rich material such as ground lime.
  • the filler particles comprise calcium oxide or silica and have a particle size (d 5 o) in the range from about 0.25 ⁇ to about 200 ⁇ (e.g., from about 0.25 ⁇ to about 150 ⁇ , from about 0.25 ⁇ to about 100 ⁇ , from about 0.25 ⁇ to about 50 ⁇ , from about 0.25 ⁇ to about 20 ⁇ , from about 0.25 ⁇ to about 10 ⁇ , from about 0.5 ⁇ to about 200 ⁇ , from about 1 ⁇ to about 200 ⁇ , from about 5 ⁇ to about 200 ⁇ , from about 10 ⁇ to about 200 ⁇ , from about 20 ⁇ to about 200 ⁇ , from about 50 ⁇ to about 200 ⁇ ).
  • a particle size (d 5 o) in the range from about 0.25 ⁇ to about 200 ⁇ e.g., from about 0.25 ⁇ to about 150 ⁇ , from about 0.25 ⁇ to about 100 ⁇ , from about 0.25 ⁇ to about 50 ⁇ , from about 0.25 ⁇ to about 20 ⁇ , from about 0.25
  • the filler particles are selected from fly ash, bottom ash, slag having particle sizes ranging from about 0.5 ⁇ to about 300 ⁇ (e.g., from about 1 ⁇ to about 300 ⁇ , from about 5 ⁇ to about 300 ⁇ , from about 10 ⁇ to about 300 ⁇ , from about 50 ⁇ to about 300 ⁇ , from about 100 ⁇ to about 300 ⁇ , from about 0.5 ⁇ to about 200 ⁇ , from about 0.5 ⁇ to about 100 ⁇ , from about 0.5 ⁇ to about 50 ⁇ , from about 0.5 ⁇ to about 20 ⁇ , from about 0.5 ⁇ to about 10 ⁇ , from about 0.5 ⁇ to about 5 ⁇ ).
  • 0.5 ⁇ to about 300 ⁇ e.g., from about 1 ⁇ to about 300 ⁇ , from about 5 ⁇ to about 300 ⁇ , from about 10 ⁇ to about 300 ⁇ , from about 50 ⁇ to about 300 ⁇ , from about 100 ⁇ to about 300 ⁇ , from about 0.5 ⁇ to about 200 ⁇ , from about
  • the filler particles are selected from limestone, miro-silica, and quartz having particle sizes ranging from about 1 ⁇ to about 500 ⁇ (e.g., from about 1 ⁇ to about 400 ⁇ , from about 1 ⁇ to about 300 ⁇ , from about 1 ⁇ to about 200 ⁇ , from about 1 ⁇ to about 100 ⁇ , from about 1 ⁇ to about 50 ⁇ , from about 1 ⁇ to about 30 ⁇ , from about 5 ⁇ to about 500 ⁇ , from about 10 ⁇ to about 500 ⁇ , from about 20 ⁇ to about 500 ⁇ , from about 50 ⁇ to about 500 ⁇ , from about 100 ⁇ to about 500 ⁇ , from about 200 ⁇ to about 500 ⁇ ).
  • ⁇ to about 500 ⁇ e.g., from about 1 ⁇ to about 400 ⁇ , from about 1 ⁇ to about 300 ⁇ , from about 1 ⁇ to about 200 ⁇ , from about 1 ⁇ to about 100 ⁇ , from about 1 ⁇ to about 50 ⁇ , from about 1 ⁇ to about 30 ⁇ , from about 5
  • the filler particles are selected from lightweight aggregates having particle sizes ranging from about 20 ⁇ to about 500 ⁇ (e.g., from about 20 ⁇ to about 400 ⁇ , from about 20 ⁇ to about 300 ⁇ , from about 20 ⁇ to about 200 ⁇ , from about 20 ⁇ to about 100 ⁇ , from about 50 ⁇ to about 500 ⁇ , from about 100 ⁇ to about 500 ⁇ , from about 200 ⁇ to about 500 ⁇ , from about 300 ⁇ to about 500 ⁇ ).
  • a lightweight aggregates having particle sizes ranging from about 20 ⁇ to about 500 ⁇ (e.g., from about 20 ⁇ to about 400 ⁇ , from about 20 ⁇ to about 300 ⁇ , from about 20 ⁇ to about 200 ⁇ , from about 20 ⁇ to about 100 ⁇ , from about 50 ⁇ to about 500 ⁇ , from about 100 ⁇ to about 500 ⁇ , from about 200 ⁇ to about 500 ⁇ , from about 300 ⁇ to about 500 ⁇ ).
  • the set-controlling admixture is selected from a gluconate and sucrose.
  • the dispersing/viscosity-modifying agent is a
  • the ground calcium silicate is ground wollastonite
  • the filler particles comprises ground limestone
  • the activating-agent is ground lime
  • the set-controlling admixture is a gluconate
  • the viscosity-modifying agent is a polycarboxilate based material
  • the aerating agent is aluminum paste.
  • magnesium silicate refers to naturally- occurring minerals or synthetic materials that are comprised of one or more of a groups of magnesium-silicon-containing compounds including, for example, Mg 2 SiO 4 (also known as “fosterite”) and (also known as "talc”), which material may include one or more other metal ions and oxides (e.g., calcium, aluminum, iron or manganese oxides), or blends thereof, or may include an amount of calcium silicate in naturally-occurring or synthetic form(s) ranging from trace amount (1%) to about 50% or more by weight.
  • additives such as dispersing, rheology modifying admixtures (to improve mixture consistency), coloring pigments, retarders, and accelerators.
  • Additive materials can include natural or recycled materials, and calcium carbonate-rich and magnesium carbonate -rich materials, as well as additives to the fluid component, such as a water-soluble dispersant.
  • the composite materials can be produced, as disclosed herein, using the energy- efficient Hydrothermal Liquid Phase Sintering (HLPS) process to create bonding elements which hold together the various components of the composite material.
  • HLPS Hydrothermal Liquid Phase Sintering
  • the composite materials can be manufactured at low cost and with favorable environmental impact.
  • C0 2 is used as a reactive species resulting in sequestration of C0 2 and the creation of bonding elements in the produced composite materials with in a carbon footprint unmatched by any existing production technology.
  • the HLPS process is
  • the kinetics of the HLPS process proceed at a reasonable rate at low temperature because a solution (aqueous or nonaqueous) is used to transport reactive species instead of using a high melting point fluid or high temperature solid- state medium.
  • calcium silicate composition refers to naturally-occurring minerals or synthetic materials that are comprised of one or more of a group of calcium-silicon- containing compounds including CS (wollastonite or pseudowollastonite, and sometimes formulated CaSi0 3 or CaO Si0 2 ), C3S2 (rankinite, and sometimes formulated as Ca 3 Si 2 0 7 or 3CaO-2Si0 2 ), C2S (belite, -Ca 2 Si0 4 or larnite, ⁇ - ⁇ 3 2 5 ⁇ 0 4 or bredigite, a-Ca 2 Si0 4 or Y-Ca 2 Si0 4 , and sometimes formulated as Ca 2 Si0 4 or 2CaO Si0 2 ), a calcium silicate rich amorphous phase, each of which materials may include one or more other metal ions and oxides (e.g., aluminum, magnesium, iron or manganese oxides), or blends thereof, or may include an amount of magnesium
  • magnesium silicate refers to naturally-occurring minerals or synthetic materials that are comprised of one or more of a groups of magnesium-silicon-containing compounds including, for example, Mg 2 SiO 4 (also known as “fosterite”), Mg 3 SiztOioCOIT ) (also known as "Talc”), and CaMgSiC ⁇ (also known as "monticellite”), each of which materials may include one or more other metal ions and oxides (e.g., calcium, aluminum, iron or manganese oxides), or blends thereof, or may include an amount of calcium silicate in naturally- occurring or synthetic form(s) ranging from trace amount (1%) to about 50% or more by weight.
  • Mg 2 SiO 4 also known as "fosterite”
  • Mg 3 SiztOioCOIT also known as "Talc”
  • CaMgSiC ⁇ also known as "monticellite”
  • quartz refers to any Si0 2 -based material, including common sands (construction and masonry), as well as glass and recycled glass.
  • the term also includes any other recycled natural and synthetic materials that contain significant amounts of Si0 2 (e.g., mica sometimes formulated as KAl 2 (AlSi 3 Oio)(OH) 2 .
  • the plurality of bonding elements are prepared by chemical transformation from ground calcium silicate compositions by reacting them with C0 2 via a gas-assisted HLPS process.
  • the composite material is characterized by a compressive strength from about 90 MPa to about 175 MPa (e.g., about 90 MPa to about 150 MPa, about 90 MPa to about 140 MPa, about 90 MPa to about 130 MPa, about 90 MPa to about 120 MPa, about 90 MPa to about 1 10 MPa, about 100 MPa to about 175 MPa, about 120 MPa to about 175 MPa, about 130 MPa to about 175 MPa, about 140 MPa to about 175 MPa, about 150 MPa to about 175 MPa, about 160 MPa to about 175 MPa).
  • the composite material is characterized by a flexural strength from about 5 MPa to about 30 MPa (e.g., about 5 MPa to about 25 MPa, about 5 MPa to about 20 MPa, about 5 MPa to about 15 MPa, about 5 MPa to about 10 MPa, about 10 MPa to about 30 MPa, about 20 MPa to about 30 MPa, about 25 MPa to about 30 MPa).
  • the composite material is characterized by water absorption of less than about 10% (e.g., less than about 8%, 5%, 4%, 3%, 2%, or 1%).
  • the composite material may display one or more of desired textures, patterns and physical properties, in particular those that are characteristic of natural stone.
  • the composite material exhibits a visual pattern similar to natural stone.
  • Other characteristics include colors (e.g., black, white, blue, pink, grey (pale to dark), green, red, yellow, brown, cyan (bluish-green) or purple) and textures.
  • industrial grade C0 2 at about 99% purity is used, which is provided by a variety of different industrial gas companies, such as Praxair, Inc., Linde AG, Air Liquide, and others.
  • This supply can be held in large pressurized holding tanks in the form of liquid carbon dioxide regulated at a temperature such that it maintains a vapor pressure of approximately 300 PSIG.
  • This gas is then piped to a C0 2 curing enclosure or chamber.
  • CO 2 is flowed through the enclosure at a rate sufficient to displace the ambient air in the enclosure.
  • the purge time will depend on the size of the enclosure and the rate that CO 2 gas is provided.
  • this process of purging the enclosure of air can be performed in times measured in minutes to get the CO 2 concentration up to a reasonable level so that curing can be performed thereafter.
  • CO 2 gas is then fed into the system at a predefined rate so s to maintain a concentration of CO 2 sufficient to drive the curing reaction.
  • This method uses the measurement of CO 2 concentration in the system directly, and employs a controller such as a PLC to control the CO 2 concentration at a set point with an electronic/automated control valve.
  • a measurement technique to measure CO 2 directly such as NDIR should preferably be employed.
  • NDIR measurement method a gas sample stream is pulled from the system via a low flow pump.
  • a chiller is used to drop moisture out of the gas stream before it is sampled by the NDIR instrument. Therefore the measurement provided by the analyzer is missing the water vapor component of the gas stream and needs be adjusted to account for the humidity that has been removed from the test sample.
  • a measurement of the humidity in the system gas flow can be performed using a dry bulb-wet bulb psychrometric technique, using a dry bulb-wet bulb humidity measurement device or using a different type of moisture sensor.
  • the true C0 2 concentration can be calculated using the computer control system or PLC. Once the true C0 2 concentration is known, the actuated proportioning control valve can add dry C0 2 into the system when it has been consumed and has gone below the set point that is desired at that time. In various embodiments, the set point can vary with time, if necessary, based on experience in curing specific compositions, shape and sizes of composite material specimens.
  • FIG. 9 is a schematic diagram of a C0 2 composite material curing chamber that provides humidification according to principles of the invention.
  • a water supply is provided and water vapor is added to the atmosphere that is circulating within the curing chamber.
  • the water can be any convenient source of potable water. In some embodiments, ordinary tap water is used.
  • the water can be converted to vapor by flowing through a misting nozzle or an atomizing spray nozzle, an electric vapor generator, a gas fired vapor generator, or by being heated above the gas temperature in the chamber so as to cause evaporation from a liquid water supply an example being a drum reactor with an immersion heater.
  • the C0 2 supply can be flowed into the systems after having been bubbled through a heated water supply in order to increase relative humidity of the incoming gas stream an example being a drum reactor configured for "flow through" or "open loop" processing.
  • Relative humidity is an important parameter in both traditional concrete curing as well as in C0 2 composite material curing.
  • a moist air atmosphere exists that is comprised of mostly nitrogen, oxygen, and water vapor.
  • relative humidity is most often measured by a standard capacitive sensor technology.
  • C0 2 curing chambers have a gas atmosphere comprised predominately of carbon dioxide that is incompatible with some types of these sensors.
  • Sensing technology such as dry-bulb wet-bulb techniques that utilize the psychrometric ratios for carbon dioxide and water vapor or dipole polarization water vapor measurement instruments or chilled mirror hygrometers or capacitive humidity sensors can be used in the C0 2 composite material curing systems described herein.
  • the humidity may need to be either decreased or increased and regulated to a specified set point.
  • Set points may range anywhere from 1% to 99% relative humidity.
  • Three different methods for humidity control may exist in C0 2 composite material curing processes that could be combined into a single system.
  • One method for humidification in one embodiment of a C0 2 curing system is represented in FIG. 9.
  • Another method allows one to remove moisture from the system to cure the composite material products with C0 2 .
  • a simple method of reducing the relative humidity is by displacing the humid gas in the system with a dry gas, such as carbon dioxide.
  • a non- purging method which in one preferred embodiment is a chilled heat exchanger that performs water extraction.
  • FIG. 10 is a schematic diagram of a curing chamber with multiple methods of humidity control as well as ability to control and replenish C0 2 using constant flow or pressure regulation and that can control the temperature according to principles of the invention.
  • This system is an example of a system that can provide closed loop control or control using feedback, in which set values of operating parameters such as C0 2 concentration, humidity, and temperature that are desired at specific times in the process cycle are provided, and
  • temperature is measured utilizing a sensor such as a thermocouple or an RTD.
  • the measurement signal is directed back to a controller or computer that is able to regulate energy into the heat exchanger and thereby adjust the temperature of the entire system over time.
  • the blower is an important component of the heating system as it is able to help transfer the heat energy to the gas which transfers to the products and the chamber itself which is an important part of controlled moisture of the samples.
  • the method of heating can be electric or gas fired. Jacket heaters may be utilized to control the temperature of the C0 2 that flows through a chamber in contact with the heating jacket, any convenient source of heat can be used.
  • the means of external heating may include but are not limited to electric heating, hot water heating, or hot oil heating.
  • Another control parameter is gas velocity across the material that is to be cured in the system.
  • the gas velocity can be very dependent on process equipment variables including but not limited to chamber design, baffle design, fan size, fan speed/power, number of fans, temperature gradient within the system, rack design within the system, and sample geometry within the system.
  • the simplest method to control the gas velocity within the chamber is by adjusting the blower speed (RPM's), typically done by utilization of a variable frequency drive to allow for control of the blower motor speed.
  • the blower can be used to circulate gas at a desired velocity in the curing chamber.
  • Gas velocity in the system is measured in the system via a variety of different techniques including but not limited to pitot tubes measurement and laser Doppler detection systems.
  • the measurement signal for gas velocity can be sent back to a computer system or programmable logic controller and be utilized as a control parameter in the curing profile.
  • the process includes: mixing a particulate composition and a liquid composition to create a slurry mixture; forming the slurry mixture into a desired shape, either by casting the slurry into a mold, pressing the slurry in a mold, pressing the slurry in a vibrating mold, extruding the slurry, slip forming the slurry, or using any other shape-forming method common in concrete production, and curing the formed slurry mixture at a temperature in the range from about 20°C to about 150°C for about 1 hour to about 80 hours under a vapor comprising water and C0 2 and having a pressure in the range from about ambient atmospheric pressure to about 50 psi above ambient atmospheric pressure and having a C0 2 concentration ranging from about 10% to about 90% to produce a composite material exhibiting a texture and/or a pattern and the desired physical properties related to compressive strength, flexural strength, density, resistance to degradation, and so forth.
  • the particulate composition includes a ground calcium silicate composition having a mean particle size in the range from about 1 ⁇ to about 100 ⁇ .
  • the particulate composition may include a ground calcium carbonate or a Si0 2 bearing material having a mean particle size in the range from about 3 ⁇ to about 25 mm.
  • the liquid composition includes water and may include a water-soluble dispersant.
  • the process can further include, before curing the casted mixture, the step of drying the casted mixture.
  • the particulate composition further comprises a pigment or a colorant as discussed herein.
  • curing the formed slurry mixture is performed at a temperature in the range from about 30°C to about 120°C for about 1 hour to about 70 hours under a vapor comprising water and C0 2 and having a pressure in the range from about ambient atmospheric pressure to about 30 psi above ambient atmospheric pressure.
  • curing the formed slurry mixture is performed at a temperature in the range from about 60°C to about 110°C for about 1 hour to about 70 hours under a vapor comprising water and C0 2 and having a pressure in the range from about ambient atmospheric pressure to about 30 psi above ambient atmospheric pressure.
  • curing the formed slurry mixture is performed at a temperature in the range from about 80°C to about 100°C for about 1 hour to about 60 hours under a vapor comprising water and C0 2 and having a pressure in the range from about ambient atmospheric pressure to about 30 psi above ambient atmospheric pressure.
  • curing the formed slurry mixture is performed at a temperature equal to or lower than about 60°C for about 1 hour to about 50 hours under a vapor comprising water and C0 2 and having an ambient atmospheric pressure.
  • the ground calcium silicate composition has a mean particle size from about 1 ⁇ to about 100 ⁇ (e.g., about 1 ⁇ , 10 ⁇ , 15 ⁇ , 20 ⁇ , 25 ⁇ , 30 ⁇ , 40 ⁇ , 50 ⁇ , 60 ⁇ , 70 ⁇ , 80 ⁇ , 90 ⁇ , 100 ⁇ ), a bulk density from about 0.5 g/mL to about 3.5 g/mL (loose, e.g., 0.5 g/mL, 1.0 g/mL, 1.5 g/mL, 2.0 g/mL, 2.5 g/mL, 2.8 g/mL, 3.0 g/mL, 3.5 g/mL) and about 1.0 g/mL to about 1.2 g/mL (tapped), a Blaine
  • 2 2 2 2 2 2 2 2 2 surface area from about 150 m7kg to about 700 m7kg (e.g., 150 m7kg, 200 m7kg, 250 m7kg, 300 m 2 /kg, 350 m 2 /kg, 400 m 2 /kg, 450 m 2 /kg, 500 m 2 /kg, 550 m2/kg, 600 m2/kg, 650 m2/kg, 700 m2/kg).
  • the liquid composition includes water and a water- soluble dispersant comprising a polymer salt (e.g., an acrylic homopolymer salt) having a concentration from about 0.1% to about 2% w/w of the liquid composition.
  • a polymer salt e.g., an acrylic homopolymer salt
  • Composite materials prepared according to a process disclosed herein can exhibit a compressive strength from about 3.0 MPa to about 30.0 MPa (e.g., about 3 MPa, 5 MPa, 10 MPa, 15 MPa, 20 MPa, 25 MPa, 30 MPa) and a flexural strength from about 0.3 MPa to about 4.0 MPa (e.g., about 0.3 MPa, 0.5 MPa, 1.0 MPa, 1.5 MPa, 2.0 MPa, 2.5 MPa, 3.0 MPa, 3.5 MPa, 4.0 MPa).
  • Any suitable precursor materials may be employed including, for example, calcium silicate composition particles formed from CS (wollastonite or pseudowollastonite, and sometimes formulated CaSi0 3 or CaO Si0 2 ), C3S2 (Rankinite, and sometimes formulated as Ca 3 Si 2 0 7 or 3CaO2Si0 2 ), C2S (belite , ⁇ 3 ⁇ 48 ⁇ 0 4 or larnite, ⁇ - ⁇ 3 2 5 ⁇ 0 4 or "bredigite, a-Ca 2 Si0 4 or Y-Ca 2 Si0 4 , and sometimes formulated as Ca 2 Si0 4 or 2CaO Si0 2 ), and a calcium silicate rich amorphous phase.
  • CS wollastonite or pseudowollastonite, and sometimes formulated CaSi0 3 or CaO Si0 2
  • C3S2 Rankinite, and sometimes formulated as Ca 3 Si 2 0 7 or 3CaO2Si0 2
  • C2S belite
  • calcium cations are leached from the calcium silicate composition particles and transform the peripheral portion of the calcium silicate composition particle into calcium-deficient state.
  • the structure of the peripheral portion eventually become unstable and breaks down, thereby transforming the calcium-deficient peripheral portion of the particle into a predominantly silica-rich first layer. Meanwhile, a predominantly calcium carbonate second layer precipitates from the water.
  • the first layer and second layer may be formed from the precursor particle according the following reactions (1-3) which can use water as a reaction medium, and not as a reagent (that is, the water is not consumed):
  • C0 2 is introduced as a gas phase that dissolves into an infiltration fluid, such as water.
  • the dissolution of C0 2 forms acidic carbonic species (such as carbonic acid, H 2 C0 3 ) that results in a decrease of pH in solution.
  • the weakly acidic solution incongruently dissolves calcium species from the calcium silicate phases.
  • Calcium may be leached from calcium containing amorphous phases through a similar mechanism.
  • the released calcium cations and the dissociated carbonate species lead to the precipitation of insoluble carbonates.
  • Silica-rich layers are thought to remain on the mineral particles as calcium depleted layers.
  • C0 2 preferentially reacts with the calcium cations of the calcium silicate composition precursor core, thereby transforming the peripheral portion of the precursor core into a silica-rich first layer and a calcium carbonate- rich second layer. Also, the presence of the first and second layers on the core act as a barrier to further reaction between calcium silicate and carbon dioxide, resulting in the bonding element having the core, first layer and second layer.
  • silicate materials having metals other than Ca or in addition to Ca for example fosterite (Mg 2 SiO 4 ), diopside (CaMgSi 2 Oe), and talc (Mg 3 Si 4 O 1 o(OH) 2 ) can react with carbon dioxide dissolved in water in a manner similar to the reaction of calcium silicate, as described above. It is believed that such silicate materials can be used, alone, in combination, and/or in combination with calcium silicate, as precursors for bonding elements according to principles of the invention.
  • fosterite Mg 2 SiO 4
  • diopside CaMgSi 2 Oe
  • talc Mg 3 Si 4 O 1 o(OH) 2
  • gas-assisted HLPS processes utilize partially infiltrated pore space so as to enable gaseous diffusion to rapidly infiltrate the porous preform and saturate thin liquid interfacial solvent films in the pores with dissolved C0 2 .
  • C0 2 -based species have low solubility in pure water (1.5 g/L at 25 °C, 1 arm.).
  • a substantial quantity of C0 2 must be continuously supplied to and distributed throughout the porous preform to enable significant carbonate conversion.
  • Utilizing gas phase diffusion offers a huge (about 100-fold) increase in diffusion length over that of diffusing soluble C0 2 an equivalent time in a liquid phase.
  • Liquid water in the pores speeds up the reaction rate because it provides a medium for ionization of both carbonic acid and calcium species.
  • water levels need to be low enough such that C0 2 gas can diffuse into the porous matrix prior to dissolution in the pore- bound water phase.
  • the actively dissolving porous preform serves as a template for expansive reactive crystal growth.
  • the bonding element and matrices can be formed with minimal distortion and residual stresses. This enables large and complex shapes to result, such as those needed for infrastructure and building materials, in addition to many other applications.
  • various combinations of curing conditions may be devised to achieve the desired production process, including varied reaction temperatures, pressures and lengths of reaction.
  • water is present in the precursor material (e.g., as residual water from prior mixing step) and liquid water is provided to precursor materials (e.g., to maintain water level and/or control the loss of water from evaporating) along with C0 2 and the curing process is conducted at about 90°C and about 20 psig (i.e., 20 psi above ambient pressure) for times ranging from about 2 to 90 hours.
  • water is present in the precursor material (e.g., as residual water from prior mixing step) and water vapor is provided to precursor materials (e.g., to maintain water level and/or control the loss of water from evaporating) along with C0 2 and the curing process is conducted at about 90°C and about 20 psig (i.e., 20 psi above ambient pressure) for times ranging from about 2 to 90 hours.
  • water is present in the precursor material (e.g., as residual water from prior mixing step) and water vapor is provided to precursor materials (e.g., to maintain water level and/or control the loss of water from evaporating) along with C0 2 and the curing process is performed at about 25 to 90°C and 0 psig (at ambient atmospheric pressure) for about 2 to 72 hours.
  • the time required for curing of a composite material object is determined by the ability of water vapor and C0 2 gas to diffuse throughout the object.
  • thicker objects take longer to cure than thinner objects.
  • objects with high density (and fewer open pore spaces) take longer to cure than objects with low density (and more open pore spaces).
  • the following table provides examples of how the curing times may vary with respect to the smallest thickness (or wall thickness or section thickness) of the three dimensions and the bulk density of an object that is being manufactured.
  • a bonding element includes a core (represented by the black inner portion), a first layer (represented by the white middle portion) and a second or encapsulating layer (represented by the outer portion).
  • the first layer may include only one layer or multiple sub-layers and may completely or partially cover the core.
  • the first layer may exist in a crystalline phase, an amorphous phase or a mixture thereof, and may be in a continuous phase or as discrete particles.
  • the second layer may include only one layer or multiple sub-layers and may also completely or partially cover the first layer.
  • the second layer may include a plurality of particles or may be of a continuous phase, with minimal discrete particles.
  • a bonding element may exhibit any size and any regular or irregular, solid or hollow morphology depending on the intended application.
  • Exemplary morphologies include: cubes, cuboids, prisms, discs, pyramids, polyhedrons or multifaceted particles, cylinders, spheres, cones, rings, tubes, crescents, needles, fibers, filaments, flakes, spheres, sub-spheres, beads, grapes, granulars, oblongs, rods, ripples, etc.
  • a bonding element is produced from reactive precursor materials (e.g., precursor particles) through a transformation process.
  • precursor materials e.g., precursor particles
  • the precursor particles may have any size and shape as long as they meet the needs of the intended application.
  • the transformation process generally leads to the corresponding bonding elements having similar sizes and shapes of the precursor particles.
  • the bonding elements may be positioned, relative to each other, in any one of a number of orientations.
  • FIGs. 12(a) - 12(f) schematically illustrate an exemplary bonding matrix that includes fiber- or platelet- shaped bonding elements in different orientations possibly diluted by the incorporation of filler material, as represented by the spacing between the bonding elements.
  • FIG. 12(a) for example, illustrates a bonding matrix that includes fiber-shaped bonding elements aligned in a one-direction ("1-D") orientation (e.g., aligned with respect to the x direction).
  • FIG. 1-D one-direction
  • FIG. 12(b) illustrates a bonding matrix that includes platelet-shaped bonding elements aligned in a two-direction ("2-D") orientation (e.g., aligned with respect to the x and y directions).
  • FIG. 12(c) illustrates a bonding matrix that includes platelet-shaped bonding elements aligned in a three-direction ("3-D") orientation (e.g., aligned with respect to the x, y and z directions).
  • FIG. 12(d) illustrates a bonding matrix that includes platelet-shaped bonding elements in a random orientation, wherein the bonding elements are not aligned with respect to any particular direction.
  • FIG. 12(e) illustrates a bonding matrix that includes a relatively high concentration of platelet-shaped bonding elements that are aligned in a 3-D orientation.
  • FIG. 12(f) illustrates a bonding matrix that includes a relatively low
  • the composite material of FIG. 12(f) achieves the percolation threshold because a large proportion of the bonding elements are touching one another such that a continuous network of contacts are formed from one end of the material to the other end.
  • the percolation threshold is the critical concentration above which bonding elements show long- range connectivity with either an ordered, e.g., FIG. 12(e), or random orientation, e.g., FIG. 12(f), of bonding elements. Examples of connectivity patterns can be found in, for example, Newnham, et al, "Connectivity and piezoelectric-pyroelectric composites", Mat. Res. Bull. Vol. 13, pp. 525-536, 1978).
  • the plurality of bonding elements may be chemically transformed from any suitable precursor materials, for example, from any suitable calcium silicate composition precursor.
  • the precursor calcium silicate composition may also include one or more chemical elements of aluminum, magnesium and iron.
  • the plurality of bonding elements may have any suitable mean particle size and size distribution dependent on the desired composite material.
  • the plurality of bonding elements have a mean particle size in the range of about 1 ⁇ to about 100 ⁇ ⁇ e.g., about 1 ⁇ to about 80 ⁇ , about 1 ⁇ to about 60 ⁇ , about 1 ⁇ to about 50 ⁇ , about 1 ⁇ to about 40 ⁇ , about 1 ⁇ to about 30 ⁇ , about 1 ⁇ to about 20 ⁇ , about 1 ⁇ to about 10 ⁇ , about 5 ⁇ to about 90 ⁇ , about 5 ⁇ to about 80 ⁇ , about 5 ⁇ to about 70 ⁇ , about 5 ⁇ to about 60 ⁇ , about 5 ⁇ to about 50 ⁇ , about 5 ⁇ to about 40 ⁇ , about 10 ⁇ to about 80 ⁇ , about 10 ⁇ to about 70 ⁇ , about 10 ⁇ to about 60 ⁇ , about 10 ⁇ to about 50 ⁇ , about 10 ⁇ to about 40 ⁇ , about 10 ⁇ to about 30 ⁇
  • a composite material includes: a plurality of bonding elements and a plurality of filler particles.
  • Each bonding element includes: a core comprising primarily calcium silicate composition, a silica-rich first or inner layer, and a calcium carbonate-rich second or outer layer.
  • the plurality of bonding elements and the plurality of filler particles together form one or more bonding matrices and the bonding elements and the filler particles are substantially evenly dispersed therein and bonded together, whereby the composite material exhibits one or more textures, patterns and physical properties.
  • the bonding elements may have a core of magnesium silicate, and a silica-rich first or inner layer, and a magnesium carbonate-rich second or outer layer.
  • the magnesium silicate can include aluminum, calcium, iron or manganese oxides.
  • the plurality of filler particles may have any suitable mean particle size and size distribution.
  • the plurality of filler particles has a mean particle size in the range from about 5 ⁇ to about 7 mm ⁇ e.g., about 5 ⁇ to about 5 mm, about 5 ⁇ to about 4 mm, about 5 ⁇ to about 3 mm, about 5 ⁇ to about 2 mm, about 5 ⁇ to about 1 mm, about
  • the filler particles are made from a calcium carbonate-rich material such as limestone (e.g., ground limestone).
  • the filler particles are made from one or more of Si0 2 -based or silicate-based material such as quartz, mica, granite, and feldspar (e.g., ground quartz, ground mica, ground granite, ground feldspar).
  • filler particles may include natural, synthetic and recycled materials such as glass, recycled glass, coal slag, calcium carbonate -rich material and
  • the weight ratio of (bonding elements : filler particles) may be any suitable ratios dependent on the desired composite material, for example, in the range of about (10 to 50) : about (50 to 90).
  • these composite materials may display various patterns, textures and other characteristics, such as visual patterns of various colors.
  • the composite materials of the invention exhibit compressive strength, flexural strength and water absorption properties similar to conventional concrete or the corresponding natural materials.
  • the composite further includes a pigment.
  • the pigment may be evenly dispersed or substantially unevenly dispersed in the bonding matrices, depending on the desired composite material.
  • the pigment may be any suitable pigment including, for example, oxides of various metals (e.g., iron oxide, cobalt oxide, chromium oxide)
  • the pigment may be of any color or colors, for example, selected from black, white, blue, gray, pink, green, red, yellow and brown.
  • the pigment may be present in any suitable amount depending on the desired composite material, for example in an amount ranging from about 0.0% to about 10% by weight (e.g., about 0.0%> to about 8%, about 0.0%> to about 6%, about 0.0%> to about 5%, about 0.0% to about 4%, about 0.0% to about 3%, about 0.0% to about 2%, about 0.0% to about 1%, about 0.0% to about 0.5%, about 0.0% to about 0.3%, about 0.0% to about 2%, about 0.0% to about 0.1%,).
  • the processes of the invention may be employed to form anticorrosive coating on reinforcement used with any types of concrete (including Portland cement-based concrete) or to form protective coatings for a variety of different components and equipment.
  • Cylinder-shaped objects (4" diameter x 8" long as shown in FIG. 13) were casted in a mold with plain carbon steel embedded inside as reinforcing components. The cylindrical objects were demolded after 2 hours of casting.
  • FIG. 14 shows the micrograph for rebar specimen cured at about 60°C. It shows plain carbon steel, iron carbonate coatings formed and the bulk cured composite material.
  • FIG. 15 shows EDX analysis of the coating formed on carbon steel rebar at 60°C. Similarly, specimens were cast and cured at the same conditions except at about 90°C. The SEM micrographs are shown in FIG. 16.
  • FIG. 17 shows EDX analysis of the coating formed on iron rebar at 90°C. In each case, EDX analyses confirmed that the coating was iron carbonate.
  • ductile cast iron specimen (0.71 diameter x 2.2055 inch long) were put in 1 M NaHCC"3 solution in 1500 mL jars. The jars were put in oven at 60°C and 90°C for 24 hours. The specimens were then removed and rinsed with tap water before XRD and SEM analysis to characterize the corrosion products formed.
  • FIG. 19 depicts XRD pattern which shows siderite coatings formed on the surface.
  • FIG. 20 shows SEM image for this specimen which confirms the formation of siderite coatings during this reaction.

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Abstract

Cette invention concerne de nouveaux procédés de protection contre la corrosion des surfaces en fer ou en acier, telles que les composants de renfort en fer ou en acier incorporés dans des matériaux composites et sur les surfaces en acier de piles et de navires. Le revêtement en sidérite unique formé pendant un durcissement par carbonatation possède d'excellentes propriétés anticorrosives et permet d'améliorer la durée de vie globale des objets revêtus.
PCT/US2014/072494 2013-12-30 2014-12-29 Revêtements anticorrosifs, procédés et leurs utilisations WO2015103107A1 (fr)

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US9926235B2 (en) 2015-03-20 2018-03-27 Solidia Technologies, Inc. Microstructured carbonatable calcium silicate clinkers and methods thereof
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WO2017155899A1 (fr) 2016-03-11 2017-09-14 Solidia Technologies, Inc. Maîtrise du ternissage des ciments et bétons à base de silicate de calcium pouvant être carbonatés
CA3024307A1 (fr) 2016-05-31 2017-12-07 Solidia Technologies, Inc. Systemes de durcissement conditionnes et procedes correspondants
EA201991989A1 (ru) 2017-03-23 2020-05-18 Солидия Текнолоджиз, Инк. Карбонизируемые цементы и бетоны на основе силиката кальция, содержащие минеральные добавки, и их способы
US11667573B2 (en) 2017-11-21 2023-06-06 Solidia Technologies, Inc Compositions and method to improve the strength development of calcium silicate-based cements and concretes
EP3713896A1 (fr) 2017-11-21 2020-09-30 Solidia Technologies, Inc. Compositions et procédé pour améliorer la durabilité de ciments et de bétons à base de silicate de calcium
EP3713894A1 (fr) 2017-11-21 2020-09-30 Solidia Technologies, Inc. Compositions et procédé pour améliorer l'esthétique de ciments et de bétons à base de silicate de calcium
WO2019165281A1 (fr) * 2018-02-22 2019-08-29 Solidia Technologies, Inc. Atténuation de la corrosion dans du béton carbonaté à base de ciment de silicate à faible teneur en calcium
JP2022551516A (ja) * 2019-10-09 2022-12-09 ソリディア テクノロジーズ インコーポレイテッド 最適なｐＨを有する硬化複合材料の形成方法、及びそれに関連する組成とシステム
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US10611690B2 (en) 2014-08-04 2020-04-07 Solidia Technologies, Inc. Carbonatable calcium silicate compositions and methods thereof
WO2016054602A1 (fr) 2014-10-03 2016-04-07 Solidia Technologies, Inc. Composition à base de ciment de silicate de calcium carbonatable contenant des matériaux d'hydratation
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US10766819B2 (en) 2014-10-03 2020-09-08 Solidia Technologies, Ltd. Compositions and methods for controling setting of carbonatable calcium silicate cements containing hydrating materials
US9926235B2 (en) 2015-03-20 2018-03-27 Solidia Technologies, Inc. Microstructured carbonatable calcium silicate clinkers and methods thereof
US10626052B2 (en) 2015-03-20 2020-04-21 Solidia Technologies, Inc. Microstructured carbonatable calcium silicate clinkers and methods thereof
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US10695949B2 (en) 2015-05-18 2020-06-30 Solidia Technologies, Ltd. Lightweight composite materials produced from carbonatable calcium silicate and methods thereof

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