# Patent

## Title
Dimensionally stable geopolymer composition and method

## Abstract

A method for making geopolymer cementitious binder compositions for cementitious products such as concrete, precast construction elements and panels, mortar and repair materials, and the like is disclosed. The geopolymer cementitious compositions of some embodiments are made by mixing a synergistic mixture of thermally activated aluminosilicate mineral, calcium aluminate cement, a calcium sulfate and a chemical activator with water.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This is a continuation of U.S. patent application Ser. No. 13/841,279, filed Mar. 15, 2013 which claims the benefit of U.S. Provisional Application No. 61/639,825, filed Apr. 27, 2012, each incorporated herein by reference.


FIELD OF THE INVENTION
This invention relates generally 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 which offer properties that are desirable in terms of setting times, dimensional stability and reduced overall material shrinkage upon curing, and other desirable properties.
BACKGROUND OF THE INVENTION
U.S. Pat. No. 6,572,698 to Ko discloses an activated aluminosilicate composition containing aluminosilicates, calcium sulphate and an activator containing alkali metal salts is disclosed. The aluminosilicates are selected from a group consisting of blast furnace slag, clay, marl and industrial by-products, such as fly ash, and has an Al2O3 content greater than 5% by weight. Blast furnace slag is present in an amount less than 35% by weight, and cement kiln dust (CKD), in an amount of from 1 to 20% by weight, is added to the mixture as an activator.
U.S. Pat. No. 4,488,909 to Galer et al discusses cementitious compositions capable of rapid setting. The cementitious composition includes portland cement, high alumina cement, calcium sulfate and lime. Pozzolans such as fly ash, montmorillonite clay, diatomaceous earth and pumicite may be added up to about 25%. The cement composition includes about 14 to 21 wt % high alumina cement. Galer et al provided aluminates using high alumina cement (HAC) and sulfate ions using gypsum to form ettringite and achieve rapid setting of their cementitious mixture.
U.S. Pat. No. 6,869,474 to Perez-Pena et al, discusses cementitious compositions for producing cement-based products such as cement boards. This is achieved by adding an alkanolamine to hydraulic cement such as portland cement, and forming a slurry with water under conditions that provide an initial slurry temperature of at least 90° F. (32° C.). Additional reactive materials may be included such as high alumina cement, calcium sulfate and a pozzolanic material such as fly ash.
U.S. Pat. No. 7,670,427 of Perez-Pena et al, discusses cementitious compositions with early-age compressive strength for producing cement-based products such as cement boards achieved by adding an alkanolamine and a phosphate to hydraulic cement such as portland cement, and forming a slurry with water under conditions that provide an initial slurry temperature of at least 90° F. (32° C.). Additional reactive materials may be included such as high alumina cement, calcium sulfate and a pozzolanic material such as fly ash.
US published patent application No. US 2010-0071597 A1 of Perez-Pena discloses formulations using fly ash and alkali metal salts of citric acid such as sodium citrate to form concrete mixes with fast setting time and relatively high early age compressive strength. Hydraulic cement and gypsum can be used up to 25 wt % of the formulation, although their use is not preferred. The activated fly ash compositions described in this application may interact with the traditional foaming systems used to entrain air and thereby make lightweight boards.
U.S. Pat. No. 5,536,310 to Brook et al disclose a cementitious composition containing 10-30 parts by weight (pbw) of a hydraulic cement such as portland cement, 50-80 pbw fly ash, and 0.5-8.0 pbw expressed as a free acid of a carboxylic acid such as citric acid or alkali metal salts thereof, e.g., tripotassium citrate or trisodium citrate, with other conventional additives, including retarder additives such as boric acid or borax.
U.S. Pat. No. 6,641,658 to Dubey discloses a Portland cement based cementitious composition which contains 35-90% Portland cement, 0-55% of a pozzolan, 5-15% of high alumina cement and 1 to 8% of insoluble anhydrite form of calcium sulfate in place of the soluble conventional landplaster/gypsum to increase the release of heat and decrease setting time despite the use of high amounts of pozzolan, e.g., fly ash. The cementitious composition can include lightweight aggregates and fillers, superplasticizers and additives such as sodium citrate.
U.S. Pat. No. 7,618,490 B2 to Nakashima et al. discloses a quick setting spraying material comprising one or more of calcium sulfoaluminate, calcium aluminosilicate, calcium hydroxide, a source of fluorine and Portland cement concrete. Calcium sulfate may be added as anhydrous or as a hemihydrate.
U.S. Pat. No. 4,655,979 to Nakano et al. discloses a process for making a cellular concrete using calcium silicate based cement, alkali metal retarder, calcium sulfo-aluminate (CSA) cement and an optional calcium sulfate that can be added to the concrete composition.
US 2008/0134943 A1 to Godfrey et al. discloses a waste encapsulation material composed of at least one sulphoaluminate salt of an alkaline earth metal with calcium sulphate, and optional inorganic filler such as blast furnace slag, pulverized fuel ash, finely divided silica, limestone, and organic and inorganic fluidizing agents. Preferably at least one sulphoaluminate salt of an alkaline earth metal comprises calcium sulphoaluminate (CSA). A suitable composition may, for example, comprise at least one sulphoaluminate salt of an alkaline earth metal in combination with gypsum and pulverized fuel ash (PFA), wherein about 86% of the gypsum particles have a particle size of less than 76 um, and roughly 88% of the PFA particles have a particle size below 45 um. One example comprises 75% (70:30CSA:CaSO4.2H2O); 25% Pulverized Fuel Ash; water/solids ratio 0.65.
U.S. Pat. No. 6,730,162 to Li et al. discloses dual cementitious compositions including a first hydraulic binder having 2.5% to 95 wt. % C4A3S which is chemical notation wherein C=CaO, S=SiO2, A=Al2O3 (in other words calcium sulfo-alumina) and 2.5 to 95 wt. % a hemihydrate and/or an anhydrite of calcium sulfate. Sulfoalumina cements or ferroalumina cements are examples of cements that contain C4A3S. It may also include mineral filler additives selected from the group consisting of slag, fly ash, pozzolan, silica soot, limestone fines, lime industrial by-products and wastes.
Chinese published application CN 101921548 A to Deng et al. discloses a composition of sulfoaluminate cement made from 90-95 wt % sulfoaluminate clinker and anhydrous gypsum, quartz sand, fly ash from waste incineration, hydroxypropyl methylcellulose ether, redispersible glue powder and fiber. The sulfoaluminate clinker and anhydrous gypsum meets the standard of sulfoaluminate cement, i.e. GB20472-2006.
Korean published application KR 549958 B1 to Jung et al. discloses a composition of alumina cement, CSA, gypsum, calcium citrate, and hydroxyl carboxylic acid.
Korean published application KR 2009085451 A to Noh, discloses a composition of powdered blast furnace slag, gypsum and CSA. The gypsum can have an average particle size of 4 micron or less.
KR 2009025683 A discloses powder type waterproof material used for concrete and mortar, is obtained by pulverizing cement, anhydrous gypsum, silica powder, waterproof powder, fly ash, calcium sulfoaluminate type expansion material and inorganic composition.
Korean published application KR 2010129104 A to Gyu et al. discloses composition for blending shotcrete, comprises (in wt. %): metakaolin (5-20), calcium sulfoaluminate (5-20), anhydrous gypsum (20-45), and fly ash (30-50).
There is a need for a dimensionally stable fly ash based geopolymeric compositions and method to reduce the amount of shrinkage, initial and final temperature behavior and reduce setting time of fly ash based compositions mixes so these formulations can be used to manufacture cementitious concrete products with improved strength.
SUMMARY OF THE INVENTION
The present invention provides improved geopolymer cementitious compositions and methods for making such compositions having at least one, and in many instances more than one, highly desirable property such as significantly improved dimensional stability during and after curing; improved and modifyable initial and final setting times; extended working times; modified temperature generation during mixing, setting and curing; and other improved properties as discussed herein. In many, if not all, of such embodiments, the improved properties are provided without significant (if any) loss in early age compressive strength, final compressive strength or other strength properties. Some embodiments, in fact, provide a surprising increase in early age and final compressive strength.
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 slurries of at least water and one or more cementitious reactive components in a dry or powder form. The cementitious reactive components comprise effective amounts of thermally activated geopolymer aluminosilicate materials, such as fly ash; calcium aluminate cements; and calcium sulfates. One or more alkali metal chemical activator, such as an alkali metal salt of citric acid, or an alkali metal base, also is added to the solutions, either in a dry form to the reactive powder, or as a liquid addition to the slurry. Optionally, the slurry or solution may incorporate other additives such as water reducing agents, set accelerating or retarding agents, air-entraining agents, foaming agents, wetting agents, lightweight or other aggregates, reinforcing materials, or other additives to provide or modify the properties of the slurry and final product.
In many preferred compositions of the invention, the cementitious reactive components in their dry or powder form comprise about 65 to about 97 weight percent thermally activated aluminosilicate mineral such as fly ash, about 2 to about 30 weight percent calcium aluminate cement, and about 0.2 to about 15 weight percent calcium sulfate, based upon the total dry weight of all the cementitious reactive components. In preferred compositions of invention, the cementitious reactive components comprise calcium aluminate cement in about 1 to about 200 parts by weight relative to 100 parts by weight of thermally activated aluminosilicate mineral.
In other embodiments, a blend of two or more types calcium aluminate cements and calcium sulfoaluminate cements may be used, and the amounts and types of calcium aluminate cements and calcium sulfoaluminate cements can vary depending upon their chemical composition and particle size (Blaine fineness). The Blaine fineness of calcium aluminate cement in such embodiments and other embodiments preferably is greater than about 3000, more preferably greater than about 4000, and most preferably greater than 5000. The Blaine fineness of calcium sulfoaluminate cement in such embodiments and other embodiments preferably is greater than about 3000, more preferably greater than about 4000, even more preferably greater than 5000, and most preferably greater than about 6000.
In some preferred embodiments, the amount of alkali metal chemical activator is from about 0.5% to about 10% by weight based upon the total dry weight of the cementitious reactive materials. More preferably, the range of alkali metal chemical activator about 1% to about 6% by total weight of the cementitious reactive materials, preferably about 1.25% to about 4%, more preferably about 1.5% to about 3.5%, and most preferably about 1.5% to 2.5%. Sodium citrate and potassium citrate are preferred alkali metal acid activators, although a blend of sodium and potassium citrate can also be used. Alkali metal bases, such as alkali metal hydroxides, and alkali metal silicates also may be used depending on the application and the needs of that application.
These and other preferred embodiments of the invention, unlike prior fly ash geopolymer compositions, are formulated to provide geopolymer cementitious compositions that are dimensionally stable and resistant to cracking upon setting and hardening under both unrestrained and restrained conditions. For example, the short term free shrinkage of certain preferred embodiments of the invention typically is less than about 0.3%, preferably less than about 0.2%, and more preferably less than about 0.1%, and most preferably less than about 0.05% (measured after initial set and within 1 to 4 hours of mixing). In such preferred embodiments, the long term shrinkage of the compositions during curing also typically is less than about 0.3%, more preferably less than about 0.2%, and most preferably less than about 0.1%.
For additional control regarding the dimensional stability and shrinkage in those embodiments, the amount of calcium aluminate cement is about 2.5 to about 100 parts by weight relative to 100 parts by weight of the thermally activated aluminosilicate mineral, more preferably about 2.5 to about 50 parts by weight relative to 100 parts by weight of the thermally activated aluminosilicate mineral, and most preferably about 5 to about 30 parts by weight relative to 100 parts by weight of thermally activated aluminosilicate mineral. For embodiments where the control on dimensional stability as indicated by the material shrinkage is of importance, the amount of alkali metal activator more preferably ranges from about 1 to about 3% by total dry weight of the cementitious reactive materials (i.e., thermally activated aluminosilicate mineral such as fly ash, calcium aluminate cement and calcium sulfate), even more preferably from about 1.25% to about 2.75% by total dry weight of the cementitious reactive materials, and most preferably from about 1.5% to about 2.5% by total dry weight of the cementitious reactive materials.
The dimensionally stable geopolymer compositions of preferred embodiments of the invention further evidence a surprising reduction in the maximum temperature rise during curing of the composition relative to prior geopolymer cementitious products. For this and related reasons, these embodiments resist thermal cracking to an unexpected degree. For example, in some preferred embodiments, the temperature rise typically is less than about 50° F. (28° C.), more preferably less than about 40° F. (22° C.), and most preferably less than about 30° F. (17° C.).
These and other preferred embodiments of the invention also exhibit an unexpected rate of early age strength development. For example, in some such embodiments, their 4-hour compressive strength may exceed about 1000 psi (6.9 MPa), preferably exceeding about 1500 psi (10.3 MPa), most preferably exceeding about 2500 psi (17.2 MPa). In such embodiments, their 24-hour compressive strength development may exceed about 1500 psi (10.3 MPa), more preferably exceeding about 2500 psi (17.2 MPa), and most preferably exceeding about 3500 psi (24.1 MPa). In those and other preferred embodiments, the 28-day compressive strength further may exceed about 3500 psi (24.1 MPa), more preferably exceeding about 4500 psi (31.0 MPa), and most preferably exceeding about 5500 psi (37.9 MPa). In yet 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 to about 5000 psi (10.3 to 34.5 MPa) after 24 hours, and most preferably from about 3500 to about 10000 psi (24.1 to 70 MPa) after 28 days.
Furthermore, the geopolymer cementitious compositions of certain of the preferred embodiments of the invention also have extremely good durability under wet conditions, with ultimate wet compressive strengths similar to dry compressive strengths. For example, in certain embodiments, their water saturated compressive strength at 28-days typically may exceed about 3500 psi (24.1 MPa), more preferably exceeding about 4500 psi (31.0 MPa), and most preferably exceeding about 5500 psi (37.9 MPa).
Because the set times from slurry to solid state for alkali metal activated geopolymers, as well as the combined calcium aluminate cements and calcium sulfates, typically are relatively short, it was expected that the preferred embodiments combining all of these components also would have short set times and limited working times. Surprisingly, however, the set times provided by the preferred embodiments of the invention are not limited to short set times (often less than 15 minutes), but provide significant control over the slurry setting reactions allowing significant extensions of the slurry set and working times.
For example, in some embodiments, the composition may be formulated for a short setting time, such as less than about 10 minutes. In other preferred embodiments, the composition may be formulated for an extended setting of between about 10 to about 30 minutes. In yet 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 most preferred embodiments, the composition may be formulated for setting times as long as about 60 to about 120 minutes, about 120 to about 240 minutes, or longer times if desired.
The setting times of such embodiments, in addition, can be selected, and if desired extended, without significant (if any) loss in shrink resistance properties, compressive strength and other strength properties. As a result, such embodiments unexpectedly can be used in applications where prior geopolymer based products and cementitious products with geopolymer components could not be used due to a need for extended set and working times without unacceptable shrinkage or strength loss.
In certain preferred embodiments, the compositions of the invention also develop exceptional tensile bond strength with an underlying substrate. For example, the preferable tensile bond strength between such embodiments and a concrete substrate preferably exceeds about 200 psi (1.4 MPa) and most preferably exceeds about 300 psi (2.1 MPa). In some embodiments, the surface pH of the fully cured and hardened dimensionally stable geopolymer cementitious compositions of the invention also are improved relative to Portland cement based materials and products, which typically have a surface pH of greater than 12 and more typically greater than 13. In certain preferred embodiments, such compositions are measured 16 hours after installation and preferably have a pH less than about 11, more preferably less than about 10.5, and most preferably less than about 10. In this context, surface pH is measured using the ASTM F-710 (2011) testing standard.
In many preferred embodiments, the geopolymer cementitious compositions of the invention do not require calcium silicate based hydraulic cements, such as Portland cements, for strength development 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 embodiment, an excess amount of Portland cement actually decreased the composition's dimensional stability during and after curing, instead of increasing its dimensional stability.
For preferred embodiments of the invention incorporating calcium silicate based hydraulic cements, the limit on such hydraulic cements may vary depending on the specific composition of the embodiment, but can be identified by an increase in shrinkage relative to the shrinkage of the same embodiment with a reduced amount of the calcium silicate hydraulic cement. In certain of such embodiments the Portland cement content should not exceed about 15 weight % of the weight of reactive powder components in another preferred embodiment, it should not exceed 10 weight % of the weight of reactive powder components, and in yet another preferred it should not exceed about 5 weight % of the weight of reactive powder components and yet another preferred embodiment, there is no substantial amount of Portland cement in the reactive powder components.
It also has surprisingly been found in some embodiments that an excess amount of calcium aluminate cement can cause a loss of dimensional stability, as indicated by an increase in shrinkage after the initial set of the composition. For applications requiring significant degree of dimensional stability and/or shrinkage control to prevent cracking, delamination and other modes of failure, the amount of calcium aluminate cement is preferably about 10 to about 60 parts by dry weight relative to 100 parts by dry weight of thermally activated aluminosilicate mineral.
In other preferred embodiments, it also has been unexpectedly found that the amount of calcium sulfate present in proportion to calcium aluminate cement in the composition can moderate potential adverse effects, such as shrinkage, caused by the calcium aluminate cement content. In such embodiments, the calcium sulfate amount is preferably about 2 to about 200 parts by weight relative to 100 parts by weight of calcium aluminate cement.
For the most effective control of material shrinkage of those embodiments, the amount of calcium sulfate is about 10 to about 100 parts by dry weight relative to 100 parts by dry weight of calcium aluminate cement, more preferably about 15 to about 75 parts by dry weight relative to 100 parts by dry weight of calcium aluminate cement, and most preferably about 20 to about 50 parts by dry weight relative to 100 parts by dry weight of calcium aluminate cement. In embodiments where an increase in early age compressive strength is important, it is preferred amount of calcium sulfate amount is about 10 to about 50 parts to about 100 parts by dry weight of calcium aluminate cement.
In yet other embodiments of the invention, the type of calcium sulfate (primarily dihydrate, hemihydrate, or anydrite) added to the composition can have a significant influence on the development of the early age compressive strength of the partially cured composition (i.e. at less than about 24 hours). Surprisingly, it has been found that various embodiments using primarily anhydrous calcium sulfate (anhydrite) have a greater early compressive strength than embodiments using primarily the dihydrate form and, in some embodiments, can have early compressive strengths comparable to those using primarily calcium sulfate hemihydrate. In other embodiments, two or more of the calcium sulfate types (dihydrate, hemihydrate, or anydrite) can be employed together, and the amounts of the different types adjusted to provide improved control of the composition's compressive strength. Similarly, the different types and amounts of calcium sulfate can be employed alone or in combination to adjust the desired shrinkage and other properties of the composition.
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 1 to about 20 microns. These embodiments provide a surprising improvement in shrinkage resistance, and in other embodiments, the calcium sulfate particle sizes in at least the preferred ranges can provide an important contribution to improved rates of strength development during curing of the compositions.
In yet other embodiments, it was surprisingly found that substantially water insoluble anhydrous calcium sulfate (anhydrite) can provide important benefits, notwithstanding its low water solubility and previously presumed limited, if any, reactivity in the composition. For example, it was unexpectedly found that anhydrite provided significant improved dimensional stability control by reducing the shrinkage during curing of those and other embodiments relative to prior art compositions. Anhydrite also provided significantly improved early and long term compressive strength relative to prior art compositions, and, in some instances, early and long term compressive strengths comparable to or better than compositions utilizing calcium sulfate hemihydrate or dihydrate as the calcium sulfate source. The selection of the type of calcium sulfate used in a particular embodiment will depend on the desired rate of early age strength development in combination with a balance of other properties, such as set time and shrinkage resistance for a particular end application.
In other embodiments, the particle size and morphology of calcium sulfate provides a significant and surprising influence on development of early age strength (less than about 24 hours) of the compositions. In such embodiments, the use of a relatively a small particle size calcium sulfate provides a more rapid development in early age compressive strength. In those embodiments, the preferred average particle size of calcium sulfate ranges from about 1 to 100 microns, more preferably from about 1 to 50 microns, and most preferably from about 1 to 20 microns.
In certain embodiments, the compositions also exhibit a self-leveling behavior after initial mixing while providing one or more of the aforementioned surprising performance characteristics. The self-leveling aspect of material is useful in a variety of situations and applications such as self-leveling underlayments for floors, concrete toppings, manufacturing of precise concrete products and panels, placement of slurry in heavily reinforced construction elements, etc. The compositions of those embodiments are self-leveling after initial mixing with water to the reactive powder of the invention at a weight ratio of about 0.15 to about 0.4, more preferably, 0.17 to 0.35, yet more preferably 0.20 to 0.30. Alternatively, in other embodiments, the compositions also can be provided in a shapeable, thick paste like consistency after initial mixing while similarly providing one or more improved performance characteristics.
A preferable formulation for self-leveling and patching compositions comprises about 65 to about 95 weight percent fly ash, about 2 to about 30 weight percent calcium aluminate cement, and about 0.2 to about 15 weight percent calcium sulfate. In some embodiments, the geopolymeric cementitious composition of the invention can be spread on a surface of a substrate, wherein the geopolymeric cementitious binder is mixed as a self-leveling product and is poured to an effective thickness of about 0.02 cm to about 7.5 cm.
The physical characteristics of such products provide good examples of benefits of those embodiments, i.e. dimensional stability, resistance to dimensional movement and physical distress, and high surface resistance to abrasion and wear, suitable for use in commercial, industrial, and other high traffic areas. Time consuming and expensive substrate surface preparation measures such as shot-blasting, scarifying, water jetting, scabbing or milling can be minimized or avoided altogether, depending on the application.
In other aspects of the invention, preferred embodiments provide methods for making dimensionally stable, cementitious compositions with setting times adaptable to specific applications, good early age strength development and ultimate compressive and other strength characteristics, improved surface pH, improved tensile bond strength with substrates and other benefits. In certain preferred embodiments, those methods comprise the steps of preparing a surprisingly effective, synergistic mixture of thermally activated aluminosilicates, preferably from Class C fly ash, calcium aluminate cement, a calcium sulfate, and an alkali metal chemical activator.
In certain preferred embodiments of such methods, the preferred mixtures are prepared using components, such as those mentioned above, to form a cementitious reactive powder comprising thermally activated Class C fly ash, calcium aluminate cement, and a calcium sulfate selected from the group consisting of calcium sulfate dihydrate, calcium sulfate hemihydrate, anhydrous calcium sulfate and mixtures thereof (preferably in a fine grain form with particle size less than about 300 microns).
In those embodiments, a chemical activator further is added to the mixture either in dry or liquid form comprising an alkali metal salt or 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 is added and optionally a superplasticizer, particularly a carboxylated plasticizer material, to form stable slurry mixtures that can be used in applications suitable for geopolymeric cementitious products.
In the preferred methods, the 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., most preferably ambient temperature of about 25° C. In such embodiments, the initial temperature of the overall mixture is measured during the first minute after the cementitious reactive powder; activator and water are first all present in the mixture. Of course the temperature of the overall mixture can vary during this first minute but in such preferred embodiments; the temperature of the slurry preferably remains within the listed range.
In some preferred embodiments, the slurry can be mixed using relatively low energies, while still achieving a well-mixed composition. In some of such preferred methods, the slurry is mixed with energies equivalent to those provided by low speed hand drill mixers or equivalent mixers having a rating of about 250 RPM or greater. Accordingly, the geopolymer compositions of such preferred embodiments are easy to mix despite the use of the relatively small amounts of water used to make the slurry used to form the final composition.
In many embodiments, other additives which are not considered cementitious reactive powder may be incorporated into the slurry and overall geopolymeric cementitious composition. Such other additives, for example, water reducing agents such as the above mentioned superplasticizers, set accelerating agents, set retarding agents, air-entraining agents, foaming agents, wetting agents, shrinkage control agents, viscosity modifying agents (thickeners), film-forming redispersible polymer powders, film-forming polymer dispersions, coloring agents, corrosion control agents, alkali-silica reaction reducing admixtures, discrete reinforcing fibers, and internal curing agents. Other additives may include fillers, such as one or more of sand and/or other aggregates, lightweight fillers, pozzolanic mineral, mineral fillers, etc.
While separately discussed above, each of the preferred geopolymeric compositions and mixtures of the invention has at least one, and can have a combination of two or more of the above mentioned distinctive advantages (as well as those apparent from the further discussion, examples and data herein) relative to prior art geopolymeric cementitious compositions.
Many, if not most, of the embodiments of the invention are environmentally sustainable, utilizing fly ash geopolymers that comprise post industrial waste as a primary raw material source. This significantly reduces the life cycle carbon footprint and the life cycle embodied energy of the manufactured product.
The geopolymer cementitious compositions of preferred embodiments of the present invention can be used where other cementitious materials are used, particularly applications where setting and working time flexibility, dimensional stability, compressive strength and/or other strength properties are important or necessary. For example, in various concrete product applications including structural concrete panels for floors, slabs, and walls, wall and floor underlayment for installation of floor-finish materials such as ceramic tiles, natural stones, vinyl tiles, VCTs and carpet, highway overlays and bridge repair, sidewalks and other slabs-on-ground, exterior stucco and finish plasters, self-leveling topping and capping underlayments, guniting and shotcrete for stabilization of earth and rocks in foundations, mountain slopes and mines, patching repair mortars for filling and smoothing cracks, holes and other uneven surfaces, statuary and murals for interior and exterior applications, as well as pavement materials for roads, bridge decks and other traffic and weight bearing surfaces.
Other examples include uses for precast concrete articles, as well as building products such as cementitious boards, masonry blocks, bricks, and pavers with excellent moisture durability. In some applications, such precast concrete products such as cement boards are preferably made under conditions which provide setting times appropriate for pouring into a stationary or moving form or over a continuously moving belt.
The geopolymer compositions of some embodiments of the invention can be used with different fillers and additives including foaming agents and air entraining agents for adding air in specific proportions to make lightweight cementitious products, including precast construction elements, construction repair products, traffic bearing structures such as road compositions with good expansion properties and no shrinkage.
Other advantages, benefits and aspects of various embodiment of the invention are discussed below, are illustrated in the accompanying figures, and will be understood by those of skill in the art from the more detailed disclosure below. All percentages, ratios and proportions herein are by weight, unless otherwise specified.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A—Graph of time of shrinkage results of Comparative Example 1.
FIG. 1B is a photograph of slump of Example 1.
FIG. 2 is a photograph of slump of Comparative Example 2.
FIG. 3A is a photograph of slump of Comparative Example 3.
FIG. 3B is a graph of time of shrinkage results of Comparative Example 3
FIG. 4A is a photograph of slump of comparative Example 4 for Mixes 1 and 2.
FIG. 4B is a graph of shrinkage behavior of Mix 1 in comparative Example 4 for mixture comprising high alumina cement, fly ash and alkali metal citrate.
FIG. 5A is a photograph of slump patty of the two mixture compositions in Example 5
FIG. 5B is a graph of shrinkage of cementitious compositions of Example 5.
FIG. 6A is a photograph of slump patty of the mixture compositions in Example 6.
FIG. 6B is a graph of shrinkage behavior of geopolymer compositions of the invention in Example 6.
FIG. 6C is a graph of slurry temperature rise of geopolymer compositions in Example 6.
FIG. 7 is a graph of shrinkage of compositions in Example 7.
FIG. 8 is a graph of shrinkage of compositions of invention (Mixes 2 to 4) in Example 8.
FIG. 9A is a graph of shrinkage of compositions in Example 9
FIG. 9B is a graph of slurry temperature rise of compositions of Example 9.
FIG. 10 is a graph of shrinkage of compositions in Example 10.
FIG. 11 is a graph of shrinkage of compositions in Example 11.
FIG. 12 is a graph of shrinkage of compositions of Example 12.
FIG. 13 is a graph of shrinkage of compositions in Example 14
FIG. 14 is a graph of shrinkage of compositions in Example 15
FIG. 15 is a graph of shrinkage of compositions in Example 16.
FIG. 16 is a graph of shrinkage of compositions in Example 17.
FIG. 17 is a graph of shrinkage of compositions of Example 18.



DETAILED DESCRIPTION OF THE INVENTION
TABLE A shows the composition of the dimensionally stable geopolymer cementitious compositions of some embodiments of the invention expressed in parts by weight (pbw) of individual or aggregated components.
TABLE A shows the dimensionally stable geopolymer cementitious compositions of some embodiments of the invention are comprised of two components—Reactive Powder Component A (also referred to herein as “Cementitious Reactive Material” and Activator Component B. Cementitious Reactive Material for purposes of this invention is defined as a thermally activated aluminosilicate, calcium aluminate cement, a calcium sulfate, and any additional reactive cement to the extent it is added to the other listed ingredients. In the following TABLES, Reactive Powder Component A is blend of materials comprising thermally activated aluminosilicate mineral comprising Class C fly ash, cement comprising calcium aluminate cement, and calcium sulfate. Activator Component B comprises an alkali metal chemical activator or mixtures thereof, which can be a powder or aqueous solution. Reactive Powder Component A and Activator Component B combined together form the reactive mixture of the geopolymer cementitious compositions of some embodiments of the invention.







TABLE A







Reactive geopolymer cementitious compositions


of some embodiments of the invention.













More



Broad
Preferred
Preferred














Reactive Powder Component A:














a.
Thermally activated
100
100
100



aluminosilicate mineral



comprising Class C Fly ash,



pbw


b.
Calcium aluminate cement,
1-100
2.5-80
 5-60



pbw per 100 pbw of thermally



activated aluminosilicate



mineral


c.
Calcium sulfate, pbw per 100
2-100
  5-75
10-50



pbw of calcium aluminate



cement.










Activator Component B:





Alkali metal chemical activator,
1 to 6%
1.25 to 4%
1.5 to 2.5%


weight % based upon the total


weight of Component A (i.e.,


weight % of total thermally


activated aluminosilicate


comprising Class C fly ash,


calcium aluminate cement, and


calcium sulfate).









TABLE B represents full density (preferably densities in the range of 100 to 160 pounds per cubic foot) formulations incorporating the composition of TABLE A and other ingredients.







TABLE B







Ingredient Amounts















More



Ingredient
Broad
Preferred
preferred














Reactive Powder Component A:














a.
Thermally activated
100
100
100



aluminosilicate mineral



comprising Class C Fly ash,



pbw


d.
Calcium aluminate cement, pbw
 2-100
2.5-80  
5-60 



per 100 pbw of thermally



activated aluminosilicate mineral


b.
Calcium sulfate, pbw per 100
 2-100
5-75 
10-50 



pbw of calcium aluminate



cement.










Activator Component B:





Alkali metal chemical activator,
1 to 6%
1.25 to 4%
1.5 to 2.5%


weight % based upon the total


weight of Component A


Superplasticizer/Reactive Powder
0 to 4.0%
0.25-2.5% 
0.50-1.5% 


Component A (weight %)


Sand/Reactive Powder Component A
0-4 
0.50-3   
0.75-1.5   


Ratio (by weight)


Inorganic Mineral Filler/Reactive
0-2 
0-1 
0-0.5


Powder Component A Ratio (by


weight)


Defoaming Agent/Reactive Powder
0-1%
  0-0.75%
  0-0.50%


Component A (weight %)


Organic Rheology Control
  0-0.50%
  0-0.25%
  0-0.15%


Agent/Reactive Powder Component A


(weight %)


Inorganic Rheology Control
0-3%
0-2%
0-1%


Agent/Reactive Powder Component A


(weight %)


Coloring Pigments/Reactive Powder
0-5%
 0-2.5%
0-1%


Component A (weight %)


Efflorescence Suppression
0-3%
0-2%
0-1%


Agent/Reactive Powder Component A


(weight %)


Film Forming Redispersible Polymer
 0-20%
 0-10%
0-5%


Powder/Reactive Powder Component


A (weight %)


Film Forming Polymer
 0-40%
 0-20%
 0-10%


Dispersion/Reactive Powder


Component A (weight %)


Water/Reactive Powder Component A
0.17-0.40 
0.20-0.35 
0.22-0.30 


Ratio (by weight)









TABLE C represents lightweight density (preferably densities in the range of 10 to 125 pounds per cubic foot) formulations incorporating the compositions of TABLE A and other ingredients.







TABLE C







Ingredient Amounts













More


Ingredient
Broad
Preferred
preferred













Reactive Powder Component A:














a.
Thermally activated
100
100
100



aluminosilicate mineral



comprising Class C Fly ash,



pbw


e.
Calcium aluminate cement, pbw
 2-100
2.5-80 
5-60 



per 100 pbw of thermally



activated aluminosilicate mineral


b.
Calcium sulfate, pbw per 100
 2-100
 5-75
10-50 



pbw of calcium aluminate



cement.










Activator Component B:





Alkali metal chemical activator,
1 to 6%
1.25 to 4%
1.5 to 2.5%


weight %, based upon the total


weight of Component A


Superplasticizer/Reactive Powder
0 to 4.0%
 0.25-2.5%
0.50-1.5% 


Component A (weight %)


Sand/Reactive Powder Component A
0-4 
0-2
0-1.0


Ratio (by weight)


Inorganic Mineral Filler/Reactive
0-2 
0-1
0-0.5


Powder Component A Ratio (by


weight)


Defoaming Agent/Reactive Powder
0-1%
   0-0.75%
  0-0.50%


Component A (weight %)


Organic Rheology Control
  0-0.50%
   0-0.25%
  0-0.15%


Agent/Reactive Powder Component A


(weight %)


Inorganic Rheology Control
0-3%
 0-2%
0-1%


Agent/Reactive Powder Component A


(weight %)


Coloring Pigments/Reactive Powder
0-5%
    0-2.5%
0-1%


Component A (weight %)


Efflorescence Suppression
0-3%
 0-2%
0-1%


Agent/Reactive Powder Component A


(weight %)


Film Forming Redispersible Polymer
 0-20%
   0-10%
0-5%


Powder/Reactive Powder Component


A (weight %)


Film Forming Polymer
 0-40%
   0-20%
 0-10%


Dispersion/Reactive Powder Component


A (weight %)


Lightweight Filler/Reactive Powder
0-2 
0.01-1  
0.02-0.75 


Component A Ratio (by weight)


Water/Reactive Powder Component A
0.17-0.40 
0.20-0.35
0.22-0.30 


Ratio (by weight)









TABLE D represents lightweight or full density (preferably densities in the range of 40 to 160 pounds per cubic foot) formulations incorporating the composition of TABLE A, coarse aggregate and other ingredients.







TABLE D







Ingredient Amounts













More


Ingredient
Broad
Preferred
preferred













Reactive Powder Component A:














a.
Thermally activated
100
100
100



aluminosilicate mineral



comprising Class C Fly



ash, pbw


b.
Calcium aluminate cement,
 2-100
2.5-80  
5-60 



pbw per 100 pbw thermally



activated aluminosilicate



mineral


c.
Calcium sulfate,
 2-100
5-75 
10-50 



pbw per 100 pbw of



Calcium aluminate



cement.










Activator Component B:





Alkali metal chemical activator,
1 to 6%
1.25 to 4%
1.5 to 2.5%


weight %, based upon the total


weight of Component A


Superplasticizer/Reactive Powder
0 to 4%
0.25-2.5% 
0.50-1.5% 


Component A (weight %)


Sand/Reactive Powder Component A
0-4 
0.50-3   
1-2 


Ratio (by weight)


Inorganic Mineral Filler/Reactive
0-2 
0-1 
0-0.5


Powder Component A Ratio (by


weight)


Defoaming Agent/Reactive Powder
0-1%
  0-0.75%
  0-0.50%


Component A (weight %)


Organic Rheology Control
 0-0.5%
  0-0.25%
  0-0.15%


Agent/Reactive Powder Component A


(weight %)


Inorganic Rheology Control
0-3%
0-2%
0-1%


Agent/Reactive Powder Component A


(weight %)


Coloring Pigments/Reactive Powder
0-5%
 0-2.5%
0-1%


Component A (weight %)


Efflorescence Suppression
0-3%
0-2%
0-1%


Agent/Reactive Powder Component A


(weight %)


Film Forming Redispersible Polymer
 0-20%
 0-10%
0-5%


Powder/Reactive Powder Component


A (weight %)


Film Forming Polymer
 0-40%
 0-20%
 0-10%


Dispersion/Reactive Powder


Component A (weight %)


Coarse Aggregate/Reactive Powder
0.5-5    
0.5-4    
1-3 


Component A Ratio (by weight)


Lightweight Filler/Reactive Powder
0-2 
0-1 
 0-0.50


Component A Ratio (by weight)


Water/Reactive Powder Component A
0.2-0.4 
0.225-0.35   
0.25-0.3   


Ratio (by weight)









The long-term free shrinkage of the geopolymer cementitious compositions mixtures of some embodiments of the invention with shrinkage measurements initiated between 1 to 4 hours after mixing to form an aqueous mixture of about 0.3% or less, preferably less than about 0.2%, and more preferably less than about 0.1%, and most preferably less than about 0.05%. As mentioned previously, the synergistic interaction between the thermally activated aluminosilicate mineral, calcium aluminate cement, appropriately selected source and amount of calcium sulfate, and appropriately selected alkali metal activator used at proper amount according to some embodiments of this invention helps to minimize the material shrinkage.
It has been very surprisingly found that the amount of calcium aluminate cement in the geopolymer cementitious compositions of some embodiments of the invention plays an important influence on controlling the degree of material shrinkage measured after the initial setting of the material. It has also been surprisingly been found that beyond a some amount of calcium aluminate cement in a given embodiment, the amount of material shrinkage occurring after the initial set of the material begins to increase.
TABLE D1 shows ingredient amounts.










TABLE D1








More


Ingredient
Broad
Preferred
preferred







In general the amount of calcium
1-200
2.5 to 100
5 to 50


aluminate cement per 100 parts by
parts by
parts by
parts by


weight thermally activated
weight
weight
weight


aluminosilicate mineral.


For most effective control on material
2.5 to 75
3.5 to 50
5 to 30


shrinkage, the amount of calcium
parts by
parts by
parts by


aluminate cement per 100 parts by
weight
weight
weight


weight thermally activated


aluminosilicate mineral.


For applications requiring very high
5 to 40
5 to 35
5 to 30


degree of shrinkage control to prevent
parts by
parts by
parts by


cracking, delamination and other
weight
weight
weight


modes of failure, the amount of


calcium aluminate cement per 100


parts by weight thermally activated


aluminosilicate mineral.









It has also been unexpectedly found the amount of calcium sulfate present in proportion to calcium aluminate cement in the mixture has a significant influence on the degree of material shrinkage of geopolymer cementitious compositions of some embodiments of the invention.
TABLE D2 shows ingredient amounts of some embodiments of the invention, the amount of calcium sulfate per 100 parts calcium aluminate cement.










TABLE D2








More


Ingredient
Broad
Preferred
preferred







In general the weight ratio of calcium
2 to 200
10 to 100
20 to 75


sulfate per 100 parts by weight calcium
parts by
parts by
parts by


aluminate cement.
weight
weight
weight


For most effective control on material
2 to 100
5 to 75
10 to 50


shrinkage of the geopolymer
parts by
parts by
parts by


cementitious compositions of some
weight
weight
weight


embodiments of the invention, the


amount of calcium sulfate per 100


parts calcium aluminate cement.









For a given amount of alkali metal activator and other components in the composition of some embodiments of the invention, usage of calcium sulfate dihydrate has been found to provide the most effective control in minimizing the material shrinkage. Usage of anhydrous calcium sulfate (anhydrite) and calcium sulfate hemi-hydrate also provide excellent control in lowering the material shrinkage of the geopolymer cementitious compositions of some embodiments of the invention. Calcium sulfate dihydrate and anhydrous calcium sulfate (anhydrite) are the preferred form of calcium sulfate of some embodiments of this invention. More preferably, the calcium sulfate dihydrate is in the form of fine grain landplaster.
It has been surprisingly found the amount of alkali metal activator has a significant influence on the degree of material shrinkage of geopolymer cementitious compositions of some embodiments of the invention. TABLE D3 shows ingredient amounts for the % amount of alkali metal activator relative to the weight of the cementitious materials (i.e. thermally activated aluminosilicate mineral, calcium aluminate cement, and calcium sulfate) preferred to achieve this.










TABLE D3








More


Ingredient
Broad
Preferred
preferred







For the most effective control
1 to 6%
1.25% to 4%
1.5% to 2.5%


on material shrinkage of the
by weight
by weight
by weight


geopolymer cementitious
of the
of the
of the


compositions of some
cementi-
cementi-
cementi-


embodiments of the invention,
tious
tious
tious


the weight % of alkali metal
materials
materials
materials


activator relative to the total


weight of the cementitious


materials (i.e., thermally


activated aluminosiicate


mineral, calcium aluminate


cement, and calcium sulfate).









Preferably, the composition comprises no Portland cement. In fact, it has quite surprisingly been found that incorporation of calcium silicate based hydraulic cements such as Portland cement to the geopolymer compositions of some embodiments of the invention has a negative influence on the dimensional stability of the resulting material. Increase in Portland cement amount added to the geopolymer compositions of some embodiments of the invention increases the shrinkage of the resulting compositions. Increase in material shrinkage in the presence of Portland cement results even when calcium aluminate cement, calcium sulfate and alkali metal chemical activator are present in the composition. For example, it has been surprisingly found incorporation of about 6%, about 14%, and about 25% by weight Portland cement in the reactive powder compositions of some embodiments of the invention, increased the 8-week material free shrinkage, measured after the material initial set, to about 0.1%, 0.16%, and 0.47%, respectively. Thus, addition of Portland cement negatively influences the synergistic interaction between the basic four reactive components (thermally activated aluminosilicate mineral comprising Class C fly ash, calcium aluminate cement, calcium sulfate and alkali metal chemical activator in some embodiments of the invention. Hence, the geopolymer cementitious compositions of some embodiments of the invention preferably do not contain Portland cement.
To form the composition of some embodiments of the invention, the Reactive Powder Component A (thermally activated aluminosilicate mineral, calcium aluminate cement, and calcium sulfate), Activator Component B (alkali metal chemical activator), and water are mixed to form a cementitious slurry at an initial temperature (temperature during the first minute the ingredients are first all present in the mixture) of about 0° C. to about 50° C., and preferably about 10 to about 35° C. As a result, geopolymerization reaction ensues, leading to formation of alumino-silicate geopolymer reaction species and setting and hardening of the resulting material. Simultaneously, hydration reactions of calcium aluminate and calcium silicate phases also occur leading to setting and hardening of the resulting material.
The dimensionally stable geopolymer compositions of some embodiments of the invention have extremely low water demand to achieve a workable mixture in the fresh state and to produce a strong and durable material in the hardened state.
The preferable water/total solids weight ratio of the dimensionally stable geopolymer cementitious compositions 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 still more preferably about 0.05 to about 0.15. The preferable water/total solids ratio of the dimensionally stable 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 still more preferably less than about 0.075. Total solids include cementitious materials, aggregate (such as sand or other aggregate), fillers and other solid additives on a water free basis.
A minimum amount of water is provided to accomplish the chemical hydration and alumino-silicate geopolymerization reactions. Preferably, in the slurry of some embodiments of the invention, the weight ratio of the water to cementitious materials is about 0.17 to about 0.4, more preferably about 0.2 to about 0.35, and still more preferably about 0.22 to about 0.3. The amount of water depends on the needs of the individual materials present in the cementitious composition. As used herein, “cementitious materials” is defined as the thermally activated aluminosilicate mineral, calcium aluminate cement, and calcium sulfate and any additional cement which may be added to the reactive mixture.
Setting of the composition is characterized by initial and final set times, as measured using Gilmore needles specified in the ASTM C266 test procedure. The final set time also corresponds to the time when a concrete product, e.g., a concrete panel, has sufficiently hardened so that it can be handled.
Geopolymeric reaction of thermally activated aluminosilicate mineral such as fly ash is an exothermic reaction. It has been unexpectedly 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 very significantly reduce the rate and amount of heat released by the material undergoing exothermic reaction. Appropriate selection of the type of calcium sulfate and its amount, the amount of calcium aluminate cement, and appropriate selection of alkali metal chemical activator and its amount are key and fundamental to reducing and minimizing the rate and amount of heat released due to the ensuing exothermic reaction.
Geopolymeric reaction of thermally activated aluminosilicate mineral such as fly ash proceeds at a very rapid rate and leads to extremely rapid gelation and setting of the material. Typically, when fly ash alone is reacted with an alkali metal chemical activator in accordance with the prior art, the gelation of the material starts within 2 to 3 minutes and the final set is reached in less than 10 minutes after the formation of an aqueous mixture. It has unexpectedly been found that thermally activated aluminosilicate mineral such as Class C fly ash, calcium aluminate cement, calcium sulfate, and alkali metal chemical activator interact synergistically with each other as part of the geopolymerization reaction of some embodiments of the invention to significantly increase the gelation time and final setting time of the resulting material. Appropriate selection of the type of calcium sulfate and its amount, the amount of calcium aluminate cement, and appropriate selection of alkali metal chemical activator and its amount are effective in prolonging the gelation rate and period and the final setting time of the resulting material. For a given amount of alkali metal activator in the composition, increase in calcium sulfate amount has been found to increase the gelation and final setting times of the resulting geopolymer cementitious compositions some embodiments of the invention. Additionally, for a given amount of alkali metal activator in the composition, increase in particle size of calcium sulfate has been found to increase the gelation and final setting times of the resulting geopolymer cementitious compositions of some embodiments of the invention. Furthermore, for a given particle size of calcium sulfate and amount of chemical activator in the composition, calcium sulfate dihydrate leads to highest increase in the gelation and final setting times, and anhydrous calcium sulfate leads to most rapid gelation and final setting times. For the geopolymer cementitious compositions of some embodiments of the invention, the gelation period ranges between 20 to 60 minutes, with final setting times of about 30 to about 120 minutes. The increased gelation and final setting times allow a longer open and working times for the geopolymer cementitious compositions of some embodiments of the invention.
Early age strength of the composition is characterized by measuring the compressive strength after about 3 to about 5 hours of curing. Relatively higher early age compressive strength can be an advantage for a cementitious material because it can withstand higher stresses without excessive deformation. Achieving high early strength allows for ease of handling and use of manufactured products. Further, due to the achievement of high early strength, the material and structures can be opened to traffic and allowed to support non-structural and structural loads at an early age. It will be understood by those skilled in the art that curing reactions continue for extended periods after the final setting time has been reached.
The geopolymer cementitious compositions of some embodiments of the invention are capable of developing extremely high early age and ultimate compressive strength. For example, the geopolymer cementitious compositions of some embodiments of the invention are capable of developing compressive strength after 1 to 4 hours of about 500 psi to about 4000 psi, about 1500 to about 5000 psi after 24 hours, and about 3,500 to about 10000 psi after 28 days.
The type of calcium sulfate has also been surprisingly found to have a very significant influence on the development of early age compressive strength (≦24 hour) of the geopolymer cementitious compositions of some embodiments of the invention. The highest increase in early age compressive strength results when anhydrous calcium sulfate (anhydrite) is used, followed by calcium sulfate hemihydrate, and that followed by calcium sulfate dihydrate.
In some embodiments, it has been found that a smaller particle size of calcium sulfate leads to a more rapid development in early age (≦24 hour) strength. When it is desirable to have an extremely rapid rate of strength 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 still more preferably about 1 to about 10 microns.
Cementitious Reactive Mixture
The cementitious reactive mixture of some embodiments of the present invention comprise Reactive Powder Component A (also known herein as Cementitious Reactive Material) and Activator Component B with preferable ranges as shown in TABLE A. The Reactive Powder Component A comprises thermally activated aluminosilicate mineral, calcium aluminate cement, and calcium sulfate. The Activator Component B comprises alkali metal chemical activator.
Preferably, the cementitious reactive mixture contains about 10 to about 40 wt. % lime. However, this lime is does not have to be added lime. Rather it is sometimes included as a chemical component of the thermally activated aluminosilicate mineral.
In addition to the thermally activated aluminosilicate mineral, calcium aluminate cement, and calcium sulfate, the cementitious reactive powder may include about 0 to about 15 wt. % of optional cementitious additives such as Portland cement. However, preferably there is an absence of Portland cement as its incorporation increases the material shrinkage making the material less dimensionally stable.
Class C Fly Ash and Other Thermally Activated Aluminosilicate Mineral
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, marl red mud, ground rock, and ground clay bricks. Preferably, they have Al2O3 content greater than about 5% by weight. Preferably clay or marl is used after thermal activation by heat treatment at temperatures of from about 600° to about 850° C. The preferred thermally activated aluminosilicate minerals of some embodiments of the invention have high lime (CaO) content in the composition, preferably greater than about 10 wt %, more preferably greater than about 15%, and still more preferably greater than about 20%. The most preferred thermally activated alumino-silicate mineral is Class C fly ash, for example, fly ash procured from coal-fired power plants. The fly ash also possesses pozzolanic properties.
ASTM C618 (2008) defines pozzolanic materials as “siliceous or siliceous and aluminous materials which in themselves possess little or no cementitious value, but will, in finely divided form and in the presence of moisture, chemically react with calcium hydroxide at ordinary temperatures to form compounds possessing cementitious properties.”
Fly ash is the preferred thermally activated alumino-silicate mineral in the cementitious reactive powder blend of some embodiments of the invention. Fly ashes containing high calcium oxide and calcium aluminate content (such as Class C fly ashes of ASTM C618 (2008) standard are preferred as explained below.
Fly ash is a fine powder byproduct formed from the combustion of coal. Electric power plant utility boilers burning pulverized coal produce most commercially available fly ashes. These fly ashes consist mainly of glassy spherical 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 depend upon the structure and composition of the coal and the combustion processes by which fly ash is formed. ASTM C618 (2008) standard recognizes two major classes of fly ashes for use in concrete—Class C and Class F. These two classes of fly ashes are generally derived from different kinds of coals that are a result of differences in the coal formation processes occurring over geological time periods. Class F fly ash is normally produced from burning anthracite or bituminous coal, whereas Class C fly ash is normally produced from lignite or sub-bituminous coal.
The ASTM C618 (2008) standard differentiates Class F and Class C fly ashes primarily according to their pozzolanic properties. Accordingly, in the ASTM C618 (2008) standard, the major specification difference between the Class F fly ash and Class C fly ash is the minimum limit of SiO2+Al2O3+Fe2O3 in the composition. The minimum limit of SiO2+Al2O3+Fe2O3 for Class F fly ash is 70% and for Class C fly ash is 50%. Thus, Class F fly ashes are more pozzolanic than the Class C fly ashes. Although not explicitly recognized in the ASTM C618 (2008) standard, Class C fly ashes preferably have high calcium oxide (lime) content.
Class C fly ash usually has cementitious properties in addition to pozzolanic properties due to free lime (calcium oxide). Class F is rarely cementitious when mixed with water alone. Presence of high calcium oxide content makes Class C fly ashes possess cementitious properties leading to the formation of calcium silicate and calcium aluminate hydrates when mixed with water. As will be seen in the examples below, Class C fly ash has been found to provide superior results.
The thermally activated aluminosilicate mineral comprises Class C fly ash, preferably, about 50 to about 100 parts Class C fly ash per 100 parts thermally activated aluminosilicate mineral, more preferably the thermally activated aluminosilicate mineral comprises about 75 parts to about 100 parts Class C fly ash per 100 parts thermally activated aluminosilicate mineral.
Other types of fly ash, such as Class F fly ash, may also be employed. Preferably, at least about 50 wt. % of the thermally activated aluminosilicate mineral in the cementitious reactive powder is Class C fly ash with the remainder Class F fly ash or any other thermally activated aluminosilicate mineral. More preferably, about 55 to about 75 wt. % of the thermally activated aluminosilicate mineral in the cementitious reactive powder is Class C fly ash with the remainder Class F or any other thermally activated aluminosilicate mineral. Preferably the thermally activated aluminosilicate mineral is about 90 to about 100% Class C fly ash, for example 100% Class C Fly ash.
The average particle size of the thermally activated alumino-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 still more preferably less that about 15 microns.
Preferably the mixture composition of some embodiments of the invention has at most about 5 parts metakaolin per 100 parts thermally activated aluminosilicate mineral. Preferably, the compositions of some embodiments of the invention has an absence of metakaolin. Presence of metakaolin has been found to increase the water demand of the mixtures hence its use is not desirable in the geopolymer compositions of some embodiments of the invention.
Minerals often found in fly ash are quartz (SiO2), mullite (Al2Si2O13), gehlenite (Ca2Al2SiO7), haematite (Fe2O3), magnetite (Fe3O4), among others. In addition, aluminum silicate polymorphs minerals commonly found in rocks such as sillimanite, kyanite and andalusite all three represented by molecular formula of Al2SiO5 are also often found in fly ash.
Fly ash can also include calcium sulfate or another source of sulfate ions which will be in the mixture composition of some embodiments of the invention.
The fineness of the fly ash is preferably such that less than about 34% is retained on a 325 mesh sieve (U.S. Series) as tested on 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 still more preferably less than about 15 microns. This fly ash is preferably recovered and used dry because of its self-setting nature.
Class C fly ash made from sub-bituminous coal has the following representative composition listed in TABLE E. This fly ash is preferably recovered and used dry because of its self-setting nature.







TABLE E







An example of suitable Class C fly ash











Proportion



Component
(wt. %)







SiO2
20-45



Al2O2
10-30



Fe2O3
 3-15



MgO
0.5-8 



SO3
0.5-5 



CaO
15-60



K2O
0.1-4 



Na2O
0.5-6 



Loss on Ignition
0-5










A preferable suitable Class F fly ash has the following composition listed in TABLE F.







TABLE F







An example of suitable Class F fly ash











Proportion



Component
(wt. %)







SiO2
50-70



Al2O2
10-40



Fe2O3
 1-10



MgO
0.5-3 



SO3
0-4



CaO
 0-10



K2O
0.1-4 



Na2O
0.1-6 



Loss on Ignition
0-5










Hydraulic Cements
Hydraulic cements for purposes of this invention is a cement that undergoes a chemical setting reaction when it comes in contact with water (hydration) and which will not only set (cure) under water but also forms a water-resistant product.
Hydraulic cements include, but are not limited to, aluminum silicate cements like Portland cement, calcium aluminate cement, calcium sulfoaluminate cement, and calcium fluoroaluminate cements.
Calcium Aluminate Cement
Calcium aluminate cement (CAC) is a hydraulic cement that forms a component of the reactive powder blend of embodiments of the invention.
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 wt % is preferably. Higher purity calcium aluminate cements are also commercially available in which the alumina content can range as high as about 80 wt %. These higher purity calcium aluminate cements tend to be relatively more expensive. The calcium aluminate cements used in the compositions of some embodiments of the invention are finely ground to facilitate entry of the aluminates into the aqueous phase so that rapid formation of ettringite and other calcium aluminate hydrates can take place. The surface area of the calcium aluminate cement that may is useful in some embodiments of the composition of the invention is greater than about 3,000 cm2/gram and preferably about 4,000 to 6,000 cm2/gram as measured by the Blaine surface area method (ASTM C 204).
Several manufacturing methods have emerged to produce calcium aluminate cement worldwide. Typically, the main raw materials used in the manufacturing of calcium aluminate cement are bauxite and limestone. One manufacturing method that has been used in the US for producing calcium aluminate cement is described as follows. The bauxite ore is first crushed and dried, then ground along with limestone. The dry powder comprising of bauxite and limestone is then fed into a rotary kiln. A pulverized low-ash coal is used as fuel in the kiln. Reaction between bauxite and limestone takes place in the kiln and the molten product collects in the lower end of the kiln and pours into a trough set at the bottom. The molten clinker is quenched with water to form granulates of the clinker, which is then conveyed to a stock-pile. This granulate is then ground to the desired fineness to produce the final cement.
Several calcium aluminate compounds are formed during the manufacturing process of calcium aluminate cements. The predominant compound formed is monocalcium aluminate (CaO.Al2O3, also referred to as CA), in one type of calcium aluminate cement. In another type of calcium aluminate cement, 12CaO.7Al2O3 also referred to as C12A7 or dodeca calcium hepta aluminate is formed as the primary calcium aluminate reactive phase. The other calcium aluminate and calcium silicate compounds that are formed in the production of calcium aluminate cements include CaO.2Al2O3 also referred as CA2 or calcium dialuminate, dicalcium silicate (2CaO.SiO2, called C2S), dicalcium alumina silicate (2CaO.Al2O3.SiO2, called C2AS). Several other compounds containing relatively high proportion of iron oxides are also formed. These include calcium ferrites such as CaO.Fe2O3 or CF and 2CaO.Fe2O3 or C2F, and calcium alumino-ferrites such as tetracalcium aluminoferrite (4CaO.Al2O3.Fe2O3 or C4AF), 6CaO.Al2O3.2Fe2O3 or C6AF2) and 6CaO.2Al2O3.Fe2O3 or C6A2F). Other minor constituents present in the calcium aluminate cement include magnesia (MgO), titanic (TiO2), sulfates and alkalis. The preferred calcium aluminate cements useful of some embodiments of the invention can have one or more of the aforementioned phases. Calcium aluminate cements having monocalcium aluminate (CaO.Al2O3 or CA) and/or dodeca calcium hepta aluminate (12CaO.7Al2O3 or C12A7) as predominant phases are particularly preferred of some embodiments of the present invention. Further, the calcium aluminate phases can be available in crystalline form and/or amorphous form. Ciment Fondu (or HAC Fondu), Secar 51, and Secar 71 are some examples of commercially available calcium aluminate cements that have the monocalcium aluminate (CA) as the primary cement phase. Ternal EV is an example of commercially available calcium aluminate cement that has the dodeca calcium hepta aluminate (12CaO.7Al2O3 or C12A7) as the predominant cement phase.
Preferably 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 still more preferably about 10-50 parts by weight calcium aluminate cement per 100 pbw of thermally activated aluminosilicate mineral.
Calcium Sulfoaluminate (CSA) Cements
Calcium sulfoaluminate (CSA) cements may be optionally used of some embodiments of the present invention. CSA cements are a different class of cements from calcium aluminate cement (CAC) or calcium silicate based hydraulic cements, for example, Portland cement. CSA cements are hydraulic cements based on calcium sulphoaluminate, rather than calcium aluminates which are the basis of CAC cement or calcium silicates which are the basis of Portland cement. Calcium sulfoaluminate cements are made from clinkers that include Ye'elimite (Ca4(AlO2)6SO4 or C4A3{hacek over (S)}) as a primary phase. Other major phases present in the sulfo may include one or more of the following: dicalcium silicate (C2S), tetracalcium aluminoferrite (C4AF), and calcium sulfate (C{hacek over (S)}). The relatively low lime requirement of calcium sulfoaluminate cements compared to Portland cement reduces energy consumption and emission of green house gases from cement production. In fact, calcium sulfoaluminate cements can be manufactured at temperatures approximately 200° C. lower than Portland cement, thus further reducing energy and green house gas emissions. The amount of Ye'elimite phase (Ca4(AlO2)6SO4 or C4A3{hacek over (S)}) present in the calcium sulfoaluminate cements useful in some embodiments of this invention is preferably about 20 to about 90 wt % and more preferably 30 to 75 wt %. When calcium sulfoaluminate (CSA) cements are used in the present invention, they may partially substitute calcium aluminate cement. The amount of calcium sulfoaluminate cement substitution in the composition of some embodiments of the invention can be up to about 49 wt % of the aggregated weight of calcium aluminate cement and calcium sulfoaluminate cement.
Portland Cement
The compositions of some embodiments of the invention may have about 0 to about 15 parts by weight total Portland cement relative to 100 parts by weight fly ash.
The low cost and widespread availability of the limestone, shales, and other naturally occurring materials make Portland cement one of the lowest-cost materials widely used over the last century throughout the world. 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 reacting with water but also forms a water-resistant product) produced by pulverizing clinkers consisting essentially of hydraulic calcium silicates, usually containing one or more of the forms of calcium sulfate as an inter ground addition.” As used herein, “clinkers” are nodules (diameters, about 0.2-about 1.0 inch [5-25 mm]) of a sintered material that are produced when a raw mixture of predetermined composition is heated to high temperature.
However, very surprisingly, it has been discovered that addition of Portland cement to the dimensionally stable compositions of the present invention comprising aluminosilicate mineral, alkali metal chemical activator, calcium aluminate cement and calcium sulfate has a negative influence on the shrinkage behavior of resulting compositions. It has been found that addition of Portland cement to the geopolymer compositions of the present invention increases the shrinkage of the resulting compositions. The magnitude of observed shrinkage increases with increase in the amount of Portland cement in the resulting compositions.
This result is highly unexpected and surprising and it underscores the extremely complex nature of chemical interactions that occur when other types of cements and/or chemical additives are introduced to the dimensionally stable geopolymer binder compositions of the present invention. Based on this understanding, no Portland cement is incorporated in some preferred embodiments of the invention. However, it is contemplated that some amount of Portland cement be used in some embodiments when desired in situations where some increase in shrinkage behavior may be acceptable. The practical limit of amount of Portland cement will depend on the amount of adverse effect on shrinkage behavior that may be acceptable, but in some preferred embodiments of the invention, no more than 15 parts by weight of Portland cement per 100 parts by weight of the thermally activated aluminosilicate mineral is included.
Calcium Fluoroaluminate
Calcium Fluoroaluminate has the chemical formula 3CaO.3Al2O3.CaF2. The calcium Fluoroaluminate is often produced by mixing lime, bauxite and fluorspar in such an amount that the mineral of the resulting product becomes 3CaO.3Al2O3.CaF2 and burning the resulting mixture at a temperature of about 1,200°-1,400° C. Calcium fluoroaluminate cements may optionally be used in the present invention.
Calcium Sulfate
Calcium sulfate forms an ingredient of the geopolymer compositions of some embodiments of the invention. Although calcium sulfate e.g. calcium sulfate dihydrate will react with water, it does not form a water resistant product and it is not considered to be hydraulic cement for purposes of this invention. Calcium sulfate types that are useful of some embodiments of the invention include calcium sulfate dihydrate, calcium sulfate hemihydrate and anhydrous calcium sulfate (anhydrite). These calcium sulfates may be available naturally or produced industrially. Calcium sulfates synergistically interact with the other fundamental components of the cementitious compositions of some embodiments of the invention and thereby help to minimize material shrinkage while imparting other useful properties to the final material.
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 its chemical composition, particle size, crystal morphology, and chemical and thermal treatment. Amongst other properties, the setting behavior, rate of strength development, ultimate compressive strength, shrinkage behavior, and cracking resistance of the geopolymer compositions of some embodiments of the invention can be tailored by selecting a proper source of calcium sulfate in the formulation. Thus, the selection of the type of calcium sulfate used of some embodiments of the invention is based on the balance of properties sought in the end application.
In the geopolymer compositions of some embodiments of the invention, a blend of two or more types of calcium sulfate is employed. When such a blend is used, the types of calcium sulfate utilized can vary depending upon their chemical composition, particle size, crystal shape and morphology, and/or surface treatment.
Particle size and morphology of calcium sulfate have been found to significantly influence the development of early age and ultimate strengths 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 a more rapid development in early age strength. When it is desirable to have an extremely rapid rate of strength 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 still more preferably about 1 to about 20 microns. Furthermore, calcium sulfates with finer particle size have also been found to result in lower material shrinkage of some embodiments.
It has further been found that for a given amount of calcium aluminate cement and other raw material components present, an increase (but not excessive increase) in the amount of calcium sulfate leads to increase in the early age compressive strength of the geopolymer compositions of some embodiments of the invention. The most dramatic increase in the early age compressive strength results when the calcium sulfate amount is about 10 to about 50% by weight of calcium aluminate cement.
All three forms of calcium sulfate (primarily hemihydrate, dihydrate and anhydrite) are useful in the four-reactive-component mixtures of some embodiments of the invention to afford the benefits of longer setting times and higher compressive strengths than Comparative Examples 1-4 below. The three different calcium sulfate forms have been found to have different and surprising effects relative to each other on setting times and compressive strengths in various embodiments of the invention.
It is well known that the most soluble form of calcium sulfate is the hemihydrate, followed by the relatively lower solubility form of the dihydrate, and then followed by the relatively insoluble form of the anhydrite. All three forms are themselves known to set (form matrices of the dihydrate chemical form) in aqueous media under appropriate conditions, and the setting times and compressive strengths of the set forms are known to follow their order of solubility. For example, all other things being equal, employed alone as the sole setting material, the hemihydrate usually has the shortest set times and the anhydrite the longest set times (typically very long set times).
Quite surprisingly, it has been found that embodiments employing predominately or all calcium sulfate hemihydrate have the longest set times, while those employing predominately or all calcium sulfate anhydrite have the shortest set times. Similarly surprisingly, in various embodiments, it has been found that those employing predominately or all calcium sulfate anhydrite have greater early compressive strengths than those employing the primarily dihydrate form. The embodiments using primarily the hemihydrate form have early compressive strength similar to those using primarily the anhydrite form.
In the geopolymer compositions of other embodiments, a blend of two or more types of calcium sulfate also may be employed to modify the set times and early compressive strength properties of the composition relative to those embodiments using predominately or all of a single type of calcium sulfate. When such a blend is used, the types of calcium sulfate utilized may vary depending upon their chemical composition, particle size, crystal shape and morphology, and/or surface treatment.
Particle size and morphology of calcium sulfate used have been found to significantly influence the development of early age and ultimate strengths of the geopolymer cementitious binder compositions of some embodiments of the invention. In general, a smaller particle size of calcium sulfate has been found to provide a more rapid development in early age strength. When it is desirable to have an extremely rapid rate of strength 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 from about 1 to about 20 microns. Furthermore, calcium sulfates with finer particle size have also been found to reduce material shrinkage.
It has further been found that for a given amount of calcium aluminate cement and other raw material components present, an increase (but not excessive increase) in the amount of calcium sulfate leads to increase in the early age compressive strength of the geopolymer binders of some embodiments of the present invention. The most dramatic increase in the early age compressive strength results when the calcium sulfate amount is about 10 to about 50% by weight of calcium aluminate cement.
It has also been unexpectedly found the amount of calcium sulfate present in proportion to calcium aluminate cement in the mixture has a significant influence on the degree of material shrinkage of geopolymer compositions of some embodiments of the invention. Preferably, those embodiments have a calcium sulfate amount of about 5 to about 200 parts by weight relative to 100 parts by weight of calcium aluminate cement. For most effective control on material shrinkage of the 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 of calcium aluminate cement, more preferably about 15 to about 75 parts by weight relative to 100 parts by weight of calcium aluminate cement, and most preferably about 20 to about 50 parts by weight relative to 100 parts by weight of calcium aluminate cement.
For given amounts of alkali metal activator and other raw material components in the composition of some embodiments of the invention, usage of calcium sulfate dihydrate has been found to provide the most effective control in minimizing the material shrinkage. Usage of anhydrous calcium sulfate (anhydrite) and calcium sulfate hemihydrate also provide excellent control in lowering the material shrinkage of the geopolymer cementitious binder compositions of such embodiments.
The selection of the type or types of calcium sulfate employed in the compositions of such embodiments is based on the desired rate of early age strength development, shrinkage control, and balance of other properties sought in the end application.
The type of calcium sulfate has also been found to have a very significant influence on the development of early age compressive strength 24 hour) of the geopolymer compositions of some embodiments of the invention. The highest increase in early age compressive strength results when anhydrous calcium sulfate (anhydrite) is used, followed by calcium sulfate hemihydrate, followed by calcium sulfate dihydrate. The selection of the type of calcium sulfate used of some composition of some embodiments of the invention is based on the desired rate of early age strength development, shrinkage control, and balance of other properties sought in the end application.
A part or the entire amount of calcium sulfate may be added as an additive component of the calcium aluminate cement in the compositions of some embodiments of the invention. When this is the case, the amount of calcium sulfate added separately in the composition is reduced by an equivalent amount included in the calcium aluminate cement.
Calcium sulfate may also be included in the fly ash in some embodiments of the composition. When such is the case, the amount of calcium sulfate added separately in the composition may be reduced. The amount of calcium sulfate added separately to the compositions of some embodiments of the invention may be adjusted based on the availability of the sulfate ions contributed by other ingredients present in the mixture. For enhanced durability of the geopolymer compositions of some embodiments of the invention, it is desirable to keep the calcium sulfate content at relatively low levels. Excess calcium sulfate or other sulfate ions in the mixture can lead to chemical distress due to material expansion caused by precipitation and hydration of the salts present in the material.
Pozzolans
Other optional silicate and aluminosilicate minerals which are pozzolans possessing substantial, little, or no cementing properties on their own in an aqueous media can be included as optional mineral additives in the compositions of some embodiments of the invention. Various natural and man-made materials have been referred to as pozzolanic materials possessing pozzolanic properties. Some examples of pozzolanic materials include silica fume, pumice, perlite, diatomaceous earth, finely ground clay, finely ground shale, finely ground slate, finely ground glass, volcanic tuff, trass, and rice husk. All of these pozzolanic materials can be used either singly or in combined form as part of the cementitious reactive powder of some embodiments of the invention.
Fillers-Aggregates, Inorganic Mineral Fillers and Lightweight Fillers
While the disclosed cementitious reactive powder blend defines the rapid 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.
One or more fillers such as sand, fine aggregate, coarse aggregate, inorganic mineral fillers, lightweight fillers may be used as a component in the geopolymeric formulations of some embodiments of the invention. These fillers are preferably not pozzolans or thermally activated aluminosilicate minerals.
Preferably inorganic mineral fillers are dolomite, limestone, calcium carbonate, ground clay, shale, slate, mica and talc. Generally they have a fine particle size with preferably 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 of some embodiments of the invention. Smectite clays and palygorskite and their mixtures are not considered inorganic mineral fillers in this invention.
Fine aggregate or sand is defined as an inorganic rock material with an average particle size of less than about 4.75 mm (0.195 inches).
Preferable sand in the invention has a mean particle size of 0.1 mm to about 2 mm. Fine sand with a mean particle size of about 1 mm or less is preferred filler in some embodiments of this invention. Sand having a maximum particle diameter of about 0.6 mm, preferably at most about 0.425 mm, a mean 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 preferable fine sand include QUIKRETE FINE No. 1961 and UNIMIN 5030 having a predominant size range of US sieve number #70-#30 (0.2-0.6 mm).
The particle size distribution and amount of sand in the formulation assists in controlling the rheological behavior of the cementitious compositions of some embodiments of the invention. Fine sand may be added in the geopolymeric cementitious compositions of some embodiments of the invention at sand/cementitious materials (reactive powder) ratio of about 0.05 to about 4. When it is desired to achieve self-leveling material rheology, the most desirable sand to cementitious materials ratio in the formulation is about 0.50 to about 2, more preferably about 0.75 to about 1.5.
Coarse aggregate is defined as an inorganic rock material with an average particle size at least 4.75 mm (0.195 inches), for example 1⁄4′′ to 11⁄2 in.′′ (0.64 to 3.81 cm). Aggregate with size larger than 11⁄2′′ (3.81 cm) may also be used in some applications for example concrete pavement. The particle shape and texture of the coarse aggregate used can be angular, rough-textured, elongated, rounded or smooth or a combination of these. Preferably coarse aggregate are made of minerals such as granite, basalt, quartz, riolite, andesite, tuff, pumice, limestone, dolomite, sandstone, marble, chert, flint, greywacke, slate, and/or gnessis.
Coarse aggregate useful in some embodiments of the invention preferably meet the specifications set out in ASTM C33 (2011) and AASHTO M6/M80 (2008) standards.
When coarse aggregate are added in the geopolymeric cementitious compositions of some embodiments of the invention, they are preferably employed at an aggregate to cementitious materials (reactive powder) ratio of about 0.25 to about 5. Some embodiments of the invention contain coarse aggregate with coarse aggregate to cementitious materials ratio of about 0.25 to about 1. Some other embodiments of the invention contain coarse aggregate with coarse aggregate to cementitious materials ratio of about 1 to about 3.
Lightweight fillers have a specific gravity of less than about 1.5, preferably less than about 1, more preferably less than about 0.75, and still more preferably less than about 0.5. In some other preferred embodiments of the invention the specific gravity of lightweight fillers is less than about 0.3, more preferably less than about 0.2 and most preferably less than about 0.1. In contrast, inorganic mineral filler preferably has a specific gravity above about 2.0. Examples of useful lightweight fillers include pumice, vermiculite, expanded forms of clay, shale, slate and perlite, scoria, expanded slag, cinders, glass microspheres, synthetic ceramic microspheres, hollow ceramic microspheres, lightweight polystyrene beads, plastic hollow microspheres, expanded plastic beads, and the like. Expanded plastic beads and hollow plastic spheres when used in the composition of some embodiments of the invention are employed in very small quantity on a weight basis owing to their extremely low specific gravity.
When lightweight fillers are utilized to reduce the weight of the material, they may be employed at a filler to cementitious materials (reactive powder) ratio of about 0.01 to about 2, preferably about 0.01 to about 1. A combination of two or more types of lightweight fillers useful in the geopolymer compositions of some embodiments of the invention.
While some embodiments of some embodiments of the invention contain only sand as the added filler, other embodiments can contain sand and inorganic mineral fillers and/or lightweight filler. Other embodiments can contain inorganic mineral filler and lightweight fillers as the 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 lightweight fillers and no sand, fine aggregate or coarse aggregate. Some embodiments of the invention containing coarse aggregate can include or exclude one of more of the following fillers—sand, lightweight filler, and inorganic mineral filler.
Some embodiments of the present invention are completely free of any added fillers.
Alkali Metal Chemical Activators
In some embodiments of the invention, alkali metal salts and bases are useful as chemical activators to activate the Reactive Powder Component A comprising thermally activated aluminosilicate mineral such as fly ash, calcium aluminate cement, and calcium sulfate. The alkali metal activators some embodiments of this invention can be added in liquid or solid form. The preferred alkali metal chemical activators of some embodiments of this invention are metal salts of organic acids. The more preferred alkali metal chemical activators of some embodiments of this invention are alkali metal salts of carboxylic acids. Alkali metal hydroxides and alkali metal silicates are some other examples of alkali metal chemical activator of some embodiments of this 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 reactive powder blend comprising thermally activated aluminosilicate mineral, calcium aluminate cement, and calcium sulfate.
In some embodiments of the present invention, employing alkali metal salts of citric acid such as sodium or potassium citrate in combination with the reactive powder blend comprising thermally activated aluminosilicate mineral comprising Class C fly ash, calcium aluminate cement, and calcium sulfate, provides mixture compositions with relatively good fluidity and which do not stiffen too quickly, after mixing the raw materials at or around ambient temperatures (about 20-25° C.).
The amount of alkali metal salt of citric acid, e.g. potassium citrate or sodium citrates, is about 0.5 to about 10 wt. %, 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 still more preferably about 2 wt % based on 100 parts of the cementitious reactive components (i.e., Reactive Powder Component A) of some embodiments of the invention. Thus, for example, for 100 pounds of cementitious reactive powder, there may be about 1.25 to about 4 total pounds of potassium and/or sodium citrates. The preferred alkali metal citrates are potassium citrates and sodium citrates and particularly tri-potassium citrate monohydrate, and tri-sodium citrate anhydrous, tri-sodium citrate monohydrate, sodium citrate dibasic sesquihydrate, tri-sodium citrate dihydrate, di-sodium citrate, and mono-sodium citrate.
Preferably the activator does not contain an alkanolamine. Also, preferably the activator does not contain a phosphate.
Set Retarders
Organic compounds such as hydroxylated carboxylic acids, carbohydrates, sugars, and starches are the preferred retarders of 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 acid, tartronic acid, mucic acid, trihydroxy benzoic acid, etc. are useful as set retarders in the dimensionally stable geopolymer cementitious compositions of some embodiments of the invention. Sodium gluconate is also useful as an organic set retarder in some embodiments of in the present invention. Cellulose based organic polymers such as hydroxyethyl-cellulose (HEC), hydroxypropyl-cellulose (HPC), hydroxypropylmethyl-cellulose (HPMC), ethyl-cellulose (EC), methylethyl-cellulose (MEC), carboxymethyl-cellulose (CMC), carboxymethylethyl-cellulose (CMEC), carboxymethylhydroxyethyl-cellulose (CMHEC) are also useful as retarders 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 mix in addition to causing retardation. Preferably inorganic acid based retarders of the type borates or boric acid are not employed in compositions of the present invention because they have been found to hinder mix rheology, cause excessive efflorescence, and reduce material bond strength to other substrates.
Other Optional Set-Control Agents
Other optional set control chemical additives include a 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, and the like. These additives when included as a part of the formulation may also influence rheology of the geopolymer compositions of some embodiments of the invention in addition to affecting their setting behavior.
Optional Materials, Fibers, and Scrims
Other optional materials and additives may be included in geopolymer compositions of some embodiments of the invention. These include at least one member selected from the group consisting of film-forming redispersible polymer powders, film-forming polymer latex dispersions, defoaming and antifoaming agents, water retaining additives, set control agents, shrinkage reducing admixtures, foaming and air entraining agents, organic and inorganic rheology control agents, viscosity modifying agents (thickeners), efflorescence control (suppression) agents, corrosion control agents, wetting agents, colorants and/or pigments, discrete fibers, long and continuous fibers and reinforcement, textile reinforcement, polyvinyl alcohol fibers, and/or glass fibers and or other discrete reinforcing fibers.
Discrete reinforcing fibers of different types may also be included in the geopolymer compositions of some embodiments of the invention. Scrims made of materials such as polymer-coated glass fibers and polymeric materials such as polypropylene, polyethylene and nylon can be used to reinforce the cement-based precast products depending upon their function and application.
Preferably the geopolymer compositions of embodiments of the invention has an absence of cement kiln dust. Cement kiln dust (CKD) is created in the kiln during the production of cement clinker. The dust is a particulate mixture of partially calcined and unreacted raw feed, clinker dust and ash, enriched with alkali sulfates, halides and other volatiles. These particulates are captured by the exhaust gases and collected in particulate matter control devices such as cyclones, baghouses and electrostatic precipitators. CKD consists primarily of calcium carbonate and silicon dioxide which is similar to the cement kiln raw feed, but the amount of alkalies, chloride and sulfate is usually considerably higher in the dust. CKD from three different types of operations: long-wet, long-dry, and alkali by-pass with precalcined have various chemical and physical traits. CKD generated from long-wet and long-dry kilns is composed of partially calcined kiln feed fines enriched with alkali sulfates and chlorides. The dust collected from the alkali by-pass of precalcined kilns tend to be coarser, more calcined, and also concentrated with alkali volatiles. However, the alkali by-pass process contains the highest amount by weight of calcium oxide and lowest loss on ignition (LOI). TABLE AA from Adaska et al., Beneficial Uses of Cement Kiln Dust, presented at 2008 IEEE/PCA 50th Cement Industry Technical Conf., Miami, Fla., May 19-22, 2008, provides the composition breakdown for the three different types of operation and includes a preferably chemical composition for Type I portland cement for comparison.







TABLE G







Composition of CKD from Different Operation Sources














Alkali by-pass
Preferably Type





from
I



Long-wet
Long-dry
preheater/
Portland



kiln (% by
kiln (% by
precalciner
cement


Constituent
weight)
weight)
(% by weight)
(% by weight)














SiO2
15.02
9.64
15.23
20.5


AL2O3
3.85
3.39
3.07
5.4


Fe2O3
1.88
1.10
2.00
2.6


CaO
41.01
44.91
61.28
63.9


MgO
1.47
1.29
2.13
2.1


SO3
6.27
6.74
8.67
3.0


K2O
2.57
2.40
2.51
<1


Loss on
25.78
30.24
4.48
0-3


Ignition


(LOI)


Free lime
0.85
0.52
27.18
<2


(CaO)









Superplasticizers and Air Entraining Agents
Water reducing agents (superplasticizers), are preferably used in the compositions of some embodiments of the invention. They may be added in the dry form or in the form of a solution. Superplasticizers help to reduce water demand of the mixture. Examples of superplasticizers include polynapthalene sulfonates, polyacrylates, polycarboxylates, polyether polycarboxylates, lignosulfonates, melamine sulfonates, caseins, and the like. Depending upon the type of superplasticizer used, the weight ratio of the superplasticizer (on dry powder basis) to the reactive powder blend preferably will be about 5 wt % or less, preferably about 2 wt. % or less, preferably about 0.1 to about 1 wt. %.
Superplasticizers based on polycarboxylate polyether chemistry are the most preferred water reducing chemical admixture of the geopolymeric cementitious compositions of some embodiments of the invention. Polycarboxylate polyether superplasticizers are the most preferred since they facilitate accomplishment of the various objectives of this invention as mentioned earlier.
Air entraining agents are added to the cementitious slurry of some embodiments of the invention to form air bubbles (foam) in situ. Air entraining agents are preferably surfactants used to purposely trap microscopic air bubbles in the concrete. Alternatively, air entraining agents are employed to externally produce foam which is 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 to externally produce foam the air entraining agent (also known as a liquid foaming agent), air and water are mixed to form foam in a suitable foam generating apparatus. A foam stabilizing agent such as polyvinyl alcohol can be added to the foam before the foam is added to the cementitious slurry.
Examples of air entraining/foaming agents include alkyl sulfonates, alkylbenzolfulfonates and alkyl ether sulfate oligomers among others. Details of the general formula for these foaming agents can be found in U.S. Pat. No. 5,643,510 incorporated herein by reference.
An air entraining agent (foaming agent) such as that conforming to standards as set forth in ASTM C 260 “Standard Specification for Air-Entraining Admixtures for Concrete” (Aug. 1, 2006) can be employed. Such air entraining agents are well known to those skilled in the art and are described in the Kosmatka et al “Design and Control of Concrete Mixtures,” Fourteenth Edition, Portland Cement Association, specifically Chapter 8 entitled, “Air Entrained Concrete,” (cited in US Patent Application Publication No. 2007/0079733 A1). Commercially available air entraining materials include vinsol wood resins, sulfonated hydrocarbons, fatty and resinous acids, aliphatic substituted aryl sulfonates, such as sulfonated lignin salts and numerous other interfacially active materials which normally take the form of anionic or nonionic surface active agents, sodium abietate, saturated or unsaturated fatty acids and salts thereof, tensides, alkyl-aryl-sulfonates, phenol ethoxylates, lignosulfonates, resin soaps, sodium hydroxystearate, lauryl sulfate, ABSs (alkylbenzenesulfonates), LASs (linear alkylbenzenesulfonates), alkanesulfonates, polyoxyethylene alkyl(phenyl)ethers, polyoxyethylene alkyl(phenyl)ether sulfate esters or salts thereof, polyoxyethylene alkyl(phenyl)ether phosphate esters or salts thereof, proteinic materials, alkenylsulfosuccinates, alpha-olefinsulfonates, a sodium salt of alpha olefin sulphonate, or sodium lauryl sulphate or sulphonate and mixtures thereof.
Preferably the air entraining (foaming) agent is about 0.01 to about 1 wt. % of the weight of the overall cementitious composition.
Bio-Polymers and Organic Rheology Control Agents
Succinoglycans, diutan gum, guar gum, wellan gum, xanthan gums and cellulose ether based organic compounds, are bio-polymers that act as hydrocolloids and rheology control agents in some embodiments of the present invention. Synthetic organic polymers such as polyacryl amides, alkali-swellable acrylic polymers, associative acrylic polymers, acrylic/acrylamid copolymers, hydrophobically modified alkali-swellable polymers, highly water-swellable organic polymers can be usefully employed as rheology control agents and thickeners in the geopolymer compositions of some embodiments of the invention.
Both associative and non-associative types of rheology control agents and thickeners can be usefully employed in the geopolymer compositions of some embodiments of the invention.
Examples of cellulose based organic polymers useful for rheology control in the geopolymer compositions of some embodiments of the present invention include hydroxyethyl-cellulose(HEC), hydroxypropyl-cellulose (HPC), hydroxypropylmethyl-cellulose (HPMC), ethyl-cellulose (EC), methylethyl-cellulose (MEC), carboxymethyl-cellulose(CMC), carboxymethylethyl-cellulose (CMEC), and carboxymethylhydroxyethyl-cellulose(CMHEC).
The organic rheology control agents and thickeners mentioned above are soluble both in cold and hot water. These additives also act as water retention agents and thereby minimize material segregation and bleeding in addition to controlling the material rheology.
Inorganic Rheology Control Agents
The geopolymer cementitious compositions of some embodiments of the invention may also include inorganic rheology control agents belonging to the family of phyllosilicates. Examples of inorganic rheology control agents particularly useful in the geopolymer compositions of invention include palygorskite, sepiolite, smectites, kaolinites, and illite. Particularly useful smectite clays in some embodiments of the present invention include hectorite, saponite, and montmorillonite. Different varieties of bentonite clays both natural and chemically treated may also be used to control rheology of the compositions of the present invention. These additives also act as water retention agents and thereby minimize material segregation and bleeding. The inorganic rheology control agents may be added in the absence of or in combination with the organic rheology control agents in some embodiments of the present invention.
Film-Forming Polymer Additives
Preferably film forming redispersible polymer powders in some embodiments of are latex powders. These polymer powders are water-redispersible and produced by spray-drying of aqueous polymer dispersions (latex).
Latex is an emulsion polymer. Latex is a water based polymer dispersion, 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 may be natural or synthetic.
The latex is preferably made from a pure acrylic, a styrene rubber, a styrene butadiene rubber, a styrene acrylic, a vinyl acrylic or an acrylated ethylene vinyl acetate copolymer and is more 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, the monomers preferably employed in emulsion polymerization include such monomers as methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, 2-ethyl hexyl acrylate, other acrylates, methacrylates and their blends, acrylic acid, methacrylic acid, styrene, vinyl toluene, vinyl acetate, vinyl esters of higher carboxylic acids than acetic acid, e.g. vinyl versatate, acrylonitrile, acrylamid, butadiene, ethylene, vinyl chloride and the like, and mixtures thereof. For example, a latex polymer can be a butyl acrylate/methyl methacrylate copolymer or a 2-ethylhexyl acrylate/methyl methacrylate copolymer. Preferably, the latex polymer is further derived from one or more monomers selected from the group consisting of styrene, alpha-methyl styrene, vinyl chloride, acrylonitrile, methacrylonitrile, ureido methacrylate, vinyl acetate, vinyl esters of branched tertiary monocarboxylic acids, itaconic acid, crotonic acid, maleic acid, fumaric acid, ethylene, and C4-C8 conjugated dienes.
Efflorescence Suppression Agent
Water repelling agents such as silanes, silicones, siloxanes, stearates are added to the cementitious compositions of some embodiments of the invention to reduce efflorescence potential of the material. Selected examples of useful efflorescence suppression agents include octyltriethoxy silane, potassium methyl siliconate, calcium stearate, butyl stearate, polymer stearates. These efflorescence control agents reduce the transport of the water within the hardened material and thereby minimize migration of salts and other soluble chemicals that can potentially cause efflorescence. Excessive efflorescence can lead to poor aesthetics, material disruption and damage from expansive reactions occurring due to salt accumulation and salt hydration, and reduction in bond strength with other substrates and surface coatings.
Defoaming Agents
Defoaming agents can be added to the geopolymer cementitious compositions of some embodiments of the invention to reduce the amount of entrapped air, increase material strength, increase material bond strength to other substrates, and to produce a defect free surface in applications where surface aesthetics is an important criteria. Examples of suitable defoaming agents useful in the geopolymer compositions of some embodiments of the invention include polyethylene oxides, polyetheramine, polyethylene glycol, polypropylene glycol, alkoxylates, polyalkoxylate, fatty alcohol alkoxylates, hydrophobic esters, tributyl phosphate, alkyl polyacrylates, silanes, silicones, polysiloxanes, polyether siloxanes, acetylenic diols, tetramethyl decynediol, secondary alcohol ethoxylates, silicone oil, hydrophobic silica, oils (mineral oil, vegetable oil, white oil), waxes (paraffin waxes, ester waxes, fatty alcohol waxes), amides, fatty acids, polyether derivatives of fatty acids, etc.
Initial Slurry Temperature
In some embodiments of the present invention, forming the slurry under conditions which provide a reduced initial mixture slurry temperature and rise of less than about 50° F. (28° C.) to a final compositions mixture slurry temperature, more preferably a rise of less than about 40° F. (22° C.) and more preferably a rise of less than about 30° F. (17° C.) for improved temperature stability and more importantly, slower gelation and final setting times of from about 10 to about 240 minutes, more preferably about 60 to about 120 minutes and more preferably about 30 to about 90 minutes, allows for more controlled working time for commercial use of the compositions of some embodiments of the invention. The initial slurry temperature is preferably about room temperature.
Increasing the initial temperature of the slurry increases the rate of temperature rise as the reactions proceed and reduces the setting time. Thus, initial slurry temperature of 95° F. (35° C.) to 105° F. (41.1° C.) used in preparing conventional fly ash based geopolymeric compositions for rapid gelation and setting times is preferably avoided since the composition formulation is designed to reduce temperature increase behavior of the mixed composition from the initial slurry temperatures. The benefit of the thermal stability obtained with some embodiments of the present invention for increasing the time for initial gelation and final setting times which, in turn, provides for increased commercially workability may be somewhat lessened if the initial slurry temperature is already relatively high.
The initial temperature is defined as the temperature of the overall mixture during the first minute after the cementitious reactive powder, activator, and water are first all present in the mixture. Of course the temperature of the overall mixture can vary during this first minute but in order to achieve preferred thermal stability it will preferably remain within an range initial temperature range of about 0 to about 50° C., preferably an initial temperature of about 10 to about 35° C., more preferably an initial temperature of about 15 to about 25° C., preferably ambient temperature.
Material Exothermic and Temperature Riser Behavior
Compositions of the present invention advantageously achieve moderate heat evolution and low temperature rise within the material during the curing stage. In such compositions of some embodiments of the invention, the maximum temperature rise occurring in the material is preferably less than about 50° F. (28° C.), more preferably less than about 40° F. (22° C.), and most preferably less than about 30° F. (17° C.). This prevents excessive thermal expansion and consequent cracking and disruption of material. This aspect becomes even more beneficial when the material is utilized in a manner where large thicknesses of material pours are involved in actual field applications. The geopolymer cementitious compositions of the present invention are beneficial in this particular aspect as they exhibit lower thermal expansion and enhanced resistance to thermal cracking in actual field applications.
EXAMPLES
In all the examples, unless otherwise indicated, calcium aluminate cement, knows as Ciment Fondu (also termed here as HAC Fondu), available from Kerneos Inc. was employed as a component of cementitious reactive powder. The oxide composition of calcium aluminate cement (Ciment Fondu) employed was as shown in TABLE AA:









TABLE AA






Weight % in Calcium
Weight % in Class C


Oxide
Aluminate Cement
Fly Ash

















CaO
35.63
24.14


SiO2
4.35
36.90


Al2O3
37.71
20.12


Fe2O3
16.52
5.96


SO3
0.06
1.19


MgO
1.16
5.44


Na2O
0.05
1.73


K2O
0.06
0.52


TiO2
1.76
1.42


MnO
0.54


P2O5
0.47
1.18


Loss on Ignition
1.67
0.52









The main calcium aluminate phase present in the Ciment Fondu (HAC Fondu) in the examples was monocalcium aluminate (CA).
In all of the examples, unless otherwise indicated, the fly ash was Class C Fly Ash from Campbell Power Plant, West Olive, Mich. This fly ash had an average particle size of about 4 microns. The measured Blaine fineness of the fly ash was about 4300 cm2/g. The oxide composition of the Class C fly ash used in these examples was as shown in TABLE AA.
The calcium sulfate used in some embodiments of the invention and in the examples has an average particle size of about 1-200 micros (micrometers) and preferably about 1-20 micros when fine-grained calcium sulfate is used.
In particular, the calcium sulfate dihydrate employed in the examples was a fine-grained calcium sulfate dihydrate, termed here as landplaster, available from United States Gypsum Company. The landplaster is a fine-grained calcium sulfate dihydrate with an average particle size of about 15 microns.
The anhydrous calcium sulfate (anhydrite) included in some of the examples was SNOW WHITE brand filler available from United States Gypsum Company. The USG SNOW WHITE filler is an insoluble form of anhydrite produced by high temperature thermal treatment of calcium sulfate, preferably gypsum. It has a very low level of chemically combined moisture, preferably around 0.35%. The average particle size of the USG SNOW WHITE filler is about 7 microns.
The calcium sulfate hemihydrate used in a number of the examples the examples was USG HYDROCAL C-Base brand calcium sulfate hemihydrate available from United States Gypsum Company. HYDROCAL C-Base is an alpha morphological form of calcium sulfate hemihydrate having blocky crystal microstructure and lower water demand. The USG HYDROCAL C-Base has an average particle size of about 17 microns.
Coarse-grained calcium sulfate dihydrate, otherwise identified here as coarse landplaster, employed in a number of the examples was procured from the USG Detroit Plant and is available from United States Gypsum Company as USG BEN FRANKLIN AG brand Coarse Gypsum. The USG BEN FRANKLIN AG brand gypsum is a coarse grained calcium sulfate dihydrate with an average particle size of about 75-80 microns.
The QUIKRETE Fine-grained No. 1961 Fine Sand and UNIMIN 5030 Sand used in some embodiments of the present invention and in some examples had a particle size as shown in TABLE BB:









TABLE BB






QUIKRETE Fine-grained No. 1961
UNIMIN 5030 Sand


Sieve Size
Sand Percent Passing (%)
Percent Passing (%)

















30 Mesh
100



40 Mesh
98
100


50 Mesh
69
73


70 Mesh
23
22


100 Mesh
5
4


140 Mesh
1
0


200 Mesh
0









Potassium citrate or sodium citrate was the alkali citrate added to the cementitious compositions of some embodiments of the invention and acted as a chemical activator, rheology modifier, and set control agent.
The time of initial setting and the time of final setting reported in the following examples were measured using the ASTM C266 (2008) standard using the Gilmore needles.
The slump and flow behavior of the cementitious geopolymer compositions of some embodiments of this invention and some of the examples were characterized by a slump test. The slump test used in the following examples utilizes a hollow cylinder about 5.08 cm. (2 in.) In diameter and about 10.16 cm. (4 in.) in length held vertically with one open end resting on a smooth plastic surface. The cylinder is filled up to the top with the cementitious mixture followed by striking off the top surface to remove the excess slurry mixture. The cylinder is then gently lifted up vertically to allow the slurry to come out from the bottom and spread on the plastic surface to form a circular patty. The diameter of the patty is then measured and recorded as the slump of the material. Compositions with good flow behavior yield a larger slump value. The flow of the slurry is characterized by rating the slurry flowability on a scale of 1 to 10 with a value of 1 representing a very poor flow behavior and a value of 10 representing excellent flow behavior.
Material shrinkage (also referred to herein as “shrinkage”) as used herein is characterized by measuring the length change of prism specimen according to the ASTM C928 (2009) test standard. The initial length measurement is taken 4 hours after the individual raw material components including water are brought together. The final measurement is taken 8 weeks after the components including water were brought together. The difference between the initial and final measurements divided by the initial length times 100% gives the shrinkage as a percentage. The 1 in.×1 in. (cross-section) length change prism specimens also referred to herein as bars, are prepared according to the ASTM C157 (2008) standard.
Compressive strength of the material was measured in accordance to the ASTM C109 (2008) test method by testing the 2 in.×2 in.×2 in. cubes to failure under compression. The cubes demolded from the brass molds after hardening and cured in sealed plastic bags until the age of testing. The cubes were tested at the age of 4-hours, 24-hours, 7-days and 28-days after the cast.
The slurry temperature rise behavior of the material was measured in the semi-adiabatic condition by putting the slurry in an insulated container and recording the material temperature using a thermocouple.
Many of the examples show physical properties of the developed geopolymeric cementitious compositions of some embodiments of the invention comprising thermally activated aluminosilicate mineral (fly ash), calcium aluminate cement, calcium sulfate and alkali metal chemical activators. This studied the influence of incorporating calcium aluminate cement in combination with calcium sulfate and alkali metal chemical activator on the material early age and long-term shrinkage behavior (chemical and drying shrinkage), early age compressive strength, ultimate compressive strength, exothermal behavior and setting characteristics of the developed geopolymeric cementitious compositions of some embodiments of the invention.
Many of the examples show physical properties of the developed geopolymer cementitious compositions of some embodiments of the invention comprising thermally activated aluminosilicate mineral (fly ash), calcium aluminate cement, calcium sulfate and alkali metal chemical activators. This illustrates the influence of incorporating calcium aluminate cement in combination with calcium sulfate and alkali metal chemical activator on the material early age and long-term shrinkage behavior (chemical and drying shrinkage), early age compressive strength, ultimate compressive strength, exothermal behavior and setting characteristics of the developed geopolymer cementitious compositions of some embodiments of the invention.
Compositions of some embodiments of the present invention advantageously achieve moderate heat evolution and low temperature rise within the material during the curing stage. In such compositions, the maximum temperature rise occurring in the material is preferably less than about 50° F. (28° C.), more preferably less than about 40° F. (22° C.) and still more preferably less than about 30° F. (17° C.). This prevents excessive thermal expansion and consequent cracking and disruption of material. This aspect becomes even more beneficial when the material is utilized in a manner where large thicknesses of material pours are involved in the actual field applications. The geopolymer cementitious compositions of the present invention investigated as discussed below are beneficial in this particular aspect as they exhibit lower thermal expansion and enhanced resistance to thermal cracking in actual field applications.
The compositions of some embodiments of the invention also achieved sufficiently long setting times to provide good workability. An extremely short setting time is problematic for some applications as a short material working life (pot life) causes significant difficulties with processing of rapid setting material with the equipment and tools used in actual field application.
Example 1
Comparative Example of Current Geopolymeric Cementitious Compositions
The following examples illustrate the physical properties of current geopolymeric cementitious compositions comprising Class C fly ash and a potassium citrate. The test results show the shrinkage behavior, early age and ultimate compressive strength; and the setting behavior of the cementitious compositions shown in TABLE 1. All three mixes were activated with potassium citrate and contained varying amounts of sand aggregate. All three mixes has 100 parts by weight Fly Ash Class C and 100 parts by weight Total Cementitious Materials. All the cementitious material was Fly Ash Class C Campbell Power Plant, West Olive, Mich. and QUIKRETE Commercial Grade Fine Sand No. 1961.







TABLE 1







Current state-of-the-art geopolymeric


compositions in Comparative Example 1










Raw Material
Mix 1
Mix 2
Mix 3













Fly Ash Class C (grams)
3000
2200
1800


Total Cementitious Materials (grams)
3000
2200
1800


Sand (grams)
2250
3300
4500


Water (grams)
825
605
495


Potassium Citrate (grams)
120
88
72


Borax (grams)
15
11
9


Water/Cementitious Materials Ratio
0.275
0.275
0.275


Sand/Cementitious Materials Ratio
0.750
1.500
2.500


Potassium Citrate/Cementitious
4%
4%
4%


Materials, wt %


Borax Amount/Cementitious
0.5%  
0.5%  
0.5%  


Materials, wt %









FIG. 1A shows the shrinkage behavior of the current state-of-the art geopolymeric cementitious compositions investigated in Comparative Example 1.
The shrinkage measurements were initiated at an age of 4-hours from the time the raw materials were mixed together and cast. It can be observed that the fly ash compositions activated with an alkali citrate demonstrated extremely high amount of shrinkage. The measured maximum shrinkage was found to be as high as 0.75% after 8-weeks of curing at 75° F./50% RH. Increase in sand content decreased the extent of shrinkage but the overall shrinkage still remained very high at unacceptable levels. Such high levels of material shrinkage render the material unsatisfactory for most construction applications. It should be noted that for most construction applications, total magnitude of shrinkage in excess of 0.10% is considered to be extremely high and undesirable.
Initial Flow Behavior, Slump, and Early Age Cracking Behavior of Material
TABLE 2 shows the initial flow behavior and slump of the current state-of-the art geopolymeric cementitious compositions investigated in Comparative Example 1.







TABLE 2







Flow and Slump of Comparative Example 1










Flow
Slump (inches)













Mix 1 (sand/cementitious material = 0.75)
10
9


Mix 2 (sand/cementitious material = 1.5)
8
7.5


Mix 3 (sand/cementitious material = 2.5)
2
2









The fly ash composition activated with an alkali citrate had a good flow behavior at sand/cement ratios of 0.75%. The slurry 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 mix became extremely stiff and had absolutely no flow characteristics.
FIG. 1B shows photograph of slump patty for Mix #1 investigated in Comparative Example 1. The slump patty developed significant cracking upon drying. The initiation of cracks in the patties occurred in less than 30 minutes of the slump test. The number of cracks and the size of cracks grew with subsequent material drying and hardening.
Time of Setting
TABLE 3 shows the setting behavior of the current state-of-the art geopolymeric cementitious compositions investigated in Comparative Example 1.







TABLE 3







Setting Times of Comparative Example 1










Initial Setting Time
Final Setting Time



(hr:min)
(hr:min)















Mix 1
0:15
0:16



Mix 2
0:14
0:15



Mix 3
0:7 
0:10










The cementitious compositions in this Example had extremely rapid setting behavior. All mixes gelled up very quickly and lost flow behavior in less than 5 minutes after the raw materials were blended together to form of an aqueous slurry.
Compressive Strength
TABLE 4 shows the compressive strength behavior of the current state-of-the-art geopolymeric cementitious compositions investigated in Comparative Example 1. All fly ash compositions showed compressive strength development in excess of 7000 psi at 28-days.







TABLE 4







Compressive Strength of Comparative Example 1










8 day (psi)
28 day (psi)













Mix 1 (sand/cementitious material = 0.75)
7215
9259


Mix 2 (sand/cementitious material = 1.5)
6950
8069


Mix 3 (sand/cementitious material = 2.5)
8138
7766









Example 2
Comparative Example
This example investigates early age dimensional stability and cracking resistance of the preferably current state-of-the art geopolymeric formulations comprising of cementitious compositions comprising fly ash and sodium citrate. TABLE 5 shows the raw material composition of the mixture composition investigated. The mixes were activated with potassium citrate and contained varying amounts of sand aggregate. The mixes had 100 parts by weight Fly Ash Class C and 100 parts by weight Total Cementitious Materials. In other words all the cementitious material was Fly Ash Class C.
The composition uses QUIKRETE Commercial Grade Fine Sand No. 1961 and BASF CASTAMENT FS20 superplasticizer.







TABLE 5







Mixture composition of Comparative


Example 2 and Comparative Example 3










Comparative
Comparative


Raw Material
Example 2 Mix
Example 3 Mix












Fly Ash Class C (grams)
3000
3750


Total Cementitious Materials (grams)
3000
3750


Sand (grams)
3150
3938


Sodium Citrate Dihydrate (grams)
60
75


Superplasticizer (grams)
15
18.75


Water (grams)
825
1031


Water/Cementitious Materials Ratio
0.275
0.275


Sand/Cementitious Materials Ratio
1.05
1.05


Sodium Citrate Dihydrate/
2%
2%


Cementitious Materials, wt %


Superplasticizer/Cementitious
0.5%  
0.5%  


Materials, wt %









Early Age Cracking Behavior of Material
FIG. 2 shows a photograph of the slump patty for the mix investigated in Comparative Example 2. The slump patty developed significant cracking upon drying. The initiation of cracks in the patty occurred in less than 30 minutes of the slump test. The number of cracks and the size of cracks grew significantly with subsequent material drying and hardening.
Compressive Strength Behavior of Composition of Comparative Example 2
Table 5A shows the compressive strength behavior of the mix in Comparative Example 2. The early age compressive strengths of the composition were relatively low, being less than about 500 psi at 4 hours and less than about 2000 psi at 24 hours. As will be shown later in the examples, the geopolymer compositions of embodiments of the invention develop significantly higher compressive strength at these same early ages with equivalent water/cement ratios. As shown in the examples of specific embodiments of the present invention the early age compressive strengths of the can easily be tailored by adjusting the type and amount of calcium sulfate, the amount of calcium aluminate cement, and the type and amount of alkali metal activator used in the compositions of embodiments of the invention.







TABLE 5A







Compressive Strength of Example 2 - (psi)












4 hour
24 hour
7 day
28 day

















Mix 1
493
1749
6454
8996










Example 3
Comparative Example
This example investigated early age dimensional stability and cracking resistance of the comparative cementitious compositions comprising fly ash and alkali metal citrate. TABLE 5 shows the raw material composition of the mixture composition investigated.
Early Age Cracking Behavior of Material
FIG. 3A shows a photograph of the slump patty for the mix investigated in the Comparative Example 3. The slump patty developed significant cracking upon drying. The initiation of cracks in the patty occurred in less than about 30 minutes after the slump test.
Compressive Strength Behavior of Composition of Comparative Example 3
Table 5B shows the compressive strength behavior of the mix in Comparative Example 3. The early age compressive strengths of the composition were relatively low being less than about 500 psi at 4 hours and less than about 1500 psi. As shown in later examples of embodiments of the invention, the early age compressive strengths can be tailored by adjusting the type and amount of calcium sulfate, the amount of calcium aluminate cement, and the type and amount of alkali metal activator used in the compositions of the invention.







TABLE 5B







Compressive Strength of Mixture Compositions of


Comparative Example 3 - (psi)












4 hour
24 hour
7 day
28 day

















Mix 1
484
1441
6503
8492










Shrinkage Behavior
FIG. 3B shows the very early age shrinkage behavior of the cementitious composition in Comparative Example 3.
The very early age shrinkage measurements were initiated at an age of 1-hour from the time the raw materials were mixed together and cast. The fly ash composition activated with an alkali metal citrate demonstrated extremely high amount of shrinkage. The measured maximum shrinkage was found to be in excess of about 1% after 8-weeks of curing at about 75° F./50% RH. Such high levels of material shrinkage render the material unsatisfactory for most construction applications. In most construction applications, shrinkage in excess of about 0.10% is considered to be undesirably high.
Example 4
Addition of Pure Calcium Aluminate Cement to Fly Ash—Comparative Example
This example shows physical properties of the cementitious compositions comprising fly ash, calcium aluminate cement and alkali citrate. This studied the influence of incorporation of calcium aluminate cement on shrinkage and cracking resistance of the investigated cementitious compositions comprising fly ash and alkali citrate.
TABLEs 6 and 7 show the raw material compositions of the various cementitious mixtures 1-4 investigated in this Example. Ciment Fondu (HAC Fondu), a calcium aluminate cement, available from Kerneos was utilized as a component of cementitious reactive powder in this investigation. The amount of calcium aluminate cement used in the various mixture compositions investigated in this Example was varied and was equal to 10 wt % and 30 wt % of the weight of fly ash. Potassium citrate was added as a source of alkali citrate in the cementitious compositions investigated in this Example. The calcium sulfate used was USG Landplaster Calcium sulfate dihydrate. QUIKRETE Commercial Grade Fine Sand No. 1961 was used along with AdvaCast 500, WR Grace superplasticizer.







TABLE 6







Cementitious Reactive Powder Compositions in


Parts by Weight for Comparative Example 4 (Mix


1 and Mix 2) and Example 5 (Mix 3 and Mix 4)












Comparative
Comparative
Mix 3
Mix 4



Mix 1 Parts
Mix 2 Parts
Parts
Parts


Raw Material
by wt.
by wt.
by wt
by wt














Fly Ash Class C
100
100
100
100


Calcium Sulfate
0
0
3.3
10


Calcium Aluminate
10
30
10
30


Cement






Total Cementitious
110
130
113
140


Materials
















TABLE 7







Cementitious Reactive Powder Compositions in


Parts by Weight for Comparative Example 4 (Mix


1 and Mix 2) and Example 5 (Mix 3 and Mix 4)












Compar-
Compar-





ative
ative


Raw Material
Mix 1
Mix 2
Mix 3
Mix 4














Fly Ash Class C
2727
2308
2647
2143


(grams)


Calcium Sulfate
0
0
88
214


Dihydrate (grams)


Calcium Aluminate
273
692
265
643


Cement (grams)






Total Cementitious
3000
3000
3000
3000


Materials (grams)


Sand (grams)
2250
2250
2250
2250


Potassium Citrate
120
120
120
120


(grams)


Superplasticizer
30
30
30
30


(grams)


Water (grams)
750
750
750
750


Water/Cementitious
0.25
0.25
0.25
0.25


Materials Ratio


Sand/Cementitious
0.75
0.75
0.75
0.75


Materials Ratio


Superplasticizer/
1%
1%
1%
1%


Cementitious


Materials, wt %


Potassium
4%
4%
4%
4%


Citrate/


Cementitious


Materials, wt %


Calcium Aluminate
10% 
10% 
10% 
30% 


Cement/Fly ash,


wt %


Calcium Sulfate/
0%
0%
33.3%  
33.3%  


Calcium Aluminate


Cement, wt %









Initial Flow Behavior, Slump, and Early Age Cracking Behavior of Material
TABLE 8 shows the initial flow behavior and slump of the binary blends of fly ash and calcium aluminate cement investigated in Example 4. Both mixes investigated had good flow behavior and high patty diameter as observed in the slump test.







TABLE 8







Flow and Slump of compositions investigated in Example


4 (Mix 1 and Mix 2) and Example 5 (Mix 3 and Mix 4)










Flow
Slump (inches)















Mix 1
9
9



Mix 2
9
9



Mix 3
8
8.5



Mix 4
7
7










FIG. 4A shows photographs of slump patties for the comparative Mixes 1 and 2 investigated in Example 4. Both slump patties developed significant cracking upon drying. The initiation of cracks in the patties began to occur as soon as 5 minutes after the raw materials were mixed together. The number of cracks and the size of cracks grew significantly with subsequent material drying and hardening. It can be concluded that addition of calcium aluminate cement to fly ash compositions activated with alkali citrates leads to a dimensionally unstable material prone to excessive cracking upon drying and hardening.
Shrinkage Behavior
Rectangular prism specimens were cast for characterization of shrinkage behavior of the mixes investigated. Prism specimens for Mix 2 cracked in the mold (prior to demolding) in less than 1 hour after the cast due to excessive material shrinkage.
FIG. 4B shows the shrinkage behavior for Mix 1. The shrinkage measurements were initiated at an age of 4-hours from the time the raw materials were mixed together to form an aqueous slurry. The material shrinkage was measured for a total duration of about 8-weeks while curing the material at 75° F./50% RH. It can be observed that prisms for Mix 1 containing a mixture of fly ash, high alumina cement, and an alkali metal citrate shrank very significantly. The measured shrinkage of the prism specimen for Mix 1 at the end of 8 weeks is about 1.08%.
Example 5
TABLES 6 and 7 show the raw material compositions of the two geopolymer cementitious mixtures (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 mixture compositions of this example was equal to 10 wt % (Mix 3) and 30 wt % (Mix 4) of the weight of fly ash. Fine-grained Landplaster was added at different amount level of 33.33 wt % based on the weight of calcium aluminate cement).
Initial Flow Behavior, Slump, and Early Age Cracking Behavior of Material
TABLE 8 shows the initial flow behavior and slump characteristics of the geopolymeric cementitious compositions of the invention (Mix 3 and Mix 4 in TABLE 8) comprising fly ash, calcium aluminate cement, fine-grain landplaster, and alkali citrate investigated in Example 5. It can be clearly observed that all mixture compositions investigated had good flow behavior. It is particularly noteworthy that such good flow properties were obtainable even at a water/cementitious materials ratio as low as 0.25.
FIG. 5A shows photograph of slump patties for the geopolymeric cementitious compositions of the invention investigated in Example 5. The slump patties of this Example did not develop any cracking upon drying as was the case for the cementitious mixtures of Comparative Example 4 containing no landplaster. Thus, incorporating a source of calcium sulfate (fine-grained landplaster) to the cementitious mixture comprising fly ash, calcium aluminate cement, and alkali citrate leads to dimensionally stable geopolymeric cementitious compositions possessing superior resistance to cracking upon drying.
Shrinkage Behavior
FIG. 5B shows a graph of shrinkage behavior of geopolymeric cementitious compositions of the invention investigated in Example 5. The main objective of this investigation was to study the influence of incorporation of calcium aluminate cement in combination with calcium sulfate (landplaster) and alkali metal citrate on shrinkage behavior of the developed geopolymeric cementitious compositions of the invention.
The shrinkage measurements were initiated at an age of 4-hours from the time the raw materials were mixed together to form an aqueous slurry. The material shrinkage was measured for a total duration of about 8-weeks while curing the material at 75° F./50% RH.
The following conclusions can be drawn from this investigation and FIG. 5B:
The incorporation of calcium sulfate (landplaster) had a significant impact on improving cracking resistance and dimensional stability of geopolymeric cementitious compositions of the invention comprising of fly ash, calcium aluminate cement and an alkali metal citrate. Contrary to the comparative Mix 1 shrinkage bars of comparative Example 4 (with no landplaster) which cracked even before de-molding, the shrinkage bars of Example 5 comprising calcium sulfate (landplaster) were completely stable and did not result in any cracks either prior to or after de-molding.
The measured maximum shrinkage of the geopolymeric cementitious compositions of the invention comprising of fly ash, calcium aluminate cement, calcium sulfate (landplaster), and alkali citrate was significantly lower than that of the cementitious compositions containing fly ash and alkali citrate only (Example 1). For example, the geopolymeric cementitious compositions of the invention comprising of fly ash, calcium aluminate cement, calcium sulfate (landplaster) and alkali citrate had maximum measured shrinkage 0.14% in comparison to the maximum shrinkage of about 0.75% for the comparative mixture containing fly ash and alkali citrate only (Example 1). Thus, it can be concluded that addition of calcium sulfate to cementitious compositions comprising of fly ash, calcium aluminate cement, and alkali citrate helps to very significantly reduce the material shrinkage.
Time of Setting
TABLE 9 shows time of setting of geopolymeric cementitious compositions of the invention investigated in Example 5.







TABLE 9







Setting Times of Example 5 (Mix 3 and Mix 4)










Initial Setting Time (hr:min)
Final Setting Time (hr:min)













Mix 3
00:19
00:24


Mix 4
00:24
00:33









Cementitious compositions investigated in Example 5 had rapid setting behavior with final setting times ranging between 20 to 40 minutes. The developed cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate (landplaster), and alkali citrate had relatively longer setting times than the cementitious compositions comprising only fly ash and alkali citrate as seen in Example 1. For the cementitious composition comprising of fly ash and alkali citrate of Example 1, the time of final setting was about 15 minutes. An extremely short setting time is a problem for most practical applications since a short material working life (pot life) causes significant difficulties with processing of rapid setting material using the equipment and tools involved in the actual field application.
Compressive Strength
TABLE 10 shows the compressive strength behavior of the developed geopolymeric cementitious compositions of the invention comprising of fly ash, calcium aluminate cement, calcium sulfate (landplaster), and alkali citrate investigated in Example 5.







TABLE 10







Compressive Strength of Example 5 (Mix 3 and Mix 4) - (psi)












4 hour
24 hour
8 day
28 day

















Mix 3
1543
4164
6883
7836



Mix 4
1461
2075
3974
4146










This studied the influence of incorporation of calcium aluminate cement in combination with calcium sulfate dihydrate (fine-grained landplaster) on both the early age and ultimate compressive strength behavior of the developed geopolymeric cementitious compositions of the invention. The data indicates the following:
The compressive strength of the geopolymeric cementitious compositions of the invention investigated in this example continued to increase as a function of time.
The early age (4-hour and 24-hour) strength of mixes increased with increase in landplaster amount in the cementitious composition.
The early age 4-hour compressive strengths of the material were in excess of 1400 psi with the use of landplaster as a component of the investigated geopolymeric cementitious compositions of the invention.
The early age 24-hour compressive strengths of the material were in excess of 2000 psi with the use of landplaster as a component of the investigated geopolymeric cementitious compositions of the invention. It is noteworthy that the 24-hour compressive strength for Mix 3 with 30 parts calcium aluminate cement and 10 parts calcium sulfate was very high at about 4150 psi.
The 28-day compressive strength of the geopolymeric cementitious compositions of the invention investigated in this example was very high, about 6900 psi for Mix 3 and about 4000 psi for Mix 4.
In the embodiments of present invention shown in this example it was unexpectedly found that when the aluminosilicate mineral, alkali metal activator, calcium aluminate cement and calcium sulfate were mixed together, the resulting reaction was less exothermic than the two separate reactions and the time of gelation and hardening times were significantly extended.
It has also been found that there is a significant reduction in material shrinkage when the aluminosilicate mineral and alkali metal activator were reacted together with calcium aluminate cement and calcium sulfate as discussed above in paragraph of the description.
Example 6
TABLE 11 shows the raw material compositions of the geopolymeric cementitious mixtures investigated in this Example, as shown in TABLE 6. The amount of calcium aluminate cement used in the mixture compositions of this example was equal to 30 wt % of the weight of fly ash. Calcium sulfate dihydrate (landplaster) was added at different amount levels (5 wt %, 10 wt %, 20 wt %, and 30 wt % of the weight of the fly ash calcium aluminate cement) in the various mixture compositions investigated. The fly ash is Class C Fly Ash, Campbell Power Plant, West Olive, Mich., the calcium sulfate dihydrate is USG Landplaster, the calcium aluminate cement is Ciment Fondu (HAC Fondu), Kerneos Inc, the sand is QUIKRETE Commercial Grade Fine Sand No. 1961 and the superplasticizer is AdvaCast 500, from WR Grace.







TABLE 11







Compositions investigated in Example 6











Raw Material
Mix 1
Mix 2
Mix 3
Mix 4














Fly Ash Class C
2222
2143
2000
1875


(grams)


Calcium Sulfate
111
214
400
562.5


Dihydrate (grams)


Calcium Aluminate
667
643
600
563


Cement (grams)






Total Cementitious
3000
3000
3000
3000


Materials (grams)


Sand (grams)
2250
2250
2250
2250


Potassium Citrate
120
120
120
120


(grams)


Superplasticizer
45
45
45
45


(grams)


Water (grams)
825
825
825
825


Water/Cementitious
0.275
0.275
0.275
0.275


Materials Ratio


Sand/Cementitious
0.75
0.75
0.75
0.75


Materials Ratio


Superplasticizer/
1.5%  
1.5%  
1.5%  
1.5%  


Cementitious


Materials, wt %


Potassium Citrate/
4%
4%
4%
4%


Cementitious


Materials, wt %


Calcium Aluminate
30% 
30% 
30% 
30% 


Cement/Fly ash,


wt %


Calcium Sulfate/
16.7%  
33.3%  
66.7%  
100% 


Calcium Aluminate


Cement, wt %









Initial Flow Behavior, Slump, and Early Age Cracking Behavior of Material
TABLE 12 shows the initial flow behavior and slump characteristics of the geopolymeric cementitious compositions of the invention comprising of fly ash, calcium aluminate cement, calcium sulfate (last plaster), and alkali citrate investigated in Example 6.







TABLE 12







Flow and Slump of Example 6










Flow
Slump (inches)















Mix 1
9
9



Mix 2
9
9



Mix 3
9
8.75



Mix 4
9
9










All mixture compositions investigated had good self-leveling, flow behavior and high patty diameter as observed in the slump test. The high slump and self-leveling behavior was obtainable at a water/cementitious materials ratio as low as 0.275.
FIG. 6A shows photographs of slump patties for the geopolymeric cementitious compositions of the invention in Example 6. The slump patties of this example did not develop any cracking upon drying in contrast to the cementitious mixtures of comparative Example 4 containing no calcium sulfate (landplaster). Thus, it can be concluded incorporation of calcium sulfate (landplaster) to the cementitious mixture comprising of fly ash, calcium aluminate cement, and alkali citrate leads to dimensionally stable geopolymeric cementitious compositions possessing superior resistance to cracking upon drying.
Shrinkage Behavior
FIG. 6B shows shrinkage behavior of geopolymeric cementitious compositions of the invention investigated in Example 6. This shows the influence of incorporation of calcium aluminate cement in combination with a calcium sulfate (calcium sulfate dihydrate or landplaster) on shrinkage behavior of the developed geopolymeric cementitious compositions of the invention.
The shrinkage measurements were initiated at an age of 4-hours from the time the raw materials were mixed together to form an aqueous slurry. The material shrinkage was measured for a total duration of 8-weeks while curing the material at 75° F./50% RH.
The following important conclusions can be drawn from this investigation and FIG. 6B:
The incorporation of calcium sulfate (landplaster) had a significant impact on improving the cracking resistance and dimensional stability of geopolymeric cementitious compositions of the invention comprising of fly ash, calcium aluminate cement and alkali citrate. Contrary to the shrinkage bars of comparative Example 4 (with no landplaster) which cracked even before de-molding, the shrinkage bars of Example 6 comprising calcium sulfate (fine-grained landplaster) were completely stable and did not result in any cracks either prior to or after de-molding.
The measured maximum shrinkage of the geopolymeric cementitious compositions of the invention comprising of fly ash, calcium aluminate cement, calcium sulfate (fine-grained landplaster), and alkali citrate was significantly lower than that of the cementitious compositions comprising of fly ash and alkali citrate only (Example 1). For example, the geopolymeric cementitious compositions of the invention comprising of fly ash, calcium aluminate cement, calcium sulfate (fine-grained landplaster), and alkali citrate had a maximum shrinkage of about 0.13% to 0.24% in comparison to a maximum shrinkage of about 0.75% for the comparative mixture comprising of fly ash and alkali citrate only (Example 1). Thus, addition of fine-grained landplaster to cementitious compositions comprising of fly ash, calcium aluminate cement, and alkali citrate helps to significantly reduce the material shrinkage.
Increase in calcium sulfate (landplaster) amount at levels used in this Example resulted in an overall decrease in the maximum shrinkage of the material. It can be observed that at a calcium sulfate (landplaster) amount of 16.7 wt %, the material shrinkage was 0.24% (Mix 1). Increase in calcium sulfate (landplaster) amount to 33.3 wt % and 66.7 wt % resulted in a decrease in material shrinkage to a value of about 0.13% (Mix 2 and Mix 3). A further increase in calcium sulfate (landplaster) amount to 100 wt % resulted in a slight increase in shrinkage to a value of about 0.15%
Heat Evolution and Slurry Temperate Rise Behavior
FIG. 6C shows the exothermic and slurry temperature rise behavior of geopolymeric cementitious compositions of the invention investigated in Example 6. The cementitious compositions of Example 6 comprising of fly ash, calcium aluminate cement, calcium sulfate (fine-grained landplaster), and alkali citrate demonstrated only a very moderate temperature rise behavior. Moderate heat evolution and low temperature rise within the material during curing stage are crucial to prevent excessive thermal expansion and consequent cracking and disruption of material. This aspect becomes even more crucial when the material is used in a manner where large thicknesses of material pours are involved in the actual field application. The geopolymeric cementitious compositions of the invention investigated in this Example are disclosed to be highly beneficial in this particular aspect as they would lead to a lower thermal expansion and enhanced resistance to thermal cracking in actual field applications.
Time of Setting
TABLE 13 shows the time of setting of geopolymeric cementitious compositions of the invention investigated in Example 6 comprising fly ash, calcium aluminate cement, calcium sulfate (fine-grained landplaster), and alkali citrate.







TABLE 13







Setting Times of Example 6










Initial Setting Time (hr:min)
Final Setting Time (hr:min)













Mix 1
00:24
00:30


Mix 2
00:27
00:31


Mix 3
00:30
00:48


Mix 4
00:34
00:48









All cementitious compositions investigated in this example showed final setting times ranging between 30 to 50 minutes. In contrast, the cementitious composition comprising fly ash and alkali citrate of Example 1 had a time of final setting of about 15 minutes.
Compressive Strength
TABLE 14 shows the early age and ultimate compressive strength behavior of the developed geopolymeric cementitious compositions of the invention comprising of fly ash, calcium aluminate cement, calcium sulfate (fine-grained landplaster), and alkali citrate of Example 6.







TABLE 14







Compressive Strength of Example 6 - (psi)












4 hour
24 hour
7 day
28 day















Mix 1
871
1601
3996
5221


Mix 2
1042
1770
3693
4108


Mix 3
1027
1711
2851
3248


Mix 4
1076
1768
2765
2855









The following observations can be drawn from this study:
The compressive strength of the geopolymeric cementitious compositions of the invention investigated in this Example continued to increase as a function of time.
The early age 4-hour compressive strengths of the material were in excess of 750 psi with the use of calcium sulfate (landplaster) as a component of the investigated geopolymeric cementitious compositions of the invention.
The early age 24-hour compressive strengths of the material were in excess of 1500 psi with the use of calcium sulfate (landplaster) as a component of the investigated geopolymeric cementitious compositions of the invention.
The 28-day compressive strength of all geopolymeric cementitious compositions of the invention investigated in this example was very high at lower amounts of calcium sulfate (landplaster) and decreased with increase in the amount of calcium sulfate. For instance, the 28-day compressive strength of Mix 1 with 16.7% calcium sulfate and Mix 2 with 33.3% calcium sulfate, were 5221 psi and 4108 psi, respectively. On the other hand, for Mix #4 with 100% calcium sulfate, the 28-day compressive strength dropped to 2855 psi.
Example 7
This example compares compositions of invention comprising calcium aluminate cement at different amount levels in the mixtures containing fly ash, calcium sulfate (fine-grained calcium sulfate dihydrate or landplaster), and alkali citrate.
TABLE 15 shows the raw material compositions of the geopolymeric cementitious mixtures investigated in this example. The amount of calcium aluminate cement used in the mixture compositions of this example was equal to 40 wt %, 60 wt % and 80 wt % of the weight of the Class C fly ash. Calcium sulfate in the form of fine-grained USG landplaster was added at the amount level of 30 wt % of the weight of calcium aluminate cement and 13.3, 20 and 26.7 wt % of the 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.







TABLE 15







Example 7 Compositions










Raw Material
Mix 1
Mix 2
Mix 3













Fly Ash Class C (grams)
1957
1667
1452


Calcium Sulfate Dihydrate (grams)
261
333
387


Calcium Aluminate Cement (grams)
783
1000
1161


Total Cementitious Materials (grams)
3000
3000
3000


Sand (grams)
2250
2250
2250


Potassium Citrate (grams)
120
120
120


Superplasticizer (grams)
12
30
30


Water (grams)
825
825
825


Water/Cementitious Materials Ratio
0.275
0.275
0.275


Sand/Cementitious Materials Ratio
0.75
0.75
0.75


Superplasticizer/Cementitious
 0.4%
  1%
  1%


Materials, wt %


Potassium Citrate/Cementitious
  4%
  4%
  4%


Materials, wt %


Calcium Aluminate Cement/Fly ash,
  40%
  60%
  80%


wt %


Calcium Sulfate/Calcium Aluminate
33.3%
33.3%
33.3%


Cement, wt %









Initial Flow Behavior, Slump, and Early Age Cracking Behavior of Material
TABLE 16 shows the initial flow behavior and slump characteristics of the geopolymeric cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate dihydrate (fine-grained last plaster), and alkali citrate investigated in Example 7.







TABLE 16







Flow and Slump of Example 7










Flow
Slump (inches)













Mix 1
9
9


Mix 2
7
8


Mix 3
7
8









All mixture compositions investigated had good flow behavior as observed in the slump test.
Shrinkage Behavior
FIG. 7 shows data for shrinkage behavior of geopolymeric cementitious compositions 7 of the invention in this example.
The shrinkage measurements were initiated at an age of 4-hours from the time the raw materials were mixed together to form an aqueous slurry. The material shrinkage was measured for a total duration of about 8-weeks while curing the material at 75° F./50% RH.
This example showed the following:
Contrary to the shrinkage bars of comparative Example 4 (with no calcium sulfate) which cracked even before de-molding, the shrinkage bars of Example 7 comprising calcium sulfate (fine-grained landplaster) were completely stable and did not result in any cracks prior to or after de-molding.
The geopolymeric cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate (fine-grained landplaster), and alkali citrate had a maximum shrinkage was extremely low at about less than 0.06% in comparison to a maximum shrinkage of about 0.75% for the comparative mixture composition containing only fly ash and alkali citrate (Example 1).
Time of Setting
TABLE 17 shows the time of setting of geopolymeric cementitious compositions of invention of Example 7.







TABLE 17







Setting Times of Example 7










Initial Setting Time (hr:min)
Final Setting Time (hr:min)













Mix 1
00:22
00:30


Mix 2
00:29
00:37


Mix 3
00:30
00:40









All geopolymer cementitious compositions of the invention demonstrated rapid setting behavior. However, the mixture composition of invention investigated in this example comprising fly ash, calcium aluminate cement, calcium sulfate (fine-grained landplaster), and alkali citrate had a relatively longer setting time than the prior art cementitious composition comprising fly ash and alkali citrate only (Example 1). The final setting times of the geopolymeric cementitious composition Mixes 1, 2, and 3 of the invention comprising fly ash, calcium aluminate cement, calcium sulfate dihydrate (landplaster), and potassium citrate was from about 30 to about 45 minutes compared to an extremely rapid final setting time of about 15 minutes for the mixture composition containing only fly ash and potassium citrate (Example 1).
Compressive Strength
TABLE 18 show the compressive strength behavior of the developed geopolymeric cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate (fine-grained landplaster), and alkali citrate investigated in Example 7.







TABLE 18







Compressive Strength of Example 7 - (psi)











4 hour
24 hour
7 day
















Mix 1
1511
1958
2679



Mix 2
1579
1924
3051



Mix 3
1883
2026
3128










The following observations can be drawn:
The compressive strength of the geopolymeric cementitious compositions of the invention investigated in this example continued to increase with time.
The early age 4-hour compressive strength of the material was in excess of 1500 psi with the use of calcium aluminate cement, calcium sulfate (fine-grained landplaster) and alkali citrate as part of the geopolymeric cementitious compositions of invention. Similarly, the 24-hour compressive strengths of the compositions of invention were in excess of 1900 psi.
Example 8
This example depicts physical properties of the developed geopolymeric cementitious compositions of the invention comprising of fly ash, calcium aluminate cement, calcium sulfate in the form of fine-grained anhydrous calcium sulfate (i.e., anhydrite) and alkali citrate, mixed as shown in TABLE 6. TABLE 19 shows the raw material compositions of the geopolymeric cementitious mixtures investigated in this Example. Mix 1 represents a comparative composition investigated in Example 8. The amount of calcium aluminate cement used in the mixture compositions of this example was equal to 0 wt %, 30 wt %, 60 wt % and 90 wt % of the weight of fly ash. Anhydrite (USG SNOW WHITE Filler) was added at a amount of 33.33 wt % of the weight of calcium aluminate cement (CIMENT Fondu HAC Fondu) and 0, 10, 20 and 30 wt. % of the fly ash in the mixture compositions investigated. QUIKRETE Commercial Grade Fine Sand No. 1961 and BASF CASTAMENT FS20 superplasticizer was used.







TABLE 19







Geopolymeric compositions of Example 8












Mix 1






Comparative


Raw Material
Composition
Mix 2
Mix 3
Mix 4














Fly Ash Class C (grams)
3000
2143
1667
1364


Anhydrous Calcium Sulfate
0
214
333
409


(Anhydrite) (grams)


Calcium Aluminate
0
643
1000
1227


Cement (grams)



Total Cementitious Materials
3000
3000
3000
3000


(grams)


Sand (grams)
2250
2250
2250
2250


Potassium Citrate (grams)
120
120
120
120


Superplasticizer (grams)
15
15
15
15


Water (grams)
750
750
750
750


Water/Cementitious
0.25
0.25
0.25
0.25


Materials Ratio


Sand/Cementitious Materials
0.75
0.75
0.75
0.75


Ratio


Superplasticizer/Cementitious
0.5%  
0.5%
0.5%
0.5%


Materials, wt %


Potassium Citrate/
4%
  4%
  4%
  4%


Cementitious Materials, wt %


Calcium Aluminate Cement/
0%
 30%
 60%
 90%


Fly ash, wt %


Calcium Sulfate/Calcium
0%
33.3% 
33.3% 
33.3% 


Aluminate Cement, wt %









Initial Flow Behavior, Slump, and Early Age Cracking Behavior of Material
TABLE 20 shows the initial flow behavior and slump characteristics of the geopolymeric cementitious compositions of the invention comprising of fly ash, calcium aluminate cement, calcium sulfate in the form of anhydrite, and alkali citrate investigated in Example 8.







TABLE 20







Flow and Slump of Example 8










Flow
Slump (inches)















Mix 1 - Comparative Composition
10
11



Mix 2
10
10



Mix 3
10
10



Mix 4
9
9.5










All mixture compositions investigated had good self-leveling, flow behavior and high patty diameter as observed in the slump test. It is particularly noteworthy that such high slump and self-leveling behavior was obtainable at a water/cementitious materials ratio as low as 0.25.
The slump patties for all four mixes comprising of calcium sulfate in the form of anhydrite were in excellent condition and developed no cracking.
Shrinkage Behavior
FIG. 8 shows shrinkage behavior of geopolymeric cementitious compositions of the invention investigated in Example 8. The shrinkage measurements were initiated at an age of 4-hours from the time the raw materials were mixed together to form an aqueous slurry. The material shrinkage was measured for a total duration of about 8-weeks while curing the material at 75° F./50% Relative Humidity (RH).
The following important conclusions can be drawn from this investigation:
Contrary to the shrinkage bars of comparative Example 4 (with no calcium sulfate) which cracked even before de-molding, the shrinkage bars of Example 8 comprising calcium aluminate cement, anhydrous calcium sulfate (anhydrite), and alkali citrate were completely stable and did not result in any cracks either prior to or after de-molding.
The geopolymeric cementitious compositions of some embodiments of the invention comprising of fly ash, calcium aluminate cement, calcium sulfate (anhydrite), and alkali citrate has a maximum shrinkage between 0.21% to 0.26% in comparison to a maximum shrinkage of about 0.75% for the comparative mixture composition containing fly ash and alkali citrate only (Example 1) and about 0.62% for comparative Mix 1 of the present example which also contains fly ash and alkali citrate only.
The lowest shrinkage was obtained for Mix 2 comprising calcium aluminate cement at 30 wt % of fly ash amount and calcium sulfate (anhydrite) at 33.3 wt % of calcium aluminate amount.
Compressive Strength
TABLE 21 shows the compressive strength behavior of the developed geopolymeric cementitious compositions of the invention comprising of fly ash, calcium aluminate cement, calcium sulfate (anhydrite), and alkali citrate investigated in Example 8.







TABLE 21







Compressive Strength of Example 8 - (psi)












4 hour
24 hour
7 day
28 day















Mix 1 - Comparative Composition
3031
5028
8339
10051


Mix 2
2831
4715
8431
12454


Mix 3
5032
6789
8462
10804


Mix 4
6173
8183
10461
12628









The example studied the influence of incorporation of calcium aluminate cement in combination with calcium sulfate in the form of anhydrite on both the early age and ultimate compressive strength behavior of the developed geopolymeric cementitious compositions of the invention. The following important observations can be drawn from this study:
The compressive strength of the geopolymer cementitious compositions of the invention investigated in this example continued to increase as a function of time.
Both the early age compressive strength and the ultimate compressive strength of the mixture composition without calcium sulfate (Comparative Mix 1) were lower in comparison to those for the cementitious compositions of the invention comprising calcium sulfate (Mixes 2 through 4).
The early age (4-hour and 24-hour) compressive strengths of geopolymeric cementitious compositions of the invention comprising calcium aluminate cement and calcium sulfate in the form of anhydrite were exceptionally high. For example, Mix 3 comprising calcium aluminate cement at a amount of 60 wt % of fly ash and anhydrite at a amount of 33.33 wt % of calcium aluminate cement achieved a compressive strength of 5032 psi in just 4 hours and 6789 psi in 24 hours. Similarly, Mix 4 comprising calcium aluminate cement at a amount of 80 wt % of fly ash and anhydrite at a amount of 33.33 wt % of calcium aluminate cement achieved a compressive strength of 6173 psi in just 4 hours and 8183 psi in 24 hours.
The 28-day compressive strengths of all geopolymeric cementitious compositions of the invention comprising fly ash, calcium aluminate, calcium sulfate in the form of anhydrite, and potassium citrate were exceptionally high and in excess of 10000 psi.
Thus it has been very surprisingly found that the use of insoluble anhydrous calcium sulfate (anhydrite or dead burnt anhydrite) provided a faster set, a superior rate of compressive strength development, and a higher ultimate compressive strength than those obtained with the use of a relatively higher soluble calcium sulfate dihydrate (see Example 7).
Another unexpected feature of embodiments of this invention is the dependence of setting behavior and compressive strength on the type of calcium sulfate used in the compositions of the invention.
Example 9
TABLE 22 shows the raw material compositions of the geopolymeric cementitious mixtures investigated in this Example, as shown in TABLE 6.
The amount of calcium aluminate cement used in the mixture compositions of this example was equal to 40 wt % of the weight of fly ash. Landplaster was added at an amount of 33.3 wt % of the weight of calcium aluminate cement and 13.3 wt % of the Class C fly ash. Sodium citrate dihydrate was used as the alkali metal chemical activator in all mixture compositions investigated. The water to cementitious materials ratio utilized in this investigation was equal to 0.30. QUIKRETE Commercial Grade Fine Sand No. 1961 and BASF CASTAMENT FS20 superplasticizer.







TABLE 22







Compositions investigated in Example 9











Raw Material
Mix # 1
Mix 2
Mix 3
Mix 4














Fly Ash Class C (grams)
1957
1957
1957
1957


Calcium Sulfate Dihydrate (grams)
261
261
261
261


Calcium Aluminate Cement
783
783
783
783


(grams)



Total Cementitious Materials
3000
3000
3000
3000


(grams)


Sand (grams)
2250
3150
4550
7500


Sodium Citrate Dihydrate
60
60
60
60


Superplasticizer (grams)
15
15
15
15


Water (grams)
900
900
900
900


Water/Cementitious Materials
0.30
0.30
0.30
0.30


Ratio


Sand/Cementitious Materials Ratio
0.75
1.05
1.50
2.5


Superplasticizer/Cementitious
0.5%
0.5%
0.5%
0.5%


Materials, wt %


Sodium Citrate/Cementitious
  2%
  2%
  2%
  2%


Materials, wt %


Calcium Aluminate Cement/Fly
 40%
 40%
 40%
 40%


ash, wt %


Calcium Sulfate/Calcium
33.3% 
33.3% 
33.3% 
33.3% 


Aluminate Cement, wt %









Slump and Early Age Cracking Behavior of Material
TABLE 23 shows the initial flow behavior and slump characteristics of the geopolymeric cementitious compositions of an embodiment of the invention comprising of fly ash, calcium aluminate cement, calcium sulfate dihydrate (fine-grained last plaster), and alkali citrate investigated in Example 9.







TABLE 23







Flow and Slump of Example 9










Flow
Slump (inches)













Mix 1
10
10


Mix 2
10
10


Mix 3
8
8


Mix 4
1
2









Mixture compositions with sand/cementitious materials ratio ranging from 0.75 to 1.50 (Mixes 1, 2 and 3) had good flow behavior as observed in the slump test. On the other hand, the mixture composition with sand/cementitious materials ratio of 2.5 (Mix 4) was very stiff with poor flow properties.
Shrinkage Behavior
FIG. 9A shows shrinkage behavior of geopolymeric cementitious compositions of the invention investigated in Example 9. The main objective of this investigation was to study the influence of incorporation of calcium aluminate cement in combination with a fine-grained calcium sulfate dihydrate (landplaster) and an alkali citrate on shrinkage behavior of the developed geopolymeric cementitious compositions of the invention containing different amount of sand in the mixture.
The shrinkage measurements were initiated at an age of 4-hours from the time the raw materials were mixed together to form an aqueous slurry. The material shrinkage was measured for a total duration of about 8-weeks while curing the material at 75° F./50% RH.
The following conclusions are drawn from this example and FIG. 9A:
Unlike the shrinkage bars of comparative Example 4 (Mix 2 with no calcium sulfate), which cracked before de-molding, the shrinkage bars of Example 9 comprising calcium sulfate dihydrate in the form of fine-grained landplaster were completely stable and did not crack prior to or after de-molding.
The geopolymeric cementitious compositions of the invention (Example 9) comprising fly ash, calcium aluminate cement, calcium sulfate dihydrate (fine-grained landplaster), and alkali citrate demonstrated very low shrinkage with a maximum shrinkage of less than 0.05% in comparison to a maximum shrinkage of about 0.75% for the comparative mixture composition containing fly ash and alkali citrate in Example 1.
Heat Evolution and Slurry Temperate Rise Behavior
FIG. 9B shows the exothermic and slurry temperature rise behavior of geopolymeric cementitious compositions of the invention investigated in Example 9. The cementitious compositions of this Example comprising fly ash, calcium aluminate cement, calcium sulfate (fine-grained landplaster), and alkali citrate demonstrated only a very moderate temperature rise behavior. The maximum temperature rise was only about 100° F. with a net temperature rise of less than 30° F. A lower degree of temperature rise is beneficial in most applications as 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.
Time of Setting
TABLE 24 shows the time of setting of geopolymeric cementitious compositions of the invention investigated in Example 9.







TABLE 24







Setting Times of Example 9










Initial Setting Time (hr:min)
Final Setting Time (hr:min)













Mix 1
00:37
 1:01


Mix 2
00:34
00:56


Mix 3
00:33
01:00


Mix 4
00:30
00:55









All cementitious compositions investigated in this example had rapid setting behavior. The final setting times of the geopolymeric cementitious compositions of the invention of this example comprising fly ash, calcium aluminate cement, calcium sulfate (landplaster), and sodium citrate ranged from about 55 minutes to about 65 minutes compared to an extremely rapid final setting time of about 15 minutes for the mixture composition containing fly ash and sodium citrate only (Example 1). An extremely short setting time is problematic for some applications.
Compressive Strength
TABLE 25 shows the compressive strength behavior of the developed geopolymeric cementitious compositions of the invention comprising of fly ash, calcium aluminate cement, calcium sulfate (fine-grained landplaster), and alkali citrate investigated in Example 9.







TABLE 25







Compressive Strength of Example 9 - (psi)












4 hour
24 hour
7 day
28 day















Mix 1
497
1307
1972
3663


Mix 2
583
1256
2450
4211


Mix 3
577
1343
2262
4123


Mix 4
578
1114
2066
2735









The following observations can be drawn from this study:
The compressive strength of the geopolymeric cementitious compositions of the invention in this example continued to increase as a function of time. It can be observed that the various geopolymer compositions of the invention investigated in this example attained satisfactory early age and ultimate strength development.
Example 10
TABLE 26 shows the raw material compositions of the geopolymeric cementitious mixtures, which are the same as in Example 9.
The amount of calcium aluminate cement used in the mixture compositions of this example was equal to 40 wt % of the weight of fly ash. Calcium sulfate dihydrate (Landplaster) was added at a amount of 33.3 wt % of the weight of calcium aluminate cement and 13.3 wt % of the Class C fly ash. Potassium citrate was used as the alkali metal chemical activator in all mixture compositions in this example. The water to cementitious materials ratio utilized in this investigation was equal to 0.25. Influence of superplasticizer amount on performance of the cementitious compositions of the invention was investigated in the Example.







TABLE 26







Compositions investigated in Example 10











Raw Material
Mix #1
Mix 2
Mix 3
Mix 4














Fly Ash Class C (grams)
1957
1957
1957
1957


Calcium Sulfate Dihydrate
261
261
261
261


(grams)


Calcium Aluminate Cement
783
783
783
783


(grams)



Total Cementitious Materials
3000
3000
3000
3000


(grams)


Sand (grams)
2250
3150
4550
7500


Potassium Citrate
120
120
120
120


Superplasticizer (grams)
0
15
15
15


Water (grams)
750
900
900
900


Water/Cementitious Materials
0.25
0.25
0.25
0.25


Ratio


Sand/Cementitious Materials
0.75
0.75
0.75
0.75


Ratio


Superplasticizer/Cementitious
0%
0.4%
0.8%
1.2%


Materials, wt %


Potassium Citrate/
4%
  4%
  4%
  4%


Cementitious Materials, wt %


Calcium Aluminate Cement/Fly
40% 
 40%
 40%
 40%


ash, wt %


Calcium Sulfate/Calcium
33.3%  
33.3% 
33.3% 
33.3% 


Aluminate Cement, wt %









Slump and Early Age Cracking Behavior of Material
TABLE 27 shows the initial flow behavior and slump characteristics of the geopolymeric cementitious compositions of the invention comprising of fly ash, calcium aluminate cement, calcium sulfate (fine-grained last plaster), and alkali citrate investigated in Example 10.







TABLE 27







Flow and Slump of Example 10










Flow
Slump (inches)













Mix 1
7
7


Mix 2
8
9


Mix 3
9
10


Mix 4
9
9.5









It can be observed that all mixture compositions of the invention investigated in this example had good flow behavior. The flow behavior of the compositions improved with incorporation of superplasticizer in the mixture compositions. No improvement in flow and slump was observed with increase in superplasticizer amount beyond 0.80%.
Shrinkage Behavior
FIG. 10 shows shrinkage behavior of geopolymeric cementitious compositions of the invention investigated in Example 10. The main objective of this investigation was to study the influence of incorporation of calcium aluminate cement in combination with a fine-grained calcium sulfate dihydrate (landplaster) and an alkali citrate on shrinkage behavior of the developed geopolymeric cementitious compositions of the invention containing different amounts of superplasticizer in the mixture.
The shrinkage measurements were initiated at an age of 4-hours from the time the raw materials were mixed together to form an aqueous slurry. The material shrinkage was measured for a total duration of about 8-weeks while curing the material at 75° F./50% RH.
The following conclusions can be drawn from this investigation and FIG. 10:
Unlike the shrinkage bars of comparative Example 4 (Mix 2 with no calcium sulfate), which cracked before de-molding, the shrinkage bars of Example 10 comprising calcium sulfate in the form of fine-grained landplaster were completely stable and did not crack, either prior to or after de-molding.
The geopolymeric cementitious compositions of one embodiment of the invention (Example 10) comprising fly ash, calcium aluminate cement, calcium sulfate dihydrate (fine-grained landplaster), and alkali citrate demonstrated very low shrinkage with a maximum shrinkage of less than 0.1% in comparison to a maximum shrinkage of about 0.75% for the comparative mixture composition containing fly ash and alkali citrate (Example 1).
The amount of shrinkage increased slightly with an increase in the amount of superplasticizer. It can be observed that for Mix 2 with a superplasticizer amount of 0.4%, the maximum shrinkage was about 0.05%; on the other hand, for Mix 4 with a superplasticizer amount of 1.2%, the maximum shrinkage had increased by a small amount to a value of about 0.08%.
Compressive Strength
TABLE 28 shows the compressive strength behavior of the developed geopolymeric cementitious compositions of the invention comprising of fly ash, calcium aluminate cement, calcium sulfate (fine-grained landplaster), and alkali citrate investigated in Example 10.







TABLE 28







Compressive Strength of Example 10 - (psi)












4 hour
24 hour
7 day
28 day

















Mix 1
2213
3362
4611
6732



Mix 2
2280
3768
5533
5890



Mix 3
2186
3187
5363
5819



Mix 4
2040
2841
4902
4897










The following observations can be drawn from this study:
The compressive strength of the geopolymeric cementitious compositions of this embodiment of the invention continued to increase as a function of time. The various compositions investigated attained satisfactory early age and ultimate strength.
The early age (4-hour and 24-hour) compressive strengths of geopolymeric cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate dihydrate (landplaster), and alkali citrate were exceptionally high and in excess of 2000 psi at the age of 4-hours and in excess of 3000 psi at the age of 24-hours.
The 28-day compressive strengths of all geopolymeric cementitious compositions of the invention comprising fly ash, calcium aluminate, calcium sulfate dihydrate (landplaster), and alkali citrate were exceptionally high ranging from about 4750 psi to about 6750 psi.
Example 11
TABLES 29 and 30 show the raw material compositions of the cementitious mixtures investigated in this Example.
The amount of calcium aluminate cement used in the mixture compositions of this example was equal to 40 wt % of the weight of fly ash. Landplaster used in this investigation added at a amount level of 33.33 wt % of the weight of calcium aluminate cement. Portland cement was added to Mix #1 through Mix #3 at amount rates of 6.1 wt %, 14 wt %, and 24.6 wt % of the total cementitious materials, respectively. The water to cementitious materials ratio was equal to 0.275 for all mixes investigated. Class C Fly Ash, Campbell Power Plant, West Olive, Mich., USG Landplaster, Ciment Fondu (HAC Fondu), Kerneos, Inc. calcium aluminate cement, Holcim Portland Cement Type I, Mason City, Iowa, QUIKRETE Commercial Grade Fine Sand No. 1961 and AdvaCast 500, WR Grace.







TABLE 29







Geopolymeric cementitious reactive powder mixture


compositions of Example 11 in parts by weight












Raw Material
Mix 1
Mix 2
Mix 3
















Fly Ash Class C
100
100
100



Calcium Sulfate Dihydrate
13.3
13.3
13.3



Calcium Aluminate Cement
40
40
40



Portland Cement Type I
10
25
50



Total Cementitious Materials
163.3
178.3
203.3

















TABLE 30







Geopolymeric cementitious compositions of Example 11










Raw Material
Mix 1
Mix 2
Mix 3













Fly Ash Class C (grams)
1837
1682
1475


Calcium Sulfate Dihydrate (grams)
245
224
197


Calcium Aluminate Cement
735
673
590


(grams)


Portland Cement Type I (grams)
184
421
738


Total Cementitious Materials
3000
3000
3000


(grams)


Sand (grams)
2250
2250
2250


Potassium Citrate (grams)
120
120
120


Superplasticizer (grams)
12
12
12


Water (grams)
825
825
825


Water/Cementitious Materials
0.275
0.275
0.275


Ratio


Sand/Cementitious Materials Ratio
0.75
0.75
0.75


Superplasticizer/Cementitious
0.4%
1%
  1%


Materials, wt %


Potassium Citrate/Fly Ash, wt %
  4%
4%
  4%


Calcium Aluminate Cement/
 40%
40% 
  40%


Fly ash, wt %


Calcium Sulfate/Calcium Aluminate
33.3% 
33.3%  
33.3%


Cement, wt %


Portland Cement/Cementitious
6.1%
14% 
24.6%


Materials, wt %









Initial Flow Behavior and Slump
TABLE 31 shows the initial flow behavior and slump characteristics of the cementitious compositions comprising of fly ash, calcium aluminate cement, calcium sulfate (landplaster), Portland cement, and alkali citrate investigated in Example 11.







TABLE 31







Flow and Slump of Example 11










Flow
Slump (inches)















Mix 1
9
9



Mix 2
9
8



Mix 3
5
6.75










The flow and slump behavior of the compositions was negatively influenced with an increase in the amount of Portland cement in the composition.
Shrinkage Behavior
FIG. 11 shows shrinkage behavior of geopolymeric cementitious compositions of the invention investigated in Example 11. The shrinkage measurements were initiated at an age of 4 hours from the time the raw materials were mixed together to form an aqueous slurry. The material shrinkage was measured for a total duration of about 8-weeks while curing the material at 75° F./50% RH.
The following important conclusions can be drawn from this example and FIG. 11:
Incorporation of Portland cement significantly increased the shrinkage of the cementitious compositions investigated. The ultimate shrinkage values for the various mixes investigated are tabulated in TABLE 37.







TABLE 32







Ultimate shrinkage values for the mixture compositions


investigated at the age of 8 weeks










Mix Identification
Ultimate shrinkage at the age of 8 weeks (%)







Mix 1
0.10%



Mix 2
0.16%



Mix 3
0.47%










As discussed in detail on the above description, this example shows the unexpected result obtained with addition of Portland cement to embodiments of the present invention were the Portland cement has a negative influence on the shrinkage behavior of the compositions. The magnitude of shrinkage is shown by this example to increase proportionately with increase in the amount of Portland cement in the compositions.
Addition of Portland cement to cementitious compositions of the invention comprising of fly ash, calcium aluminate cement, calcium sulfate, and alkali citrate significantly increasing the material shrinkage.
Based on the testing of this embodiment, addition of Portland cement in the dimensionally stable geopolymer compositions of the invention is not recommended and should be limited to very small amount, preferably not exceeding 15 wt % of the total weight of cementitious materials.
Example 12
TABLE 33 shows the raw material composition of the geopolymeric cementitious mixture investigated in this Example 12.
This example investigated incorporation of both sand and lightweight ceramic microspheres as fillers in the composition. Sodium citrate was added at an amount 2 wt % of the weight of the total cementitious materials. Calcium sulfate dihydrate as added at 13.3 wt % of the fly ash and calcium aluminate was added at 40 wt % of the Class C fly ash. Class C Fly Ash (Campbell Power Plant, West Olive, Mich.,) 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.







TABLE 33







compositions of Example 12










Raw Material
Mix A














Fly Ash Class C (grams)
1957



Calcium Sulfate Dihydrate (grams)
261



Calcium Aluminate Cement (grams)
783



Total Cementitious Materials (grams)
3000



Sand (grams)
3150



Ceramic Microspheres (grams)
300



Sodium Citrate Dihydrate (grams)
60



Superplasticizer (grams)
15



Water (grams)
900



Water/Cementitious Materials Ratio
0.30



Sand/Cementitious Materials Ratio
1.05



Ceramic Microspheres/Cementitious Materials Ratio
0.10



Superplasticizer/Cementitious Materials, wt %
 0.5%



Sodium Citrate/Cementitious Materials, wt %
  2%



Calcium Aluminate Cement/Fly ash, wt %
  40%



Calcium Sulfate/Fly Ash wt %
13.3%










Initial Flow Behavior, Slump, and Early Age Cracking Behavior of Material
TABLE 34 shows the initial flow behavior and slump of the geopolymeric cementitious composition investigated in this example comprising lightweight filler.







TABLE 34







Flow and Slump of Example 12










Flow
Slump (inches)















Mix A
7
8










Based on the results shown in TABLE 34 it can be concluded that the mixture compositions of the invention comprising lightweight fillers have good workability and self-leveling properties.
Shrinkage Behavior
FIG. 12 shows the shrinkage behavior of geopolymeric cementitious composition of the invention investigated in Example 12.
The shrinkage measurements were initiated at an age of 4-hours from the time the raw materials were mixed together to form an aqueous slurry. The material shrinkage was measured for a total duration of about 8-weeks while curing the material at 75° F./50% RH.
It is observed that the cementitious composition of the invention incorporating lightweight filler exhibited extremely low dimensional movement as a function of time.
pH
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 conduct the surface pH measurements.
Example 13
TABLE 35 shows the raw material composition of the geopolymeric cementitious mixture investigated in this Example 13.
This example incorporates both calcium aluminate cement and calcium sulfoaluminate cement in the composition. Calcium sulfate dihydrate was added at 10 wt % of the Class C fly ash and calcium aluminate cement was added at 10, 20 and 40 wt % of the fly ash. Calcium sulfoaluminate cement was added at 20 wt % of the fly ash. The fly ash is Class C Fly Ash, (Campbell Power Plant, West Olive, Mich.), USG Landplaster calcium sulfate dihydrate, (Denka SC1) calcium aluminate cement, FASTROCK 500 (CTS Company) calcium sulfoaluminate, QUIKRETE Commercial Grade Fine Sand No. 1961 and BASF Castament FS 20 superplasticizer were employed. Sodium citrate was added at an amount 2 wt % of the weight of the cementitious materials.







TABLE 35







Geopolymeric cementitious compositions of Example 13










Raw Material
Mix 1
Mix 2
Mix 3













Fly Ash Class C (grams)
2857
3000
2353


Calcium Sulfate Dihydrate (grams)
286
300
235


Calcium Aluminate Cement (grams)
286
600
941


Calcium Sulfoaluminate Cement (grams)
571
300
476


Total Cementitious Materials (grams)
4000
4500
4000


Sand (grams)
4200
4725
4200


Sodium Citrate dihydrate (grams)
80
90
80


Superplasticizer (grams)
20
23
20


Water (grams)
880
990
880


Water/Cementitious Materials Ratio
0.22
0.22
0.22


Sand/Cementitious Materials Ratio
1.05
1.05
1.05


Superplasticizer/Cementitious Materials,
0.5% 
0.5% 
0.5% 


wt %


Sodium Citrate/Fly Ash, wt %
 2%
 2%
 2%


Calcium Aluminate Cement/Fly ash, wt %
10%
20%
40%


Calcium Sulfoaluminate Cement/Fly ash,
20%
20%
20%


wt %


Calcium Sulfate/Calcium Sulfoaluminate
10%
10%
10%


Cement, wt %









Initial Flow Behavior and Slump
TABLE 36 shows the initial flow behavior and slump characteristics of the cementitious compositions of some embodiments of the invention comprising of fly ash, calcium aluminate cement, calcium sulfoaluminate cement, calcium sulfate (landplaster), and alkali citrate investigated in Example 13.







TABLE 36







Flow and Slump of Example 13










Flow
Slump (inches)















Mix 1
8
8.5



Mix 2
8
8.25



Mix 3
5
7.75










Based on the results shown in TABLE 36, the mixture compositions of the invention comprising calcium aluminate cement and calcium sulfoaluminate cement have good workability and self-leveling properties.
Compressive Strength
TABLE 37 shows the compressive strength behavior of the developed geopolymeric cementitious compositions of some embodiments of the invention comprising of fly ash, calcium aluminate cement, calcium sulfoaluminate cement, calcium sulfate dihydrate (fine-grained landplaster), and alkali citrate investigated in Example 13.







TABLE 37







Compressive Strength of Example 13 - (psi)












4 hour
24 hour
7 day
28 day

















Mix 1
2662
3448
4556
7039



Mix 2
2893
3848
4889
7826



Mix 3
2899
4827
6744
9915










The following conclusions are drawn from this study:
The compressive strength of the geopolymeric cementitious compositions of some embodiments of the invention comprising both calcium aluminate cement and calcium sulfoaluminate cement continued to increase as a function of time. The various compositions investigated attained satisfactory early age and ultimate strength.
The early age (4-hour and 24-hour) compressive strengths of geopolymeric cementitious compositions of some embodiments of the invention comprising fly ash, calcium aluminate cement, calcium sulfoaluminate cement, calcium sulfate dihydrate (landplaster), and alkali citrate were exceptionally high and in excess of about 2500 psi at the age of 4-hours and in excess of about 3400 psi at the age of 24-hours.
The 28-day compressive strengths of all geopolymeric cementitious compositions of some embodiments of the invention comprising fly ash, calcium aluminate, calcium sulfoaluminate cement, calcium sulfate (landplaster), and alkali citrate were exceptionally high and in excess of about 7000 psi.
Example 14
This example shows the physical properties of the developed geopolymer cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate in the form of fine-grained calcium sulfate dihydrate and alkali citrate. TABLE 38 shows the raw material compositions of the geopolymer cementitious mixtures investigated in this Example. All mixtures contained calcium aluminate cement in which the main calcium aluminate phase was dodecacalcium hepta-aluminate (12CaO.7Al2O3 or C12A7). This calcium aluminate cement is commercially available with trade name TERNAL EV from Kerneos Inc. The amount of calcium aluminate cement used in the mixture compositions of this example was equal to 10 wt %, 20 wt %, 30 wt % and 40 wt % of the weight of fly ash. The fine grained calcium sulfate dihydrate used in this example had a mean particle size equal to 13 microns available from the USG Company with trade name USG Terra Alba Filler. Calcium sulfate dihydrate was added at a amount of 50 wt % of the weight of calcium aluminate cement and 5, 10, 15 and 20 wt. % of the fly ash in the mixture compositions investigated.







TABLE 38







Geopolymer compositions of Example 14











Raw Material
Mix 1
Mix 2
Mix 3
Mix 4














Fly Ash Class C (grams)1
5217
4615
4138
3750


Calcium Sulfate Dihydrate2
261
462
621
750


(grams)


Calcium Aluminate Cement3
522
923
1241
1500


(grams)



Total Cementitious Materials
6000
6000
6000
6000


(grams)


Sand (grams)4
6900
6900
6900
6900


Potassium Citrate Tribasic
120
120
120
120


Monohydrate (grams)


Superplasticizer (grams)5
30
30
30
30


Citric Acid Anhydrous
30
30
30
30


Sodium Gluconate
15
15
15
15


Defoamer and Wetting Agent6
12
12
12
12


Rheology Modifier7
0.36
0.36
0.36
0.36


Smectite Clay8
0.60
0.60
0.60
0.60


Colorant9
4.5
4.5
4.5
4.5


Water (grams)
1800
1800
1800
1800


Water/Cementitious Materials
0.30
0.30
0.30
0.30


Ratio


Sand/Cementitious Materials Ratio
1.15
1.15
1.15
1.15


Superplasticizer/Cementitious
0.5% 
0.5% 
0.5% 
0.5% 


Materials, wt %


Potassium Citrate/Cementitious
 2%
 2%
 2%
 2%


Materials, wt %


Calcium Aluminate Cement/Fly
10%
20%
30%
40%


ash, wt %


Calcium Sulfate/Calcium
50%
50%
50%
50%


Aluminate Cement, wt %





1Class C Fly Ash, Campbell Power Plant, West Olive, MI


2USG Terra Alba Filler


3Ternal EV, Kerneos Inc.


4QUIKRETE Commercial Grade Fine Sand No. 1961


5BASF CASTAMENT FS20


6SURFYNOL 500S


7MOMENTIVE AXILAT RH 100 XP


8BENTONE CT HECTORITE clay


9Yipin Black S350M Iron Oxide Pigment






Slump Behavior and Early Age Cracking Behavior of Material
TABLE 39 shows the slump behavior of the geopolymer cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate dihydrate, and alkali citrate in Example 14.







TABLE 39







Flow and Slump of Example 14









Slump (inches)














Mix 1
67⁄8′′



Mix 2
83⁄8′′



Mix 3
83⁄4′′



Mix 4
81⁄2′′










All mixture compositions investigated had good fluidity as observed in the slump test.
The slump patties for all four mixes comprising fine-grained calcium sulfate dihydrate were in excellent condition and did not develop any cracking.
Shrinkage Behavior
FIG. 13 shows shrinkage behavior of geopolymer cementitious compositions of the invention in Example 14. The shrinkage measurements were initiated at an age of 4-hours from the time the raw materials were mixed together to form an aqueous slurry. The material shrinkage was measured for a total duration of about 8-weeks while curing the material at 75° F./50% Relative Humidity (RH).
The following important conclusions can be drawn from this investigation:
Contrary to the shrinkage bars of comparative Example 4 (with no calcium sulfate) which cracked even before de-molding, the shrinkage bars of Example 14 comprising calcium aluminate cement, calcium sulfate dihydrate, and alkali citrate were completely stable and did not result in any cracks either prior to or after de-molding.
The geopolymer cementitious compositions of some embodiments of the invention comprising fly ash, calcium aluminate cement, calcium sulfate dihydrate, and alkali citrate has a maximum shrinkage between 0.04% to 0.08% in comparison to a maximum shrinkage of about 0.75% for the comparative mixture composition containing fly ash and alkali citrate only (Example 1).
The amount of maximum shrinkage decreased with increase in the amount of calcium aluminate cement in the composition. Mix 1 comprising calcium aluminate cement at 10 wt % of fly ash amount had a maximum shrinkage of about 0.08%; on the other hand, the Mix 3 comprising calcium aluminate cement at 30 wt % of fly ash amount had a maximum shrinkage of only about 0.05% and the Mix 4 comprising calcium aluminate cement at 40 wt % of fly ash amount had a maximum shrinkage of only about 0.04%.
Time of Setting
TABLE 40 shows the time of setting of geopolymer cementitious compositions of the invention investigated in Example 14.







TABLE 40







Setting Times of Example 14










Initial Setting Time (hr:min)
Final Setting Time (hr:min)













Mix 1
01:07
 1:09


Mix 2
01:07
01:11


Mix 3
01:08
01:16


Mix 4
01:09
01:15









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







TABLE 41







Compressive Strength of Example 14 (psi)













4 hour
24 hour
7 day
28 day
56 day


















Mix 1
569
910
2067
7479
8318



Mix 2
955
1527
2559
7793
9691



Mix 3
1318
2012
2704
5348
8636



Mix 4
1733
2494
2832
5239
7134










The example studied the influence of incorporation of calcium aluminate cement in combination with fine-grained calcium sulfate dihydrate on both the early age and ultimate compressive strength behavior of the developed geopolymer cementitious compositions of the invention. The following important observations can be drawn from this study:
The compressive strength of the geopolymer cementitious compositions of the invention investigated in this example continued to increase as a function of time. The 28-day compressive strengths of all geopolymer cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate dihydrate, and potassium citrate were exceptionally high and in excess of 5000 psi. Moreover, the 56-day compressive strengths of all geopolymer cementitious compositions of the invention were even greater and in excess of 7000 psi.
The Mix 2 comprising calcium aluminate cement at 20 wt % of fly ash amount yielded the highest ultimate compressive strength in excess of 9500 psi at the age of 56 days.
Example 15
This example depicts influence of different forms of calcium sulfates on the physical properties of the developed geopolymer cementitious compositions of the invention comprising fly ash, calcium aluminate cement, calcium sulfate, and an alkali citrate. Three different types of calcium sulfates were compared—calcium sulfate dihydrate, anhydrous calcium sulfate (anhydrite), and calcium sulfate dihydrate. TABLE 42 shows the raw material compositions of the geopolymer cementitious mixtures investigated in this Example. All mixtures contained calcium aluminate cement in which the main calcium aluminate phase was dodecacalcium hepta-aluminate (12CaO.7Al2O3 or C12A7). This calcium aluminate cement is commercially available with trade name TERNAL EV from Kerneos Inc. The amount of calcium aluminate cement used in the mixture compositions of this example was equal to 20 wt % of the weight of fly ash. The type of calcium sulfate contained in the various mixture compositions investigated in this example was as follows: calcium sulfate dihydrate in Mix 1, anhydrous calcium sulfate (anhydrite) in Mix 2, and calcium sulfate hemihydrate in Mix 3. All calcium sulfates were added at an amount equal to 50 wt % of the weight of calcium aluminate cement and 10 wt. % of the fly ash in the mixture compositions investigated.







TABLE 42







Geopolymer compositions of Example 15










Raw Material
Mix 1
Mix 2
Mix 3













Fly Ash Class C (grams)1
4615
4615
4615


Calcium Sulfate Dihydrate2 (grams)
462
—
—


Anhydrous Calcium Sulfate (Anhydrite)3
—
462
—


(grams)


Calcium Sulfate Hemihydrate4 (grams)
—
—
462


Calcium Aluminate Cement5 (grams)
923
923
923


Total Cementitious Materials (grams)
6000
6000
6000


Sand (grams)6
6900
6900
6900


Potassium Citrate Tribasic Monohydrate
120
120
120


(grams)


Superplasticizer (grams)7
30
30
30


Citric Acid Anhydrous
30
30
30


Sodium Gluconate
12
12
12


Defoamer and Wetting Agent8
15
15
15


Rheology Modifier9
0.36
0.36
0.36


Smectite Clay10
0.60
0.60
0.60


Colorant11
4.5
4.5
4.5


Water (grams)
1800
1800
1800


Water/Cementitious Materials Ratio
0.30
0.30
0.30


Sand/Cementitious Materials Ratio
1.15
1.15
1.15


Superplasticizer/Cementitious Materials,
0.5% 
0.5% 
0.5% 


wt %


Potassium Citrate/Cementitious
 2%
 2%
 2%


Materials, wt %


Calcium Aluminate Cement/Fly ash, wt %
20%
20%
20%


Calcium Sulfate/Calcium Aluminate
50%
50%
50%


Cement, wt %





1Class C Fly Ash, Campbell Power Plant, West Olive, MI


2USG Terra Alba Filler


3USG Snow White Filler


4USG Hydrocal C-Base


5Ternal EV, Kerneos Inc.


6QUIKRETE Commercial Grade Fine Sand No. 1961


7BASF CASTAMENT FS20


8SURFYNOL 500S


9MOMENTIVE AXILAT RH 100 XP


10BENTONE CT HECTORITE clay


11Yipin Black S350M Iron Oxide Pigment






Slump Behavior and Early Age Cracking Behavior of Material
TABLE 43 shows the slump behavior of the geopolymer cementitious compositions of the invention investigated in Example 15.







TABLE 43







Slump behavior of Example 15









Slump (inches)














Mix 1
83⁄8′′



Mix 2
111⁄4′′



Mix 3
101⁄2′′










All mixture compositions investigated had good fluidity as observed in the slump test. It is noteworthy that the mixture compositions with anhydrous calcium sulfate (Mix 2) and calcium sulfate hemihydrate (Mix 3) yielded better fluidity in comparison to the mix containing calcium sulfate dihydrate (Mix 1).
The slump patties for all three mixes comprising different forms of calcium sulfate were in excellent condition and did not develop any cracking.
Shrinkage Behavior
FIG. 14 shows shrinkage behavior of geopolymer cementitious compositions of the invention investigated in Example 15. The shrinkage measurements were initiated at an age of 4-hours from the time the raw materials were mixed together to form an aqueous slurry. The material shrinkage was measured for a total duration of about 8-weeks while curing the material at 75° F./50% Relative Humidity (RH).
The following important conclusions can be drawn from this investigation:
Contrary to the shrinkage bars of comparative Example 4 (with no calcium sulfate) which cracked before de-molding, the shrinkage bars of Example 15 comprising calcium aluminate cement, different forms of calcium sulfate, and alkali citrate were completely stable and did not result in any cracks prior to or after de-molding.
The geopolymer cementitious compositions of some embodiments of the invention comprising fly ash, calcium aluminate cement, different forms of calcium sulfate, and alkali citrate had a maximum shrinkage between 0.06% to 0.10% in comparison to a maximum shrinkage of about 0.75% for the comparative mixture composition containing fly ash and alkali citrate only (Example 1).
The amount of maximum shrinkage varied with the type of calcium sulfate in the composition. Mix 1 comprising calcium sulfate dihydrate and Mix 3 comprising calcium sulfate hemihydrate, had a lower maximum shrinkage of about 0.06% in comparison to Mix 3 comprising anhydrous calcium sulfate (anhydrite) that yielded a maximum shrinkage of about 0.10%
Time of Setting
TABLE 44 shows the time of setting of geopolymer cementitious compositions of the invention investigated in Example 15.







TABLE 44







Setting Times of Example 15










Initial Setting Time (hr:min)
Final Setting Time (hr:min)













Mix 1
01:07
01:11


Mix 2
00:33
00:42


Mix 3
00:45
00:55









All geopolymer cementitious compositions investigated in this example demonstrated a rapid setting behavior. The final setting times of the geopolymer cementitious compositions of the invention of this example ranged from about 42 minutes to about 71 minutes compared to an extremely rapid final setting time of about 15 minutes for the mixture composition containing fly ash and sodium citrate only (Example 1). It should be noted that an extremely short setting time can be problematic for some applications.
Time of setting of the geopolymer cementitious compositions of the invention depended upon the type of calcium sulfate employed as part of the mixture composition. The composition comprising anhydrous calcium sulfate (anhydrite) (Mix 2) yielded the fastest time of setting; on the hand, the other inventive composition (Mix 1) comprising calcium sulfate dihydrate provided the longest time of setting.
Compressive Strength
TABLE 45 shows the compressive strength behavior of the developed geopolymer cementitious compositions of the invention comprising different types of calcium sulfate investigated in Example 15.







TABLE 45







Compressive Strength of Example 15 (psi)













4 hour
24 hour
7 day
28 day
56 day


















Mix 1
955
1527
2559
7793
9691



Mix 2
1538
2363
3477
10522
11239



Mix 3
1064
1661
2585
7114
7605










This example studied the influence of incorporation of different types of calcium sulfate on both the early age and ultimate compressive strength behavior of the developed geopolymer cementitious compositions of the invention. The following important observations can be drawn from this study:
The compressive strength of the geopolymer cementitious compositions of the invention continued to increase as a function of time irrespective of the type of calcium sulfate used in the mixture.
Both the 28-day and 56-day compressive strengths of the geopolymer cementitious compositions of the invention comprising different types of calcium sulfate, fly ash, calcium aluminate cement, and potassium citrate were exceptionally high and in excess of 7000 psi.
Mix 2 comprising anhydrous calcium sulfate (anhydrite) had the fastest rate of compressive strength development and the highest ultimate compressive strength in comparison to the mixes with calcium sulfate dihydrate (Mix 1) and calcium sulfate hemihydrate (Mix 3).
The ultimate compressive strength of the geopolymer composition of the invention comprising anhydrous calcium sulfate (anhydrite) was in excess of 10,000 psi.
Examples 16
This example studies the physical properties of developed geopolymer cementitious compositions of this embodiment of the invention comprising fly ash, calcium aluminate cement, calcium sulfate hemihydrate with either an alkali metal hydroxide (sodium hydroxide) or a mixture of an alkali metal hydroxide (sodium hydroxide) and an alkali metal acid (citric acid).
TABLE 46 shows the raw material compositions of the geopolymer cementitious mixtures investigated in this example. All mixtures contained calcium aluminate cement in which the main calcium aluminate phase was dodecacalcium hepta-aluminate (12CaO.7Al2O3 or C12A7). This calcium aluminate cement is commercially available with trade name TERNAL EV from Kerneos Inc. The amount of calcium aluminate cement used in the mixture compositions of this example was equal to 20 wt % the weight of fly ash. One mix (Mix 2) investigated contained only sodium hydroxide as the chemical activator and no 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 mixes (Mix 1) contained only citric acid for chemical activation and no sodium hydroxide.







TABLE 46







Geopolymer compositions of Example 16












Raw Material
Mix 1
Mix 2
Mix 3
Mix 4
Mix 5















Fly Ash Class C (grams)1
4615
4615
4615
4615
4615


Calcium Sulfate Hemihydrate2 (grams)
462
462
462
462
462


Calcium Aluminate Cement3 (grams)
923
923
923
923
923


Total Cementitious Materials (grams)
6000
6000
6000
6000
6000


Sand (grams)4
6900
6900
6900
6900
6900


Sodium Hydroxide (grams)
0
60
60
60
60


Superplasticizer (grams)5
30
30
30
30
30


Citric Acid Anhydrous (grams)
60
0
30
60
120


Sodium Gluconate (grams)
15
15
15
15
15


Defoamer and Wetting Agent6 (grams)
12
12
12
12
12


Rheology Modifier7 (grams)
0.24
0.24
0.24
0.24
0.24


Colorant8 (grams)
4.5
4.5
4.5
4.5
4.5


Water (grams)
1800
1800
1800
1800
1800


Water/Cementitious Materials Ratio
0.30
0.30
0.30
0.30
0.30


Sand/Cementitious Materials Ratio
1.15
1.15
1.15
1.15
1.15


Superplasticizer/Cementitious Materials,
0.5% 
0.5% 
0.5% 
0.5% 
0.5% 


wt %


Calcium Aluminate Cement/Fly ash, wt %
20%
20%
20%
20%
20%


Calcium Sulfate/Calcium Aluminate
50%
50%
50%
50%
50%


Cement, wt %





1Class C Fly Ash, Campbell Power Plant, West Olive, MI


2USG Hydrocal C-Base


3Ternal EV, Kerneos Inc.


4QUIKRETE Commercial Grade Fine Sand No. 1961


5BASF CASTAMENT FS20


6SURFYNOL 500S


7MOMENTIVE AXILAT RH 100 XP


8Yipin Black S350M Iron Oxide Pigment






Slump Behavior
TABLE 47 shows the slump behavior of the geopolymer cementitious compositions of the invention investigated in Example 16.







TABLE 47







Slump behavior of Example 16









Slump (inches)














Mix 1
2′′



Mix 2
81⁄2′′



Mix 3
91⁄4′′



Mix 4
93⁄8′′



Mix 5
103⁄4′′










For Mix 1 containing citric acid but no sodium hydroxide, the mixer material was extremely stiff and completely unworkable upon mixing. On the other hand, mixture compositions containing sodium hydroxide (Mix 2) or a blend of sodium hydroxide and citric acid (Mix 3, Mix 4 and Mix 5), were easily workable as also indicated by their relatively large patty diameter in the slump test. This good workability was obtainable even at an extremely low water/cementitious materials ratio of about 0.30. For standard Portland cement based or gypsum based materials, such flow properties and self leveling behavior are only obtainable when the water/cementitious materials ratio is in excess of about 0.45.
Shrinkage Behavior
FIG. 15 shows shrinkage behavior of geopolymer cementitious compositions of the invention investigated in Example 16. The shrinkage measurements were initiated at an age of 4-hours from the time the raw materials were mixed together to form an aqueous slurry. The material shrinkage was measured for a total duration of about 8-weeks while curing the material at 75° F./50% Relative Humidity (RH).
The following important conclusions can be drawn from this investigation and FIG. 15:
Contrary to the shrinkage bars of comparative Example 4 (with no calcium sulfate) which cracked even before de-molding, the shrinkage bars of Example 16 comprising calcium aluminate cement, calcium sulfate hemihydrate, alkali metal hydroxide (with or without citric acid) were completely stable and did not result in any cracks either prior to or after de-molding.
The cementitious composition of the invention comprising sodium hydroxide only as a chemical activator (Mix 2) demonstrated a very low maximum shrinkage of about less than 0.05%. The cementitious compositions of the invention comprising a blend 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 about less than 0.10%. It is noteworthy that the cementitious compositions containing 1% sodium hydroxide and citric acid up to 1% (Mix 3 and Mix 4) had very low maximum shrinkage of about less than 0.05%. For Mix 5 containing 1% sodium hydroxide and 2% citric acid, the maximum shrinkage increased to about 0.08%.
Time of Setting
TABLE 48 shows the time of setting of geopolymer cementitious compositions of the invention investigated in Example 16.







TABLE 48







Setting Times of Example 16










Initial Setting Time (hr:min)
Final Setting Time (hr:min)













Mix 1
04:45
 5:22


Mix 2
01:52
02:14


Mix 3
01:54
02:52


Mix 4
01:00
01:07


Mix 5
00:56
01:02









All geopolymer cementitious compositions investigated in this example (Mix 2 though Mix 5) demonstrated a very rapid setting behavior with final setting times ranging from about 62 minutes to 172 minutes. In the case of Mix 1, with no sodium hydroxide, the final setting time was extremely long in excess of 5 hours. On the other hand, the mixes containing a blend of sodium hydroxide and citric acid (Mix 4 and Mix 5) yielded an extremely rapid setting behavior with final setting time of about 1 hour.
Compressive Strength
TABLE 49 shows the compressive strength behavior of the developed geopolymer cementitious compositions of the invention investigated in Example 16.







TABLE 49







Compressive Strength of Example 16 (psi)













4 hour
24 hour
7 day
28 day
56 day


















Mix 1
92
847
1171
1686
1946



Mix 2
701
1198
2440
3618
3797



Mix 3
846
1754
3952
6481
8233



Mix 4
953
1533
3480
5574
7941



Mix 5
139
1615
2943
7050
8429










The following important conclusions can be drawn from this study:
The cementitious composition without alkali metal base (sodium hydroxide) (Mix 1) yielded extremely poor compressive strength behavior. Both the early age and the ultimate compressive strength for this mix (Mix 1) were extremely low and significantly inferior to the geopolymer compositions of the invention comprising either sodium hydroxide (Mix 2) or a mixture of sodium hydroxide and citric acid (Mix 3 through Mix 5).
The 28-day compressive strengths of all geopolymer cementitious compositions of the invention comprising a mixture of sodium hydroxide and citric acid (Mix 3 through Mix 5) were exceptionally high and in excess of 5000 psi. Moreover, the 56-day compressive strengths of all geopolymer cementitious compositions of the invention comprising a mixture of sodium hydroxide and citric acid (Mix 3 through Mix 5) were even greater and in excess of 7500 psi.
Example 17
This example studies the physical properties of the developed geopolymer cementitious compositions of this embodiment of the invention comprising fly ash, calcium aluminate cement, calcium sulfate hemihydrate with either an alkali metal silicate (sodium silicate) or a mixture of an alkali metal silicate (sodium silicate) and an alkali metal acid (citric acid).
TABLE 50 shows the raw material compositions of the geopolymer cementitious mixtures investigated in this example. All mixtures contained calcium aluminate cement in which the main calcium aluminate phase was dodecacalcium hepta-aluminate (12CaO.7Al2O3 or C12A7). This calcium aluminate cement is commercially available with trade name TERNAL EV from Kerneos Inc. The amount of calcium aluminate cement used in the mixture compositions of this example was equal to 20 wt % the weight of fly ash. Mix 1 through Mix 3 contained 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.







TABLE 50







Geopolymer compositions of Example 17












Raw Material
Mix 1
Mix 2
Mix 3
Mix 4
Mix 5















Fly Ash Class C (grams)1
4615
4615
4615
4615
4615


Calcium Sulfate Hemihydrate2 (grams)
462
462
462
462
462


Calcium Aluminate Cement3 (grams)
923
923
923
923
923


Total Cementitious Materials (grams)
6000
6000
6000
6000
6000


Sand (grams)4
6900
6900
6900
6900
6900


Sodium Silicate (grams)
30
60
120
60
60


Superplasticizer (grams)5
30
30
30
30
30


Citric Acid Anhydrous (grams)
0
0
0
30
60


Sodium Gluconate (grams)
15
15
15
15
15


Defoamer and Wetting Agent6 (grams)
12
12
12
12
12


Rheology Modifier7 (grams)
0.24
0.24
0.24
0.24
0.24


Colorant8 (grams)
4.5
4.5
4.5
4.5
4.5


Water (grams)
1800
1800
1800
1800
1800


Water/Cementitious Materials Ratio
0.30
0.30
0.30
0.30
0.30


Sand/Cementitious Materials Ratio
1.15
1.15
1.15
1.15
1.15


Superplasticizer/Cementitious Materials,
0.5% 
0.5% 
0.5% 
0.5% 
0.5% 


wt %


Calcium Aluminate Cement/Fly ash, wt %
20%
20%
20%
20%
20%


Calcium Sulfate/Calcium Aluminate
50%
50%
50%
50%
50%


Cement, wt %





1Class C Fly Ash, Campbell Power Plant, West Olive, MI


2USG Hydrocal C-Base


3Ternal EV, Kerneos Inc.


4QUIKRETE Commercial Grade Fine Sand No. 1961


5BASF CASTAMENT FS20


6SURFYNOL 500S


7MOMENTIVE AXILAT RH 100 XP


8Yipin Black S350M Iron Oxide Pigment






Slump Behavior
TABLE 51 shows the slump behavior of the geopolymer cementitious compositions of the invention investigated in Example 17.







TABLE 51







Slump behavior of Example 17









Slump (inches)














Mix 1
113⁄4′′



Mix 2
115⁄8′′



Mix 3
10′′



Mix 4
97⁄8′′



Mix 5
77⁄8′′










The mixture compositions containing sodium silicate only (Mix 1 through Mix 3) or a blend of sodium silicate and citric acid (Mix 4 and Mix 5) were easily workable as indicated by their relatively large patty diameter in the slump test. Good workability was obtainable even at an extremely low water/cementitious materials ratio of about 0.30. For standard Portland cement based upon gypsum based materials, such flow properties and self leveling behavior are only obtainable when the water/cementitious materials ratio is in excess of about 0.45.
Shrinkage Behavior
FIG. 16 shows shrinkage behavior of geopolymer cementitious compositions of the invention investigated in Example 17. The shrinkage measurements were initiated at an age of 4-hours from the time the raw materials were mixed together to form an aqueous slurry. The material shrinkage was measured for a total duration of about 8-weeks while curing the material at 75° F./50% Relative Humidity (RH).
The following important conclusions can be drawn from this investigation and FIG. 16:
Contrary to the shrinkage bars of comparative Example 4 (with no calcium sulfate) which cracked before de-molding, the shrinkage bars of Example 17 comprising calcium aluminate cement, calcium sulfate hemihydrate, alkali metal silicate (with or without citric acid) were completely stable and did not result in any cracks prior to or after de-molding.
All geopolymer cementitious composition of the invention comprising either sodium silicate or a blend of sodium silicate and citric acid as a chemical activator demonstrated a very low maximum shrinkage of about less than 0.05%.
Time of Setting
TABLE 52 shows the time of setting of geopolymer cementitious compositions of the invention investigated in Example 17.







TABLE 52







Setting Times of Example 17










Initial Setting Time (hr:min)
Final Setting Time (hr:min)













Mix 1
>05:00
>05:00


Mix 2
>05:00
>05:00


Mix 3
>05:00
>05:00


Mix 4
>05:00
>05:00


Mix 5
 03:30
 03:45









All 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 through Mix 4 had a final setting time in excess of 5 hours. Mix 5 comprising a blend of sodium silicate and citric acid set fastest with a final setting time of about 3 hours and 45 minutes.
Compressive Strength
TABLE 53 shows the compressive strength behavior of the developed geopolymerementitious compositions of the invention investigated in Example 17.







TABLE 53







Compressive Strength of Example 17 (psi)













24 hour
7 day
14 day
28 day
56 day


















Mix 1
218
1733
3745
4622
5314



Mix 2
560
1326
3149
4526
5463



Mix 3
1562
2002
2895
3579
4223



Mix 4
1223
2185
2352
2587
4473



Mix 5
1759
2120
3046
3287
4303










The following important conclusions can be drawn from this study:
The cementitious composition without alkali metal base (sodium silicate) (Mix 1 of Example 16) yielded extremely poor compressive strength behavior. The ultimate compressive strength of the mixture compositions comprising either sodium silicate or a blend of sodium silicate and citric acid s a chemical activator was significantly superior to the compressive strength of the mixture in the absence of sodium silicate (Mix 1 of Example 16).
The ultimate compressive strengths of all geopolymer cementitious compositions of the invention investigated in this example comprising either sodium silicate or a blend of sodium silicate and citric acid were satisfactory and in excess of about 4000 psi.
Example 18
The objective of this example was to study the influence of blends of calcium aluminate cement and calcium sulfoaluminate cement on physical properties of the geopolymer cementitious compositions of the invention. TABLE 54 shows the raw material compositions of the geopolymer cementitious mixtures investigated in this Example. All mixtures contained calcium aluminate cement in which the main calcium aluminate phase was dodecacalcium hepta-aluminate (12CaO.7Al2O3 or C12A7). This calcium aluminate cement is commercially available with trade name TERNAL EV from Kerneos Inc. The Mix 2 through Mix 5 contained a blend of calcium aluminate cement and calcium sulfoaluminate cement. The calcium sulfoaluminate cement used was Fastrock 500 from the CTS Company. Mix 5 demonstrates the performance of the geopolymer composition of the invention comprising lithium carbonate.







TABLE 54







Geopolymer compositions of Example 18












Raw Material
Mix 1
Mix 2
Mix 3
Mix 4
Mix 5















Fly Ash Class C 1 (grams)
4615
4615.5
4138
3750
3750


Calcium Sulfate Hemihydrate2 (grams)
462
461.5
620
750
3750


Calcium Aluminate Cement3 (grams)
923
461.5
414
750
750


Calcium Sulfoaluminate Cement4 (grams)

461.5
828
750
750


Total Cementitious Materials (grams)
6000
6000
6000
6000
6000


Sand 5 (grams)
6900
6900
6900
6900
6900


Potassium Citrate Tribasic
120
120
120
120
120


Monohydrate (grams)


Superplasticizer 6 (grams)
30
30
30
30
30


Citric Acid Anhydrous
30
30
30
30
30


Sodium Gluconate
12
12
12
12
12


Defoamer and Wetting Agent7 (grams)
15
15
15
15
15


Rheology Modifier8 (grams)
0.36
0.36
0.36
0.36
0.36


Smectite Clay9 (grams)
0.60
0.60
0.60
0.60
0.60


Colorant10 (grams)
4.5
4.5
4.5
4.5
4.5


Lithium Carbonate (grams)
—
—
—
—
30


Water (grams)
1800
1800
1800
1800
1800


Water/Cementitious Materials Ratio
0.30
0.30
0.30
0.30
0.30


Sand/Cementitious Materials Ratio
1.15
1.15
1.15
1.15
1.15


Superplasticizer/Cementitious
0.5%  
0.5%  
0.5%  
0.5%  
0.5%  


Materials, wt %


Potassium Citrate/Cementitious
2%
2%
2%
2%
2%


Materials, wt %





1 Class C Fly Ash, Campbell Power Plant, West Olive, MI


2USG Hydrocal C-Base


3Ternal EV, Kerneos Inc.


4Fastrock 500, CTS Company


5 QUIKRETE Commercial Grade Fine Sand No. 1961


6 BASF CASTAMENT FS20


7SURFYNOL 500S


8MOMENTIVE AXILAT RH 100 XP


9BENTONE CT HECTORITE clay


10Yipin Black S350M Iron Oxide Pigment






Slump Behavior and Early Age Cracking Behavior of Material
TABLE 55 shows the slump behavior of the geopolymer cementitious compositions of the invention investigated in Example 18.







TABLE 55







Flow and Slump of Example 18









Slump (inches)














Mix 1
101⁄2′′



Mix 2
91⁄2′′



Mix 3
83⁄4′′



Mix 4
85⁄8′′



Mix 5
83⁄4′′










All mixture compositions investigated had good fluidity as observed in the slump test.
The slump patties for all five mixes were in excellent condition and did not develop any cracking.
Shrinkage Behavior
FIG. 17 shows shrinkage behavior of geopolymer cementitious compositions of the invention investigated in Example 18. The shrinkage measurements were initiated at an age of 4-hours from the time the raw materials were mixed together to form an aqueous slurry. The material shrinkage was measured for a total duration of about 8-weeks while curing the material at 75° F./50% Relative Humidity (RH).
The following important conclusions can be drawn from this investigation:
Contrary to the shrinkage bars of comparative Example 4 (with no calcium sulfate) which cracked even before de-molding, the shrinkage bars of Example 18 were completely stable and did not result in any cracks either prior to or after de-molding.
The geopolymer cementitious compositions of the embodiments of the invention investigated in this example had a maximum shrinkage less than 0.10% in comparison to a maximum shrinkage of about 0.75% for the comparative mixture composition containing fly ash and alkali citrate only (Example 1).
The results from this example also demonstrate that the geopolymer cementitious compositions of the invention comprising different blends of calcium aluminate cement and calcium sulfoaluminate cement are capable of providing excellent dimensional stability with extremely low shrinkage.
Time of Setting
TABLE 56 shows the time of setting of geopolymer cementitious compositions of the invention investigated in Example 18.







TABLE 56







Setting Times of Example 18










Initial Setting Time (hr:min)
Final Setting Time (hr:min)













Mix 1
00:52
 1:06


Mix 2
01:33
01:45


Mix 3
01:35
01:53


Mix 4
01:36
01:46


Mix 5
02:04
02:30









All geopolymer cementitious compositions investigated in this example had a rapid setting behavior. The final setting times of the geopolymer cementitious compositions of the invention of this example ranged from about 66 minutes to about 150 minutes compared to an extremely rapid final setting time of about 15 minutes for the mixture composition containing fly ash and sodium citrate only (Example 1). It must be noted that an extremely short setting time is problematic for most practical applications.
The results from this example also demonstrate that the geopolymer cementitious compositions of the invention comprising different blends of calcium aluminate cement and calcium sulfoaluminate cement are capable of providing a rapid setting behavior while maintaining a sufficiently long open time.
Comparison of results for Mix 4 and Mix 5 clearly demonstrates that addition of lithium carbonate has an effect of increasing the time of setting of some embodiments of the geopolymer compositions of this invention. This result is very surprising and unexpected in that the lithium salt (lithium carbonate) is observed to act as a retarder in some embodiments of this invention. It should be noted that this observed behavior is contrary to what is well known in the art on the effect of lithium salts such as lithium carbonate on the setting behavior of the calcium aluminate cement based binder systems. The present state-of-the-art on calcium aluminate cements teaches that lithium salts such as lithium carbonate act as set accelerators thus reducing the initial and final time of setting of the material. The present finding as shown in this example teaches away from what is well known in the art and establishes that lithium salts such as lithium carbonate have a retarding effect on the early stages of the reaction (the initial and final time of setting) of some embodiments of the geopolymer cementitious compositions of the invention.
Compressive Strength
TABLE 57 shows the compressive strength behavior of the developed geopolymer cementitious compositions of the invention investigated in Example 18.







TABLE 57







Compressive Strength of Example 18 (psi)












4 hour
24 hour
7 day
28 day

















Mix 1
965
1521
2369
6966



Mix 2
1158
2353
2244
3388



Mix 3
835
2590
3664
5057



Mix 4
2149
3387
4769
5935



Mix 5
1441
5597
7757
8267










The following important observations can be drawn from this study:
The results from this example demonstrate that the geopolymer cementitious compositions of the invention comprising different blends of calcium aluminate cement and calcium sulfoaluminate cement are capable of providing a rapid a rate of compressive strength development. The rate of strength development can be tailored by adjusting the amount of calcium aluminate cement and calcium sulfoaluminate cement and their relative proportion in the geopolymer cementitious compositions of the invention.
The compressive strength of the geopolymer cementitious compositions of the invention investigated in this example continued to increase as a function of time. The 28-day compressive strengths of some embodiments of geopolymer cementitious compositions of the invention were exceptionally high providing results in excess of 5000 psi.
The time of setting and compressive strength results for Mix 5 are again very surprising and unexpected. Comparing the time of setting and compressive strength results for Mix 4 and Mix 5 at various ages, it can be observed and concluded that during the early stages of hydration reaction the lithium carbonate acts as a set retarder thus increasing the initial and final time of setting of some embodiments of geopolymer cementitious compositions of this invention; on the other hand, during the later stages of hydration reaction, the same (lithium carbonate) acts as an accelerator thus increasing the rate of strength development and ultimate strength of some embodiments of geopolymer cementitious compositions of this invention.
Example 19
The objective of this example was to study the influence of addition of a lithium salt on setting behavior of the geopolymer cementitious compositions of the invention. TABLE 58 shows the raw material compositions of the geopolymer cementitious mixtures investigated in this Example. All mixtures contained calcium aluminate cement in which the main calcium aluminate phase was dodecacalcium hepta-aluminate (12CaO.7Al2O3 or C12A7). This calcium aluminate cement is commercially available with trade name TERNAL EV from Kerneos Inc. The Mix 2 and Mix 3 contained a lithium salt in the form of lithium carbonate.







TABLE 58







Geopolymer compositions of Example 19










Raw Material
Mix 1
Mix 2
Mix 3













Fly Ash Class C 1 (grams)
4615
4615
4615


Calcium Sulfate Hemihydrate2 (grams)
462
462
462


Calcium Aluminate Cement3 (grams)
923
923
923


Total Cementitious Materials (grams)
6000
6000
6000


Sand4 (grams)
6900
6900
6900


Potassium Citrate Tribasic Monohydrate (grams)
120
120
120


Superplasticizer 5 (grams)
30
30
30


Citric Acid Anhydrous
30
30
30


Sodium Gluconate
12
12
12


Defoamer and Wetting Agent6 (grams)
15
15
15


Rheology Modifier7 (grams)
0.36
0.36
0.36


Smectite Clay8 (grams)
0.60
0.60
0.60


Colorant9 (grams)
4.5
4.5
4.5


Lithium Carbonate (grams)
—
30
60


Water (grams)
1800
1800
1800


Water/Cementitious Materials Ratio
0.30
0.30
0.30


Sand/Cementitious Materials Ratio
1.15
1.15
1.15


Superplasticizer/Cementitious Materials, wt %
0.5%  
0.5%  
0.5%  


Potassium Citrate/Cementitious Materials, wt %
2%
2%
2%





1 Class C Fly Ash, Campbell Power Plant, West Olive, MI


2USG Hydrocal C-Base


3Ternal EV, Kerneos Inc.


4QUIKRETE Commercial Grade Fine Sand No. 1961


5 BASF CASTAMENT FS20


6SURFYNOL 500S


7MOMENTIVE AXILAT RH 100 XP


8BENTONE CT HECTORITE clay


9Yipin Black S350M Iron Oxide Pigment






Time of Setting
TABLE 59 shows the time of setting of geopolymer cementitious compositions of the invention investigated in Example 19.







TABLE 59







Setting Times of Example 19










Initial Setting Time
Final Setting Time



(hr:min)
(hr:min)















Mix 1
00:42
 1:15



Mix 2
01:18
01:31



Mix 3
02:02
02:12










All geopolymer cementitious compositions investigated in this example had a rapid setting behavior. The final setting times of the geopolymer cementitious compositions of the invention of this example ranged from about 75 minutes to about 132 minutes compared to an extremely rapid final setting time of about 15 minutes for the mixture composition containing fly ash and sodium citrate only (Example 1). It must be noted that an extremely short setting time is problematic for most practical applications.
The results from this example clearly demonstrate that addition of lithium carbonate has an effect of increasing the time of setting of some embodiments of this invention. This result is very surprising and unexpected in that the lithium salt (lithium carbonate) is observed to act as a retarder in some embodiments of this invention. It should be noted that this observed behavior is contrary to what is well known in the art on the effect of lithium salts such as lithium carbonate on the setting behavior of the calcium aluminate cement based binder systems. The present state-of-the-art on calcium aluminate cements teaches that lithium salts such as lithium carbonate act as set accelerators thus reducing the initial and final time of setting of the material. The present finding as shown in this example teaches away from what is well known in the art and establishes that lithium salts such as lithium carbonate have a retarding effect on the early stages of the reaction (the initial and final time of setting) of some embodiments of the geopolymer cementitious compositions of the invention.
The geopolymer compositions of some preferred embodiments of the invention shown in the examples have application in a number of commercial products. In particular the compositions can be used for; Road repair and road patch products, traffic bearing surfaces and pavements, as shown by some properties disclosed in examples 5, 6, 9, 10, 14, 15, 16, 18 and 19; Bricks and synthetic stones, as shown by some properties disclosed in examples 5, 6, 9, 12 and 14; Repair materials for wall, floors and ceiling and Bonding mortars, plasters and surfacing materials, as shown by some properties disclosed in examples 9, 10, 11, 14, 18, and 19; Roofing materials, as shown by some properties in examples 5, 6, 14 and 18; Shotcrete products which are sprayed cementitious products used for soil and rock stabilization and as lining materials, as shown by some properties disclosed in examples 5, 6, 7, 9 and 15; Weight bearing structures, as shown by some properties disclosed in examples 8, 10, 13, 14, 15, 16, 17, and 18; Statuaries and architectural moldings, as shown by some properties disclosed in examples 5-19; and Self leveling underlayments, as shown by some properties disclosed in examples 9, 10, and 12-19.
Although we have described the preferred embodiments for implementing our invention, it will be understood by those skilled in the art to which this disclosure is directed that modifications and additions may be made to our invention without departing from its scope.

## Claims

1. An aluminosilicate geopolymer cementitious composition for bridge decks and overlays, road repair and road patch comprising a reaction product of:
a cementitious reactive powder comprising:
about 35 to about 96% by weight a thermally activated aluminosilicate mineral comprising Class C fly ash;
about 9 to about 45% by weight a calcium aluminate cement; and
about 1 to about 45% by weight a calcium sulfate selected from the group consisting of calcium sulfate dihydrate, calcium sulfate hemihydrate, anhydrous calcium sulfate and mixtures thereof; and

a chemical activator selected from at least one member selected from the group consisting of alkali metal citrates in an amount equal to about 1.0 to about 6.0% by weight based on total weight of the cementitious reactive powder; and
at least one member of the group consisting of superplasticizers, air entraining agents, defoaming agents, organic rheology control agents, and film-forming polymers; and
water;
wherein the reaction product is formed from calcium sulfate with an average particle size from about 1 to about 100 microns.

2. The composition of claim 1, wherein the cementitious reactive powder contains calcium sulfate dihydrate; wherein the calcium sulfate dihydrate has an average particle size of about 1 to about 30 microns.

3. The composition of claim 1, wherein the chemical activator is present in an amount equal to about 1.25 to 4.00% by weight based on total weight of the cementitious reactive powder, wherein the chemical activator is selected from at least one member of the group consisting of sodium citrate and potassium citrate, and the cementitious reactive powder comprises about 35 to about 96% by weight Class C fly ash.

4. The composition of claim 1, wherein the calcium sulfate comprises calcium sulfate hemihydrate.

5. The composition of claim 1, wherein the composition comprises the air entraining agent in an amount of about 0.01 to about 1 wt. % of the weight of the aluminosilicate geopolymer cementitious composition.

6. The composition of claim 1, wherein the composition comprises at least one said organic rheology control agent.

7. The composition of claim 6, wherein said at least one rheology control agent comprises a biopolymer.

8. The composition of claim 1,
wherein the cementitious reactive powder comprises about 10% to about 36% by weight calcium aluminate cement,
wherein the chemical activator is selected from at least one member of the group consisting of sodium citrate and potassium citrate,
wherein the cementitious reactive powder comprises about 35 to about 96% by weight Class C fly ash,
wherein calcium sulfate dihydrate is present in an amount equal to 5 to 30 wt. % of the total of the fly ash and calcium aluminate cement, and
wherein the composition comprises said superplasticizer.

9. The composition of claim 1, wherein the cementitious reactive powder contains anhydrous calcium sulfate, wherein the anhydrous calcium sulfate has an average particle size of about 1 to about 20 microns.

10. The composition of claim 1, wherein the reaction product is formed from
the water;
the cementitious reactive powder comprising:
about 40% to about 85% by weight thermally activated aluminosilicate mineral, wherein the thermally activated aluminosilicate mineral comprises about 75 parts to about 100 parts Class C fly ash per 100 parts thermally activated aluminosilicate mineral;
about 9% to about 40% by weight calcium aluminate cement, and
about 3.0% to about 24% by weight calcium sulfate; and

about 1.25 to 4.00% by weight said chemical activator based on weight of the cementitious reactive powder.

11. The composition of claim 1, wherein the reaction product is formed from
the water;
the cementitious reactive powder comprising:
about 50% to about 80% by weight thermally activated mineral, wherein said thermally activated mineral comprises about 75 parts to about 100 parts Class C fly ash per 100 parts thermally activated aluminosilicate mineral,
about 10% to about 36% by weight calcium aluminate cement, and
about 5.0% to about 18% by weight calcium sulfate; and

about 1.25 to 4.00% by weight said chemical activator based on weight of the cementitious reactive powder, said chemical activator selected from at least one member of the group consisting of sodium citrate and potassium citrate.

12. The composition of claim 1, wherein the composition has an absence of Portland cement.

13. The composition of claim 1, wherein the cementitious reactive powder has less than about 15% by weight Portland cement.

14. The composition of claim 1, wherein the weight ratio of water to the cementitious reactive powder is about 0.15 to about 0.4 and the cementitious reactive powder has at most 5 wt. % Portland cement.

15. A settable composition for forming an aluminosilicate geopolymer cementitious composition when reacted in water, comprising
a settable mixture of:
a cementitious reactive powder comprising:
about 35 to about 96% by weight of a thermally activated aluminosilicate mineral comprising Class C fly ash;
about 9 to about 45% by weight of a calcium aluminate cement;
about 1 to about 45% by weight of a calcium sulfate selected from the group consisting of calcium sulfate dihydrate, calcium sulfate hemihydrate, anhydrous calcium sulfate and mixtures thereof; and

a chemical activator selected from the group consisting of alkali metal citrates in an amount equal to about 1.0 to about 6.0% by weight based on total weight of the cementitious reactive powder; and
at least one member of the group consisting of superplasticizers, air entraining agents, defoaming agents, organic rheology control agents, and film-forming polymers; and
wherein the reaction product is formed from calcium sulfate with an average particle size from about 1 to about 100 microns.

16. The aluminosilicate geopolymer composition formed from the reaction of the mixture of claim 15 with water,
wherein the weight ratio of the water to cementitious reactive powder is about 0.15 to about 0.4,
wherein the cementitious reactive powder comprises about 35 to about 96% by weight Class C fly ash,
wherein the cementitious reactive powder has at most 5 wt. % Portland cement,
wherein the alkali metal citrate is selected from at least one member of the group consisting of potassium citrate sodium and citrate.

17. The composition of claim 1 forming a repair material for traffic bearing surfaces.

18. A method of preparing the aluminosilicate geopolymer cementitious composition of claim 1, comprising:
reacting the thermally activated aluminosilicate mineral, the calcium aluminate cement, the calcium sulfate selected from the group consisting of calcium sulfate dihydrate, calcium sulfate hemihydrate, anhydrous calcium sulfate, and mixtures thereof, the chemical activator selected from the group consisting of the alkali metal citrates, the at least one member of the group consisting of superplasticizers, air entraining agents, defoaming agents, organic rheology control agents, and film-forming polymers; and the water.

19. The composition of claim 1, further comprising calcium sulfoaluminate cement.

20. The composition of claim 1, wherein the composition comprises a lithium salt in the form of lithium carbonate.

21. The composition of claim 1, wherein the reaction product is formed from
the water;
the cementitious reactive powder comprising:
about 45% to about 88% by weight Class C fly ash,
about 9% to about 41% by weight calcium aluminate cement, and
about 3.0% to about 24% by weight calcium sulfate; and

about 1.25 to 4.00% by weight said chemical activator based on weight of the cementitious reactive powder, said chemical activator selected from at least one member of the group consisting of sodium citrate and potassium citrate; and
the superplasticizer.