EP3720828A1 - Matériaux composites, leurs procédés de production et leurs utilisations - Google Patents

Matériaux composites, leurs procédés de production et leurs utilisations

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Publication number
EP3720828A1
EP3720828A1 EP17933872.8A EP17933872A EP3720828A1 EP 3720828 A1 EP3720828 A1 EP 3720828A1 EP 17933872 A EP17933872 A EP 17933872A EP 3720828 A1 EP3720828 A1 EP 3720828A1
Authority
EP
European Patent Office
Prior art keywords
objects
discrete
article
channels
chamber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP17933872.8A
Other languages
German (de)
English (en)
Other versions
EP3720828A4 (fr
Inventor
Larry E. Mccandlish
Orlando NARINE
Daniel CASTORO
Vahit Atakan
Devin PATTEN
John P. KUPPLER
Sean Camron QUINN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solidia Technologies Inc
Original Assignee
Solidia Technologies Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Solidia Technologies Inc filed Critical Solidia Technologies Inc
Publication of EP3720828A1 publication Critical patent/EP3720828A1/fr
Publication of EP3720828A4 publication Critical patent/EP3720828A4/fr
Pending legal-status Critical Current

Links

Classifications

    • EFIXED CONSTRUCTIONS
    • E04BUILDING
    • E04CSTRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C2/00Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
    • E04C2/02Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
    • E04C2/04Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of concrete or other stone-like material; of asbestos cement; of cement and other mineral fibres
    • E04C2/06Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of concrete or other stone-like material; of asbestos cement; of cement and other mineral fibres reinforced
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B28WORKING CEMENT, CLAY, OR STONE
    • B28BSHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B11/00Apparatus or processes for treating or working the shaped or preshaped articles
    • B28B11/24Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
    • B28B11/245Curing concrete articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B28WORKING CEMENT, CLAY, OR STONE
    • B28BSHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B11/00Apparatus or processes for treating or working the shaped or preshaped articles
    • B28B11/24Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
    • B28B11/247Controlling the humidity during curing, setting or hardening
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/18Compositions 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 mixtures of the silica-lime type
    • C04B28/186Compositions 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 mixtures of the silica-lime type containing formed Ca-silicates before the final hardening step
    • C04B28/188Compositions 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 mixtures of the silica-lime type containing formed Ca-silicates before the final hardening step the Ca-silicates being present in the starting mixture
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00Technologies relating to the processing of minerals
    • Y02P40/10Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • Y02P40/18Carbon capture and storage [CCS]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete

Definitions

  • the invention generally relates to articles of composite materials and systems and processes for making the same. More particularly, the invention relates to novel articles or assemblages of articles of composite materials (e.g., pavers, blocks, roof tiles and hollow core slabs), and formulations and methods for their manufacture and uses. These concrete-type objects are suitable for a variety of applications in construction, pavements and landscaping, and infrastructure.
  • Concrete is the most consumed man-made material in the world.
  • a typical concrete is made by mixing Portland cement, water and aggregates such as sand and crushed stone.
  • Portland cement is a synthetic material made by burning a mixture of ground limestone and clay, or materials of similar composition in a rotary kiln at a sintering temperature of around 1,450 °C.
  • Pavers are concrete blocks that are made by using a casting process, a pressing process, a compacting process, or a combination of vibration and pressing. Pavers are generally laid in interlocking pattern. These pavers are also sometime referred as paving stones. These pavers can be removed when damaged during service life with a new one reducing any service interruption.
  • Interlocking pavers could be designed to have a gap between the patterns that provides for draining of water to sub layers.
  • ASTM C 936 provides criteria that concrete pavers need to satisfy but is not limited to the following: an average compressive strength of 8,000 psi; an average water absorption no greater than 5%; and resistance to at least 50 freeze-thaw cycles with average material loss not exceeding 1%. In addition to the ASTM requirements, one may also wish that the pavers satisfy additional
  • blocks are also pre-cast concrete produced either by casting or pressing processes, or similar compacting processes.
  • Blocks are also referred to as concrete masonry units (CMUs), hollow blocks and concrete blocks. When these blocks are made with fly ash they are called cinder blocks. These blocks generally have a hollow structure.
  • CMUs concrete masonry units
  • cinder blocks When these blocks are made with fly ash they are called cinder blocks.
  • These blocks generally have a hollow structure.
  • Artificial or man-made paving stones and construction block materials have been studied in efforts to replace the expensive and scarce natural material with low-cost, readily produced mimics. Such efforts, however, have yet to produce in a synthetic material that possesses the desired appearance, texture, density, hardness, porosity and other aesthetics characteristic of stone while at the same can be manufactured in large quantities at low cost with minimal environmental impact.
  • Blocks are expected to provide better structural property compared to clay bricks (for load bearing masonry structure), and a smoother surface when producing a masonry wall.
  • interlocking concrete masonry units do not require mortar to bind the units.
  • Some blocks can be used to build a hollow structure that results in good sound and thermal insulation as compared to a solid structure.
  • Blocks have to generally comply with the requirements of ASTM C90, Standard
  • Hollow-core slabs sometimes referred to as voided slabs or hollow core planks, are precast slabs of concrete. They are often used in building constructions, for example, as floors, walls or roofs in multi-story buildings.
  • the precast concrete slab typically has tubular voids extending the full length of the slab, making the slab lighter than a massive floor slab of equal thickness or strength. Reduced weight lowers material and transportation cost.
  • Typical slabs are about 120 cm wide with a standard thickness between 15 cm and 50 cm.
  • the precast concrete I-beams between the holes contain steel wire ropes that provide bending resistance to bending moment from loads.
  • the manufacturing process involves extruding wet concrete around the prestressed steel wire rope from a moving mold. After curing the continuous slab is cut according to the required lengths and width.
  • Hollow-core floor slabs are also made in rebar reinforced concrete (not prestressed). Hollow-core wall panels are made without reinforcement.
  • this new cement sequesters C0 2 when cured into concrete products because C0 2 is needed to react with the carbonatable calcium silicate materials during the curing process to form concrete products.
  • the invention is based in part on the unexpected discovery of improved products and production technologies for manufacturing various concrete objects (e.g., pavers, blocks, roof tiles and hollow core slabs) from carbonatable calcium silicate.
  • the manufactured products possess excellent physical and performance characteristics matching or exceeding existing concrete products including toughness, flexibility, abrasion resistance and durability.
  • the concrete objects of the invention can be readily produced from widely available, low cost raw materials by a process suitable for large-scale production with lower energy consumption, therefore enjoying desirable carbon footprints with minimal environmental impact.
  • the raw materials include precursor materials such as particulate calcium silicate.
  • the calcium silicate precursor material typically comprises a blend of discrete calcium silicate phases, selected from one or more of CS (wollastonite or pseudowollastonite), C3S2 (rankinite), C2S (belite or lamite or bredigite) and a calcium-silicate based amorphous phase comprising about 30% or more of the total phases, where “C” refers to calcium oxide or lime, wherein“S” refers to silicon dioxide or silica, along with certain traces of impurities that become bonding elements, and particulate filler materials (e.g., calcium oxide-containing material such as limestone, xonotlite, miro-silica, and quartz, lightweight aggregates such as perlite or vermiculite, or even industrial waste materials
  • a fluid component is also provided as a reaction medium, comprising liquid water and/or water vapor and a reagent, carbon dioxide (C0 2 ), which is consumed in the production as a reactive species and ends up sequestered in the final product.
  • the bonding elements react at controlled temperatures and pressures either using the process of hydration in which the reaction occurs between water and water vapor, or using water vapor and C0 2 .
  • various other 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 invention generally relates to an article of manufacture having a composite material distributed as a plurality of discrete concrete objects.
  • One or more ducts or channels are arranged between or through the plurality of discrete concrete objects to form a fluid transport system within the one or more ducts or channels and/or with an exterior of the plurality of discrete objects.
  • the composite material includes: a plurality of bonding elements, wherein, each bonding element having 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.
  • 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 plurality of discrete concrete objects are arranged within an envelope or chamber.
  • the invention generally relates to a system for manufacturing an article.
  • the system includes an envelope or chamber and enclosed therein, a composite material distributed as a plurality of discrete concrete objects.
  • One or more ducts or channels are arranged between or through the plurality of discrete concrete objects forming a fluid transport system within the one or more ducts and channels and with an exterior of the plurality of discrete objects.
  • the system also optionally includes one or more boards on which the plurality of discrete concrete objects is placed and one or more racks, tarps, walls or panels with planar, flat, convex or concave faces, that form one or more ducts or channels and facilitate a fluid flow profile in the fluid transport system.
  • the invention generally relates to a process for producing an article of manufacture.
  • the process includes: mixing a particulate composition and a liquid composition to form a mixture; casting or extruding or otherwise forming the mixture in a mold to generate a casted or extruded or otherwise formed green body comprising a plurality of discrete concrete objects, wherein one or more ducts or channels are arranged between or through the plurality of discrete concrete objects and an exterior of the plurality of discrete objects; maintaining an atmosphere of C0 2 and/or water vapor in the one or more interior ducts or channels and the exterior of the plurality of discrete objects; and curing the plurality of discrete objects at a temperature in the range from about 20°C to about l50°C for about 1 hour to about 80 hours under an atmosphere of water and/or C0 2 having a pressure in the range from ambient atmospheric pressure to about 60 psi above ambient and having a C0 2 concentration ranging from about 10% to about 90%.
  • maintaining an atmosphere of CO2 and/or water vapor in the one or more interior ducts or channels and/or the exterior of the plurality of discrete objects includes: containing the atmosphere within the one or more interior channels and/or the exterior of the plurality of discrete objects; circulating the contained atmosphere of CO2 and/or water vapor; removing or adding water vapor to or from the contained atmosphere; and heating the contained atmosphere.
  • the invention generally relates to an article prepared by a process disclosed herein.
  • the article of the invention may be of any suitable size or shape or for any suitable purposes, for example, selected from pavers, blocks, roof tiles, hollow core slabs, precast concrete objects with or without reinforcement.
  • FIG. 1 is a pressure-temperature phase diagram showing the phases present in the reversible reaction CaCCh +S1O2 CaSiCh (calcium silicate) + CO2.
  • FIG. 2 is a pressure-temperature phase diagram showing the phases present in the reversible reaction 3CaCC> 3 + 2CaSiC> 3 2Ca2Si04-CaC03 + CO2.
  • FIG. 3 is a phase diagram of the CaO-SiC -CC system at a pressure of 1 kilobar.
  • FIG. 4 is a pressure-temperature phase diagram showing the phases present in the reversible reaction MgO + CO2 MgCCh.
  • FIG. 5 is a pressure-temperature phase diagram showing the equilibrium curves for the reversible reaction MgO + CO2 MgC03 as a function of the proportion of CO2 in an inert gas.
  • FIG. 6 is a temperature-composition phase diagram that illustrates the stability regions for various phases in the CaC03-MgC03 system.
  • FIG. 7 is a tetrahedron diagram illustrating the phase relationships among the compounds CaO, MgO, S1O2 and CO2, and showing the CO2 deficient region below the Cc-Di-Wo and the Cc- Wo-Mo planes (shaded), where Cc denotes calcite, Wo denotes Wollastonite, Ak denotes
  • FIG. 8 is a pressure-temperature phase diagram illustrating the phase relationships among the compounds CaO, MgO, SiCh and CO 2. with univariant curves emanating from the quaternary invariant point involving the phases cal cite (Cc), diopside (Di), forsterite (Fo), monticellite (Mo), Akermanite (Ak), and CO2.
  • the inset is the phase diagram for the three compound systems of CaC03, MgO and S1O2.
  • FIG. 9 is a schematic diagram of a CO2 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 CO2 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)
  • FIG. 13 shows exemplary images of an example of bonding elements with (a)-(c) showing energy-dispersive X-ray spectroscopy (EDS) chemical mapping of a bonding matrix according to an exemplary embodiment of the present invention, illustrating superposition of Si (a) and Ca (b) map.
  • EDS energy-dispersive X-ray spectroscopy
  • FIG. 14 shows an exemplary embodiment where a plurality of discrete objects (201) are dry cast onto a board (202) and arranged within an envelope or a chamber (203).
  • the fluid flow is directed between the one or more ducts or channels (101), and between the exterior of the plurality of discrete objects and the envelope or chamber (102), and the exterior of the plurality of the discrete concrete objects and a chamber component (103).
  • the chamber component is a board in this example.
  • Other embodiments of chamber components such as baffle plates, flow regulating and directing plates, rack components and similar structures.
  • FIG. 15 shows an exemplary photograph of a curing system with adjustable racking.
  • the channel height between the top of the concrete objects and the bottom of the next product board (101) can be adjusted to change the velocity of the process gas (102).
  • FIG. 16 shows an illustrative drawing of an exemplary curing system with reversible flow.
  • the flow direction can be changed to follow the directions by arrow (101) and arrow (102).
  • the flow and direction of the gas is controlled by an external condition system connected to the system at the flanges marked (103).
  • FIG. 17 shows an exemplary magnified view of a curing system with reversible flow.
  • the gas inlet plenum is designed so that flow is distributed to the channels between concrete objects
  • FIG. 18 shows an exemplary hollow-core slab made according to the invention.
  • FIG. 19 depicts an exemplary embodiment of the invention, wherein the gas flow of C0 2 and water vapor may be controlled such as to oscillate in directions when passing through the interior ducts or channels and around the exterior surfaces to establish time averaged mirror symmetry along the length while maintaining side-to-side mirror symmetry.
  • FIG. 20 shows an exemplary chamber humidity measurement at the end walls by the Vaisala sensors throughout the cure as well as the cumulative amount of condensed water collected throughout the run.
  • FIG. 21 shows an exemplary picture of the curing apparatus for curing a dry hollow-core casting.
  • FIG. 22 shows an exemplary hollow-core casting that was cured in the apparatus of FIG.
  • the invention provides exceptional concrete objects possessing excellent physical and performance characteristics matching or exceeding existing concrete objects.
  • the concrete objects of the invention can be readily produced from widely available, low cost raw materials by a process suitable for large-scale production with improved energy consumption, reduced production cycle (e.g., less curing time), and more desirable carbon footprint.
  • 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.
  • Concrete objects herein refer to objects and articles with geometries typical for the consumer market including but not limited to: pavers, bricks, segmented retaining wall, wet-cast stone slabs, concrete masonry units (CMU), or concrete hollow-core objects.
  • Hollow-core objects herein refer to objects and articles having hollow cores, channels or otherwise being hollowed out (for example, to reduce diffusion distances and facilitate curing).
  • the concrete objects of the invention can be use as various building and construction components including, for example, pavements, floors, roofs, walls, doors, tablets, bridges, frames, pathways, barriers, linings, foundations, fences, sound barriers, pipes, culverts utility vaults, septic tanks, dry wells, and storm drains. They may be manufactured with or without embedded
  • reinforcement elements e.g., pre-tensioned and/or post-tensioned and/or pre-stressed
  • features that increase the capacity and durability of the articles.
  • Reinforcement elements where present may be solid bars, wires or cables made with materials of desired characteristics, for example, steel, polymeric materials, glass, or a combination thereof.
  • the invention generally relates to an article of manufacture having a composite material distributed as a plurality of discrete concrete objects.
  • One or more ducts or channels are arranged between or through the plurality of discrete concrete objects to form a fluid transport system within the one or more ducts or channels and/or with an exterior of the plurality of discrete objects.
  • the composite material includes: a plurality of bonding elements, wherein, each bonding element having 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.
  • 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.
  • a key feature of an article of the invention is that ducts or channels (including hollow space) creates interior volumes whose thicknesses are small compared to the overall volume of the article. Access for the curing fluid to faces on sides of the interior volume significantly increases the surface area over which carbon dioxide and water must diffuse to affect curing. In addition, for monolithic bodies, the ducts or channels reduce the overall material use and product weight, resulting in savings in materials and other associated cost in transportation and installation.
  • the plurality of discrete concrete objects are arranged within chamber or envelope.
  • chamber or envelope For the purposes of this disclosure, the terms“chamber” and“envelope” are used interchangeably.
  • Concrete objects when produced in mass can be arranged and/or orientated by the forming process or during the curing chamber loading process so that interior or exterior faces are arrayed to maximize the exposure to the curing fluid (e.g., CO 2 and water vapor) and to minimize the diffusion distance of C0 2 and water relative to the total volume of the discrete objects.
  • Arrangement of the interior or exterior faces of the discrete objects relative to the fluid flow profile is a critical consideration for ensuring a uniform and/or fast curing process.
  • the discrete objects can be arrayed in a curing chamber with respect to the fluid flow profile to maximize carbon dioxide and water diffusion.
  • the spacing between concrete objects arrayed in the chamber can be manipulated to create channels parallel to the fluid flow while maintaining a similar envelope volume of concrete.
  • the concentration of fluid flow in the channels where the faces of the discrete objects are exposed improves curing uniformity and/or speed.
  • the geometry of the discrete objects and the fluid flow profile of the curing system determines the optimum inter-object spacing, object orientation, and spacing between the discrete objects and the fluid distribution system to induce a high carbon dioxide and water diffusion rates across the channel-forming object faces.
  • Manipulation of the spacing between the concrete objects arrayed in the chamber and chamber components such as racks, boards and the fluid distribution components such as gas inlets, outlets, plenums, or perforated plates can create channels between the faces of the concrete object faces and the chamber components.
  • Faces of the discrete objects in the proximity of the chamber features such as racks create channels adjacent to and/or between the discrete objects and the chamber, where fluid flow is concentrated.
  • concentration of fluid flow in the channels between the discrete object faces and the chamber components improves curing uniformity and speed.
  • the geometry of the discrete objects and the fluid flow profile of the curing system determines the optimum object orientation, spacing between the discrete objects and the chamber components, and spacing between the discrete objects and the fluid distribution system to induce high carbon dioxide and water diffusion rates across the channel-forming discrete object faces and the chamber components.
  • each of the plurality of discrete concrete objects does not comprise any reinforcement elements.
  • each of the plurality of discrete concrete objects comprises one or more reinforcement elements embedded therein.
  • the one or more reinforcement elements are selected from bars, wires and cables.
  • the one or more reinforcement bars may be made of any suitable materials, for example, iron, steel, polymeric materials, glass, or a combination thereof.
  • the plurality of bonding elements are chemically transformed from a ground calcium silicate composition, including one or more of natural or synthetic wollastonite, pseudo-wollastonite, rankinite, gehlenite, belite, alite and amorphous phase.
  • the gas comprises carbon dioxide.
  • the plurality of bonding elements are prepared by a chemical transformation from ground calcium silicate by reacting it with C0 2 via a controlled hydrothermal liquid phase sintering process.
  • the gas comprises carbon dioxide.
  • the plurality of bonding elements are chemically transformed from a precursor calcium silicate other than synthetic wollastonite or pseudo-wollastonite.
  • the weight ratio of bonding elements : filler particles is about 1 : 5.
  • the plurality of discrete concrete objects have a water absorption of less than about 10 %.
  • the fluid transport system is adapted to flowing a gas through the one or more ducts or channels and the exterior of the plurality of discrete objects.
  • the fluid that flows through the one or more ducts or channels and the exterior of the plurality of discrete objects changes it direction at least once.
  • the fluid that flows through the one or more ducts or channels and the exterior of the plurality of discrete objects changes its velocity at least once.
  • the fluid transport system within the exterior of the plurality of discrete objects comprises of a flow between the envelope or chamber or a chamber component within the envelope or chamber.
  • 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 CaSiCh or CaO SiCh), C3S2 (rankinite, and sometimes formulated as CasS ⁇ Ov or 3CaO2Si0 2 ), C2S (belite , -Ca2SiC>4 or lamite, -Ca2SiC>4 or bredigite, a-Ca2SiC>4 or y-Ca2Si04, and sometimes formulated as Ca2SiC>4 or 2CaO SiCk), 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
  • 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 S1O2 (silica).
  • the calcium silicate composition may also include small quantities of C3S (alite, Ca ⁇ SiCk).
  • 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 (Ca,Na,K) 2 [(Mg, Fe 2+ ,Fe 3+ ,Al,Si)30v] and ferrite type minerals (ferrite or brownmillerite or C4AF) with the general formula Ca2(Al,Fe 3+ )205.
  • 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 kinetics of hydration when exposed to water and is quickly converted to CaC03 during CO2 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 CO2.
  • 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 20 wt%); C3S2
  • 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 CO2.
  • 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 CaCCE with mass gain of about 20% or more.
  • the mass gain reflects the net sequestration of CO2 in the carbonated products.
  • the composition is suitable for carbonation with CO2 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 CaCCE 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 pm to about 25 pm, with 10% of particles (dlO) sized below about 0.1 pm to about 3 pm, and 90% of particles (d90) sized above about 35 pm to about 100 pm.
  • the ratio of d90 : dlO is selected to allow improved powder flow or decreased water demand for casting. In certain embodiments, the ratio of d50 : dlO is selected to allow improved reactivity, improved packing, or decreased water demand for casting. In certain embodiments, 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, xonotbte, 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 (dso) in the range from about 0.25 pm to about 200 pm (e.g., from about 0.25 pm to about 150 pm, from about 0.25 pm to about 100 pm, from about 0.25 pm to about 50 pm, from about 0.25 pm to about 20 pm, from about 0.25 pm to about 10 pm, from about 0.5 pm to about 200 pm, from about 1 pm to about 200 pm, from about 5 pm to about 200 pm, from about 10 pm to about 200 pm, from about 20 pm to about 200 pm, from about 50 pm to about 200 pm).
  • a particle size in the range from about 0.25 pm to about 200 pm (e.g., from about 0.25 pm to about 150 pm, from about 0.25 pm to about 100 pm, from about 0.25 pm to about 50 pm, from about 0.25 pm to about 20 pm, from about 0.25 pm to about 10 pm, from about 0.5 pm to about 200 pm, from about 1 pm to about 200 pm, from about 5 pm to about 200 pm, from about 10 pm to about 200
  • the filler particles are selected from fly ash, bottom ash, slag having particle sizes ranging from about 0.5 pm to about 300 pm (e.g., from about 1 pm to about 300 pm, from about 5 pm to about 300 pm, from about 10 pm to about 300 pm, from about 50 pm to about 300 pm, from about 100 pm to about 300 pm, from about 0.5 pm to about 200 pm, from about 0.5 pm to about 100 pm, from about 0.5 pm to about 50 pm, from about 0.5 pm to about 20 pm, from about 0.5 pm to about 10 pm, from about 0.5 pm to about 5 pm).
  • 0.5 pm to about 300 pm e.g., from about 1 pm to about 300 pm, from about 5 pm to about 300 pm, from about 10 pm to about 300 pm, from about 50 pm to about 300 pm, from about 100 pm to about 300 pm, from about 0.5 pm to about 200 pm, from about 0.5 pm to about 100 pm, from about 0.5 pm to about 50 pm, from about 0.5 pm to about 20 pm, from about 0.5 pm to about 10 pm, from
  • ground calcium silicate particles used have a particle size having a cumulative 10% diameter greater than 1 pm in the volume distribution of the particle size distribution.
  • the filler particles are selected from limestone, miro-silica, and quartz having particle sizes ranging from about 1 pm to about 500 pm (e.g., from about 1 pm to about 400 pm, from about 1 pm to about 300 pm, from about 1 pm to about 200 pm, from about 1 pm to about 100 pm, from about 1 pm to about 50 pm, from about 1 pm to about 30 pm, from about 5 pm to about 500 pm, from about 10 pm to about 500 pm, from about 20 pm to about 500 pm, from about 50 pm to about 500 pm, from about 100 pm to about 500 pm, from about 200 pm to about 500 pm).
  • a pm to about 500 pm e.g., from about 1 pm to about 400 pm, from about 1 pm to about 300 pm, from about 1 pm to about 200 pm, from about 1 pm to about 100 pm, from about 1 pm to about 50 pm, from about 1 pm to about 30 pm, from about 5 pm to about 500 pm, from about 10 pm to about 500 pm, from about 20 pm to about 500 pm, from about 50 pm to about 500 pm, from about 100 pm to
  • the filler particles are selected from lightweight aggregates having particle sizes ranging from about 20 pm to about 500 pm (e.g., from about 20 pm to about 400 pm, from about 20 pm to about 300 pm, from about 20 pm to about 200 pm, from about 20 pm to about 100 pm, from about 50 pm to about 500 pm, from about 100 pm to about 500 pm, from about 200 pm to about 500 pm, from about 300 pm to about 500 pm).
  • the set-controlling admixture is selected from a gluconate and sucrose.
  • the dispersing/viscosity-modifying agent is a polycarboxilate based material.
  • 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 Si0 4 (also known as“fosterite”) and Mg 3 Si40io(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 Si0 4 also known as“fosterite”
  • Mg 3 Si40io(OH) 2 also known as“talc”
  • 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 0io)(OH) 2 .
  • the invention generally relates to a system for manufacturing an article.
  • the system includes an envelope or chamber and enclosed therein, a composite material distributed as a plurality of discrete concrete objects.
  • One or more ducts or channels are arranged between or through the plurality of discrete concrete objects forming a fluid transport system within the one or more ducts and channels and with an exterior of the plurality of discrete objects.
  • the system also optionally includes one or more boards on which the plurality of discrete concrete objects are placed and one or more racks, tarps, walls or panels with planar, flat, convex or concave faces, that form one or more ducts or channels and facilitate a fluid flow profile in the fluid transport system.
  • the system includes a fluid distribution component that controls the fluid flow profile of at least a portion of the envelope or chamber.
  • the system includes a fluid distribution component that controls the fluid flow profile throughout the envelope or chamber.
  • the fluid distribution component that controls the fluid flow profile throughout the envelope or chamber changes the direction of the gas flow at least once.
  • the fluid distribution component that controls the fluid flow profile throughout the envelope or chamber changes the velocity of the gas flow at least once.
  • the fluid distribution component comprises one or more of fluid inlets, outlets, plenums, or perforated plates, or combinations thereof.
  • the envelope or chamber is made of a material selected from, a metal, alloy, plastic, polymer, polymeric composite, ceramic composite, or combinations thereof. In some embodiments, the envelope or chamber is made of concrete material, or, steel, or tarp, or combinations thereof. [0094] In yet another aspect, the invention generally relates to a process for producing an article of manufacture.
  • the process includes: mixing a particulate composition and a liquid composition to form a mixture; casting or extruding or otherwise forming the mixture in a mold to generate a casted or extruded or otherwise formed green body comprising a plurality of discrete concrete objects, wherein one or more ducts or channels are arranged between or through the plurality of discrete concrete objects and an exterior of the plurality of discrete objects; maintaining an atmosphere of C0 2 and/or water vapor in the one or more interior ducts or channels and the exterior of the plurality of discrete objects; and curing the plurality of discrete objects at a temperature in the range from about 20°C to about l50°C for about 1 hour to about 80 hours under an atmosphere of water and/or CO2 having a pressure in the range from ambient atmospheric pressure to about 60 psi above ambient and having a CO2 concentration ranging from about 10% to about 90%.
  • maintaining an atmosphere of CO2 and/or water vapor in the one or more interior ducts or channels and/or the exterior of the plurality of discrete objects includes: containing the atmosphere within the one or more interior channels and/or the exterior of the plurality of discrete objects; circulating the contained atmosphere of CO2 and/or water vapor; removing or adding water vapor to or from the contained atmosphere; and heating the contained atmosphere.
  • maintaining an atmosphere of CO2 and/or water vapor in the one or more interior ducts or channels comprises changing the direction or velocity of the fluid flow of CO2 and/or water vapor at least once during the period of curing the body.
  • the particulate composition includes a ground calcium silicate, comprising one or more of natural or synthetic wollastonite, pseudo-wollastonite, rankinite, gehlenite, belite, and alite and having a median particle size in the range from about 1 pm to about 100 pm and the liquid composition comprises water.
  • curing the casted mixture is performed at a temperature equal to or lower than about 60°C for about 10 to about 50 hours under a vapor comprising water and CO2 and having an ambient atmospheric pressure.
  • the ground calcium silicate is substantially that of ground wollastonite.
  • the process further includes embedding one or more
  • the one or more reinforcement bars may be made of any suitable materials, for example, iron, steel, polymeric materials, glass, or a combination thereof.
  • the one or more reinforcement elements may be any suitable size and shape, for example, in the form of bars, wires and cables.
  • the invention generally relates to an article prepared by a process disclosed herein.
  • the article may be of any suitable size or shape or for any suitable purposes, for example, selected from pavers, blocks, roof tiles, hollow core slabs, precast concrete objects with or without reinforcement.
  • the one or more ducts or channels is an important feature and affects the overall characteristics and performance of the discrete objects, including overall weight, mechanical properties, and functionalities.
  • the discrete objects, along with the chamber components and the chamber itself, may form any suitable number of ducts or channels in pre-designed pattern and inter-connectivity.
  • These ducts or channels may take any suitable sizes and shapes (e.g., circular, oval, polygonal, rectangular or square). They may be arranged in any suitable pattern or inter connectivity.
  • the number, shape, size and configuration of the ducts and channels will impact various mechanical properties of the hollow core articles. As discussed in more details herein, the number, shape, size and configuration of the ducts and channels can also be utilized to the advantages of the manufacturing, for example, to speed up the curing process and to achieve more uniform curing.
  • the volume of the ducts or channels may account for any suitable fraction of the volume of the plurality of discrete objects dependent on the product mold geometry and any post-forming changes to product spacing, for example, from about 5 vol.% to about 95 vol.% (e.g., from about 10 vol.% to about 95 vol.%, from about 20 vol.% to about 95 vol.%, from about 30 vol.% to about 95 vol.%, from about 50 vol.% to about 95 vol.%, from about 70 vol.% to about 95 vol.%, from about 5 vol.% to about 90 vol.%, from about 5 vol.% to about 70 vol.%, from about 5 vol.% to about 50 vol.%, from about 5 vol.% to about 30 vol.%, from about 5 vol.% to about 20 vol.%) of the overall volume of the plurality of concrete objects.
  • about 5 vol.% to about 95 vol.% e.g., from about 10 vol.% to about 95 vol.%, from about 20 vol.% to about 95 vol.%, from about 30 vol.
  • the discrete objects of the invention can be manufactured to various sizes and dimensions.
  • Typical dry-cast pavers range in height from 40 mm to 120 mm and may be pressed in an area up to 1.45 m x 1.45 m resulting in a distribution of a plurality of concrete objects with a volume of up to 0.26 m 3 per production board.
  • typical dry-cast concrete masonry units are 200 mm in height and may be pressed in an area up 1.45 m x 1.45 m resulting in a distribution of a plurality of concrete objects with a volume of up to 0.43 m 3 per production board.
  • the number, shape, size and configuration of the channels can be utilized to enhance the manufacturing process by improving the speed and uniformity of curing.
  • the dimensions are in the ranges of 1” to 24” in length, 1” to 24” in width, and 0.5” to 6” in height. In certain embodiments, the dimensions are in the ranges of 4” to 12” in length, 4” to 12” in width, and 1.5” to 5” in height.
  • the dimensions are in the ranges of 7 l/2”to 16” in length, 3 1 ⁇ 2” to 12” in width, and 4” to 16” in height.
  • the dimensions are in the range of 7 l/2”to 16” in length, 3 1 ⁇ 2” to 12” in width, and 6” to 12” in height.
  • the dimensions are in the ranges of 2” to 24” in length, 2” to 24” in width, and 0.25” to 2” in thickness. In certain embodiments where the discrete objects are roof tiles, the dimensions are in the ranges of 2” to 24” in length, 2” to 24” in width, and 0.25” to 2” in thickness. In certain embodiments where the discrete objects are roof tiles, the dimensions are in the ranges of 2” to 24” in length, 2” to 24” in width, and 0.25” to 2” in thickness. In certain embodiments where the discrete objects are roof tiles, the dimensions are in the ranges of 2” to 24” in length, 2” to 24” in width, and 0.25” to 2” in thickness. In certain embodiments where the discrete objects are roof tiles, the dimensions are in the ranges of 2” to 24” in length, 2” to 24” in width, and 0.25” to 2” in thickness.
  • the dimensions are in the range of 4” to 12” in length, 4” to 12” in width, and 0.25” to 1” in thickness.
  • the dimensions are in the ranges of 4” to 48” in length, 4” to 48” in width, and 1.5” to 5” in height. In certain embodiments, the dimensions are in the ranges of 4” to 48” in length, 4” to 48” in width, and 1.5” to 5” in height, and are typically have a footprint larger than 144 inches squared.
  • the discrete objects are typically pressed onto a production board in such a manner to maximize the concrete volume produced per board.
  • a production board When products of uniform lateral geometry are produced, parallel gaps between objects are left, resulting in channels between the plurality of discrete objects.
  • the number, shape, size and configuration of the channels can also be utilized to the advantages of the manufacturing, for example, to speed up the curing process and to achieve more uniform curing.
  • the plurality of concrete objects are loaded in a regular manner into the chamber.
  • the curing chamber forms the chamber or envelope.
  • boards are stacked and arranged for curing.
  • the orientation and spacing of boards may be manipulated to produce channels consisting of an exterior plane of the plurality of discrete objects, consisting of a number of individual object faces, and a chamber component, such as another stacked production board, where fluid flow can be directed.
  • the geometry of the discrete objects and the fluid flow profile of the curing chamber determines the optimum object orientation, spacing between the objects and the chamber components, and spacing between the objects and the fluid distribution system to induce high carbon dioxide and water diffusion rates across the channel -forming object faces.
  • the concrete mold used to produce a set of discrete objects is modified to change the spacing between the plurality of the discrete objects according the chambers flow distribution profile and improve the carbon dioxide and water diffusion rates across the channel forming object faces.
  • the discrete objects are separated or otherwise moved following the forming operation to change the spacing between concrete objects according the chambers flow distribution profile and improve the improve the carbon dioxide and water diffusion rates across the channel-forming object faces.
  • the product board spacing and/or the product board orientation can be adjusted relative to the fluid distribution system to increase the fluid flow through the channel created by the exterior of the faces of the plurality of the discrete objects and the envelope and the plurality of the discrete objects and the chamber components. This increases carbon dioxide and water diffusion rates between the associated exterior faces of the plurality of the discrete objects and the chamber and the associated exterior faces of the plurality of the discrete objects and the chamber components.
  • the step of forming a mixture includes/involves mixing aggregates, sand, calcium silicate and water in a mixer.
  • the mixer may be any mixer of a type typically used in mixing conventional concrete. Aggregates, sand and enough water to slightly wet the solids are thoroughly mixed. Next, calcium silicate is added to the batch along with the remaining water and any admixtures. The mixture is thoroughly mixed and the water adjusted to achieve the desired moisture level.
  • the step of casting or extruding the slurry mixture in a mold configured to generate a casted or extruded or otherwise formed body having one or more interior ducts or channels includes/involves pouring the mixture into the mold or the extrusion machine.
  • the mixture may be vibrated by vibrating the mold or by inserting vibrating wands into the mixture within the mold in order to facilitate removal of entrapped air and promote particle rearrangement to density the mixture.
  • the extruder may be fixed or moving. A fixed extruder pushes the mixture through channels that shape the mixture to the desired shape and promotes particle rearrangement to density the article.
  • the article is pushed out of the die within the extruder where upon it may be cut to a desired length and the article stacked for curing.
  • a moving extruder pushes the mixture against a fixed stop and through channels that shape the mixture to the desired shape. As the mixture is pushed against the fixed stop the pressure increases within the mixture, particles rearrange and the mixture is densified. As more and more material is extruded the compacted mixture pushes the extruder along an extrusion bed.
  • the step of maintaining an atmosphere of C0 2 and water vapor in the one or more interior ducts or channels includes/involves containing the atmosphere within the ducts or channels and/or around the exterior or the article; circulating the contained atmosphere of C0 2 and/or water vapor; removing or adding water vapor to or from the contained atmosphere; and heating the contained atmosphere.
  • the number, shape, size and configuration of the ducts and channels may be designed to increase the contact area of C0 2 and water vapor with the wall of extruded body.
  • temperature and concentration gradients will develop within the contained atmosphere and within the article itself as the curing proceeds. These gradients are recognized and controlled to achieve uniform curing of the article.
  • the gas flow of C0 2 and water vapor may be controlled, for example, such as to oscillate in opposite directions to reverse the gradients when passing through the interior ducts or channels and outside the exterior of the article so that the effect of the temperature and concentration gradients average out over the curing period.
  • the step of maintaining an atmosphere of C0 2 and water vapor in the one or more channels within the plurality of the concrete objects or between the plurality of concrete objects and the envelope or between the of the plurality of concrete objects and a chamber component includes/involves containing the atmosphere within the channels and/or around the exterior of the concrete object; circulating the contained atmosphere of C0 2 and/or water vapor; removing or adding water vapor to or from the contained atmosphere; and heating the contained atmosphere.
  • the number, shape, size and configuration of the channels may be designed to increase the contact area of C0 2 and water vapor with the wall of extruded body.
  • temperature and concentration gradients will develop within the contained atmosphere and within the article itself as the curing proceeds. These gradients are recognized and controlled to achieve uniform curing of the article.
  • the gas flow of C0 2 and water vapor may be controlled, for example, the direction of the gas flow is reversed altematingly from one direction to the other to reverse the gradients when passing through the channels and outside the exterior faces of the article so that the effect of the temperature and concentration gradients average out over the curing period.
  • the step of curing the casted or extruded body includes/involves contacting the article with an atmosphere of C0 2 and/or water vapor for a period of time.
  • Curing temperature and time may be adjusted according to the desired end product, for example, at a temperature in the range from about 20°C to about l50°C (e.g., from about 20°C to about l40°C, from about 20°C to about l20°C, from about 20°C to about l00°C, from about 20°C to about 90°C, from about 20°C to about 80°C, from about 20°C to about 70°C, from about 20°C to about 60°C, from about 30°C to about l00°C, from about 30°C to about 90°C, from about 30°C to about 80°C, from about 30°C to about 70°C, from about 30°C to about 60°C) for about 1 hour to about 80 hours (e.g., for about 1 hour to about 70 hours, for about 1 hour to about 60 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,
  • 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 a C0 2 concentration ranging
  • the materials used are ground calcium silicate.
  • the calcium silicate composition of the invention ground calcium silicate particles used have a particle size having a cumulative 10% diameter greater than 1 pm in the volume distribution of the particle size distribution.
  • the ground calcium silicate may have a median particle size from about 1 pm to about 100 pm (e.g., about 1 pm to about 80 pm, about 1 pm to about 60 pm, about 1 pm to about 50 pm, about 1 pm to about 40 pm, about 1 pm to about 30 pm, about 1 pm to about 20 pm, about 1 pm to about 10 pm, about 5 pm to about 90 pm, about 5 pm to about 80 pm, about 5 pm to about 70 pm, about 5 pm to about 60 pm, about 5 pm to about 50 pm, about 5 pm to about 40 pm, about 10 pm to about 80 pm, about 10 pm to about 70 pm, about 10 pm to about 60 pm, about 10 pm to about 50 pm, about 10 pm to about 40 pm, about 10 pm to about 30 pm, about 10 pm to about 20 pm, about 1 pm, 10 pm, 15 pm, 20 pm, 25 pm, 30 pm, 40 pm, 50 pm, 60 pm, 70 pm, 80 pm, 90 pm, 100 pm), a bulk density from about 0.5 g/mL to about 3.5 g/mL (loose
  • 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. % to about 95 wt.%, about 50 wt.% to about 95 wt.%, about 60 wt.% to about 95 wt.%, about 20 wt.% to about 90 wt.%, about 20 wt.% to about 80 wt.%, about 20 wt.% to about 70 wt.%, about 30 wt.% to about 80 wt.%, about 50 wt.% to about 80 wt.%).
  • ground calcium silicate materials e.g., about 20 wt.% to about 95 wt.%, about 30 wt. % to about 95 wt.%, about 50 wt.% to about 95 wt.%, about 60 wt.% to about 95 wt.
  • Chemical admixtures may be included for the manufacture of the discrete objects; for example, 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. [00130] In certain embodiments, 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., 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%).
  • 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.
  • curing techniques e.g., C0 2 delivery, system pressure and temperature
  • the hollow-core articles of the invention provide a number of benefits in performance over the hollow-core products made from conventional concrete, for example, superior stable properties are achievable in much shorter times than is the case for precast concrete articles made using ordinary Portland cement.
  • 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 calcium silicate compositions may be comprised of a ground product containing a variety of calcium silicate phases (including, for example, CS, C3S2, C2S and a calcium silicate based amorphous phase).
  • 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.
  • 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.
  • 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 thermodynamically driven by the free energy of the chemical reaction(s) and reduction of surface energy (area) caused by crystal growth.
  • 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.
  • FIG. 1 through FIG. 8 are phase diagrams that show various phase interrelationships among some of the materials described.
  • the plurality of bonding elements are prepared by chemical transformation from ground calcium silicate compositions by reacting them with CCf 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 110 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).
  • 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 CO 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.
  • C0 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 CO2 gas is provided.
  • this process of purging the enclosure of air can be performed in times measured in minutes to get the CO2 concentration up to a reasonable level so that curing can be performed thereafter.
  • CO2 gas is then fed into the system at a predefined rate so to maintain a concentration of CO2 sufficient to drive the curing reaction.
  • 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 CO 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 CO2 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 CO2 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 CO2 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.
  • CO2 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 CO2 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 measurements are taken to see whether the actual value of the parameter being controlled is the desired value. If deviation from the desired value is measured, corrective action is taken to bring the value of the parameter into agreement with the desired value.
  • Such control systems can be expensive and complex, and may be useful with regard to high value products or products that require very precise process conditions.
  • 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.
  • a general process for preparing a composite material 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 l50°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 CO2 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 pm to about 100 pm.
  • the particulate composition may include a ground calcium carbonate or a S1O2 bearing material having a mean particle size in the range from about 3 pm 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 l20°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 1 l0°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 l00°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 pm to about 100 pm (e.g., about 1 pm, 10 pm, 15 pm, 20 pm, 25 pm, 30 pm, 40 pm, 50 pm, 60 pm, 70 pm, 80 pm, 90 pm, 100 pm), 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 surface area from about 150 m 2 /kg to about 700 m 2 /kg (e.g., 150 m 2 /kg, 200 m 2 /kg, 250 m 2 /kg, 300 m 2 /kg, 350
  • 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 disclosed herein. It is believed that 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. As the calcium cations continue to be leached from the peripheral portion of the particle, 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. An example of this three-layer structure is shown in FIG. 13, reproduced from U.S. Pub. No. 2013/0122267 Al (FIG.
  • FIG. 13c the regions of CaSiO, Si0 2 , and CaCO, are referenced by arrows.
  • the wollastonite (CaSiO,) core particles are encapsulated by Si0 2 rich regions and surrounded by CaCCE particles. Different elements of bonding matrix are held together by CaCCE particles.
  • XRD of this composition revealed that CaSiCE and CaCCE (calcite) are crystalline phases, whereas silica rich regions are amorphous.
  • the term“coarse” and“fine” filler particles refers to any suitable material, having a suitable particle size and size distribution.
  • 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, fly ash, calcium carbonate-rich material and magnesium carbonate-rich material.
  • the plurality of“coarse” and“fine” filler particles have a mean particle size in the range from about 5 pm to about 7 mm (e.g., about 5 .tm to about 5 mm, about 5 i.tm to about 4 mm, about 5 pm to about 3 mm, about 5 pm to about 2 mm, about 5 pm to about 1 mm, about 5 pm to about 500 pm, about 5 pm to about 300 pm, about 20 pm to about 5 mm, about 20 pm to about 4 mm, about 20 pm to about 3 mm, about 20 pm to about 2 mm, about 20 pm to about 1 mm, about 20 pm to about 500 pm, about 20 pm to about 300 pm, about 100 pm to about 5 mm, about 100 mih to about 4 mm, about 100 mih to about 3 mm, about 100 mih to about 2 mm, about 100 mih to about 1 mm).
  • about 5 pm to about 7 mm e.g., about 5 .tm to about 5 mm, about 5 i.tm
  • the weight ratio of bonding elements to the“coarse” and“fine” filler particles may be any suitable ratio dependent on the intended application for the composite material product.
  • the weight ratio of bonding elements to the“coarse” or“fine” filler particles may be in the range from about (50 to 99): about (1 to 50), e.g., from about (60 to 99): about (1 to 40), from about (80 to 99): about (1 to 20), from about (90 to 99): about (1 to 10), from about (50 to 90): about (10 to 50), from about (50 to 70): about (30 to 50).
  • the weight ratio of bonding elements to filler particles may be in the range from about (10 to 50): about (50 to 90), e.g., from about (30 to 50): about (50 to 70), from about (40 to 50): about (50 to 60).
  • 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 Si0 4 ), diopside (CaMgS Cf), and talc (Mg 3 Si40io(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.
  • 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 atm.).
  • 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 lOO-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 CO 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 (“l-D”) orientation (e.g., aligned with respect to the x direction).
  • l-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 concentration of platelet- shaped bonding elements that are situated in a random orientation (a percolation network).
  • 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 pm to about 100 pm (e.g., about 1 pm to about 80 pm, about 1 pm to about 60 pm, about 1 pm to about 50 pm, about 1 pm to about 40 pm, about 1 pm to about 30 pm, about 1 pm to about 20 pm, about 1 pm to about 10 pm, about 5 pm to about 90 pm, about 5 pm to about 80 pm, about 5 pm to about 70 pm, about 5 pm to about 60 pm, about 5 pm to about 50 pm, about 5 pm to about 40 pm, about 10 pm to about 80 pm, about 10 pm to about 70 pm, about 10 pm to about 60 pm, about 10 pm to about 50 pm, about 10 pm to about 40 pm, about 10 pm to about 30 pm, about 10 pm to about 20 pm).
  • 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, paterns 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.
  • these composite materials may display various patterns, textures and other characteristics, such as visual paterns 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%,).
  • 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%,).
  • a curing system was fabricated wherein the spacing between product boards can be adjusted. Increasing or decreasing the spacing between the boards on which the discrete concrete objects were placed changes the size of the channel 101 formed between the top of the discrete concrete objects and the bottom of the board above the discrete concrete object. The size of this channel 101, governed by the gap between the boards and the dimensions of the discrete concrete objects, impact the velocity of the fluid traveling across the objects. For a constant volume of fluid flow between the boards, a smaller channel 101 increases the velocity and widening the channel 101 decreases the velocity.
  • the bonding element to filler ratio is high, it may be desirable to increase the size of channel 101 to improve the properties of the finished objects and optimize the total process time requirement.
  • the bonding element to filler ratio is low, it may be desirable to decrease the size of channel 101 to improve the properties of the finished objects optimize the total process time requirement.
  • multiple categories of discrete concrete objects with differing bonding element to filler ratio, water content, degree of compaction or dimensions will be processed in the same chamber or envelope.
  • the size of channel 101 can be adjusted independently for each product board according to the concrete object type adjacent to the channel. This method enables adjusting the velocity of the process gas according to the optimum velocity for each category of concrete objects in order to unify the properties of the finished objects and optimize the total process time requirement.
  • a curing system was designed wherein the flow of the process gas is directed to channels between the discrete concrete objects as well as between discrete concrete objects and chamber components.
  • the direction of flow in both the channels is reversible.
  • the envelopes or chambers capable of accommodating a plurality of discrete concrete objects arranged in an array as the fluid flows over these concrete objects.
  • the conditions of the fluid such as temperature, relative humidity or moisture content and velocity changes.
  • the condition of the fluid in the channels between the chamber components and the channels between the discrete concrete objects becomes unsuitable for optimal curing.
  • the temperature of the fluid drops and the relative humidity or moisture content of the fluid increases beyond a threshold suitable for the curing of the discrete concrete objects.
  • the fluid is considered unsuitable for use when the temperature of the fluid is reduced below 60°C, or below 55°C, or below 50°C, or below 45°C, or below 40°C or below 35°C, or below 30°C or below 25°C.
  • the fluid is considered unsuitable for use for curing when the moisture content of the fluid, expressed as relative humidity, is above 20%, or is above 30%, or is above 40%, or is above 50%, or is above 60%, or is above 70%, or is above 80%, or is above 90%.
  • the length of the array of the discrete concrete objects that can be cured can be increased. In doing so, the discrete concrete objects located downstream, that gets exposed to the colder and fluid with higher moisture content are now exposed to a drier and fluid with lower moisture content for at least part of the curing cycle. In some embodiments, this length can be increased to double the length at which the conditions of the gas become unsuitable for the gas to be used for curing in the set-up with a uni-directional flow throughout the curing cycle. Overall, this concept helps with increasing the capacity of the envelope or chamber.
  • FIG. 16 A large-scale drawing of an exemplary system is shown in FIG. 16. A close of drawing of the proposed system with concrete objects within is shown in FIG. 17.
  • the products can be stacked on boards above one another as shown in FIG. 15 and included inside a modified version of the proposed system shown in FIGs. 16 and 17, wherein the chamber height is increased to accommodate multiple racks.
  • Example 3 Curing a hollow-core slab using the desorption isotherm method
  • a Sicoma T08 Series planetary mixer (model MP 250/375 WWWSW) was used for mixing the components of the concrete mix design.
  • the planetary speed was 18.5 RPM.
  • Five Kg of water, 168 g of Glenium 7500 admixture (BASF) and 120 g of air entrainment admixture were added to the dry-mix and the combination mixed for an additional 90 seconds.
  • a hollow-core slab was extruded on the steel bed by a commercial Elematic EL 600/8 extrusion machine using an auger speed of 55 RPM.
  • the extruded slab was 18 feet long by 4 feet wide by 8 inches high and contained six (6” diameter) hollow cores. Adjacent cores were separated by a 1.25” thick wall.
  • FIG. 18 shows a picture of the hollow-core slab.
  • FIG. 19 is a schematic drawing of the curing apparatus.
  • the bed was heated by circulating hot water through pipes within the steel bed during the cure.
  • the temperature of the heating water was maintained by a gas-fired boiler held at 8l°C.
  • the temperature at the top surface of the steel bed was around 49°C.
  • Cold water from a chiller (maintained at lO°C) was circulated through the condenser to remove moisture from the circulating gas stream.
  • An electric heater (3.75 kW) was maintained at 87°C to heat the dried circulating gas stream before it returns to the curing chamber.
  • the speed of the circulation blower was controlled by a variable frequency drive.
  • the initial blower speed was 30 Hz.
  • Dry C0 2 was supplied on demand to the curing system through an Alicat mass flow controller.
  • the curing chamber comprised the steel extrusion bed and a
  • polyethylene sheet which functioned as a canopy and separated the CO /H O stream from the ambient atmosphere.
  • the canopy covered the hollow-core slab and was stretched between support walls at each end of the slab.
  • the canopy was sealed along the steel extrusion bed and to the end walls with magnetic strips and was inflated by the circulating gas stream.
  • Each end wall of curing chamber had the same cross sectional shape as the slab except that the walls were 9.25” rather than 8” high.
  • Each end wall served as the front of rectangular box forming a chamber with 1 gas entrance port opposite 6 holes through which gas entered or exited the curing chamber.
  • the 6 holes were covered with a perforated metal sheet so that the end chamber acted as a plenum that functioned to distribute and smooth the gas flow into the curing chamber.
  • One of the two ports belonging to a differential pressure transmitter was inserted through one end wall into the curing chamber. The other port was left open to the ambient atmosphere.
  • the sampling probe of a NDIR C0 2 meter was inserted through the end wall at the other end of the curing chamber to monitor the C0 2 concentration in the chamber throughout the curing run.
  • Two Vaisala Humidity /Temperature probes were placed within the curing chamber, one at each end just inside the end walls.
  • FIG. 20 shows the chamber humidity measured at the end walls by the Vaisala sensors throughout the cure as well as the cumulative amount of condensed water collected throughout the run.
  • the strength of the hollow-core slab was estimated using a rebound hammer at 44 points on the top surface of the slab.
  • the rebound measures indicated an average compressive strength of 30 MPa.
  • Example 4 Curing a hollow-core casting using the adsorption isotherm method
  • the mix design consisted of six solid components: (1) 3/8” aggregate, 29% (2) 1 ⁇ 4” aggregate, 15% (3) 2mm crushed quartz, 12% (4) construction sand, 20% (5) marble white 200, 11% and (6) NYCO 400 wollastonite 13%.
  • the components were“dry” mixed in a Kercher Industries 12” lab-scale mixer for 2 minutes. Water (570 g) with gum additive was added to the dry components and the resulting mixture mixed an additional 4 minutes. More water (265g) was added and the mixture mixed an additional 4 minutes. Finally, more water (260g) was added and the mixture mixed an additional 2 minutes.
  • the wet mixture was cast in a 4” x 4” x 20” rectangular mold with the long dimension placed horizontally.
  • a 2” diameter x 20” long pvc pipe that had be wrapped in waxed paper was secured in the center of the mold so as to form a 2” diameter core along the length of the casting.
  • the concrete mix was cast in 6 layers with 30 seconds of vibration at each layer except for the last, which was vibrated for 60 seconds.
  • the hollow-core casting was slowly dried to prevent cracking. It was allowed to air-dry over night and was then placed in a drying oven at 90°C for 51 hours, followed by an additional 20 hours at l00°C. After drying, the hollow-core casting was removed from its mold and the pvc pipe removed from the core of the casting. The net weight of the hollow-core casting was 8769 grams.
  • FIG. 21 is a picture of the curing setup.
  • a PVC pipe fitting was inserted into each end of the core with tube fittings screwed into the pipe fittings so that curing gases could be passed through the casting.
  • the hollow-core casting was encased in 1” thick aluminum-foil-backed fiberglass insulation.
  • One of the tube fittings from the core (the entrance tube assembly) was attached with 1 ⁇ 4’ stainless steel tubing to a gas saturator (heated vessel that contained water).
  • the other tube fitting from the core (the exit tube assembly) was attached to a 1 ⁇ 4” plastic tube that lead to a vent.
  • Each tube assembly was fit with a thermocouple so that the temperature of the curing gas could be measured before and after passing through the core.
  • Each tube assembly was insulated with fiberglass insulation.
  • the water in the saturator was maintained at 65°C throughout the curing run. Carbon dioxide gas was bubbled through the water at 6.5 liters/minute to saturate the gas stream with water vapor. All of the heat and water for the curing reaction was carried into the hollow core by the saturated carbon dioxide stream. The temperature at the core inlet rose from 26°C to 60°C over a period of one hour where it stayed for the rest of the curing run. It took another 90 minutes for the temperature at the core exit to rise to 53°C where it stayed for the rest of the curing period. The curing run was terminated after 20 hours.
  • the dried hollow-core casting was cut in half to assess the uniformity of the cure, since the two ends of the casting were visually different. Some material was lost from the kerf on cutting through the casting and some material was lost from spalling of the outside edges of the cut caused by the saw blade. The spalling pattern was symmetrical and approximately the same on both halves of the costing thus the cutting losses were approximately the same for both pieces. The total weight of cutting losses amounted to 137 grams.
  • the inside edges (e.g., the core surface) cut cleanly, which suggests that the inside of the casting had reacted better than the outside and that the extent of reaction varied in a radial pattern around the core.
  • the weight of the inlet half of the dried casting was 4429 grams while the weight of the outlet half of the dried casting was 4373 grams.
  • the mass remaining after cutting the slab was evenly distributed in the two halves (50.3% inlet end; 49.7% outlet end). Therefore the extent of carbonation was distributed evenly along the length of the hollow-core casting.
  • composition and/or method may be practiced without one or more of the specific details, or with other methods, components, materials, and so forth.
  • well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of the disclosure.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Structural Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Architecture (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Civil Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Cultivation Of Plants (AREA)
  • Laminated Bodies (AREA)
  • Road Paving Structures (AREA)
  • Devices For Post-Treatments, Processing, Supply, Discharge, And Other Processes (AREA)

Abstract

L'invention concerne de nouveaux articles de matériaux composites présentant des canaux ou passages intérieurs creux, ou autrement évidés, ainsi que des formulations, et leurs procédés de fabrication et leurs utilisations. Lesdits objets à coeur creux sont appropriés pour une diversité d'applications dans la construction, les chaussées et l'aménagement paysager, ainsi que l'infrastructure.
EP17933872.8A 2017-12-04 2017-12-04 Matériaux composites, leurs procédés de production et leurs utilisations Pending EP3720828A4 (fr)

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WO2021243441A1 (fr) 2020-06-03 2021-12-09 Carbicrete Inc. Procédé de fabrication de produits en béton préfabriqué carbonatés à durabilité améliorée
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WO2019112555A1 (fr) 2019-06-13
CN111615503A (zh) 2020-09-01
CA3083371A1 (fr) 2019-06-13
SA520412093B1 (ar) 2024-03-13
JP2023159143A (ja) 2023-10-31
EP3720828A4 (fr) 2021-07-14
JP2021505523A (ja) 2021-02-18
EA202091075A1 (ru) 2020-12-15

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