GEOPOLIMERIC COMPOSITIONS AND METHOD TO PREPARE THEIR COMPOSITION AND CEMENT MIXTURE TO FORM

专利摘要:
dimensionally stable geopolymer compositions and method a method for making cementitious geopolymer compositions for cementitious products such as concrete, precast building elements and panels, mortar and repair materials, and the like is disclosed. the cement compositions of the geopolymer of some modalities are made by mixing a synergistic mixture of thermally activated aluminosilicate mineral, calcium aluminate cement, calcium sulfate and a chemical activator with water.
公开号:BR112014025056B1
申请号:R112014025056-1
申请日:2013-04-19
公开日:2021-03-30
发明作者:Ashish Dubey
申请人:United States Gypsum Company；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[1] The invention generally relates to cementitious compositions containing aluminosilicate based geopolymers that can be used for a variety of applications. In particular, the invention generally relates to such cementitious compositions that offer properties that are desirable in terms of fixation times, dimensional stability and less significant overall shrinkage in curing and other desirable properties. BACKGROUND OF THE INVENTION
[2] U.S. Patent 6,572,698 to Ko discloses a composition of activated aluminum silicate containing aluminum silicates, calcium sulfate and an activator containing alkali metal salts is described. Aluminum silicates are selected from a group consisting of blast furnace slag, clay, marl and industrial by-products such as fly ash, and have an Al2O3 content of more than 5% by weight. Blast furnace slag is present in an amount of less than 35% by weight, and the cement kiln powder (CKD), in an amount of 1 to 20% by weight, is added to the mixture as an activator.
[3] U.S. Patent No. 4,488,909 to Galer et al discusses cementitious compositions capable of rapid fixation. The cementitious composition includes portland cement, high alumina cement, calcium sulfate and lime. Pozzolans, such as fly ash, montmorillonite clay can be added up to about 25%. The cementitious composition includes about 14 to 21% by weight of high alumina cementitious. Galer et al supplied aluminates using high alumina cement (HAC) and sulfate ions using plaster to form etringitis and achieve fast fixation of its cementitious mixture.
[4] U.S. Patent No. 6869474 to Perez-Pena et al, discusses cementitious compositions for the production of cement-based products, such as cementitious slabs. This is accomplished by adding an alkanolamine to hydraulic cement, such as portland cement, and forming a paste with water under conditions that provide an initial suspension temperature of at least 90 ° F (32 ° C). Additional reactive materials can be included, such as high alumina cement, calcium sulfate and a pozzolanic material, such as fly ash.
[5] US Patent No. 7,670,427 to Perez-Pena et al, discusses cementitious compositions with resistance to initial compression for the production of cement-based products, such as cementitious slabs obtained by the addition of a hydraulic cement phosphate, such as portland cement, and the formation of a paste with water under conditions that provide an initial suspension temperature of at least 90 ° F (32 ° C). Additional reactive materials can be included, such as high alumina cement, calcium sulfate and a pozzolanic material, such as fly ash.
[6] Published US patent application No. US 2010-0071597 A1 from Perez-Pena features formulations using fly ash cement and citric acid alkali metal salts such as sodium citrate, to form concrete mixtures with a fast fixation and relatively high resistance to initial compression. Hydraulic cement and plaster can be used up to 25% by weight of the formulation, although their use is not preferred. Composition of activated fly ash described in the present application can interact with the traditional foaming systems used to drag air and thus make light plates.
[7] US Patent No. 5,536,310 to Brook et al presents a cementitious composition that contains 10-30 parts by weight (bpw) of a hydraulic cement such as portland cement, 50-80 parts by weight of fly ash, and 0 , 5-8.0 pbw expressed as an acid free of a carboxylic acid, such as citric acid or its alkali metal salts thereof, for example, tripotassium citrate or trisodium citrate, with other conventional additives, including retarding additives, such as like boric acid or borax.
[8] US Patent No. 6,641,658 to Dubey presents a Portland cementitious composition based on cement, which contains 35-90% Portland cements, 0-55% of a pozzolan, 5-15% high alumina cementitious and 1 to 8% insoluble calcium sulphate anhydrite form instead of conventional landplaster / soluble plaster to increase heat release and decrease fixation time, despite the use of large amounts of pozzolan, for example, fly ash. The cementitious composition can include light aggregates and fillers, superplasticizers and additives, such as sodium citrate.
[9] U. S. Patent No. 7618490 B2 No. to Nakashima et al. features a fast-setting spray material comprising one or more of calcium sulfoaluminate, calcium aluminum silicate, calcium hydroxide, a source of fluorine and Portland cement. Calcium sulfate can be added as anhydrous or as a hemihydrate.
[10] U. S. Patent No. 4655979 to Nakano et al. presents a process to manufacture cellular concrete using calcium silicate based cement, alkali metal retardant, calcium sulfo-aluminate (CSA) and an optional calcium sulfate cement that can be added to the concrete composition.
[11] Published U.S. patent application No. 2008/0134943 A1 to Godfrey et al. features a waste encapsulation material consisting of at least one alkaline earth metal sulfoaluminate salt with calcium sulphate and optional inorganic filler, such as blast furnace slag, pulverized fuel ashes, silica finely divided, limestone, and organic and inorganic fluidizing agents. Preferably at least one alkaline earth metal sulfoaluminate salt comprises calcium sulfoaluminate (CSA). A suitable composition may, for example, comprise at least one sulfoaluminate salt of an alkaline earth metal, in combination with plaster and pulverized fuel ash (PFA), in which about 86% of the plaster particles have a particle size less than 76 µm, and about 88% of the PFA particles have a particle size of less than 45 µm. An example comprises 75% (70: 30CSA: CaSO4.2H2O); 25% ash from pulverized fuel; water / solids ratio 0.65.
[12] US patent No. 6730162 to Li et al. features double cementitious compositions including a first hydraulic binder with 2.5% by weight at 95.% C4A3S, which is chemical notation where C = CaO, S = SiO2, A = Al2O3 (in other words calcium sulfo-alumina) and 2 , 5-95% by weight of a hemihydrate and / or a calcium sulfate anhydrite. Sulfoalumina cements or ferroalumin cements are cementitious examples that contain C4A3S. It may also include mineral filler additives selected from the group consisting of slag, fly ash, pozzolan, soot silica, limestone fines, industrial lime by-products and waste.
[13] Chinese published application CN 101921548 A to Deng et al. presents a sulfoaluminate cementitious composition made of 90-95% by weight sulfoaluminate clinker and anhydrous plaster, quartz, sand, fly ash from incineration of residues, hydroxypropylmethylcellulose ether, powder and redispersible glue fiber. Sulfoaluminate clinker and anhydrous plaster meet the sulfoaluminate cementitious standard, ie GB20472-2006.
[14] Korean published application KR 549,958 B1 to Jung et al. presents a cement composition of alumina, CSA, plaster, calcium citrate, and hydroxyl carboxylic acid.
[15] Korean published application KR 2009085451 A to Noh describes a blast furnace slag powder composition, plaster and CSA. Plaster can have an average particle size of 4 microns or less.
[16] Korean published application KR 2009025683 A presents powder-type waterproof material used for concrete and mortar, it is obtained by spraying cementitious, anhydrous plaster, silica powder, waterproof powder, ash, calcium sulfoaluminate expansion material and inorganic composition.
[17] Korean published application KR 2010129104 A to Gyu et al. has a composition for the mixture of shotcrete, comprising (in% by weight): metakaolin (5-20), calcium sulfoaluminate (5-20), anhydrous plaster (20-45) and fly ash (30-50).
[18] There is a need for geopolymeric compositions based on dimensionally stable fly ash and a method to reduce the amount of shrinkage, the behavior of the initial and final temperature and to reduce the fixing time of mixtures of fly ash based compositions so these formulations can be used to manufacture cementitious concrete products with greater strength. SUMMARY OF THE INVENTION
[19] The present invention provides for improved geopolymer cementitious compositions and methods for making such compositions having at least one, and, in many cases, more than one, highly desirable properties, such as significantly improved dimensional stability, during and after curing; improved and modifiable start and end fix times; extended working hours; generation of modified temperature during mixing, fixing and curing; and other improved properties, as discussed herein. In many, if not all of these modalities, the improved properties are provided without significant (if any) loss of initial compressive strength, final compressive strength, or other strength properties. Some modalities, in fact, predict a surprising increase in resistance to initial and final compression.
[20] The improved properties of those and other embodiments of the invention provide distinct advantages over prior geopolymeric binders, such as fly ash-based binders, as well as other cementitious binders that may contain a significant geopolymer content. In some preferred embodiments, the geopolymer cementitious compositions of the invention are formed from solutions or suspensions of at least water and one or more reactive cementitious components in a dry or powdered form. Reactive cementitious components comprise effective amounts of thermally activated geopolymeric aluminum silicate materials, such as fly ash; calcium aluminate cements; and calcium sulfates. One or more alkali metal chemical activator, such as a citric acid alkali metal salt, or an alkali metal base, is also added to the solutions, either in a dry form for the reactive powder, or as an addition of liquids to the paste . Optionally, the suspension or solution can incorporate other additives, such as water reducing agents, adjusted to acceleration or retardation, air retention agents, foaming agents, wetting agents, light aggregates or other materials, or other additives to provide reinforcement or modify the properties of the paste and the final product.
[21] In many preferred compositions of the invention, the reactive cementitious components, in dry or powder form comprise about 65 to about 97 percent by weight of thermally activated alumino silicate mineral such as fly ash, about 2 to about 30 percent by weight calcium aluminate cement, and about 0.2 to calcium sulfate about 15 percent by weight, based on the total dry weight of all cementitious reactive components. In the preferred compositions of the invention, the reactive cementitious components comprise calcium aluminate cement of about 1 to about 200 parts by weight relative to 100 parts by weight of thermally activated aluminum-silicate mineral.
[22] In other embodiments, a mixture of two or more types of calcium aluminate cement and calcium sulfoaluminate cements can be used, and the amounts and types of calcium aluminate cement and calcium sulfoaluminate cement can vary depending on its chemical composition and particle size (Blaine fineness). The Blaine fineness of the calcium aluminate cement, in such embodiments and the other preferred embodiments is greater than about 3000, more preferably greater than about 4000, and more preferably greater than 5000 The Blaine fineness of the calcium sulfoaluminate cement in such embodiments and in other embodiments, it is preferably greater than about 3000, more preferably greater than about 4000, even more preferably greater than 5000, and more preferably greater than about 6000.
[23] In some preferred embodiments, the amount of alkaline chemical activator for the metal is about 0.5% to about 10%, by weight, based on the total dry weight of the cementitious reactive materials. More preferably, the range of alkali activating metal chemicals is about 1% to about 6% of the total weight of the cementitious reactive materials, preferably about 1.25% to about 4%, more preferably about 1.5 % to about 3.5%, and more preferably about 1.5% to 2.5%. Sodium citrate and potassium citrate alkaline metal acid activators are preferred, although a mixture of sodium citrate and potassium can also be used. Alkali metal bases, such as alkali metal hydroxides and alkali metal silicates, can also be used, depending on the application and the needs of that application.
[24] These and other preferred embodiments of the invention, unlike previous fly ash geopolymeric compositions, are formulated to provide the geopolymer cementitious compositions that are dimensionally stable and resistant to cracking at the time of fixing and hardening under both unrestricted and immobilized conditions . For example, the short-term free shrinkage of certain preferred embodiments of the invention, is typically less than about 0.3%, preferably less than about 0.2%, and more preferably less than about 0.1% , and more preferably less than about 0.05% (measured after initial set and within 1 to 4 hours after mixing). In such preferred embodiments, the long-term shrinkage of the compositions during curing is also typically less than about 0.3%, more preferably less than about 0.2%, and more preferably less than about 0.1 %.
[25] For additional control over dimensional stability and shrinkage in modalities, the amount of calcium is the aluminate cement of about 2.5 to about 100 parts by weight relative to 100 parts by weight of the aluminum silicate mineral thermally activated, more preferably about 2.5 to about 50 parts by weight relative to 100 parts by weight of the thermally activated aluminum-silicate mineral, and more preferably about 5 to about 30 parts by weight relative to 100 parts by weight of thermally activated aluminum-silicate mineral. For modalities in which control over dimensional stability, as indicated by the shrinkage of the material is of importance, the amount of alkali metal activator varies most preferably between about 1 to about 3% of the total dry weight of the cementitious reactive materials ( that is, thermally activated alumino mineral silicate, such as fly ash, calcium aluminate cement and calcium sulphate), even more preferably from about 1.25% to about 2.75% of the total dry weight of the cementitious reactive materials , and even more preferably from about 1.5% to about 2.5% of the total dry weight of the cementitious reactive materials.
[26] The dimensionally stable geopolymer compositions of preferred embodiments of the invention, further evidence of a surprising reduction in the maximum temperature rise during curing of the composition over previous geopolymer cement products. For this and similar reasons, these modalities resist thermal cracking to an unexpected degree. For example, in some preferred embodiments, the temperature rise is usually less than about 50 ° F (28 ° C), more preferably less than about 40 ° F (22 ° C), and more preferably less than about 30 ° F (17 ° C).
[27] These and other preferred embodiments of the invention also exhibit an unexpected rate of initial strength development. For example, in some of these embodiments, the compressive strength at 4 hours may be greater than about 1000 psi (6.9 MPa), preferably greater than about 1500 psi (10.3 MPa), more preferably greater than about 2500 psi (17.2 MPa). In such embodiments, the 24 hours of development of compressive strength can be greater than about 1500 psi (10.3 MPa), more preferably greater than about 2500 psi (17.2 MPa), and more preferably greater than about 3500 psi (24.1 MPa). In those and other preferred embodiments, in 28 days the compressive strength most can exceed about 3500 psi (24.1 MPa), more preferably greater than about 4500 psi (31.0 MPa), and more preferably greater than about 5500 psi (37.9 MPa). In still other embodiments, the compositions are capable of developing compressive strength after 1 to 4 hours, from about 500 psi (3.5 MPa) to about 4000 psi (27.6 MPa), more preferably from about 1500 up to about 5000 psi (10.3-34.5 MPa) after 24 hours, and more preferably from about 3500 to about 10,000 psi (24.1-70 MPa) after 28 days.
[28] In addition, the geopolymer cementitious compositions of some of the preferred embodiments of the invention also have very good durability in wet conditions, with similar final wet compressive forces to dry compressive forces. For example, in certain embodiments, 28 days of compressive strength saturated water can typically exceed about 3500 psi (24.1 MPa), more preferably greater than about 4500 psi (31.0 MPa), and more preferably greater at about 5500 psi (37.9 MPa).
[29] Because the set slurry times for the solid state for activated alkali metal geopolymers, as well as combined calcium aluminate and calcium sulphate cements, are typically relatively short, it was expected that the preferred modalities of combining all of these components would also be would have short defined times and limits working time. Surprisingly, however, the fixation times provided by the preferred embodiments of the invention are not limited to short fixation times (often less than 15 minutes), but provide significant control over reactions allowing the attachment of significant lengths of the set of suspension and suspension working time.
[30] For example, in some embodiments, the composition can be formulated for a short fixation time, such as less than about 10 minutes. In other preferred embodiments, the composition can be formulated for an extended fixation of between about 10 to about 30 minutes. In still other more preferred embodiments, the composition formulation is preferably selected to provide a setting time of about 30 to about 60 minutes. In still other more preferred embodiments, the composition can be formulated to define times, as long as about 60 to about 120 minutes, about 120 to about 240 minutes, or more times, if desired.
[31] The fixation times of such modalities, in addition, can be selected and, if desired extended, without significant (if any) loss of properties of shrinkage strength, compressive strength and other strength properties. As a result, these modalities can unexpectedly be used in applications where previous cement-based geopolymer products and products with geopolymeric components cannot be used due to the need for an extended set and working times without shrinkage or unacceptable loss of strength.
[32] In certain preferred embodiments, the compositions of the invention also develop exceptional tensile bond strength with an underlying substrate. For example, the bond strength between these preferred embodiments and a concrete substrate, preferably greater than about 200 psi (1.4 MPa) and more preferably greater than about 300 psi (2.1 MPa). In some embodiments, the surface pH of the dimensionally stable fully cured and hardened geopolymer cementitious compositions of the invention are also improved over Portland cement-based materials and products, which typically have a surface pH greater than 12 and more typically greater than 13. In certain preferred embodiments, these compositions are measured 16 hours after installation and preferably have a pH less than about 11, more preferably less than about 10.5, and more preferably less than about 10 In this context, the pH of the surface is measured using the ASTM F-710 (2011) test standard.
[33] In many preferred embodiments, the geopolymer cementitious compositions of the invention do not require hydraulic cement based on calcium silicate, such as Portland cements, for the development of strength and dimensional stability. In other embodiments, Portland cements can be incorporated to provide specific desired properties. However, it was surprisingly found that, depending on the specific composition of the modality, an excess amount of Portland cements actually reduced the dimensional stability of the composition during and after curing, instead of increasing its dimensional stability.
[34] For preferred embodiments of the invention that incorporate calcium silicate based hydraulic cements, the limit of such hydraulic cements may vary depending on the specific composition of the modality, but can be identified by an increase in shrinkage in relation to its shrinkage. modality with a reduced amount of calcium silicate hydraulic cement. In some embodiments, the Portland cement content should not exceed about 15% by weight of the reactive powder components, in another preferred embodiment, which should not exceed 10% by weight of the reactive powder components, and still a further preferred embodiment should not exceed about 5% by weight of the reactive powder weight of components, and in yet another preferred embodiment, there is no substantial amount of Portland cements in the reactive components.
[35] It has also surprisingly been found that in some embodiments an excess amount of calcium aluminate cement can cause a loss of dimensional stability, as indicated by an increase in shrinkage after the initial fixation of the composition. For applications that require a significant degree of dimensional stability and / or control to prevent crack shrinkage, delamination and other failure modes, the calcium aluminate cement amount is preferably about 10 to about 60 parts by dry weight in 100 parts per dry weight of thermally activated alumino silicate mineral.
[36] In other preferred embodiments, it was also unexpectedly found that the amount of calcium sulfate present in the calcium aluminate cement ratio in the composition can moderate potential adverse effects, such as shrinkage, caused by the calcium aluminate cement content. In such embodiments, the amount of calcium sulfate is preferably about 2 to about 200 parts by weight relative to 100 parts by weight calcium aluminate cement.
[37] For a more effective control of the shrinkage material of these modalities, the amount of calcium sulfate is about 10 to about 100 parts by dry weight in relation to 100 parts by dry weight of calcium aluminate cement, more preferably about 15 to about 75 parts by dry weight with respect to 100 parts by dry weight of calcium aluminate cement, and more preferably about 20 to about 50 parts by dry weight with respect to 100 parts by dry weight of calcium. calcium aluminate cement. In embodiments where an increase in initial compressive strength is important, a preferred amount of calcium sulfate amount is from about 10 to about 50 parts to about 100 parts by dry weight of the calcium aluminate cement.
[38] In still other embodiments of the invention, the type of calcium sulfate (mainly dihydrate, hemihydrate, or anhydrite) added to the composition can have a significant influence on the development of the initial compressive strength of the partially cured composition ( ie at least about 24 hours). Surprisingly, it was found that several modalities that use essentially anhydrous calcium sulphate (anhydrite) have a higher initial resistance to compression than modalities that use mainly the dihydrate form and, in some modalities, may have comparable initial compression strengths. to those who mainly use calcium sulfate hemihydrate. In other embodiments, two or more of the types of calcium sulfate (dihydrate, hemihydrate, or anhydrite) can be used together, and the quantities of different types adapted to provide a better control of the compressive strength of the composition. Likewise, the different types and amounts of calcium sulfate can be used alone or in combination, to adjust the desired shrinkage and other properties of the composition.
[39] Where shrinkage performance is of central concern, other embodiments of the invention incorporate calcium sulfates with average particle sizes preferably from about 1 to about 100 microns, about 1 to about 50 microns, and about from 1 to about 20 microns. These modalities provide a surprising improvement in the shrinkage resistance, and in other embodiments, the dimensions of the calcium sulfate particles in at least the preferred ranges can provide an important contribution to the improved rates of strength development during curing of the compositions.
[40] In still other embodiments, it has been surprisingly found that sulfate substantially insoluble in anhydrous calcium water (anhydrite) can provide important benefits, despite its low solubility in water and previously assumed to be limited, if any, to reactivity in the composition. For example, anhydrite has unexpectedly been found to provide significant improved dimensional stability control, reducing shrinkage during curing of this and other modalities in relation to prior art compositions. Anhydrite also provided significantly improved in the short and long term, the compressive strength over prior art compositions, and in some cases earlier and longer compressive forces comparable or better than compositions using calcium sulfate hemihydrate or dihydrate, as the source of calcium sulfate. The selection of the type of calcium sulphate used in the particular modality will depend on the desired age rate of development of initial strength in combination with a balance of other properties, such as the shrinkage time and joint strength for a particular final application.
[41] In other embodiments, the particle size and calcium sulfate morphology provides a significant and surprising influence on the development of early (less than about 24 hours) resistance of the compositions. In such embodiments, the use of a sulfate of a relatively small size of the calcium particles provides a faster development in early compressive strength. In these embodiments, the preferred average calcium sulfate particle size ranges from about 1 to 100 microns, more preferably from about 1 to 50 microns, and most preferably from about 1 to 20 microns.
[42] In certain embodiments, the compositions also exhibit self-leveling behavior after the initial mixing, providing one or more of the surprising performance characteristics mentioned above. The self-leveling material aspect is useful in a variety of situations and applications, such as self-leveling floors, roofs, making precise concrete products and panels, placing paste on heavily reinforced building elements, etc. The compositions of these modalities are self-leveling after the initial mixing with water of the reactive powder of the invention at a weight ratio of about 0.15 to about 0.4, more preferably, 0.17-0.35, even more preferably 0.20 to 0.30. Alternatively, in other embodiments, the compositions may also be supplied in a thick moldable paste as a consistency after initial mixing in a similar manner, providing one or more improved performance characteristics.
[43] A formulation preferably for self-leveling and compositions comprises about 65 to about 95 percent by weight of fly ash, about 2 to about 30 percent by weight, calcium aluminate cement, and about 0, 2 to about 15 weight percent calcium sulfate. In some embodiments, the geopolymer cementitious composition of the invention can be spread over a substrate surface, where the geopolymer cementitious binder is mixed as a self-leveling product and is poured to an effective thickness of about 0.02 cm at about 7.5 cm.
[44] The physical characteristics of such products offer good examples of the benefits of these modalities, that is, dimensional stability, resistance to dimensional movement and physical suffering and high surface resistance to abrasion and wear, suitable for use in areas of high commercial traffic, industrial and others. Time and surface preparation of the expensive substrate, such as shot blasting, chiseling, water jet, crusting or grinding can be minimized or avoided, depending on the application.
[45] In other aspects of the invention, preferred embodiments provide methods for producing cementitious compositions, dimensionally stable, with adaptable times for specific applications, good development of early and definitive compression strength and other strength characteristics, surface improvement pH fixation, improved bond strength and other benefits with substrates. In certain preferred embodiments, methods comprising the steps of preparing a surprisingly effective mixture, synergistic of thermally activated aluminum silicates, preferably from Class C fly ash, calcium aluminate cement, calcium sulfate, and a chemical activator of an alkali metal.
[46] In certain preferred embodiments of such methods, preferred mixtures are prepared using the components, such as those mentioned above, to form a cementitious powder comprising thermally activated reactive Class C ash, calcium aluminate cement, calcium sulphate and one selected from the group consisting of calcium sulphate dihydrate, calcium sulphate hemihydrate, anhydrous calcium sulphate and mixtures thereof (preferably in a fine-grained form with a particle size less than about 300 microns).
[47] In these embodiments, an additional chemical activator is added to the mixture, either in dry or liquid form, comprising an alkali metal salt or a base, preferably selected from the group consisting of alkali metal salts of organic acids, alkali metal hydroxides and alkali metal silicates. In subsequent steps, water and, optionally, a superplasticizer, particularly a carboxylated plasticizer material, are added to form stable mixtures of pastes that can be used in applications suitable for geopolymer cement products.
[48] In preferred methods, mixtures are prepared at an initial temperature of about 0 ° C to about 50 ° C, more preferably an initial temperature of about 5 ° C to about 40 ° C, even more preferably an initial temperature of about 10 ° C to about 35 ° C, more preferably room temperature of about 25 ° C. In such modalities, the initial temperature of the total mixture is measured during the first minute after the reactive cement powder; activator and water are primarily present in the mixture. Of course, the temperature of the total mixture may vary during the first minute, but in such preferred embodiments; the temperature of the suspension is preferably kept within the indicated range.
[49] In some preferred embodiments, the suspension can be mixed at relatively low energies, while still achieving a well-mixed composition. In some of these preferred methods, the paste is mixed with energies equivalent to those envisaged by low speed hand drill mixers or equivalent mixers with a rating of about 250 RPM or higher. Therefore, the geopolymer compositions of such preferred embodiments are easy to mix, despite the use of relatively small amounts of water used to make the suspension used to form the final composition.
[50] In many embodiments, other additives that are not considered to be cementitious reactive powder can be incorporated into the cementitious composition and global geopolymeric paste. Such other additives, for example, water reducing agents, such as the aforementioned superplasticizers, define accelerating agents, defined retarding agents, air retaining agents, foaming agents, wetting agents, shrinkage control agents, air modifying agents viscosity (thickeners), forming redispersible powders of film-forming polymers, dispersions of film-forming polymers, coloring agents, corrosion control agents, alkali-silica reaction reducing additives, reinforcing fibers, discrete and internal curing agents. Other additives may include fillers, such as one or more sand and / or other aggregates, lightweight fillers, pozzolanic minerals, mineral fillers, etc.
[51] While separately discussed above, each of the preferred geopolymeric compositions and mixtures of the invention has at least one, and may have a combination of two or more of the distinct advantages mentioned above (as well as those evident from the further discussion, examples and data here), in relation to geopolymer cement compositions.
[52] Many, if not most, of the modalities of the invention are environmentally sustainable, using fly ash geopolymers, which comprise post-industrial waste as a source of primary raw materials. This significantly reduces the carbon footprint of the life cycle and the energy incorporated in the life cycle of the manufactured product.
[53] Geopolymer cementitious compositions of preferred embodiments of the present invention can be used where other cementitious materials are used, especially applications where fixing time and flexibility of working hours, dimensional stability, compressive strength and / or other properties of resistance are important or necessary. For example, in various applications of concrete products, including structural concrete panels for floors, slabs and walls, wall and floor for installation of finishing floor materials, such as ceramic tiles, natural stones, vinyl floors, VCTs and rugs, floor coverings. road and bridge repair, sidewalks and other on-ground boards, exterior plaster and plaster finishes, self-leveling cover and shotcrete for the stabilization of soil and rocks in foundations, mountain slopes and mines, mending repair mortars for filling and smoothing cracks, holes and other uneven surfaces, statues and murals for indoor and outdoor applications, as well as road paving materials, bridge decks and other traffic and weight bearing surfaces.
[54] Other examples include uses for precast concrete articles, as well as construction products, such as cement slabs, masonry blocks, bricks with excellent moisture durability. In some applications, such precast concrete products, such as cementitious slabs, are preferably made under conditions that provide the appropriate fixing times for pouring in a fixed or moving form or on a continuously moving belt.
[55] The geopolymer compositions of some embodiments of the invention can be used with different fillers and additives, including air-retaining agents and foaming agents for adding air in specific proportions to manufacture light cement products, including elements of prefabricated construction, construction repair products, traffic bearing structures, such as road compositions with good expansion properties and without shrinkage.
[56] Other advantages, benefits and aspects of various modalities of the invention are discussed below, are illustrated in the attached figures, and will be understood by those skilled in the art from the more detailed description below. All percentages, ratios and proportions presented here are by weight, unless otherwise stated.
[57] BRIEF DESCRIPTION OF THE FIGURES
[58] Fig. 1A - Graph of shrinkage time results of Comparative Example 1.
[59] Fig. 1B is a fall photograph of Example 1.
[60] Fig. 2 is a falling photograph of Comparative Example 2.
[61] Fig. 3 A is a photograph of the fall of Comparative Example 3.
[62] Fig. 3B is a graph of shrinkage time results from Comparative Example 3
[63] Fig. 4A is a fall photograph of Comparative Example 4 for mixtures 1 and 2.
[64] Fig. 4B is a graph of the shrinkage behavior of Mixture 1 in Comparative Example 4 for a mixture comprising high alumina cement, fly ash and alkali metal citrate.
[65] Fig. 5A is a photograph of the cracking wafer of the two mixing compositions of Example 5
[66] Fig. 5B is a graph of shrinkage of cementitious compositions from Example 5.
[67] Fig. 6A is a photograph of the cracking wafer of the mix compositions of Example 6.
[68] Fig. 6B is a graph of the geopolymer shrinkage behavior of the compositions of the invention in Example 6.
[69] Fig. 6C is a graph of the temperature rise of the geopolymeric compositions paste in Example 6.
[70] Fig. 7 is a graph of the shrinkage of the compositions in Example 7.
[71] Fig. 8 is a graph of shrinkage of the compositions of the invention (mixtures 2 to 4) in Example 8.
[72] Fig. 9A is a graph of the shrinkage of compositions in Example 9
[73] Fig. 9B is a graph of the rise in paste temperature in Example 9.
[74] Fig. 10 is a graph of the shrinkage of the compositions in Example 10.
[75] Fig. 11 is a graph of the shrinkage of the compositions in Example 11.
[76] Fig. 12 is a graph of shrinkage of the compositions of Example 12.
[77] Fig. 13 is a graph of the shrinkage of compositions in Example 14
[78] Fig. 14 is a graph of the shrinkage of compositions in Example 15
[79] Fig. 15 is a graph of the shrinkage of the compositions in Example 16.
[80] Fig. 16 is a shrinkage graph of the compositions in Example 17.
[81] Fig. 17 is a graph of the shrinkage of the compositions in Example 18. DETAILED DESCRIPTION OF THE INVENTION
[82] TABLE A shows the composition of the dimensionally stable geopolymer cement compositions of some modalities of the invention, expressed in parts by weight (bpw) of individual or aggregate components.
[83] TABLE B shows the dimensionally stable geopolymer cementitious compositions of some embodiments of the invention are composed of two components - Reactive Powder Component A (also referred to here as "reactive cementitious material" and Activator Component B. reactive cementitious materials for the purposes of this invention is defined as a thermally activated aluminosilicate, calcium aluminate cement, a calcium sulphate, and any additional reactive cement as it is added to the other ingredients listed In the following tables, Reactive Powder Component A is a mixture of materials comprising thermally activated aluminosilicate mineral comprising Class C fly ash, cement comprising calcium aluminate cement and calcium sulphate Component B activator comprises an alkaline chemical activator metal, or mixtures thereof, which may be a powder or an aqueous solution. Component A and Component B Activator combined to together form the reactive mixing of the geopolymer cementitious compositions of some modalities of the invention.


[084] TABLE B represents the total density (preferably densities in the range of 100 to 160 pounds per cubic foot) formulations that incorporate the composition of Table A and other ingredients.



[85] TABLE C represents the light density (preferably densities in the range 10-125 pounds per cubic foot) formulations that incorporate the compositions in Table A and other ingredients.


[086] TABLE D represents light or complete density (preferably densities in the range 40 to 160 pounds per cubic foot) formulations that incorporate the composition of Table A, coarse aggregates and other ingredients.



[87] The long-term free shrinkage of mixtures of geopolymer cementitious compositions of some embodiments of the invention, with measurements of shrinkage initiated between 1 and 4 hours after mixing to form an aqueous mixture of about 0.3% or less, of preferably less than about 0.2%, and more preferably less than about 0.1%, and more preferably less than about 0.05%. As previously mentioned, the synergistic interaction between the thermally activated aluminum-silicate mineral, calcium aluminate cement, appropriately source and the amount of calcium sulfate selected, and appropriately selected alkali metal activator used in the correct amount according to some modalities of the present invention helps to minimize material shrinkage.
[88] It has been quite surprisingly that the amount of calcium aluminate cement in the geopolymer cementitious compositions of some embodiments of the invention has an important influence in controlling the degree of material shrinkage measured after the initial fixation of the material. It has also been surprisingly found that in addition to a certain amount of calcium aluminate cement, in a given modality, the amount of shrinkage material that occurs after the initial fixation of the material begins to increase.
[89] TABLE D1 shows the quantity of the ingredients.


[90] It was also unexpectedly verified the amount of calcium sulfate present in the calcium aluminate cement ratio, in which the mixture has a significant influence on the degree of shrinkage of the material of geopolymer cementitious compositions of some modalities of the invention.
[91] TABLE D2 shows the amount of ingredients of some embodiments of the invention, the amount of calcium sulfate per 100 parts of calcium aluminate cement.


[92] For a given amount of alkali metal activator and other components in the composition of some embodiments of the invention, the use of calcium sulfate dihydrate has been found to provide the most effective control to minimize material shrinkage. Use of anhydrous calcium sulfate (anhydrite) and hemihydrate calcium sulfate, also provide excellent control in reducing the material shrinkage of geopolymeric cement compositions of some modalities of the invention. Calcium sulphate dihydrate and anhydrous calcium sulphate (anhydrite) are the preferred form of calcium sulphate in some embodiments of the present invention. More preferably, the calcium sulfate dihydrate is in the form of a fine-grained landplaster.
[93] It has surprisingly been discovered the amount of alkali metal activator has a significant influence on the degree of shrinkage of the geopolymer cementitious material compositions of some embodiments of the invention. TABLE D3 shows the amount of ingredients for the% alkali metal activator value in relation to the weight of the cementitious materials (i.e. thermally activated aluminosilicate mineral, calcium aluminate cement, and calcium sulfate) to achieve this goal.


[94] Preferably, the composition of Portland cements. In fact, it has been surprisingly found that the incorporation of calcium silicate-based hydraulic cementitious, such as Portland cement into the geopolymer compositions of some embodiments of the invention, has a negative influence on the dimensional stability of the resulting material. Increasing the amount of Portland cements added to the geopolymer composition of some embodiments of the invention increases the shrinkage of the resulting compositions. Increased material shrinkage in the presence of Portland cements results, even when calcium aluminate cement, calcium sulfate and alkali metal chemical activator are present in the composition. For example, there was, surprisingly, the incorporation of about 6%, about 14%, and about 25% by weight of Portland cement in the reactive powder composition of some modalities of the invention, the increase of 8 weeks of free shrinkage of material, measured after the initial set of material, at about 0.1%, 0.16%, and 0.4 to 7%, respectively. Thus, the addition of Portland cements, negatively influences the synergistic interaction between the four basic reactive components (thermally activated aluminosilicate mineral comprising Class C fly ash, calcium aluminate cement, calcium sulfate and alkali metal chemical activator, in some modalities of Thus, geopolymer cementitious compositions of some embodiments of the invention, preferably do not contain Portland cement.
[95] To form the composition of some embodiments of the invention, the reactive powder Component A (thermally activated aluminosilicate mineral, calcium aluminate), Component B Activator (chemical alkali metal activator), and water are mixed to form a cementitious paste to a initial temperature (temperature during the first minute, the ingredients are all present in the first mixture a) from about 0 ° C to about 50 ° C, and preferably about 10 to about 35 ° C. As a result, the reaction results from geopolymerization, leading to the formation of aluminum-silicate geopolymer reaction species and fixation and hardening of the resulting material. Simultaneously, the calcium aluminate hydration reactions and the calcium silicate phases can also occur leading to the creation and hardening of the resulting material.
[96] The dimensionally stable geopolymer composition of some embodiments of the invention has extremely low water demand to obtain a workable mixture in the fresh state and produce a strong and resistant material in the hardened state.
[97] The water of total solids in the weight ratio of the dimensionally stable geopolymer cementitious composition of some embodiments of the invention, in the absence of coarse aggregate is about 0.04 to about 0.25, preferably about 0, 04 to about 0.20, more preferably about 0.05 to about 0.175 and even more preferably about 0.05 to about 0.15. Water ratio of dimensionally stable total solid geopolymer compositions of some embodiments of the invention, in the presence of coarse aggregate is preferably less than about 0.125, more preferably less than about 0.10 and even more preferably less than about 0.075. Total solids in cementitious materials, aggregates (such as sand or other aggregate), fillers and other solid additives, on a water-free basis.
[98] A minimum amount of water is provided to carry out chemical hydration and aluminum-silicate geopolymerization reactions. Preferably, in suspending some embodiments of the invention, the weight ratio of water to cementitious materials is about 0.17 to about 0.4, more preferably about 0.2 to about 0.35, and even more preferably about 0.22 to about 0.3. The amount of water depends on the individual needs of the materials present in the cementitious composition. As used herein, "cementitious materials" is defined as the thermally activated aluminosilicate mineral, calcium aluminate cement, calcium sulfate and cement and any additives that can be added to the reactive mixture.
[99] Composition fixation is characterized by final and initial fixation times, as measured using Gilmore needles specified in the ASTM C266 test procedure. The final fixing time also corresponds to the time when a concrete product, for example, a concrete panel, has hardened enough so that it can be manipulated.
[100] Geopolymeric reaction of thermally activated aluminosilicate mineral like fly ash is an exothermic reaction. It has unexpectedly been found that fly ash, calcium aluminate cement, calcium sulfate and alkali metal chemical activator synergistically interact with each other in some embodiments of the invention as part of the geopolymerization reaction to significantly reduce the rate and amount of heat released by the material subject to exothermic reaction. Adequate selection of the type of calcium sulfate and its amount, the amount of calcium aluminate cement, and adequate selection of chemical activator of alkali metals and their amount are essential and fundamental to reduce and minimize the rate and amount of heat released due to the which followed an exothermic reaction.
[101] Geopolymeric reaction of thermally activated aluminosilicate mineral like fly ash proceeds at a very fast rate and leads to extremely fast gelation and fixation of the material. It has been unexpectedly discovered that thermally activated mineral such as Class C fly ash aluminosilicate, calcium aluminate cement, calcium sulfate and alkali metal chemical activator interact synergistically with each other as part of the geopolymerization reaction of some modalities of the invention, to increase significantly the gelation time and final fixation time of the resulting material. Adequate selection of the type of calcium sulphate and its amount, the amount of calcium aluminate cement, and adequate selection of alkali metal chemical activator and its amount are effective in prolonging the gelling rate and period and the final fixing time of the resulting material . For a given amount of alkali metal activator in the composition, calcium sulfate in increasing quantity was found to increase the gelation and final fixation times of the resulting geopolymeric cement compositions in some embodiments of the invention. In addition, for a given amount of alkali metal activator in the composition, increasing the size of the calcium sulfate particles has been found to increase the gelation and final fixation times of the resulting geopolymer cement compositions of some embodiments of the invention. In addition, for a given calcium sulfate particle size and an amount of chemical activator in the composition, calcium sulfate dihydrate leads to a higher increase in gelation and final fixation times, and anhydrous calcium sulfate leads to more rapid gelation and final fixation times. For the geopolymer cementitious compositions of some embodiments of the invention, the gelation period intervals between 20 to 60 minutes, with fine fixation about 30 times to about 120 minutes. The increase in gelling and final fixation times allow a longer opening and working time for the geopolymer cementitious compositions of some modalities of the invention.
[102] Initial strength of the composition is characterized by measuring the compressive strength after about 3 to about 5 hours of curing. Relatively higher resistance to initial compression can be an advantage for a cementitious material, because it can withstand higher stresses without excessive deformation. Reaching the high initial resistance allows easy handling and use of manufactured products. It will be understood by those skilled in the art that the healing reactions continue for long periods after the final fixation time has been reached.
[103] The geopolymer cementitious compositions of some embodiments of the invention are capable of developing extremely high resistance to initial and final compression. For example, geopolymer cementitious compositions of some embodiments of the invention are capable of developing compressive strength after 1 to 4 hours, from about 500 psi to about 4000 psi, about 1500 to about 5000 psi, after 24 hours, and about 3,500 to about 10,000 psi after 28 days.
[104] The type of calcium sulfate was also surprisingly found to have a very significant influence on the development of initial compressive strength (<24 hours) of the geopolymer cementitious compositions of some embodiments of the invention. The greatest increase in resistance to initial compression results when anhydrous calcium sulfate (anhydrite) is used, followed by calcium sulfate hemihydrate, and that followed by calcium sulfate dihydrate.
[105] In some embodiments, a smaller calcium sulfate particle size has been found to lead to a faster development in initial resistance (<24 hours). When it is desirable to have an extremely rapid rate of resistance development, the preferred average particle size of calcium sulfate is about 1 to about 30 microns, more preferably about 1 to about 20 microns, and even more preferably about from 1 to about 10 microns. Reactive cement mix
[106] The reactive cement mix of some embodiments of the present invention comprises Reactive powder Component A (also known here as reactive cement material) and activator of Component B, with preferred ranges, as shown in TABLE A. A Reactive powder Component A comprises thermally activated mineral aluminosilicate, calcium aluminate cement and calcium sulphate. Component B Activator comprises alkali metal chemical activator.
[107] Preferably, the reactive cement mixture contains about 10 to about 40 wt.% Lima. However, this lime does not have to be added. On the contrary, it is sometimes included as a chemical component of the thermally activated mineral aluminosilicate.
[108] In addition to the thermally activated aluminosilicate mineral, calcium aluminate cement and calcium sulfate, reactive powder cement can include about 0 to about 15% by weight of optional additives such as portland cement. However, preferably, there is an absence of Portland cement as its incorporation increases the material shrinkage than the less dimensionally stable material. Fly ash class C and other thermally activated aluminosilicate minerals
[109] The thermally activated aluminosilicate minerals are in some embodiments selected from a group consisting of fly ash, blast furnace slag, thermally activated clays, shales, metakaolin, zeolites, soil rock, and soil clay bricks. Preferably, they have an Al2O3 content greater than about 5% by weight. Preferably clay or loam is used after thermal activation by heat treatment at temperatures of about 600 ° to about 850 ° C. The thermally activated aluminosilicate mineral preferred in some embodiments of the invention has a high content of lime (CaO) in the composition, preferably greater than about 10% by weight, more preferably greater than about 15%, an even more preferably greater d that about 20%. The most preferred thermally activated aluminum-silicate mineral is Class C Ash, for example, ash purchased from coal-fired power plants. Fly ash also has pozzolanic properties.
[110] ASTM C618 (2008) defines pozzolanic materials as "siliceous or siliceous and aluminous materials that in themselves have little or no cement value, but, in a finely divided form and in the presence of moisture, react chemically with calcium hydroxide at normal temperatures to form compounds that have cement properties.
[111] Fly ash is the preferred thermally activated aluminum-silicate mineral in the reactive cementitious powder mixture of some embodiments of the invention. Fly ash containing high calcium oxide and calcium aluminate (such as Class C fly ash from ASTM C618 (2008) is preferred, as explained below.
[112] Fly ash is a fine powder by-product formed from the combustion of coal. Utility boilers for power plant burning pulverized coal commercially produce more fly ash available. These fly ash consists mainly of spherical glassy particles, as well as residues of hematite and magnetite, char, and some crystalline phases formed during cooling. The structure, composition and properties of fly ash particles will depend on the structure and composition of coal and the combustion processes, through which fly ash is formed. ASTM C618 (2008) standard recognizes two main classes of fly ash for concrete - Class C and Class F. These two classes of fly ash are generally derived from different types of coal, which are the result of differences in the processes of coal formation that occur over geological time periods. Class F ash is normally produced from anthracite or burning bituminous coal, whereas Class C ash is normally produced from lignite or sub-bituminous coal.
[113] The ASTM C618 (2008) standard differentiates Class F and Fly ash Class C, mainly according to their pozzolanic properties. Therefore, in the ASTM C618 (2008) standard, the main difference between the Fly ash Class F Class C and fly ash specification is the lower limit of SiO2 + Al2 O3 + Fe2O3 in the composition. The minimum limit for SiO2 + Al2O3 + Fe2O3 for Class F Ash is 70% and for Class C flywheel is 50%. Thus, Fly ash Class F are more pozzolanic than fly ash Class C. Although not explicitly recognized in the ASTM C618 (2008) standard, Fly ash Class C preferably has a high content of calcium oxide (lime).
[114] Fly ash Class C usually has cementitious properties, in addition to pozzolanic properties, due to free lime (calcium oxide). Class F is rarely cement, when mixed with water only. The presence of high calcium oxide makes fly ash Class C have cement properties, leading to the formation of calcium silicates and calcium aluminate hydrates when mixed with water. As will be seen in the following examples, Class C fly ash provided superior results.
[115] The thermally activated aluminosilicate mineral comprises Class C fly ash, preferably about 50 to about 100 parts of Class C ash per 100 thermally activated aluminosilicate mineral, more preferably, the thermally activated aluminosilicate mineral comprises about from 75 parts to about 100 parts of Class C flywheel per 100 parts of thermally activated mineral aluminosilicate.
[116] Other types of fly ash, such as Class F Ash, can also be used. Preferably, at least about 50% by weight of the thermally activated aluminosilicate mineral, in which the cement powder is reactive Fly ash Class C with the remainder of Fly ash Class F, or any other thermally activated aluminosilicate mineral. More preferably, about 55 to about 75% by weight of the thermally activated aluminosilicate mineral, where the cement powder is reactive Fly ash Class C with the rest of Class F, or any other thermally activated aluminosilicate mineral. Preferably, the thermally activated aluminosilicate mineral is from about 90 to about 10% of Class C fly ash, for example 100% of Class C fly ash.
[117] The average particle size of the thermally activated aluminum-silicate minerals of some embodiments of the invention is preferably less than about 100 microns, preferably less than about 50 microns, more preferably less than about 25 microns, and even more preferably less than about 15 microns.
[118] Preferably, the mixture composition of some embodiments of the invention has a maximum of about 5 parts per 100 parts of metakaolin thermally activated mineral aluminosilicate. Preferably, the compositions according to some embodiments of the invention have an absence of metakaolin. Presence of metakaolin was found to increase the demand for water from the mixtures, hence its use is not desirable in the geopolymeric compositions of some modalities of the invention.
[119] Minerals often found in fly ash are quartz (SiO2), mullite (Al2Si2O13), gelenite (Ca2 Al2SiO7), hematite (Fe2 O3), magnetite (Fe3O4), among others. In addition, aluminum silicate polymorphs minerals commonly found in rocks, such as similanite, kyanite, Andalusia all three represented by the molecular formula of Al2 SiO5 are also often found in ash.
[120] Fly ash may also include calcium sulphate or another source of sulphate ions, which will be the mixture composition of some embodiments of the invention.
[121] The fineness of fly ash is preferably such that less than about 34% is retained on a 325 mesh sieve (USA Series) as tested in ASTM Test Procedure C-311 (2011) ("Sampling and Testing Procedures for Fly Ash as Mineral Admixture for Portland Cement Concrete "). The average particle size of the fly ash materials of some embodiments of the invention is preferably less than about 50 microns, preferably less than about 35 microns, more preferably less than about 25 microns, and even more preferably less than that about 15 microns. These fly ash are preferably recovered and used dry because of their self-fixing nature.
[122] Class C fly ash made from sub-bituminous coal has the following representative composition listed in TABLE E. Fly ash is preferably recovered and used dry due to its self-fixing nature.

[123] A suitable preferred ash class has the following composition listed in Table F.
Hydraulic Cements
[124] Hydraulic cements for the purposes of the present invention is a cement that undergoes a chemical fixation reaction when it comes into contact with water (hydration), which will not only define (cure) under water, but also constitute a water resistant product .
[125] Hydraulic cements include, but are not limited to, aluminum silicate cements such as Portland cement, calcium aluminate cement, cementitious calcium sulfoaluminate, and calcium fluoroaluminate cements. Calcium aluminate cement
[126] Calcium aluminate cement (CAC) is a hydraulic cement that forms a component of the reactive powder mixture of modalities of the invention.
[127] Calcium aluminate cement (CAC) is also commonly referred to as aluminous cement or high alumina cement. Calcium aluminate cements have a high alumina content, about 30-45% by weight is preferably. Higher-purity calcium aluminate cements are also commercially available in which the alumina content can vary as much as about 80% by weight. These higher purity calcium aluminate cements tend to be relatively more expensive. The calcium aluminate cement used in the compositions of some embodiments of the invention is finely ground to facilitate the entry of the aluminates into the aqueous phase so that the rapid formation of etringitis and other calcium aluminate hydrates can take place. The surface area of the calcium aluminate that the cement can be useful in some embodiments of the composition of the present invention is greater than about 3,000 cm2 / gram and preferably about 4,000 to 6,000 cm2 / gram, as measured by the surface area method de Blaine (ASTM C 204).
[128] Various manufacturing methods have emerged to produce calcium aluminate cement worldwide. Typically, the main raw materials used in the manufacture of calcium aluminate cement are bauxite and limestone. A manufacturing method that has been used in the USA for the production of calcium aluminate cement is described as follows. The bauxite ore is crushed and dried first, then ground together with the limestone. The dry powder comprising bauxite and limestone is then fed to a rotary kiln. A pulverized low ash coal is used as fuel in the oven. The reaction between bauxite and limestone takes place in the oven and collects the molten product at the bottom end of the oven and dumps it into a channel defined at the bottom. The molten clinker is quenched with water to form clinker granules, which is then transported to an accumulation unit. This granulate is then ground to the desired degree of fineness, to produce the final cement.
[129] Various calcium aluminate compounds are formed during the process of making calcium aluminate cements. The compound is formed predominantly of monocalcium aluminate (CaO ^ Al2O3, also referred to as CA), in a type of calcium aluminate cement. In another type of calcium aluminate cement, 12CaO ^ 7A ^ O3 also referred to as C12A7 or dodeca aluminate hepta calcium is formed as the reactive primary calcium aluminate phase. The other calcium aluminate and calcium silicate compounds that form in the production of calcium aluminate cements include CaO ^ 2Al2O3 also referred to as CA2 or calcium dialuminate, dicalcium silicate (2CaO ^ SiO2, called C2S), dicalcium alumina silicate ( 2CaO ^ Al2O3 ^ SiO2, called C2AS). Several other compounds, which contain a relatively high proportion of iron oxides, also form. These include calcium ferrites, such as CaO ^ Fe2O3 or CF and 2CaO • Fe2O3 or C2F and aluminum-ferrite calcium such as tetra-calcium aluminoferrite (4CaO ^ Al2O3 ^ Fe2O3 or C4AF), 6CaO ^ Al2O3 ^ 2Fe2O3 or C6A2 * 2 and 66A2 * 2 and 6 Fe2O3 or C6A2F). Other minor components present in calcium aluminate cement include magnesia (MgO), titanium oxide (TiO2), sulfates and alkalis. The preferred calcium aluminate cement useful in some embodiments of the invention may have one or more of the above steps. Calcium aluminate cements with monocalcium aluminate (CaO ^ O3 or CA) and / or calcium altamate hepta dodeca (12CaO ^ 7Al2O3 or C12A7) as predominant phases are particularly preferred in some embodiments of the present invention. In addition, the calcium aluminate phases may be available in crystalline and / or amorphous form. Ciment Fondu (or Fondu HAC), Secar 51, and Secar 71 are some examples of commercially available calcium aluminate cements, which have monocalcium aluminate (CA) as the primary cement phase. Ternal EV is a commercially available example of calcium aluminate cement, which has hepta dodeca calcium aluminate (12CaO ^ 7Al2O3 or C12A7) as the predominant cement phase.
[130] Preferably the compositions of some embodiments of the invention comprise about 1-200 parts by weight, preferably about 2 to 100 parts by weight, more preferably about 5-75 parts by weight, and even more preferably about 10-50 parts by weight of calcium aluminate cement per 100 bpw of thermally activated aluminosilicate mineral. Calcium sulfoaluminate cements (CSA)
[131] Calcium sulfoaluminate (CSA) cements can optionally be used in some embodiments of the present invention. CSA cements are a different class of calcium aluminate cement (CAC) cements of calcium silicate or other hydraulic cements based on, for example, Portland cement. CSA cements are hydraulic cements based on calcium sulfoaluminate, instead of calcium aluminate, which are the basis of CAC cement or calcium silicates, which are the basis of Portland cement. Calcium sulfoaluminate cements are made from coal slag that includes Ye'elimite (Ca4 (AlO2) 6SO4 or C4A3S) as the primary phase. Other major phases present in sulfo may include one or more of the following characteristics: dicalcium silicate (C2S), aluminum-ferrite tetracalcium (C4AF), and calcium sulfate (CS). The relatively low need for calcium sulfate sulfoaluminate cements in relation to Portland cement reduces energy consumption and greenhouse gas emissions from cement production. In fact, calcium sulfoaluminate cements can be manufactured at temperatures of approximately 200 ° C lower than Portland cement, thereby further reducing energy and greenhouse gas emissions. The amount of Ye'elimite (Ca4 (AlO2) 6SO4 or C4A3S) phase present in the calcium sulfoaluminate cement useful in some embodiments of the present invention is preferably about 20 to about 90% by weight and more preferably 30 to 75 % by weight. When calcium sulfoaluminate (CSA) cements are used in the present invention, they can partially replace calcium aluminate cement. The amount of calcium sulfoaluminate cement replacement in the composition of some embodiments of the invention can be up to about 49% by weight of the aggregate weight of calcium aluminate cement and calcium sulfoaluminate cement. Portland cement
[132] Compositions according to some embodiments of the invention can have from 0 to about 15 parts, by weight of Portland cement, relative to 100 parts by weight of fly ash.
[133] The low cost and wide availability of limestone, shale, and other naturally occurring materials make Portland cement one of the lowest cost materials widely used during the past century worldwide. As used herein, "Portland cement" is a calcium silicate-based hydraulic cement. ASTM C 150 defines Portland cement as "hydraulic cement (cement that not only hardens by reaction with water, but also constitutes a water resistant product), produced by clinker spraying, which essentially consists of hydraulic calcium silicates, usually containing one or more of the forms of calcium sulfate as a complement between earth. ”As used herein," clinker "are nodules (diameters, about 0.2 - about 1.0 inches [5-25 mm]) of a material porous, which are produced when a crude mixture of the predetermined composition is heated to high temperature.
[134] However, very surprisingly, it has been found that the addition of Portland cements to the dimensionally stable compositions of the present invention comprising mineral aluminum silicate, an alkali metal chemical activator, calcium aluminate cement and calcium sulfate has a negative influence on the shrinkage behavior of the resulting compositions. It has been found that the addition of Portland cements to the geopolymer compositions of the present invention increases the shrinkage of the resulting compositions. The magnitude of the observed shrinkage increases with the increase in the amount of Portland cements in the resulting compositions.
[135] This result is highly unexpected and surprising and highlights the extremely complex nature of chemical interactions that occur when other cementitious types and / or chemical additives are introduced into the dimensionally stable geopolymer binder compositions of the present invention. Based on this knowledge, no Portland cement is incorporated in some preferred embodiments of the invention. However, it is considered that a certain amount of Portland cements will be used in some modalities, when desired, in situations where a certain increase in shrinkage behavior may be acceptable. The practical limit on the amount of Portland cements will depend on the amount of adverse effect on the shrinkage behavior that may be acceptable, but in some preferred embodiments of the invention, no more than 15 parts by weight Portland cements to 100 parts by weight of the aluminum aluminosilicate thermally activated is included. Calcium Fluoroaluminate
[136] Calcium fluoroaluminate has the chemical formula 3CaO. 3Al2O3. CaF2. Calcium fluoroaluminate is often produced by mixing lime, bauxite and fluorite in an amount such that the mineral of the resulting product becomes 3CaO.3Al2O3. CaF2e the resulting mixture is burned at a temperature of about 1200 ° -1400 ° C. Calcium fluoroaluminate cements can optionally be used in the present invention. Calcium Sulfate
[137] Calcium sulfate is an ingredient in the geopolymer compositions of some embodiments of the invention. Although calcium sulfate, for example calcium sulfate dihydrate, reacts with water, it does not form a water resistant product and is not considered to be hydraulic cement for the purposes of the present invention. Types of calcium sulfate that are useful in some embodiments of the invention include calcium sulfate dihydrate, calcium sulfate hemihydrate and anhydrous calcium sulfate (anhydrite). These calcium sulfates can be available naturally or industrially produced. Calcium sulphates synergistically interact with the other fundamental components of the cementitious compositions of some embodiments of the invention and, thus, help to minimize the shrinkage material while transmitting other useful properties to the final material.
[138] Different morphological forms of calcium sulfate can be usefully employed in various embodiments of the present invention. The properties of the geopolymer compositions and composites of some embodiments of the invention have been found to depend significantly on the type of calcium sulfate used based on their chemical composition, particle size, crystal morphology, and chemical and heat treatment. Among other properties, the fixation behavior, the rate of development of strength, resistance to final compression, the behavior of shrinkage, cracking and strength of the geopolymer compositions of some modalities of the invention can be adapted by selecting a suitable source of calcium sulfate in the formulation . Thus, the selection of the type of calcium sulfate used for some modalities of the invention is based on the balance of properties desired in the final application.
[139] In the geopolymer compositions of some embodiments of the invention, a mixture of two or more types of calcium sulfate is used. When such a mixture is used, the types of calcium sulphate used can vary depending on their chemical composition, particle size, crystal shape and morphology, and / or the surface treatment.
[140] The size of the particles and the morphology of calcium sulfate have been found to significantly influence the development of early and final strength of the geopolymer cementitious compositions of some embodiments of the invention. In general, a smaller particle size of calcium sulfate has been found to provide rapid strength development earlier. When it is desirable to have an extremely rapid rate of resistance development, the preferred average particle size of calcium sulfate ranges is about 1 to about 100 microns, more preferably about 1 to about 50 microns, and even more preferably about 1 to about 20 microns. In addition, calcium sulfates with a finer particle size have also been found as a result of less material shrinkage of some modalities.
[141] It was further found that, for a given amount of calcium aluminate cement and other components of raw material present, an increase in (but not excessive increase) in the amount of calcium sulfate leads to an increase in the initial compressive strength geopolymeric compositions of some modalities of the invention. The most dramatic increase in initial compressive strength occurs when the amount of calcium sulfate is about 10 to about 50% by weight of calcium aluminate cement.
[142] All three forms of calcium sulphate (mainly hemihydrate, dihydrate and anhydrite) are useful in mixtures of four reactive components of some embodiments of the invention, to provide the most often fixing benefits and bond strengths. higher compression ratios than in Comparative Examples 1-4 below. The three different forms of calcium sulfate have been found to have different and surprising effects relative to each other on the times of compressive strength and fixation in various embodiments of the invention.
[143] It is well known that the most soluble form of calcium sulphate is hemihydrate, followed by the form of relatively low solubility of the dihydrate, and then followed by the relatively insoluble form of anhydrite. All three forms are known to be defined (form matrices of the chemical form dihydrate) in aqueous medium under appropriate conditions, and the fixation times and compressive strength of the indicated forms are known to follow their order of solubility. For example, all other things being equal, employed alone as the single fixing material, the hemihydrate generally in the shortest fixing times and anhydrating the longest fixing times (typically very long fixing times).
[144] Quite surprisingly, it was found that modalities that predominantly employs or calcium sulfate hemihydrate all have longer fixation times, while those that predominantly use or calcium sulfate anhydrite have the shortest defined times. Likewise, surprisingly, in several modalities, it was found that those that use all anhydrite or predominantly calcium sulfate have a greater resistance to compression than the former employing the dihydrate form mainly. The modalities that use mainly the hemihydrate form have initial resistance to compression similar to that which use mainly the anhydrite form.
[145] In geopolymeric compositions of other modalities, a mixture of two or more types of calcium sulfate can also be used to modify the fixation times and the initial compressive strength properties of the composition in relation to these modalities using predominantly or all of a single type of calcium sulfate. When such a mixture is used, the types of calcium sulphate used can vary depending on their chemical composition, particle size, crystal shape and morphology, and / or the surface treatment.
[146] The size of the particles and the calcium sulphate morphology used has been found to significantly influence the development of initial and final strengths of the geopolymeric cementitious binder compositions of some embodiments of the invention. In general, a smaller particle size of calcium sulfate has been found to provide rapid strength development earlier. When it is desirable to have an extremely rapid rate of resistance development, the preferred average particle size of calcium sulfate ranges from about 1 to about 100 microns, more preferably from about 1 to about 50 microns, and most preferably about from 1 to about 20 microns. In addition, calcium sulfates with a finer particle size have also been found to reduce shrinkage material.
[147] It was further found that, for a given amount of calcium aluminate cement and other components of raw material present, an increase in (but not excessive increase) in the amount of calcium sulfate leads to an increase in resistance to initial compression of the geopolymeric binders of some embodiments of the present invention. The most dramatic increase in initial compressive strength occurs when the amount of calcium sulfate is about 10 to about 50% by weight of calcium aluminate cement.
[148] It was also unexpectedly verified the amount of calcium sulfate present in the calcium aluminate cement ratio, where the mixture has a significant influence on the degree of shrinkage of the material of geopolymer compositions of some embodiments of the invention. Preferably, these embodiments have an amount of calcium sulfate of about 5 to about 200 parts by weight relative to 100 parts by weight of calcium aluminate cement. For more effective control over the material shrinkage of geopolymer compositions in such embodiments, the amount of calcium sulfate is about 10 to about 100 parts by weight relative to 100 parts by weight calcium aluminate cement, more preferably about 15 to about 75 parts by weight relative to 100 parts by weight calcium aluminate cement, and more preferably about 20 to about 50 parts by weight relative to 100 parts by weight calcium aluminate cement.
[149] For given amounts of alkali metal activator and other raw material components in the composition of some embodiments of the invention, the use of calcium sulfate dihydrate has been found to provide the most effective control to minimize material shrinkage. Use of anhydrous calcium sulfate (anhydrite) and calcium sulfate hemihydrate also provide excellent control in reducing the material shrinkage of one of the geopolymeric cementitious binder compositions of such modalities.
[150] The selection of the type or types of calcium sulphate employed in the compositions of such modalities is based on the desired rate of age at the beginning of the development of strength, control of shrinkage, and the balance of other properties desired in the final application.
[151] The type of calcium sulphate has also been found to have a very significant influence on the development of initial compressive strength (<24 hours) of the geopolymer compositions of some embodiments of the invention. The greatest increase in resistance to initial compression results when anhydrous calcium sulfate (anhydrite) is used, followed by hemihydrate calcium sulfate, followed by dihydrate calcium sulfate. The selection of the type of calcium sulphate used in some composition of some modalities of the invention is based on the desired rate of age at the beginning of the development of strength, control of shrinkage, and the balance of other properties desired in the final application.
[152] A part or all of the amount of calcium sulfate can be added as a calcium aluminate cement additive component in the compositions of some embodiments of the invention. When this is the case, the amount of calcium sulphate added separately is reduced by an equivalent amount included in the calcium aluminate cement.
[153] Calcium sulfate can also be included in fly ash in some modalities of the composition. When this is the case, the amount of calcium sulphate added separately can be reduced. The amount of calcium sulfate added separately to the compositions of some embodiments of the invention can be adjusted based on the availability of the sulfate ions contributed by the other components present in the mixture. In order to increase the durability of the geopolymer compositions of some embodiments of the invention, it is desirable to keep the calcium sulfate content at relatively low levels. The excess of calcium sulfate or other sulfate ions in the mixture can lead to chemical discomfort due to the expansion of the material caused by hydration and precipitation of the salts present in the material. Pozzolans
[154] Other aluminosilicate mineral silicates and optional ones that are pozzolans, having little or no substantial cementing properties on their own in an aqueous medium can be included as optional mineral additives in the compositions of some embodiments of the invention. Various natural and artificial materials have been referred to as pozzolanic materials that have pozzolanic properties. Some examples of pozzolanic materials include silica powder, pumice, perlite, diatomaceous earth, finely ground clay, finely ground shale, finely ground slate, finely ground glass, volcanic tufts, trass, and rice husk. All of these pozzolanic materials can be used either alone or in combined form as part of the reactive cementitious powder of some embodiments of the invention. Fillers - Aggregates, inorganic minerals Fillers and light fillers
[155] While the cementitious reactive powder mixture presented defines the fast-setting component of the cementitious composition of some embodiments of the invention, it will be understood by those skilled in the art that other materials may be included in the composition, depending on its intended use and application.
[156] One or more fillers such as sand, fine aggregate, coarse aggregate, inorganic mineral fillers, lightweight fillers can be used as a component in the geopolymeric formulations of some embodiments of the invention. These filling materials are preferably not thermally activated pozzolans or aluminosilicate minerals.
[157] Preferably, inorganic mineral fillers are dolomite, limestone, calcium carbonate, ground clay, shale, slate, mica and talc. They generally have a fine particle size, preferably with an average particle diameter of less than about 100 microns, preferably less than about 50 microns, and more preferably less than about 25 microns in the compositions according to some embodiments of the invention. Smectite and paligorsquite clays and their mixtures are not considered inorganic mineral fillers in this invention.
[158] Fine aggregate or sand is defined as an inorganic rock material with an average particle size of less than about 4.75 millimeters (0.195 inches).
[159] Sand preferably in the present invention has an average particle size of 0.1 mm to about 2 mm. Fine sand with an average particle size of about 1 mm or less is preferred in some embodiments of this invention. Sand, with a maximum particle diameter of about 0.6 mm, preferably a maximum of about 0.425 mm, an average particle diameter within a range of about 0.1 to about 0.5 mm, preferably about 0.1 mm to about 0.3 mm are useful in other embodiments of the invention. Examples of fine sand preferably include QUIKRETE FINE No. 1961 and UNIMIN 5030 with a predominant size range of US # 70 - # 30 sieve number (0.2-0.6 mm.).
[160] The particle size distribution and the amount of sand in the formulations helps to control the rheological behavior of the cementitious compositions of some modalities of the invention. Fine sand can be added in geopolymer cementitious compositions of some modalities of the invention in sand / cementitious materials (reactive powder) ratio of about 0.05 to about 4. When it is desired to achieve self-leveling of the material rheology, the most desirable ratio of sand cementitious materials in the formulation is approximately 0.50 to about 2, more preferably about 0.75 to about 1.5.
[161] Coarse aggregate is defined as an inorganic rock material with an average particle size of at least 4.75 millimeters (0.195 inches), for example 1/4 '' to 1-1 / 2 in. "(0, 64-3 0.8 1 cm). Aggregate larger than 1-1 / 2 "(0.8 3 of 1 cm), can also be used in some applications, for example, concrete floors. The particle shape and texture of the coarse aggregate can be used angular, rough, elongated, rounded or smooth or a combination of these. Preferably, coarse aggregates are made of minerals such as granite, basalt, quartz, riolite, andesite, tuff, pumice, limestone, dolomite, sandstone, marble, flint, slate, and / or gnessis.
[162] Coarse aggregate useful in some modalities of the invention, preferably to meet the specifications established in the standard ASTM C33 (2011) and AASHTO M6 / M80 (200 8).
[163] When coarse aggregate is added in geopolymer cementitious compositions of some embodiments of the invention, they are preferably employed in an aggregate of cementitious materials (reactive powder) in the range of about 0.25 to about 5. Some embodiments of the invention contain coarse aggregate with coarse aggregate in cementitious materials at a rate of about 0.25 to about 1. Some other embodiments of the invention contain coarse aggregate with a coarse aggregate for a cementitious material ratio of about 1 to about 3.
[164] Light fillers have a specific gravity of less than about 1.5, preferably less than about 1, more preferably less than about 0.75, and even more preferably less than about 0.5. In some other preferred embodiments of the invention, the lightweight fill density is less than about 0.3, more preferably less than about 0.2 and more preferably less than about 0.1. In contrast, the inorganic mineral filler material preferably has a specific gravity greater than about 2.0. Examples of useful light fillers include pumice, vermiculite, expanded forms of clay, shale, slate and perlite, slag, expanded slag, ash, glass microspheres, synthetic ceramic microspheres, hollow ceramic microspheres, light polystyrene spheres, hollow microspheres of plastic, expanded plastic spheres, and the like. Expanded plastic granules and hollow plastic spheres when used in the composition of some embodiments of the invention are used in very small quantities, on a weight basis, due to their very low density.
[165] When lightweight fillers are used to reduce the weight of the material, they can be used to fill a cementitious material (reactive powder) in the range of about 0.01 to about 2, preferably about 0, 01 to about 1. A combination of two or more types of light fillers useful in the geopolymer compositions of some embodiments of the invention.
[166] While some embodiments of some embodiments of the invention contain only sand as additional filler material, other embodiments may contain sand and inorganic mineral fillers and / or lightweight fillers. Other embodiments may contain inorganic mineral fillers and light fillers such as added fillers. Some other embodiments of the invention contain sand, inorganic mineral filler and lightweight filler as the added fillers. Some other embodiments of the invention contain only inorganic mineral fillers or light fillers and not sand, fine aggregate or coarse aggregate. Some embodiments of the invention containing coarse aggregates may include or exclude one or more of the following fillers - sand, lightweight filler, and inorganic mineral filler.
[167] Some embodiments of the present invention are completely free of any added filler materials. Chemical activators of alkali metals
[168] In some embodiments of the invention, alkali metal salts and bases are useful as chemical activators to activate the reactive powder Component A which comprises the thermally activated mineral aluminosilicate such as fly ash, calcium aluminate cement and calcium sulfate. Alkali metal activators, of some embodiments of the present invention can be added in liquid or solid form. Preferred alkali metal chemical activators of some embodiments of the present invention are metallic salts of organic acids. The most preferred chemical alkali metal activators of some embodiments of this invention are the alkali metal salts of carboxylic acids. Alkali metal hydroxides and alkali metal silicates are some other examples of alkali activating metal chemistry of some embodiments of the present invention. Alternatively, alkali metal hydroxides and alkali metal silicates can also be used in combination with carboxylic acids, such as citric acid to provide chemical activation of the reactive mixture comprising thermally activated aluminosilicate mineral powder, calcium aluminate cement and calcium sulphate calcium.
[169] In some embodiments of the present invention, which employs citric acid alkali metal salts such as sodium or potassium citrate in combination with the reactive powder mixture comprising thermally activated aluminosilicate mineral comprising Class C fly ash, aluminate cement of calcium and calcium sulphate, provides mixing compositions with relatively good fluidity and that do not harden very quickly, after mixing the raw materials or around ambient temperatures (about 20-25 oC).
[170] The amount of citric acid alkali metal salt, for example, potassium citrate or sodium citrate, is about 0.5 to about 10% by weight, preferably about 1.0 to about 6 wt%, Preferably about 1.25 to about 4 wt%, more preferably about 1.5 to about 2.5 wt% and even more preferably about 2 wt% based in 100 parts of cementitious reactive components (ie Component A reactive powder), of some embodiments of the invention. So, for example, per 100 pounds of reactive cement powder, there can be about 1.25 to about 4 pounds total of potassium and / or sodium citrates. The preferred alkali metal citrates are potassium citrates and sodium citrates and particularly tri-potassium citrate monohydrate, and anhydrous sodium tri-citrate, tri-sodium citrate monohydrate, dry sodium citrate -dibasic hydrate, tri-sodium citrate dihydrate, di-sodium citrate, and sodium mono-citrate.
[171] Preferably, the activator does not contain an alkanolamine. In addition, the activator preferably does not contain a phosphate. Retarders
[172] Organic compounds, such as carboxylic acids, carbohydrates, sugars, starches and retardants are preferred in some embodiments of the invention. Organic acids, such as citric acid, tartaric acid, malic acid, gluconic acid, succinic acid, glycolic acid, malonic acid, butyric acid, malic acid, fumaric acid, formic acid, glutamic acid, pentanoic acid, glutaric acid , gluconic, tartronic, musclic acid, tridhydroxy benzoic acid, etc., are useful as retarders in the dimensionally stable geopolymer cement compositions of some embodiments of the invention. Sodium gluconate is also useful as a combined organic retardant in some embodiments of the present invention. Organic cellulose-based polymers, such as hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC), ethyl cellulose (EC), methyl ethyl cellulose (MEC), cellulose carboxymethyl cellulose (CMC) , carboxymethylethylcellulose (CMEC), carboxymethylhydroxyethylcellulose (CMHEC), are also useful as retardants in the compositions of some embodiments of the present invention. These cellulose-based retarders when added to the Composition of some embodiments of the invention also significantly increase the viscosity of the mixture in addition to causing retardation. Base retardants preferably inorganic acid like borate or boric acid are not employed in the composition of the present invention, because they prevent the rheology of the mixture, cause excessive efflorescence, and reduce the bond strength of material to other substrates. Other optional control agents
[173] Other optional chemical control additives include sodium carbonate, potassium carbonate, calcium nitrate, calcium nitrite, calcium formate, calcium acetate, calcium chloride, lithium carbonate, lithium nitrate, lithium nitrite, aluminum sulfate, sodium aluminate, alkanolamines, polyphosphates. These additives, when included as part of the formulation, can also influence the rheology of the geopolymer compositions of some modalities of the invention, in addition to affecting the fixation behavior. Optional materials, fibers and fabrics
[174] Other materials and optional additives can be included in geopolymer compositions of some embodiments of the invention. These include at least one member selected from the group consisting of redispersible polymer film-forming powder from polymer dispersions, film-forming latex, defoaming agents, water retention additives, defined control agents, reducing mixtures shrinkage agents, foaming and air retention agents, organic and inorganic rheology control agents, viscosity modifying agents (thickeners), efflorescence control (suppression), corrosion control agents, dyes and / or pigments, discrete, long fibers and continuous fibers and reinforcement, textile reinforcement, polyvinyl alcohol fibers, and / or glass fiber or other discrete reinforcement fibers.
[175] Discrete reinforcement fibers of different types can also be included in the geopolymer compositions of some embodiments of the invention. Screens made of materials such as glass fibers coated with polymers and polymeric materials such as polypropylene, polyethylene and nylon can be used to reinforce the precast cement-based product, depending on function and application.
[176] Preferably, the geopolymer compositions of embodiments of the invention have an absence of cement kiln dust. Cement kiln powder (CKD) is created inside the kiln during the production of cement clinker. The powder is a mixture of partially calcined and unreacted raw food particles, dust and clinker ash, enriched with alkaline sulfates, halides and other volatiles. These particles are captured by the exhaust gases and collected in particulate material control devices, such as cyclones, bag filters and electrostatic precipitators. CKD consists mainly of calcium carbonate and silicon dioxide, which is similar to the raw cement kiln feed, but the amount of alkali, chloride and sulfate is normally considerably higher in the powder. CKD from three different types of operations: long wet, long dry, and alkaline with precalcined have several chemical and physical characteristics. CKD generated from long-wet and long-dry furnaces is composed of partially calcined fines from the furnace enriched with sulfates and alkali chlorides. The dust collected from the alkaline of pre-calcined furnaces tends to be thicker, more disaggregated, and also concentrated with volatile alkalis. However, the alkaline derivation process contains the largest amount by weight of calcium oxide and the lowest loss on ignition (LOI). TABLE AA by Adaska et al., Beneficial Uses of Cement Kiln Dust, presented at IEEE 2008 / PCA 50 Conf. Cement Industry Technique, Miami, FL, May 19-22, 2008, presents the composition for the three different types of operation and preferably includes a chemical composition for the Type I Portland cement for comparison.
Superplasticizers and Air Retention Agents
[177] Water-reducing agents (superplasticizers) are preferably used in the compositions of some embodiments of the invention. They can be added in the dry form or in the form of a solution. Superplasticizers help to reduce the water demand of the mixture. Examples include polyphthalene superplasticizer sulfonates, polyacrylates, polycarboxylates, polyether polycarboxylates, lignosulfonates, melamine sulfonates, caseins, and the like. Depending on the type of superplasticizer used, the weight ratio of the superplasticizer (on a dry powder basis) to the reactive powder mixture will preferably be about 5% by weight or less, preferably about 2 p. % Or less, preferably about 0.1 to about 1 wt%.
[178] Polyether-based superplasticizers are the most preferred water chemical polycarboxylate for reducing the chemical mixture of the geopolymer cementitious compositions of some embodiments of the invention. Polyether polycarboxylate superplasticizers are most preferred as they facilitate the achievement of the various objectives of this invention, as mentioned earlier.
[179] Air retention agents are added to the cementitious paste of some embodiments of the invention, to form air bubbles (foam) in situ. Air retention agents are preferably surfactants used to purposely trap microscopic air bubbles in concrete. Alternatively, air-retaining agents are used for the production of foam, which is externally introduced into the mixtures of the compositions of some embodiments of the invention, during the mixing operation to reduce the density of the product. Preferably externally to foam the air-trapping agent (also known as a liquid foaming agent), air and water are mixed to form foam in a suitable foaming apparatus. A foam stabilizing agent, such as polyvinyl alcohol can be added to the foam before the foam is added to the cementitious paste.
[180] Examples of air retention / foaming agents include alkylsulfonates, alkylbenzolphonates and alkyl ether sulfate oligomers, among others. Details of the general formula for these foaming agents can be found in US Patent 5,643,510 incorporated herein by reference.
[181] An air retention agent (foaming agent) as conforming to the standards, as set out in ASTM C 260 "Standard Specification for Air Retention Additives for Concrete" (August 1, 2006) can be employed. Such air retention agents are well known to those of skill in the art and are described in Kosmatka et al "Design and Control of Concrete Mixtures," Fourteenth Edition, Portland Cement Association, specifically Chapter 8, entitled "Air Entrained Concrete" (cited in Publication of US Patent Application No. 2007/0079733 A1). Commercially available air-retaining materials include wood resins, sulfonated hydrocarbons and fatty, resinous, aliphatic substituted aryl sulfonates, such as sulfonated lignin salts and numerous other interfacially active materials, which normally take the form of anionic or non-ionic surfactants , sodium abietate, saturated or unsaturated fatty acids and their salts, surfactants, alkyl aryl sulfonates, phenol ethoxylates, lignosulfonates, resin soaps, sodium hydroxystearate, lauryl sulfate, ABSs (alkylbenzenesulfonates), alkylbenzenesulfonates linear, alkanesulfonates, polyoxyethylene alkyl (phenyl) ethers, polyoxyethylene alkyl (phenyl) ether sulfate esters or their salts, polyoxyethylene alkyl (phenyl) ether phosphate esters or their salts, proteinaceous materials, alpha- olefinsulfonates, an alpha olefin sulfonate sodium salt, or sodium lauryl sulfate or sulfonate and mi sturas even.
[182] Preferably, the air-trapping (foaming) agent is from about 0.01 to about 1 weight% of the total cementitious composition. Biopolymers and Organic Rheology Control Agents
[183] Succinoglycans, diutan gum, guar gum, wellan gum, xanthan gums and organic compounds based on cellulose ether, are biopolymers that act as hydrocolloids and rheology control agents in some embodiments of the present invention. Synthetic organic polymers, such as polyacrylic amides, swellable alkaline acrylic polymers, associative acrylic polymers, acrylic / acrylamide copolymers, hydrophobically modified dilatable alkaline polymers, highly water-expandable organic polymers can be usefully used as rheology control agents and thickening agents in geopolymeric compositions of some modalities of the invention.
[184] The associative and non-associative types of rheology control agents and thickening agents can be usefully used in the geopolymeric compositions of some modalities of the invention.
[185] Examples of cellulose based on organic polymers useful for rheology control in the geopolymer compositions of some embodiments of the present invention include hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), hydroxypropylmethylcellulose (HPMC), ethylcellulose (EC ), methyl ethyl cellulose (MEC), carboxymethyl cellulose (CMC), carboxymethyl ethyl cellulose (CMEC), and carboxymethyl hydroxyethyl cellulose (MHEC).
[186] The organic and thickening rheology control agents mentioned above are soluble in cold and hot water. These additives also act as water retention agents and, thus, minimize material segregation and bleeding in addition to controlling the rheology of the material. Inorganic Rheology Control Agents
[187] The geopolymer cementitious compositions of some embodiments of the invention may also include inorganic rheology control agents that belong to the phyllosilicate family. Examples of inorganic rheology control agents particularly useful in the geopolymeric compositions of the invention include sepiolite, smectite, kaolinite and illite. Smectite clays, particularly useful in some embodiments of the present invention include hectorite, saponite and montmorillonite. Different varieties of natural and chemically treated bentonite clay can also be used to control the rheology of the compositions according to the present invention. These additives also act as water retention agents and thus minimize material segregation and bleeding. Inorganic rheology control agents can be added in the absence of, or in combination with, organic rheology control agents in some embodiments of the present invention. Film-forming polymer additives
[188] Preferably, redispersible film-forming polymer powders in some embodiments are latex powders. These polymers in water redispersible powder are produced by spray drying of aqueous polymer dispersions (latex).
[189] Latex is an emulsion polymer. Latex is a dispersion of water-based polymer, widely used in industrial applications. Latex is a stable dispersion (colloidal emulsion) of polymer microparticles in an aqueous medium. Thus, it is a suspension / dispersion of rubber or plastic polymer microparticles in water. Latexes can be natural or synthetic.
[190] Latex is preferably made from pure acrylic, a styrene rubber, styrene butadiene rubber, an acrylic styrene, a vinyl acrylic or a copolymer of ethylene vinyl acetate and is most preferably a pure acrylic. Preferably, latex polymer is derived from at least one acrylic monomer selected from the group consisting of acrylic acid, acrylic acid esters, methacrylic acid, and methacrylic acid esters. For example, monomers, preferably employed in emulsion polymerization include monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, 2-ethyl hexyl acrylate, other acrylates, methacrylates and mixtures thereof, acrylic acid , methacrylic acid, styrene, vinyl toluene, vinyl acetate, vinyl esters of higher carboxylic acids than acetic acid, for example, vinyl versatate, acrylonitrile, acrylamide, butadiene, ethylene, vinyl chloride and the like, and mixtures thereof. For example, a latex polymer can be a butyl acrylate / methyl methacrylate or copolymer of a 2-ethylhexyl methacrylate / methyl acrylate copolymer. Preferably, the polymer latex is further derived from one or more monomers selected from the group consisting of styrene, alpha-methyl-styrene, vinyl chloride, acrylonitrile, methacrylonitrile, urea methacrylate, vinyl acetate, vinyl esters of acid acids tertiary branched monocarboxylic acids, itaconic acid, crotonic acid, maleic acid, fumaric acid, ethylene and C4-C8 conjugated dienes. Efflorescence suppression agent
[191] Water-repellent agents such as silanes, silicones, siloxanes, are added to the cementitious compositions of some embodiments of the invention to reduce the potential for efflorescence of the material. Selected examples of useful efflorescence suppressing agents include octyltriethoxysilane, potassium methyl siliconate, calcium stearate, butyl stearate, polymer stearate. These efflorescence control agents reduce water transport within the hardened material and thus minimize the migration of salts and other soluble chemicals that can cause efflorescence. Excessive efflorescence can lead to poor aesthetics, material damage and disruption of expansive reactions that occur due to salt build-up and salt hydration, and reduced bond strength with other substrates and surface coatings. Defoaming agents
[192] Anti-foam agents can be added to the geopolymer cementitious compositions of some embodiments of the invention to reduce the amount of trapped air, increase the strength of the material, increase the bond strength of material to other substrates, and to produce a free surface defect in applications where surface appearance is an important criterion. Examples of suitable defoaming agents useful in the geopolymer compositions of some embodiments of the invention include polyethylene oxides, polyethylene, polyethylene glycol, polypropylene glycol, alkoxylates, polyalkoxylate, fatty alcohol alkoxylates, hydrophobic esters, tributyl phosphate, polyacrylates of alkyl, silanes, silicones, polysiloxanes, polyether siloxanes, acetylenic diols, tetramethyl decinediol, secondary alcohol ethoxylates, silicone oil, hydrophobic silica, oils (mineral oil, vegetable oil, white oil), waxes (paraffin waxes, esters waxes, fatty alcohol waxes), amides, fatty acids, fatty acid polyether derivatives, etc. Initial suspension temperature
[193] In some embodiments of the present invention, which constitute the suspension, under conditions that provide for reduced initial mix suppression temperature and increase of less than about 50 ° F (28 ° C) to a mixture suppression temperature of final compositions, more preferably an increase of less than about 40 ° F (22 ° C) and more preferably an increase of less than about 30 ° F (17 ° C) to improve temperature stability and, most importantly, slower gelation and final fixation times of about 10 to about 240 minutes, more preferably about 60 to about 120 minutes and more preferably about 30 to about 90 minutes, allows more control of the working time for commercial use of the compositions of some embodiments of the invention. The initial temperature of the suspension is preferably about room temperature.
[194] Increasing the initial temperature of the suspension increases the rate of temperature increase as the reactions proceed and reduces the setting time. Thus, the temperature of the initial suspension from 95 ° F (35 ° C) to 105 ° F (41.1 ° C), used in the preparation of conventional geopolymeric compositions based on fly ash for rapid gelation and fixation times is, preferably avoided since the composition formulation is designed to reduce the temperature rise behavior of the mixed composition from the initial paste temperatures. The benefit of thermal stability obtained with some modalities of the present invention to increase the initial gelation time and final fixation times, which, in turn, allows for greater commercial workability can be somewhat reduced, if the initial temperature of the suspension is already relatively low. elevated.
[195] The initial temperature is defined as the temperature of the total mixture, during the first hour after the reactive cement powder, activator, and water are all present in the mixture. Of course, the temperature of the total mixture may vary during the first minute, but in order to achieve the preferred thermal stability it will preferably remain within a range of initial temperature range from about 0 to about 50 ° C, preferably a temperature from about 10 to about 35 ° C, more preferably an initial temperature from about 15 to about 25 ° C, preferably at room temperature. Exothermic material and temperature rise behavior
[196] The compositions of the present invention advantageously achieve moderate heat release and low temperature rise within the material during the curing phase. In such compositions of some embodiments of the invention, the maximum temperature increase that occurs in the material is preferably less than about 50 ° C (28 ° C), more preferably less than about 40 ° C (22 ° C), and more preferably less than about 30 ° C (17 ° C). This avoids thermal expansion and the consequent excessive cracking and rupture of material. This aspect becomes even more advantageous when the material is used in a way where large leaks of material are involved in real field applications. The geopolymer cementitious compositions of the present invention are beneficial in this particular aspect as they exhibit the lowest thermal expansion and greatest resistance to thermal cracking in real field applications. EXAMPLES
[197] In all examples, unless otherwise stated, calcium aluminate cement, known as Ciment Fondu (also referred to here as Fondu HAC), available from Kerneos Inc. has been employed as a component of cement powder reactive. The composition of calcium aluminate oxide cement (Ciment Fondu) used was as shown in table AA:

[198] The main phase of calcium aluminate present in Ciment Fondu (HAC Fondu) in the examples was monocalcium aluminate (CA).
[199] In all examples, except where otherwise noted, fly ash was Class C Gray from Campbell Power Plant, West Olive, MI. This fly ash had an average particle size of about 4 microns. The measured Blaine fineness of fly ash was about 4300 cm2 / g. The composition of the Class C fly ash oxide used in the examples was as shown in Table AA.
[200] The calcium sulfate used in some embodiments of the invention and in the examples has an average particle size of about 1-2 00 microns (micrometers) and preferably about 1-20 microns when refined calcium sulfate is used.
[201] In particular, the calcium hydrate dihydrate employed in the examples was a refined calcium sulfate dihydrate, referred to here as landplaster, available from the United States Gypsum Company. Landplaster is a fine-grained calcium sulfate dihydrate with an average particle size of about 15 microns.
[202] The anhydrous calcium sulfate (anhydrite) included in some of the examples was the filler brand SNOW WHITE available from the United States Gypsum Company. The USG SNOW WHITE filling is an insoluble form of anhydrite produced by high temperature heat treatment of calcium sulphate, preferably plaster. It has a very low level of humidity chemically combined, preferably about 0.35%. The average particle size of the USG SNOW WHITE filler is about 7 microns.
[203] The calcium sulfate hemihydrate used in several of the examples, the examples was USG Hydrocal C-Base branded calcium sulfate hemihydrate available from the United States Gypsum Company. Hidrocal C-Base is an alpha morphological form of hemi-hydrated calcium sulfate having a massive crystal microstructure and less water demand. The US Hydrocal C-base has an average particle size of about 17 microns.
[204] Coarse dihydrate calcium sulphate, otherwise identified here as coarse landplaster, used in a number of examples was obtained from the USG Detroit Plant and is available from the United States Gypsum Company as USG Ben Franklin AG brand Coarse Gypsum. The plaster brand USG Ben Franklin AG is a coarse dihydrate calcium sulfate with an average particle size of about 75-80 microns.
[205] Refined sand Quikrete no. 1961 and Unimin used in some embodiments of the present invention, and in some examples it had a particle size as indicated in TABLE BB:

[206] Potassium citrate or sodium citrate was added to alkaline citrate for the cementitious compositions of some embodiments of the invention and acted as a chemical activator, rheology modifier, and defined control agent.
[207] The initial fixation time and the final fixation time shown in the examples below were measured using the ASTM C266 (2008) standard, using Gilmore needles.
[208] The drop in flow and behavior of the geopolymer cementitious compositions of some embodiments of the present invention, and some of the examples were characterized by a drop test. The drop test used in the following examples uses a hollow cylinder, about 5.08 cm. (2 in.) In diameter and about 10.16 cm. (4 in.) In length held vertically with an open end resting on a smooth plastic surface. The cylinder is filled to the top with the cementitious mixture, followed by the removal of the upper surface to remove excess paste mixture. The cylinder is then gently lifted upwards vertically to allow the slurry to come out from the bottom and spread over the plastic surface to form a circular tablet. The insert diameter is then measured and recorded as the drop in material. Compositions with good flow behavior yield a higher drop value. The flow of the pulp is characterized by the classification of the fluidity of the paste on a scale of 1 to 10, with a value of 1 representing a very weak flow behavior and a value of 10 representing excellent flow behavior.
[209] Shrinkage of the material (also referred to here as "shrinkage") as used here is characterized by measuring the length variation of the prism sample according to the ASTM C928 (2009) test standard. The measurement of the initial length is made 4 hours after the components of individual raw materials including water are brought together. The final measurement is made 8 weeks after the components, including water, have been collected. The difference between the initial and final measurements divided by the initial 100% length times gives the shrinkage as a percentage. Specimens of changing the prism length also referred to here as bars, are prepared according to the ASTM C157 (2008) standard.
[210] The compressive strength of the material was measured according to the test method ASTM C109 (2008) testing the cubes at 2 in x2 in x2 in cubes for failure under compression. The cubes demoulded from the bronze molds, after hardening and curing in sealed plastic bags until the testing time. The cubes were tested at the age of four hours, 24 hours, 7 days and 28 days after the mold.
[211] The temperature rise behavior of the material paste was measured in the semi-adiabatic state, placing the suspension in an insulated container, and the temperature of the recording material using a thermocouple.
[212] Many of the examples show the physical properties of the geopolymer cementitious compositions developed from some embodiments of the invention comprising thermally activated aluminosilicate mineral (fly ash), calcium aluminate cement, calcium sulphate and alkali metal chemical activators. He studied the influence of the incorporation of calcium aluminate cement in combination with calcium sulfate and alkali metal chemical activator in the long-term and early shrinkage behavior of the material (chemical shrinkage and drying), resistance to initial compression, resistance to final compression, exothermic behavior and fixation characteristics of the geopolymer cementitious compositions developed from some modalities of the invention.
[213] Many of the examples show the physical properties of the geopolymer cementitious compositions developed from some embodiments of the invention comprising thermally activated aluminosilicate mineral (fly ash), calcium aluminate cement, calcium sulphate and alkali metal chemical activators. This example illustrates the influence incorporating calcium aluminate cement, in combination with calcium sulfate and alkali metal chemical activator on the material's long-term and early shrinkage behavior (chemical and drying shrinkage), initial compressive strength, resistance to final compression, exothermic behavior and fixation characteristics of the geopolymer cementitious compositions developed from some modalities of the invention.
[214] Compositions of some embodiments of the present invention are advantageously able to achieve moderate heat and low temperature rise within the material during the curing phase. In such compositions, the maximum temperature increase that occurs in the material is preferably less than about 50 ° F (28 ° C), more preferably less than about 40 ° F (22 ° C) and even more preferably less than about 30 ° F (17 ° C). This avoids thermal expansion and the consequent excessive cracking and rupture of material. This aspect becomes even more advantageous when the material is used in a way in which large thicknesses of material leakage are involved in real field applications. The geopolymer cementitious compositions of the present invention investigated as discussed below are beneficial in this particular aspect as they have lower thermal expansion and greater resistance to thermal cracking in real field applications.
[215] Compositions according to some embodiments of the invention have also achieved sufficiently long fixation times to provide good operability. A very short clamping time is problematic for some applications, as a short service life causes difficulties with the processing of fast clamping material with the equipment and tools used in the real field application. Example 1: Comparative example of current geopolymer cement compositions
[216] The following examples illustrate the physical properties of cementitious compositions comprising current Class C geopolymer and potassium citrate fly ash. The test results show the shrinkage behavior, resistance to initial and final compression; and the fixation behavior of the cementitious compositions shown in TABLE 1. All three mixtures were activated with potassium citrate and contained varying amounts of aggregated sand. All three mixtures have 100 parts by weight of fly ash Class C and 100 parts by weight Total cementitious materials. All cementitious material was Campbell C Plant Class C flywheel, West Olive, MI and QUIKRETE Commercial Grade Fine Sand No. 1961.
[217] Fig. 1A shows the shrinkage behavior of the current state-of-the-art geopolymer cementitious compositions investigated in Comparative Example 1.


[218] Shrinkage measurements were started at an age of 4 hours from the time the raw materials were mixed and melted. It can be seen that the fly ash compositions activated with an alkaline citrate showed an extremely high amount of shrinkage. The maximum measured shrinkage was found to be as high as 0.75% after 8 weeks of curing at 75 oC / 50% RH. Increased sand content has decreased the degree of shrinkage, but the global shrinkage is still very high at unacceptable levels. These high levels of material shrinkage make the material unsatisfactory for most construction applications. It should be noted that for most construction applications, the total magnitude of shrinkage above 0.10% is considered to be extremely high and undesirable. Initial flow behavior, Breakage, and early material cracking
[219] TABLE 2 shows the behavior of the initial flow and breaking of the current state-of-the-art geopolymer cement compositions investigated in Comparative Example 1.

[220] The composition of fly ash activated with an alkaline citrate had a good flow behavior in a sand / cement ratio of 0.75%. The paste lost its fluidity to a small extent, when the sand / cement ratio was increased to 1.50%. Finally, at a sand / cement ratio of 2.50, the mixture became extremely rigid and had absolutely no flow characteristics.
[221] Fig. 1B shows a photograph of the abatement wafer for Mixture # 1 investigated in Comparative Example 1 The abatement wafer developed a significant crack after drying. The initiation of cracks in the inserts occurred in less than 30 minutes of the drop test. The number of cracks and the size of the cracks grew with the subsequent drying of the material and hardening. Fixing time
[222] TABLE 3 shows the fixation behavior of current state-of-the-art geopolymer cement compositions investigated in Comparative Example 1.

[223] The cementitious compositions in this Example had extremely fast fixation behavior. All mixtures gelled very quickly and lost flow behavior in less than 5 minutes after the raw materials were mixed to form an aqueous paste. Compressive strength
[224] TABLE 4 shows the compressive strength behavior of the current state-of-the-art geopolymer cementitious compositions investigated in Comparative Example 1 All the fly ash compositions showed a compressive strength development greater than 7000 psi in 28 days.

Example 2: Comparative Example
[225] This example investigates the initial dimensional stability and crack resistance of current state-of-the-art current preferred geopolymeric formulations comprising cementitious compositions comprising fly ash and sodium citrate. TABLE 5 shows the composition of the raw materials of the investigated mixture composition. The mixtures were activated with potassium citrate and varying amounts of aggregated sand. The mixtures had 100 parts by weight Fly ash Class C and 100 parts by total weight of cementitious materials. In other words, all the cementitious material was Class C flywheel Gray.
[226] The composition uses QUIKRETE No. 1961 Commercial Grade Fine Sand and BASF CASTAMENT FS20 Superplasticizer.
Initial Material Cracking Behavior
[227] Fig. 2 shows a photograph of the abatement wafer for the mixture investigated in Comparative Example 2 The abatement wafer developed a significant crack after drying. Crack crack initiation occurred in less than 30 minutes of the drop test. The number of cracks and the size of the cracks increased significantly with the subsequent drying of the material and hardening. Compression Strength Behavior of Comparative Example 2 Composition
[228] Table 5A shows the behavior of the Compression Strength of the mixture in Comparative Example 2. The compressive strengths in the initial composition stage were relatively low, being less than approximately 500 psi in 4 hours and less than approximately 2000 psi in 24 hours . As will be shown later in the examples, the geopolymer compositions of the modalities of the invention develop significantly higher Compression Strength at these same initial stages with the equivalent water / cement ratio. As shown in the examples of the specific embodiments of the present invention, compressive strengths in the early stage can be easily adapted by adjusting the type and amount of calcium sulfate, the amount of calcium aluminate cement, and the type and amount of alkaline activator. used in the compositions of the modalities of the invention.
Example 3: Comparative Example
[229] This example investigates the dimensional stability and early breaking strength of comparative cement compositions comprising fly ash and alkali metal citrate. TABLE 5 shows the raw material composition of the investigated composition mixture. Initial Stage Material Cracking Behavior
[230] FIG. 3A shows a photograph of the abatement wafer for the mixture investigated in Comparative Example 3. The abatement wafer developed significant cracks upon drying. The crack cracking started less than approximately 30 minutes after the slump test. Compression Strength Behavior of Comparative Example 3 Composition
[231] Table 5B shows the behavior of the Compression Strength of the mixture in Comparative Example 3. The compressive strengths in the initial composition stage were relatively low, being less than approximately 500 psi in 4 hours and less than approximately 1500 psi. As shown in the later examples of the specific embodiments of the invention, the compressive strengths in the initial stage can be easily adapted by adjusting the type and amount of calcium sulfate, the amount of calcium aluminate cement, and the type and amount of alkaline activator. used in the compositions of the modalities of the invention.
Shrinkage Behavior
[232] FIG. 3B shows the early-stage shrinkage behavior of the cementitious composition in Comparative Example 3.
[233] Initial stage shrinkage measurements were initiated at the 1 hour stage from the time when the raw materials were mixed together and molded. The fly ash composition activated with an alkali metal metal showed an extremely high amount of shrinkage. The maximum measured shrinkage found being in excess of approximately 1% after 8 weeks of curing at approximately 75 ° F / 50% RH. Such high levels of material shrinkage yield unsatisfactory material for most construction applications. For most construction applications, shrinkage in excess of approximately 0.10% is considered to be undesirably high. Example 4: addition of cement with pure calcium aluminate to fly ash - Comparative Example
[234] This example shows the physical properties of cementitious compositions comprising fly ash, calcium aluminate cement and alkaline citrate. This studied the influence of the incorporation of calcium aluminate cement on the shrinkage and crack resistance of the investigated cement compositions that comprise fly ash and alkaline citrate.
[235] TABLES 6 and 7 show the raw material compositions of the various cement mixtures 1-4 investigated in this Example. Cement Fondu (HAC Fondu), a calcium aluminate cement, made available by Kerneos, was used as a component of the reactive cement powder in this investigation. The amount of calcium aluminate cement used in the various mixing compositions investigated in this Example was varied and was equal to 10% by weight and 30% despite the weight of fly ash. Potassium citrate was added as an alkaline citrate source in the cementitious compositions investigated in this example. The calcium sulfate used was calcium sulfate dihydrate from USG Landplaster. QUIKRETE Commercial Grade Fine Sand No. 1961 was used in conjunction with AdvaCast 500 superplasticizer, WR Grace.

Initial Flow Behavior, Slump and Cracking Behavior at an Early Stage of Material
[236] TABLE 8 shows the initial flow behavior and the abatement of the binary mixtures of fly ash cement and calcium aluminate investigated in Example 4. Both investigated mixtures had a good flow behavior and high wafer diameter as observed in slaughter test.

[237] FIG. 4A shows the photos of the abatement wafer for Comparative Mixtures 1 and 2 investigated in Example 4. Both abatement wafers developed significant cracks upon drying. The cracking in the crackers started to occur 5 minutes after the raw materials were mixed together. The number of cracks and the size of the cracks increased significantly with the subsequent drying of the material and further hardening. It can be concluded that the addition of calcium aluminate cement to the fly ash compositions activated with alkaline citrates produces a dimensionally unstable material prone to excessive cracking through drying and subsequent hardening. Shrinkage Behavior
[238] Specimens in the form of rectangular prisms were molded to characterize the shrinkage behavior of the investigated mixtures. The prism specimens for Mix 2 cracked in the mold (before demoulding) in less than 1 hour after the mold due to excessive material shrinkage.
[239] FIG. 4B shows the shrinkage behavior for Mix 1. Shrinkage measurements were started at the 4 hour stage from the time when the raw materials were mixed together to form an aqueous paste. The shrinkage of the material was measured for a total duration of approximately 8 weeks when curing the material at 75oF / 50% RH. It can be seen that the prisms for Mix 1 containing a mixture of fly ash, high alumina cement and an alkali metal citrate have shrunk significantly. The measured shrinkage of the prism specimen for Mixture 1 at the end of 8 weeks is approximately 1.08%. Example 5
[240] TABLES 6 and 7 show the raw material compositions of the two geopolymer cement mixes (Mix 3 and Mix 4 in Tables 6 and 7) of this invention investigated in Example 5. The amount of calcium aluminate cement used in the Mixing compositions in this example were equal to 10% by weight (Mix 3) and 30% by weight (Mix 4) of fly ash. Fine-grained plaster was added at a different amount level of 33.33% by weight based on the weight of the calcium aluminate cement).
[241]] Initial Flow Behavior, Slump and Cracking Behavior at Initial Stage of Material
[242] TABLE 8 shows the initial flow behavior and initial characteristics of the geopolymer cementitious compositions of the invention (Mix 3 and Mix 4 in TABLE 8) comprising fly ash, calcium aluminate cement, fine-grained plaster, and investigated alkaline citrate in Example 5. We can clearly see that all of the investigated mixing compositions had a good flow behavior. It is particularly noteworthy that such good flow properties were obtained even when the water / cement ratio was as low as 0.25.
[243] FIG. 5A shows the photograph of the abatement wafers for the geopolymer cementitious compositions of the invention investigated in Example 5. The abatement wafers of this Example did not develop any crack upon drying as was the case for the cement mixtures of Comparative Example 4 which do not contain any plaster. Thus, incorporating a source of calcium sulfate (fine-grained plaster) into the cement mix comprising fly ash, calcium aluminate cement, and alkaline citrate produces dimensionally stable geopolymer cement compositions that have a greater resistance to cracking upon drying. Shrinkage Behavior
[244] FIG. 5B shows a graph of the shrinkage behavior of the geopolymer cementitious compositions of the invention investigated in Example 5. The main objective of this investigation was to study the influence of the incorporation of calcium aluminate cement in combination with calcium sulfate (gypsum) and alkaline citrate in the shrinkage behavior of the developed geopolymeric cement compositions of the invention.
[245] Shrinkage measurements were started at the 4-hour stage from the time the raw materials were mixed together to form an aqueous paste. The shrinkage of the material was measured for a total duration of approximately 8 weeks when curing the material at 75oF / 50% RH.
[246] The following conclusions can be drawn from this investigation and FIG. 5B:
[247] The incorporation of calcium sulfate (gypsum) had a significant impact on improving the crack resistance and dimensional stability of geopolymeric cementitious compositions of the invention comprising fly ash, calcium aluminate cement and an alkaline citrate. Unlike the comparative Mix 1 shrinkage bars of Comparative Example 4 (without any plaster) that cracked even before demolding, the Example 5 shrinkage bars comprising calcium sulphate (plaster) were completely stable and did not result in any cracking before or after unmold it.
[248] The maximum measured shrinkage of the geopolymer cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulphate (plaster), and alkaline citrate was significantly less than that of cementitious compositions containing only fly ash and citrate alkaline (Example 1). For example, the geopolymer cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulphate (plaster) and alkaline citrate had the maximum measured shrinkage of 0.14% compared to the maximum shrinkage of approximately 0.75% of the comparative mixture that contains only fly ash and alkaline citrate (Example 1). Thus, it can be concluded that the addition of calcium sulfate to cementitious compositions comprising fly ash, calcium aluminate cement, and alkaline citrate helps to significantly reduce the shrinkage of the material. Setup Time
[249] TABLE 9 shows the setting time of the geopolymer cementitious compositions of the invention investigated in Example 5.

[250] The cementitious compositions investigated in Example 5 had a quick setting behavior with the final setting times varying between 20 to 40 minutes. The developed cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate (plaster), and alkaline citrate had relatively longer setting times than cement compositions which comprise only fly ash and alkaline citrate as seen in Example 1. For the cementitious composition comprising fly ash and alkaline citrate from Example 1, the final setting time was approximately 15 minutes. An extremely short pick-up time is a problem for most practical applications since a short service life (usage time after preparation) of the material causes significant difficulties for processing material with quick pick using equipment and tools involved in the actual application in the field. Compressive Strength
[251] TABLE 10 shows the behavior of the compressive strength of the developed geopolymer cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate (plaster), and alkaline citrate investigated in Example 5.

[252] This studied the influence of the incorporation of calcium aluminate cement in combination with calcium sulphate dihydrate (fine-grained plaster) both in the initial stage and in the last compressive strength behavior of the developed geopolymer cement compositions of the invention. The data indicate the following:
[253] The compressive strength of the geopolymer cementitious compositions of the invention investigated in this example continued to increase over time.
[254] The resistance of the initial stage (4 hours and 24 hours) of the mixtures increased with an increase in the amount of gypsum in the cementitious composition.
[255] The compressive strength in the initial 4-hour stage of the material was greater than 1400 psi with the use of plaster as a component of the investigated geopolymer cement compositions of the invention.
[256] The compressive strengths in the initial 24-hour stage of the material were greater than 2000 psi with the use of plaster as a component of the investigated geopolymer cement compositions of the invention. It should be noted that the 24-hour compressive strength for Mixture 3 with 30 parts of calcium aluminate cement and 10 parts of calcium sulfate was very high, approximately 4150 psi.
[257] The 28-day compressive strength of the geopolymer cementitious compositions of the invention investigated in this example was very high, approximately 6900 psi for Mixture 3 and approximately 4000 psi for Mixture 4.
[258] In the modalities of the current invention shown in this example, it was unexpectedly discovered that when the aluminosilicate mineral, the alkali metal activator, calcium aluminate cement and calcium sulfate are mixed together, the resulting reaction was less less exothermic than the two separate reactions and the gelling time and hardening times were significantly prolonged.
[259] It has also been found that there is a significant reduction in material shrinkage when the aluminosilicate mineral and the alkali metal activator have been reacted together with calcium aluminate cement and calcium sulfate as discussed above in the description paragraph. Example 6
[260] TABLE 11 shows the compositions of the raw material of the geopolymer cement mixtures investigated in this example, as shown in TABLE 6. The amount of calcium aluminate cement used in the mix compositions in this example was equal to 30% by weight of the flywheel gray. Calcium sulfate dihydrate (plaster) was added in different levels of quantity (5% by weight, 10% by weight, 20% by weight, and 30% by weight of fly ash and calcium aluminate cement) in the various compositions of the investigated mixture. The fly ash is Campbell Power Plant Fly Ash Class C, West Olive, MI, the calcium sulphate dihydrate is USG Landplaster, the calcium aluminate cement is Ciment Fondu (HAC Fondu), Kerneos Inc, the sand is QUIKRETE Commercial Grade Fine Sand N ° 1961 and the superplasticizer is AdvaCast 500, from WR Grace.

Initial Flow Behavior, Slump and Cracking Behavior at an Early Stage of Material
[261] TABLE 12 shows the behavior characteristics of the initial flow and slump of the geopolymer cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulphate (plaster), and alkaline citrate investigated in Example 6.

[262] All investigated mix compositions had good flow self-leveling behavior and high wafer diameter as seen in the slump test. The high slump and self-leveling behavior were obtained in a water / cementitious ratio as low as 0.275.
[263] FIG. 6A shows the photographs of the abatement wafers for the geopolymer cementitious compositions of the invention in Example 6. The abatement wafers of this example did not develop any crack upon drying compared to the case of the cementitious mixtures of Comparative Example 4 that do not contain calcium sulfate ( plaster). Thus, it can be concluded that incorporating a source of calcium sulfate (plaster) into the cement mix comprising fly ash, calcium aluminate cement, and alkaline citrate produces dimensionally stable geopolymer cement compositions that have a greater resistance to cracking upon drying. Shrinkage Behavior
[264] FIG. 6B shows the shrinkage behavior of the geopolymer cementitious compositions of the invention investigated in Example 6. This shows the influence of the incorporation of calcium aluminate cement in combination with calcium sulphate (calcium sulphate dihydrate or plaster) on the shrinkage behavior of the compositions geopolymer cementitious materials developed from the invention.
[265] Shrinkage measurements were started at the 4-hour stage from the time the raw materials were mixed together to form an aqueous paste. The shrinkage of the material was measured for a total duration of approximately 8 weeks of curing of the material at 75oF / 50% RH.
[266] The following important conclusions can be drawn from this investigation and FIG. 6B
[267] The incorporation of calcium sulfate (gypsum) had a significant impact in improving the crack resistance and dimensional stability of geopolymer cementitious compositions of the invention comprising fly ash, calcium aluminate cement and an alkaline citrate. Contrary to the shrinkage bars of Comparative Example 4 (without any plaster) that cracked even before demolding, the shrinkage bars of Example 6 comprising calcium sulphate (fine-grained plaster) were completely stable and did not result in any cracking before or after unmold it.
[268] The maximum measured shrinkage of the geopolymer cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulphate (fine-grained plaster), and alkaline citrate was significantly less than that of cementitious compositions comprising only fly ash and alkaline citrate (Example 1). For example, the geopolymer cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate (fine-grained plaster) and alkaline citrate had a maximum measured shrinkage of 0.13% to 0.24% compared to a maximum shrinkage of approximately 0.75% for the comparative mixture comprising only fly ash and alkaline citrate (Example 1). Thus, the addition of fine-grained plaster to cementitious compositions comprising fly ash, calcium aluminate cement, and alkaline citrate helps to significantly reduce material shrinkage.
[269] The increase in an amount of calcium sulfate (gypsum) at levels used in this Example resulted in a total decrease in the maximum shrinkage of the material. It can be seen that in an amount of calcium sulfate (plaster) of 16.7% by weight, the material shrinkage was 0.24% (Mix 1). The increase in an amount of calcium sulfate (plaster) to 33.3% by weight and 66.7% by weight resulted in a decrease in material shrinkage to a value of approximately 0.13% (Mixture 2 and Mixture 3). An additional increase in the amount of calcium sulfate (plaster) at 100% by weight resulted in a slight increase in shrinkage to a value of approximately 0.15% Heat Evolution Behavior and Tempered Paste Rise
[270] FIG. 6C shows the rising behavior of the exothermic temperature and paste of the geopolymer cementitious compositions of the invention investigated in Example 6. The cementitious compositions of Example 6 comprising fly ash, calcium aluminate cement, calcium sulfate (fine-grained plaster), and alkaline citrate showed only a very moderate temperature rise behavior. Moderate heat evolution and low temperature rise within the material during the curing stage are crucial to prevent excessive thermal expansion and consequent cracking and rupture of the material. This aspect becomes even more crucial when the material is used in a way in which large thicknesses of concreting materials are involved in the present real application. The geopolymer cementitious compositions of the present invention investigated in this Example have been disclosed as highly beneficial in this specific aspect since they would lead to lower thermal expansion and greater resistance to thermal cracking in real field applications. Pick-up time
[271] TABLE 13 shows the setting time of the geopolymer cementitious compositions of the invention investigated in Example 6 comprising fly ash, calcium aluminate cement, calcium sulfate (fine-grained plaster), and alkaline citrate.

[272] All cementitious compositions investigated in this example showed final setting times ranging from 30 to 50 minutes. In comparison, the cementitious composition comprising fly ash and alkaline citrate of Example 1 had a final setting time of approximately 15 minutes. Compressive Strength
[273] TABLE 14 shows the behavior of compressive strength in the initial and final stages of the developed geopolymer cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate (plaster and fine granulation), and alkali metal citrate of Example 6.

[274] The following observations can be made from this study:
[275] The compressive strength of the geopolymer cementitious compositions of the invention investigated in this Example continued to increase over time.
[276] The compressive strength in the initial 4-hour stage of the material was greater than 750 psi with the use of calcium sulphate (plaster) as a component of the investigated geopolymer cement compositions of the invention.
[277] The compressive strengths in the initial 24-hour stage of the material were greater than 1500 psi with the use of calcium sulfate (plaster) as a component of the investigated geopolymer cement compositions of the invention.
[278] The compressive strength after 28 days of all the geopolymer cementitious compositions of the invention investigated in this example was very high in lower amounts of calcium sulfate (plaster) and decreased with increasing amount of calcium sulfate. For example, the compressive strength after 28 days of Mixture 1 with 16.7% calcium sulfate and Mixture 2 with 33.3% calcium sulfate, was 5221 psi and 4108 psi, respectively. On the other hand, for Mixture 4 with 100% calcium sulfate, the compressive strength after 28 days dropped to 2855 psi. Example 7
[279] This example compares the compositions of the invention which comprise calcium aluminate cement at different levels of quantity in mixtures containing fly ash, calcium sulphate (calcium sulphate dihydrate or fine-grained plaster), and alkaline citrate.
[280] TABLE 15 shows the compositions of the raw material of the geopolymeric cement mixtures investigated in this example. The amount of calcium aluminate cement used in the mixing compositions in this example was 40% by weight, 60% by weight and 80% by weight of Class C fly ash. Calcium sulphate in the form of granulation USG plaster Fine was added at the quantity level of 30% by weight of the calcium aluminate cement weight and 13.3, 20 and 26.7% by weight of fly ash. The calcium aluminate cement was Ciment Fondu (HAC Fondu), Kerneos, Inc., the sand is QUIKRETE Commercial Grade Fine Sand No 1961 and the superplasticizer is AdvaCast 500, WR Grace.
Initial Flow Behavior, Slump and Cracking Behavior at an Early Stage of Material
[281] TABLE 16 shows the behavior characteristics of the initial flow and slump of the geopolymer cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate dihydrate (fine-grained plaster), and alkaline citrate investigated in Example 7 .

[282] All compositions of the investigated mixtures had good flow behavior, as seen in the slump test. Shrinkage Behavior
[283] FIG. 7 shows the data for the shrinkage behavior of the geopolymer cementitious compositions 7 of the invention in this Example.
[284] Shrinkage measurements were started at the 4-hour stage from the time the raw materials were mixed together to form an aqueous paste. The shrinkage of the material was measured for a total duration of approximately 8 weeks when curing the material at 75oF / 50% RH.
[285] This example showed the following:
[286] Unlike the shrink bars of Comparative Example 4 (without calcium sulphate), which cracked even before demoulding, the shrink bars of Example 7 which comprise calcium sulphate (fine-grained plaster) were completely stable and not resulted in any cracks both before and after demoulding.
[287] The geopolymer cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulphate (fine-grained plaster) and alkaline citrate had an extremely low maximum shrinkage, of approximately less than 0.06% compared to one maximum shrinkage of approximately 0.75% for the composition of the comparative mixture containing only fly ash and alkaline citrate (Example 1). Pick-up time
[288] TABLE 17 shows the setting time of the geopolymer cementitious compositions of the invention in Example 7.

[289] All the geopolymer cement compositions of the invention demonstrated very fast setting behavior. However, the composition of the mixture of the invention investigated in this example, which comprises fly ash, calcium aluminate cement, calcium sulphate (fine-grained plaster) and alkaline citrate, had a relatively longer setting time than the state cement composition. of the technique comprising only fly ash and alkaline citrate (Example 1). The final setting times of the geopolymer cementitious compositions of Mixtures 1, 2, and 3 of the invention comprising fly ash, calcium aluminate cement, calcium sulfate dihydrate (plaster), and potassium citrate were about 30 to about 45 minutes, compared to an extremely fast final set-up time of about 15 minutes of the composition of the comparative mixture containing only fly ash and potassium citrate (Example 1). Compressive Strength
[290] TABLE 18 shows the compressive strength behavior of the developed geopolymer cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate (fine-grained plaster), and alkaline citrate investigated in Example 7.


[291] The following observations can be made:
[292] The compressive strength of the geopolymer cementitious compositions of the invention investigated in this example continued to increase over time.
[293] The 4-hour early stage compressive strength of the material was greater than 1500 psi with the use of calcium aluminate cement, calcium sulfate (fine-grained plaster) and alkaline citrate as part of the geopolymer cementitious compositions of the invention . Similarly, the 24-hour compressive strengths of the compositions of the invention were greater than 1900 psi. Example 8
[294] This example describes physical properties of the developed geopolymer cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate in the form of anhydrous fine-grained calcium sulfate (ie anhydrite) and alkaline citrate, mixed as shown in TABLE 6. TABLE 19 shows the raw material compositions of the geopolymer cement mixtures investigated in this Example. Mixture 1 represents a comparative composition investigated in Example 8. The amount of calcium aluminate cement used in the mixing compositions in this example was 0% by weight, 30% by weight, 60% by weight and 90% by weight of fly ash weight. Anhydrite (USG SNOW WHITE Filler) was added in an amount of 33.33% by weight of the calcium aluminate cement (CIMENT Fondu HAC Fondu) and 0, 10, 20 and 30% by weight of fly ash in the investigated mix compositions. QUIKRETE Commercial Grade Fine Sand No. 1961 sand and BASF CASTAMENT FS20 superplasticizer were used.

Initial Flow Behavior, Slump and Cracking Behavior at an Early Stage of Material
[295] TABLE 20 shows the behavior characteristics of the initial flow and slump of the geopolymer cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate in the form of anhydrite, and alkaline citrate investigated in Example 8.

[296] All investigated mix compositions had good flow self-leveling behavior and high wafer diameter as seen in the slump test. It is observed in particular that this high slump and self-leveling behavior was obtained in a water / cementitious ratio as low as about 0.25.
[297] The slaughter wafers for all four mixtures comprising calcium sulfate in the form of anhydrite were in excellent condition and did not develop any crack. Shrinkage Behavior
[298] FIG. 8 shows the shrinkage behavior of the geopolymer cementitious compositions of the invention investigated in Example 8. Shrinkage measurements were started at the 4 hour stage from the time when the raw materials were mixed together to form an aqueous paste. The shrinkage of the material was measured for a total duration of approximately 8 weeks when curing the material at 75oF / 50% Relative Humidity (RH).
[299] The following important conclusions can be drawn from this investigation:
[300] Unlike the shrink bars of Comparative Example 4 (without calcium sulphate), which cracked even before demoulding, the shrink bars of Example 8 which comprise calcium aluminate cement, anhydrous calcium sulphate (anhydrite) and alkaline citrate were completely stable and did not result in any cracking either before or after demoulding.
[301] The geopolymer cementitious compositions of some embodiments of the invention comprising fly ash, calcium aluminate cement, calcium sulfate (anhydrite), and alkaline citrate had a maximum shrinkage between about 0.21% to 0.26% compared to a maximum shrinkage about 0.75% for the comparative mix composition containing only fly ash and alkaline citrate (Example 1) and about 0.62% for Comparative Mix 1 of the present example which also contains only fly ash and alkaline citrate.
[302] The lowest shrinkage was obtained with Mixture 2, which comprises calcium aluminate cement by 30% by weight of the amount of fly ash and calcium sulfate (anhydrite) by 33.3% by weight of the amount of calcium aluminate. Compressive Strength
[303] TABLE 21 shows the compressive strength behavior of the developed geopolymer cement compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate (anhydrite), and alkaline citrate investigated in Example 8.

[304] The example studied the influence of the incorporation of calcium aluminate cement in combination with calcium sulfate in anhydrite form in both the initial and the last stage of the compressive strength of the developed geopolymer cement compositions of the invention. The following important observations can be drawn from this study:
[305] The compressive strength of the geopolymer cementitious compositions of the invention investigated in this example continued to increase over time.
[306] Both the compressive strength in the initial stage and the compressive strength of the composition of the mixture without calcium sulfate (Comparative Mixture 1) were lower compared to those of the cementitious compositions of the invention that comprise calcium sulfate (Mixtures 2 up to 4).
[307] The compressive strengths at an early stage (4 hours and 24 hours) of the geopolymer cementitious compositions of the invention comprising calcium aluminate cement and calcium sulfate in the form of anhydrite were exceptionally high. For example, Mixture 3 comprising calcium aluminate cement in an amount of 60% by weight of fly ash and anhydrite in an amount of 33.33% by weight of calcium aluminate cement obtained a compressive strength of 5032 psi in just 4 hours and 6789 psi in 24 hours. Similarly, Mixture 4 comprising calcium aluminate cement in an amount of 80% by weight of fly ash and anhydrite in an amount of 33.33% by weight of calcium aluminate cement obtained a compressive strength of 6173 psi in only 4 hours and 8183 psi in 24 hours.
[308] The compressive strengths of the 28th of all geopolymer cementitious compositions of the invention comprising fly ash, calcium aluminate, calcium sulfate in the form of anhydrite, and potassium citrate were exceptionally high and above 10,000 psi (69 MPa ).
[309] Thus, it was very surprising to find that the use of insoluble anhydrous calcium sulfate (anhydrite or calcined anhydrite) provided a faster pickup, a higher rate of development of compressive strength, and a higher final compressive strength than those obtained using a relatively higher soluble calcium sulfate dihydrate (see Example 7).
[310] Another unexpected feature of the modalities of this invention is the dependence on the gripping behavior and the compressive strength of the type of calcium sulfate used in the compositions of the invention. Example 9
[311] TABLE 22 shows the raw material compositions of the geopolymer cement mixtures investigated in this Example, as shown in TABLE 6.
[312] The amount of calcium aluminate cement used in the mix compositions in this example was equal to 40% by weight of fly ash. Plaster at the level of 33.3% by weight of the weight of calcium aluminate cement and 13.3% by weight of Class C fly ash was added. Sodium citrate dihydrate was used as the alkali metal chemical activator in all investigated mix compositions. The water-to-cement ratio used in this investigation was 0.30. QUIKRETE Commercial Grade Fine Sand No. 1961 sand and BASF CASTAMENT FS20 superplasticizer.

Cracking Behavior and Cracking Behavior at Materia's Initial Stage
[313] TABLE 23 shows the behavior characteristics of the initial flow and slump of the geopolymer cementitious compositions of a modality of the invention that comprises fly ash, calcium aluminate cement, dihydrated calcium sulfate (fine-grained plaster), and alkaline citrate investigated in Example 9.

[314] The compositions of the mixture with the ratio of sand / cementitious materials ranging from 0.75 to 1.50 (Mixtures 1, 2 and 3) had a good flow behavior as observed in the slump test. On the other hand, the composition of the mixture with a sand / cementitious material ratio of 2.5 (mixture 4) was very hard with poor flow properties. Shrinkage Behavior
[315] FIG. 9A shows the shrinkage behavior of the geopolymer cementitious compositions of the invention investigated in Example 9. The main objective of this investigation was to study the influence of the incorporation of calcium aluminate cement in combination with a fine-grained dihydrate calcium sulfate (plaster) and a citrate alkaline in the shrinkage behavior of the geopolymer cementitious compositions of the invention containing different amounts of sand in the mixture.
[316] Shrinkage measurements were started at the 4-hour stage from the time the raw materials were mixed together to form an aqueous paste. The shrinkage of the material was measured for a total duration of approximately 8 weeks when curing the material at 75oF / 50% RH.
[317] The following conclusions are drawn from this example and FIG. 9A:
[318] Unlike the shrink bars of Comparative Example 4 (Mixture 2 without calcium sulfate), which cracked even before demoulding, the shrink bars of Example 9 which comprise calcium sulphate dihydrate in the form of fine-grained plaster completely stable and did not result in any cracks either before or after demoulding.
[319] The geopolymer cementitious compositions of the invention (Example 9) comprising fly ash, calcium aluminate cement, calcium sulphate dihydrate (fine-grained plaster) and alkaline citrate demonstrated an extremely low maximum shrinkage, with a maximum shrinkage of less than than 0.05%, compared to the maximum shrinkage of approximately 0.75% for the composition of the comparative mixture containing only fly ash and alkaline citrate in Example 1. Heat evolution behavior and temperate rise of the paste
[320] FIG. 9B shows the rising behavior of the exothermic temperature and the slurry of the geopolymer cementitious compositions of the invention investigated in Example 9. The cementitious compositions of this Example comprising fly ash, calcium aluminate cement, calcium sulphate (fine-grained plaster), and alkaline citrate showed only a very moderate temperature rise behavior. The rise in maximum temperature was only about 100oF with a net temperature rise of less than 30oF. A lower degree of temperature rise is beneficial in most applications because it provides superior thermal stability and reduced potential for thermal movement and thermal cracking particularly when the material is weak during the very early stages of curing. Pega Time
[321] TABLE 24 shows the setting time of the geopolymer cementitious compositions of the invention investigated in Example 9.

[322] All the cementitious compositions investigated in this example had the quick pick behavior. The final setting times of the geopolymer cement compositions of the invention in this example comprising fly ash, calcium aluminate cement, calcium sulphate (plaster), and sodium citrate ranged from about 55 to about 65 minutes, compared to a extremely fast final setting time of about 15 minutes of the mixture composition containing only fly ash and sodium citrate (Example 1). An extremely short pick-up time is problematic for some applications. Compressive Strength
[323] TABLE 25 shows the compressive strength behavior of the developed geopolymer cement compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate (fine-grained plaster), and alkaline citrate investigated in Example 9.

[324] The following observations can be made from this study:
[325] The compressive strength of the geopolymer cementitious compositions of the invention in this example continued to increase over time. It can be seen that the various geopolymer compositions of the invention investigated in this example have achieved satisfactory development of resistance in the initial and final stages. Example 10
[326] TABLE 26 shows the compositions of the raw material of the geopolymer cement mixtures, which are the same as in Example 9.
[327] The amount of calcium aluminate cement used in the mix compositions in this example was equal to 40% by weight of fly ash. Calcium sulfate dihydrate (Plaster) was added in an amount of 33.3% by weight of the calcium aluminate cement and 13.3% by weight of Class C fly ash. Potassium citrate was used as the chemical activator metal alkaline in all of the mix compositions in this example. The water to cement ratio used in this investigation was 0.25. The influence of a quantity of the superplasticizer on the performance of the cementitious compositions of the invention was investigated in the Example.

Cracking Behavior and Cracking Behavior at Materia's Initial Stage
[328] TABLE 27 shows the behavior characteristics of the initial flow and slump of the geopolymer cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate (fine-grained plaster), and alkaline citrate investigated in Example 10.

[329] We can clearly see that all the mixing compositions of the invention investigated in this example had a good flow behavior. The flow behavior of the compositions improved with the incorporation of the superplasticizer in the mix compositions. No improvement in flow and slaughter was observed with an increase in the amount of superplasticizer beyond 0.80%. Shrinkage Behavior
[330] FIG. 10 shows the shrinkage behavior of the geopolymer cement compositions of the invention investigated in Example 10. The main objective of this investigation was to study the influence of the incorporation of calcium aluminate cement in combination with a fine-grained calcium sulfate dihydrate (plaster) and a citrate alkaline in the shrinkage behavior of the geopolymer cementitious compositions of the invention containing different amounts of superplasticizer in the mixture.
[331] Shrinkage measurements were started at the 4-hour stage from the time the raw materials were mixed together to form an aqueous paste. The shrinkage of the material was measured for a total duration of approximately 8 weeks when curing the material at 75oF / 50% RH.
[332] The following conclusions can be drawn from this investigation and FIG. 10:
[333] Unlike the shrink bars of Comparative Example 4 (Mixture 2 without calcium sulfate), which cracked even before demoulding, the shrink bars of Example 10 which comprise calcium sulphate in the form of fine-grained plaster were completely stable and did not crack, either before or after demoulding.
[334] The geopolymer cementitious compositions of an embodiment of the invention (Example 10) comprising fly ash, calcium aluminate cement, calcium sulphate dihydrate (fine-grained plaster) and alkaline citrate demonstrated an extremely low maximum shrinkage, with maximum shrinkage less than 0.1%, compared to the maximum shrinkage of approximately 0.75% for the composition of the comparative mixture containing fly ash and alkaline citrate (Example 1).
[335] The amount of shrinkage increased slightly with an increase in the amount of superplasticizer. It can be seen that for Mixture 2 with a superplasticizer amount of 0.4%, the maximum shrinkage was approximately 0.05%; on the other hand, for Mixture 4 with a superplasticizer amount of 1.2%, the maximum shrinkage was increased by a small amount to a value of approximately 0.08%. Compressive Strength
[336] TABLE 28 shows the behavior of the compressive strength of the developed geopolymer cement compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate (fine-grained plaster), and alkaline citrate investigated in Example 10.

[337] The following observations can be made from this study:
[338] The compressive strength of the geopolymer cementitious compositions of this embodiment of the invention continued to increase over time. The various investigated compositions achieved satisfactory resistance in the initial and final stages.
[339] The compressive strengths at an early stage (4 hours and 24 hours) of the geopolymer cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate dihydrate (plaster), and alkaline citrate were exceptionally high and greater than 2000 psi in the initial 4-hour stage and greater than 3000 psi in the initial 24-hour stage.
[340] The compressive strengths of the 28th of all geopolymer cementitious compositions of the invention comprising fly ash, calcium aluminate, calcium sulfate dihydrate (plaster), and alkaline citrate were exceptionally high, ranging from approximately 4750 psi to approximately 6750 psi. Example 11
[341] TABLES 29 and 30 show the compositions of the raw materials of the cement mixtures investigated in this Example.
[342] The amount of calcium aluminate cement used in the mix compositions in this example was 40% by weight of fly ash. The plaster used in this investigation added in an amount level of 33.33% by weight of the weight of the calcium aluminate cement. Portland cement was added to Blend # 1 through Blend # 3 at rate rates of 6.1% by weight, 14% by weight, and 24.6% by weight of total cementitious materials, respectively. The water to cement ratio was 0.275 for all investigated mixtures. Class C Flywheel, Campbell Power Plant, West Olive, MI, USG Landplaster, Ciment Fondu (HAC Fondu), Kerneos, Inc. Calcium aluminate cement, Holcim Portland Cement Type, Mason City, Iowa, QUIKRETE Commercial Grade Fine Sand No. 1961 and AdvaCast 500, WR Grace.


Initial Flow and Slaughter Behavior
[343] TABLE 31 shows the behavior characteristics of the initial flow and slump of the geopolymer cementitious compositions comprising fly ash, calcium aluminate cement, calcium sulfate (plaster), Portland cement and alkaline citrate investigated in Example 11.

[344] The flow and slump behavior of the compositions was negatively influenced by an increase in the amount of Portland cement in the composition. Shrinkage Behavior
[345] FIG. 11 shows the shrinkage behavior of the geopolymer cementitious compositions of the invention investigated in Example 11. Shrinkage measurements were started at the 4 hour stage from the time when the raw materials were mixed together to form an aqueous paste. The shrinkage of the material was measured for a total duration of approximately 8 weeks when curing the material at 75oF / 50% RH.
[346] The following important conclusions can be drawn from this investigation and from FIG. 11: The incorporation of Portland cement significantly increased the shrinkage of the investigated cement compositions. The final shrinkage values for the various mixtures investigated were tabulated in TABLE 32.

[347] As discussed in more detail in the description above, this example shows that the unexpected result obtained with the addition of Portland cement to the modalities of the present invention was that Portland cement has a negative influence on the shrinkage behavior of the compositions. The shrinkage value is shown by this example as increased proportionally with the increase in the amount of Portland cement in the compositions.
[348] The addition of Portland cement to the cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate and alkaline citrate helps significantly increase the material's shrinkage.
[349] Based on testing this modality, the addition of Portland cement in the dimensionally stable geopolymer compositions of the invention is not recommended and should be limited to a very small amount, preferably not exceeding 15% by weight of the total weight of cementitious materials. Example 12
[350] TABLE 33 shows the compositions of the raw material of the geopolymer cement mixtures investigated in this Example 12.
[351] This example investigated the incorporation of sand and light-weight ceramic microspheres as fillers in the composition. Sodium citrate was added in an amount 2% by weight of the weight of the total cementitious materials. Calcium sulfate dihydrate was added in an amount of 13.3% fly ash and calcium aluminate was added in 40% by weight of Class C fly ash. Class C fly ash (Campbell Power Plant, West Olive, MI,) USG Landplaster, calcium aluminate cement (Ciment Fondu (HAC Fondu), Kerneos, Inc), QUIKRETE Commercial Grade Fine Sand No. 1961, Ceramic microspheres (Kish Company) and BASF CASTAMENT FS20 superplasticizer.
Initial Flow Behavior, Slump and Cracking Behavior at an Early Stage of Material
[352] TABLE 34 shows the initial flow and slump behavior of the geopolymer cementitious compositions investigated in this example comprising a lightweight filler.


[353] Based on the results shown in TABLE 34, it can be concluded that the compositions of the mixture of the invention that comprise lightweight fillers have good workability and self-leveling properties. Shrinkage Behavior
[354] FIG. 12 shows the shrinkage behavior of the geopolymer cementitious compositions of the invention investigated in Example 12.
[355] Shrinkage measurements were started at the 4 hour stage from the time the raw materials were mixed together to form an aqueous paste. The shrinkage of the material was measured for a total duration of approximately 8 weeks when curing the material at 75oF / 50% RH.
[356] It is observed that the cementitious composition of the invention that incorporates the lightweight filler exhibited extremely low dimensional movement as a function of time. pH
[357] The surface pH of the fully cured geopolymer compositions mentioned in TABLE 39 was measured according to the ASTM F710-11 test method and found to be 9.82. The Extech PH150-C Exstick concrete Ph meter was used to perform surface pH measurements. Example 13
[358] TABLE 35 shows the raw material compositions of the geopolymer cement mixtures investigated in this Example 13. This example incorporates both calcium aluminate cement and calcium sulfoaluminate cement in the composition. Calcium sulfate dihydrate was added in 10% by weight of Class C fly ash and calcium aluminate cement was added in 10, 20, and 40% by weight of fly ash. Calcium sulfoaluminate cement was added in 20% by weight of fly ash. Fly ash is Class C fly ash, (Campbell Power Plant, West Olive, MI), USG Landplaster dihydrate calcium sulfate, (Denka SC1) calcium aluminate cement, calcium sulfoaluminate FASTROCK 500 (CTS Company), sand QUIKRETE Commercial Grade Fine Sand No. 1961 and BASF Castament FS 20 superplasticizer were used. Sodium citrate was added in an amount of 2% by weight of the cementitious materials.
Initial Flow and Slaughter Behavior
[359] TABLE 36 shows the behavior characteristics of the initial flow and subsidence of the cement compositions of some modalities of the invention that include fly ash, calcium aluminate cement, calcium sulfoaluminate cement, calcium sulfate (plaster), and citrate alkali investigated in Example 13.

[360] Based on the results shown in TABLE 36, the compositions of the mixture of the invention comprising calcium aluminate cement and calcium sulfoaluminate cement have good workability and self-leveling properties. Compressive Strength
[361] TABLE 37 shows the compressive strength behavior of geopolymer cementitious compositions developed from some modalities of the invention comprising fly ash, calcium aluminate cement, calcium sulfoaluminate cement, calcium sulfate dihydrate (fine-grained plaster), and alkaline citrate investigated in Example 13.

[362] The following conclusions are drawn from this study:
[363] The compressive strength of geopolymer cementitious compositions of some embodiments of the invention comprising both calcium aluminate cement and calcium sulfoaluminate cement continued to increase over time. The various investigated compositions achieved satisfactory resistance in the initial and final stages.
[364] The compressive strengths in the initial stage (4 hours and 24 hours) of the geopolymer cementitious compositions of some modalities of the invention comprising fly ash, calcium aluminate cement, calcium sulfoaluminate cement, calcium sulphate dihydrate (plaster) , and the alkaline citrate were exceptionally high and greater than approximately 2500 psi in the 4-hour stage and greater than approximately 3400 psi in the 24-hour stage.
[365] The compressive strengths of the 28th of all geopolymer cementitious compositions of some embodiments of the invention comprising fly ash, calcium aluminate, calcium sulfoaluminate cement, calcium sulphate (plaster) and alkaline citrate were very high and above approximately 7000 psi. Example 14
[366] This example presents the physical properties of the developed geopolymer cement compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate in the form of fine-grained calcium sulfate dihydrate and alkaline citrate. TABLE 38 shows the compositions of the raw materials of geopolymer cement mixtures investigated in this Example. All mixtures contain calcium aluminate cement in which the main phase of calcium aluminate was dodecacalcium heptaaluminate (12CaO ^ 7Al2O3 or C12A7). This calcium aluminate cement is commercially available under the trade name TERNAL EV from Kerneos Inc. The amount of calcium aluminate cement used in the mix compositions in this example was 10% by weight, 20% by weight, at 30 % by weight and 40% by weight of fly ash. The fine-grained dihydrated calcium sulfate used in this example has an average particle size of 13 microns available from the USG Company under the trade name USG Terra Alba Filler. Calcium sulfate dihydrate was added in the amount of 50% by weight of the calcium aluminate cement weight and 5, 10, 15 and 20% by weight of fly ash in the investigated mix compositions.


Slaughter and Cracking Behavior in the Early Stage of Material
[367] TABLE 39 shows the abatement behavior of the geopolymer cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate dihydrate, and alkaline citrate in Example 14.

[368] All compositions of the investigated mixtures had good fluidity, as seen in the slump test.
[369] The slaughter wafers for all four mixtures comprising fine-grained calcium sulfate dihydrate were in excellent condition and did not develop any cracking. Shrinkage Behavior
[370] FIG. 13 shows the shrinkage behavior of the geopolymer cementitious compositions of the invention in Example 14. Shrinkage measurements were started at the 4 hour stage from the time when the raw materials were mixed together to form an aqueous paste. The shrinkage of the material was measured for a total duration of approximately 8 weeks when curing the material at 75oF / 50% Relative Humidity (RH).
[371] The following important conclusions can be drawn from this investigation:
[372] Unlike the comparative Example 4 shrink bars (without calcium sulfate), which cracked even before demoulding, the Example 14 shrink bars that comprise calcium aluminate cement, calcium sulfate dihydrate and alkaline citrate completely stable and did not result in any cracks either before or after demoulding.
[373] The geopolymer cement compositions of some embodiments of the invention comprising fly ash, calcium aluminate cement, calcium sulfate dihydrate, and alkaline citrate have a maximum shrinkage between 0.04% to 0.08%, compared to a maximum shrinkage of about 0.75% for the composition of the comparative mixture containing only fly ash and alkaline citrate (Example 1).
[374] The amount of maximum shrinkage decreased with an increase in the amount of calcium aluminate cement in the composition. Mix 1 comprising calcium aluminate cement at 10% by weight of an amount of fly ash had a maximum shrinkage of approximately 0.08%; on the other hand, Mix 3 comprising calcium aluminate cement at 30% by weight of an amount of fly ash had a maximum shrinkage of only approximately 0.05% and Mix 4 comprising calcium aluminate cement at 40% by weight of a amount of fly ash had a maximum shrinkage of only approximately 0.04%. Pega Time
[375] TABLE 40 shows the setting time of the geopolymer cementitious compositions of the invention investigated in Example 14.

[376] All of the geopolymer cementitious compositions investigated in this example had a quick pick behavior. The final setting times of the geopolymer cementitious compositions of the invention in this example ranged from about 69 minutes to about 76 minutes, compared to an extremely fast final setting time of about 15 minutes of the mixture composition containing only fly ash and citrate sodium (Example 1). It should be noted that an extremely short pick-up time can be problematic for some applications. Compressive Strength
[377] TABLE 41 shows the compressive strength behavior of the developed geopolymer cement compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate dihydrate, and alkaline citrate investigated in Example 14.

[378] The example studied the influence of the incorporation of calcium aluminate cement in combination with fine-grained calcium sulfate dihydrate both at the beginning and at the end for the compressive strength behavior of the developed geopolymer cement compositions of the invention. The following important observations can be drawn from this study:
[379] The compressive strength of the geopolymer cement compositions of the invention investigated in this example continued to increase over time. The compressive strengths of day 28 of all geopolymer cement compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate dihydrate, and potassium citrate were exceptionally high and above 5000 psi. In addition, the compressive strengths of day 56 of all the geopolymer cementitious compositions of the invention were even higher and higher than 7000 psi.
[380] Mixture 2 comprising calcium aluminate cement at 20% by weight of an amount of fly ash produced the highest final compressive strength in excess of 9500 psi at the 56 day stage. Example 15
[381] This example describes the influence of different forms of calcium sulfates on the physical properties of the developed geopolymer cement compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate and an alkaline citrate. Three different types of calcium sulfates were compared - calcium sulfate dihydrate, calcium sulfate anhydrous (anhydrite), and calcium sulfate hemihydrate. TABLE 42 shows the compositions of the raw materials of geopolymer cement mixtures investigated in this Example. All mixtures contain calcium aluminate cement in which the main phase of calcium aluminate was dodecacalcium hepta-aluminate (12CaO ^ 7Al2O3 or C12A7). This calcium aluminate cement is commercially available under the trade name TERNAL EV from Kerneos Inc. The amount of calcium aluminate cement used in the mix compositions of this example was equal to 20% by weight of the fly ash. The type of calcium sulfate contained in the various compositions of the mixture investigated in this example was as follows: calcium sulfate dihydrate in Mixture 1, calcium sulfate anhydrous (anhydrite) in Mixture 2, and calcium sulfate hemihydrate in Mixture 3. All sulfates were added in an amount equal to 50% by weight of the calcium aluminate cement weight and 10% by weight of fly ash in the investigated mix compositions.


[382] Initial Stage Material Slaughter and Cracking Behavior
[383] TABLE 43 shows the abatement behavior of the geopolymer cementitious compositions of the invention investigated in Example 15.

[384] All investigated compositions had good fluidity, as seen in the slump test. It should be noted that the compositions of the mixture with anhydrous calcium sulfate (Mixture 2) and hemihydrate calcium sulfate (Mixture 3) produced a better fluidity compared to the mixture containing the dihydrate calcium sulfate (Mixture 1).
[385] The slaughter wafers for all three mixtures that comprise different forms of calcium sulphate were in excellent condition and did not develop any cracking. Shrinkage Behavior
[386] FIG. 14 shows the shrinkage behavior of the geopolymer cementitious compositions of the invention investigated in Example 15. Shrinkage measurements were initiated at the 4 hour stage from the time the raw materials were mixed together to form an aqueous paste. The shrinkage of the material was measured for a total duration of approximately 8 weeks when curing the material at 75 ° F / 50% Relative Humidity (RH).
[387] The following important conclusions can be drawn from this investigation:
[388] Unlike the shrink bars of Comparative Example 4 (without calcium sulfate), which cracked even before demoulding, the shrink bars of Example 15 which comprise calcium aluminate cement, different forms of calcium sulfate and citrate alkali were completely stable and did not result in any cracks either before or after demoulding.
[389] The geopolymer cement compositions of some embodiments of the invention comprising fly ash, calcium aluminate cement, different forms of calcium sulphate, and alkaline citrate have a maximum shrinkage between 0.06% to 0.10%, compared to a maximum shrinkage of about 0.75% for the composition of the comparative mixture containing only fly ash and alkaline citrate (Example 1).
[390] The amount of maximum shrinkage varied with the type of calcium sulfate in the composition. Mixture 1 comprising calcium sulphate dihydrate and Mixture 3 comprising calcium sulphate hemihydrate had a lower maximum shrinkage of approximately 0.06% compared to Mixture 3 comprising anhydrous calcium sulphate (anhydrite) which produced a shrinkage maximum of approximately 0.10% Pickup Time
[391] TABLE 44 shows the setting time of the geopolymer cementitious compositions of the invention investigated in Example 15.

[392] All of the geopolymer cementitious compositions investigated in this example demonstrated quick pick behavior. The final set-up times of the geopolymer cement compositions of the invention in this example ranged from about 42 minutes to about 71 minutes, compared to an extremely fast final set-up time of about 15 minutes of the mixture composition containing only fly ash and sodium citrate (Example 1). It should be noted that an extremely short pick-up time can be problematic for some applications.
[393] The setting time of the cement compositions of the geopolymer of the invention depends on the type of calcium sulphate used as part of the composition of the mixture. The composition comprising anhydrous calcium sulfate (anhydrite) (Mix 2) produced the fastest setting time; on the other hand, the other inventive composition (Mix 1) comprising calcium sulfate dihydrate provided the longest setting time. Compressive Strength
[394] TABLE 45 shows the compressive strength behavior of the developed geopolymer cement compositions of the invention that comprise different types of calcium sulfate investigated in Example 15.

[395] This example studied the influence of the incorporation of different types of calcium sulphate both at the initial and at the end of the compressive strength behavior of the developed geopolymer cement compositions of the invention. The following important observations can be drawn from this study:
[396] The compressive strength of the cement compositions of the geopolymer of the invention continued to increase with time regardless of the type of calcium sulfate used in the mixture.
[397] The compressive strengths of the 28th and 56th of the geopolymer cement compositions of the invention comprising different types of calcium sulfate, fly ash, calcium aluminate cement and potassium citrate were exceptionally high and above 7000 psi .
[398] Mix 2 comprising anhydrous calcium sulfate (anhydrite) had the fastest rate of development of compressive strength and the highest final compressive strength compared to mixtures with dihydrated calcium sulfate (Mix 1) and sulfate hemi-hydrated calcium (Mix 3).
[399] The ultimate compressive strength of the geopolymer composition of the invention comprising anhydrous calcium sulfate (anhydrite) was greater than 10,000 psi. Example 16
[400] This example studies the physical properties of the developed geopolymer cement compositions of this embodiment of the invention which comprises fly ash, calcium aluminate cement, calcium sulfate hemihydrate with an alkaline hydroxide (sodium hydroxide) or a mixture of a alkali metal hydroxide (sodium hydroxide) and an acid (citric acid).
[401] TABLE 46 shows the compositions of the raw materials of the geopolymer cement mixtures investigated in this Example. All mixtures contain calcium aluminate cement in which the main phase of calcium aluminate was dodecacalcium hepta-aluminate (12CaO ^ 7Al2O3 or C12A7). This calcium aluminate cement is commercially available under the trade name TERNAL EV from Kerneos Inc. The amount of calcium aluminate cement used in the mix compositions of this example was equal to 20% by weight of the fly ash. One mixture (Mixture 2) investigated contained only sodium hydroxide as the chemical activator and without citric acid. In Mix 3, Mix 4 and Mix 5, a mixture of sodium hydroxide and citric acid was added to the cementitious compositions of the invention to act as a chemical activator. Similarly, one of the mixtures (Mix 1) contained only citric acid for chemical activation and no sodium hydroxide.


Slaughter Behavior
[402] TABLE 47 shows the abatement behavior of the geopolymer cementitious compositions of the invention investigated in Example 16.

[403] For Mixture 1 containing citric acid but without sodium hydroxide, the mixer material was extremely hard and completely unworkable with mixing. On the other hand, the mix compositions containing sodium hydroxide (Mix 2) or a mixture of sodium hydroxide and citric acid (Mix 3, Mix 4 and Mix 5), were easily workable as indicated also by their relatively large diameter of the wafer in the slump test. This good workability was obtained even in extremely low water / cementitious ratios of approximately 0.30. For standard Portland cement or gypsum-based materials, such flow properties and self-regulating behavior are only obtainable when the water / cement materials ratio is in excess of approximately 0.45. Shrinkage Behavior
[404] FIG. 15 shows the shrinkage behavior of the geopolymer cementitious compositions of the invention investigated in Example 16. Shrinkage measurements were started at the 4 hour stage from the time when the raw materials were mixed together to form an aqueous paste. The shrinkage of the material was measured for a total duration of approximately 8 weeks when curing the material at 75oF / 50% Relative Humidity (RH).
[405] The following important conclusions can be drawn from this investigation and from FIG 15:
[406] Unlike the shrink bars of Comparative Example 4 (without calcium sulphate), which cracked even before demoulding, the shrink bars of Example 16 which comprise calcium aluminate cement, hemihydrate calcium sulphate and citrate alkali metal (with or without citric acid) were completely stable and did not result in any cracking either before or after demoulding.
[407] The cementitious composition of the invention comprising sodium hydroxide only as a chemical activator (Mix 2) has demonstrated a very low maximum shrinkage of approximately less than 0.05%. The cementitious compositions of the invention comprising a mixture of sodium hydroxide and citric acid as a chemical activator (Mix 3, Mix 4 and Mix 5) also demonstrated a very low maximum shrinkage of approximately less than 0.10%. It should be noted that cementitious compositions containing 1% sodium hydroxide and up to 1% citric acid (Mix 3 and Mix 4) had a very low maximum shrinkage of approximately less than 0.05%. For Mixture 5 containing 1% sodium hydroxide and 2% citric acid, the maximum shrinkage increased to approximately 0.08%. Pega Time
[408] TABLE 48 shows the setting time of the geopolymer cementitious compositions of the invention investigated in Example 16.

[409] All of the geopolymer cementitious compositions investigated in this example (Mix 2 to Mix 5) demonstrated very fast configuration behavior with final configuration times ranging from approximately 62 to approximately 172 minutes. In the case of Mixture 1, without sodium hydroxide, the final setting time was extremely long, exceeding 5 hours. On the other hand, mixtures containing a mixture of sodium hydroxide and citric acid (Mix 4 and Mix 5) produced an extremely fast setting behavior with a final setting time of approximately 1 hour. Compressive Strength
[410] TABLE 49 shows the compressive strength behavior of the developed geopolymer cement compositions of the invention investigated in example 16.

[411] The following important conclusions can be drawn from this study:
[412] The cementitious composition without an alkali metal base (sodium hydroxide) (Mix 1) produced an extremely weak compressive strength behavior. The compressive strength in both the initial and final stages for this mixture (Mix 1) was extremely low and significantly lower than the compositions of the geopolymer of the invention comprising sodium hydroxide (Mix 2) or a mixture of sodium hydroxide and acid citrus (Mix 3 to Mix 5).
[413] The compressive strengths of day 28 of all cement compositions of the geopolymer of the invention comprising a mixture of sodium hydroxide and citric acid (Mix 3 to Mix 5) were exceptionally high and above 5000 psi. In addition, the compressive strengths of day 56 of all cement compositions of the geopolymer of the invention comprising a mixture of sodium hydroxide and citric acid (Mix 3 to Mix 5) were even greater and greater than 7500 psi. Example 17
[414] This example studies the physical properties of the developed geopolymer cement compositions of this embodiment of the invention which comprises fly ash, calcium aluminate cement, calcium sulfate hemihydrate with an alkali metal silicate (sodium silicate) or a mixture of an alkali metal silicate (sodium silicate) and an acid (citric acid).
[415] TABLE 50 shows the compositions of the raw materials of the geopolymer cement mixtures investigated in this Example. All mixtures contain calcium aluminate cement in which the main phase of calcium aluminate was dodecacalcium hepta-aluminate (12CaO ^ 7Al2Os or C12A7). This calcium aluminate cement is commercially available under the trade name TERNAL EV from Kerneos Inc. The amount of calcium aluminate cement used in the mix compositions of this example was equal to 20% by weight of the fly ash. Mixture 1 through Mixture 3 contains only sodium silicate as the chemical activator and no citric acid. In Mix 4 and Mix 5, a mixture of sodium silicate and citric acid was added to the cementitious compositions of the invention to act as a chemical activator.

Slaughter Behavior
[416] TABLE 51 shows the abatement behavior of the geopolymer cementitious compositions of the invention investigated in Example 17.

[417] On the other hand, mix compositions containing only sodium silicate (Mix 1 to Mix 3) or a mixture of sodium silicate and citric acid (Mix 4 and Mix 5), were easily workable as indicated by their relatively large diameter of the wafer in the slump test. Good workability was achieved even at extremely low water / cementitious ratios of approximately 0.30. For standard Portland cement or gypsum-based materials, such flow properties and self-leveling behavior are only obtainable when the water / cementitious ratio is greater than approximately 0.45. Shrinkage Behavior
[418] FIG. 16 shows the shrinkage behavior of the geopolymer cement compositions of the invention investigated in Example 17. Shrinkage measurements were started at the 4 hour stage from the time when the raw materials were mixed together to form an aqueous paste. The shrinkage of the material was measured for a total duration of approximately 8 weeks when curing the material at 75oF / 50% Relative Humidity (RH).
[419] The following important conclusions can be drawn from this investigation and from FIG 16:
[420] Unlike the shrink bars of Comparative Example 4 (without calcium sulphate), which cracked even before demoulding, the shrink bars of Example 17 which comprise calcium aluminate cement, calcium sulphate hemihydrate and silicate alkali metal (with or without citric acid) were completely stable and did not result in any cracking either before or after demoulding.
[421] The entire geopolymer cement composition of the invention comprising sodium silicate or a mixture of sodium silicate and citric acid as a chemical activator has demonstrated a very low maximum shrinkage of approximately less than 0.05%. Pega Time
[422] TABLE 52 shows the setting time of the geopolymer cementitious compositions of the invention investigated in Example 17.

[423] All of the geopolymer cementitious compositions investigated in this example comprising sodium silicate demonstrated a slower setting behavior compared to the geopolymer compositions of the invention investigated in example 16 comprising sodium hydroxide. Mix 1 to Mix 4 had a final setting time of more than 5 hours. Mixture 5 comprising a mixture of sodium silicate and citric acid adjusted as quickly as possible with a final setting time of approximately 3 hours and 45 minutes. Compressive Strength
[424] TABLE 53 shows the compressive strength behavior of the developed geopolymer cement compositions of the invention investigated in example 17.

[425] The following important conclusions can be drawn from this study:
[426] The cementitious composition without alkali metal base (sodium silicate) (Mix 1 of Example 16) produced an extremely weak compressive strength behavior. The final compressive strength of the mixture compositions comprising sodium silicate or a mixture of sodium silicate and citric acid as a chemical activator was significantly superior to the compressive strength of the mixture in the absence of sodium silicate (Mix 1 of Example 16).
[427] The final compressive strengths of all cement compositions of the geopolymer of the invention investigated in this example comprising sodium silicate or a mixture of sodium silicate and citric acid were satisfactory and greater than approximately 4000 psi. Example 18
[428] The purpose of this example was to study the influence of mixtures of calcium aluminate cement and calcium sulfoaluminate cement on the physical properties of the cement compositions of the geopolymer of the invention. TABLE 54 shows the compositions of the raw materials of geopolymer cement mixtures investigated in this Example. All mixtures contain calcium aluminate cement in which the main phase of calcium aluminate was dodecacalcium hepta-aluminate (12CaO ^ 7Al2O3 or C12A7). This calcium aluminate cement is commercially available under the trade name TERNAL EV from Kerneos Inc. Mix 2 through Mix 5 contains a mixture of calcium aluminate cement and calcium sulfoaluminate cement. The calcium sulfoaluminate cement used was Fastrock 500 from CTS Company. Mix 5 demonstrates the performance of the geopolymer composition of the invention which comprises lithium carbonate.


[429] Initial Stage Material Slaughter and Cracking Behavior
[430] TABLE 55 shows the abatement behavior of the geopolymer cementitious compositions of the invention investigated in Example 18.

[431] All compositions of the investigated mixtures had good fluidity, as seen in the slump test.
[432] The slaughter wafers for all mixes were in excellent condition and did not develop any cracking. Shrinkage Behavior
[433] FIG. 17 shows the shrinkage behavior of the geopolymer cementitious compositions of the invention investigated in Example 18. Shrinkage measurements were started at the 4 hour stage from the time the raw materials were mixed together to form an aqueous paste. The shrinkage of the material was measured for a total duration of approximately 8 weeks when curing the material at 75oF / 50% Relative Humidity (RH).
[434] The following important conclusions can be drawn from this investigation:
[435] Contrary to the shrink bars of Comparative Example 4 (without calcium sulphate) that cracked even before demoulding, the shrinkage bars of Example 18 were completely stable and did not result in any cracking before or after demolding.
[436] The geopolymer cement compositions of the modalities of the invention investigated in this example had a maximum shrinkage of less than 0.10% compared to a maximum shrinkage of approximately 0.75% for the composition of the comparative mixture that contains only fly ash and alkaline citrate (Example 1).
[437] The results of this example also demonstrate that the cement compositions of the geopolymer of the invention comprising mixtures other than calcium aluminate cement and calcium sulfoaluminate cement are capable of providing excellent dimensional stability with extremely low shrinkage. Pega Time
[438] TABLE 56 shows the setting time of the geopolymer cementitious compositions of the invention investigated in Example 18.

[439] All of the geopolymer cementitious compositions investigated in this example had a quick pick behavior. The final setting times of the geopolymer cementitious compositions of the invention in this example ranged from about 66 minutes to about 150 minutes, compared to an extremely fast final setting time of about 15 minutes of the mixture composition containing only fly ash and citrate sodium (Example 1). It should be noted that an extremely short pick-up time is problematic for most practical applications.
[440] The results of this example also demonstrate that the cement compositions of the geopolymer of the invention comprising mixtures other than calcium aluminate cement and calcium sulfoaluminate cement are capable of providing fast setting behavior while maintaining a sufficiently long open time .
[441] Comparison of the results for Mixture 4 and Mixture 5 clearly demonstrates that the addition of lithium carbonate has an effect on increasing the setting time of some modalities of the geopolymer compositions of this invention. This result is very surprising and unexpected since the lithium salt (lithium carbonate) is observed to act as a retardant in some embodiments of this invention. It should be noted that this observed behavior is contrary to what is known in the art on the effect of lithium salts such as lithium carbonate on the gripping behavior of calcium aluminate cement based bonding systems. The state of the art in calcium aluminate cements teaches that lithium salts such as lithium carbonate act as setting accelerators, thus reducing the initial and final setting time of the material. The findings present as shown in this example teach outside of the art and establish that lithium salts such as lithium carbonate have a delaying effect in the early stages of the reaction (initial and final set-up time) of some modalities of the geopolymer cement compositions of the invention. Compressive Strength
[442] TABLE 57 shows the compressive strength behavior of the developed geopolymer cement compositions of the invention investigated in example 18.

[443] The following important observations can be made from this study:
[444] The results of this example also demonstrate that the cement compositions of the geopolymer of the invention comprising mixtures other than calcium aluminate cement and calcium sulfoaluminate cement are capable of providing rapid development of a rate of compressive strength. The rate of resistance development can be adequate by adjusting the amount of calcium aluminate cement and calcium sulfoaluminate cement and their relative ratio in the cement compositions of the inventive geopolymer.
[445] The compressive strength of the geopolymer cement compositions of the invention investigated in this example continued to increase over time. The 28-day compressive strengths of some embodiments of the geopolymer cement compositions of the invention were exceptionally high, providing results in excess of 5000 psi.
[446] The results of the setting time and compressive strength for Mixture 5 are again very surprising and unexpected. Comparing the results of the setting time and compressive strength for mixture 4 and mixture 5 in several stages, it can be observed and concluded that during the early stages of the hydration reaction, lithium carbonate acts as a setting retardant that increases thus, the initial and final setting time of some modalities of the cement compositions of the geopolymer of this invention; on the other hand, during the final stages of the hydration reaction, the same (lithium carbonate) acts as an accelerator, thereby increasing the rate of development of the compressive strength and the final strength of some modalities of the cement compositions of the geopolymer of this invention . Example 19
[447] The purpose of this example was to study the influence of the addition of a lithium salt on the setting behavior of the cementitious compositions of the geopolymer of the invention. TABLE 58 shows the compositions of the raw materials of geopolymer cement mixtures investigated in this Example. All mixtures contain calcium aluminate cement in which the main phase of calcium aluminate was dodecacalcium heptaaluminate (12CaO ^ 7Al2O3 or C12A7). This calcium aluminate cement is commercially available under the trade name TERNAL EV from Kerneos Inc. Mixture 2 and Mixture 3 contain a lithium salt in the form of lithium carbonate.

Pega Time
[448] TABLE 59 shows the setting time of the geopolymer cementitious compositions of the invention investigated in Example 19.

[449] All the geopolymer cement compositions investigated in this example had a quick pick behavior. The final setting times of the geopolymer cementitious compositions of the invention in this example ranged from about 75 minutes to about 132 minutes, compared to an extremely fast final setting time of about 15 minutes of the mixture composition containing only fly ash and citrate sodium (Example 1). It should be noted that an extremely short pick-up time is problematic for most practical applications.
[450] The comparison of this example clearly demonstrates that the addition of lithium carbonate has an effect in increasing the setting time of some modalities of the geopolymer compositions of this invention. This result is very surprising and unexpected since the lithium salt (lithium carbonate) is observed to act as a retardant in some embodiments of this invention. It should be noted that this observed behavior is contrary to what is known in the art on the effect of lithium salts such as lithium carbonate on the gripping behavior of calcium aluminate cement based bonding systems. The state of the art in calcium aluminate cements teaches that lithium salts such as lithium carbonate act as setting accelerators, thus reducing the initial and final setting time of the material. The findings present as shown in this example teach outside of the art and establish that lithium salts such as lithium carbonate have a delaying effect in the early stages of the reaction (initial and final set-up time) of some modalities of the geopolymer cement compositions of the invention.
[451] The geopolymer compositions of some preferred embodiments of the invention shown in the examples have application in a number of commercial products. Specifically, the compositions can be used for;
[452] Products for road repair and road patching, rolling surfaces and traffic pavements, as shown by some properties disclosed in examples 5, 6, 9, 10, 14, 15, 16, 18 and 19;
[453] Bricks and synthetic stones, as shown by some properties disclosed in examples 5.6, 9, 12 and 14;
[454] Materials for wall, floor and ceiling repair and bonding mortars, plasters and surface materials, as shown by some properties disclosed in examples 9.10.11.14, 18, and 19;
[455] Roofing materials, as shown by some properties in examples 5, 6, 14 and 18;
[456] Shotcrete products which are pulverized cementitious products used for the stabilization of soil and rock and as lining materials, as shown by some properties disclosed in examples 5, 6, 7, 9 and 15;
[457] Weight bearing structures, as shown by some properties disclosed in examples 8, 10, 13, 14, 15, 16, 17, and 18;
[458] Statuary and architectural molding, as shown by some properties disclosed in examples 5-19; and
[459] Self-leveling of sub-pavements, as shown by some properties disclosed in examples 9, 10, and 12-19.
[460] Although we describe the preferred modalities for carrying out our invention, it will be understood by those skilled in the art, to whom this disclosure is addressed, that modifications and additions can be made to our invention without departing from its scope

权利要求:
Claims (14)
[0001]
1. Composition of aluminosilicate geopolymer, characterized by the fact that it comprises the product of the reaction of: water; a chemical activator selected from the group consisting of an alkali metal citrate, an alkali metal hydroxide and alkali metal silicate and mixtures thereof; and cementitious reactive material, in which the cementitious reactive material comprises: a thermally activated aluminosilicate mineral comprising class C fly ash; a calcium aluminate cement; and a calcium sulphate selected from the group consisting of calcium sulphate dihydrate, calcium sulphate hemihydrate, anhydrous calcium sulphate and mixtures thereof, where the amount of the chemical activator is 0.5% to 10% by weight based on the weight of the reactive cementitious materials; and in which the cementitious reactive materials comprise: from 65% to 97% by weight of the thermally activated aluminosilicate mineral, from 2% to 30% by weight of calcium aluminate cement, from 0.2% to 15% by weight of sulfate of calcium, where calcium sulfate has an average particle size of 1 to 100 μm.
[0002]
2. Composition, according to claim 1, characterized by the fact that the chemical activator is from 1% to 6% by weight; where the weight ratio of water to the cementitious reactive material is 0.17 to 0.40: 1; wherein the weight ratio of the calcium aluminate cement to the thermally activated mineral aluminosilicate is 2 to 100: 100; and wherein the weight ratio of calcium sulfate to calcium aluminate cement is 2 to 100: 100.
[0003]
3. Composition according to claim 1, characterized by the fact that the chemical activator comprises an alkali metal citrate and the thermally activated aluminosilicate mineral comprises class C fly ash.
[0004]
4. Composition according to claim 1, characterized by the fact that the reactive cementitious material contains calcium sulfate dihydrate; and where the calcium sulfate dihydrate has an average particle size of 1 to 30 μm.
[0005]
5. Composition, according to claim 1, characterized by the fact that the reactive cementitious material contains anhydrous calcium sulfate; where anhydrous calcium sulfate has an average particle size of 1 to 20 μm.
[0006]
6. Composition according to claim 1, characterized by the fact that the reaction product comprises quantities of the calcium aluminate cement, calcium sulfate, and the chemical activator relative to the quantities of the thermally activated aluminosilicate mineral to limit the shrinkage of the composition by less than 0.3%.
[0007]
7. Composition, according to claim 1, characterized by the fact that the thermally activated aluminosilicate mineral comprises Class C fly ash; where the reactive cement material comprises: 65% to 95% by weight of fly ash, 2% to 30% by weight of calcium aluminate cement, and 0.2% to 15% by weight of calcium sulphate .
[0008]
8. Composition according to claim 1, characterized by the fact that the reaction product results from an exothermic reaction in a water paste, in which the amount of calcium aluminate cement, calcium sulfate and chemical activator in relation to the amount of thermally activated aluminosilicate mineral, they are effective in limiting the maximum rise in paste temperature to 10 ° C (50 ° F).
[0009]
9. Composition, according to claim 1, characterized by the fact that the composition has sufficient fluidity and workability in the dipping test to produce the dipping wafers that have diameters from 17.8 to 25.4 cm (7 to 11 inches) and no crack.
[0010]
10. Composition according to claim 1, characterized by the fact that the reaction product of the reactive cementitious material has: a 4-hour compressive strength from 500 psi (3.5 MPa) to 4000 psi (28 MPa); 24-hour compressive strength from 1500 psi (10 MPa) to 5000 psi (34.5 MPa); 28-day compressive strength from 3500 psi (24 MPa) to 10,000 psi (69 MPa); and wherein the mixture has a final setting time of 10 minutes to 240 minutes after having reacted with the water mixture.
[0011]
11. Composition according to claim 1, characterized by the fact that in the form selected from the group consisting of a construction repair material, a floor repair material, a self-leveling floor underlay on a substrate, a structure of the load bearing, a flattening material of the panel, a paste in building materials, a building material selected from the group consisting of brick, blocks and stones, a wall cladding material, a pavement material for traffic bearing surfaces , a repair material for traffic bearing surfaces, a material for weight bearing structures, a roofing material, a reinforced concrete material and a mortar.
[0012]
12. Method for preparing an aluminosilicate geopolymer composition according to any of claims 1-11, characterized in that it comprises the reaction of a mixture of: water; a chemical activator selected from the group consisting of an alkali metal salt, an alkali metal base and mixtures thereof; and cementitious reactive material, in which the cementitious reactive material comprises: a thermally activated aluminosilicate mineral: a calcium aluminate cement; and a calcium sulphate selected from the group consisting of calcium sulphate dihydrate, calcium sulphate hemihydrate, anhydrous calcium sulphate and mixtures thereof.
[0013]
13. Cement mixture to form a composition of the aluminosilicate geopolymer, as defined in claim 1, comprising: a reactive cement material comprising 65% to 97% by weight of a thermally activated aluminosilicate mineral, characterized by the fact that the aluminosilicate mineral thermally activated comprises class C fly ash; from 2% to 30% by weight of a calcium aluminate cement, from 0.2% to 15% by weight of a calcium sulphate selected from the group consisting of calcium sulphate dihydrate, calcium sulphate hemihydrate, sodium sulphate anhydrous calcium and mixtures thereof; and a chemical activator selected from the group consisting of an alkali metal citrate, an alkali metal hydroxide and mixtures thereof, wherein the amount of the chemical activator is 1% to 6% by weight based on the weight of the cementitious reactive materials; where calcium sulfate has an average particle size of 1 to 100 μm.
[0014]
14. Cement mixture according to claim 13, characterized by the fact that it comprises: a reactive cement material comprising from 65% to 85% by weight of the thermally activated aluminosilicate mineral comprises class C fly ash; from 6% to 30% by weight of calcium aluminate cement, and from 2% to 15% by weight of a calcium sulphate selected from the group consisting of calcium sulphate dihydrate, calcium sulphate hemihydrate, calcium sulphate anhydrous and their mixtures and a chemical activator selected from the group consisting of alkali metal citrate, alkali metal hydroxide, alkali metal silicate and mixtures thereof in which the amount of the chemical activator is 1% to 6% by weight with based on the weight of the cementitious reactive materials; wherein the reaction product is formed from calcium sulfate with an average particle size of about 1 to about 100 μm.

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-06-09| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-01-26| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-03-30| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/04/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201261639825P| true| 2012-04-27|2012-04-27|

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US61/639,825|2012-04-27|

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US13/841,279|US9321681B2|2012-04-27|2013-03-15|Dimensionally stable geopolymer compositions and method|

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US13/841,279|2013-03-15|

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PCT/US2013/037271|WO2013163010A1|2012-04-27|2013-04-19|Dimensionally stable geopolymer compositions and method|

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