WO2013066561A1

WO2013066561A1 - Inorganic polymer compositions subjected to vibrations

Info

Publication number: WO2013066561A1
Application number: PCT/US2012/058847
Authority: WO
Inventors: Russell L. Hill
Original assignee: Boral Industries Inc.
Priority date: 2011-10-31
Filing date: 2012-10-05
Publication date: 2013-05-10

Abstract

Inorganic polymer products and methods for their preparation are described herein. The inorganic polymer products have a first surface and a cross section parallel to the first surface. The inorganic polymer products include inorganic polymer compositions comprising the reaction product of reactive powder, an activator, and optionally a retardant reacted in the presence of water and a filler having a bulk density of 20 lb/ft³ or less. The concentration of the filler adjacent the first surface of the product is greater than the concentration of the filler along the cross section of the product.

Description

Inorganic Polymer Compositions Subjected to Vibrations

CROSS-REFERENCE TO PRIORITY APPLICATIONS

This application claims priority to U.S. Provisional Application No. 61/553,558, filed

October 31, 2011, which is incorporated herein by reference in its entirety.

BACKGROUND

Certain building materials can be prepared from cementitious mixtures based on portland cement and can contain additives to enhance the properties of the materials. Fly ash is used in cementitious mixtures to provide enhanced durability and reduced permeability of the cementitious products. In addition to imparting improved performance properties, the use of fly ash is desirable because it is a recyclable product and would otherwise be a waste material. Furthermore, fly ash is less expensive than portland cement. Thus, there is a desire to provide high strength building products that are based on fly ash.

SUMMARY

Inorganic polymer products and methods for their preparation are described. The inorganic polymer products have a first surface and a cross section parallel to the first surface, and comprise an inorganic polymer composition. The inorganic polymer compositions include the reaction product of reactive powder, an activator, and optionally a retardant in the presence of water and a filler having a bulk density of 20 lb/ft³ or less (e.g., 15 lb/ft³ or less or 10 lb/ft³ or less). The reactive powder includes fly ash and less than 10% by weight portland cement. The concentration of the filler adjacent the first surface of the product is greater than a concentration of the filler along the cross section of the product. In some examples, the product includes gas bubbles adjacent to the first surface of the product. In some examples, the inorganic polymer composition further comprises a second filler having a bulk density of 30 lb/ft³ or greater.

In some embodiments, the inorganic polymer product has a core and a second surface opposing the first surface and the cross section can be adjacent the core. In these examples, the concentration of the filler adjacent the first surface and the concentration of the filler adjacent the second surface of the product can each be greater than the concentration of filler along the cross section. The density can gradually increase from the first surface and from the second surface to the core. In other embodiments, the cross section is adjacent a second surface of the inorganic polymer product opposing the first surface. In these examples, the density can gradually increase from the first surface to the second surface.

The fly ash can be present in an amount of greater than 85% based on the weight of reactive powder (e.g., greater than 90% by weight or greater than 95% by weight). In some examples, the fly ash includes a calcium oxide content of from 18% to 35% by weight (e.g., from 23% to 30% by weight). The fly ash present in the reactive powder can include Class C fly ash. In some examples, greater than 75%, greater than 85%, or greater than 95% of the fly ash comprises Class C fly ash. The reactive powder can further include portland cement in an amount of less than 10% by weight based on the weight of reactive powder. For example, the reactive powder can include less than 5% by weight or less, 3% by weight or less, or 1% by weight or less portland cement.

In some embodiments, the activator used to prepare the inorganic polymers can include citric acid and/or sodium hydroxide. In some examples, the activator is present in an amount of from 1.5% to 8.5% based on the weight of the reactive powder. Optionally, a retardant (e.g., borax, boric acid, gypsum, phosphates, gluconates, or a mixture of these) is included in the composition. The retardant can be present, for example, in an amount of from 0.4% to 7.5% based on the weight of the reactive powder. In some examples, the weight ratio of water to reactive powder is from 0.06: 1 to 0.25: 1 (e.g., 0.06: 1 to less than 0.15: 1). In some examples, the composition is substantially free from retardants.

The filler present in the inorganic polymer compositions can be expanded polystyrene. In some examples, the inorganic compositions further include a foaming agent and/or a blowing agent (e.g., aluminum powder, sodium perborate, hydrogen peroxide, or a mixture of these). The inorganic polymer compositions can further include aggregate, such as lightweight aggregate. The compositions can further include a water reducer, a plasticizer (e.g., clay or a polymer), or a pigment.

Also described are building materials including the compositions described herein. The building materials can be, for example, roofing tiles, ceramic tiles, synthetic stone, thin bricks, bricks, pavers, panels, or underlay.

Further described is a method of producing an inorganic polymer product, which includes mixing water, a filler having a bulk density of 20 lb/ft³ or less, and reactants, feeding the resulting mixture into a mold, and vibrating the mold to produce an inorganic polymer product. The reactants include a reactive powder comprising fly ash, an activator, and optionally a retardant. The inorganic polymer product has a first surface and a cross section parallel to said first surface. A concentration of the filler adjacent the first surface of the product is greater than a concentration of the filler along the cross section of the product.

The filler in these methods can include expanded polystyrene. In some methods, the mixing step further comprises mixing a foaming agent and/or a blowing agent (e.g., aluminum powder, sodium perborate, and/or hydrogen peroxide) with the water, filler, and reactants. In some examples, the mixing is performed for a mixing time of 15 seconds or less (e.g., from 2 seconds to 10 seconds). The mixing can be performed at ambient temperature. In some examples, the activator includes citric acid and sodium hydroxide. Optionally, the citric acid and sodium hydroxide are combined prior to mixing with the reactants.

The vibrating step can include vertically and/or horizontally vibrating the mold. The mold can be vertically vibrated at a frequency of 60 Hz or less and/or horizontally vibrated at a frequency of 10 Hz or less. In some examples, the vibrating is performed at ambient temperature. The vibrating step can result in the migration of gas bubbles in the direction of the first surface of the product.

The details of one or more embodiments are set forth in the description below. Other features, objects, and advantages will be apparent from the description and from the claims.

DETAILED DESCRIPTION

Inorganic polymer products and methods for their preparation are described herein. The inorganic polymer products have a first surface and a cross section parallel to the first surface. The inorganic polymer products comprise inorganic polymer compositions comprising the reaction product of a reactive powder, an activator, and optionally a retardant reacted in the presence of water and a filler having a bulk density of 20 lb/ft³ or less. The concentration of the filler adjacent the first surface of the product is greater than the concentration of the filler along the cross section of the product.

The reactive powder is a reactant used to form the inorganic polymer compositions described herein. The reactive powder for use in the reactions includes fly ash. Fly ash is produced from the combustion of pulverized coal in electrical power generating plants. Fly ash produced by coal-fueled power plants is suitable for use in reactive powder described herein. The fly ash can include Class C fly ash, Class F fly ash, or a mixture thereof. As such, the calcium content of the fly ash can vary. In exemplary compositions, the fly ash included in the reactive powder can have a calcium content, expressed as the oxide form (i.e., calcium oxide), of from 18% to 35% by weight. In some examples, the calcium oxide content of the fly ash is from 23% to 30% by weight.

In some examples, the majority of the fly ash present is Class C fly ash (i.e., greater than 50% of the fly ash present is Class C fly ash). In some examples, greater than 75%, greater than 85%, or greater than 95% of the fly ash present is Class C fly ash. For example, greater than 75%, greater than 76%, greater than 77%, greater than 78%, greater than 79%, greater than 80%, greater than 81%, greater than 82%, greater than 83%, greater than 84%, greater than 85%, greater than 86%, greater than 87%, greater than 88%, greater than 89%, greater than 90%, greater than 91%, greater than 92%, greater than 93%, greater than 94%, greater than 95%, greater than 96%, greater than 97%, greater than 98%, or greater than 99% of the fly ash present is Class C fly ash. In some embodiments, only Class C fly ash is used. In some embodiments, blends of Class C fly ash and Class F fly ash can be used, particularly if the overall CaO content is as discussed above.

Optionally, the majority of the fly ash present can be Class F fly ash (i.e., greater than 50% of the fly ash present is Class F fly ash). In some examples, greater than 75%, greater than 85%, or greater than 95% of the fly ash present is Class F fly ash. For example, greater than 75%, greater than 76%, greater than 77%, greater than 78%, greater than 79%, greater than 80%, greater than 81%, greater than 82%, greater than 83%, greater than 84%, greater than 85%, greater than 86%, greater than 87%, greater than 88%, greater than 89%, greater than 90%, greater than 91%, greater than 92%, greater than 93%, greater than 94%, greater than 95%, greater than 96%, greater than 97%, greater than 98%, or greater than 99% of the fly ash present is Class F fly ash. In some embodiments, only Class F fly ash is used.

The fly ash used in the reactive powder can be a fine fly ash. The use of a fine fly ash provides a higher surface area. As used herein, fine fly ash refers to fly ash having an average particle size of 25 microns or less. The average particle size for the fly ash can be from 5 microns to 25 microns, or from 10 microns to 20 microns.

Optionally, the fly ash is the principal component of the reactive powder. In some examples, the fly ash is present in an amount of greater than 85% by weight of the reactive powder, greater than 90% by weight of the reactive powder, or greater than 95% by weight of the reactive powder. For example, the fly ash can be present in an amount of greater than 85% by weight, greater than 86% by weight, greater than 87% by weight, greater than 88% by weight, greater than 89% by weight, greater than 90% by weight, greater than 91% by weight, greater than 92% by weight, greater than 93% by weight, greater than 94% by weight, greater than 95% by weight, greater than 96% by weight, greater than 97% by weight, greater than 98% by weight, or greater than 99% by weight based on the weight of the reactive powder.

The reactive powder for use as a reactant to form the inorganic polymer compositions can further include cementitious components, including portland cement, calcium aluminate cement, and/or slag. Optionally, portland cement can be included as a component of the reactive powder. Suitable types of portland cement include, for example, Type I ordinary portland cement (OPC), Type II OPC, Type III OPC, Type IV OPC, Type V OPC, low alkali versions of these portland cements, and mixtures of these portland cements. In these examples, less than 10% by weight of portland cement is included in the reactive powder. In some examples, the reactive powder includes less than 5% by weight, less than 3% by weight, or less than 1% by weight of portland cement. For example, the reactive powder can include portland cement in an amount of less than 10% by weight, less than 9% by weight, less than 8% by weight, less than 7% by weight, less than 6% by weight, less than 5% by weight, less than 4% by weight, less than 3% by weight, less than 2% by weight, less than 1% by weight, or less than 0.5% by weight. In some examples, the reactive powder is substantially free from portland cement. For example, the reactive powder can include less than 0.1% by weight, less than 0.01% by weight, or less than 0.001% by weight of portland cement based on the weight of the reactive powder. In some embodiments, the reactive powder includes no portland cement.

Optionally, calcium aluminate cement (i.e., high aluminate cement) can be included in the reactive powder. In some examples, the calcium aluminate cement is present in an amount of 5% or less by weight of the reactive powder. For example, the reactive powder can include calcium aluminate cement in an amount of 5% or less, 4% or less, 3% or less, 2% or less, 1% or less, 0.9% or less, 0.8% or less, 0.7% or less, 0.6% or less, 0.5% or less, 0.4% or less, 0.3% or less, 0.2% or less, or 0.1% or less by weight. In some examples, the reactive powder can include calcium aluminate cement in an amount of from 0.5% to 5%, from 1% to 4.5%, or from 2% to 4% by weight. The calcium aluminate cement can be used, in some examples, in compositions that include less than 3% hydrated or semihydrated forms of calcium sulfate (e.g., gypsum). In some examples, the reactive powder is substantially free from calcium aluminate cement or includes no calcium aluminate cement. The reactive powder can also include a ground slag such as blast furnace slag in an amount of 10% or less by weight. For example, the reactive powder can include slag in an amount of 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, or 1% or less by weight.

The reactive powder can also include calcium sources such as limestone (e.g., ground limestone), quicklime, slaked lime, or hydrated lime in an amount of 10% or less by weight of the reactive powder. For example, limestone can be present in an amount of 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, or 1% or less by weight of the reactive powder.

The reactive powder can also include a tricalcium aluminate additive. As would be understood by those skilled in the art, tricalcium aluminate is present in a small amount in Portland cement. The tricalcium aluminate would be present as an additive, wherein the tricalcium aluminate is not a portland cement constituent. The tricalcium aluminate additive can be present in an amount of from 0.1% to 10% by weight, or 1% to 5% of the reactive powder.

Anhydrous calcium sulfate can be optionally included as an additional reactant used to form the inorganic polymer compositions described herein. The anhydrous calcium sulfate can be present as a reactant in an amount of 0.1% by weight or greater based on the weight of the reactive powder and has been found to increase the compressive strength of the inorganic polymer products. In some examples, the anhydrous calcium sulfate can be present in an amount of from 1% to 10%, 2% to 8%, 2.5% to 7%, or 3 % to 6% by weight of the reactive powder. For example, the amount of anhydrous calcium sulfate can be 0.5% or greater, 1% or greater, 1.5% or greater, 2% or greater, 2.5% or greater, 3% or greater, 3.5% or greater, 4% or greater, 4.5% or greater, or 5% or greater based on the weight of the reactive powder.

An activator is a further reactant used to form the inorganic polymer compositions described herein. The activator allows for rapid setting of the inorganic polymer compositions and also imparts compressive strength to the compositions. The activator can include one or more of acidic, basic, and/or salt components. For example, the activator can include citrates, hydroxides, metasilicates, carbonates, aluminates, sulfates, and/or tartrates. The activator can also include other multifunctional acids that are capable of complexing or chelating calcium ions (e.g., EDTA). Specific examples of suitable citrates for use as activators include citric acid and its salts, including, for example, sodium citrate and potassium citrate. Specific examples of suitable tartrates include tartaric acid and its salts (e.g., sodium tartrate and potassium tartrate). In some examples, the activator can include alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide. Further examples of suitable activators include metasilicates (e.g., sodium metasilicate and potassium metasilicate); carbonates (e.g., sodium carbonate and potassium carbonate); aluminates (e.g., sodium aluminate and potassium aluminate); and sulfates (e.g., sodium sulfate and potassium sulfate). In some examples, the activator includes citric acid, tartaric acid, or mixtures thereof. In some examples, the activator includes sodium hydroxide. In some examples, the activator includes a mixture of citric acid and sodium hydroxide. In examples including a mixture of citric acid and sodium hydroxide, the weight ratio of citric acid present in the mixture to sodium hydroxide present in the mixture is from 0.4: 1 to 2.0: 1, 0.6: 1 to 1.9: 1, 0.8: 1 to 1.8: 1, 0.9: 1 to 1.7: 1, or 1.0: 1 to 1.6: 1. The activator components can be pre- mixed prior to being added to the other reactive components in the inorganic polymer or added separately to the other reactive components. For example, citric acid and sodium hydroxide could be combined to produce sodium citrate and the mixture can include possibly one or more of citric acid and sodium hydroxide in stoichiometric excess. In some embodiments, the activator includes a stoichiometric excess of sodium hydroxide. The total amount of activators can include less than 95% by weight of citrate salts. For example, the total amount of activator can include from 25-85%, 30-75%, or 35-65% citrate salts by weight. The mixture in solution and the mixture when combined with reactive powder can have a pH of from 12 to 13.5 or about 13.

The activator can be present as a reactant in an amount of from 1.5% to 8.5% dry weight based on the weight of the reactive powder. For example, the activator can be present in an amount of from 2% to 8%, from 3% to 7%, or from 4% to 6%. In some examples, the activator can be present in an amount of 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% or 8.5% dry weight based on the weight of the reactive powder. For example, when sodium hydroxide and citric acid are used as the activators, the amount of sodium hydroxide used in the activator solution can be from 0.3 to 15.6, 0.5 to 10, 0.75 to 7.5, or 1 to 5 dry parts by weight based on the weight of reactive powder and the amount of citric acid used in the activator solution can be from 0.25 to 8.5, 0.5 to 0.7, 0.75 to 0.6, or 1 to 4.5 dry parts by weight based on the weight of reactive powder. The resulting activator solution can include sodium citrate and optionally one or more of citric acid or sodium hydroxide.

The activator can be provided, for example, as a solution. In some examples, the activator can be provided in water as an aqueous solution in a concentration of from 10% to 50% or from 20% to 40% based on the weight of the solution. For example, the concentration of the activator in the aqueous solution can be from 25% to 35% or from 28% to 32% based on the weight of the solution. Examples of suitable concentrations for the activator in the aqueous solution include 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% based on the weight of the solution.

The reactants used to form the inorganic polymer compositions can further include a retardant. Retardants are optionally included to prevent the composition from stiffening too rapidly, which can result in a reduction of strength in the structure. Examples of suitable retardants for inclusion as reactants include borax, boric acid, gypsum, phosphates, gluconates, or a mixture of these. The retardant can be provided in solution with the activator (e.g., borax or boric acid) and/or can be provided as an additive with the reactive powder (e.g., gypsum). In some examples, the retardant is present in an amount of from 0.4% to 7.5% based on the weight of the reactive powder. For example, the retardant can be present in an amount of from 0.5% to 5%, 0.6% to 3%, 0.7 to 2.5%, or 0.75% to 2.0% based on the weight of the reactive powder. In some embodiments, when gypsum is used as a retardant, it is used in an amount of 3% by weight or less based on the weight of the reactive powder. In some embodiments, borax is used as the retardant. When citric acid and sodium hydroxide are used as the activators, the weight ratio of borax to sodium hydroxide can be 0.3: 1 to 1.2: 1 (e.g., 0.8: 1 to 1.0: 1). In some examples, lower ratios of 0.3: 1 to 0.8: 1 can be the result of including an additional retardant such as gypsum. In some examples, the composition is substantially free from retardants or includes no retardants.

The reactants described herein can optionally include less than 3.5% by weight of additional sulfates. As would be understood by those skilled in the art, sulfates are present in the fly ash. Thus, "additional sulfates" refers to sulfates other than those provided by the fly ash. In some examples, the composition can include less than 3.5% by weight of sulfates based on the amount of reactive powder other than those provided by the fly ash. For example, the composition can include less than 3.5% by weight, less than 3% by weight, less than 2.5% by weight, less than 2% by weight, less than 1.5% by weight, less than 1% by weight, or less than 0.5% by weight of sulfates based on the amount of reactive powder other than those provided by the fly ash. In some examples, the composition is substantially free from additional sulfates. For example, the composition can include less than 0.1% by weight, less than 0.01% by weight, or less than 0.001% by weight of additional sulfates based on the amount of reactive powder. In some embodiments, the composition includes no additional sulfates. When present, the additional sulfates can be provided in the form of gypsum (i.e., calcium sulfate dihydrate). As described above, gypsum can be present in the composition as a retardant. In some examples, the composition includes gypsum in an amount of less than 3.5% by weight based on the amount of reactive powder. For example, the composition can include gypsum in an amount of less than 3.5% by weight, less than 3% by weight, less than 2.5% by weight, less than 2% by weight, less than 1.5% by weight, less than 1% by weight, or less than 0.5% by weight.

The inorganic polymer compositions described herein can optionally be prepared in the presence of blowing agents. Blowing agents can be included in the compositions to produce a gas and generate a foamed composition. Examples of suitable blowing agents include aluminum powder, perborates (e.g., sodium perborate), peroxides (e.g., ¾(¾ or an organic peroxide), and chloride dioxide. The blowing agent can be present in an amount of from 0.1% to 10% by weight of the reactive powder. In some examples, the blowing agents can be included in the compositions in an amount of from 0.5% by weight to 9% by weight, from 1% by weight to 8% by weight, or from 2% by weight to 7% by weight. In some examples, the blowing agents can be included in the compositions in an amount of from 0.5% to 5% by weight of the reactive powder. For example, the composition can include blowing agents in an amount of 10% by weight or less, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, 1% by weight or less, or 0.5% by weight or less based on the weight of the reactive powder.

Optionally, the inorganic polymer compositions described herein can be prepared in the presence of foaming agents. Foaming agents, such as air-entraining agents, can be used to help the system maintain air or other gases, e.g., from the mixing process in the composition. The foaming agents can include non-ionic surfactants, anionic surfactants, and/or cationic surfactants. In some embodiments, the foaming agents are non-ionic surfactants. Examples of suitable foaming agents include sodium alkyl ether sulfate, ammonium alkyl ether sulfate, sodium alpha olefin sulfonate, sodium deceth sulfate, ammonium deceth sulfate, sodium laureth sulfate, and sodium dodecylbenzene sulfonate. The foaming agents can be provided in an amount of 0.1% or less based on the weight of the reactive powder. In some examples, the foaming agents can be included in the compositions in an amount of from 0.5% by weight to 9% by weight, from 1% by weight to 8% by weight, or from 2% by weight to 7% by weight. In some examples, the foaming agents can be included in the compositions in an amount of from 0.5% to 5% by weight of the reactive powder. For example, the composition can include foaming agents in an amount of 10% by weight or less, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, 1% by weight or less, or 0.5% by weight or less based on the weight of the reactive powder.

The reactants are provided in the reactive mixture in the presence of water. The water can be provided in the reactive mixture by providing the activator and optionally the retardant in solution and/or by adding water directly to the reactive mixture. The solution to binder or solution to reactive powder weight ratio (i.e., the ratio of the solution including activator and optionally the retardant to reactive powder) can be from 0.12: 1 to 0.5: 1, depending on the product being made and the process being used for producing the product. The water to reactive powder (or water to binder) weight ratio can be from 0.06: 1 to 0.4: 1, depending on the product being made and the process being used for producing the product. In some embodiments, the water to binder ratio can be from 0.06: 1 to 0.25: 1, from 0.09: 1 to less than 0.15: 1, or from 0.095:1 to less than 0.14:1 (e.g., less than 0.10:1). For example, the water to binder ratio can be from 0.06: 1 to less than 0.15: 1. In some embodiments, the water to binder ratio can be from 0.15: 1 to 0.4: 1, particularly when aggregate is used that absorbs a significant amount of water or solution (e.g., 20-30%). In some embodiments, the water to binder ratio is from 0.15: 1 to 0.25: 1 or can be from 0.25 to 0.4:1. The water to binder ratio can be 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.10:1,0.11:1,0.12:1,0.13:1,0.14:1,0.15:1,0.16:1,0.17:1,0.18:1,0.19:1,0.20:1,0.21:1, 0.22:1, 0.23:1, 0.24:1, 0.25:1, 0.26:1, 0.27:1, 0.28:1, 0.29:1, 0.30:1, 0.31:1, 0.32:1, 0.33:1, 0.34:1, 0.35:1, 0.36:1, 0.37:1, 0.38:1, 0.39:1, or 0.40:1.

The reactants once combined with water can have a density of from 70 lb/ft³ to 140 lb/ft³. In some examples, the combination of reactants and water can have a density from 80 lb/ft³ to 135 lb/ft³, from 90 lb/ft³ to 130 lb/ft³, or from 100 lb/ft³ to 120 lb/ft³. For example, the combination of reactants and water can have a density of 140 lb/ft³ or less, 130 lb/ft³ or less, 120 lb/ft³ or less, 110 lb/ft³ or less, 100 lb/ft³ or less, 90 lb/ft³ or less, 80 lb/ft³ or less, 75 lb/ft³ or

3 3 3 3 3 more, 85 lb/ft or more, 95 lb/ft or more, 105 lb/ft or more, 115 lb/ft or more, 125 lb/ft or more, or 135 lb/ft³ or more.

The inorganic polymer can have a calcia to silica molar ratio of from 0.6: 1 to 1.1:1. For example, the calcia to silica molar ratio can be 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, or 1.1:1. One or more aggregates or fillers are used in the inorganic polymer compositions described herein. The filler includes a filler having a bulk density of 20 lb/ft³ or less. In some examples, the filler has a bulk density of 20 lb/ft³ or less, 19 lb/ft³ or less, 18 lb/ft³ or less, 17 lb/ft³ or less, 16 lb/ft³ or less, 15 lb/ft³ or less, 14 lb/ft³ or less, 13 lb/ft³ or less, 12 lb/ft³ or less, 11 lb/ft³ or less, 10 lb/ft³ or less, 9 lb/ft³ or less, 8 lb/ft³ or less, 7 lb/ft³ or less, 6 lb/ft³ or less, or 5 lb/ft³ or less. The lower bulk density fillers can include expanded polyurethane, expanded polystyrene or other expanded polymers, expanded clay, expanded perlite, expanded vermiculite, zeolites, hollow glass spheres, and mixtures of these. The lower bulk density fillers can be in the form of beads or hollow spheres. In some examples, the filler includes expanded plastic beads such as polystyrene beads.

In some examples, the filler includes a second filler having a higher bulk density, e.g., 30 lb/ft³ or more. Examples of higher density fillers include some lightweight aggregates such as bottom ash, expanded shale, perlite (non-expanded), vermiculite (non-expanded), volcanic tuff, pumice, ground tire rubber, and mixtures of these.

Further examples of suitable aggregates and fillers having a higher bulk density include other types of ash such as those produced by firing fuels including industrial gases, petroleum coke, petroleum products, municipal solid waste, paper sludge, wood, sawdust, refuse derived fuels, switchgrass, or other biomass material; ground/recycled glass (e.g., window or bottle glass); milled glass; glass spheres; glass flakes; activated carbon; calcium carbonate; aluminum trihydrate (ATH); silica; sand; alluvial sand; natural river sand; ground sand; crushed granite; crushed limestone; silica fume; slate dust; crusher fines; red mud; amorphous carbon (e.g., carbon black); clays (e.g., kaolin); mica; talc; wollastonite; alumina; feldspar; bentonite; quartz; garnet; saponite; beidellite; granite; calcium oxide; calcium hydroxide; antimony trioxide;

barium sulfate; magnesium oxide; titanium dioxide; zinc carbonate; zinc oxide; nepheline syenite; perlite; diatomite; pyrophillite; flue gas desulfurization (FGD) material; soda ash; trona; soy meal; pulverized foam; and mixtures thereof.

In some examples, the filler is used in combination with other aggregate. For example, both polystyrene and expanded shale can be included in an inorganic polymer composition. The volume percentage of filler in a suitable aggregate and filler blend can be from 0.1 to 99.9% by volume. In some embodiments, the volume percentage of filler can be from 0.5% to 90% by volume, from 1% to 80% by volume, from 5% to 60% by volume, or from 10% to 50% by volume. For example, the volume percentage of filler can be 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, or 1% or less by volume.

In some embodiments, inorganic fibers or organic fibers can be included in the inorganic polymer compositions, e.g., to provide increased strength, stiffness or toughness. In some examples, fire resistant or retardant glass fibers can be included to impart fire resistance or retarding properties to the inorganic polymer compositions. Fibers suitable for use with the inorganic polymer compositions described herein can be provided in the form of individual fibers, fabrics, rovings, or tows. These can be chopped and can be provided before or during the mixing of the inorganic polymer reactants to provide desired fiber lengths. Alternately, the fibers can be added after the inorganic polymer reactants have been mixed. The fibers can be up to about 2 in. in length. In some examples, the fibers are about 10 mm in length. The fibers can be provided in a random orientation or can be axially oriented. The fibers can be coated with a sizing to modify performance to make the fibers reactive. Exemplary fibers include glass, polyvinyl alcohol (PVA), carbon, basalt, wollastonite, and natural (e.g., bamboo or coconut) fibers. Examples of suitable fibers and methods of providing fibers in cementitious

compositions are found, for example, in U.S. Patent No. 5, 108,679, which is herein incorporated by reference. The fibers can be included in an amount of 0.1% to 6% based on the weight of reactive powder. For example, the fibers can be included in an amount of 0.5% to 5%, 0.75% to 4%, or 1% to 3% based on the weight of reactive powder. In some embodiments, the fibers are provided in an amount of 2% or less by weight, based on the weight of the cementitious composition including aggregate.

The inclusion of aggregate or filler in the inorganic polymer compositions described herein can modify and/or improve the chemical and mechanical properties of the compositions. For example, the optimization of various properties of the compositions allows their use in building materials and other structural applications. High aggregate and filler loading levels can be used in combination with the compositions without a substantial reduction of (and potentially an improvement in) the intrinsic structural and physical properties of the inorganic polymer compositions. Further, the use of lightweight aggregate provides lightweight building products without compromising the mechanical properties of the inorganic polymer compositions.

The aggregate or filler can be added to the composition at a weight ratio of 0.5: 1 to 4.0: 1 based on the weight of reactive powder (i.e., aggregate to binder weight ratio). In some embodiments, the aggregate to binder weight ratio can be from 0.5: 1 to 2.5: 1 or from 1 : 1 to 2: 1 depending on the product to be produced. In some embodiments, the aggregate to binder weight ratio can be from 1.5: 1 to 4: 1 or from 2: 1 to 3.5: 1. For example, the aggregate to binder weight ratio can be 0.5: 1, 0.6: 1, 0.7: 1, 0.8: 1, 0.9: 1, 1.0: 1, 1.1 : 1, 1.2: 1, 1.3 : 1, 1.4: 1, 1.5: 1, 1.6: 1, 1.7: 1, 1.8: 1, 1.9: 1, 2.0: 1, 2.1 : 1, 2.2: 1, 2.3 : 1, 2.4: 1, 2.5: 1, 2.6: 1, 2.7: 1, 2.8: 1, 2.9: 1, 3.0: 1, 3.1 : 1, 3.2: 1, 3.3: 1, 3.4: 1, 3.5: 1, 3.6: 1, 3.7: 1, 3.8: 1, 3.9: 1, or 4.0: 1.

Additional components useful with the compositions described herein include water reducers, plasticizers, pigments, anti-efflorescence agents, photocatalysts, ultraviolet light stabilizers, fire retardants, antimicrobials, and antioxidants.

Water reducers can be included in the compositions described herein to reduce the amount of water in the composition while maintaining the workability, fluidity, and/or plasticity of the composition. In some examples, the water reducer is a high-range water reducer, such as, for example, a superplasticizer admixture. Examples of suitable water reducers include lignin, naphthalene, melamine, polycarboxylates, lignosulfates and formaldehyde condensates (e.g., sodium naphthalene sulfonate formaldehyde condensate). Water reducers can be provided in an amount of from greater than 0 to 1% by weight based on the weight of reactive powder.

Plasticizers can also be included in the compositions described herein. Plasticizers enhance the extrudability of the inorganic polymer compositions. Examples of suitable plasticizers for use with the compositions described herein include clays (e.g., bentonite, expanded clay, and kaolin clay) and polymers (e.g., JEFFSPERSE X3202, JEFFSPERSE X3202RF, and JEFFSPERSE X3204, each commercially available from Huntsman

Polyurethanes; Geismar, LA).

Pigments or dyes can optionally be added to the compositions described herein. An example of a pigment is iron oxide, which can be added in amounts ranging from 1 wt % to 7 wt % or 2 wt % to 6 wt %, based on the weight of reactive powder.

Anti-efflorescence agents can be included in the compositions to limit the transport of water through the structure and thus limit the unbound salts that are brought to the surface of the structure thereby limiting the aesthetic properties of the structure. Suitable anti-efflorescence agents include siloxanes, silanes, stearates, amines, fatty acids (e.g., oleic acid and linoleic acid), organic sealants (e.g., polyurethanes or acrylics), and inorganic sealants (e.g., polysilicates). Anti-efflorescence agents can be included in the compositions in an amount of from 0.01 wt % to about 1 wt % based on the weight of the reactive powder. Photocatalysts such as anatase (titanium dioxide) can be used that produce superoxidants that can oxidize ΝΟχ and VOC's to reduce pollution. The photocatalysts can make the system super hydrophobic and self-cleaning (e.g., in the presence of smog). These materials can also act as antimicrobials and have impact on algae, mold, and/or mildew growth.

Ultraviolet (UV) light stabilizers, such as UV absorbers, can be added to the

compositions described herein. Examples of UV light stabilizers include hindered amine type stabilizers and opaque pigments like carbon black powder. Fire retardants can be included to increase the flame or fire resistance of the compositions. Antimicrobials, such as copper complexes, can be used to limit the growth of mildew and other organisms on the surface of the compositions. Antioxidants, such as phenolic antioxidants, can also be added. Antioxidants can provide increased UV protection, as well as thermal oxidation protection.

The inorganic polymer compositions described herein are included in an inorganic polymer product. The product includes a first surface and a cross section parallel to the first surface. The concentration of filler adjacent the first surface is greater than the concentration of the filler along the cross section of the product. In some embodiments, the cross section is adjacent a core of the product and the concentration of filler adjacent the first surface of the product and a second surface opposing the first surface are each greater than the concentration of filler along the cross section of the product. In these examples, the density can gradually increase from the first and second surfaces to the core. In other embodiments, the cross section is adjacent a second surface of the inorganic polymer product opposing the first surface. In these examples, the density can gradually increase from the first surface to the second surface. The density at the cross section can be from 1 to 25%, from 4 to 22%, from 7 to 21%, or from 10 to 20% greater than the density at the first surface.

The inorganic polymer product with the described filler distribution is prepared from the inorganic polymer composition described herein. Specifically, the method includes mixing water, filler having a bulk density of 20 lb/ft³ or less, and reactants comprising a reactive powder, an activator, and optionally a retardant. In some examples, the mixing step can further include mixing a foaming agent and/or a blowing agent with the water, filler, and reactants. As described above, the reactive powder comprises fly ash. The components can be mixed from 2 seconds to 5 minutes. In some examples, the reactants are mixed for a period of 15 seconds or less (e.g., 2 to 10 or 4 to 10 seconds). The mixing times, even in the order of 15 seconds or less, result in a homogenous mixture. The mixing can be performed at an elevated temperature (e.g., up to 160°F) or at ambient temperature. In some embodiments, the mixing occurs at ambient temperature. The reactants are allowed to react to form the inorganic polymer composition.

The compositions can be produced using a batch, semi-batch, or continuous process. At least a portion of the mixing step, reacting step, or both, can be conducted in a mixing apparatus such as a high speed mixer or an extruder. The method can further include the step of extruding the resulting composition through a die or nozzle. In examples where the activator includes more than one component, the components can be pre-mixed prior to reacting with the reactive powder and optionally the retardant, as noted above. In some embodiments, a mixing step of the method used to prepare the compositions described herein includes: (1) combining the activators in either solid form or aqueous solution (e.g., combining an aqueous solution of citric acid with an aqueous solution of sodium hydroxide) and adding any additional water to provide a desired concentration for the activator solution; and 2) mixing the activator solution with the reactive powder, filler, and aggregate.

After mixing the components (e.g., for less than 15 seconds), the resultant mixture can be fed into a shaping mold and the mold can be vibrated. The vibrating step can result in gas bubbles migrating from the bottom and core of the product to the surface of the product.

Additionally, the vibrating step can result in the migration of fillers, such as expanded polystyrene, to the surface of the product. The vibrating step can further provide enhanced mixing and/or wetting of the various components of the compositions described herein. Such enhanced mixing and/or wetting can allow a high concentration of reactive powder to be mixed with the other reactants.

An ultrasonic or vibrating device can be used for the vibrating step. The ultrasonic or vibrating device produces an ultrasound of a certain frequency that can be varied during the vibrating process. Alternatively, a mechanical vibrating device can be used. The mold can be vibrated vertically and/or horizontally. In some examples, the mold is vibrated vertically at a frequency of 60 Hz or less. For example, the mold can be vertically vibrated at a frequency of from 10 Hz to 60 Hz, from 20 Hz to 50 Hz, or from 30 Hz to 40 Hz. The mold can be vibrated horizontally at a frequency of 10 Hz or less. For example, the mold can be horizontally vibrated at a frequency from 1 Hz to 10 Hz or from 2 Hz to 8 Hz (e.g., 5 Hz). In some examples, the vibrating is performed at ambient temperature. The ultrasonic or vibrating device useful in the preparation of products described herein can be attached to or adjacent to an extruder and/or mixer. For example, the ultrasonic or vibrating device can be attached to a die or nozzle or to the exit port of an extruder or mixer. An ultrasonic or vibrating device may provide de-aeration of undesired gas bubbles and better mixing for the other components, such as blowing agents, plasticizers, and pigments.

The resulting inorganic polymer products include a concentration of filler adjacent to the first surface that is higher than the concentration of filler along the cross section. In addition, gas bubbles present in the composition, particularly in the event blowing agents and/or foaming agents are used in the composition, can migrate in the direction of the first surface of the product upon vibration. Thus, the cross section of the product (and the areas adjacent the cross section of the product) can have a higher density than the first surface of the product (and the areas adjacent the first surface of the product). For example, in some examples where the cross section is adjacent the core, the first surface and second surface opposing the first surface can have a lower density than the core. In some examples where the cross section is adjacent a second surface, the first surface can have a lower density than the second surface. In some embodiments, the product can have a gradient density with the density gradually increasing from the first surface to the cross section of the product. For example, the product can have a density that increases gradually from the first surface to the core and from the second surface to the core. Alternatively, the product can have a density that increases gradually from the first surface to the second surface.

The method can further include allowing the product to set. The product can be allowed to set, for example, in the shaping mold used in the forming step. The composition can have a set time in the mold, for example, of from 1 to 300 minutes and can be less than 15 minutes (e.g., 2-5 minutes).

The inorganic polymer products can be formed into shaped articles and used in various applications, including building materials. Examples of such building materials include roofing tiles (e.g., shake and slate tile), ceramic tiles, synthetic stone, architectural stone, thin bricks, bricks, pavers, panels, underlay (e.g., bathroom underlay), banisters, lintels, pipe, posts, signs, guard rails, retaining walls, park benches, tables, railroad ties, and other shaped articles.

The examples below are intended to further illustrate certain aspects of the methods and compositions described herein, and are not intended to limit the scope of the claims. Parts and percentages are provided on a weight basis herein, unless indicated otherwise. EXAMPLES

Examples of inorganic polymer compositions as described herein were prepared by combining a reactive powder, an activator, a retardant, and aggregate in the presence of water and filler as described below in Table 1.

In Example 1 (Table 1), the reactive powder included Class C fly ash. The activator included citric acid and sodium hydroxide, which were combined prior to mixing with the other components. The retardants included gypsum and borax. The aggregate in Comparative Example 1 included sand and expanded shale. The higher density filler in Example 1 was expanded shale having a density of 40 lb/ft³ and the lower density filler was a polystyrene bead having a density of 5 lb/ft³. The components were mixed for 3-4 minutes at ambient temperature, fed into molds, and vibrated horizontally at a frequency of 5 Hz to prepare the inorganic polymer product.

The compositions, materials, and methods of the appended claims are not limited in scope by the specific compositions, materials, and methods described herein, which are intended as illustrations of a few aspects of the claims and any compositions, materials, and methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the compositions, materials, and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims. Further, while only certain representative materials and method steps disclosed herein are specifically described, other combinations of the materials and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein; however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated. The term "comprising" and variations thereof as used herein is used synonymously with the term "including" and variations thereof and are open, non-limiting terms. Although the terms "comprising" and "including" have been used herein to describe various embodiments, the terms "consisting essentially of and "consisting of can be used in place of "comprising" and "including" to provide for more specific embodiments and are also disclosed.

Claims

WHAT IS CLAIMED IS:

1. An inorganic polymer product, comprising:

an inorganic polymer composition, comprising:

the reaction product of reactive powder comprising fly ash and less than 10% by weight portland cement; an activator; and optionally a retardant reacted in the presence of water; and

a filler having a bulk density of 20 lb/ft³ or less,

wherein the inorganic polymer product has a first surface and a cross section parallel to the first surface, and

wherein a concentration of the filler adjacent the first surface of the product is greater than a concentration of the filler along the cross section of the product.

2. The product of claim 1, wherein the inorganic polymer product has a core and a second surface opposing said first surface, wherein the cross section is adjacent the core and the concentration of the filler adjacent the first surface of the product and a concentration of the filler adjacent the second surface of the product are each greater than a concentration of the filler along the cross section of the product.

3. The product of claim 2, wherein the density gradually increases from said first surface to said core and from said second surface to said core.

4. The product of claim 1, wherein the cross section is adjacent a second surface of the inorganic polymer product opposing said first surface.

5. The product of claim 4, wherein the density gradually increases from said first surface to said second surface.

6. The product of any of claims 1-5, wherein the reactive powder includes less than 5% by weight portland cement.

7. The product of any of claims 1-6, wherein greater than 75% of the fly ash comprises Class C fly ash.

8. The product of any of claims 1-7, wherein greater than 95% of the fly ash comprises Class C fly ash.

9. The product of any of claims 1-8, wherein the fly ash is present in an amount of greater than 85% by weight of the reactive powder.

10. The product of any of claims 1-9, wherein the fly ash is present in an amount of greater than 95% by weight of the reactive powder.

11. The product of any of claims 1-10, wherein the fly ash includes a calcium oxide content of from 23% to 30% by weight.

12. The product of any of claims 1-11, wherein the activator includes citric acid.

13. The product of any of claims 1-12, wherein the activator includes sodium hydroxide.

14. The product of any of claims 1-13, wherein the reactants include a retardant and the retardant includes borax, boric acid, gypsum, phosphates, gluconates, or a mixture of these.

15. The product of any of claims 1-14, wherein the weight ratio of water to reactive powder is from 0.06:1 to 0.25: 1.

16. The product of any of claims 1-14, wherein the weight ratio of water to reactive powder is from 0.06: 1 to less than 0.15: 1.

17. The product of any of claims 1-16, wherein the filler includes expanded polystyrene.

18. The product of any of claims 1-17, wherein the inorganic polymer composition further comprises a foaming agent.

19. The product of any of claims 1-18, wherein the inorganic polymer composition further comprises a blowing agent.

20. The product of claim 19, wherein the blowing agent includes aluminum powder, sodium perborate, hydrogen peroxide, or a mixture of these.

21. The product of any of claims 1-20, wherein the product includes gas bubbles adjacent to the first surface of the product.

22. The product of any of claims 1-21, wherein the filler has a bulk density of 15 lb/ft³ or less.

23. The product of any of claims 1-22, wherein the inorganic polymer composition further comprises a second filler having a bulk density of 30 lb/ft³ or greater.

24. The product of any of claims 1-23, wherein the product is a building material.

25. The product of claim 24, wherein the building material is selected from the group consisting of a roofing tile, a ceramic tile, a synthetic stone, a thin brick, a brick, a paver, a panel, or an underlay.

26. A method of producing an inorganic polymer product, comprising:

mixing water, a filler having a bulk density of 20 lb/ft³ or less, and reactants including reactive powder comprising fly ash, an activator, and optionally a retardant; feeding the resulting mixture into a mold; and

vibrating the mold to produce an inorganic polymer product having a first surface and a cross section parallel to said first surface, wherein a concentration of the filler adjacent the first surface of the product is greater than a concentration of the filler along the cross section of the product.