EA044255B1 - COMPOSITE MATERIALS, METHODS OF THEIR PRODUCTION AND APPLICATION - Google Patents

Description

Field of technology

The present invention generally relates to composite materials products and systems and methods for their production. More specifically, the present invention relates to new products or prefabricated products made from composite materials (eg, road slabs, blocks, tiles and hollow-core slabs), as well as compositions and methods for their preparation and use. These concrete products are suitable for a variety of applications in construction, paving, landscape architecture and infrastructure.

State of the art

Concrete is the most consumed man-made material in the world. Typical concrete is made by mixing Portland cement, water and aggregates such as sand and crushed stone. Portland cement is a synthetic material produced by burning a mixture of ground limestone and clay or materials of similar composition in a rotary kiln at a sintering temperature of approximately 1450°C.

Road slabs are concrete blocks made through a casting process, a pressing process, a compaction process, or a combination of vibration and pressing processes. In general, road slabs are laid according to the plan in a dressing. Such road slabs are also sometimes called paving stones. If damaged during their service life, these road slabs can be replaced with new slabs, which reduces interruption in operation. Road slabs for laying in a dressing can be made in such a way as to have a gap between the slabs, ensuring the drainage of water into the underlying layers.

ASTM C 936 contains criteria that concrete paving slabs must meet, but is not limited to the following: average compressive strength of 8000 psi (approximately 55 MPa); average water absorption no more than 5%; and resistance to at least 50 freeze-thaw cycles with average material loss not exceeding 1%. In addition to ASTM requirements, it is desirable for pavements to meet additional requirements, including reduced weathering (eg, reduced reaction product leaching due to concentration gradients); good color fastness; and abrasion resistance depending on where the road slabs are used.

Like pavement slabs, blocks are also precast concrete produced using either casting or pressing processes or similar compaction processes. The blocks are also called concrete building units (CMU), hollow blocks and concrete blocks. When such blocks are made using fly ash, they are called cinder blocks. These blocks usually have a hollow structure. In order to replace expensive and scarce natural materials with inexpensive, easily obtained imitation materials, synthetic or artificial paving stones and building block materials have been investigated. However, such efforts have yet to produce a synthetic material that has the desired appearance, texture, density, hardness, porosity and other aesthetic characteristics of stone, while being able to be produced in large quantities at low cost with minimal environmental impact.

These blocks are expected to provide better structural properties than clay bricks (for a load-bearing masonry structure) and a smoother surface when making a masonry wall. In addition, concrete building blocks for bonding do not require the use of mortar to join the blocks. Some blocks can be used to create a hollow structure, providing good sound and heat insulation compared to a solid structure.

In general, blocks must meet the requirements of ASTM C90, Standard Specification for Loadbearing Concrete Masonry Units. It can be ensured that blocks meeting this standard are acceptable in terms of strength, geometric dimensions, durability and fire resistance, and are generally suitable for use in typical commercial building projects.

Hollow-core slabs, sometimes called channel slabs or hollow slabs, are precast concrete slabs. They are often used in building structures, for example as floors, walls or roofs in multi-storey buildings. A precast concrete slab typically has tubular voids running the full length of the slab, making the slab lighter than a solid floor slab of equal thickness or strength. The reduced weight reduces material and transportation costs.

Typical slabs are approximately 120 cm wide with a standard thickness of 15 to 50 cm. Precast concrete I-beams contain steel wire ropes between the holes to provide bending resistance against the bending moment generated by the loads. The manufacturing process involves extruding wet concrete around prestressed steel wire rope from a moving mold. Once cured, the solid slab is cut to the required length and width. Hollow-core floor slabs are also made from reinforced concrete (without prestressing). Hollow wall

- 1 044255 panels are made without reinforcement.

However, concrete products are not optimal in terms of both economics and environmental impact. Current production technologies are characterized by high energy consumption and carbon dioxide emissions, resulting in unfavorable carbon footprints. The production of Portland cement is not only an energy-intensive process, but also a process that emits significant amounts of greenhouse gases (CO2). The cement industry accounts for approximately 5% of global anthropogenic CO2 emissions. More than 60% of this CO ₂ is produced by chemical decomposition or calcination of limestone.

Recently, a revolutionary form of cement based on calcium silicate materials capable of carbonization has emerged as a promising replacement for traditional cements. The production of cements based on calcium silicate, which is capable of carbonation, is characterized by a significant reduction in CO2 emissions and energy consumption. In addition, this new cement allows CO2 to be sequestered during curing in concrete products, since CO2 is required to react with calcium silicate materials capable of carbonation during the curing process to produce concrete products.

Thus, there is a constant need for new and improved cement and concrete products and production technologies that can be used in mass production at lower costs with improved energy consumption and a more desirable carbon footprint.

Brief description of the invention

The present invention is based in part on the unexpected discovery of improved products and manufacturing techniques for producing various concrete objects (eg, paving slabs, blocks, tiles and hollow core slabs) from calcium silicate that is carbonizable. Such resulting products have superior physical and performance characteristics that match or exceed those of existing concrete products, including toughness, flexibility, abrasion resistance and durability.

The concrete objects of the present invention can be easily produced from widely available low-cost raw materials through a process suitable for large-scale production, with lower energy consumption, hence achieving the required carbon footprint with minimal environmental impact. Raw materials include precursor materials such as particulate calcium silicate. The calcium silicate precursor material typically contains a mixture of individual calcium silicate phases selected from one or more phases including CS (wollastonite or pseudowollastonite), C ₃ S ₂ (rankinite), C2S (belite or larnite or bredigitite) and an amorphous phase on a calcium silicate base comprising about 30% or more of the total phases, wherein C refers to calcium oxide or lime, where S refers to silica or silica, together with some trace amounts of impurities which become binding elements, and filler materials in particulate (for example, calcium oxide containing material such as limestone, xonotlite, fumed silica and quartz, lightweight aggregates such as perlite or vermiculite, or even industrial wastes such as fly ash, bottom ash and slag). In addition, the fluid component is used as a reaction medium containing liquid water and/or steam and a reactant, carbon dioxide (CO2), which is consumed during production as a reactive compound and is ultimately isolated in the finished product. The binding elements interact at controlled temperatures and pressures, either through a hydration process in which a reaction occurs between water and steam, or using steam and CO2.

Depending on the end user's requirements, various other additives can be used, such as dispersants, rheology modifiers (to improve the consistency of the mixture), color pigments, retarders and accelerators. Additive materials may include natural or recycled materials and materials enriched with calcium carbonate and magnesium carbonate, as well as additives in the liquid component, such as a water-soluble dispersant.

In one aspect, the present invention generally relates to an article comprising a composite material distributed as a plurality of individual concrete objects. One or more passages or channels are located between or extend through said plurality of individual concrete objects to form a system for transporting fluid within the one or more passages or channels and/or from the outside of the plurality of individual objects. The composite material contains: a plurality of binding elements, each binding element having a core comprising predominantly calcium silicate, a first or inner layer enriched in silica, and a second or outer layer enriched in calcium carbonate; and filler particles containing coarse filler particles and/or fine filler particles. A plurality of binding elements and a plurality of filler particles together form one or more binding matrices, wherein said binding elements and filler particles are substantially uniformly distributed in said matrix and bonded together. In certain embodiments, a plurality of individual concrete objects are located within an enclosure or chamber.

- 2 044255

According to another aspect, the present invention generally relates to a system for manufacturing an article. The system includes a shell or chamber and an enclosed composite material distributed in the form of a plurality of individual concrete objects. One or more passages or channels are located between or extend through said plurality of individual concrete objects to form a system for transporting fluid within the one or more passages and channels and from the exterior of the plurality of individual objects. The proposed system also optionally includes one or more slabs on which a plurality of individual concrete objects are placed, and one or more racks, canvases, walls or panels with planar, flat, convex or concave facing surfaces defining one or more passages or channels and providing fluid flow profile in a fluid transport system.

According to another aspect, the present invention generally relates to a method for producing an article. The proposed method includes: mixing a particulate composition and a liquid composition to form a mixture; casting or extruding or otherwise molding said mixture in a mold to produce a cast or extruded or otherwise molded compact (green body) containing a plurality of individual concrete objects, wherein one or more passages or channels are located between said plurality of individual concrete objects and the outside of or pass through a plurality of individual objects; maintaining an atmosphere of CO2 and/or water vapor in one or more internal passages or channels and the exterior of a plurality of individual objects; and curing the plurality of individual objects at a temperature ranging from about 20° C. to about 150° C. for from about 1 hour to about 80 hours in an atmosphere of water and/or CO ₂ at a pressure of from external atmospheric pressure to a pressure of about 60 psi (approximately 413 kPa) above external pressure, and the CO2 concentration ranges from about 10% to about 90%.

In some embodiments, maintaining an atmosphere of CO2 and/or water vapor within one or more internal passages or channels and/or an exterior portion of the plurality of distinct entities includes: maintaining an atmosphere within one or more internal passages or channels and/or an exterior portion of the plurality of distinct entities; circulation of a retained atmosphere of CO ₂ and/or water vapor; removing water vapor from the retained atmosphere or adding water vapor to the retained atmosphere; and heating the retained atmosphere.

In another aspect, the present invention generally relates to an article produced by the method described herein. The product of the present invention may be of any suitable size or shape or suitable for any suitable purpose, for example selected from paving slabs, blocks, tiles, hollow core slabs, precast concrete products with or without reinforcement.

Brief description of graphic materials

The objects and features of the present invention can be better understood with reference to the drawings and claims described below. These drawings are not necessarily to scale, but rather, emphasis is placed generally on illustrating the principles of the present invention. In the drawings, the same numbers are used to indicate the same parts in all the different images.

Fig. 1 is a pressure-temperature phase diagram showing the phases present in the reversible reaction CaCO ₃ +SiO ₂ θCaSiO ₃ (calcium silicate) + CO ₂ .

Fig. 2 is a pressure-temperature phase diagram showing the phases present in the reversible reaction 3CaCO ₃ +2CaSiO ₃ θ2Ca ₂ SiO4-CaCO ₃ +CO ₂ .

Fig. 3 is a phase diagram of the CaO-SiO ₂ -CO ₂ system at a pressure of 1 kilobar.

Fig. 4 is a pressure-temperature phase diagram showing the phases present in the reversible reaction MgO+CO ₂ θ MgCO ₃ .

Fig. 5 is a pressure-temperature phase diagram showing the equilibrium curves for the reversible reaction MgO+CO2+MgCO3 as a function of the fraction of CO2 in the inert gas.

Fig. 6 is a temperature-composition phase diagram illustrating the stability regions for various phases in the CaCO3-MgCO3 system.

Fig. 7 is a tetrahedral diagram illustrating the phase relationships between the compounds CaO, MgO, SiO ₂ and CO ₂ and showing the CO ₂ deficient region below the Cc-Di-Wo and Cc-Wo-Mo planes (shaded), where Cc denotes calcite , Wo stands for wollastonite, Ak stands for ackermanite, Di stands for diopside and Mo stands for monticellite (CaMgSiO4).

Fig. 8 is a pressure-temperature phase diagram illustrating the phase relationships between the compounds CaO, MgO, SiO2 and CO2, with the single-variant curves originating from a quaternary invariant point comprising the phases of calcite (Cc), diopside (Di), forsterite (Fo), monticellite (Mo), ackermanite (Ak) and CO2. The inset shows a phase diagram for systems of three compounds CaCO ₃ , MgO and SiO ₂ .

Fig. 9 is a schematic illustration of a CO2 curing chamber providing humidification according to the principles of the present invention.

Fig. 10 is a schematic representation of a curing chamber with several methods of humidity control, as well as the ability to regulate and replenish CO ₂ by regulating a constant flow or pressure, in which the temperature can be controlled according to the principles of the present invention.

Fig. 11(a)-11(c) are schematic cross-sectional views of coupling elements according to exemplary embodiments of the present invention, including the morphology of three typical cores: (a) fibrous, (b) elliptical, and (c) equiaxed.

Fig. 12(a)-12(f) are schematic side and cross-sectional views of composite materials according to exemplary embodiments of the present invention, showing (a) 1D oriented fiber-shaped bonding elements in a dilute bonding matrix (the bonding elements are not touching ), (b) 2D oriented plate-shaped binding elements in a dilute binding matrix (connecting elements not touching), (c) 3D oriented plate-shaped connecting elements in a dilute binding matrix (connecting elements not touching), and (d) randomly oriented plate-shaped connecting elements forms in a dilute binding matrix (the binding elements are not in contact), wherein said composite materials contain a binding matrix and filler components such as polymers, metals, inorganic particles, fillers, etc., (f) a concentrated binding matrix (with a volume fraction (f) a concentrated binding matrix (with a volume fraction sufficient to create a percolation network) of randomly oriented binding elements, which may include filler components such as polymers, metals, inorganic particles, fillers, etc.

In fig. 13 are illustrative images of an example of coupling elements (a)-(c), showing energy dispersive X-ray spectroscopy (EDS) chemical mapping of coupling matrices according to an exemplary embodiment of the present invention, illustrating the superposition of the location map of Si (a) and Ca ( b). In image (c), the CaSiO, SiO ₂ and CaCO ₃ regions are indicated by arrows. Wollastonite (CaSiO ₃ ) core particles in the form of fibers are encapsulated in SiO ₂ -rich regions and surrounded by CaCO ₃ particles.

In fig. 14 shows an exemplary embodiment in which a plurality of individual objects (201) are dry cast onto a plate (202) and housed within a shell or chamber (203). Fluid flow is directed between one or more passages or channels (101) and between the exterior of the plurality of discrete objects and the shell or chamber (102), and the exterior of the plurality of discrete concrete objects and the chamber component (103). In such an example, the chamber component is a plate. Other embodiments of chamber components may be used, such as baffles, flow control and direction plates, rack components, and similar structures.

In fig. 15 shows an illustrative photograph of a curing system with an adjustable rack. The height of the channel between the top of the concrete objects and the bottom of the next product placement slab (101) can be adjusted to change the speed of the process gas (102).

In fig. 16 is an illustrative drawing of a typical reversible flow curing system. The flow direction can be changed to follow the directions indicated by arrow (101) and arrow (102). The flow and direction of the gas is controlled by an external conditioning system connected to the proposed system at flanges designated as (103).

In fig. 17 is an exemplary enlarged view of a reversible flow curing system. The receiving chamber for gas is configured to distribute the flow into channels between concrete objects (101) and channels formed by the outer surfaces of concrete objects and the walls of the chamber (102).

In fig. 18 shows an exemplary hollow core slab produced in accordance with the present invention.

In fig. 19 depicts an illustrative embodiment of the present invention in which the gas flow of CO ₂ and water vapor can be adjusted to move in different directions as it passes through internal passages or channels and around external surfaces to create a time-averaged mirror symmetry along its length while maintaining mirror symmetry in the transverse direction (side-to-side). Such symmetries reduce the influence of temperature and gas composition gradients that occur during the curing process.

In fig. Figure 20 shows moisture measurements in a typical end-wall chamber using Vaisala sensors throughout the curing process, as well as the total amount of condensed water collected throughout the cycle.

In fig. 21 shows an illustrative view of a curing apparatus for dry curing

- 4 044255 hollow casting.

In fig. 22 shows an exemplary hollow casting that has been cured in the apparatus shown in FIG. 21.

Detailed Description of the Invention

The present invention provides unique concrete objects having superior physical and performance characteristics that match or exceed existing concrete objects. The concrete objects of the present invention can be easily produced from widely available low-cost raw materials in a process suitable for large-scale production, with reduced energy consumption, shortened production cycle (eg, shorter curing time) and a more desirable carbon footprint. When using the production method according to the present invention, large quantities of CO ₂ are consumed, resulting in a CO ₂ sequestering product, thereby making the proposed method carbon neutral and environmentally friendly. The concrete objects described herein refer to objects and products with geometric dimensions typical of the consumer market and include, but are not limited to: paving slabs, bricks, segmented retaining walls, wet cast stone slabs, concrete building blocks (CMU) or concrete hollow objects. Hollow objects described herein refer to objects and articles that have hollow cores, channels, or are otherwise made hollow (eg, to reduce diffusion distances and facilitate cure).

Concrete objects according to the present invention can be used as various components of buildings and structures, including, for example, as sidewalks, floors, roofs, walls, doors, tiles, bridges, frames, walkways, barriers, cladding, foundations, fences, sound barriers barriers, pipes, culverts, underground utility wells, septic tanks, dry wells and storm drains. These objects can be manufactured with or without the use of embedded reinforcement elements (eg, pre-tensioned and/or post-tensioned and/or pre-tensioned), components that increase the performance and durability of the products. Reinforcing elements, if present, may be solid bars, wires or ropes made from materials with the required characteristics, such as steel, polymeric materials, glass or a combination of these.

In one aspect, the present invention generally relates to an article comprising a composite material distributed as a plurality of individual concrete objects. One or more passages or channels are located between or extend through said plurality of individual concrete objects to form a system for transporting fluid within the one or more passages or channels and/or from the outside of the plurality of individual objects. The composite material contains: a plurality of binding elements, each binding element having a core comprising predominantly calcium silicate, a first or inner layer enriched in silica, and a second or outer layer enriched in calcium carbonate; and filler particles containing coarse filler particles and/or fine filler particles. A plurality of binding elements and a plurality of filler particles together form one or more binding matrices, wherein said binding elements and filler particles are substantially uniformly distributed in said matrix and bonded together.

A key feature of the article according to the present invention is that the passages or channels (including hollow space) create internal volumes, the thickness of which is small compared to the overall volume of the article. Access of the curing fluid to the facing surfaces from the internal volume significantly increases the surface area over which carbon dioxide and water must diffuse to effect curing. In addition, for monolithic compacts, such passages or channels reduce the overall material consumption and product weight, which leads to savings in materials and other associated costs during transportation and installation.

In certain embodiments, a plurality of individual concrete objects are located within a chamber or shell. For purposes of this description, the terms chamber and shell are used interchangeably.

Concrete objects, when produced in large mass, can be positioned and/or oriented through the forming process or during the loading process of the curing chamber so that the internal or external faces are positioned to maximize exposure to the curing fluid (e.g., CO2 and water vapor ) and minimizing the diffusion distance of CO2 and water relative to the total volume of individual objects. The location of the internal or external faces of individual objects relative to the fluid flow profile is critical to ensuring a uniform and/or rapid curing process.

Individual objects can be positioned in the curing chamber relative to the flow profile

- 5 044255 fluid in such a way as to maximize the diffusion of carbon dioxide and water. The distance between concrete objects located in the chamber can be controlled to create channels parallel to the fluid flow while maintaining a similar volume of concrete shell. Concentrating fluid flow in channels in which the faces of individual objects are open improves uniformity and/or speed of cure. The geometry of the individual objects and the fluid flow profile in the curing system determines the optimal spacing between objects, the orientation of the object, and the distance between the individual objects and the fluid distribution system to induce high diffusion rates of carbon dioxide and water through the faces of the objects forming the channel.

Varying the distance between concrete objects located in the chamber and chamber components, such as racks, slabs, and fluid distribution components such as gas inlets, gas outlets, cavities, or perforated plates, allows channels to be created between the facing surfaces of the concrete objects. and camera components.

The front surfaces of individual objects in close proximity to chamber components, such as shelving, form channels adjacent to and/or between the individual objects and the chamber, wherein fluid flow is concentrated. Concentrating fluid flow in channels between individual object faces and chamber components improves uniformity and cure speed. The geometry of the individual objects and fluid flow profile in the curing system determines the optimal orientation of the object, the distance between the individual objects and chamber components, and the distance between the individual objects and the fluid distribution system so as to induce high rates of diffusion of carbon dioxide and water through the faces of the individual objects , forming the channel, and chamber components.

In certain embodiments, each of the plurality of individual concrete objects does not contain any reinforcement elements.

In certain embodiments, each of the plurality of individual concrete objects includes one or more reinforcing elements embedded in the object.

In certain embodiments, one or more reinforcing elements are selected from bars, wires, and ropes. The one or more reinforcing bars may be made of any suitable materials, such as iron, steel, polymeric materials, glass, or a combination thereof.

In some embodiments, a plurality of binding elements are chemically converted from a ground calcium silicate composition comprising one or more of natural or synthetic wollastonite, pseudowollastonite, rankinite, gehlenite, belite, alite, and an amorphous phase.

In certain embodiments, the gas contains carbon dioxide. In some embodiments, a plurality of binding elements are produced by chemical conversion from ground calcium silicate by reacting it with CO2 through a controlled hydrothermal liquid phase sintering process.

In certain embodiments, the gas contains carbon dioxide. In some embodiments, the plurality of linking elements are chemically converted from calcium silicate as a precursor other than synthetic wollastonite or pseudowollastonite.

In certain embodiments, the weight ratio of binder:filler particles is approximately 1:5.

In certain embodiments, the water absorption of the plurality of individual concrete objects is less than about 10%.

In certain embodiments, the proposed fluid transport system is configured to allow gas to pass through one or more passages or channels and the exterior of a plurality of separate entities.

In some embodiments, fluid passing through one or more passages or channels and the exterior of the plurality of discrete objects changes direction at least once.

In certain embodiments, fluid passing through one or more passages or channels and the exterior of the plurality of individual objects changes its velocity at least once.

In some embodiments, a proposed fluid transport system within the exterior of a plurality of discrete objects comprises flow between an enclosure or chamber or a chamber component within the enclosure or chamber.

Any suitable calcium silicate composition can be used as a precursor for the linking elements. As used herein, the term calcium silicate composition generally refers to natural minerals or synthetic materials that are composed of one or more group of calcium silicate phases, including a CS phase (wollastonite or pseudo-wollastonite, and sometimes expressed as CaSiO ₃ or CaOSiO ₂ ), a C3S2 phase (rankinitis, and sometimes expressed form

- 6 044255 lami Ca ₃ Si ₂ O7 or 3CaO ₂ SiO ₂ ), C2S phase (belite, e-Ca ₂ SiO ₄ , or larnite, e-Ca ₂ SiO ₄ , or bredigite, a-Ca ₂ SiO ₄ , or y -Ca ₂ SiO ₄ , and sometimes expressed by the formulas Ca ₂ SiO ₄ or 2CaOSiO ₂ ), an amorphous phase based on calcium silicate, each of these substances may contain one or more ions and oxides of other metals (for example, oxides of aluminum, magnesium, iron or manganese) or mixtures thereof, or may contain some magnesium silicate in natural or synthetic form(s) ranging from a trace amount (1%) to about 50% or more by weight.

Calcium silicate compositions may contain amorphous (non-crystalline) calcium silicate phases along with the crystalline phases described above. The amorphous phase may further include Al, Fe and Mg ions and other impurity ions present in the raw materials. Calcium silicate compositions may also contain small amounts of residual CaO (lime) and SiO ₂ (silicon dioxide). The calcium silicate composition may also include small amounts of a C3S phase (alite, Ca3SiO ₅ ).

Calcium silicate compositions may also retain some inert phases, such as melilite-type minerals (melilite or helenite or ackermanite) with the general formula (Ca,Na,K) ₂ [(Mg,Fe ²⁺ ,Fe ³⁺ ,Al, Si)3O7] and ferrite type minerals (ferrite or brownmillerite or C4AF) with the general formula Ca2(Al,Fe ³⁺ )2O ₅ . In certain embodiments, the proposed calcium silicate composition consists of only amorphous phases. In certain embodiments, the calcium silicate contains only crystalline phases. In certain embodiments, some portion of the calcium silicate composition is in the amorphous phase and another portion is in the crystalline phase.

It should be noted that the calcium silicate compositions of the present invention are preferably not hydrated. However, minor amounts of hydratable calcium silicate phases (eg C ₂ S, C ₃ S and CaO) may be present. _C2S exhibits slow hydration kinetics when exposed to water and is rapidly converted to CaCO3 during curing processes in the presence of CO2, C3S and CaO hydrate rapidly when exposed to water and thus should be limited to <5% by weight.

In some preferred embodiments, the molar ratio of elemental Ca to elemental Si in the calcium silicate composition is from about 0.80 to about 1.20. In some preferred embodiments, the molar ratio of Ca to Si in the present composition is from about 0.85 to about 1.15. In some preferred embodiments, the molar ratio of Ca to Si in the present composition is from about 0.90 to about 1.10. In some preferred embodiments, the molar ratio of Ca to Si in the present composition is from about 0.95 to about 1.05. In some preferred embodiments, the molar ratio of Ca to Si in the present composition is from about 0.98 to about 1.02. In some preferred embodiments, the molar ratio of Ca to Si in the present composition is from about 0.99 to about 1.01.

The content of Al, Fe and Mg oxides in the present calcium silicate composition is generally adjusted to be less than about 30%. In some preferred embodiments, the present composition contains about 20% or less Al, Fe, and Mg oxides based on the total weight of the oxides. In certain preferred embodiments, the present composition contains about 15% or less of Al, Fe and Mg oxides based on the total weight of the oxides. In some preferred embodiments, the present composition contains about 12% or less of Al, Fe and Mg oxides based on the total weight of the oxides. In certain preferred embodiments, the present composition contains about 10% or less of Al, Fe, and Mg oxides based on the total weight of the oxides. In some preferred embodiments, the present composition contains about 5% or less of Al, Fe, and Mg oxides based on the total weight of the oxides.

Each of the calcium silicate phases listed is suitable for carbonation with CO2. In the following, the individual calcium silicate phases suitable for carbonization will be referred to as reactive phases.

The various reactive phases may be present in any suitable proportions relative to all reactive phases. In some preferred embodiments, the reactive phases are present: CS in an amount of from about 10 to about 60 wt.%, (for example, from about 15 wt.% to about 60 wt.%, from about 20 wt.% to about 60 wt.% , from about 25 wt.% to about 60 wt.%, from about 30 wt.% to about 60 wt.%, from about 35 wt.% to about 60 wt.%, from about 40 wt.% to about 60 wt. .%, from about 10 wt.% to about 50 wt.%, from about 10 wt.% to about 40 wt.%, from about 10 wt.% to about 30 wt.%, from about 10 wt.% to about 25 wt.%, from about 10 wt.% to about 20 wt.%); C ₃ S ₂ in an amount of about 5 to 50 wt.%, (for example, about 10 to 50 wt.%, about 15 to 50 wt.%, about 20 to 50 wt.%, about 30 to 50 wt.%, about 40 to 50 wt.%, about

- 7 044255 from 5 to 40 wt.%, from about 5 to 30 wt.%, from about 5 to 25 wt.%, from about 5 to 20 wt.%, from about 5 to 15 wt.%); and C ₂ S in an amount of from about 5 to 60 wt.%, (for example, from about 10 wt.% to about 60 wt.%, from about 20 wt.% to about 60 wt.%, from about 25 wt.% to about 60% by weight, from about 30% by weight to about 60% by weight, from about 35% by weight to about 60% by weight, from about 40% by weight to about 60% by weight, from about 5% by weight .% to about 50 wt.%, from about 5 wt.% to about 40 wt.%, from about 5 wt.% to about 30 wt.%, from about 5 wt.% to about 25 wt.%, from about 5 wt.% to about 20 wt.%) and C in an amount of from about 0 to 3 wt.%, (for example, 0 wt.%, 1 wt.% or less, 2 wt.% or less, 3 wt.%, or less, about 1 to 2 wt.%, about 1 to 3 wt.%, about 2 to 3 wt.%).

In certain embodiments, the reactive phases include an amorphous calcium silicate phase, for example, in an amount of 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 weight relative to the weight of all phases. It should be noted that the amorphous phase may further include impurity ions present in the raw materials.

The calcium silicate compositions of the present invention are suitable for carbonation with CO2. In particular, the calcium silicate composition is suitable for carbonation with CO2 at a temperature of from about 30°C to about 90°C to produce CaCO ₃ with a weight gain of about 20% or more. The weight gain corresponds to the actual sequestration of CO2 in carbonated products. In some preferred embodiments, the present composition is suitable for carbonation with CO2 at a temperature of from about 30°C to about 90°C (e.g., from about 40°C to about 90°C, from about 50°C to about 90°C, from about 60°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, from about 40°C to about 80°C, about 40°C to about 70°C, about 40°C to about 60°C) to form CaCO ₃ at a weight gain of 10% or more (e.g., 15% or more, 20% or more, 25% or more, 30% or more).

Calcium silicate precursor compositions are typically used in powder form having an average particle size ( _d50 ) of from about 8 microns to about 25 microns, with 10% of the particles ( _d10 ) having a particle size less than about 0.1 microns to about 3 µm, and 90% of particles (d ₉₀ ) have a size greater than 35 µm to 100 µm.

In certain embodiments, the d ₉₀ : d ₁₀ ratio is selected to provide improved powder flow or reduced casting water requirements. In certain embodiments, the d ₅₀ : d ₁₀ ratio is selected to provide improved reactivity, improved packaging, or reduced casting water requirements. In some embodiments, the d ₉₀ : d ₅₀ ratio is selected to provide improved reactivity, improved packaging, or reduced casting water requirements.

Any suitable filler particles may be used, for example calcium oxide or silica containing materials. Typical aggregate particles include lime, quartz (including sand), wollastonite, xonotlite, burnt oil shale, fly or volcanic ash, furnace dust, crushed clay, and pumice dust. Materials such as industrial waste (eg fly ash, slag, fine silica powder) can also be used as fillers. Additionally, in some preferred embodiments, lightweight aggregates such as perlite or vermiculite can be used as fillers. In some preferred embodiments, the filler particles are made from a calcium oxide rich material such as ground lime.

The filler particles include calcium oxide or silica and have a size (d5 ₀ ) of about 0.25 μm to about 200 μm (e.g., from about 0.25 μm to about 150 μm, from about 0.25 μm to about 100 μm, from about 0.25 μm to about 50 μm, from about 0.25 μm to about 20 μm, from about 0.25 μm to about 10 μm, from about 0.5 μm to about 200 μm, from about 1 μm to about 200 µm, about 5 µm to about 200 µm, about 10 µm to about 200 µm, about 20 µm to about 200 µm, about 50 µm to about 200 µm).

In certain embodiments, the filler particles are selected from fly ash, bottom ash, slag, with particle sizes ranging from about 0.5 μm to about 300 μm (e.g., from about 1 μm to about 300 μm, from about 5 μm to about 300 μm, from from about 10 µm to about 300 µm, from about 50 µm to about 300 µm, from about 100 µm to about 300 µm, from about 0.5 µm to about 200 µm, from about 0.5 µm to about 100 µm, from about 0.5 µm to about 50 µm, about 0.5 µm to about 20 µm, about 0.5 µm to about 10 µm, about 0.5 µm to about 5 µm).

According to illustrative embodiments of the carbonization of a calcium silicate composition,

- 8 044255 proposed in the present invention, the particles of ground calcium silicate have a size such that a total of 10% of these particles have a diameter greater than 1 μm, in a volumetric particle size distribution.

In some embodiments, the filler particles are selected from limestone, silica fume, and quartz, with particle sizes ranging from about 1 μm to about 500 μm (e.g., from about 1 μm to about 400 μm, from about 1 μm to about 300 μm, from about 1 µm to about 200 µm, from about 1 µm to about 100 µm, from about 1 µm to about 50 µm, from about 1 µm to about 30 µm, from about 5 µm to about 500 µm, from about 10 µm to about 500 µm , from about 20 μm to about 500 μm, from about 50 μm to about 500 μm, from about 100 μm to about 500 μm, from about 200 μm to about 500 μm).

In certain embodiments, the filler particles are selected from lightweight aggregates having particle sizes ranging from about 20 μm to about 500 μm (e.g., from about 20 μm to about 400 μm, from about 20 μm to about 300 μm, from about 20 μm to about 200 µm, about 20 µm to about 100 µm, about 50 µm to about 500 µm, about 100 µm to about 500 µm, about 200 µm to about 500 µm, about 300 µm to about 500 µm).

In certain embodiments, the set control additive is selected from gluconate and sucrose. In some embodiments, the dispersant/viscosity modifier is a polycarboxylate-based material.

In exemplary embodiments, the ground calcium silicate is ground wollastonite, the filler particles comprise ground limestone and silica, the activating agent is ground lime, the set control additive is a gluconate, the viscosity modifier is a polycarboxylate-based material, and the venting agent is a paste of aluminum powder.

It should be understood that the calcium silicate compositions, calcium silicate phases and methods described herein can be adapted to use magnesium silicate phases instead of or along with calcium silicate phases. As used herein, the term magnesium silicate refers to natural minerals or synthetic substances consisting of one or more groups of compounds containing magnesium and silicon, including, for example, Mg ₂ SiO ₄ (also known as fosterite) and Mg ₃ S ₁₄ O ₁₀ (OH) ₂ (also known as talc), which material may contain one or more other metal ions and oxides (for example, oxides of calcium, aluminum, iron or manganese) or mixtures thereof, or may include some calcium silicate in natural or synthetic form(s) ranging from a trace amount (1%) to about 50% or more by weight.

As used herein, the term quartz refers to any SiO ₂ -based material, including common sands (mortar and mortar sands) as well as glass and recycled glass. The term also includes any other secondary natural and synthetic materials containing significant amounts of SiO2 (for example, mica, sometimes expressed by the formula KAl ₂ (AlSi ₃ O ₁₀ )(OH) ₂ .

According to another aspect, the present invention generally relates to a system for manufacturing an article. Such a system includes a shell or chamber and an enclosed composite material distributed in the form of a plurality of individual concrete objects. One or more passages or channels are located between or extend through said plurality of individual concrete objects to form a system for transporting fluid within the one or more passages and channels and from the exterior of the plurality of individual objects. The proposed system also optionally includes one or more slabs on which a plurality of individual concrete objects are placed, and one or more racks, canvases, walls or panels with planar, flat, convex or concave facing surfaces defining one or more passages or channels and providing fluid flow profile in a fluid transport system.

In certain embodiments, the proposed system includes a fluid distribution component that controls the fluid flow profile of at least a portion of the shell or chamber.

In certain embodiments, the proposed system includes a fluid distribution component that controls the fluid flow profile throughout the enclosure or chamber.

In some embodiments, the fluid distribution component, which controls the fluid flow profile throughout the enclosure or chamber, changes the direction of the gas flow at least once.

In some embodiments, the fluid distribution component, which controls the fluid flow profile throughout the enclosure or chamber, changes the gas flow rate at least once.

In certain embodiments, the fluid distribution component includes one or more components selected from fluid inlets, fluid outlets, cavities or perforated plates, or combinations thereof.

- 9 044255

In certain embodiments, the shell or chamber is made of a material selected from metal, alloy, plastic, polymer, polymer composite, ceramic composite, or combinations thereof. In some embodiments, the shell or chamber is made of concrete material, or steel, or canvas, or combinations thereof.

According to another aspect, the present invention generally relates to a method for producing an article. The proposed method includes: mixing a particulate composition and a liquid composition to form a mixture; casting or extruding or otherwise molding said mixture in a mold to produce a cast or extruded or otherwise molded compact (green body) containing a plurality of individual concrete objects, wherein one or more passages or channels are located between said plurality of individual concrete objects and the outside of or pass through a plurality of individual objects; maintaining an atmosphere of CO2 and/or water vapor in one or more internal passages or channels and the exterior of a plurality of individual objects; and curing the plurality of individual objects at a temperature ranging from about 20° C. to about 150° C. for from about 1 hour to about 80 hours in an atmosphere of water and/or CO ₂ at a pressure of from external atmospheric pressure to a pressure of about 60 psi (approximately 413 kPa) above external pressure, and the CO2 concentration ranges from about 10% to about 90%.

In certain embodiments, maintaining an atmosphere of CO ₂ and/or water vapor within one or more internal passages or channels and/or an exterior portion of the plurality of distinct entities includes: maintaining an atmosphere within one or more internal passages or channels and/or an exterior portion of the plurality of distinct entities; circulation of a retained atmosphere of CO2 and/or water vapor; removing water vapor from the retained atmosphere or adding water vapor to the retained atmosphere; and heating the retained atmosphere.

In some embodiments, maintaining an atmosphere of CO2 and/or water vapor in one or more internal passages or channels includes changing the direction or rate of flow of _CO2 and/or water vapor at least once during the curing period of the compact.

In certain embodiments, said particulate composition comprises ground calcium silicate containing one or more substances selected from natural or synthetic wollastonite, pseudowollastonite, rankinite, galenite, belite, and alite, the average particle size of which is from about 1 μm to about 100 μm , wherein said liquid composition contains water.

In some embodiments, the cast mixture is cured at a temperature equal to or less than about 60° C. for about 10 hours to about 50 hours in a steam atmosphere containing water and CO2 and having external atmospheric pressure.

In certain embodiments, the ground calcium silicate is essentially calcium silicate in the form of ground wollastonite.

In certain embodiments, the proposed method further includes introducing one or more reinforcing elements into the mixture.

The one or more reinforcing bars may be made of any suitable materials, such as iron, steel, polymeric materials, glass, or a combination thereof.

The one or more reinforcing elements may be of any suitable size and shape, for example, in the form of rods, wires and ropes.

In yet another aspect, the present invention generally relates to an article made by the method described herein.

The product provided may be of any suitable size or shape or suitable for any suitable purpose, for example selected from paving slabs, blocks, tiles, hollow core slabs, precast concrete products with or without reinforcement.

One or more passages or channels (including hollow spaces) are an important feature and affect the overall characteristics and properties of individual objects, including overall mass, mechanical properties and functionality. Individual objects, along with camera components and the camera itself, can form any suitable number of passages or channels according to a pre-designed pattern and interconnectivity. Such passages or channels may be of any suitable size and shape (eg, round, oval, polygonal, rectangular or square). They may be arranged according to any suitable pattern or interconnection.

The number, shape, size and configuration of passages and channels will affect the various mechanical properties of hollow products. As discussed in more detail herein, the number, shape, size and configuration of passages and channels can also be used to provide manufacturing benefits, such as speeding up the curing process and providing more uniform curing.

The volume of the passages or channels may be any suitable fraction of the volume of the plurality of individual objects depending on the geometric dimensions of the product mold and any post-molding changes in product arrangement, 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.% up to about 50% by volume, from about 5% by volume to about 30% by volume, from about 5% by volume to about 20% by volume, relative to the total volume of the plurality of concrete objects.

Individual objects according to the present invention can be manufactured with different sizes and dimensions. Typical dry cast road slabs range in height from 40mm to 120mm and can be pressed over an area of up to 1.45m x 1.45m, resulting in the distribution of multiple concrete objects with a volume of up to ^0.26m3 per slab for product placement. For example, typical dry cast concrete building units (CMUs) are 200 mm high and can be compacted over an area of up to 1.45 m x 1.45 m, resulting in the distribution of multiple concrete objects with a volume of up to 0.43 m ³ per plate for placing the product. The number, shape, size and configuration of channels can be used to improve the manufacturing process by increasing the speed and improving the uniformity of cure.

In some embodiments in which the individual objects are road slabs, the dimensions range from 1 inch to 24 inches in length, 1 inch to 24 inches (approx. 61 cm) wide and 0.5 inch (1.27 cm) to 6 inches (approx. 15 cm) high. In some embodiments, such dimensions are from 4 inches (about 10 cm) to 12 inches (about 30 cm) in length, from 4 inches (about 10 cm) to 12 inches (about 30 cm) in width, and from 1.5 inches (approx. 3.8 cm) to 5 inches (approx. 13 cm) high.

In certain embodiments in which the individual objects are blocks, the dimensions range from 7/4 inches (about 19 cm) to 16 inches (about 41 cm) in length, from 3/4 inches (about 9 cm) to 12 inches (approx. 30cm) wide and 4" (approx. 10cm) to 16" (approx. 41cm) high. In some embodiments, such dimensions are from 7/4 inches (about 19 cm) to 16 inches (about 41 cm) in length, from 3/4 inches (about 9 cm) to 12 inches (about 30 cm) in width, and from 6 inches (approx. 15 cm) to 12 inches (approx. 30 cm) high.

In some embodiments in which the individual objects are shingles, the dimensions range from 2 inches (about 5.1 cm) to 24 inches (about 61 cm) in length, from 2 inches (about 5.1 cm) to 24 inches (approximately 61 cm) wide and 0.25 inches (approximately 0.64 cm) to 2 inches (approximately 5.1 cm) thick. In some embodiments, such dimensions are from 4 inches (about 10 cm) to 12 inches (about 30 cm) in length, from 4 inches (about 10 cm) to 12 inches (about 30 cm) in width, and from 0.25 inch (about 0.64 cm) to 1 inch (about 2.5 cm) thick.

In some embodiments in which the individual objects are slabs, the dimensions range from 4 inches (about 10 cm) to 48 inches (about 122) in length, from 4 inches (about 10 cm) to 48 inches (about 122) in wide and 1.5 inches (approx. 3.8 cm) to 5 inches (approx. 13 cm) high. In some embodiments, such dimensions are from 4 inches (about 10 cm) to 48 inches (about 122) in length, from 4 inches (about 10 cm) to 48 inches (about 122) in width, and from 1.5 inches (about 3.8 cm) to 5 inches (approximately 13 cm) in height and typically have a base area greater than 144 square inches (approximately 929 cm ² ).

Individual objects are typically pressed against the product placement slab in such a way as to maximize the volume of concrete produced per product placement slab. When products with identical horizontal geometric dimensions are produced, parallel gaps remain between objects, resulting in channels being formed between many individual objects. The number, shape, size and configuration of channels can also be used to provide manufacturing benefits, such as speeding up the cure process and providing more uniform cure.

Many concrete objects are loaded into the chamber on a regular basis. In some embodiments, the curing chamber forms a chamber or shell. Inside the chamber, the slabs are stacked and placed to cure. In the chamber, the orientation and spacing of the plates can be adjusted to create channels consisting of an outer plane of a plurality of individual objects, consisting of several facing surfaces of the individual objects, and a chamber component, such as another stacked product placement plate, into which fluid flow can be directed . The geometry of individual objects and the fluid flow profile in the curing system determines the optimal orientation of objects, the distance between objects and chamber components, and the distance between objects and the fluid distribution system so as to induce high rates of diffusion of carbon dioxide and water through the faces of objects, forming

- 11 044255 channel.

In certain embodiments, a concrete mold used to produce a set of individual objects is modified to vary the distance between the plurality of individual objects in accordance with the flow profile of the chambers and to increase the diffusion rates of carbon dioxide and water through the faces of the objects forming the channel.

In certain embodiments, the individual objects are separated or otherwise moved after the forming operation to change the distance between the concrete objects in accordance with the flow profile of the chambers and to increase the diffusion rates of carbon dioxide and water through the faces of the objects forming the channel.

In some embodiments, the placement of the product placement plate and/or the orientation of the product placement plate can be adjusted relative to the fluid distribution system to increase the flow of fluid through the channel created by the outer portion of the faces of the plurality of discrete objects and the shell and the plurality of discrete objects and camera components. This allows the diffusion rates of carbon dioxide and water to be increased between the respective outer face surfaces of the plurality of individual objects and the camera and the respective outer face surfaces of the plurality of individual objects and the camera components.

In certain embodiments, the mixing step includes/involves mixing aggregates, sand, calcium silicate, and water in a mixer. Said mixer may be any type of mixer commonly used in mixing conventional concrete. The aggregates, sand and a quantity of water sufficient to slightly moisten the solids are thoroughly mixed. The calcium silicate is then added to the batch along with the remaining water and any additives. The mixture is thoroughly mixed and the amount of water is adjusted to achieve the required humidity level.

In some preferred embodiments, the step of casting or extruding a slurry mixture into a mold configured to create a cast or extruded or otherwise shaped compact comprising one or more internal passages or channels comprises pouring said mixture into the mold or extruder . For example, in the case of making a casting, the mixture can be vibrated by vibrating the mold or by introducing vibration probes into the mixture within the mold to facilitate the removal of trapped air and promote particle rearrangement to compact said mixture. In the case of extrusion, the extruder can be stationary or movable. A stationary extruder forces the mixture through channels that shape the mixture into the desired shape and helps regroup the particles to compact the product. The product is ejected from the die inside the extruder, after which it can be cut to the required length, and the product is stacked to cure. The moving extruder pushes the mixture against a stationary stop and through channels that give the mixture the desired shape. When the mixture is pressed against a fixed stop, the pressure inside the mixture increases, the particles regroup and the mixture becomes denser. As more material is extruded, the compacted mixture pushes against the extruder along the extrusion frame.

In some preferred embodiments, the step of maintaining an atmosphere of CO2 and water vapor in one or more internal passages or channels comprises maintaining the atmosphere within the passages or channels and/or near the exterior of the article; circulation of a retained atmosphere of CO2 and/or water vapor; removing water vapor from the retained atmosphere or adding water vapor to the retained atmosphere; and heating the retained atmosphere. To achieve rapid and/or uniform curing, the number, shape, size and configuration of passages and channels can be designed to increase the contact area of CO2 and water vapor with the extruded compact wall. In general, during the curing process, temperature and concentration gradients will be created within the retained atmosphere and within the product itself. Such gradients are detected and adjusted to achieve uniform cure of the product. The gas flow of CO2 and water vapor can be controlled, for example, to move in opposite directions to reverse gradients through internal passages or channels and out of the outside of the product so as to average out the effects of temperature and concentration gradients during the curing period .

In some preferred embodiments, the step of maintaining an atmosphere of CO2 and water vapor in one or more channels within the plurality of concrete objects, or between the plurality of concrete objects and the shell, or between the plurality of concrete objects and the chamber component, comprises maintaining the atmosphere within the channels and/or near the exterior of the concrete object; circulation of a retained atmosphere of CO2 and/or water vapor; removing water vapor from the retained atmosphere or adding water vapor to the retained atmosphere; and heating the retained atmosphere.

To achieve rapid and/or uniform curing, the number, shape, size and configuration of channels can be designed to increase the contact area between CO ₂ and water.

- 12 044255 pair with an extruded compact wall. In general, during the curing process, temperature and concentration gradients will be created within the retained atmosphere and within the product itself. Such gradients are detected and adjusted to achieve uniform cure of the product. For example, the gas flow of CO2 and water vapor can be controlled, whereby the direction of the gas flow is changed alternately from one direction to the other to reverse gradients as it passes through channels and beyond the outer faces of the product so as to average out the effects of temperature and concentration gradients over a period curing.

In some preferred embodiments, the step of curing the cast or extruded compact involves exposing the product to an atmosphere of CO2 and/or water vapor for a specified period of time.

The curing temperature and time can be adjusted according to the desired end product, for example, curing can be carried out at a temperature of from about 20°C to about 150°C (e.g., from about 20°C to about 140°C, from about 20°C to about 120°C, from about 20°C to about 100°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, about 30°C to about 100°C, about 30°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) 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, for about 10 hours to about 70 hours, for about 10 hours to about 60 hours, from about 15 hours to about 60 hours, from about 15 hours to about 50 hours, for about 20 hours) under an atmosphere of water and CO ₂ .

The relative humidity of the curing environment can be adjusted to suit the desired result, for example, in the range of 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%, about 80% to about 98%, about 90% to about 98%, about 10% to about 90%, about 10% to about 70%, about 10% to about 50%, about 10% to about 40%, about 10% to about 30%, about 10% to about 20%), with CO ₂ pressure ranging from about outside atmospheric pressure to a pressure of about 100 psi ( about 689 kPa) above external atmospheric pressure (e.g., from about external atmospheric pressure to a pressure of about 90 psi (about 621 kPa) above external atmospheric pressure, from about external atmospheric pressure to a pressure of about 80 psi (about 552 kPa) above external atmospheric pressure, from about external atmospheric pressure to a pressure about 70 psi (about 483 kPa) above external atmospheric pressure, from about external atmospheric pressure to a pressure about 60 psi (about 413 kPa) above external atmospheric pressure, from a pressure of about 20 psi (about 138 kPa) above external atmospheric pressure to a pressure of about 100 psi (about 689 kPa) above external atmospheric pressure, from a pressure of about 30 psi (about 207 kPa) above external atmospheric pressure to pressure, about 100 psi (about 689 kPa) above external atmospheric pressure) and a CO ₂ concentration ranging from about 10% to about 90% or higher (e.g., from about 20% to about 90%, from about 30% to about 90%, from about 40% to about 90%, from about 10% to about 70%, from about 10% to about 50%), obtaining a composite material having a uniform, homogeneous and porous structure.

In typical production, for example, according to some embodiments of the present invention, the materials used are ground calcium silicate. In exemplary embodiments of the calcium silicate composition of the present invention, the ground calcium silicate particles used are of a size such that a total of 10% of said particles have a diameter greater than 1 micron in a volumetric particle size distribution.

The ground calcium silicate may have an average particle size of from about 1 μm to about 100 μm (e.g., from about 1 μm to about 80 μm, from about 1 μm to about 60 μm, from about 1 μm to about 50 μm, from about 1 μm to about 40 μm, from about 1 μm to about 30 μm, from about 1 μm to about 20 μm, from about 1 μm to about 10 μm, from about 5 μm to about 90 μm, from about 5 μm to about 80 μm, from about 5 μm to about 70 μm, from about 5 μm to about 60 μm, from about 5 μm to about 50 μm, from about 5 μm to about 40 μm, from about 10 μm to about 80 μm, from about 10 μm to about 70 μm, about 10 μm to about 60 μm, about 10 μm to about 50 μm, about 10 μm to about 40 μm, about 10 μm to about 30 μm, about 10 μm to about 20 μm, about 1, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, 100 µm), bulk density from about 0.5 g/ml to about 3.5 g/ml (bulk density, for example, 0.5, 1.0, 1.5, 2.0, 2.5, 2.8, 3.0, 3.5 g/ml) and from about 1.0 g/ml to about 1. 2 g/ml (bulk density after compaction), surface area from about 1.5 m ² /g to about 3.5 m ² /g (for example, 1.5, 2.0, 2.3, 2.5, 2.8, 3.0, 3.2, 3.5 ^m2 /g).

- 13 044255

In certain preferred embodiments, the present particulate composition contains from about 10 wt.% to about 95 wt.%, particulate calcium silicate materials (for example, from about 20 wt.% to about 95 wt.%, from about 30 wt. % to about 95 wt.%, from about 50 wt.% to about 95 wt.%, from about 60 wt.% to about 95 wt.%, from about 20 wt.% to about 90 wt.%, from about 20 wt.% to about 80 wt.%, from about 20 wt.% to about 70 wt.%, from about 30 wt.% to about 80 wt.%, from about 50 wt.% to about 80 wt.%).

To obtain these individual objects, chemical additives can be introduced; for example, plasticizers, retarders, accelerators, dispersants and other rheology modifying agents. Certain commercially available chemical additives may also be included, such as Glenium™ 7500 from BASF® Chemicals and Acumer™ from Dow Chemical Company. In some embodiments, depending on the desired composite material, one or more pigments may be uniformly distributed or substantially non-uniformly distributed in the binding matrices. Such pigment may be any suitable pigment, including, for example, oxides of various metals (eg, black iron oxide pigment, cobalt oxide and chromium oxide). The pigment may be any color or colors, for example selected from black, white, blue, grey, 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 of from about 0.0% to about 10% by weight.

In some embodiments, the pigment may be uniformly distributed or substantially unevenly distributed in the binding matrices depending on the desired composite material. The pigment may be any suitable pigment, including, for example, oxides of various metals (eg, black iron oxide pigment, cobalt oxide, and chromium oxide). The pigment may be any color or colors, for example selected from black, white, blue, grey, 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 of from about 0.0% to about 10% by weight (e.g., from about 0.0% to about 8%, from about 0.0% to about 6%, from about 0.0% to about 5%, from about 0.0% to about 4%, from about 0.0% to about 3%, from about 0.0% to about 2%, from about 0.0% to about 1%, from about 0.0% to about 0.5%, from about 0.0% to about 0.3%, from about 0.0% to about 2%, from about 0 .0% to approximately 0.1%).

Thus, different combinations of curing conditions can be developed to achieve the required production process, including different reaction temperatures, pressures and reaction times. In a first exemplary embodiment, water in liquid form along with CO ₂ gas is supplied to an article that has been previously dried in an oven and the curing process is carried out at a temperature of about 90° C. and a pressure of about 20 psig (about 138 kPa g). i.e., 20 psi (about 138 kPa) above external pressure) for about 48 hours. In a second exemplary embodiment, water is present in the precursor material (e.g., as residual water from a previous mixing step), and gaseous CO ₂ , wherein the curing process is carried out at a temperature of about 60°C and a pressure of 0 psig (about 0 kPag) (at external atmospheric pressure) for about 19 hours. In a third illustrative embodiment, water is supplied to the product in the form of steam together with CO2, and the curing process is carried out at a temperature of about 90°C and a pressure of 20 psig (about 138 kPa g) (20 psi (about 138 kPa) above external atmospheric pressure) for about 19 hours.

It should be noted that the properties, production time and size of the product can be finely adjusted based on the description herein, for example, by adjusting the curing methods (eg, CO2 supply, system pressure and temperature), and the proportions and components of the mixture.

In addition to the materials used and the manufacturing process providing favorable environmental and economic benefits, the hollow products of the present invention provide a number of performance advantages over hollow products made from conventional concrete, for example, superior stable properties can be achieved in a much shorter time frame than in the case of precast concrete products made using ordinary Portland cement.

Binding elements connecting matrices and composite materials.

Discussion from a chemical point of view.

The present invention provides apparatus and methods used to produce new composite materials that cure primarily through a CO2 absorption reaction. The proposed materials have beneficial properties and can be easily produced from widely available, inexpensive precursor materials in a manner suitable for large-scale production with minimal environmental impact. Predecessor materials include

- 14 044255 low-cost and widely available compositions enriched with calcium silicate, fine particles and large particles. Calcium silicate compositions may consist of a ground product containing various phases of calcium silicate (including, for example, CS, C ₃ S ₂ , C2S and an amorphous calcium silicate phase). The fine and coarse particles may consist of ground limestone or other calcium carbonate based materials, ground quartz or other SiO ₂ based materials, sand and crushed stone. The fine and coarse particles may also consist of ground minerals such as granite, mica and feldspar. Other technical components include water and CO2. Various additives may be used to modify and finely tune the physical appearance and/or mechanical properties of the resulting composite material, such as additives selected from one or more pigments (eg, black iron oxide pigment, cobalt oxide, and chromium oxide), colored glass, and/or colored quartz. Additives related to reducing water consumption and changing rheological properties can also be used.

Composite materials can be produced, as described herein, using an energy-efficient hydrothermal liquid phase sintering (HLPS) process to create bonding elements that hold together the various components of the composite material. Such composite materials can be produced at low cost and with a beneficial impact on the environment. For example, preferred embodiments of the present invention utilize CO2 as the reactive compound, resulting in _CO2 sequestration and bonding elements in the resulting composite materials with a carbon footprint unmatched by any existing manufacturing technology. The HLPS process is thermodynamically initiated by the free energy of the chemical reaction(s) and the decrease in surface energy (area) caused by crystal growth. The kinetics of the HLPS process proceeds at a reasonable rate at low temperature because a solution (aqueous or non-aqueous) is used to transport the reactive substances instead of using a high melting point fluid or a high temperature solid state medium.

A discussion of the various features of HLPS, carbonizable calcium silicate cements, carbonization and binder production, associated apparatus and processes, and related issues can be found in US Patent No. 8114367, US Patent Publication No. US 2009/0143211 (Application No. 12/ Pub. US Patent No. 2012/0312194 (Application No. 13/491098), WO 2009/102360 (PCT/US2008/083606), WO 2011/053598 (PCT/US2010/054146), WO 2011/090967 (PCT/US2011/02162 3), U.S. Provisional Patent Application No. 61/708423, filed October 1, 2012, and U.S. Patent Publication No. 2014/0127450 (Application No. 14/045758), U.S. Patent Publication No. 2015/0266778 (Application No. 14/045519), Patent Publication No. US Patent No. 2014/0127458 (Application No. 14/045766), US Patent Publication No. 2014/0342124 (Application No. 14/045540), US Patent Publication No. 2014/0272216 (Application No. 14/207413), US Patent Publication No. 2014/0263683 (Application No. 14/207421), US Patent Publication No. 2014/0314990 (Application No. 14/207920), US Patent No. 9221027 (Application No. 14/209238), US Patent Publication No. 2014/0363665 (Application No. 14/295601), US Patent Publication No. 2014/0361471 (Application No. 14/295402), US Patent Publication No. 2016/0355439 (Application No. 14/506079), US Patent Publication No. 2015/0225295 (Application No. 14/602313), US Patent Publication No. 2015 /0056437 (Application No. 14/463901), US Patent Publication No. 2016/0168720 (Application No. 14/584249), US Patent Publication No. 2015/0336852 (Application No. 14/818629), US Patent Publication No. 2016/0031757 (Application No. 14/817193), US Patent Publication No. 2016/0272544 (Application No. 15/074659), US Patent Publication No. 2016/0096773 (Application No. 14/874350), US Patent Publication No. 2016/0340261 (Application No. 14/715497), US Patent Publication No. 2016/0272545 (Application No. 15/074692), US Patent Publication No. 2017/0102373 (Application No. 15/290328), US Patent Publication No. 2017/0121223 (Application No. 15/335520), US Patent Publication No. 2017 /0204010 (application no. 15/409352), US patent publication no. 2017/0253530 (application no. 15/449736), US patent publication no. 2017/0260096 (application no. 15/451344), US patent publication no. 2017/0320781 (application no. 15/587705), US Patent Application No. 15/609908, filed May 31, 2017, US Patent Application No. 15/716392, filed September 26, 2017, each of which is expressly incorporated in its entirety incorporated herein by reference for all purposes.

Fig. 1-8 are phase diagrams showing various phase relationships between some of the materials described.

In some preferred embodiments, a plurality of binding elements are produced by chemical conversion from ground calcium silicate compositions by reacting them with CO2 in a gas-assisted HLPS process.

In some embodiments, the composite material has a compressive strength of from about 90 MPa to about 175 MPa (e.g., from about 90 MPa to about 150 MPa, from about 90 MPa to about 140 MPa, from about 90 MPa to about 130 MPa, from about 90 MPa to about 120 MPa, from about 90 MPa to about 110 MPa,

- 15 044255 from about 100 MPa to about 175 MPa, from about 120 MPa to about 175 MPa, from about

130 MPa to about 175 MPa, from about 140 MPa to about 175 MPa, from about 150 MPa to

175 MPa, from about 160 MPa to about 175 MPa).

In some embodiments, the composite material has a flexural strength of from about 5 MPa to about 30 MPa (e.g., from about 5 MPa to about 25 MPa, from about 5 MPa to about 20 MPa, from about 5 MPa to about 15 MPa, from about 5 MPa to about 10 MPa, from about 10 MPa to about 30 MPa, from about 20 MPa to about 30 MPa, from about 25 MPa to about 30 MPa).

In certain embodiments, the composite material has a water absorption of less than about 10% (for example, less than about 8, 5, 4, 3, 2, or 1%).

The composite material may have one or more of desired textures, patterns and physical properties, particularly those characteristic of natural stone. In certain preferred embodiments, the composite material has a visible pattern similar to natural stone. Other characteristics include colors (such as black, white, blue, pink, gray (pale to dark), green, red, yellow, brown, blue (bluish green), or violet) and textures.

Discussion of equipment and processing.

CO ₂ regulation.

The described embodiments utilize approximately 99% pure technical grade CO2, which is available from a number of different industrial gas companies such as Praxair, Inc., Linde AG, Air Liquide, and others. Such supplied feedstock may be contained in large sealed storage tanks in the form of liquid carbon dioxide, the temperature of which is controlled to maintain a vapor pressure of approximately 300 psig. This gas is then piped into the shell or curing chamber using CO2. In the simplest system, CO2 is forced through the shell at a rate sufficient to displace the surrounding air contained in the shell. In general, the purge time will depend on the size of the shell and the rate at which CO ₂ gas is supplied. In many systems, this process of purging air from the shell can be accomplished in the amount of time, measured in minutes, required to bring the CO ₂ concentration to a reasonable level so that the curing process can subsequently proceed. In simple systems, CO ₂ gas is then introduced into the system at a predetermined rate to maintain a CO ₂ concentration sufficient to initiate the curing reaction.

As an example, the inventors describe herein a method for maintaining carbon dioxide concentrations during a reaction that is well suited to maintaining a fairly constant concentration, although the method is a closed loop process, which is typically the most expensive process. This method uses the measurement of CO2 concentration directly in the system and uses a controller such as a PLC (Programmable Logic Controller) to regulate the _CO2 concentration at a given point using an electronic/automatic control valve. To measure CO2 directly, the preferred measurement method is NDIR (near infrared detection). In the NDIR measurement method, a sample gas stream is drawn from the system using a low-capacity pump. A cooler is used to remove moisture from the gas stream before sampling the gas with the NDIR instrument. Accordingly, measurements made with such an analyzer do not include the water vapor component of the gas stream, and the results of such measurements must be corrected to account for moisture that has been removed from the test sample. Measuring the humidity in the gas stream of the system can be accomplished using a psychrometric method using a dry-bulb and a wet-bulb, using a humidity measuring instrument equipped with a dry-bulb and a wet-bulb (psychrometer), or using another type of humidity sensor. The true CO ₂ concentration can be calculated using a computer control system or PLC. Once the true CO ₂ concentration is known, dry CO ₂ can be added to the system using a motorized metering control valve if it has been consumed and the level has fallen below the set point required at that time. In various embodiments, the set point may change over time, as necessary, based on experience with the curing of specific compositions and the shape and size of the composite material samples.

Humidity regulation.

Fig. 9 is a schematic illustration of a CO2 curing chamber providing humidification according to the principles of the present invention. As shown in FIG. 9, water is supplied, while water vapor is added to the atmosphere circulating inside the curing chamber. The water may be any suitable source of potable water. In some embodiments, regular tap water is used. In some embodiments, water may be converted to steam by passing through

- 16 044255 fogging nozzle or atomizing nozzle, electric steam generator, gas-fired steam generator, or by heating above the temperature of the gas in the chamber so as to cause the liquid water feed to evaporate, one example being a drum reactor with an immersion heater. In yet another embodiment, the CO2 feed can be directed to these systems after bubbling through the hot water feed to increase the relative humidity of the incoming gas stream, one example being a drum reactor configured for flow or open loop processing.

Relative humidity is an important parameter in both conventional concrete curing and CO2 curing of composite materials. In a traditional curing chamber, there is a humid air atmosphere consisting mainly of nitrogen, oxygen and water vapor. In such systems, relative humidity is most often measured using standard capacitive sensor technology. However, CO2 curing chambers contain a gas atmosphere consisting primarily of carbon dioxide, which is not compatible with some of these types of sensors. The CO ₂ curing systems described herein for composite materials may use sensor technologies such as dry- and wet-bulb methods that use psychrometric ratios of carbon dioxide and water vapor, or water vapor dipole polarization instruments, hygrometers with chilled mirror or capacitive humidity sensors.

Depending on the type and geometric dimensions of the product being cured, the design of the chamber and the efficiency of placement of the product in the chamber, it may be necessary to either reduce or increase the humidity and adjust it to a specified set point. Setpoints can range from approximately 1 to 99% relative humidity. Methods for curing composite materials using CO2 can involve three different moisture control methods that can be combined into one system. One humidification method according to one embodiment of a CO2 curing system is shown in FIG. 9. Another method removes moisture from the system by curing composite products with CO2. A simple way to reduce relative humidity is to replace the wet gas in the system with a dry gas such as carbon dioxide. In another embodiment, it is possible to reduce the relative humidity and therefore remove water vapor from the gas using a no-purge process, which in one preferred embodiment is a refrigerated heat exchanger in which the water is removed.

Fig. 10 is a schematic representation of a curing chamber with several methods of humidity control, as well as the ability to regulate and replenish CO2 by regulating a constant flow or pressure, which chamber allows temperature control according to the principles of the present invention. The proposed system is an example of a system in which closed-loop or feedback control can be implemented and in which operating parameters such as CO2 concentration, humidity and temperature are set and measured at certain points in time in the production cycle to determine whether the actual value of the monitored parameter is the required value. When a deviation from the required value is determined, corrective actions are taken to bring the parameter value into line with the required value. Such control systems can be expensive and complex and may be useful for high value products or products that require very precise process conditions.

Temperature regulation.

In some embodiments, temperature is measured using a sensor, such as a thermocouple or RTD (resistive temperature sensor).

The measured signal is sent back to the controller or computer, which is able to regulate the energy in the heat exchanger and thereby adjust the temperature of the entire system over time. The blower is an important component of the heating system because it can help transfer thermal energy to the gas, which transfers it to the products and the chamber itself, an important part of controlling the humidity of the samples. The heating method can be electric or by burning gas. Jacket heaters can be used to control the temperature of CO ₂ passing through the chamber in contact with the heating jacket, and any suitable heat source can be used. External heating means may include, but are not limited to, electrical heating, hot water heating, or hot oil heating. For CO2 curing chambers, indirect combustion systems have so far been used and direct combustion burners have been avoided as they will draw air and combustion products into the system, thereby diluting the CO2 and making control of CO2 concentration problematic. Some smaller-scale systems, such as drum reactors, use electric jacket heaters to heat the entire surface of the chamber rather than a heating element within the chamber.

Gas flow regulation.

- 17 044255

Another controlled parameter is the gas velocity through the material to be cured in the system. Gas velocity can be highly 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 inside the system. The simplest method of regulating the gas velocity within a chamber is based on regulating the blower speed (RPM), usually accomplished by using a variable frequency drive to control the speed of the blower motor. A blower can be used to circulate gas at the desired speed in the curing chamber. The gas velocity in the proposed system is measured in the system using a number of different methods, including, but not limited to, pitot tube and laser Doppler detection systems. The measured gas velocity signal can be sent back to a computer system or programmable logic controller and used as a monitored parameter in the cure profile.

Method for producing composite material.

A general method for preparing a composite material includes: mixing a particulate composition and a liquid composition to form a suspension mixture; molding the slurry mixture into the desired shape either by pouring the slurry into a mold, pressing the slurry into a mold, pressing the slurry into a vibration mold, extruding the slurry, molding the slurry through a clamping ring or frame, or using any other forming method, commonly used in the manufacture of concrete, and curing the molded slurry mixture at a temperature ranging from about 20°C to about 150°C for from about 1 hour to about 80 hours in a steam atmosphere containing water and CO ₂ and having a pressure ranging from from about external atmospheric pressure to a pressure of about 50 psi (about 345 kPa) above external atmospheric pressure, and a CO2 concentration ranging from about 10% to about 90%, to produce a composite material having texture and/or pattern and the desired physical properties related to compressive strength, flexural strength, density, fracture resistance, etc.

The particulate composition includes a particulate calcium silicate composition having an average particle size of from about 1 micron to about 100 microns. In addition, the particulate composition may include particulate calcium carbonate or SiO ₂ -containing material having an average particle size of from about 3 microns to about 25 mm. The liquid composition includes water and may include a water-soluble dispersant.

The proposed method may further include the step of drying the cast mixture before curing said cast mixture. The particulate composition further contains a pigment or dye as described herein.

In some embodiments, the molded slurry mixture is cured at a temperature ranging from about 30° C. to about 120° C. for about 1 hour to about 70 hours in an atmosphere of steam containing water and CO2 and having a pressure ranging from about outside atmospheric pressure to a pressure approximately 30 psi (approximately 207 kPa) above external atmospheric pressure.

In some embodiments, the molded slurry mixture is cured at a temperature ranging from about 60° C. to about 110° C. for about 1 hour to about 70 hours in an atmosphere of steam containing water and CO2 and having a pressure ranging from about outside atmospheric pressure to a pressure approximately 30 psi (approximately 207 kPa) above external atmospheric pressure.

In some embodiments, the molded slurry mixture is cured at a temperature ranging from about 80° C. to about 100° C. for about 1 hour to about 60 hours in an atmosphere of steam containing water and CO2 and having a pressure ranging from about outside atmospheric pressure to a pressure approximately 30 psi (approximately 207 kPa) above external atmospheric pressure.

In certain embodiments, the molded slurry mixture is cured at a temperature equal to or less than about 60° C. for about 1 hour to about 50 hours in a steam atmosphere containing water and CO2 and having external atmospheric pressure.

For example, in some embodiments, the present ground calcium silicate composition has an average particle size of from about 1 μm to about 100 μm (e.g., about 1, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90 , 100 µm), bulk density from about 0.5 g/ml to about 3.5 g/ml (bulk density, e.g. 0.5, 1.0, 1.5, 2.0, 2.5, 2 .8, 3.0, 3.5 g/ml) and from about 1.0 g/ml to about 1.2 g/ml (bulk density after compaction), Blaine specific surface from about 150 m ² /kg to about 700 m ² /kg (for example, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700 m ² /kg).

In some preferred embodiments, the liquid composition includes water

- 18 044255 and a water-soluble dispersant containing a polymer salt (for example, an acrylic homopolymer salt) at a concentration of from about 0.1 to about 2 wt./wt.%, based on the weight of the liquid composition.

Composite materials produced according to the method described herein may have a compressive strength ranging from about 3.0 MPa to about 30.0 MPa (for example, about 3, 5, 10, 15, 20, 25, 30 MPa) , and a flexural strength of from about 0.3 MPa to about 4.0 MPa (for example, about 0.3, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0 , 3.5, 4.0 MPa).

Any suitable precursor materials may be used, including, for example, the calcium silicate composition described herein. It is believed that calcium cations are leached from the calcium silicate composition particles and convert the peripheral portion of the calcium silicate composition particle into a calcium-deficient state. As calcium cations continue to leach from the periphery of such a particle, the structure of the periphery becomes unstable over time and breaks down, thereby converting the calcium-depleted periphery of the particle into a first layer predominantly enriched in silica. Meanwhile, a second layer is precipitated from the water, containing predominantly calcium carbonate. An example of such a three-layer structure is shown in FIG. 13, reprinted from US Patent Publication No. 2013/0122267 A1 (FIGS. 6(a)-6(c)), which provides examples of energy dispersive X-ray spectroscopy (EDS) chemical mapping of a typical binding matrix and shows a superposition of the location map Si (Fig. 13a) and Ca (Fig. 13b). In fig. 13c, the CaSiO, SiO ₂ and CaCO ₃ regions are indicated by arrows. Wollastonite (CaSiO ₃ ) core particles are encapsulated in SiO ₂ -rich regions and surrounded by CaCO ₃ particles. The various elements of the binding matrix are held together by CaCO ₃ particles. X-ray diffraction (XRD) of such a composition revealed that CaSiO ₃ and CaCO ₃ (calcite) are crystalline phases, while the silica-rich regions are amorphous.

As used herein, the term coarse and fine filler particles refers to any suitable material having a suitable particle size and size distribution. In some preferred embodiments, for example, the filler particles are made from a calcium carbonate-rich material such as limestone (eg, ground limestone). In some materials, the filler particles are made from one or more SiO ₂ -based or silicate-based materials such as quartz, mica, granite, and feldspar (eg, ground quartz, ground mica, ground granite, ground feldspar).

In some embodiments, the 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.

In some embodiments, the average particle size of the plurality of coarse and fine filler particles is from about 5 µm to about 7 mm (e.g., from about 5 µm to about 5 mm, from about 5 µm to about 4 mm, from about 5 µm to about 3 mm, from about 5 µm to about 2 mm, from about 5 µm to about 1 mm, from about 5 µm to about 500 µm, from about 5 µm to about 300 µm, from about 20 µm to about 5 mm, from about 20 µm to about 4 mm, from about 20 µm to about 3 mm, from about 20 µm to about 2 mm, from about 20 µm to about 1 mm, from about 20 µm to about 500 µm, from about 20 µm to about 300 µm , from about 100 μm to about 5 mm, from about 100 μm to about 4 mm, from about 100 μm to about 3 mm, from about 100 μm to about 2 mm, from about 100 μm to about 1 mm).

In some embodiments, the weight ratio of binder elements to coarse and fine filler particles may be any suitable ratio depending on the intended use of the composite material product. For example, the weight ratio of binding elements to coarse or fine filler particles may be from about 50-99: to about 1-50, for example, from about 60-99: to about 1-40, from about (80-99) : to about (1-20), from about (90-99) : to about (1-10), from about (50-90) : to about (10-50), from about (50 -70) : to approximately (30-50). In certain embodiments, depending on the application, the weight ratio of binder elements to filler particles can be from about (10-50): to about (50-90), for example, from about (30-50): to about (50-70) , from about (40-50) : to about (50-60).

More specifically, the first layer and the second layer can be made from a precursor particle according to the following reactions (1-3), in which water can be used as a reaction medium rather than as a reactant (that is, water is not consumed):

CaSiO ₃ (s) + CO ₂ (g) CaCO3 (s) + SiO ₂ (s)(1)

Ca ₃ Si ₂ O ₇ (s) + 3CO ₂ (g) 3СаСОз (s) + 2SiO ₂ (s)(2)

Ca ₂ SiO ₄ (s) + 2CO ₂ (g) 2CaCO ₃ (s) + SiO ₂ (s)(3)

For example, in the carbonation reaction of silicate minerals, such as calcium silicate compositions, CO2 is introduced as a gas phase, which dissolves in an infiltration fluid such as water. When CO2 dissolves, acidic carbon compounds (such as carbon dioxide, H ₂ CO ₃ ) are formed, which leads to a decrease in the pH of the solution. The weakly acidic solution incongruently dissolves calcium compounds from the calcium silicate phases. Calcium can be leached from calcium-containing amorphous phases through a similar mechanism. Released calcium cations and dissociated carbonate compounds lead to the precipitation of insoluble carbonates. It is assumed that the silica-rich layers remain on the mineral particles as calcium-depleted layers.

Thus, according to a preferred embodiment of the present invention, CO2 preferentially reacts with calcium cations contained in the core of the calcium silicate precursor composition, thereby converting the peripheral portion of the precursor core into a first silica-rich layer and a second calcium carbonate-rich layer. In addition, the presence of the first and second layers on the core acts as a barrier to further reaction between the calcium silicate and carbon dioxide, resulting in the binding element having a core, a first layer and a second layer.

In some embodiments, silicate materials containing metals other than or in addition to Ca, such as fosterite (Mg ₂ SiO ₄ ), diopside (CaMgSi ₂ O ₆ ), and talc (Mg ₃ Si ₄ O ₁₀ (OH) ₂ ), can react with carbon dioxide dissolved in water in a manner similar to the calcium silicate reaction described above. It is contemplated that such silicate materials may be used alone, in combination and/or in combination with calcium silicate as precursors to prepare binders according to the principles of the present invention.

Gas-assisted HLPS processes preferably utilize a partially infiltrated porous space to allow gas diffusion to rapidly infiltrate the porous preform and saturate the thin liquid interfacial films of solvent in the pores with dissolved CO2. CO2-based compounds have low solubility in pure water (1.5 g/l at 25°C, 1 atm.). Thus, a significant amount of CO ₂ must be continuously supplied and distributed throughout the porous workpiece in order to ensure significant carbonate conversion. The use of gas phase diffusion provides a huge (about 100 times) increase in diffusion length compared to the diffusion length of soluble CO2 for an equivalent time in the liquid phase. (Handbook of chemistry and physics, Editor: DR Lide, Chapters 6 and 8, ^87th Edition 2006-2007, CRC). This partially infiltrated state allows the reaction to proceed with a high degree of carbonation over a fixed period of time.

Liquid water in the pores speeds up the rate of reaction because it provides a medium for the ionization of both carbon dioxide and calcium compounds. However, the water level must be low enough to allow CO2 gas to diffuse into the porous matrix before dissolving in the aqueous phase associated with the pores. In addition, the actively dissolving porous preform serves as a template for the expansive growth of reactive crystals. In this way, the connecting element and matrices can be obtained with minimal distortion and residual stresses. This allows the resulting large and complex shapes, such as those required for infrastructure and building materials, among many other applications.

Thus, different combinations of curing conditions can be developed to achieve the required production process, including different reaction temperatures, reaction pressures and reaction times. In a first exemplary embodiment, water is present in the precursor material (e.g., as residual water from a previous mixing step), wherein liquid water is directed to the precursor materials (e.g., to maintain water levels and/or control water loss due to evaporation) along with CO2, and conduct the curing process at a temperature of about 90°C and a pressure of about 20 psig (about 138 kPa g) (i.e., 20 psi (about 138 kPa) above external pressure) for a time of about 2 to 90 hours

In a second exemplary embodiment, water is present in the precursor material (e.g., as residual water from a previous mixing step), wherein water vapor is directed to the precursor materials (e.g., to maintain water levels and/or control water loss due to evaporation) along with CO ₂ and conduct the curing process at a temperature of about 90° C. and a pressure of about 20 psig (about 138 kPa g) (i.e., 20 psi (about 138 kPa) above external pressure) for a time of about 2 to 90 hours

In a third exemplary embodiment, water is present in the precursor material (e.g., as residual water from a previous mixing step), wherein water vapor is directed to the precursor materials (e.g., to maintain water levels and/or control water loss due to evaporation) along with CO2 and carry out the curing process at a temperature of 25 to 90°C and a pressure of 0 psig (atmospheric pressure) for 2 to 72 hours.

According to the embodiments described above, the time required to cure an object from

- 20 044255 composite material, is determined by the ability of water vapor and CO2 gas to diffuse throughout the entire object. In general, thicker objects will take longer to cure than thinner objects. Likewise, objects with high density (and less open pore volume) will take longer to cure than objects with low density (and more open pore volume). The following table provides examples of how cure times can vary depending on the smallest thickness (or wall thickness or section thickness) of the three dimensions and the bulk density of the resulting object.

Examples of curing time and thinnest thickness

Minimum thickness of composite material (mm) Bulk density of composite material (g/cm ³ ) Approximate curing time (hours) 25 1.6-2.3 8-12 75 2.1-2.3 16 100 0.4-0.8 8-12 200 1.5 72 200 2.4 72

Discussion of the obtained microstructures.

As schematically shown in FIG. 11(a)-11(c), the bonding member comprises a core (shown as a black inner portion), a first layer (shown as a white middle portion), and a second or encapsulating layer (shown as an outer portion). The first layer may include only one layer or several sublayers and may completely or partially cover the core. The first layer may be in a crystalline phase, an amorphous phase, or a mixture thereof, and may also exist in a continuous phase or as discrete particles. The second layer may include only one layer or several sublayers and may also completely or partially cover the first layer. The second layer may include many particles or may be a continuous phase with a minimum number of discrete particles.

The coupling element can be of any size and any regular, irregular, solid or hollow material morphology depending on the intended application. Typical morphologies include: cubes, cuboids, prisms, disks, pyramids, polyhedra or polyhedral particles, cylinders, spheres, cones, rings, tubes, crescents, needles, fibers, threads, flakes, spheres, subspheres, balls, grapes, granules, oblongs elements, rods, scales, etc.

In general, as described in more detail herein, the coupling element is obtained from reactive precursor materials (eg, precursor particles) through a conversion process. The precursor particles can be of any size or shape as long as they meet the requirements of the intended application. The conversion process usually results in the production of corresponding linking elements having similar sizes and shapes of the precursor particles.

Within the bonding matrix, the bonding elements may be positioned relative to each other in any of several orientations. In fig. 12(a)-12(!) schematically show a typical bonding matrix containing bonding elements in the form of fibers or plates in various orientations, possibly diluted by the addition of a filler material, as depicted by the spacing between the bonding elements. In fig. 12(a), for example, shows a bonding matrix comprising fiber-shaped bonding elements arranged in a row in a unidirectional (1-D) orientation (eg, aligned with the x-direction). In fig. 12(b) shows a bonding matrix comprising plate-like bonding elements arranged in a row in a bidirectional (2-D) orientation (eg, aligned with respect to the x and y directions). In fig. 12(c) shows a bonding matrix comprising plate-like bonding elements arranged in a row in a three-directional (3-D) orientation (eg, aligned with respect to the x, y, and z directions). In fig. 12(d) shows a bonding matrix containing plate-like bonding elements in random orientation, wherein said bonding elements are not aligned with respect to any particular direction. In fig. 12(e) shows a bonding matrix containing a relatively high concentration of plate-like bonding elements arranged in a row in a three-dimensional orientation. In fig. 12(f) shows a binding matrix containing a relatively low concentration of plate-like binding elements arranged in a random orientation (in a percolation network). The composite material shown in FIG. 12(f) provides a percolation threshold because most of the connecting elements are in contact with each other so that a continuous network of contacts is formed from one end of the material to the other end. The percolation threshold is a critical concentration above which the binding elements exhibit long-range connectivity with any ordered, for example, FIG. 12(e), or in random orientation, such as FIG. 12(f), connecting elements. Examples of connectivity patterns can be found, for example, in Newnham et al., Connectivity and piezoelectricpyroelectric composites, Mat. Res. Bull. Vol. 13, pp. 525-536, 1978).

The plurality of binding elements may be chemically converted from any suitable precursor materials, for example, from any suitable calcium silicate precursor composition. The calcium silicate composition as a precursor may also contain one or more chemical elements selected from aluminum, magnesium and iron.

The plurality of binding elements may have any suitable average particle size and size distribution depending on the desired composite material. In some embodiments, the average particle size of the plurality of coupling elements is from about 1 μm to about 100 μm (e.g., from about 1 μm to about 80 μm, from about 1 μm to about 60 μm, from about 1 μm to about 50 μm, from about 1 µm to about 40 µm, about 1 µm to about 30 µm, about 1 µm to about 20 µm, about 1 µm to about 10 µm, about 5 µm to about 90 µm, about 5 µm to about 80 μm, from about 5 μm to about 70 μm, from about 5 μm to about 60 μm, from about 5 μm to about 50 μm, from about 5 μm to about 40 μm, from about 10 μm to about 80 μm, from about 10 µm to about 70 µm, from about 10 µm to about 60 µm, from about 10 µm to about 50 µm, from about 10 µm to about 40 µm, from about 10 µm to about 30 µm, from about 10 µm to about 20 µm ).

In some cases, the composite material contains: a plurality of binding elements and a plurality of filler particles. Each binding element comprises: a core comprising predominantly a calcium silicate composition, a first or inner layer enriched in silica, and a second or outer layer enriched in calcium carbonate. A plurality of binding elements and a plurality of filler particles together form one or more binding matrices, wherein said binding elements and filler particles are substantially uniformly distributed in said matrix and bonded together, whereby the resulting composite material has one or more properties selected from textures, patterns and physical properties. In some cases, the bonding elements may have a magnesium silicate core and a first or inner layer enriched in silica and a second or outer layer enriched in magnesium carbonate. Magnesium silicate may include oxides of aluminum, calcium, iron or manganese.

In certain embodiments, such composite materials may have different patterns, textures, and other characteristics, such as visible patterns of different colors. In addition, the composite materials of the present invention have compressive strength, flexural strength and water absorption characteristics similar to conventional concrete or corresponding natural materials.

In some embodiments, the composite material further comprises a pigment. The pigment may be uniformly distributed or substantially unevenly distributed in the binding matrices depending on the desired composite material. The pigment may be any suitable pigment, including, for example, oxides of various metals (eg, iron oxide, cobalt oxide, chromium oxide). The pigment may be any color or colors, for example selected from black, white, blue, grey, 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 of from about 0.0% to about 10% by weight (e.g., from about 0.0% to about 8%, from about 0.0% to about 6% from about 0.0% to about 5%, from about 0.0% to about 4%, from about 0.0% to about 3%, from about 0.0% to about 2%, from about 0.0% to about 1%, from about 0.0% to about 0.5%, from about 0.0% to about 0.3%, from about 0.0% to about 2%, from about 0. 0% to approximately 0.1%).

Examples

Example 1.

Curing system with adjustable spacing between chamber components.

A curing system was manufactured in which the distance between the plates could be adjusted to accommodate the product. Increasing or decreasing the distance between the slabs on which the individual concrete objects were placed resulted in a change in the size of the channel 101 formed between the top of the individual concrete objects and the bottom of the slab located above the individual concrete object. The size of such a channel 101, determined by the gap between the slabs and the dimensions of the individual concrete objects, influenced the speed of movement of the fluid through the objects. At a constant volume of fluid flow between the plates, the smaller channel 101 increased the speed, and the expansion of the channel 101 resulted in a decrease in speed.

Depending on the ratio of the binder to the filler, the water content, the degree of compaction and the size of the uncured individual concrete objects, it is desirable to change the rate of fluid flow through the channel 101 of an increased or decreased size. An image of such a system is shown in Fig. 15

In some embodiments in which the binder 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 overall process time requirements.

In some embodiments in which the binder to filler ratio is low, it may be desirable to reduce the size of the channel 101 to improve the properties of the finished objects and optimize overall process time requirements.

In some embodiments, multiple categories of individual concrete objects with different binder-to-aggregate ratios, water content, degree of compaction, or dimensions will be processed in the same chamber or shell. In such an embodiment, the size of the channel 101 can be independently adjusted for each product placement slab according to the type of concrete object adjacent to the channel. This method allows you to adjust the speed of the process gas in accordance with the optimal speed for each category of concrete objects in order to unify the properties of the finished objects and optimize the requirement for the overall duration of the process.

Example 2.

Reversible flow curing system.

A curing system was developed in which a flow of process gas was directed into channels between individual concrete objects, and between individual concrete objects and chamber components. The flow direction in both channels was reversible. In shells or chambers capable of containing a plurality of individual concrete objects, said objects are arranged in an array as fluid flows through such concrete objects. As the fluid passes through a plurality of individual objects, fluid conditions such as temperature, relative humidity or moisture content, and speed change. After traveling a certain length, which is determined by the initial state of the fluid and the properties of the plurality of individual concrete objects, such as the ratio of the bonding element to the filler, the water content, the degree of compaction and dimensions, the state of the fluid in the channels between the chamber components and the channels between the individual concrete objects became unsuitable for optimal curing. In other words, the temperature of the fluid dropped and the relative humidity or moisture content of the fluid increased beyond the threshold value suitable for curing individual concrete objects.

In some embodiments, a fluid is considered unsuitable for use when the temperature of the fluid decreases 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.

In some embodiments, a fluid is considered unsuitable for curing use when the fluid's moisture content, expressed as relative humidity, is greater than 20%, or greater than 30%, or greater than 40%, or greater than 50%, or greater than 60% , or more than 70%, or more than 80%, or more than 90%.

However, by reversing the direction of fluid flow at least once during the curing cycle, it is possible to increase the length of the array of individual concrete objects that can be cured. Thus, individual downstream concrete objects that were exposed to the cooler, higher moisture content fluid are now exposed to the drier, lower moisture content fluid for at least part of the curing cycle. In some embodiments, this length may be increased to double the length at which the gas conditions become unsuitable for use of a curing gas in a unidirectional flow unit throughout the curing cycle. Overall, this concept helps to increase the capacity of the shell or chamber.

A large scale drawing of an exemplary system is shown in FIG. 16. An approximate drawing of the proposed system with concrete objects located inside is shown in FIG. 17.

According to another embodiment, the products can be stacked on slabs one on top of the other, as shown in FIG. 15 and introduced into a modified version of the proposed system shown in FIG. 16 and 17, in which the height of the chamber is increased to accommodate several racks.

Example 3.

Curing of hollow core slab using isothermal desorption method. Mixing.

To mix the components when designing the composition of the concrete mixture, a planetary mixer of the Sicoma TO8 series (model MP 250/375 WWWSW) was used. The speed of the planetary mixer was 18.5 rpm. The filler material in the form of 293.8 kg of ^1/4 inch (approximately _0.64 cm) aggregate and 160.3 kg of sand was dry mixed for 90 seconds. 5 kg of water, 168 g of Glenium 7500 (BASF) and 120 g of air entraining additive were added to the dry mixture and the resulting combination was mixed for an additional 90 seconds. A binder in the form of 80.1 kg of Solidia cement (Solidia Technologies) was added to the wet material in the mixer.

- 23 044255 (4% pseudowollastonite, 19% wollastonite, 13% larnite, 2% calcite and 62% amorphous oxides) along with an additional 16 kg of water. The resulting combination was stirred for another 90 seconds. The final moisture content of the mixture was found to be 3.68% when measured using a Sartorius MA100 moisture analyzer. A total of three such batches were transferred to the extruder for hollow core board extrusion.

Extrusion.

Two 40-inch (approximately 102 cm) long, 3/8-inch (approximately 0.95 cm) diameter steel ropes (7-strand low relaxation wire, Sumiden Wire Products Corp.) were stretched to an elongation of 3 inches (approximately 7 inch). .6 cm) along the length of the steel extrusion frame. The ropes were installed in such a way as to place one of them symmetrically between the bottom of the slab and cores 1 and 2; and the other symmetrically between the bottom of the plate and cores 5 and 6.

The hollow core board was extruded on a steel frame using an Elematic EL 600/8 industrial extruder using a screw speed of 55 rpm. The extruded board was 18 feet long, 4 feet wide, 8 inches high, and contained six hollow cores (6 inches in diameter). Adjacent cores were separated by a 1.25-inch (approximately 3.18 cm) thick wall. In fig. Figure 18 shows an image of such a hollow-core slab.

Curing.

Fig. 19 is a schematic drawing of a curing apparatus. During curing, the frame was heated by circulating hot water through pipes inside the steel frame. The temperature of the heating water was maintained using a gas-fired boiler, the temperature of which was set at 81°C. The temperature on the top surface of the steel frame was approximately 49°C. To remove moisture from the circulating gas stream, cold water from the cooler was circulated through the condenser (maintained at 10°C). The temperature in the electric heater (3.75 kW) was maintained at 87°C to heat the dried cycle gas stream before returning it to the curing chamber. The speed of the circulation blower was controlled using a variable frequency drive. The initial speed of the blower was 30 Hz. Dry CO ₂ was supplied as needed to the curing system through an Alicat mass flow controller. The curing chamber contained a steel extrusion frame and a polyethylene sheet, which acted as a canopy and separated the flow of CO ₂ /H ₂ O from the surrounding atmosphere. The canopy covered the hollow-core slab and was stretched between the supporting walls at each end of the slab. The canopy was sealed along the steel extrusion frame and at the end walls using magnetic strips and filled with a flow of circulating gas. The pressure difference between the inside of the canopy and the outside of the canopy was maintained slightly above atmospheric pressure (pressure difference = +0.2 inches (about 0.5 cm) of water column). Each end wall of the curing chamber had the same cross-sectional shape as the slab, except that the height of the walls was 9.25 inches (about 23.50 cm) rather than 8 inches (about 20 cm). Each end wall served as the front side of a rectangular box, forming a chamber with 1 gas inlet located opposite the 6 holes through which gas entered or exited the curing chamber. The 6 said holes were covered with a perforated metal sheet so that the end chamber acted as a cavity functioning to distribute and equalize the gas flow entering the curing chamber. One of the two holes belonging to the differential pressure sensor was built through one of the end walls into the curing chamber. The other hole remained open to the surrounding atmosphere. To monitor the CO2 concentration in the chamber throughout the cure cycle, a CO2 meter NDIR sampling probe was integrated through the end wall at the other end of the cure chamber. Two Vaisala humidity/temperature sensors were placed inside the curing chamber, one at each end just inside the end walls.

The curing chamber was purged with CO2 gas for 10 min.

During the curing process, the direction of gas circulation was changed every 60 min. The blower speed was reduced to 15 Hz 90 min after the start of cure and then increased to 45 Hz 209 min after the start of cure, where it remained until the end of the cure cycle at 490 min.

In fig. Figure 20 shows chamber humidity, measured at the end walls using Vaisala sensors, throughout the curing process, as well as the total amount of condensed water collected throughout the cycle.

The strength of a hollow-core slab was assessed using the elastic rebound method of a hammer at 44 points on the upper surface of the slab. Rebound parameters showed an average compressive strength of 30 MPa.

Example 4.

Curing of hollow casting using isothermal adsorption method.

Mixing.

Mix design included the use of six solid components: (1) 3/8-inch aggregate, 29%; (2) _1/4 inch aggregate, 15%; (3) crushed quartz with a particle size of 2 mm, 15%; (4) construction sand, 20%; (5) white marble 200, 11%; and (6) wollastonite NYCO 400, 13%. The components were mixed dry in a Kercher Industries 12 laboratory mixer for 2 minutes. Water (570 g) with the addition of gum was added to the dry components and the resulting mixture was stirred for another 4 minutes. More water (265 g) was added and the mixture was stirred for an additional 4 minutes. Finally, more water (260 g) was added and the mixture was stirred for an additional 2 minutes.

Casting.

The wet mixture was cast into a rectangular mold measuring 4 x 4 x 20 inches (approximately 10 x 10 x 51 cm), with the largest side placed horizontally. A 2 inch (about 5.1 cm) diameter, 20 inch (about 51 cm) long polyvinyl chloride tube, wrapped in wax paper, was secured in the center of the mold so as to form a 2 inch (about 5.1 cm) diameter core along the length castings 6 layers of concrete mixture were cast, with each layer being vibrated for 30 s, with the exception of the last layer, which was vibrated for 60 s.

Drying.

The hollow casting was dried slowly to prevent cracking. The casting was left to air dry overnight and then placed in a drying oven at 90°C for 51 hours and then an additional 20 hours at 100°C. After drying, the hollow casting was removed from the mold and the PVC pipe was removed from the core of the casting. The net weight of the hollow casting was 8769 g.

Curing.

Fig. 21 is a view of a curing setup.

PVC pipe fittings were inserted into each end of the core using pipe fittings screwed to the pipe fittings so that the curing gases could pass through the casting. The hollow casting was encased in 1 inch (approximately 2.5 cm) thick fiberglass insulation material on an aluminum foil backing. One of the tube fittings from the core (the inlet) was attached using _1/4 inch (about 0.64 cm) stainless steel tubing to a gas saturator (a heated vessel containing water). The other pipe fitting from the core (outlet pipe) was attached to a _1/4 inch (about 0.64 cm) plastic pipe leading to the vent. Each nozzle was equipped with a thermocouple so that the temperature of the curing gas could be measured before and after passing through the core. Each pipe was insulated with fiberglass insulation material.

The water in the saturator was maintained at a temperature of 65°C throughout the entire curing cycle. Carbon dioxide gas was bubbled through the water at a rate of 6.5 L/min to saturate the gas stream with water vapor. All heat and water for the curing reaction was transferred into the hollow core using a stream of saturated carbon dioxide. The core inlet temperature increased from 26°C to 60°C within one hour, where it remained until the end of the curing cycle. It took another 90 minutes for the core exit temperature to rise to 53°C, where it remained until the end of the curing period. The curing process was completed after 20 hours.

The insulating material surrounding the hollow casting during the curing process was removed. The first third of the casting (entry end) appeared wet and darker in appearance than the rest of the casting, which appeared lighter and drier (Fig. 22). The casting was completely dried in a drying oven to a constant weight of 8939 g, resulting in an increase of 170 g due to carbonation. According to calculations, the average degree of carbonization was 40% of the weight gain.

The dried hollow casting was cut in half to assess uniformity of cure since the two ends of the casting were visually different. Some material was lost due to kerfing when cutting the casting, and some material was lost due to chipping of the outer cut edges caused by the saw blade. The chip structure was symmetrical and approximately the same on both halves of the casting, so the cutting losses were approximately the same for both parts. The total cutting loss was 137 g. The inner edges (eg, the core surface) were cut cleanly, indicating that the inside of the casting reacted better than the outside and that the degree of interaction varied radially around the core. The mass of the entry half of the dried casting was 4429 g, while the mass of the exit half of the dried casting was 4373 g. Thus, the mass remaining after cutting the slab was evenly distributed over the two halves (50.3% entry end; 49.7% exit end ). Thus, the degree of carbonation was evenly distributed along the length of the hollow casting.

The invention presented by the applicant is described herein according to preferred embodiments with reference to the figures in which like numbers represent

-

Claims (14)

identical or similar elements. As used herein, reference to an embodiment, embodiment, or the like means that the particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, the appearance in this specification of the phrases according to one of the embodiments, according to an embodiment and similar expressions may, but do not necessarily, refer to the same embodiment. The described features, structures or characteristics of the invention presented by the applicant may be combined in any suitable manner in one or more embodiments. To provide a thorough understanding of the embodiments of the present invention, numerous specific details are set forth herein in the description. However, one skilled in the art will appreciate that the composition and/or method proposed by the applicant may be practiced without the use of one or more specific parts or using other methods, components, materials, and the like. In other cases, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of the present invention. In this specification and the accompanying claims, the singular forms include a reference to the plural unless the context clearly indicates otherwise. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly used by those skilled in the art. Although any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention, preferred methods and materials are described herein. The methods set forth herein may be performed in any order that is logically possible, along with the specific order described. Incorporation by reference. Throughout this specification, references have been made and cited to other documents such as patents, patent applications, patent publications, journals, books, documents, website content. All documents listed are therefore incorporated herein by reference in their entirety for all purposes. Any material or portion thereof which is stated to be incorporated herein by reference but which conflicts with existing definitions, statements or other disclosures expressly set forth herein is incorporated only to the extent that no conflict arises. between such included material and the material described in the present invention. In the event of such a conflict, it shall be resolved in favor of the present description as the preferred description. Equivalents. The representative examples described herein are intended to assist in illustrating the present invention and are not intended to limit the scope of the present invention and should not be construed as such. Indeed, various modifications of the present invention and many additional embodiments thereof, along with the embodiments shown and described herein, will become apparent to those skilled in the art from the entire contents of this document, which includes the following examples and references to scientific and patent literature cited in this document. The examples provided provide important additional information, illustrative examples and guidance that may be adapted to practice the present invention according to its various embodiments and their equivalents. CLAIM 1. A system for manufacturing an article comprising a shell or chamber and a fluid distribution component enclosed therein, configured to change the direction of gas flow within said shell or chamber at least once, a composite material distributed in the form of a plurality of individual concrete objects, where the plurality of individual concrete objects are located along many parallel planes; wherein one or more passages or channels are located between or through each of said individual concrete objects to form a system for transporting fluid within said one or more passages and channels and from the outside of the plurality of separate objects; one or more racks, canvases, walls or panels with planar, flat, convex or concave facing surfaces defining one or more passages or channels and providing a fluid flow profile in a fluid conveying system. 2. The system of claim 1, wherein the fluid distribution component controls the flow profile - 26 044255 fluid of at least part of the shell or chamber. 3. The system of claim 1, wherein the fluid distribution component changes the velocity of the gas within said enclosure or chamber at least once. 4. The system according to any one of claims 1 to 3, wherein the fluid distribution component includes one or more components selected from fluid inlets, fluid outlets, cavities or perforated plates, or combinations thereof. 5. A system according to any one of claims 1 to 4, wherein the shell or chamber is made of a material selected from metal, alloy, plastic, polymer, polymer composite material, ceramic composite material, or combinations thereof. 6. A system according to any one of claims 1 to 5, wherein the shell or chamber is made of concrete material, steel, or canvas, or combinations thereof. 7. The system of claim 1, further comprising one or more slabs on which said plurality of individual concrete objects are placed. 8. A method for producing a product, including: mixing the particulate composition and the liquid composition to form a mixture; casting or extruding said mixture in a mold to produce a cast or extruded raw material containing a plurality of individual concrete objects; wherein one or more passages or channels are located between each of the specified individual concrete objects and outside the plurality of individual objects or extend through all of them; maintaining an atmosphere of CO2 and/or water vapor in one or more internal passages or channels and outside of a plurality of individual objects; and curing the plurality of individual objects at a temperature ranging from about 20°C to about 150°C for from about 1 hour to about 80 hours in an atmosphere of water and/or CO2, the pressure of which is in the range of external atmospheric pressure to a pressure of about 60 psi (about 413 kPa) above the external pressure, and the CO2 concentration in which is from about 10% to about 90%, and maintaining an atmosphere of _CO2 and/or water vapor in one or more internal passages involves changing the direction of flow CO ₂ and/or water vapor at least once during the curing of said raw material. 9. The method of claim 8, wherein maintaining an atmosphere of CO2 and/or water vapor in one or more internal passages or channels and/or the exterior of the plurality of individual objects comprises: containing the atmosphere within one or more internal channels and/or the external part of a plurality of separate objects; circulation of a retained atmosphere of CO2 and/or water vapor; removing water vapor from the retained atmosphere or adding water vapor to the retained atmosphere; and heating the retained atmosphere. 10. The method of claim 8 or 9, wherein maintaining an atmosphere of CO2 and/or water vapor in said one or more internal passages or channels includes changing the flow rate of _CO2 and/or water vapor at least once during the period raw hardening. 11. The method according to any one of claims 8 to 10, wherein the particulate composition comprises ground calcium silicate containing one or more substances selected from natural or synthetic wollastonite, pseudowollastonite, rankinite, gehlenite, belite and alite, the average particle size of which is from about 1 μm to about 100 μm, wherein said liquid composition contains water. 12. The method according to any one of claims 8 to 11, wherein curing of the cast mixture is carried out at a temperature equal to or less than about 60°C for from about 10 to about 50 hours in an atmosphere of steam containing water and CO2 and having external atmospheric pressure. 13. The method according to any one of claims 8 to 12, wherein the ground calcium silicate is essentially calcium silicate in the form of ground wollastonite. 14. The method according to any one of claims 8-13, additionally including introducing one or more reinforcing elements into the mixture. -