(19)
(11)EP 3 052 454 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
11.03.2020 Bulletin 2020/11

(21)Application number: 14851379.9

(22)Date of filing:  03.10.2014
(51)International Patent Classification (IPC): 
C04B 20/12(2006.01)
C04B 40/02(2006.01)
E04B 5/04(2006.01)
C04B 28/18(2006.01)
E04C 2/18(2006.01)
(86)International application number:
PCT/US2014/059024
(87)International publication number:
WO 2015/051243 (09.04.2015 Gazette  2015/14)

(54)

HOLLOW CORE SLABS AND METHOD OF PRODUCTION THEREOF

HOHLKERNPLATTEN UND VERFAHREN ZU IHRER HERSTELLUNG

DALLES À ÂME CREUSE ET PROCÉDÉ DE SA FABRICATION


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 04.10.2013 US 201361886936 P

(43)Date of publication of application:
10.08.2016 Bulletin 2016/32

(73)Proprietor: Solidia Technologies, Inc.
Piscataway, NJ 08854 (US)

(72)Inventors:
  • MCCANDLISH, Larry, E.
    Piscataway, NJ 08854 (US)
  • NARINE, Orlando
    Piscataway, NJ 08854 (US)
  • CASTRO, Daniel
    Piscataway, NJ 08854 (US)
  • ATAKAN, Vahit
    West Windsor, NJ 08540 (US)
  • PATTEN, Devin
    Red Bank, NJ 07701 (US)
  • KUPPLER, John, P.
    Greenbrook, NJ 08812 (US)

(74)Representative: Dentons Patent Solutions Rechtsanwaltsgesellschaft mbH 
Jungfernturmstraße 2
80333 München
80333 München (DE)


(56)References cited: : 
WO-A1-2014/165252
WO-A2-2012/122031
JP-A- 2001 302 295
RU-C1- 2 363 821
WO-A1-2014/165257
CN-A- 101 139 182
NL-C- 2 007 927
SU-A1- 1 260 363
  
  • DATABASE WPI Week 199825 Thomson Scientific, London, GB; AN 1998-280317 XP002770014, & JP H10 95651 A (MITSUBISHI MATERIALS CORP) 14 April 1998 (1998-04-14)
  • D. DAVAL ET AL: "Mechanism of wollastonite carbonation deduced from micro- to nanometer length scale observations", THE AMERICAN MINERALOGIST, vol. 94, no. 11-12, 1 November 2009 (2009-11-01), pages 1707-1726, XP055126736, ISSN: 0003-004X, DOI: 10.2138/am.2009.3294
  • ALBERTO SANTOS ET AL: "Reactivity of CO2 traps in aerogel-wollastonite composites", JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY, KLUWER ACADEMIC PUBLISHERS, BO, vol. 48, no. 1-2, 18 March 2008 (2008-03-18), pages 224-230, XP019646179, ISSN: 1573-4846, DOI: 10.1007/S10971-008-1719-Y
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

Field of the Invention



[0001] The invention generally relates to articles of composite materials having hollow cores, channels. More particularly, the invention relates to slabs of composite materials having hollow interior ducts, channels and chambers or otherwise being hollowed out, and formulations and methods for their manufacture and uses. These hollow-core slabs are suitable for a variety of applications in construction, pavements and landscaping, and infrastructure.

Background of the Invention



[0002] Hollow-core slabs, sometimes referred to as voided slabs or hollow core planks, are precast slabs of concrete. They are often used in building constructions, for example, as floors, walls or roofs in multi-story buildings. The precast concrete slab typically has tubular voids extending the full length of the slab, making the slab lighter than a massive floor slab of equal thickness or strength. Reduced weight lowers material and transportation cost.

[0003] Typical slabs are about 120 cm wide with a standard thickness between 15 cm and 50 cm. The precast concrete I-beams between the holes contain steel wire ropes that provide bending resistance to bending moment from loads. The manufacturing process involves extruding wet concrete around the prestressed steel wire rope from a moving mold. After curing the continuous slab is cut according to the required lengths and width. Hollow-core floor slabs are also made in rebar reinforced concrete (not prestressed). Hollow-core wall panels are made without reinforcement.

[0004] Most hollow-core slabs manufactured today are made from conventional concrete. For the most part, existing concrete hollow-core slabs are operative and reliable for the intended purposes. Concrete hollow-core objects, however, are not optimal in terms of both economics and environmental impact. Existing production technologies involve large energy consumption and carbon dioxide emission, leading to unfavorable carbon footprints.

[0005] Thus, there is an on-going need for novel hollow-core objects prepared from composite materials that match or exceed the physical and performance characteristics of conventional hollow-core objects manufactured using conventional concretes, and that can be mass-produced at lower cost with improved energy consumption and more desirable carbon footprint.

[0006] D. Daval et al. in "Mechanism of wollastonite carbonation deduced from micro- to nanometer length scale observations", The American Mineralogist, 1 November 2009, vol. 94 discloses the study of micro structural evolution of CaSiO3 wollastonite when subjected to carbonation reactions at T = 90 °C and pCO2 = 25 MPa at three different starting conditions: (1) pure water; (2) aqueous alkaline solution (0.44 M NaOH); and (3) supercritical CO2. Scanning and transmission electron microscopy on reacted grains prepared in cross-section always revealed unaltered wollastonite cores surrounded by micrometer-thick pseudomorphic silica rims that were amorphous, highly porous, and fractured. The fractures were occasionally filled with nanometer-sized crystals of calcite and Ca-phyllosilicates. Nanoscale chemical profiles measured across the wollastonite-silica interfacial region always revealed sharp, step-like decreases in Ca concentration. Comparison of the Ca profiles with diffusion modeling suggests that the silica rims were not formed by preferential cation leaching (leached layer), but rather by interfacial dissolution-precipitation.

[0007] WO-A-2014/165257 discloses novel railroad ties manufactured from novel composite materials that possess excellent physical and performance characteristics matching or exceeding existing concrete RRTs. The RRTs of the disclosure can be readily produced from widely available, low cost raw materials by a process suitable for large-scale production with improved energy consumption and more desirable carbon footprint and minimal environmental impact.

[0008] WO-A-2014/165252 discloses novel aerated composite materials that possess excellent physical and performance characteristics of aerated concretes, and methods of production and uses thereof. These composite materials can be readily produced from widely available, low cost raw materials by a process suitable for large-scale production with improved energy consumption, desirable carbon footprint and minimal environmental impact.

[0009] WO-A-2012/122031 discloses a bonding element, a bonding element matrix and composite materials with a wide range of attractive properties that may be optimized, including, but not limited to, mechanical properties, thermal properties, magnetic properties, optical properties and nuclear properties, as a result of a first layer and second layer structure or core, first layer, and second layer structure of the bonding elements, as well as methods for making the bonding elements and the corresponding ceramic and/or composite materials.

[0010] JP-A-2001/302295 discloses a carbonated inorganic cured body of high texture stability that can be produced by low-temperature carbonation treatment in a short time. In this method of producing a carbonated inorganic cured body, wollastonite that has ≤1 µm of 10% cumulation diameter in the grain size volume distribution and ≥1 m2/g of nitrogen adsorption specific surface area is mixed with water, formed and the formed product is subjected to the carbonation treatment at 30-200 °C under the conditions of atmospheric pressure (0 MPa)-20 MPa.

Summary of the Invention



[0011] The invention is based in part on the unexpected discovery of novel hollow-core objects manufactured from novel composite materials that possess excellent physical and performance characteristics matching or exceeding existing concrete hollow-core objects, including toughness, flexibility, abrasion resistance and durability.

[0012] The hollow-core slabs of the invention can be readily produced from widely available, low cost raw materials by a process suitable for large-scale production with lower energy consumption, therefore enjoying desirable carbon footprints with minimal environmental impact. The raw materials include precursor materials such as particulate calcium silicate. The calcium silicate precursor material typically comprises a blend of discrete calcium silicate phases, selected from one or more of CS (wollastonite or pseudowollastonite), C3S2 (rankinite), C2S (belite or larnite or bredigite) and a calcium-silicate based amorphous phase comprising about 30% or more of the total phases, where "C" refers to calcium oxide or lime, wherein "S" refers to silicon dioxide or silica, along with certain traces of impurities that become bonding elements, and particulate filler materials (e.g., calcium oxide-containing material such as limestone, xonotlite, miro-silica, and quartz, lightweight aggregates such as perlite or vermiculite, or even industrial waste materials such as fly ash, bottom ash and slag). A fluid component is also provided as a reaction medium, comprising liquid water and/or water vapor and a reagent, carbon dioxide (CO2), which is consumed in the production as a reactive species and ends up sequestered in the final product. The bonding elements react at controlled temperatures and pressures either using the process of hydration in which the reaction occurs between water and water vapor, or using water vapor and CO2.

[0013] Depending on end user requirements, various other additives such as dispersing, rheology modifying admixtures (to improve mixture consistency), coloring pigments, retarders, and accelerators. Additive materials can include natural or recycled materials, and calcium carbonate-rich and magnesium carbonate-rich materials, as well as additives to the fluid component, such as a water-soluble dispersant.

[0014] In a first aspect, the invention relates to a hollow core slab having a body prepared from a composite material. The body has one or more interior ducts or channels extending the full length of the slab, exhibiting one or more surfaces capable of fluid communication with an exterior of the body. The composite material is comprised of: a plurality of bonding elements, wherein each bonding element comprises: a core comprising primarily calcium silicate, a silica-rich first or inner layer, and a calcium carbonate-rich second or outer layer; and filler particles comprising coarse filler particles and/or fine filler particles, wherein the plurality of bonding elements and the plurality of filler particles together form one or more bonding matrices and the bonding elements and the filler particles are substantially evenly dispersed therein and bonded together. The hollow core slab further comprises one or more reinforcement elements selected from bars, wires or cables embedded in the body, wherein the hollow core slab has a longitudinal dimension from about 4 m to about 250 m, a transverse dimension from about 0.5 m to about 2 m, and a thickness from about 10 cm to about 50 cm.

[0015] In a second aspect, the invention relates to a process for producing the hollow core slab of the first aspect. The process includes: mixing a particulate composition, a liquid composition and filler particles to form a mixture; embedding one or more reinforcement elements selected from bars, wires or cables in the mixture; casting or extruding or otherwise forming the mixture in a mold to generate a casted or extruded or otherwise formed hollow core body having the reinforcement element embedded therein and one or more interior ducts or channels in the formed body extending the full length of the slab, exhibiting one or more surfaces and capable of fluid communication with interior of the body wall; maintaining an atmosphere of CO2 and water vapor in the one or more interior ducts or channels; and curing the casted or extruded body at a temperature in the range from about 20°C to about 150°C for about 1 hour to about 80 hours under an atmosphere of water and CO2 having a pressure in the range from ambient atmospheric pressure to about 60 psi (414 kPa) above ambient and having a CO2 concentration ranging from about 10% to about 90%. The particulate composition includes a ground calcium silicate, comprising one or more of natural or synthetic wollastonite, pseudo-wollastonite, rankinite, gehlenite, belite, and a calcium silicate based amorphous phase and having a median particle size in the range from about 1 µm to about 100 µm. The liquid composition comprises water, and the filler particles comprise coarse filler particles and/or fine filler particles.

Brief Description of the Drawings



[0016] The objects and features of the invention can be better understood with reference to the drawings described below, and the claims. The drawings are not necessarily to scale, emphasis instead generally being placed upon illustrating the principles of the invention. In the drawings, like numerals are used to indicate like parts throughout the various views.

FIG. 1 is a pressure-temperature phase diagram showing the phases present in the reversible reaction CaCO3 +SiO2 ↔ CaSiO3 (calcium silicate) + CO2.

FIG. 2 is a pressure-temperature phase diagram showing the phases present in the reversible reaction 3CaCO3 + 2CaSiO3 ↔ 2Ca2SiO4·CaCO3 + CO2.

FIG. 3 is a phase diagram of the CaO-SiO2-CO2 system at a pressure of 1 kilobar.

FIG. 4 is a pressure-temperature phase diagram showing the phases present in the reversible reaction MgO + CO2 ↔ MgCO3.

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

FIG. 6 is a temperature-composition phase diagram that illustrates the stability regions for various phases in the CaCO3-MgCO3 system.

FIG. 7 is a tetrahedron diagram illustrating the phase relationships among the compounds CaO, MgO, SiO2 and CO2, and showing the CO2 deficient region below the Cc-Di-Wo and the Cc-Wo-Mo planes (shaded), where Cc denotes calcite, Wo denotes Wollastonite, Ak denotes Akermanite, Di denotes diopside, and Mo denotes monticellite (CaMgSiO4).

FIG. 8 is a pressure-temperature phase diagram illustrating the phase relationships among the compounds CaO, MgO, SiO2 and CO2, with univariant curves emanating from the quaternary invariant point involving the phases calcite (Cc), diopside (Di), forsterite (Fo), monticellite (Mo), Akermanite (Ak), and CO2. The inset is the phase diagram for the three compound systems of CaCO3, MgO and SiO2.

FIG. 9 is a schematic diagram of a CO2 composite material curing chamber that provides humidification according to principles of the invention.

FIG. 10 is a schematic diagram of a curing chamber with multiple methods of humidity control as well as ability to control and replenish CO2 using constant flow or pressure regulation and that can control the temperature according to principles of the invention.

FIGs. 11(a)-11(c) are schematic illustrations of cross-sections of bonding elements according to exemplary embodiments of the present invention, including three exemplary core morphologies: (a) fibrous, (b) elliptical, and (c) equiaxed.

FIGs. 12(a)-12(f) are schematic illustrations of side view and cross section views of composite materials illustrating (a) 1D oriented fiber-shaped bonding elements in a dilute bonding matrix (bonding elements are not touching), (b) 2D oriented platelet shaped bonding elements in a dilute bonding matrix (bonding elements are not touching), (c) 3D oriented platelet shaped bonding elements in a dilute bonding matrix (bonding elements are not touching), and (d) randomly oriented platelet shaped bonding elements in a dilute bonding matrix (bonding elements are not touching), wherein the composite materials includes the bonding matrix and filler components such as polymers, metals, inorganic particles, aggregates etc., (e) a concentrated bonding matrix (with a volume fraction sufficient to establish a percolation network) of bonding elements where the matrix is 3D oriented, and (f) a concentrated bonding matrix (with a volume fraction sufficient to establish a percolation network) of randomly oriented bonding elements, wherein filler components such as polymers, metals, inorganic particles, aggregates etc. may be included.

FIG. 13 shows an exemplary hollow-core slab made according to the invention.

FIG. 14 depicts an exemplary embodiment of the invention, wherein the gas flow of CO2 and water vapor may be controlled such as to oscillate in directions when passing through the interior ducts or channels and around the exterior surfaces to establish time averaged mirror symmetry along the length while maintaining side-to-side mirror symmetry. These symmetries reduce the effects of temperature and gas composition gradients that arise during the curing process.

FIG. 15 shows the chamber humidity measured at the end walls by the Vaisala sensors throughout the cure as well as the cumulative amount of condensed water collected throughout the run.

FIG. 16 shows a picture of the curing apparatus for curing a dry hollow-core casting.

FIG. 17 shows a hollow-core casting that was cured in the apparatus of FIG 16.


Detailed Description of the Invention



[0017] The invention provides exceptional hollow-core slabs possessing excellent physical and performance characteristics matching or exceeding existing concrete hollow-core objects. The hollow-core slabs of the invention can be readily produced from widely available, low cost raw materials by a process suitable for large-scale production with improved energy consumption, reduced production cycle (e.g., less curing time), and more desirable carbon footprint. The production method of the invention consumes large quantities of CO2 resulting in a CO2 sequestrated product thereby making it carbon-neutral and environmentally friendly. Hollow-core slabs herein refer to slabs having hollow cores, channels or otherwise being hollowed out (for example, to reduce diffusion distances and facilitate curing).

[0018] The hollow-core slabs of the invention can be used as various building and construction components including, for example, floors, roofs, walls, doors, tablets, bridges, frames, pathways, barriers, linings, foundations, fences, sound barriers, pipes, culverts utility vaults, septic tanks, dry wells, and storm drains. They are manufactured with embedded reinforcement elements that are pre-tensioned and/or post-tensioned and/or pre-stressed, features that increase the capacity and durability of the hollow-core slabs. Reinforcement elements are selected from solid bars, wires or cables made with materials of desired characteristics, for example, steel, polymeric materials, glass, or a combination thereof.

[0019] A key feature of a hollow-core slab of the invention is that the core or channel or duct or hollow space creates walls whose thicknesses are small compared to the overall dimensions of the article. Access for the curing fluid to both sides of the wall significantly cuts the maximum distance over which carbon dioxide and water must diffuse to affect curing. Furthermore, the hollow space reduces the overall material use and product weight, resulting in savings in materials and other associated cost in transportation and installation.

[0020] In one aspect, the invention relates to a hollow core slab as defined in the appended claims.

[0021] Any suitable calcium silicate composition may be used as a precursor for the bonding elements. As used herein, the term "calcium silicate composition" generally refers to naturally-occurring minerals or synthetic materials that are comprised of one or more of a group of calcium silicate phases including CS (wollastonite or pseudowollastonite, and sometimes formulated CaSiO3 or CaO·SiO2), C3S2 (rankinite, and sometimes formulated as Ca3Si2O7 or 3CaO·2SiO2), C2S (belite , β-Ca2SiO4 or larnite, β-Ca2SiO4 or bredigite, α-Ca2SiO4 or γ-Ca2SiO4, and sometimes formulated as Ca2SiO4 or 2CaO·SiO2), a calcium-silicate based amorphous phase, each of which material may include one or more other metal ions and oxides (e.g., aluminum, magnesium, iron or manganese oxides), or blends thereof, or may include an amount of magnesium silicate in naturally-occurring or synthetic form(s) ranging from trace amount (1%) to about 50% or more by weight.

[0022] Calcium silicate compositions may contain amorphous (non-crystalline) calcium silicate phases in addition to the crystalline phases described above. The amorphous phase may additionally incorporate Al, Fe and Mg ions and other impurity ions present in the raw materials. The calcium silicate compositions may also include small quantities of residual CaO (lime) and SiO2 (silica). The calcium silicate composition may also include small quantities of C3S (alite, Ca3SiO5).

[0023] The calcium silicate compositions may also include quantities of inert phases such as melilite type minerals (melilite or gehlenite or akermanite) with the general formula (Ca,Na,K)2[(Mg, Fe2+,Fe3+,Al,Si)3O7] and ferrite type minerals (ferrite or brownmillerite or C4AF) with the general formula Ca2(Al,Fe3+)2O5. In certain embodiments, the calcium silicate composition is comprised only of amorphous phases. In certain embodiments, the calcium silicate comprises only of crystalline phases. In certain embodiments, some of the calcium silicate composition exists in an amorphous phase and some exists in a crystalline phase.

[0024] It is noted that preferably the calcium silicate compositions of the invention do not hydrate. However, minor amounts of hydratable calcium silicate phases (e.g., C2S, C3S and CaO) may be present. C2S exhibits slow kinetics of hydration when exposed to water and is quickly converted to CaCO3 during CO2 curing processes. C3S and CaO hydrate quickly upon exposure to water and thus should be limited to <5% by mass.

[0025] In certain preferred embodiments, the molar ratio of elemental Ca to elemental Si of the calcium silicate composition is from about 0.80 to about 1.20. In certain preferred embodiments, the molar ratio of Ca to Si of the composition is from about 0.85 to about 1.15. In certain preferred embodiments, the molar ratio of Ca to Si of the composition is from about 0.90 to about 1.10. In certain preferred embodiments, the molar ratio of Ca to Si of the composition is from about 0.95 to about 1.05. In certain preferred embodiments, the molar ratio of Ca to Si of the composition is from about 0.98 to about 1.02. In certain preferred embodiments, the molar ratio of Ca to Si of the composition is from about 0.99 to about 1.01.

[0026] The metal oxides of Al, Fe and Mg contained within the calcium silicate composition are generally controlled to be less than about 30%. In certain preferred embodiments, the composition has about 20% or less of metal oxides of Al, Fe and Mg by total oxide mass. In certain preferred embodiments, the composition has about 15% or less of metal oxides of Al, Fe and Mg by total oxide mass. In certain preferred embodiments, the composition has about 12% or less of metal oxides of Al, Fe and Mg by total oxide mass. In certain preferred embodiments, the composition has about 10% or less of metal oxides of Al, Fe and Mg by total oxide mass. In certain preferred embodiments, the composition has about 5% or less of metal oxides of Al, Fe and Mg by total oxide mass.

[0027] Each of these calcium silicate phases is suitable for carbonation with CO2. Hereafter, the discrete calcium silicate phases that are suitable for carbonation will be referred to as reactive phases.

[0028] The various reactive phases may account for any suitable portions of the overall reactive phases. In certain preferred embodiments, the reactive phases of CS are present at about 10 to about 60 wt% (e.g., about 15 wt% to about 60 wt%, about 20 wt% to about 60 wt%, about 25 wt% to about 60 wt%, about 30 wt% to about 60 wt%, about 35 wt% to about 60 wt%, about 40 wt% to about 60 wt%, about 10 wt% to about 50 wt%, about 10 wt% to about 40 wt%, about 10 wt% to about 30 wt%, about 10 wt% to about 25 wt%, about 10 wt% to about 20 wt%); C3S2 in about 5 to 50 wt% (e.g., about 10 wt% to 50 wt%, about 15 wt% to 50 wt%, about 20 wt% to 50 wt%, about 30 wt% to 50 wt%, about 40 wt% to 50 wt%, about 5 wt% to 40 wt%, about 5 wt% to 30 wt%, about 5 wt% to 25 wt%, about 5 wt% to 20 wt%, about 5 wt% to 15 wt%); and C2S in about 5 wt% to 60 wt% (e.g., about 10 wt% to about 60 wt%, about 20 wt% to about 60 wt%, about 25 wt% to about 60 wt%, about 30 wt% to about 60 wt%, about 35 wt% to about 60 wt%, about 40 wt% to about 60 wt%, about 5 wt% to about 50 wt%, about 5 wt% to about 40 wt%, about 5 wt% to about 30 wt%, about 5 wt% to about 25 wt%, about 5 wt% to about 20 wt%, about 5 wt% to about 20 wt%), and C in about 0 wt% to 3 wt% (e.g., 0 wt%, 1 wt% or less, 2 wt% or less, 3 wt% or less, about 1 wt% to 2 wt%, about 1 wt% to 3 wt%, about 2 wt% to 3 wt%).

[0029] In certain embodiments, the reactive phases comprise a calcium-silicate based amorphous phase, for example, at about 40% or more (e.g., about 45% or more, about 50% or more, about 55% or more, about 60% or more, about 65% or more, about 70% or more, about 75% or more, about 80% or more, about 85% or more, about 90% or more, about 95% or more) by mass of the total phases. It is noted that the amorphous phase may additionally incorporate impurity ions present in the raw materials.

[0030] The calcium silicate compositions of the invention are suitable for carbonation with CO2. In particular, the composition of calcium silicate is suitable for carbonation with CO2 at a temperature of about 30 °C to about 90 °C to form CaCO3 with mass gain of about 20% or more. The mass gain reflects the net sequestration of CO2 in the carbonated products. In certain preferred embodiments, the composition is suitable for carbonation with CO2 at a temperature of about 30 °C to about 90 °C (e.g., about 40 °C to about 90 °C, about 50 °C to about 90 °C, about 60 °C to about 90 °C, about 30 °C to about 80 °C, about 30 °C to about 70 °C, about 30 °C to about 60 °C, about 40 °C to about 80 °C, about 40 °C to about 70 °C, about 40 °C to about 60 °C) to form CaCO3 with mass gain of 10% or more (e.g., 15% or more, 20% or more, 25% or more, 30% or more).

[0031] Precursor calcium silicate compositions are typically used in powder form having a mean particle size (d50) of about 8 µm to about 25 µm, with 10% of particles (d10) sized below about 0.1 µm to about 3 µm, and 90% of particles (d90) sized above about 35 µm to about 100 µm.

[0032] In certain embodiments, the ratio of d90 : d10 is selected to allow improved powder flow or decreased water demand for casting. In certain embodiments, the ratio of d50 : d10 is selected to allow improved reactivity, improved packing, or decreased water demand for casting. In certain embodiments, the ratio of d90 : d50 is selected to allow improved the reactivity, improved packing, or decreased water demand for casting.

[0033] Any suitable filler particles may be used, for example, calcium oxide-containing or silica-containing materials. Exemplary filler particles include lime, quartz (including sand), wollastonite, xonotlite, burned oil shale, fly - or volcanic-ash, stack dust from kilns, ground clay, pumice dust. Materials such as industrial waste materials (e.g., fly ash, slag, silica fume) may also be used as fillers. In certain preferred embodiments, light-weight aggregates such as perlite or vermiculite may also be used as fillers. In certain preferred embodiments, filler particles are made from a calcium oxide-rich material such as ground lime.

[0034] The filler particles comprise calcium oxide or silica and have a particle size (d50) in the range from 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, from about 5 µm to about 200 µm, from about 10 µm to about 200 µm, from about 20 µm to about 200 µm, from about 50 µm to about 200 µm).

[0035] In certain embodiments, the filler particles are selected from fly ash, bottom ash, slag having 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 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, from about 0.5 µm to about 20 µm, from about 0.5 µm to about 10 µm, from about 0.5 µm to about 5 µm).

[0036] In certain embodiments, the filler particles are selected from limestone, miro-silica, and quartz having 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).

[0037] 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, from about 20 µm to about 100 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, from about 300 µm to about 500 µm).

[0038] In certain embodiments, the set-controlling admixture is selected from a gluconate and sucrose. In certain embodiments, the dispersing/viscosity-modifying agent is a polycarboxilate based material.

[0039] In exemplary embodiments, the ground calcium silicate is ground wollastonite, the filler particles comprises ground limestone, and silica, the activating-agent is ground lime, the set-controlling admixture is a gluconate, the viscosity-modifying agent is a polycarboxilate based material, and the aerating agent is aluminum paste.

[0040] It should be understood that, calcium silicate compositions, phases and methods disclosed herein can be adopted to use magnesium silicate phases in addition to calcium silicate phases. As used herein, the term "magnesium silicate" refers to naturally-occurring minerals or synthetic materials that are comprised of one or more of a groups of magnesium-silicon-containing compounds including, for example, Mg2SiO4 (also known as "fosterite") and Mg3Si4O10(OH)2 (also known as "talc"), which material may include one or more other metal ions and oxides (e.g., calcium, aluminum, iron or manganese oxides), or blends thereof, or may include an amount of calcium silicate in naturally-occurring or synthetic form(s) ranging from trace amount (1%) to about 50% or more by weight.

[0041] The hollow-core slabs of the invention can be manufactured to various sizes and dimensions in accordance with the appended claims. A typical hollow-core slab extrusion can be 300 (91 m) to 500 feet (152 m) long, even up to 1000 feet (305 m) long by 4 feet (122 cm) wide (not according to the invention) before cutting to smaller lengths used directly in construction of structures. A precast concrete box culvert (not according to the invention) can be as small as 2 feet (61 cm) by 3 feet (91 cm) or as large as 12 feet (366 cm) by 12 feet (366 cm). Box culvert wall thicknesses vary between 4 inches (10 cm) and 12 inches (30 cm). Precast concrete pipe (not according to the invention) can be as small as 1 foot (30 cm) in diameter with a wall thickness of 2 inches (5 cm) and up to 9 feet (274 cm) in diameter with a wall thickness of 10 inches (25 cm).

[0042] The one or more cores or channels, ducts or hollow spaces is an important feature and affects the overall characteristics and performance of a hollow core article, including overall weight, mechanical properties, and functionalities. The hollow core articles may have about 1 to about 10 or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10) ducts or channels as desired. The ducts or channels may take various shapes (e.g., circular, oval, polygonal, rectangular or square). The number, shape, size and configuration of the ducts and channels will impact various mechanical properties of the hollow core articles. As discussed in more details herein, the number, shape, size and configuration of the ducts and channels can also be utilized to the advantages of the manufacturing, for example, to speed up the curing process and to achieve more uniform curing.

[0043] The ducts or channels may account for any suitable fraction of the overall volume of the hollow core article dependent on the desired properties and applications at hand, for example, from about 5 vol.% to about 95 vol.% (e.g., from about 10 vol.% to about 95 vol.%, from about 20 vol.% to about 95 vol.%, from about 30 vol.% to about 95 vol.%, from about 50 vol.% to about 95 vol.%, from about 70 vol.% to about 95 vol.%, from about 5 vol.% to about 90 vol.%, from about 5 vol.% to about 70 vol.%, from about 5 vol.% to about 50 vol.%, from about 5 vol.% to about 30 vol.%, from about 5 vol.% to about 20 vol.%) of the overall volume of the hollow core article.

[0044] The hollow core slab is embedded with one or more reinforcement elements embedded in the body. The one or more reinforcement elements are selected from bars, wires or cables or combinations thereof. In certain embodiments, the one or more reinforcement bars are made of iron, steel, polymeric materials, glass, or a combination thereof. In certain preferred embodiments, the one or more reinforcement elements are pre-stressed.

[0045] Reinforcement elements are solid bars, wires or cables. The reinforcement elements may take any suitable physical dimensions, for examples, as a solid bar having a cross section from about ¼ inch (0.6 cm) to about 3 inches (8 cm) (e.g., from about ¼ inch (0.6 cm) to about 2 and ½ inches (6 cm), from about ¼ inch (0.6 cm) to about 2 inches (5 cm), from about ¼ inch (0.6 cm) to about 1 and ½ inches (4 cm), from about ¼ inch (0.6 cm) to about 1 inch (3 cm), from about ½ inch (1 cm) to about 3 inches (8 cm), from about 1 inch (3 cm) to about 3 inches (8 cm), from about 1 and ½ inches (4 cm) to about 3 inches (8 cm), from about 2 inches (5 cm) to about 3 inches (8 cm)) in diameter and up to about 40 feet (12 m) or more (e.g., about 50 feet (15 m), about 80 feet (24 m), about 100 feet (30 m), or more) in length, as a flexible cable with a cross section from about ¼ inch (0.6 cm) to 4 inches (10 cm) (e.g., from about ¼ inch (0.6 cm) to about 3 and ½ inches (9 cm), from about ¼ inch (0.6 cm) to about 3 inches (8 cm), from about ¼ inch (0.6 cm) to about 2 and ½ inches (6 cm), from about ¼ inch (0.6 cm) to about 2 inches (5 cm), from about ¼ inch (0.6 cm) to about 1 inch (3 cm), from about ½ inch (1 cm) to about 4 inches (10 cm), from about 1 inch (3 cm) to about 4 inches (10 cm), from about 1 and ½ inches (4 cm) to about 4 inches (10 cm), from about 2 inches (5 cm) to about 4 inches (10 cm), from about 3 inches (8 cm) to about 4 inches (10 cm)) in diameter and up to about 100 feet (30 m) or more (e.g., about 120 feet (37 m), about 150 feet (46 m), about 200 feet (61 m), or more) in length.

[0046] A cable may be a plurality of wires or filaments bundled together. The reinforcement elements may be made with materials of desired characteristics, for example, iron, steel, polymeric materials, glass, or a combination thereof. In certain preferred embodiments, the reinforcement elements are steel bars. In certain preferred embodiments, the reinforcement elements are steel cables. In certain preferred embodiments, the reinforcement elements are steel wires.

[0047] Chemical admixtures may also be included in the composite material; for example, plasticizers, retarders, accelerators, dispersants and other rheology-modifying agents. Certain commercially available chemical admixtures such as Glenium™ 7500 by BASF® Chemicals and Acumer™ by Dow Chemical Company may also be included. In certain embodiments, one or more pigments may be evenly dispersed or substantially unevenly dispersed in the bonding matrices, depending on the desired composite material. The pigment may be any suitable pigment including, for example, oxides of various metals (e.g., black iron oxide, cobalt oxide and chromium oxide). The pigment may be of any color or colors, for example, selected from black, white, blue, gray, pink, green, red, yellow and brown. The pigment may be present in any suitable amount depending on the desired composite material, for example in an amount ranging from about 0.0% to about 10% by weight.

[0048] In certain embodiments, the pigment may be evenly dispersed or substantially unevenly dispersed in the bonding matrices, depending on the desired composite material. The pigment may be any suitable pigment including, for example, oxides of various metals (e.g., black iron oxide, cobalt oxide and chromium oxide). The pigment may be of any color or colors, for example, selected from black, white, blue, gray, pink, green, red, yellow and brown. The pigment may be present in any suitable amount depending on the desired composite material, for example in an amount ranging from about 0.0% to about 10% by weight (e.g., about 0.0% to about 8%, about 0.0% to about 6%, about 0.0% to about 5%, about 0.0% to about 4%, about 0.0% to about 3%, about 0.0% to about 2%, about 0.0% to about 1%, about 0.0% to about 0.5%, about 0.0% to about 0.3%, about 0.0% to about 2%, about 0.0% to about 0.1%).

[0049] In another aspect, the invention relates to a process as defined in the appended claims for producing a hollow core slab.

[0050] The step of forming a mixture includes/involves mixing aggregates, sand, calcium silicate and water in a mixer. The mixer may be any mixer of a type typically used in mixing conventional concrete. Aggregates, sand and enough water to slightly wet the solids are thoroughly mixed. Next, calcium silicate is added to the batch along with the remaining water and any admixtures. The mixture is thoroughly mixed and the water adjusted to achieve the desired moisture level.

[0051] The step of casting or extruding the slurry mixture in a mold configured to generate a casted or extruded or otherwise formed body having one or more interior ducts or channels includes/involves pouring the mixture into the mold or the extrusion machine. For example, in the case of making a casting, the mixture may be vibrated by vibrating the mold or by inserting vibrating wands into the mixture within the mold in order to facilitate removal of entrapped air and promote particle rearrangement to densify the mixture. In the case of extrusion, the extruder may be fixed or moving. A fixed extruder pushes the mixture through channels that shape the mixture to the desired shape and promotes particle rearrangement to densify the article. The article is pushed out of the die within the extruder where upon it may be cut to a desired length and the article stacked for curing. A moving extruder pushes the mixture against a fixed stop and through channels that shape the mixture to the desired shape. As the mixture is pushed against the fixed stop the pressure increases within the mixture, particles rearrange and the mixture is densified. As more and more material is extruded the compacted mixture pushes the extruder along an extrusion bed.

[0052] The step of maintaining an atmosphere of CO2 and water vapor in the one or more interior ducts or channels includes/involves containing the atmosphere within the ducts or channels and/or around the exterior or the article; circulating the contained atmosphere of CO2 and/or water vapor; removing or adding water vapor to or from the contained atmosphere; and heating the contained atmosphere. To achieve rapid and/or uniform curing, the number, shape, size and configuration of the ducts and channels may be designed to increase the contact area of CO2 and water vapor with the wall of extruded body. Generally, temperature and concentration gradients will develop within the contained atmosphere and within the article itself as the curing proceeds. These gradients are recognized and controlled to achieve uniform curing of the article. The gas flow of CO2 and water vapor may be controlled, for example, such as to oscillate in opposite directions to reverse the gradients when passing through the interior ducts or channels and outside the exterior of the article so that the effect of the temperature and concentration gradients average out over the curing period.

[0053] The step of curing the casted or extruded body includes/involves contacting the article with an atmosphere of CO2 and water vapor for a period of time.

[0054] The curing temperature is in the range 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, from about 30°C to about 100°C, from about 30°C to about 90°C, from about 30°C to about 80°C, from about 30°C to about 70°C, from about 30°C to about 60°C) and the curing time is 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, for about 15 hours to about 60 hours, for about 15 hours to about 50 hours, for about 20 hours) under an atmosphere of water vapor and CO2.

[0055] The relative humidity environment of the curing process may be adjusted to fit the desired outcome, for example, ranging from about 10% to about 98% (e.g., from about 20% to about 98%, from about 30% to about 98%, from about 50% to about 98%, from about 80% to about 98%, from about 90% to about 98%, from about 10% to about 90%, from about 10% to about 70%, from about 10% to about 50%, from about 10% to about 40%, from about 10% to about 30%, from about 10% to about 20%). The CO2 pressure is ranging from about ambient atmospheric pressure to about 60 psi (410 kPa) above ambient, and having a CO2 concentration ranging from about 10% to about 90% and above (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%) to produce a composite material exhibiting a uniform, homogeneous, and porous structure.

[0056] In exemplary productions as in some embodiments of the invention, the materials used are ground calcium silicate.

[0057] The ground calcium silicate has a median particle size from about 1 µm to about 100 µm (e.g., about 1 µm to about 80 µm, about 1 µm to about 60 µm, about 1 µm to about 50 µm, 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, about 5 µm to about 70 µm, about 5 µm to about 60 µm, about 5 µm to about 50 µm, about 5 µm to about 40 µm, about 10 µm to about 80 µm, 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 µm, 10 µm, 15 µm, 20 µm, 25 µm, 30 µm, 40 µm, 50 µm, 60 µm, 70 µm, 80 µm, 90 µm, 100 µm), a bulk density from about 0.5 g/mL to about 3.5 g/mL (loose, e.g., 0.5 g/mL, 1.0 g/mL, 1.5 g/mL, 2.0 g/mL, 2.5 g/mL, 2.8 g/mL, 3.0 g/mL, 3.5 g/mL) and about 1.0 g/mL to about 1.2 g/mL (tapped), a surface area from about 1.5 m2/g to about 3.5 m2/g (e.g., 1.5 m2/g, 2.0 m2/g, 2.3 m2/g, 2.5 m2/g, 2.8 m2/g, 3.0 m2/g, 3.2 m2/g, 3.5 m2/g).

[0058] In certain preferred embodiments, the particulate composition comprises about 10 wt.% to about 95 wt.% of ground calcium silicate materials (e.g., about 20 wt.% to about 95 wt.%, about 30 wt. % to about 95 wt.%, about 50 wt.% to about 95 wt.%, about 60 wt.% to about 95 wt.%, about 20 wt.% to about 90 wt.%, about 20 wt.% to about 80 wt.%, about 20 wt.% to about 70 wt.%, about 30 wt.% to about 80 wt.%, about 50 wt.% to about 80 wt.%).

[0059] Thus, various combinations of curing conditions may be devised to achieve the desired production process, including varied reaction temperatures, pressures and lengths of reaction. In a first exemplary embodiment, water in liquid form along with CO2 gas is delivered to an article that has been pre-dried in a drying oven and the curing process is conducted at about 90°C and about 20 psig (i.e., 20 psi (140 kPa) above ambient pressure) for about 48 hours. In a second exemplary embodiment, water is present in the precursor material (e.g., as residual water from prior mixing step) and CO2 gas is delivered to an article and the curing process is performed at about 60°C and 0 psig (at ambient atmospheric pressure) for about 19 hours. In a third exemplary embodiment, water is delivered to an article in vapor form along with CO2 and the curing process is performed at about 90°C and 20 psig (20 psi (140 kPa) above ambient atmospheric pressure) for about 19 hours.

[0060] It is noted that the properties, production time and scale of the article can be fine tuned based on the disclosures herein, for example, by adjusting curing techniques (e.g., CO2 delivery, system pressure and temperature) as well as mixture proportions and constituents.

[0061] In addition to the materials used and the manufacturing process offering favorable environmental and economical benefits, the hollow-core slabs of the invention provide a number of benefits in performance over the hollow-core products made from conventional concrete, for example, superior stable properties are achievable in much shorter times than is the case for precast concrete articles made using ordinary Portland cement.

Bonding Elements, Bonding Matrices and Composite Materials


Chemical Discussion



[0062] This invention provides apparatus and methods used to manufacture novel composite materials that are cured predominantly by a CO2 consumption reaction. The materials exhibit useful properties and can be readily produced from widely available, low cost precursor materials by a process suitable for large-scale production with minimal environmental impact. The precursor materials include inexpensive and abundant calcium silicate rich compositions, fine particles and coarse particles. The calcium silicate compositions may be comprised of a ground product containing a variety of calcium silicate phases (including, for example, CS, C3S2, C2S and a calcium silicate based amorphous phase). The fine and coarse particles may be comprised of ground limestone or other calcium carbonate based materials, ground quartz or other SiO2 based materials, sand and crushed rock. The fine and coarse particles may also be comprised of crushed minerals such as granite, mica and feldspar. Other process components include water and CO2. Various additives can be used to modify and fine-tune the physical appearance and/or mechanical properties of the resulting composite material, such as additives selected from one or more of pigments (e.g., black iron oxide, cobalt oxide and chromium oxide), colored glass and/or colored quartz. Additives regarding water usage reduction and changes in rheology can also be used.

[0063] The composite materials can be produced, as disclosed herein, using the energy-efficient Hydrothermal Liquid Phase Sintering (HLPS) process to create bonding elements which hold together the various components of the composite material. The composite materials can be manufactured at low cost and with favorable environmental impact. For example in preferred embodiments of the invention, CO2 is used as a reactive species resulting in sequestration of CO2 and the creation of bonding elements in the produced composite materials with in a carbon footprint unmatched by any existing production technology. The HLPS process is thermodynamically driven by the free energy of the chemical reaction(s) and reduction of surface energy (area) caused by crystal growth. The kinetics of the HLPS process proceed at a reasonable rate at low temperature because a solution (aqueous or nonaqueous) is used to transport reactive species instead of using a high melting point fluid or high temperature solid-state medium.

[0064] Discussions of various features of HLPS can be found in U.S. Patent No. 8,114,367, U.S. Pub. No. US 2009/0143211 (Appl. Serial No. 12/271,566), U.S. Pub. No. US 2011/0104469 (Appl. Serial No. 12/984,299), U.S. Pub. No. 2009/0142578 (Appl. Serial No. 12/271,513), U.S. Pub. No. 2013/0122267 (Appl. Serial No. 13/411,218), U.S. Pub. No. 2012/0312194 (Appl. Serial No. 13/491,098), WO 2009/102360 (PCT/US2008/083606), WO 2011/053598 (PCT/US2010/054146), WO 2011/090967 (PCT/US2011/021623), U.S. Provisional Patent Application No. 61/708,423 filed October 1, 2012, and U.S. Patent Application Nos. 14/045,758, 14/045,519, 14/045,766, 14045540, all filed October 3, 2013, U.S. Patent Application Nos. 14/207,413, 14/207,421, filed March 12, 2014, U.S. Patent Application Nos. 14/207,920, 14/209,238, filed March 13, 2014, U.S. Patent Application Nos. 14/295,601, 14/295,402, filed June 4, 2014.

[0065] As used herein, the term "calcium silicate composition" refers to naturally-occurring minerals or synthetic materials that are comprised of one or more of a group of calcium-silicon-containing compounds including CS (wollastonite or pseudowollastonite, and sometimes formulated CaSiO3 or CaO·SiO2), C3S2 (rankinite, and sometimes formulated as Ca3Si2O7 or 3CaO·2SiO2), C2S (belite, β-Ca2SiO4 or larnite, β-Ca2SiO4 or bredigite, α-Ca2SiO4 or γ-Ca2SiO4, and sometimes formulated as Ca2SiO4 or 2CaO·SiO2), a calcium silicate rich amorphous phase, each of which materials may include one or more other metal ions and oxides (e.g., aluminum, magnesium, iron or manganese oxides), or blends thereof, or may include an amount of magnesium silicate in naturally-occurring or synthetic form(s) ranging from trace amount (1%) to about 50% or more by weight. FIG. 1 through FIG. 8 are phase diagrams that show various phase interrelationships among some of the materials described.

[0066] It should be understood that, compositions and methods disclosed herein can be adopted to use magnesium silicate phases in addition to calcium silicate phases. As used herein, the term "magnesium silicate" refers to naturally-occurring minerals or synthetic materials that are comprised of one or more of a groups of magnesium-silicon-containing compounds including, for example, Mg2SiO4 (also known as "fosterite"), Mg3Si4O10(OH)2) (also known as "Talc"), and CaMgSiO4 (also known as "monticellite"), each of which materials may include one or more other metal ions and oxides (e.g., calcium, aluminum, iron or manganese oxides), or blends thereof, or may include an amount of calcium silicate in naturally-occurring or synthetic form(s) ranging from trace amount (1%) to about 50% or more by weight.

[0067] The term "quartz", as used herein, refers to any SiO2-based material, including common sands (construction and masonry), as well as glass and recycled glass. The term also includes any other recycled natural and synthetic materials that contain significant amounts of SiO2 (e.g., mica sometimes formulated as KAl2(AlSi3O10)(OH)2.

[0068] In certain preferred embodiments, the plurality of bonding elements are prepared by chemical transformation from ground calcium silicate compositions by reacting them with CO2 via a gas-assisted HLPS process.

[0069] In certain embodiments, the composite material is characterized by a compressive strength from about 90 MPa to about 175 MPa (e.g., about 90 MPa to about 150 MPa, about 90 MPa to about 140 MPa, about 90 MPa to about 130 MPa, about 90 MPa to about 120 MPa, about 90 MPa to about 110 MPa, about 100 MPa to about 175 MPa, about 120 MPa to about 175 MPa, about 130 MPa to about 175 MPa, about 140 MPa to about 175 MPa, about 150 MPa to about 175 MPa, about 160 MPa to about 175 MPa).

[0070] In certain embodiments, the composite material is characterized by a flexural strength from about 5 MPa to about 30 MPa (e.g., about 5 MPa to about 25 MPa, about 5 MPa to about 20 MPa, about 5 MPa to about 15 MPa, about 5 MPa to about 10 MPa, about 10 MPa to about 30 MPa, about 20 MPa to about 30 MPa, about 25 MPa to about 30 MPa).

[0071] In certain embodiments, the composite material is characterized by water absorption of less than about 10% (e.g., less than about 8%, 5%, 4%, 3%, 2%, or 1%).

[0072] The composite material may display one or more of desired textures, patterns and physical properties, in particular those that are characteristic of natural stone. In certain preferred embodiments, the composite material exhibits a visual pattern similar to natural stone. Other characteristics include colors (e.g., black, white, blue, pink, grey (pale to dark), green, red, yellow, brown, cyan (bluish-green) or purple) and textures.

Equipment and Processing Discussion


CO2 Control



[0073] In the embodiments described, industrial grade CO2 at about 99% purity is used, which is provided by a variety of different industrial gas companies, such as Praxair, Inc., Linde AG, Air Liquide, and others. This supply can be held in large pressurized holding tanks in the form of liquid carbon dioxide regulated at a temperature such that it maintains a vapor gauge pressure of approximately 300 PSI (2070 kPa). This gas is then piped to a CO2 curing enclosure or chamber. In the simplest system, CO2 is flowed through the enclosure at a rate sufficient to displace the ambient air in the enclosure. In general, the purge time will depend on the size of the enclosure and the rate that CO2 gas is provided. In many systems, this process of purging the enclosure of air can be performed in times measured in minutes to get the CO2 concentration up to a reasonable level so that curing can be performed thereafter. In simple systems, CO2 gas is then fed into the system at a predefined rate so s to maintain a concentration of CO2 sufficient to drive the curing reaction.

[0074] As an example, we now describe a method for sustaining carbon dioxide concentrations during the reaction that is well suited for keeping a highly consistent concentration, although it is a "closed loop" process which tends to be the most expensive technique. This method uses the measurement of CO2 concentration in the system directly, and employs a controller such as a PLC to control the CO2 concentration at a set point with an electronic/automated control valve. A measurement technique to measure CO2 directly such as NDIR should preferably be employed. In the NDIR measurement method, a gas sample stream is pulled from the system via a low flow pump. A chiller is used to drop moisture out of the gas stream before it is sampled by the NDIR instrument. Therefore the measurement provided by the analyzer is missing the water vapor component of the gas stream and needs be adjusted to account for the humidity that has been removed from the test sample. A measurement of the humidity in the system gas flow can be performed using a dry bulb-wet bulb psychrometric technique, using a dry bulb-wet bulb humidity measurement device or using a different type of moisture sensor. The true CO2 concentration can be calculated using the computer control system or PLC. Once the true CO2 concentration is known, the actuated proportioning control valve can add dry CO2 into the system when it has been consumed and has gone below the set point that is desired at that time. In various embodiments, the set point can vary with time, if necessary, based on experience in curing specific compositions, shape and sizes of composite material specimens.

Humidity Control



[0075] FIG. 9 is a schematic diagram of a CO2 composite material curing chamber that provides humidification according to principles of the invention. In FIG. 9, a water supply is provided and water vapor is added to the atmosphere that is circulating within the curing chamber. The water can be any convenient source of potable water. In some embodiments, ordinary tap water is used. In some embodiments, the water can be converted to vapor by flowing through a misting nozzle or an atomizing spray nozzle, an electric vapor generator, a gas fired vapor generator, or by being heated above the gas temperature in the chamber so as to cause evaporation from a liquid water supply an example being a drum reactor with an immersion heater. In yet another embodiment, the CO2 supply can be flowed into the systems after having been bubbled through a heated water supply in order to increase relative humidity of the incoming gas stream an example being a drum reactor configured for "flow through" or "open loop" processing.

[0076] Relative humidity is an important parameter in both traditional concrete curing as well as in CO2 composite material curing. In a traditional curing chamber a moist air atmosphere exists that is comprised of mostly nitrogen, oxygen, and water vapor. In these systems relative humidity is most often measured by a standard capacitive sensor technology. However, CO2 curing chambers have a gas atmosphere comprised predominately of carbon dioxide that is incompatible with some types of these sensors. Sensing technology such as dry-bulb wet-bulb techniques that utilize the psychrometric ratios for carbon dioxide and water vapor or dipole polarization water vapor measurement instruments or chilled mirror hygrometers or capacitive humidity sensors can be used in the CO2 composite material curing systems described herein.

[0077] Depending on the type and geometry of the product being cured, the design of the chamber, and the packing efficiency of product in the chamber the humidity may need to be either decreased or increased and regulated to a specified set point. Set points may range anywhere from 1% to 99% relative humidity. Three different methods for humidity control may exist in CO2 composite material curing processes that could be combined into a single system. One method for humidification in one embodiment of a CO2 curing system is represented in FIG. 9. Another method allows one to remove moisture from the system to cure the composite material products with CO2. A simple method of reducing the relative humidity is by displacing the humid gas in the system with a dry gas, such as carbon dioxide. In still another embodiment, one can reduce relative humidity and therefore remove water vapor from the gas by a non-purging method, which in one preferred embodiment is a chilled heat exchanger that performs water extraction.

[0078] FIG. 10 is a schematic diagram of a curing chamber with multiple methods of humidity control as well as ability to control and replenish CO2 using constant flow or pressure regulation and that can control the temperature according to principles of the invention. This system is an example of a system that can provide closed loop control or control using feedback, in which set values of operating parameters such as CO2 concentration, humidity, and temperature that are desired at specific times in the process cycle are provided, and measurements are taken to see whether the actual value of the parameter being controlled is the desired value. If deviation from the desired value is measured, corrective action is taken to bring the value of the parameter into agreement with the desired value. Such control systems can be expensive and complex, and may be useful with regard to high value products or products that require very precise process conditions.

Temperature Control



[0079] In some embodiments, temperature is measured utilizing a sensor such as a thermocouple or an RTD. The measurement signal is directed back to a controller or computer that is able to regulate energy into the heat exchanger and thereby adjust the temperature of the entire system over time. The blower is an important component of the heating system as it is able to help transfer the heat energy to the gas which transfers to the products and the chamber itself which is an important part of controlled moisture of the samples. The method of heating can be electric or gas fired. Jacket heaters may be utilized to control the temperature of the CO2 that flows through a chamber in contact with the heating jacket, any convenient source of heat can be used. The means of external heating may include but are not limited to electric heating, hot water heating, or hot oil heating. For CO2 curing chambers indirect gas fired systems have been utilized thus far and direct fired gas burners have been avoided because they will pull air and products of combustion into the system, thereby diluting the CO2 and making control of the CO2 concentration problematic. Some smaller scale systems such as the Drum Reactors utilize electric jacket heaters to heat the entire surface of the chamber rather than a heating element within the chamber.

Gas Flow Control



[0080] Another control parameter is gas velocity across the material that is to be cured in the system. The gas velocity can be very dependent on process equipment variables including but not limited to chamber design, baffle design, fan size, fan speed/power, number of fans, temperature gradient within the system, rack design within the system, and sample geometry within the system. The simplest method to control the gas velocity within the chamber is by adjusting the blower speed (RPM's), typically done by utilization of a variable frequency drive to allow for control of the blower motor speed. The blower can be used to circulate gas at a desired velocity in the curing chamber. Gas velocity in the system is measured in the system via a variety of different techniques including but not limited to pitot tubes measurement and laser Doppler detection systems. The measurement signal for gas velocity can be sent back to a computer system or programmable logic controller and be utilized as a control parameter in the curing profile.

Process of Preparing a Composite Material



[0081] The process for preparing the hollow core slab according to the invention is described in claim 8.

[0082] The particulate composition includes a ground calcium silicate composition having a mean particle size in the range from about 1 µm to about 100 µm. In addition the particulate composition may include a ground calcium carbonate or a SiO2 bearing material having a mean particle size in the range from about 3 µm to about 25 mm. The liquid composition includes water and may include a water-soluble dispersant.

[0083] The process can further include, before curing the casted mixture, the step of drying the casted mixture. The particulate composition further comprises a pigment or a colorant as discussed herein.

[0084] In certain embodiments, curing the formed slurry mixture is performed at a temperature in the range from about 30°C to about 120°C for about 1 hour to about 70 hours under a vapor comprising water and CO2 and having a pressure in the range from about ambient atmospheric pressure to about 30 psi (210 kPa) above ambient atmospheric pressure.

[0085] In certain embodiments, curing the formed slurry mixture is performed at a temperature in the range from about 60°C to about 110°C for about 1 hour to about 70 hours under a vapor comprising water and CO2 and having a pressure in the range from about ambient atmospheric pressure to about 30 psi (210 kPa) above ambient atmospheric pressure.

[0086] In certain embodiments, curing the formed slurry mixture is performed at a temperature in the range from about 80°C to about 100°C for about 1 hour to about 60 hours under a vapor comprising water and CO2 and having a pressure in the range from about ambient atmospheric pressure to about 30 psi (210 kPa) above ambient atmospheric pressure.

[0087] The ground calcium silicate composition has a mean particle size from about 1 µm to about 100 µm (e.g., about 1 µm, 10 µm, 15 µm, 20 µm, 25 µm, 30 µm, 40 µm, 50 µm, 60 µm, 70 µm, 80 µm, 90 µm, 100 µm), a bulk density from about 0.5 g/mL to about 3.5 g/mL (loose, e.g., 0.5 g/mL, 1.0 g/mL, 1.5 g/mL, 2.0 g/mL, 2.5 g/mL, 2.8 g/mL, 3.0 g/mL, 3.5 g/mL) and about 1.0 g/mL to about 1.2 g/mL (tapped), a Blaine surface area from about 150 m2/kg to about 700 m2/kg (e.g., 150 m2/kg, 200 m2/kg, 250 m2/kg, 300 m2/kg, 350 m2/kg, 400 m2/kg, 450 m2/kg, 500 m2/kg, 550 m2/kg, 600 m2/kg, 650 m2/kg, 700 m2/kg).

[0088] In certain preferred embodiments, the liquid composition includes water and a water-soluble dispersant comprising a polymer salt (e.g., an acrylic homopolymer salt) having a concentration from about 0.1% to about 2% w/w of the liquid composition.

[0089] Composite materials prepared according to a process disclosed herein can exhibit a compressive strength from about 3.0 MPa to about 30.0 MPa (e.g., about 3 MPa, 5 MPa, 10 MPa, 15 MPa, 20 MPa, 25 MPa, 30 MPa) and a flexural strength from about 0.3 MPa to about 4.0 MPa (e.g., about 0.3 MPa, 0.5 MPa, 1.0 MPa, 1.5 MPa, 2.0 MPa, 2.5 MPa, 3.0 MPa, 3.5 MPa, 4.0 MPa).

[0090] Any suitable precursor materials may be employed including, for example, calcium silicate composition particles formed from CS (wollastonite or pseudowollastonite, and sometimes formulated CaSiO3 or CaO·SiO2), C3S2 (Rankinite, and sometimes formulated as Ca3Si2O7 or 3CaO·2SiO2), C2S (belite , β-Ca2SiO4 or larnite, β-Ca2SiO4 or "bredigite, α-Ca2SiO4 or γ-Ca2SiO4, and sometimes formulated as Ca2SiO4 or 2CaO·SiO2), and a calcium silicate rich amorphous phase. It is believed that calcium cations are leached from the calcium silicate composition particles and transform the peripheral portion of the calcium silicate composition particle into calcium-deficient state. As the calcium cations continue to be leached from the peripheral portion of the particle, the structure of the peripheral portion eventually become unstable and breaks down, thereby transforming the calcium-deficient peripheral portion of the particle into a predominantly silica-rich first layer. Meanwhile, a predominantly calcium carbonate second layer precipitates from the water.

[0091] More specifically, the first layer and second layer may be formed from the precursor particle according the following reactions (1-3) which can use water as a reaction medium, and not as a reagent (that is, the water is not consumed):

        CaSiO3 (s) + CO2 (g) → CaCO3 (s) + SiO2 (s)     (1)

        Ca3Si2O7 (s) + 3CO2 (g) → 3CaCO3 (s) + 2SiO2 (s)     (2)

        Ca2SiO4 (s) + 2CO2 (g) → 2CaCO3 (s) + SiO2 (s)     (3)



[0092] For example, in a silicate mineral carbonation reaction such as with calcium silicate compositions, CO2 is introduced as a gas phase that dissolves into an infiltration fluid, such as water. The dissolution of CO2 forms acidic carbonic species (such as carbonic acid, H2CO3) that results in a decrease of pH in solution. The weakly acidic solution incongruently dissolves calcium species from the calcium silicate phases. Calcium may be leached from calcium containing amorphous phases through a similar mechanism. The released calcium cations and the dissociated carbonate species lead to the precipitation of insoluble carbonates. Silica-rich layers are thought to remain on the mineral particles as calcium depleted layers.

[0093] Thus, according to a preferred embodiment of the invention, CO2 preferentially reacts with the calcium cations of the calcium silicate composition precursor core, thereby transforming the peripheral portion of the precursor core into a silica-rich first layer and a calcium carbonate-rich second layer. Also, the presence of the first and second layers on the core act as a barrier to further reaction between calcium silicate and carbon dioxide, resulting in the bonding element having the core, first layer and second layer.

[0094] In some embodiments, silicate materials having other metals in addition to Ca, for example fosterite (Mg2SiO4), diopside (CaMgSi2O6), and talc (Mg3Si4O10(OH)2) can react with carbon dioxide dissolved in water in a manner similar to the reaction of calcium silicate, as described above. It is believed that such silicate materials can be used in combination with calcium silicate, as precursors for bonding elements according to principles of the invention.

[0095] Preferably, gas-assisted HLPS processes utilize partially infiltrated pore space so as to enable gaseous diffusion to rapidly infiltrate the porous preform and saturate thin liquid interfacial solvent films in the pores with dissolved CO2. CO2-based species have low solubility in pure water (1.5 g/L at 25 °C, 1 atm.). Thus, a substantial quantity of CO2 must be continuously supplied to and distributed throughout the porous preform to enable significant carbonate conversion. Utilizing gas phase diffusion offers a huge (about 100-fold) increase in diffusion length over that of diffusing soluble CO2 an equivalent time in a liquid phase. ("Handbook of chemistry and physics", Editor: D. R. Lide, Chapters 6 and 8, 87th Edition 2006-2007, CRC.) This partially infiltrated state enables the reaction to proceed to a high degree of carbonation in a fixed period of time.

[0096] Liquid water in the pores speeds up the reaction rate because it provides a medium for ionization of both carbonic acid and calcium species. However, water levels need to be low enough such that CO2 gas can diffuse into the porous matrix prior to dissolution in the pore-bound water phase. Furthermore, the actively dissolving porous preform serves as a template for expansive reactive crystal growth. Thus, the bonding element and matrices can be formed with minimal distortion and residual stresses. This enables large and complex shapes to result, such as those needed for infrastructure and building materials, in addition to many other applications.

[0097] Thus, various combinations of curing conditions may be devised to achieve the desired production process, including varied reaction temperatures, pressures and lengths of reaction.

[0098] In an exemplary embodiment, water is present in the precursor material (e.g., as residual water from prior mixing step) and water vapor is provided to precursor materials (e.g., to maintain water level and/or control the loss of water from evaporating) along with CO2 and the curing process is performed at about 25 to 90°C and 0 psig (at ambient atmospheric pressure) for about 2 to 72 hours.

[0099] The time required for curing of a composite material object is determined by the ability of water vapor and CO2 gas to diffuse throughout the object. In general, thicker objects take longer to cure than thinner objects. Similarly, objects with high density (and fewer open pore spaces) take longer to cure than objects with low density (and more open pore spaces). The following table provides examples of how the curing times may vary with respect to the smallest thickness (or wall thickness or section thickness) of the three dimensions and the bulk density of an object that is being manufactured.
Table 1. Examples of Curing Times and Smallest Thickness
Composite Material Smallest Thickness (mm)Composite Material Bulk Density (g/cm3)Approximate Curing Time (h)
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 Manufactured Microstructures



[0100] As schematically illustrated in FIGs. 11(a) - 11(c), a bonding element includes a core (represented by the black inner portion), a first layer (represented by the white middle portion) and a second or encapsulating layer (represented by the outer portion). The first layer may include only one layer or multiple sub-layers and may completely or partially cover the core. The first layer may exist in a crystalline phase, an amorphous phase or a mixture thereof, and may be in a continuous phase or as discrete particles. The second layer may include only one layer or multiple sub-layers and may also completely or partially cover the first layer. The second layer may include a plurality of particles or may be of a continuous phase, with minimal discrete particles.

[0101] A bonding element may exhibit any size and any regular or irregular, solid or hollow morphology depending on the intended application. Exemplary morphologies include: cubes, cuboids, prisms, discs, pyramids, polyhedrons or multifaceted particles, cylinders, spheres, cones, rings, tubes, crescents, needles, fibers, filaments, flakes, spheres, sub-spheres, beads, grapes, granulars, oblongs, rods, ripples, etc.

[0102] In general, as discussed in greater detail herein, a bonding element is produced from reactive precursor materials (e.g., precursor particles) through a transformation process. The precursor particles may have any size and shape as long as they meet the needs of the intended application. The transformation process generally leads to the corresponding bonding elements having similar sizes and shapes of the precursor particles.

[0103] Within the bonding matrix, the bonding elements may be positioned, relative to each other, in any one of a number of orientations. FIGs. 12(a) - 12(f) schematically illustrate an exemplary bonding matrix that includes fiber- or platelet- shaped bonding elements in different orientations possibly diluted by the incorporation of filler material, as represented by the spacing between the bonding elements. FIG. 12(a), for example, illustrates a bonding matrix that includes fiber-shaped bonding elements aligned in a one-direction ("1-D") orientation (e.g., aligned with respect to the x direction). FIG. 12(b) illustrates a bonding matrix that includes platelet-shaped bonding elements aligned in a two-direction ("2-D") orientation (e.g., aligned with respect to the x and y directions). FIG. 12(c) illustrates a bonding matrix that includes platelet-shaped bonding elements aligned in a three-direction ("3-D") orientation (e.g., aligned with respect to the x, y and z directions). FIG. 12(d) illustrates a bonding matrix that includes platelet-shaped bonding elements in a random orientation, wherein the bonding elements are not aligned with respect to any particular direction. FIG. 12(e) illustrates a bonding matrix that includes a relatively high concentration of platelet-shaped bonding elements that are aligned in a 3-D orientation. FIG. 12(f) illustrates a bonding matrix that includes a relatively low concentration of platelet- shaped bonding elements that are situated in a random orientation (a percolation network). The composite material of FIG. 12(f) achieves the percolation threshold because a large proportion of the bonding elements are touching one another such that a continuous network of contacts are formed from one end of the material to the other end. The percolation threshold is the critical concentration above which bonding elements show long-range connectivity with either an ordered, e.g., FIG. 12(e), or random orientation, e.g., FIG. 12(f), of bonding elements. Examples of connectivity patterns can be found in, for example, Newnham, et al., "Connectivity and piezoelectric-pyroelectric composites", Mat. Res. Bull. Vol. 13, pp. 525-536, 1978).

[0104] The plurality of bonding elements may be chemically transformed from any suitable precursor materials, for example, from any suitable calcium silicate composition precursor. The precursor calcium silicate composition may also include one or more chemical elements of aluminum, magnesium and iron.

[0105] The plurality of bonding elements may have any suitable mean particle size and size distribution dependent on the desired composite material. In certain embodiments, the plurality of bonding elements have a mean particle size in the range of about 1 µm to about 100 µm (e.g., about 1 µm to about 80 µm, about 1 µm to about 60 µm, about 1 µm to about 50 µm, 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, about 5 µm to about 70 µm, about 5 µm to about 60 µm, about 5 µm to about 50 µm, about 5 µm to about 40 µm, about 10 µm to about 80 µm, 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).

[0106] The composite material includes: a plurality of bonding elements and a plurality of filler particles. Each bonding element includes: a core comprising primarily calcium silicate composition, a silica-rich first or inner layer, and a calcium carbonate-rich second or outer layer. The plurality of bonding elements and the plurality of filler particles together form one or more bonding matrices and the bonding elements and the filler particles are substantially evenly dispersed therein and bonded together, whereby the composite material exhibits one or more textures, patterns and physical properties.

[0107] The plurality of filler particles may have any suitable mean particle size and size distribution. In certain embodiments, the plurality of filler particles has a mean particle size in the range from about 5 µm to about 7 mm (e.g., about 5 µm to about 5 mm, about 5 µm to about 4 mm, about 5 µm to about 3 mm, about 5 µm to about 2 mm, about 5 µm to about 1 mm, about 5 µm to about 500 µm, about 5 µm to about 300 µm, about 20 µm to about 5 mm, about 20 µm to about 4 mm, about 20 µm to about 3 mm, about 20 µm to about 2 mm, about 20 µm to about 1 mm, about 20 µm to about 500 µm, about 20 µm to about 300 µm, about 100 µm to about 5 mm, about 100 µm to about 4 mm, about 100 µm to about 3 mm, about 100 µm to about 2 mm, about 100 µm to about 1 mm).

[0108] In certain preferred embodiments, the filler particles are made from a calcium carbonate-rich material such as limestone (e.g., ground limestone). In certain materials, the filler particles are made from one or more of SiO2-based or silicate-based material such as quartz, mica, granite, and feldspar (e.g., ground quartz, ground mica, ground granite, ground feldspar).

[0109] In certain embodiments, filler particles may include natural, synthetic and recycled materials such as glass, recycled glass, coal slag, calcium carbonate-rich material and magnesium carbonate-rich material.

[0110] The weight ratio of (bonding elements : filler particles) may be any suitable ratios dependent on the desired composite material, for example, in the range of about (10 to 50) : about (50 to 90).

[0111] In certain embodiments, these composite materials may display various patterns, textures and other characteristics, such as visual patterns of various colors. In addition, the composite materials of the invention exhibit compressive strength, flexural strength and water absorption properties similar to conventional concrete or the corresponding natural materials.

[0112] In certain embodiments, the composite further includes a pigment. The pigment may be evenly dispersed or substantially unevenly dispersed in the bonding matrices, depending on the desired composite material. The pigment may be any suitable pigment including, for example, oxides of various metals (e.g., iron oxide, cobalt oxide, chromium oxide) The pigment may be of any color or colors, for example, selected from black, white, blue, gray, pink, green, red, yellow and brown. The pigment may be present in any suitable amount depending on the desired composite material, for example in an amount ranging from about 0.0% to about 10% by weight (e.g., about 0.0% to about 8%, about 0.0% to about 6%, about 0.0% to about 5%, about 0.0% to about 4%, about 0.0% to about 3%, about 0.0% to about 2%, about 0.0% to about 1%, about 0.0% to about 0.5%, about 0.0% to about 0.3%, about 0.0% to about 2%, about 0.0% to about 0.1%,).

Examples


Example 1: Curing a hollow-core slab using the desorption isotherm method


Mixing



[0113] A Sicoma TO8 Series planetary mixer (model MP 250/375 WWWSW) was used for mixing the components of the concrete mix design. The planetary speed was 18.5 RPM. Filler material in the form of 293.8 kg of ¼" (0.6 cm) Aggregate and 160.3 Kg of sand were dry-mixed for 90 seconds. Five Kg of water, 168 g of Glenium 7500 admixture (BASF) and 120 g of air entrainment admixture were added to the dry-mix and the combination mixed for an additional 90 seconds. Binder in the form of 80.1 Kg of Solidia cement (Solidia Technologies) (4% Pseudowollastonite, 19% Wollastonite, 13% Larnite, 2% Calcite and 62% amorphous oxides) was added to the wet material in the mixer along with an additional 16 Kg of water. The combination was mixed for an additional 90 seconds. The final moisture content of the mixture was found to be 3.68% as measured with a Sartorius MA100 moisture analyzer. A total of three such batches were transferred to an extruder for extrusion of a hollow-core slab. Extrusion:

[0114] Two 40' (12 m) long by 3/8" (1 cm) diameter steel cables (low relaxation 7-wire strand, Sumiden Wire Products Corp.) were tensioned to an elongation of 3" (8 cm) along the length of the steel extrusion bed. The cables were placed such as to locate one of them symmetrically between the slab bottom and cores 1 and 2; and the other symmetrically between the slab bottom and cores 5 and 6.

[0115] A hollow-core slab was extruded on the steel bed by a commercial Elematic EL 600/8 extrusion machine using an auger speed of 55 RPM. The extruded slab was 18 feet (5 m) long by 4 feet (1 m) wide by 8 inches (20 cm) high and contained six (6" diameter (15 cm)) hollow cores. Adjacent cores were separated by a 1.25" (3.18 cm) thick wall. FIG. 13 shows a picture of the hollow-core slab.

Curing



[0116] FIG. 14 is a schematic drawing of the curing apparatus. The bed was heated by circulating hot water through pipes within the steel bed during the cure. The temperature of the heating water was maintained by a gas-fired boiler held at 81°C. The temperature at the top surface of the steel bed was around 49°C. Cold water from a chiller (maintained at 10°C) was circulated through the condenser to remove moisture from the circulating gas stream. An electric heater (3.75 kW) was maintained at 87°C to heat the dried circulating gas stream before it returns to the curing chamber. The speed of the circulation blower was controlled by a variable frequency drive. The initial blower speed was 30 Hz. Dry CO2 was supplied on demand to the curing system through an Alicat mass flow controller. The curing chamber comprised the steel extrusion bed and a polyethylene sheet, which functioned as a canopy and separated the CO2/H2O stream from the ambient atmosphere. The canopy covered the hollow-core slab and was stretched between support walls at each end of the slab. The canopy was sealed along the steel extrusion bed and to the end walls with magnetic strips and was inflated by the circulating gas stream. The differential pressure between the inside and the outside of the canopy was maintained slightly above atmospheric pressure (Differential Pressure = +0.2 inches (0.5 cm)-of-water-column). Each end wall of curing chamber had the same cross sectional shape as the slab except that the walls were 9.25" (23.5 cm) rather than 8" (20 cm) high. Each end wall served as the front of rectangular box forming a chamber with 1 gas entrance port opposite 6 holes through which gas entered or exited the curing chamber. The 6 holes were covered with a perforated metal sheet so that the end chamber acted as a plenum that functioned to distribute and smooth the gas flow into the curing chamber. One of the two ports belonging to a differential pressure transmitter was inserted through one end wall into the curing chamber. The other port was left open to the ambient atmosphere. The sampling probe of a NDIR CO2 meter was inserted through the end wall at the other end of the curing chamber to monitor the CO2 concentration in the chamber throughout the curing run. Two Vaisala Humidity/Temperature probes were placed within the curing chamber, one at each end just inside the end walls.

[0117] The curing chamber was purged for 10 minutes with CO2 gas. The gas circulation was reversed every 60 minutes during the curing run. The blower speed was reduced to 15 Hz at 90 minutes into the cure, and then increased to 45 Hz at 209 minutes into the cure where it remained until the curing run was terminated at 490 minutes.

[0118] FIG. 15 shows the chamber humidity measured at the end walls by the Vaisala sensors throughout the cure as well as the cumulative amount of condensed water collected throughout the run.

[0119] The strength of the hollow-core slab was estimated using a rebound hammer at 44 points on the top surface of the slab. The rebound measures indicated an average compressive strength of 30 MPa.

Example 2: Curing a hollow-core casting using the adsorption isotherm method (not according to the invention)


Mixing



[0120] The mix design consisted of six solid components: (1) 3/8" (1 cm) aggregate, 29% (2) ¼" (0.6 cm) aggregate, 15% (3) 2mm crushed quartz, 12% (4) construction sand, 20% (5) marble white 200, 11% and (6) NYCO 400 wollastonite 13%. The components were "dry" mixed in a Kercher Industries 12" (30 cm) lab-scale mixer for 2 minutes. Water (570 g) with gum additive was added to the dry components and the resulting mixture mixed an additional 4 minutes. More water (265g) was added and the mixture mixed an additional 4 minutes. Finally, more water (260g) was added and the mixture mixed an additional 2 minutes.

Casting



[0121] The wet mixture was cast in a 4" (10 cm) x 4" (10 cm) x 20" (50 cm) rectangular mold with the long dimension placed horizontally. A 2" (5 cm) diameter x 20" (50 cm) long pvc pipe that had be wrapped in waxed paper was secured in the center of the mold so as to form a 2" (5 cm) diameter core along the length of the casting. The concrete mix was cast in 6 layers with 30 seconds of vibration at each layer except for the last, which was vibrated for 60 seconds.

Drying



[0122] The hollow-core casting was slowly dried to prevent cracking. It was allowed to airdry over night and was then placed in a drying oven at 90°C for 51 hours, followed by an additional 20 hours at 100°C. After drying, the hollow-core casting was removed from its mold and the pvc pipe removed from the core of the casting. The net weight of the hollow-core casting was 8769 grams.

Curing



[0123] FIG. 16 is a picture of the curing setup. A PVC pipe fitting was inserted into each end of the core with tube fittings screwed into the pipe fittings so that curing gases could be passed through the casting. The hollow-core casting was encased in 1" (3 cm) thick aluminum-foil-backed fiberglass insulation. One of the tube fittings from the core (the entrance tube assembly) was attached with ¼' (8 cm) stainless steel tubing to a gas saturator (heated vessel that contained water). The other tube fitting from the core (the exit tube assembly) was attached to a ¼" (0.6 cm) plastic tube that lead to a vent. Each tube assembly was fit with a thermocouple so that the temperature of the curing gas could be measured before and after passing through the core. Each tube assembly was insulated with fiberglass insulation.

[0124] The water in the saturator was maintained at 65°C throughout the curing run. Carbon dioxide gas was bubbled through the water at 6.5 liters/minute to saturate the gas stream with water vapor. All of the heat and water for the curing reaction was carried into the hollow core by the saturated carbon dioxide stream. The temperature at the core inlet rose from 26°C to 60°C over a period of one hour where it stayed for the rest of the curing run. It took another 90 minutes for the temperature at the core exit to rise to 53°C where it stayed for the rest of the curing period. The curing run was terminated after 20 hours.

[0125] The insulation that surrounded the hollow-core casting during the curing run was removed. The first third of the casting (inlet end) appeared wet and darker on the outside than the remainder of the casting, which appeared lighter and dry (FIG. 17). The casting was dried completely in a drying oven to a constant weight of 8939 grams, for a gain of 170 grams due to carbonation. The average extent of carbonation was calculated to be 40% from the weight gain.

[0126] The dried hollow-core casting was cut in half to assess the uniformity of the cure, since the two ends of the casting were visually different. Some material was lost from the kerf on cutting through the casting and some material was lost from spalling of the outside edges of the cut caused by the saw blade. The spalling pattern was symmetrical and approximately the same on both halves of the costing thus the cutting losses were approximately the same for both pieces. The total weight of cutting losses amounted to 137 grams.

[0127] The inside edges (e.g., the core surface) cut cleanly, which suggests that the inside of the casting had reacted better than the outside and that the extent of reaction varied in a radial pattern around the core. The weight of the inlet half of the dried casting was 4429 grams while the weight of the outlet half of the dried casting was 4373 grams. Thus the mass remaining after cutting the slab was evenly distributed in the two halves (50.3% inlet end; 49.7% outlet end). Therefore the extent of carbonation was distributed evenly along the length of the hollow-core casting.

[0128] In this specification and the appended claims, the singular forms "a," "an," and "the" include plural reference, unless the context clearly dictates otherwise.

[0129] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Methods recited herein may be carried out in any order that is logically possible, in addition to a particular order disclosed.

Equivalents



[0130] The representative examples disclosed herein are intended to help illustrate the invention, and are not intended to, nor should they be construed to, limit the scope of the invention. Indeed, various modifications of the invention and many further embodiments thereof, in addition to those shown and described herein, will become apparent to those skilled in the art from the full contents of this document, including the examples which follow and the references to the scientific and patent literature cited herein.


Claims

1. A hollow core slab having a body prepared from a composite material,
wherein the body comprises one or more interior ducts or channels extending the full length of the slab, exhibiting one or more surfaces capable of fluid communication with an exterior of the body, and the composite material comprises:

a plurality of bonding elements, wherein each bonding element comprises: a core comprising primarily calcium silicate, a silica-rich first or inner layer, and a calcium carbonate-rich second or outer layer; and

filler particles comprising coarse filler particles and/or fine filler particles, wherein the plurality of bonding elements and the plurality of filler particles together form one or more bonding matrices and the bonding elements and the filler particles are substantially evenly dispersed therein and bonded together; and further comprising one or more reinforcement elements selected from bars, wires or cables embedded in the body, wherein the hollow core slab has a longitudinal dimension from about 4 m to about 250 m, a transverse dimension from about 0.5 m to about 2 m, and a thickness from about 10 cm to about 50 cm.


 
2. The hollow core slab of Claim 1, wherein the one or more reinforcement bars are made of iron, steel, polymeric materials, glass, or a combination thereof.
 
3. The hollow core slab of Claim 1, wherein the one or more reinforcement elements are pre-stressed.
 
4. The hollow core slab of Claim 1, wherein the plurality of bonding elements have a median particle size in the range from about 5 µm to about 100 µm.
 
5. The hollow core slab of Claim 1, wherein the plurality of bonding elements are chemically transformed from ground calcium silicate, comprising one or more of natural or synthetic wollastonite, pseudo-wollastonite, rankinite, gehlenite, belite and a calcium silicate based amorphous phase, and wherein the plurality of bonding elements are prepared by a chemical transformation from ground calcium silicate by reacting it with CO2 via a controlled hydrothermal liquid phase sintering process.
 
6. The hollow core slab of Claim 1, wherein the weight ratio of bonding elements : filler particles is about 1 : 5.
 
7. The hollow core slab of Claim 1, wherein the body is elongated in shape comprising four or more longitudinally disposed ducts or channels.
 
8. A process for producing the hollow core slab of claim 1, comprising:

mixing a particulate composition, a liquid composition and filler particles to form a mixture;

embedding one or more reinforcement elements selected from bars, wires or cables in the mixture;

casting or extruding or otherwise forming the mixture in a mold to generate a casted or extruded or otherwise formed hollow core body having the one or more reinforcement elements embedded therein and one or more interior ducts or channels in the formed body extending the full length of the slab, exhibiting one or more surfaces and capable of fluid communication with interior of the body wall;

maintaining an atmosphere of CO2 and water vapor in the one or more interior ducts or channels; and

curing the casted or extruded body at a temperature in the range from about 20°C to about 150°C for about 1 hour to about 80 hours under an atmosphere of water and CO2 having a pressure in the range from ambient atmospheric pressure to about 60 psi (414 kPa) above ambient and having a CO2 concentration ranging from about 10% to about 90%,
wherein the particulate composition comprises a ground calcium silicate, comprising one or more of natural or synthetic wollastonite, pseudo-wollastonite, rankinite, gehlenite, belite and a calcium silicate based amorphous phase having a median particle size in the range from about 1 µm to about 100 µm,

the liquid composition comprises water, and

the filler particles comprise coarse filler particles and/or fine filler particles.


 
9. The process of Claim 8, wherein curing the casted mixture is performed at a temperature equal to or lower than about 60°C for about 10 to about 50 hours under a vapor comprising water and CO2 and having an ambient atmospheric pressure.
 


Ansprüche

1. Hohlkernplatte mit einem Körper, der aus einem Verbundmaterial hergestellt ist,
wobei der Körper einen oder mehrere innere Kanäle oder Rinnen umfasst, die sich über die gesamte Länge der Platte erstrecken und eine oder mehrere Oberflächen aufweisen, die in der Lage sind, eine Fluidverbindung mit dem Äußeren des Körpers herzustellen, und wobei das Verbundmaterial Folgendes umfasst:

mehrere Bindungselemente, wobei jedes Bindungselement Folgendes aufweist: einen Kern, der hauptsächlich Calciumsilikat aufweist, eine erste oder innere Schicht, die reich an Siliziumdioxid ist, und eine zweite oder äußere Schicht, die reich an Calciumcarbonat ist; und

Füllstoffpartikel, umfassend grobe Füllstoffpartikel und/oder feine Füllstoffpartikel, wobei die mehreren Bindungselemente und die mehreren Füllstoffpartikel zusammen eine oder mehrere Bindematrizen bilden und wobei die Bindungselemente und die Füllstoffpartikel im Wesentlichen gleichmäßig darin dispergiert und miteinander verbunden sind; und ferner umfassend ein oder mehrere Verstärkungselemente, ausgewählt aus Stäben, Drähten oder Kabeln, die in den Körper eingebettet sind, wobei die Hohlkernplatte eine Längsabmessung von etwa 4 m bis etwa 250 m, eine Querabmessung von etwa 0,5 m bis etwa 2 m und eine Dicke von etwa 10 cm bis etwa 50 cm aufweist.


 
2. Hohlkernplatte nach Anspruch 1, bei der ein oder mehrere Verstärkungsstäbe aus Eisen, Stahl, polymeren Materialien, Glas oder einer Kombination davon hergestellt sind.
 
3. Hohlkernplatte nach Anspruch 1, bei der ein oder mehrere Verstärkungselemente vorgespannt sind.
 
4. Hohlkernplatte nach Anspruch 1, wobei die mehreren Bindungselemente eine mittlere Teilchengröße im Bereich von etwa 5 µm bis etwa 100 µm aufweisen.
 
5. Hohlkernplatte nach Anspruch 1, wobei die mehreren Bindungselemente aus gemahlenem Calciumsilikat chemisch umgewandelt werden, das ein oder mehrere von natürlichem oder synthetischem Wollastonit, Pseudowollastonit, Rankinit, Gehlenit, Belit und eine amorphe Phase auf Calciumsilikatbasis umfasst, und wobei die mehreren Bindungselemente durch eine chemische Umwandlung von gemahlenem Calciumsilikat durch Reaktion mit CO2 über ein gesteuertes hydrothermales Flüssigphasen-Sinterverfahren hergestellt werden.
 
6. Hohlkernplatte nach Anspruch 1, wobei das Gewichtsverhältnis von Bindeelementen zu Füllstoffpartikeln etwa 1 : 5 beträgt.
 
7. Hohlkernplatte nach Anspruch 1, wobei der Körper eine längliche Form hat und vier oder mehr in Längsrichtung angeordnete Kanäle oder Rinnen umfasst.
 
8. Verfahren zur Herstellung der Hohlkernplatte nach Anspruch 1, Folgendes umfassend:

Mischen einer teilchenförmigen Zusammensetzung, einer flüssigen Zusammensetzung und von Füllstoffteilchen zur Bildung einer Mischung;

Einbetten eines oder mehrerer Verstärkungselemente, ausgewählt aus Stäben, Drähten oder Kabeln, in die Mischung;

Gießen oder Extrudieren oder anderweitiges Formen der Mischung in einer Form, um einen gegossenen oder extrudierten oder anderweitig geformten Hohlkernkörper mit einem oder mehreren darin eingebetteten Verstärkungselementen und einem oder mehreren inneren Kanälen oder Rinnen in dem geformten Körper zu erzeugen, der sich über die gesamte Länge der Platte erstreckt, eine oder mehrere Oberflächen aufweist und für eine Fluidverbindung mit dem Inneren der Körperwand geeignet ist;

Aufrechterhaltung einer CO2- und Wasserdampf-Atmosphäre in einem oder mehreren inneren Kanälen oder Rinnen; und

Aushärten des gegossenen oder extrudierten Körpers bei einer Temperatur im Bereich von etwa 20 °C bis etwa 150 °C für etwa 1 Stunde bis etwa 80 Stunden unter einer Atmosphäre aus Wasser und CO2 mit einem Druck im Bereich von atmosphärischem Umgebungsdruck bis etwa 60 psi (414 kPa) über Umgebungsdruck und mit einer CO2-Konzentration im Bereich von etwa 10 % bis etwa 90 %,
wobei die teilchenförmige Zusammensetzung ein gemahlenes Calciumsilikat umfasst, das eines oder mehrere von natürlichem oder synthetischem Wollastonit, Pseudowollastonit, Rankinit, Gehlenit, Belit und eine amorphe Phase auf Calciumsilikatbasis mit einer mittleren Teilchengröße im Bereich von etwa 1 µm bis etwa 100 µm umfasst,

wobei die flüssige Zusammensetzung Wasser enthält, und

die Füllstoffpartikel grobe Füllstoffpartikel und/oder feine Füllstoffpartikel umfassen.


 
9. Verfahren nach Anspruch 8, wobei das Härten der gegossenen Mischung bei einer Temperatur gleich oder niedriger als etwa 60 °C für etwa 10 bis etwa 50 Stunden unter einem Dampf, der Wasser und CO2 enthält und einen atmosphärischen Umgebungsdruck aufweist, durchgeführt wird.
 


Revendications

1. Dalle alvéolée ayant un corps préparé à partir d'un matériau composite,
le corps comprenant un ou plusieurs conduits ou canaux intérieurs s'étendant sur toute la longueur de la dalle, présentant une ou plusieurs surfaces capables d'une communication fluide avec un extérieur du corps, et le matériau composite comprenant :

une pluralité d'éléments de liaison, chaque élément de liaison comprenant : un noyau comprenant principalement du silicate de calcium, une première couche ou couche intérieure riche en silice, et une seconde couche ou couche externe riche en carbonate de calcium ; et

des particules de charge comprenant des particules de charge grossières et/ou des particules de charge fines, la pluralité d'éléments de liaison et la pluralité de particules de charge formant ensemble une ou plusieurs matrices de liaison et les éléments de liaison et les particules de charge étant dispersés sensiblement uniformément à l'intérieur de celles-ci et étant liés ensemble ; et comprenant en outre un ou plusieurs éléments de renforcement choisis parmi des barres, des fils ou des câbles incorporés dans le corps, la dalle alvéolée ayant une dimension longitudinale d'environ 4 m à environ 250 m, une dimension transversale d'environ 0,5 m à environ 2 m, et une épaisseur d'environ 10 cm à environ 50 cm.


 
2. Dalle alvéolée selon la revendication 1, la ou les barres de renforcement étant en fer, en acier, en matériaux polymères, en verre ou une combinaison de ceux-ci.
 
3. Dalle alvéolée selon la revendication 1, le ou les éléments de renforcement étant précontraints.
 
4. Dalle alvéolée selon la revendication 1, la pluralité d'éléments de liaison ayant une taille médiane de particule dans la plage d'environ 5 µm à environ 100 µm.
 
5. Dalle alvéolée selon la revendication 1, la pluralité d'éléments de liaison étant chimiquement transformés à partir de silicate de calcium broyé, comprenant un ou plusieurs parmi la wollastonite naturelle ou synthétique, la pseudo-wollastonite, la rankinite, la géhlénite, la bélite et une phase amorphe à base de silicate de calcium et la pluralité d'éléments de liaison étant préparés par une transformation chimique à partir de silicate de calcium broyé en le faisant réagir au moyen de CO2 par l'intermédiaire d'un processus de frittage hydrothermique en phase liquide contrôlé.
 
6. Dalle alvéolée selon la revendication 1, le rapport pondéral d'éléments de liaison/particules de charge étant d'environ 1:5.
 
7. Dalle alvéolée selon la revendication 1, le corps étant de forme allongée comprenant quatre ou plus de quatre conduits ou canaux disposés longitudinalement.
 
8. Procédé de fabrication de la dalle alvéolée selon la revendication 1, comprenant :

le mélange d'une composition particulaire, une composition liquide et des particules de charge pour former un mélange ;

l'incorporation d'un ou plusieurs éléments de renforcement choisis parmi des barres, des fils ou des câbles dans le mélange ;

le moulage ou l'extrusion ou un autre moyen de formation du mélange dans un moule pour générer un corps alvéolé coulé ou extrudé ou autrement formé ayant un ou plusieurs éléments de renforcement incorporés à l'intérieur, et un ou plusieurs conduits ou canaux intérieurs dans le corps formé s'étendant sur toute la longueur de la dalle, présentant une ou plusieurs surfaces et capables d'une communication fluide avec l'intérieur de la paroi de corps ;

le maintien d'une atmosphère de CO2 et de vapeur d'eau dans le ou les conduits ou canaux intérieurs ; et

le durcissement du corps coulé ou extrudé à une température dans la plage d'environ 20 °C à environ 150 °C pendant environ 1 heure à environ 80 heures sous une atmosphère d'eau et de CO2 ayant une pression dans la plage de la pression atmosphérique ambiante à environ 60 psi (414 kPa) au-dessus de la température ambiante et ayant une concentration de CO2 allant d'environ 10 % à environ 90 %, la composition particulaire comprenant un silicate de calcium broyé, comprenant un ou plusieurs parmi la wollastonite, la pseudo-wollastonite, la rankinite, la géhlénite, la bélite et une phase amorphe à base de silicate de calcium ayant une taille médiane de particule dans la plage d'environ 1 µm à environ 100 µm,

la composition liquide comprenant de l'eau, et

les particules de charge comprenant des particules de charge grossières et/ou des particules de charge fines.


 
9. Procédé selon la revendication 8, le durcissement du mélange coulé étant effectué à une température égale ou inférieure à environ 60 °C pendant environ 10 à environ 50 heures sous une vapeur comprenant de l'eau et du CO2 et ayant une pression atmosphérique ambiante.
 




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Cited references

REFERENCES CITED IN THE DESCRIPTION



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Patent documents cited in the description




Non-patent literature cited in the description