MIXTURE OF ULTRA-HIGH PERFORMANCE GEOPOLIMERIC CONCRETE MIXTURE (GCUAD) AND METHOD OF MANUFACTURING

专利摘要:
geopolymeric composite for ultra-high performance concretes a geopolymeric composite of ultra-high performance concrete (gcuad), and methods of manufacturing it, are provided in this, the gcuad comprising: (a) a binder comprising one or more selected from the group consisting of reactive aluminosilicate or reactive alkaline earth aluminosilicate; (b) an alkaline activator comprising an aqueous solution of metal hydroxide and metal silicate; and (c) one or more aggregates.
公开号:BR112013014685B1
申请号:R112013014685-0
申请日:2011-12-16
公开日:2020-09-29
发明作者:Weiliang Gong；Werner Lutze；Ian Pegg
申请人:The Catholic University Of America；
IPC主号:

专利说明:

CROSS REFERENCE TO RELATIVE PATENT APPLICATIONS
This order claims priority to US Order No. Serial 61/457, 052, filed on December 17, 2010, hereby incorporated by reference in its entirety. FIELD OF THE INVENTION
The present invention relates to a binder geopolymer composite for ultra high performance concrete and methods of producing and using it. BACKGROUND OF THE INVENTION
The following description of the background of the invention is provided simply as an aid to understanding the invention and is not permitted to describe or constitute prior art to the invention.
Over the past ten years, considerable advances have been made in the development of high-performance, or more recently, ultra-high-performance concretes, with Portland cement. Ultra-high-performance concrete (CUAD) represents an important development step on high-performance concrete (CAD), through the achievement of very high strength and very low permeability. Typically, the compressive strength of CUAD ranges from about 120 to 400 MPa, its tensile strength ranges from about 10 to 30 MPa, and its modulus of elasticity is in the range of about 60 to 100 GPa.
Benefits of CUAD for being a "minimal defect" material - a material with a minimum of defects, such as micro cracks and interconnected pores with a maximum packing density. One approach for minimizing defects is the Macro Defect Free (MDF) approach, which uses polymers to fill the pores in the concrete matrix. The process required for the manufacture of MDF concrete is very demanding, and includes lamination and pressing. MDF concrete is susceptible to water damage, has a large amount of deformation, and is very fragile. Another approach to minimize defects is the Densified with Small Particles (DSP) approach, which uses large amounts of superplasticizer and active silica in the concrete mix. DSP concretes must use very rigid coarse aggregates or eliminate them completely, in order to prevent aggregates from being the weakest component of the mixture. DSP concretes do not require the extreme production conditions that MDF concretes do, but DSP concretes have a much lower tensile strength. The addition of steel fibers was considered to improve the ductility of DSP concrete.
Principles used in conventional CUAD include improving homogeneity by eliminating crude aggregate; packaging density improved by optimizing the granular mix through a wide distribution of powder size classes; matrix properties improved through the addition of a pozzolanic additive, such as active silica; matrix properties improved by reducing the water / binder ratio; improved ductility through the inclusion of small steel fibers; and greater mechanical performance, through heat treatment after adjustment (90-150 ° C) to transform hydrated amorphous into crystalline products, making an improved microstructure (tobermorite, xonotlite) possible.
Various types of CUAD have been developed in different countries and by different manufacturers. The main difference between the various types of CUAD is the type and amount of fibers used. The four main types of CUAD are Ceracem / BSI, compact reinforced composites (CRC), multi-scale cement composite (MSCC) and reactive powder concrete (RPC). RPC is the most commonly available CUAD and a product of this type is currently marketed under the name Ductual® by Tafarge, Bouygues and Rhodia.
RPC concrete mixtures generally contain fine sand (150-600 pm), Portland cement (<100 pm), silica fume (0.1-0.2 pm), crushed quartz (5-30 pm), short fibers, superplasticizer and Water. A typical RPC concrete mixture has about 38.8% sand, 22.7% Portland cement, 10.6% active silica, 8.1% crushed quartz, 2.0% steel fiber or fiber organic, 1.4% superplasticizer, and 16.5% water (all in volume percentage).
Portland cement is the primary binder used in conventional CUAD, but in a much larger proportion compared to common concrete or CAD. Cement with high proportions of tricalcium aluminate (C3A) and tricalcium silicate (C3S), and a lower Blaine fineness are desirable for conventional CUAD, as C3A and C3S contribute to a high initial strength and lower Blaine fineness reduces demand of water. The addition of silica fume fulfills several roles, including packaging of particles, increasing fluidity due to the spherical nature and pozzolanic reactivity (reaction with the weakest hydration product of calcium hydroxide), leading to the production of calcium silicates. Quartz sand with a maximum diameter of about 600 pm is the largest component, in addition to steel fibers. Both ground quartz (about 10 pm) and quartz sand contribute to optimized packaging. By reducing the amount of water needed to produce a mixture of fluids, and therefore permeability, the polycarboxylate superplasticizer also contributes to improving workability and durability. Finally, the addition of steel fibers helps to prevent the spread of micro-cracks and macro-cracks and thus limits crack width and permeability.
Despite the performance advantages offered by CUAD, implementation has been slow. There are several possible reasons for this, including the lack of a clear financial benefit for manufacturers. As would be expected, the costs of manufacturing CUAD components are significantly higher than the costs of manufacturing conventional concrete components. In addition, the high cost of the constituent materials in CUAD necessarily means that CUAD has a higher cost per unit volume than conventional and high-performance concretes. Much of CUAD's cost comes from its steel fiber, superplasticizer and high purity of active silica. Ultra-high performance fiber reinforced concrete is generally cured with heat and / or pressure, to improve its properties and to accelerate the hydration reaction of the binder, which also increases the manufacturing cost.
The present invention relates to the use of bonding geopolymer (CG) composites, instead of Portland cement, for ultra high performance cement (GCUAD) applications. SUMMARY OF THE INVENTION
One aspect of the present invention provides a blend of ultra high performance concrete geopolymer composite (GCUAD), comprising: (a) a binder comprising one or more selected from the group consisting of reactive aluminum silicate and alkali aluminum silicate -reactive earth and (b) an alkaline activator comprising an aqueous solution of metal hydroxide and metal silicate, and (c) one or more aggregates.
In some embodiments, the binder comprises about 10 to 50% by weight of the GCUAD mixture. In some embodiments, the binder comprises one or more reactive aluminosilicate comprising about 0 to 30% by weight of the GCUAD mixture. In some related embodiments, the one or more reactive aluminum silicate is selected from the group consisting of meta-kaolin, reactive aluminosilicate glasses and Class F ultrafine fly ash. In some embodiments, the one or more aluminum reactive comprises metakaolin. [0014] In some embodiments, the binder comprises one or more reactive alkaline earth aluminosilicate comprising about 2 to 40% by weight of the GCUAD mixture. In some related embodiments, the one or more reactive alkaline aluminosilicate earth reactive is selected from the group consisting of granulated high kiln slag, glassy calcium aluminum silicate (VCAS), class C fly ash, and cement kiln dust . In some related embodiments, one or more reactive alkaline earth aluminum aluminosilicate comprises granulated blast furnace slag.
In some embodiments, the binder comprises reactive aluminosilicate and reactive alkaline earth aluminosilicate. In some related embodiments, the mass of the reactive aluminosilicate is up to about 10 times, preferably up to about 1.5 times, preferably about 0.2 to about 0.8 times, the mass of the aluminosilicate reactive alkaline earth. In some related embodiments, the mass of the reactive alkaline earth aluminosilicate is up to about 20 times, and preferably between about 2 to about 5 times, the mass of the reactive aluminosilicate. In some related embodiments, the one or more reactive aluminosilicate comprises about 2 to about 15% by weight of the GCUAD mixture. In some related embodiments, the reactive alkaline earth aluminosilicate comprises about 8 to about 25% by weight of the GCUAD mixture.
In some embodiments, the GCUAD mixture further comprises one or more fillers, comprising up to about 35% by weight, preferably from about 2 to about 25% by weight, of the GCUAD mixture. In some related embodiments, the filler one or more comprises one or more reactive fillers. In some related embodiments, the one or more filler is selected from the group consisting of ground quartz powder, Class F ash, Class C fly ash, zeolite, ground glass, silica powder, ultrafine fly ash, silica precipitated and micron alumina. In some related embodiments, the one or more filler comprises active silica. In some related embodiments, the one or more filler comprises ground quartz powder and active silica. In some related embodiments, the one or more filler comprises Class C fly ash. In some related embodiments, the one or more filler comprises Class F fly ash. In some related embodiments, the one or more filler comprises silica. active and Class F flywheel. In some related embodiments, the one or more filler comprises active silica and Class C flywheel. In some related embodiments, the filler one or more has a particle size between 1 and 75 pm, and is selected from the group consisting of ground quartz, Class F ash fly ash of Class C, zeolite, ground glass, metakaolin, crushed granulated blast furnace slag, ultra-fine kiln slag, and ultra-fine ash. In some related embodiments, the filler one or more has a particle size of between about 0.05 and 1 pm, and is selected from the group consisting of silica fume, precipitated silica, ultrafine calcium carbonate, alumina micron, and the submicron particles of metal oxides.
In some embodiments, the one or more aggregate comprises about 0 to 75% by weight, preferably about 30 to 60% by weight, of the GCUAD mixture. In some related embodiments, the one or more aggregate comprises particles with a particle size of about 0.075 to 10 mm. In some related embodiments, the one or more aggregate comprises one or more crude aggregate having a particle size between about 0.075 and about 10 mm, which is selected from the group consisting of quartz sand, granite, basalt , gneiss, granulated blast furnace slag, limestone and calcined bauxite sand. In some related embodiments, the one or more aggregate comprises a fine aggregate with a particle size between about 0.075 and 0.75 mm. In some related embodiments, the one or more aggregate comprises masonry sand, fine river sand, or both.
In some embodiments, the alkaline activator solution comprises about 10 to 40% by weight, more preferably about 15 to about 25% by weight, of the GCUAD mixture. In some embodiments, the metal hydroxide comprises about 2 to 15% by weight as M20 of the GCUAD mixture. In some embodiments, the metal hydroxide comprises sodium hydroxide, potassium hydroxide, or both. In some embodiments, the metal hydroxide comprises about 2 to 10% by weight as M2O of the GCUAD mixture. In some embodiments, the water in the alkaline activator solution comprises about 4 to 25% by weight, more preferably about 5 to 15% by weight, of the GCUAD mixture.
In some embodiments, the metal silicate comprises about 2 to 10% by weight of SiO2 of the GCUAD mixture. In some embodiments, the metal silicate comprises an alkali metal silicate or an alkaline earth metal silicate. In some embodiments, the metal silicate comprises sodium silicate, potassium silicate, or both.
In some embodiments, the GCUAD blend further comprises one or more fibers, which comprises about 0 to 15% by weight of the GCUAD blend. In some related embodiments, the one or more fibers comprises one or more fibers selected from the group consisting of organic fibers, glass fibers, carbon fibers, nano fibers, and metal fibers. In some related embodiments, one or more fibers comprise steel fibers.
In some embodiments, the GCUAD mixture further comprises one or more force enhancers, which comprise up to about 2% by weight of the GCUAD mixture. In some related embodiments, the one or more force enhancer is selected from the group consisting of aluminum hydroxide, alkaline carbonate, alkaline phosphate, alkaline sulfate, alkaline oxalate and alkaline fluoride. In some related embodiments, the one or more enhancing forces are selected from the group consisting of aluminum hydroxide, sodium carbonate, sodium phosphate, sodium sulfate, sodium oxalate and sodium fluoride.
In some embodiments, the GCUAD mixture further comprises superplasticizer solids, which comprise up to about 5% by weight of the GCUAD mixture.
In some embodiments, the GCUAD mixture further comprises a retarder assembly. In some related embodiments, the retarder assembly comprises up to about 5% by weight of the GCUAD mixture.
In some embodiments, the packing density of all solid components in the GCUAD mixture is at least 0.5 (v / v), such as at least 0.6 (v / v), such as at least 0, 75 (v / v).
In some embodiments, the results of mixing GCUAD into a GCUAD product with a 28-day compressive strength of at least about 10,000 psi, such as at least about 20,000 psi, such as at least about 25,000 psi .
In some embodiments, the results of mixing GCUAD into a GCUAD product with a fixation time of about 30 minutes to 3 hours.
In some embodiments, the results of mixing GCUAD in a GCUAD product with a temperature setting between about 0 and 150 ° C, such as between about 20 and 90 ° C. In another aspect, methods of producing ultra-high performance concrete geopolymer composite (GCUAD) products from the GCUAD mixtures described herein are provided. In some methods, a dry GCUAD mixture is mixed with an activator solution to form a GCUAD paste, which is established and cured to form a GCUAD product. In these methods, the dry GCUAD mixture comprises a binder of about 10 to 50% by weight, the binder comprises one or more selected from the group consisting of reactive aluminum silicate and reactive alkaline earth aluminum silicate, and the solution of The activator comprises an aqueous solution of metal hydroxide and metal silicate. The GCUAD dry blend further comprises one or more selected from the group consisting of aggregate, filler and fiber.
In some embodiments, the alkali metal hydroxide comprises one or more of sodium hydroxide and potassium hydroxide or both.
In some embodiments, mixing is carried out with an intensive mixer.
In some embodiments, the GCUAD paste further comprises one or more selected from the group consisting of force enhancer, solid superplasticizers and retarder assembly.
In some embodiments, the GCUAD product comprises one or more fibers, which are added to the GCUAD slurry prior to configuration.
In some embodiments, the GCUAD product comprises one or more force enhancers, which are added to the aqueous solution of one or more alkaline activators, before mixing with the dry GCUAD mixture.
In some embodiments, the activator solution has a molar concentration of alkali hydroxide from about 5 to about 15, preferably from about 7 to about 12.
In another aspect, methods of preparing an ultra-high performance concrete geopolymer composite product (GCUAD) from a mixture of GCUAD are provided where the components of a mixture of GCUAD are mixed in an intensive mixer until the mixture progresses to a granulate as a consistency and develop a smooth slurry with continued mixing. In these embodiments, the GCUAD mixture comprises an activator solution and a binder; the activator solution comprising an aqueous solution of metal hydroxide and metal silicate, the binder comprises one or more selected from the group consisting of reactive aluminum silicate and reactive alkaline earth aluminum silicate. In some embodiments, the GCUAD mixture has a water to geopolymer solids (W / C) ratio between about 0.12 to 0.65; such as between about 0.2 to 0.5, such as between about 0.3 to 0.45.
The term "about" as used herein in reference to quantitative measurements, not including measurement of the mass of an ion, refers to the indicated value plus or minus 10%. Unless otherwise specified, "one" or "one" means "one or more". The summary of the invention described above is not limiting and other features and advantages of the invention will be apparent from the following detailed description of the invention, and from the claims. BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows a graph of the compressive strength of several GCUAD samples as a function of curing time. Details are discussed in Example 14. DETAILED DESCRIPTION OF THE INVENTION
One aspect described here provides an ultra-high performance geopolymer concrete composite composition (GCUAD). At a minimum, a mixture of GCUAD includes: i) a binder comprising at least one reactive amorphous aluminum silicate material, such as metakaolin, and / or at least one reactive amorphous earth alkaline aluminosilicate, such as granulated blast furnace slag , and ii) an aqueous solution comprising at least one alkaline activator.
In some embodiments, additional components can be included in the GCUAD mixture. For example, filler (reactive and / or non-reactive) with a particle size up to about 75 pm, and / or aggregates, such as fine particle size masonry sand between about 75 to 750 pm, such as about 250 pm can also be included in the mix. In addition, components such as fibers, force intensifiers, superplasticizer and retarder set can also be included to affect GCUAD performance.
To form a GCUAD, the dry constituents of the GCUAD mix composition (binder and filler and aggregates, if present) are combined with an alkaline activator solution. The constituents are mixed to form a slurry, which lays on a GCUAD product while the constituents form geopolymers. Geopolymers consist of atoms of silicon and aluminum, linked through oxygen atoms in a polymer network. The geopolymer formation process involves dissolution / condensation / poly condensation / polymerization reactions, which start as early as certain reactive aluminum silicate materials are exposed to an alkaline solution. Using certain aluminosilicate materials, which are highly reactive in alkaline solutions and optimizing the compositions and properties of the solutions of alkaline activators allow to produce very dense, durable geopolymer matrices of extremely high mechanical resistance.
Through the use of certain true principles for conventional CUAD, such as increasing homogeneity excluding crude aggregates and increasing aggregate packaging, selecting particle size distributions, a CUAD with geopolymer composite can be obtained using the above compressive strength 20,000 psi. Unlike conventional CUAD, the use of heat treatment and the addition of a large amount of reducing agent are not necessary to achieve ultra-high performance. With an intensive mixer, water to geopolymer solids (W / C) ratios can be reduced without significant doping with a superplasticizer. In contrast, conventional CUAD uses large amounts of reducing agent to reduce W / C ratios. In addition, GCUAD has absolutely no Portland cement, uses mainly industrial residues, and does not emit carbon dioxide in production. Thus, GCUAD is much less expensive than conventional CUAD, being a much greener concrete. GCUAD also exhibits much better resistance to heat, impact and acid heat than conventional CUAD. GCUAD Principles
It is well known that the performance of geopolymeric products depends on the reactivity and the mass of the gel formed. The inventors have found that the alkaline activation of the reactive aluminum silicate material, such as metakaolin, generates a large amount of alkaline aluminum silicate gel (AAS gel).
Alkaline activation of reactive alkaline earth aluminosilicate materials, such as granulated blast furnace slag, vitreous calcium aluminosilicate, or fly ash of class C, also produces calcium silicate hydrate (CSH) abundant in gel and / or gels related and / or calcium aluminum silicate hydrate (CASH) gel, in addition to EAA gel.
Alkaline activation of reactive aluminosilicate and reactive alkaline earth aluminosilicate is very fast with reactions completed in a few hours (eg metakaolin) a few days ago (eg, granulated blast furnace slag, Class C fly ash) at temperature environment. Increasing the temperature significantly increases alkaline activation and hardening processes.
The inventors also found that a geopolymeric composite made of two or more reactive aluminosilicate materials results in a hybrid matrix of EAA CSH and / or related gels, and / or hydrated calcium aluminosilicate (CASH) with a higher strength rate as well as higher final strength of the geopolymeric product. Optimization of the AAS gel to CSH gel ratio in a geopolymer composite matrix can yield maximum strength performance.
Basic principles for conventional CUAD are also true for GCUAD, such as increasing homogeneity by excluding crude aggregates and increasing aggregate packaging by selecting particle size distributions. In some embodiments, readily available river sand or masonry sand (for example, particle size about 75-750 pm) can be used as a fine aggregate in order to reduce the cost of production. In other embodiments, other sands, such as masonry sand, can be used as an aggregate. In certain embodiments, one or more thin and / or ultrafine reactive fillers can be used having a particle size of between about 3 to 75 pm, thus eliminating the ground quartz powder (5 to 30 pm) found in typical reactive powder concrete (RPC) mixtures. In some embodiments, submicron fillers with a particle size ranging from about 0.05 to about 1 pm can be used. While the reactive fillers (thin, ultrafine and submicron) act as filling in the voids in the next widest granular class in the mixture, the fillers also react with alkaline sources (pozzolanic reaction) with increasing curing time and produce additional AAS gel to support long-term strength growth.
In some embodiments, the inclusion of aggregates and fillers in the GCUAD mixtures results in a packing density of all solid additives (i.e., binder materials, aggregate (if present), and filler (if present)). at least 0.5 (v / v), such as at least 0.6 (v / v), such as 0.75 (v / v).
Geopolymeric water / solids ratio (W / C) was used as an indicator of concrete strength. The term geopolymeric solids is defined as the sum of the components of binder and dissolved silica and alkaline oxides in the activator solution. W / C affects the porosity and pore size distributions of the geopolymeric matrix. A lower W / C ratio generally results in a geopolymeric gel with smaller pores (for example, about 20 to 100 nm in size) and in turn the higher compressive strength.
The inventors have determined that a mixture of GCUAD with excellent or near-optimal W / C shows a characteristic progression through several phases in intensive continuous mixing. With an excellent or almost optimal W / C ratio, it is observed that the GCUAD mixture initially develops a sand or consistency as granules, which suggests that an insufficient amount of water is present. However, continued mixing, without adding additional water, results in the sand or mixture as granules, forming a mixture with a paste-like consistency, and, finally, a viable, flowable homogeneous paste that is ready for pouring. The inventors further determined that GCUAD products made from mixtures of GCUAD that exhibit this sequence are exceptionally strong, with a compressive strength of more than 20,000 psi cured for 28 days at room temperature.
The inventors have determined that the preferred W / C range for GCUAD mixtures as described herein is within the range of about 0.12 to about 0.65, such as about 0.2 to about 0.5, such as about 0.3 to about 0.45.
The following is a more detailed description of the various components that may be present in certain GCUAD mixtures of the present invention. The constituents from which the GCUAD is made include at least one binder comprising at least one reactive aluminosilicate and / or at least one reactive alkaline earth aluminosilicate and an aqueous activator solution. Additional components included in certain embodiments discussed herein include filler, aggregates, fibers, strength enhancers, superplasticizer, retarder assembly, and any combination thereof. This list is not intended to be exhaustive, and as understood by one skilled in the art, other components may also be included. Reactive aluminosilicate materials
The first constituent of a GCUAD mixture is the binder, which comprises reactive aluminosilicate and / or reactive alkaline earth aluminosilicate. Examples of materials containing aluminosilicate reagents suitable for use in the present invention include metakaolin (MK), granulated kiln slag (GGBFS), vitreous calcium aluminosilicate (VCAS), class F (FFA) fly ash, and Class C fly ash (CFA).
Metacaolin is one of the most reactive Pozzolan aluminum silicates, a finely divided material (for example, within the range of about 0.1 to 20 microns) that reacts with the lime off at normal temperature and in the presence of moisture to form a strong cement. slow hardening Metacaolin is formed by calcination of the purified kaolinite, usually between 650-700 ° C, in a rotary kiln. Alkaline activation of metakaolin can be completed within a few hours.
Depending on the chemical composition and the production method, ground granulated blast furnace slag (GGBFS) is a glassy granular material, which ranges from a crude, friable popcorn-like structure with a particle size greater than about 4.75mm in diameter, to dense, the size of grains of sand. Grinding reduces particle size to cement fineness, allowing it to be used as a supplementary cementitious material in cement-based Portland concrete. Typical ground granulated blast furnace slag includes about 27-38% SiC> 2, 7-12% AI2O3, 34- 43% CaO, 7-15% MgO, 0.2-1.6% Fe2O3, 0.1 -0.76% MnO and 1.0- 1.9% others by weight. Because GGBFS is almost 100% glassy (or "amorphous"), it is generally more reactive than most fly ash. GGBFS produces a greater proportion of the improved strength of calcium silicate hydrate (CSH) than Portland cement, thus resulting in higher final strength than concrete made with Portland cement.
Fly ash is a by-product of fine powder formed from the combustion of coal. A pulverized coal burning utility power plant produces most of the fly ash available on the market. These fly ash are made up mainly of substantially spherical glass particles, as well as hematite, magnetite, unburned carbon, and some crystalline phases formed during cooling. American Society for Testing and Materials (ASTM) C618 standard recognizes two main classes of fly ash for use in concrete: Class C and Class F. In ASTM C618, a big difference in specification between Class F ash and Class C ash is the lower limit of (SiO2 + A12O3 + Fe2O3) in the composition. The lower limit of (SiO2 + A12O3 + Fe2O3) for Class F fly ash is 70% and this for Class C fly ash is 50%. Thus, fly ash of class F generally has a content of about 15% by weight or less of calcium oxide, while fly ash of class C generally has a high content of calcium oxide (for example, greater than 15% by weight). , such as about 20 to 40% by weight) High calcium oxide content makes Class C fly ash possess cement properties, leading to the formation of calcium silicate hydrates and calcium aluminate when mixed with water.
Any reactive aluminosilicate known in the art can be used, but metakaolin is the most favorable, as it is readily available and has a small particle size, such as about 0.5 to 20 pm. The rates of dissolution of metakaolin and polymerization in an alkaline solution can be very high (that is, from minutes to hours), and the water expelled during geopolymerization can help to improve the workability of the paste and increase the GCUAD alkaline activation / hydration of a reactive faulty alkali aluminosilicate.
Some synthetic pozzolanic materials are even more reactive than metakaolin. For example, the inventors synthesized reactive vitreous aluminosilicate with chemical compositions analogous to fly ash of class C, at temperatures between about 1400 ° C and 1500 ° C. Raw materials useful for the synthesis of reactive vitreous aluminosilicate include Class C fly ash with the addition of a small amount of flow components (such as sodium carbonate) or other individual chemicals Before use in GCUAD mixtures, synthetic glass can be milled to 325 mesh. Alkaline activation of synthetic glass powders generally produces a compressive strength of more than 20,000 psi after curing for 28 days.
In general, Class F fly ash is less reactive than metakaolin, although Class F ash is essentially a glassy aluminum silicate. The reactivity of Class F fly ash depends on the amount of the amorphous phase contained therein, the particle size of the solid spherical fly ash, and the curing temperature. According to the inventors' measurements, the hydration activation energy can be as high as about 100 kJ / mol for conventional Class F fly ash based geopolymer in the temperature range of about 20 to 75 ° C. By comparison, the hydration activation energies of Portland cements and kiln slag vary from about 20 to 50 kJ / mol. Without post-fixed heat treatment, as normally applied for the manufacture of conventional CUAD, conventional Class F fly ash cannot be a preferred reactive aluminosilicate in a GCUAD depending on particle size.
To be used as an aluminum silicate in a reactive mixture of GCUAD cured at room temperature, Class F fly ash preferably has a particle size less than about 15 pm, as well as small amounts of unburned coal, such as less than about 1% by weight. Such class F fly ash preferably has an average particle size of about 3 pm, and can be processed from raw fly ash by mechanically removing coarse particles. Ultra-fine ash can also be produced by a grinding process. Fly ash with an average particle size in the range of 6 to 10 pm can be generated in this way. Alkaline earth alkali silicate Reactive
As already discussed, the binder comprises reactive aluminosilicate and / or reactive alkaline earth aluminosilicate. Examples of reactive alkaline earth aluminosilicate materials are granulated blast furnace slag (GGBFS), vitreous calcium aluminum silicate (VCAS), Class C ash (CFA) and cement kiln dust (CKD). GGBFS is the most favorable reactive alkaline earth aluminum silicate, due to its high reactivity in alkaline solution and its low cost. Although all three types of kiln slag (ie 80, 100 and 120 per ASTM C989-92) are suitable for a GCUAD mixture, grade 120 kiln slag is preferred because it exhibits greater reactivity in alkaline solution. In addition, ultrafine GGBFS is even more reactive to grade 120 kiln slag. For example MC-500® Microfine® Cement (from Neef Construction Chemicals) is an ultrafine kiln slag with particle sizes less than about 10 pm and specific surface area of about 800 m2 / kg, which is more reactive than kiln slag 120. VCAS is a by-product of fiberglass production. In a representative fiberglass manufacturing facility, typically about 10-20% by weight of the processed glass material is not converted into the final product, and is discarded as a by-product or residue from VCAS and sent for disposal to a landfill. VCAS is 100% amorphous and its composition is very consistent, mainly comprising about 50-55% by weight of SiO2, 15-20% by weight of AI2O3, and 20-25% by weight of CaO. Base VCAS has pozzolanic activity comparable to active silica and metakaolin when tested in accordance with ASTM C618 and Cl 240. Therefore, it can be very reactive alkaline earth aluminosilicate, forming additional cement compounds, such as CSH and CASH gels. CKD is a by-product of Portland cement manufacturing, and therefore an industrial waste. More than 30 million tons of CKD are produced annually worldwide, with significant quantities placed in landfills. Typical CKD contains about 38-64% by weight of CaO, 9-16% by weight of SiO2, 2.6-6.0% by weight of AI2O3, 1.0-4.0% by weight of Fe2O3, 0 , 0-3.2 wt% MgO, 2.4-13 wt% K2O, 0.0-2.0 wt% Na2O, 1.6-18 wt% SO3, 0.0 -5.3% by weight of Cl ", and 5.0-25% by weight, LOT. CDK is generally a very fine powder (for example, about 4,600-14,000 cm2 / g of specific surface area) and is a good reactive alkaline earth aluminosilicate.When CKD is used in a GCUAD formulation, high concentrations of the alkaline oxides contained therein improve geopolymerization.Additional CSH gel formation, etringitis (3CaO. / or singenite (a mixed alkali-calcium sulfate) can help to develop early GCUAD strength.
The concrete composition comprises about 2 to 40% by weight of reactive alkaline earth aluminum silicate, and preferably about 8 to 25% by weight. The concrete composition comprises up to 30% by weight of reactive aluminosilicate. The binding materials comprise reactive alkaline earth aluminum silicate and reactive aluminum silicate, which contribute up to about 50% by weight, such as about 20 to 40% by weight, such as about 15 to 30% by weight, of a mixture GCUAD. In the binder, a mass ratio of reactive aluminosilicate to reactive alkaline earth aluminosilicate ranges from about 0.0 to about 10, with a mass ratio between about 0.2 and about 0.8 is preferred. . In the binder, an alkaline earth aluminosilicate mass ratio reactive to reactive aluminosilicate of between about 0.0 to 20 is preferred, such as between about 1 to 10, such as between about 2 and 5. Activator Solution
The second critical component in a GCUAD mixture is the activator solution. In addition to the binder described above, an alkaline activating solution ("activator solution") must be added to a GCUAD dry mix component to form a complete GCUAD mix. The activator is in fact a solution of one or more metal hydroxides and one or more metal silicates.
In one embodiment, the one or more metal hydroxides comprise one or more alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide, or both.
One or more metal silicates can comprise one or more alkali metal silicates and / or one or more alkaline earth metal silicate. Alkali metal silicates, particularly a mixed solution of potassium and sodium silicates, are desirable.
Active silica or microsilica is composed of very small glassy silica particles (SiO2) (for example, about 0.1 pm in size), which are substantially spherical, with a specific surface area of the order of 20 m2 / g. Active silica is extremely reactive in alkaline solution. An activator solution is prepared by dissolving active silica in the alkali metal hydroxide solution. In some embodiments of the present invention, active silica is also applied as a reactive filer. Unlike conventional Portland cement based on CUAD, GCUAD is tolerant of the unburned carbon present in industrial silica residues of up to about 5% by weight, as in active silica from the production of silicon and ferro-silicon alloys. GCUAD made from such industrial residues of active silica may appear gray or darker in color. However, GCUAD comprising white active silica, as from the zirconium industry, contain much less unburned carbon and appear white in color. Thus, certain dyes or pigments can be added to GCUADs made from white active silica to achieve a variety of colors in the final product.
In some embodiments, active silica can be used to make the activator solution by dissolving it in an alkali metal hydroxide solution, together with strength enhancers (if present). In other embodiments, alkaline silicate glass powders can be dissolved in an alkali metal hydroxide solution to prepare an activator solution. Elevated temperature can help to increase the rate of dissolution of alkaline silicate glass powder. Commercially available examples of soluble alkaline silicate glasses include SS® sodium silicate and Kasolv® potassium silicate from PQ Corporation. In other embodiments, commercially available alkali metal silicate solutions can be used to prepare activator solutions. Examples of such alkali metal silicate solutions include Ru ™ sodium silicate solution and KASIL®6 potassium silicate solution from PQ Corporation. When these commercially soluble alkali metal silicate materials are used to prepare activator solutions, GCUAD products are generally light in color. If desired, certain pigments can be added to create various finishing colors.
The activator solution contributes to the GCUAD mixture as follows: metal hydroxide such as M2O (M = Na, K, or both) in about 2 to 15% by weight, silicate like SiO2 at about 2 to 15% in weight, and water from 4 to 25% by weight.
Preferably, the metal hydroxide is added as sodium hydroxides, potassium, or both, more preferably, about 2 to 10% by weight, of Na2O (added as NaOH), K2O (added as KOH), or both; more preferably, about 2 to 8% by weight, of Na2O (added as NaOH), K2O (added as KOH), or both.
Preferably, it is added as active silica. Preferably, dissolved SiO2 is present in the GCUAD mixture at about 2 to 10% by weight, more preferably about 2 to 8% by weight
Preferably, water is present in the GCUAD mixture at about 4 to 25% by weight, more preferably at about 7 to 15% by weight. Filling
An optional component in a GCUAD mixture is filling with a particle size up to about 75 pm. Two types of fillers can be classified in terms of particle sizes and their reactivity in alkaline solution. One type of filler material mainly comprises reactive submicron particles having a particle size of between about 0.05 to 1 pm. Another type of filler includes fine and ultrafine particles with particle sizes between about 1 to 75 pm. The combined filling material can comprise up to about 35% by weight of a mixture of GCUAD. Preferably, the combined filling comprises between about 2 and 35% by weight. More preferably, the combined filling material comprises between about 2 and 25% by weight.
Exemplary thin and ultrafine fillers include calcined zeolites, Class F fly ash, Class C fly ash, coal gasification fly ash, volcanic ash, and ground glass powder. In general, these particles of filler material are also very reactive after exposure to an alkaline solution. Fly ash, including Class F and fly ash of Class C, generally has a particle size between about 5 and 75 pm. Of fly ash, with smaller particle sizes are preferred, such as ultrafine fly ash (UFFA) with an average particle size of about 1 to 10 pm. UFFA is carefully processed by mechanically separating the ultrafine fraction from the parent fly ash. Coal gasification ashes are discharged from coal gasification plants, generally as substantially rich spherical particles of SiO2, with a maximum particle size of carbon gasification are also suitable fillers.
Class F ashes are essentially an aluminum silicate glass, which is less reactive than metakaolin, in alkaline solution. The reactivity of Class F fly ash depends on the amount of the amorphous phase it contains, on the particle size of the solid fly ash, and on the curing temperature. According to the inventors' measurements, the hydration activation energy can be as high as about 100 kJ / mol for Class F geopolymer fly ash based on the temperature range of about 20 to 75 ° C. By comparison, the hydration activation energies of Portland cements vary from about 20 to 50 kJ / mol. Class F fly ash can be used as a filling material, as it generally has an average particle size of less than 75 microns, thus allowing the elimination of ground quartz, one of the key components in conventional CUAD. Class F fly ash with less unburned carbon content (for example, less than about 2% by weight) is preferable.
Granulated blast furnace slag and metakaolin can also be included as a reactive filler, while they work well as a binder. Both materials have a particle size between 0.5 and 75 pm. They fill in the blanks to improve the packing density of the GCUAD mixture and react with the alkaline silicate solution to form additional AAS and CHS and / or CASH gels.
Examples of zeolites include Zeolite Type 5A, Zeolite type 13X, clinoptilolite and phyllipsite. The zeolite phases have SiO2 / AI2O3 molar ratios of between about 2 to 7, which are within the favorable range of formation of geopolymeric compositions. The heat treatment of zeolitic materials, at temperatures between about 500 to 800 ° C makes them amorphous in structure and reactive after exposure to the highly alkaline solution. Calcined zeolitic materials typically have a particle size between about 0.5 and 10 pm.
Examples of submicron fillers useful in the present invention include active silica, precipitated silica, micron sized alumina, with active silica being the most preferred. These submicron fillers are typically extremely reactive after exposure to the alkaline solution. Ultrafine calcium carbonate particles having a specific surface area equal to or greater than about 10 m2 / g can also be used as a submicron filler, although less reactive than active silica. Other materials that have a particle size of less than about 1 pm can also be used as a submicron filler, although they may not necessarily be reactive. Examples of such submicron particles include Fe2θ3, ZrO2, and SiC particles of appropriate size.
As used in conventional CUAD, ground quartz powder having a particle size between about 1 and 75 pm, and more preferably between about 5 and 30 pm, can be used to improve optimization of the particle size distribution and is considered inert. However, ground quartz can become relatively reactive in GCUAD as quartz particles with a high surface area dissolve in highly alkaline solutions with a pH> 14.
Therefore, in GCUAD mixtures of the present invention, ground quartz powder can be classified as a weak reactive filler.
In some embodiments, a single filler material, preferably a single reactive filler material, is incorporated into a mixture of GCUAD. In some of these embodiments, the only filler is active silica. In these embodiments, up to about 5% by weight of active silica is incorporated into the GCUAD mixtures. In other embodiments, various fillers, which may or may not include one or more reactive fillers, are incorporated into the GCUAD mixtures. For example, two fillers can be incorporated into a mixture of GCUAD. In certain embodiments, active silica and calcined zeolite type 5A can be incorporated into a mixture of GCUAD with combined amounts of up to about 10% by weight. In other embodiments, active silica and ground quartz powder can be incorporated into a mixture of GCUAD with the amount of ground quartz powder being up to about 25% by weight, such as up to about 10% by weight, and the amount of active silica of up to about 8% by weight, such as up to about 5% by weight. In yet other embodiments, Class C active silica and fly ash can be incorporated into a mixture of GCUAD with an amount of active silica of up to about 8% by weight, such as up to about 5% by weight, and the amount of Class C fly ash up to about 25% by weight, such as up to about 10% by weight. In yet other embodiments, Class F active silica and fly ash can be incorporated into a mixture of GCUAD with the amount of active silica up to about 8% by weight and the amount of Class C fly ash up to about 25% by weight . In still other embodiments, more than two, such as three, four, or more, fillers can be incorporated into a mixture of GCUAD.
In a mixture of GCUAD, fillers with different average particle sizes and reactivities can be added together to achieve the highest packing density of a mixture of GCUAD and to improve geopolymerization, which can lead to an improvement in product performance. Both active silica / fly ash (Class C and / or Class F) and active silica / ground quartz powder are preferred examples of such combinations. Aggregates
An optional second element in a GCUAD mixture is an aggregate. Aggregates limit the geopolymeric matrix to add strength, and can be fine or crude, with fine aggregates understood to have a particle size ranging from about 0.075 mm to 1 mm, such as from about 0.15 to 0.60 mm. If a fine aggregate is used in the GCUAD mixture, any aggregate well known in the art can be used. An exemplary fine aggregate is ordinary fine river sand, which can be added to a mixture of GCUAD by up to about 75% by weight, such as from about 30 to 60% by weight, such as from about 40 to 60% % by weight, such as from about 25 to 55% by weight, such as up to about 50% by weight, such as from about 10 to 30%, such as from about 15 to 25% by weight.
Optionally, the aggregate with a particle size between about 0.75 and 10 mm, such as between about 1 and 5 mm, such as between about 1 and 2 mm, can also be added to a mixture of GCUAD in up to about 50% by weight, preferably together with fine aggregates. Examples of crude aggregates include, but are not limited to, ground quartz, granite, gneiss, basalt, limestone and calcined bauxite sands.
Blast granulated blast furnace slag with a particle size between about 0.1 and 10 mm can also be used as an aggregate in a GCUAD mixture. Strong connection between the aggregated particles and the geopolymeric matrix can be observed in such mixtures, due to the high reactivity of the furnace slag in alkaline solution Strength Enhancers
Optionally, at least one resistance enhancer can be added to the activator solution of up to about 2% by weight, such as from about 0 to 3% by weight, such as from about 0 to 2% by weight, such as from about 0.5 to 1.5% by weight, or as about 0 to 1.5% by weight, such as about 0-0.75% by weight of the GCUAD mixture. Any force enhancer known in the art, or a combination thereof, can be used. Exemplary strength enhancers include, but are not limited to, sodium fluoride, potassium fluoride, sodium sulfate, sodium oxalate, sodium phosphate and related compounds, and aluminum hydroxide. Reinforcement fibers
Optionally, fiber can be added to a GCUAD mixture up to about 15% by weight, such as up to about 10%, such as up to about 7.5% by weight, in order to ensure a desirable ductile behavior of the hardened product. .
Examples of fibers include short fibers, such as: organic fibers (for example, polyvinyl alcohol fibers and polyacrylonitrile fibers), glass fibers (for example, basalt fibers), carbon fibers, and metal fibers.
Metal fibers are preferred because of their malleability; and the substantial increase in ductility that they give to a GCUAD product. Metal fibers are generally chosen from steel fibers, such as high strength steel fibers and stainless steel fibers. The individual length of the metal fibers is generally at least 2 mm and preferably between about 10 and 30 mm. The length to diameter ratio of the metal fibers used for reinforcement is typically in the range of about 10 to 300, and is preferably within the range of about 30 to 100. Fibers with a variable geometry (such as being crimped, wavy) , or hooked at the end) can be used. The bonding of metallic fibers in the geopolymeric matrix can be improved by treating the surfaces of the fibers by methods known in the art, such as acid pickling or coating the fibers with ceramic layers. DRAMIX® steel fibers (such as 13 mm long and 0.20 mm in diameter) from Bekaert Corporation are exemplary metal fibers that were used by the inventors to prepare certain exemplary GCUAD products. Water Reducers / Solids Superplasticizers
Optionally, water reducers or superplasticizer solids can be used to decrease the activator solution for a GCUAD mixture. Superplasticizer solids belong to a new class of water reducers capable of reducing the water content by about 30% for Portland cement-based concretes. Newer superplasticizers include polycarboxylic compounds, such as polyacrylates, although any reducing agent known in the art can be used.
If included, superplasticizer solids are preferably used at up to about 5% by weight, such as up to about 2.5% by weight, such as up to about 1.5% by weight. Set Retarders
Optionally, one or more assembly retarders (eg, boric acid, certain commercial products, such as Daratar 17 from Grace-constructions, etc.) can be included to extend fixation times of a GCUAD paste. Any set retarder known in the art can be included at appropriate levels. Generic Preparation Method and Summary of Constituents
In one embodiment, the activator solution is prepared by dissolving silica fume in the alkali metal hydroxide solution. Optionally, the activator solution can be aged with intermittent agitation. The dry constituents described above, except for the submicron filler, are pre-mixed in an appropriate mixer, such as an intensive mixer. Then, the alkaline activation solution, together with the superplasticizer (if any) and / or resistance enhancer (if any), are poured over the dry mixture and mixed. With a W / C ratio close to optimum, the dry mixture becomes a granular mixture, which becomes a sand mixture under continuous mixing at high shear speed, for example, at about 250 revolutions per minute or higher. Filling submicron, such as active silica, is then added and mixed, and the mixture like sand becomes a mixture like dough that finally becomes a homogeneous, functional, fluid, paste that is ready for filling. Short fibers (if any) are preferably added towards the end of the mixing process, such as, together with submicron filler material or later.
The ultra-high performance geopolymeric concretes (GCUAD) of the present invention can be manufactured by known methods, such as the known methods of mixing dry constituents, together with an activator solution, molding and placing (molding, filling, injection, pumping) , extrusion, roller compaction, etc.), curing and hardening. The GHUPC curing process according to the present invention is not subject to any particular limitations. Any common curing process can be used for cast-in-place and precast concretes.
The constituents and their proportions in various mixtures of GCUAD are compiled and presented in Tables 1 and 2. Table 1. Constituents and their proportions in the mixture of GCUAD
Table 2. Constituents and their preferred proportions in GCUAD mixture
Restriction Parameters
Restriction parameters and their respective 5 intervals can be used to define some non-limiting formulations of GCUAD. Restrictive parameters are defined for the specific components used in the GCUAD mixture.
In embodiments metakaolin is used as a reactive aluminosilicate, the metakaolin restricting parameters include a set of molar ratios of SiO2 / AI2O3, M2O / AI2O3, and H2O / M2O, where M represents one or more alkali metals (for example, Na , K, Li) or alkaline earth metals. The molar ratio SÍO2 / AI2O3 θmmetacaulim is about 2. Alkali hydroxide and alkaline silicate are added to the solution to obtain the values necessary for the characteristic molar ratios of an activation solution. These characteristic molar ratios are SiO2 / AI2O3 between about 3.0 to 6.0, such as from about 3.25 to 4.5, as from about 3.5 to 4.0M2θ / Al2C> 3 of about 0.7 to 1.5, such as from about 0.9 to 1.25, or about 1.0 to 1.35, with and H2O / M2O from about 5.0 to 18, 0, such as from about 5.0 to 14.0, such as about 6.0 to 10.0.
In embodiments where ashes from synthetic glass powder are used as a reactive aluminosilicate; vitreous calcium aluminum silicate is used as a reactive alkaline earth aluminum silicate; blast furnace slag is used as a reactive alkaline earth aluminum silicate, or some combination thereof, the restrictive parameters are as follows. The restrictive parameters include a set of mass fractions of M2O, SiO2, H2O, and SiO2 / H2O molar ratio, which are used to formulate an activation solution. Both reactive aluminosilicate and reactive alkaline earth aluminosilicate are pozzolanic materials responsible for the formation of a geopolymeric matrix. Mass fractions of M2O or SiO2 from pozzolanic materials can vary from about 0.03 to 0.15, such as about 0.05 to 0.10. The SiO2 / M2O molar ratio ranges from about 0.2 to 2.5, such as about 0.8 to 1.5. The mass fraction of H2O ranges from about 0.15 to 0.40, such as about 0.25 to 0.30. Alkali metals can be any of Na, K or Li, or any combination, with Na particularly useful for cost savings. The amounts of alkaline hydroxide, alkaline silicate and water needed for the reactive components are added together to formulate an activation solution composition.
Parameter restriction for CKD as a reactive alkaline earth aluminum silicate includes mass fractions of SiO2 (dissolved silica or any other source of amorphous silica material - for example, micro-silica, active silica, etc.), AI2O3 (dissolved aluminate, alumina, aluminum hydroxides, etc.), and H2O. CKD is rich in free lime and plaster, showing strong hydraulic pozzolanic properties. Mass fractions of SiO2 range from about 0.05 to 0.75, such as about 0.25 to 0.5. The mass fraction of AI2O3 ranges from about 0.00 to 1.0 and the mass fraction of water ranges from about 0.15 to 0.6, preferably from about 0.25 to 0.35. The resulting gel compositions will include CSH, etringitis, CASH and AAS.
No restrictive parameters are required for the use of one or more of active silica, precipitated silica, alumina or calcined zeolite as reactive filler material, if these reactive fillers are added to a GCUAD mixture in a small amount, for example, less than about 2% by weight of the mixture. However, if the combined reactive fillers exceed 2% by weight of the mixture, certain restrictive parameters need to be applied. Mass fractions of M2O for the indicated reactive fillers can vary from about 0.0-0.10, such as about 0.025 to 0.05. The mass fraction of H2O ranges from about 0.0-0.15, such as from about 0.025 to 0.05.
In embodiments where fly ash is used as a reactive filler material, additional soluble silica can be added to the activator solution with mass fractions of SiO2 from the reactive fillers ranging from about 0.0-0.10, such as about 0.025 to 0.05. The SiO2 / H2O molar ratios range from about 0.2 to 2.5, such as about 0.8 to 1.5.
Water for the mass ratio of geopolymeric solids (W / C) is a very important parameter for a GCUAD mixture. As used herein, the term "geopolymer solids" is defined as the sum of the masses of the reactive components in the binder (i.e., reactive aluminosilicate and / or reactive alkaline earth aluminosilicate) and dissolved alkaline oxide and silicon dioxide masses on the activator. The W / C ratio is determined by a set of parameters, such as the H2O / M2O molar ratio for metakaolin (if present), H2O mass fraction, for 15 reactive alkaline earth aluminosilicate and other reactive aluminosilicate materials other than metakaolin (if any), H2O mass fraction for reactive fillers, as well as when and when a superplasticizer is applied. In certain examples presented here, masonry sand with a humidity of about 2.5% by weight is used as a fine aggregate. If the moisture content of the fine aggregate deviates by about 2.5% by weight, the mixture must be corrected for the H2O difference. Typically, the W / C ratios in the GCUAD mixture range from about 0.12 to 0.60 such as about 0.20-0.50, such as about 0.30-0.45. Table 3 shows general restrictions and preferred values used to formulate the activator solution for a mixture of GCUAD. Table 3. Restrictions and preferred ranges for activator solution
* BFS stands for reactive alkaline earth aluminosilicate GCUAD mixture formulation
What follows is a general approach to formulating a mixture of GCUAD. First, percentages by weight of aggregate, filler, fiber (if any), and superplasticizer solids (if any) are prescribed.
Secondly, the percentage of the weight of reactive alkaline earth aluminum silicate and reactive aluminum silicate is defined with a desired mass ratio. Third, the proportions of aggregate, filler and binder can then be optimized in terms of the maximum density theory. The composition of an activation solution is formulated based on a set of parameter restrictions and their respective ranges for the constituents (ie reactive aluminosilicate, reactive alkaline earth aluminosilicate and certain reactive fillers) by adding the quantities required of alkali metal hydroxide, dissolved silica and / or dissolved alumina (if any), and water. Finally, the binder (reactive aluminosilicate and / or reactive alkaline earth aluminosilicate), filler (if any), aggregates (if any), fiber (if any), superplasticizers (if any), retarder assemblies (if any) and the activation solution are then normalized so that the total amounts of GCUAD composition mix are 100% by weight.
In principle, GCUAD's performance is at least partially dependent on the packing density of all particles of the dry constituents, including reactive aluminosilicate, reactive alkaline earth silicate, aggregate and filler. Because GCUAD products can be manufactured from locally available materials, it is beneficial to determine packaging densities of test samples with different proportions of components using both dry and wet pressing methods. Compositions with a higher density of packaging particles can then be subjected to optimization processes.
Typical reasons for an activation solution include the W / C ratio, the activator for geopolymeric solids ratios, alkaline oxide for geopolymeric solids ratios, soluble silica for geopolymeric solids ratios, and soluble silica for alkaline oxide, all by weight. The preferred ranges of these characteristic ratios are determined by the restriction of parameters and their respective defined intervals for each of the GCUAD components where they apply. The M2O (M = K, Na) of the ratio of geopolymer solids, by weight, is generally in the range of about 0.01 to 0.25, such as about 0.02 to 0.15, such as about 0 , 05 to 0.10. The SiO2 of the geopolymeric solids ratio is generally in the range of about 0.01 to 0.25, such as about 0.03 to 0.25, such as about 0.02 to 0.20, such as 0, 05 to 0.15. The Si2 of the Na2 <0 weight ratio is generally in the range of about 0.1 to 2.0, such as about 0.5 to 1.5, such as about 0.75 to 1.25. The activator for weight ratio of geopolymer solids is generally in the range of about 0.20-1.25, such as about 0.50 to 1.0. The activator for the total solid ratio is generally in the range of about 0.05 to 0.70, such as about 0.30 to 0.50. For an activation solution, the preferred metal silicate is a mixture of alkali metal silicates, such as potassium and sodium with mass ratios of K2θ / Na2θ from about 0 to 5; and the preferred alkali metal hydroxide is a mixture of alkali metal hydroxides, such as and Na with mass ratios of K2θ / Na2θ from about 0.1 to 3.
The molar concentrations of alkaline hydroxide (eg, KOH and NaOH) in activator solution are generally in the range of about 5 to 15 M, preferably from about 7.5 to 12 M. The moisture present in the aggregate is generally included in such calculations.
Activator solution ranges from about 10% by weight to about 40% by weight of the concrete mixture.
Manipulation of the proportions of constituents within certain intervals (see, for example, Table 1), allows the optimization of GCUAD mixing compositions to achieve rapid strength growth and high final strength. GCUAD mixtures described herein can be formulated for applications at ambient temperatures, or specifically formulated for any application at any other temperature normally applied in the construction industry, such as for precast applications, which generally require curing at elevated temperatures for achieve high production rates. An advantage of the GCUAD mixture described here is that, in addition to the high compressive strength of the final product, thermal curing may not be necessary. The curing temperature can be lower than those for conventional CUAD. For example, curing can be performed at less than or equal to about 250 ° C, such as less than or equal to about 100 ° C, such as less than or equal to about 75 ° C, such as less than or equal to about 50 ° C, such as less than or equal to about 45 ° C, such as less than or equal to about 30 ° C, such as less than or equal to about 25 ° C, such as less than or equal to about 20 ° C.
Initial adjustment time for GCUAD mixtures described herein can be from about 0.5 to about 3 hours, such as about 0.5 to 1 hour. After the composition is adjusted, it is cured for 24 hours or more, such as 24 hours to a week or more, at a curing temperature between about 20 ° C and about 75 ° C. Desired adjustment times can be obtained by optimizing the binder composition and filler material (for example, choosing binder and filler compositions with different reactivities in alkaline solutions), or by other methods known in the art.
The following examples serve to illustrate the invention. These examples are in no way intended to limit the scope of the methods. EXAMPLES
In the following Examples, all GCUAD pastes were cured at room temperature, for example, about 25 ° C, unless other curing temperatures are specified.
Masonry sand from Industrial Aggregates was used as a fine aggregate that has a particle size between 50 and 600 pm with an average size of about 250 pm. The moisture of the fine aggregate was about 2.5% by weight at room temperature. The fine aggregate moisture was included to calculate the molar concentrations of alkaline hydroxide and water to the ratio of geopolymeric solids. Actual moisture deviation of 2.5% by weight has been corrected. # 4 QROK was used as raw quartz sand having a particle size between 0.6 and 1.7 mm and Min U-SIL® was used as a ground quartz powder having a particle size between 1 to 25 pm with a average diameter of about 5 pm. Both quartz products were from U.S. Silica.
Metacaulino (Kaorock) was from Thiele Kaolin Company, Sandersville, GA. The metakaolin had a particle size between 0.5 and 50 pm with 50% by volume less than 4 pm.
Class 120 milled granulated blast furnace slag (NewCem Slag cement) was from Lafarge, North America Inc. (Baltimore Terminal). The oven slag had a particle size between 0.5 and 60 pm, with 50% in volume less than 7 pm.
Active silica, a product of the Fe-Si alloy industrial residue, was from Norchem Inc. The active silica contained 2.42% by weight of carbon. Active silica was used to prepare activator solutions by dissolving active silica in the alkali metal hydroxide solution, or added as a submicron reactive filling material.
A fly ash class F (Micron3) was from Boral Material Technologies Inc. Boral fly ash had a particle size between 0.5 and 125 pm with 50% by volume below 15 pm. Another class of F ash from Brandon Shores Power Station, Baltimore, MD, was from Separation Technologies LLC. Brandon Shores fly ash showed lower CaO (0.9% by weight) and low ignition loss (<1.5%) and was marketed under ProAsh. Brandon Shores ash had a particle size between 0.6 and 300 pm with 50% by volume below 26 pm. Another class of F ash from Limestone Power Station, Jewett, Texas, was from Headwater Resources. Jewett fly ash contained about 12% by weight of CaO and had a particle size between 0.5 and 300 pm with 50% by volume below 15 pm.
DRAMIX® steel fibers (13 mm long and 0.20 mm in diameter) from Bekaert Corporation were used to improve ductility.
The compressive strength was measured on a Test Mark CM-4000-SD compression machine, according to the ASTM C39 / C39M method. During the test, all samples were covered with rubber blocks, because the upper and lower surfaces are not sufficiently plane-parallel for bare measurement. Example 1
KOH (90%) and NaOH (98%) were dissolved in tap water to make the solution alkaline with a mechanical stirrer, and active silica was dissolved in NaOH and KOH solution. Norchem Inc. active silica contained about 2.42% by weight of carbon. The activator solution was black due to undissolved carbon. The activator solution was aged for about two days before sample preparation. Masonry sand with about 2.5% moisture by weight was used as fine aggregate. To prepare the GCUAD, the following components were first mixed dry: Metacaolin as reactive aluminosilicate (12.65% by weight), granulated blast furnace slag ground as alkaline earth aluminosilicates (32.65% by weight), calcined zeolites 13X and active silica as reactive fillers (total of 2% by weight), and Masonry sand as fine aggregate (19.00% by weight). Then, the activator was prepared by mixing: Na2O (2.52% by weight) as NaOH, K2O (6.18% by weight) as KOH SiO2 (8.44% by weight) as active silica, H2O (16.55 % by weight), and strength enhancers. Force enhancers used in the mixture included aluminum hydroxide, sodium carbonate, sodium phosphate, sodium sulfate, sodium oxalate and fluoride. Total addition was about 1.25% by weight of the concrete mix. These were dissolved in water before using. The activator solution was mixed with the dry components premixed with a UNITEC EHR23 hand mixer (maximum speed 275 rpm). During mixing, the following phases were observed: dry mixture, mixture like sand, mixture like granules, mixture like dough, and finally, the dough-like mixture became a thin paste, which could be poured, indicating that the combination had an almost excellent or excellent W / C ratio. The functional time of the final phase (the thin paste) was about 50 min. The paste was placed in cylindrical molds (2 by 4 inches), vibrated during filling for about 3 minutes so that the bubbles escape, and then cured at room temperature. After 24 hours, the cylinders were demolded and stored at room temperature. After curing for 28 days, the compressive strength of the samples was measured to be 23341 psi. Example 2
A second example of GCUAD was prepared as follows. KOH (90%) and NaOH (98%) were dissolved in tap water to make the solution alkaline with a mechanical stirrer, and high purity active silica (about 99.5% by weight) from Cabot Corporation was dissolved in the KOH and NaOH solution. Sodium fluoride, used as a resistance enhancer, was first dissolved in tap water. The addition was about 0.5% by weight of the concrete mixture. The following constituents (unless otherwise indicated, obtained from the sources indicated above) were mixed dry: Reactive metakaolin as reactive aluminosilicate (12.87% by weight), Granulated blast furnace slag ground as alkaline earth aluminosilicate (33, 20% by weight), calcined Zeolite 13X and active silica as reactive fillers (total of 2% by weight), sodium fluoride as a strength enhancer (about 0.6% by weight of dry GCUAD), and Masonry sand as fine aggregate (19.00% by weight). Then, the activator was prepared by mixing: Na2O (2.57% by weight) as NaOH, K2O (6.28% by weight) as KOH, SiO2 (8.59% by weight) as active silica, and H2O (15 , 50% by weight). Grace Constructions ADVA 140M superplasticizer was added to the activator before mixing with the pre-mixed dry components. The superplasticizer dose was about 1,500 ml per 100 kg of dry product. During the mixing of the dry constituents together with the activator solution, the same phases were observed (dry mixture, mixture like sand, mixture like granules, mixture like mass, and, finally, a fine paste). The functional time of the final phase (the thin paste) was about 50 min. As in Example 1, the samples were poured, cured at room temperature, de-molded after curing for 24 hours and stored at room temperature. After a 28 day cure, the compressive strength of the samples was measured to be 21248 psi. Example 3
Using the same procedure described in Example 1, with no reducing agent added, additional GCUAD samples (Samples 3-9) were prepared to test the effect of individual strength enhancers on the activator solution. Individual strength enhancers evaluated in samples 2-4 and 6-9 were tin fluoride, sodium fluoride, sodium oxalate, sodium sulfate, and aluminum hydroxide. Each addition was about 0.5% by weight of the concrete mixtures. No force enhancers were included in Example 5. Compressive strengths were measured after curing for 28 days. All samples were measured above 20000 psi of compressive strength. The composition, W / C, the concentration of alkaline hydroxides in the activator solution, and the compressive strength of the additional samples are shown in Table 4. Table 4. Composition (% by weight) / W / C, molar concentration of alkaline hydroxides in activator solution, and compressive strength (psi) from GCUAD samples *
* SFF = active silica filling; ZT = zeolite; Na2O and K2O added as hydroxides, and SiO2 added as active silica (eg Fe-Si residue alloy) to prepare activator solutions. Example 4
Using the same procedure as described in Example 1, additional GCUAD samples (Samples 10-16) were prepared. Compressive strengths were measured after curing for 28 days. About 1.2% by weight of superplasticizer solids (Grace Constructions' ADVA 575 mold) was added to reduce water demand and to improve the fluidity of pastes. Force enhancers, including sodium fluoride, sodium oxalate, sodium sulfate and aluminum hydroxide together were added to about 1.15% by weight. In Example 13, steel fibers from Bekaert Corporation at about 2% by weight (not shown in Table 5) were added in the last mixing step to improve ductility. The composition, W / C, concentration of alkali hydroxides in activator solution and resistance to compression of the additional samples are shown in Table 5. Table 5. Composition (% by weight), W / C, molar concentration of alkali hydroxides in solution of activator, and compressive strength (psi) from additional GCUAD samples *
* SFF = active silica filling; ZT = zeolite; SP = superplasticizer solids; Na2O and K2O added as respective hydroxides and SiO2 added as active silica (e.g., Fe-Si residue alloy) to prepare activator solutions. Example 5
Using the same procedure as described in Example 1, additional GCUAD samples (Samples 17-33) were prepared. The samples were cured at room temperature and their compression forces were measured after curing for 28 days. Ground quartz (QZ) with an average particle size of 15 pm from US Silica was used as a weak reactive filler to improve the packaging density of the products. No superplasticizers were added. In Examples 18, 23, 29 and 32, about 2% by weight of steel fiber from Bekaert Corporation was added to improve ductility. In Examples 20-22, molar fluoride (F) / Si in an activator solution was increased from 0.2 to 0.3 and 0.4, respectively, to test the effect of fluoride concentration on performance. Likewise, sodium fluoride 5 was increased from 0.90, 1.35, to 1.79% by weight of the concrete mixture. The composition, W / C, concentration of alkaline hydroxides in activator solution, and compressive strength of the additional samples are shown in Table 6. Table 6. Composition (% by weight), W / C, molar concentration of alkaline hydroxides in solution of activator, and compressive strength (psi) from additional GCUAD samples
* SFF = active silica fillers; ZT = zeolite; Fiber = steel fiber; QZ = crushed quartz, Na2O and K2O added as hydroXides and SiO2 added as active silica (for example, Fe-Si residue alloy) to prepare activator solutions. Example 6
Using the same procedure as described in Example 1, additional samples of GCUAD were prepared (Samples 34-42). The samples were cured at room temperature and their compression forces were measured after curing for 28 days. In these samples, masonry sand was used as a fine aggregate and active silica and zeolite were added together as reactive fillers. Force enhancers, including sodium fluoride, sodium oxalate, sodium sulfate, and aluminum hydroxide together were added to about 1.15% by weight of the concrete mixture in Samples 34-40. Sodium fluoride and sodium oxalate were added to about 0.8% by weight of the concrete mixture in Samples 41 and 42. No superplasticizers were added. In Example 40, steel fibers from Bekaert Corporation were added to improve ductility. The composition, W / C, concentration of alkaline hydroxides in activator solution, and compressive strength of the additional samples are shown in Table 7. Table 7. Composition (% weight), W / C, molar concentration of alkaline hydroxides in activator solution , and compressive strength (psi) from additional samples of GCUAD *
* SFF = active silica fillers; ZT = zeolite; Fiber = steel fiber; Na2O and K2O added as hydroxides respectively and SiO2 added as active silica (e.g., Fe-Si residue alloy) to prepare activator solutions. Example 7
Using the same procedure as described in Example 1, additional GCUAD samples (Samples 43-48) were prepared. The samples were cured at room temperature and their compression forces were measured after curing for 28 days. In these samples, masonry sand was used as fine aggregate, and silica fume and / or zeolite were added as reactive fillers. Force enhancers, including sodium fluoride, sodium oxalate, sodium sulfate and aluminum hydroxide together were added to about 1.15% by weight of the concrete mixture in Samples 43-45. Sodium fluoride and / or sodium oxalate were added as strength enhancers in about 0.7% by weight of the concrete mixture in Samples 46-48. No superplasticizers were added. Class F ash from Boral Material Technologies was used as a reactive filler. The composition, W / C, concentration of alkaline hydroxides in activator solution and resistance to compression of the additional samples are shown in Table 8. Table 8. Composition (% by weight), W / C, molar concentration of alkaline hydroxides in solution of activator and compressive strength (psi) from additional GCUAD samples
* SFF = silica filler; ZT = zeolite; FFA = fly ash class F; Na2O and K2O added as hydroXides and SiO2 added as active silica (for example, Fe-Si residue alloy) to prepare activator solutions EXAMPLE 8
Using the same procedure as described in EXAMPLE 1, additional GCUAD samples (Samples 49-52) were prepared. The samples were cured at room temperature and their compressive strengths were measured after curing for 28 days. In these samples, masonry sand was used as a fine aggregate and active silica and / or zeolite were added as a reactive filler. Ground quartz (QZ) with an average particle size of 15 µm from US Silica was used as a weak reactive filler. In addition, coarse quartz sand (# 4 Q-ROK) from US Silica was added to improve the packing density. Force enhancers used in these samples included aluminum hydroxide, sodium carbonate, sodium phosphate, sodium sulfate, sodium oxalate and fluorine. Total addition of force enhancers was about 0.85% by weight of the concrete mixture in Samples 49 and 51. Sodium fluoride alone was added as a strength enhancer of about 0.25% by weight of the concrete mixture in Samples 50 and 52. No superplasticizers were added. The composition, W / C, concentration of alkaline hydroxides in activator solution, and compressive strength of the additional samples are shown in Table 9. Table 9. Composition (% by weight), W / C, molar concentration of alkaline hydroxides in solution of activator, and compressive strength (psi) from additional GCUAD samples
* SFF = silica filler; CA = gross aggregate; Qz = ground quartz; Fiber = steel fiber; Na2O and K2O added as respective hydroXides and SiO2 added as active silica (for example, residual De-Si llifa) to prepare activator solutions EXAMPLE 9
Using the same procedure as described in EXAMPLE 1, additional GCUAD samples (Samples 53-56) were prepared. The samples were cured at room temperature and their compression forces were measured after curing for 28 days. In these samples, masonry sand was used as a fine aggregate and silica fume was added as a submicron reactive filler. US Silica's ground quartz (QZ) was used as a weak reactive filler. Sodium fluoride (NaF) at about 0.25% by weight of the concrete mixture was added as a strength enhancer. No superplasticizers were added. In Example 55, steel fibers from Bekaert Corporation were added to improve ductility. The composition, W / C, concentration of alkaline hydroxides in activator solution, and compressive strength of the additional samples are shown in Table 10. Table 10. Composition (% by weight), W / C, molar concentration of alkaline hydroxides in solution of activator, and compressive strength (psi) from additional GCUAD samples *
* SFF = silica fills, QZ = ground quartz; Fiber = steel fiber; Na2O and K2O added as hydroxides and SiO2 added as silica fume (eg Fe-Si binds residue) to prepare activator solutions Example 10
Using the same procedure as described in Example 1, additional GCUAD samples (Samples 57-64) were prepared. The samples were cured at room temperature and their compression forces were measured after curing for 28 days. In these samples, masonry sand was used as a fine aggregate and active silica and / or zeolite were added as a reactive load. US Silica ground quartz (QZ) was used as a weak reactive filler in samples 62 and 64. Activator solutions were prepared using predominantly sodium hydroxide and industrial silica residues from Norchem Inc. Force enhancers used in these samples included hydroxide aluminum, sodium carbonate, sodium phosphate, sodium sulfate, sodium oxalate and fluorine. Total addition of strength enhancers was less than about 1.0% by weight of the concrete mix. These were dissolved in water before the alkali hydroxides dissolved. No superplasticizers were added. The composition, W / C, concentration of alkaline hydroxides in activator solution and compressive strength of the additional samples are shown in Table 11. Table 11. Composition (% by weight), W / C, the molar concentration of alkaline hydroxides in solution of activator, and compressive strength (psi) from additional GCUAD samples *
* SFF = active silica fillers; QZ = ground quartz; Fiber = steel fiber; Na2O and K20 added as respective hydroxides and SiO2 added as active silica (eg Fe-Si residue alloy) to prepare activator solutions Example 11
Using a procedure similar to that described in Example 1, additional GCUAD samples (Samples 65-67) were prepared. The samples were cured at room temperature and their compression forces were measured after curing for 28 days. In these samples, masonry sand was used as a fine aggregate and active silica from Norchem Inc. was used as a reactive submicron filler. US Silica ground quartz (QZ) was used as a weak reactive filler in samples 65 and 66. Boral Material Technologies Class F ash was used to replace ground quartz powder in sample 67. Activator solutions were prepared using silicate solution commercially available sodium (Ru ™ sodium silicate solution, PQ Inc.), instead of dissolving the active silica in an alkaline hydroxide solution. The sodium fluoride (NaF) at about 0.25% by weight of the concrete mixture was added as a force enhancer. No superplasticizers were added. The composition, W / C, concentration of alkaline hydroxides in activator solution, and compressive strength of the additional samples are shown in Table 12. Table 12. Composition (% by weight), W / C, molar concentration of alkaline hydroxides in solution of activator, and compressive strength (psi) from additional GCUAD samples
* SFF = active silica filling; QZ = ground quartz; FFA = class F ash Example 12
Using the same procedure as described in Example 1, additional GCUAD samples were prepared (Samples 68-70). The samples were cured at room temperature and their compressive strengths were measured after curing for 28 days. In these samples, masonry sand was used as fine aggregate and active silica from Boral Material Technologies were used as reactive filler in samples 68 and 70. Active silica together with the ground quartz (QZ) from US Silica were used as reactive filler in Sample 69 The activator solutions were prepared by dissolving active silica from Norchem Inc. in an alkaline hydroxide solution with a mass ratio of K2O / Na2O of about 0.8. Sodium fluoride (NaF) at about 0.25% by weight of the concrete mixture was added as a strength enhancer. No superplasticizers were added. The composition, W / C, concentration of alkaline hydroxides in activator solution, and compressive strength of the additional samples are shown in Table 13. Table 13. Composition (% by weight), W / C, molar concentration of alkaline hydroxides in solution of activator, and compressive strength (psi) from additional GCUAD samples
* SFF = active silica fillers; QZ = ground quartz; Fiber = steel fiber; Na2O and K20 added as respective hydroxides and SiO2 added as active silica (eg Fe-Si residue alloy) to prepare activator solutions EXAMPLE 13
Using a procedure similar to that described in Example 1, additional GCUAD samples (Samples 71-88) were prepared. Mixing was carried out with an intensive elbow mixer (Mixer K-Lab by Lancaster Products). The samples were cured at room temperature and their compression forces were measured after curing for 28 days. In these samples, masonry sand was used as a fine aggregate and active silica from Norchem Inc. together with milled quartz (QZ) from US Silica were used in samples 71-79. Active silica in conjunction with Boral Material Technologies class F ash was used as a reactive filler in samples 80-86. Zeolite was used as a reactive filler in samples 87 and 88. The activator solutions were prepared by dissolving active silica from Norchem Inc. in alkaline hydroxide solution with mass ratios of I <2θ / Na2θ from about 2 to about 3 Steel fiber from Bekaert Corporation was added to improve ductility in samples 71, 73, 76, 81, 85 and 87. Sodium fluoride (NaF) at about 0.25% by weight of the concrete mixture 15 was added as a strength enhancer. No superplasticizers were added. The composition, W / C, concentration of alkaline hydroxides in activator solution, and compressive strength of the additional samples are shown in Table 14. Table 14. Composition (% by weight), W / C, molar concentration of alkaline hydroxides in solution of activator, and compressive strength (psi) from additional GCUAD samples *
* SFF = active silica filling; QZ = ground quartz; FAF = Class F ash, Na2O and K20 added as respective hydroxides and SiO2 added as silica fume (eg Fe-Si residue alloy) to prepare activator solutions ** Zeolite Example 14
Using the same procedure as described in Examples 71-88, additional GCUAD samples (Samples 89-92) were prepared. Mixing was performed with a high intensive mixer (Mixer K-Lab from Lancaster Products). Initial adjustment time was determined using a Vicat system. The samples were cured at room temperature and their compression forces were measured after curing for 3 hours, 6 hours, 1 day, 3 days, 7 days, 15 days, 21 days and 28 days. In these samples, masonry sand was used as a fine aggregate and active silica from Norchem Inc., together with class F ash from Boral Material Technologies was used as a reactive filler in Example 89. Active silica together with US milled quartz (QZ) Silica were used as reactive filler in samples 90-92. Activator solutions were prepared by dissolving silica fume from Norchem Inc. in an alkaline hydroxide solution with a mass ratio of K2O / Na2O of about 2.2. No superplasticizers were added. Sodium fluoride (NaF) was added as a strength enhancer. The composition, W / C, concentration of alkaline hydroxides in activator solution of the additional samples are shown in Table 15. Compressive forces of Samples 89-92 at the times indicated above are shown in Table 16. A portion of these compressive forces versus time of curing is shown in Figure 1. Table 15. Composition (% by weight), W / C, molar concentration of alkaline hydroxides in activator solution, and compressive strength (psi) from additional GCUAD samples *
* SFF = active silica filling; QZ = ground quartz; FAF = Class F ash, Na2O and K20 added as hydroxides and SiO2 added as active silica (for example Fe-Si residue alloy) to prepare activator solutions Table 16. Compressive strength (psi) of samples pasted during different times
Example 15
Using the same procedure as described in Example 13, additional GCUAD samples (Samples 93-98) were prepared. Mixing was carried out with a high intensive mixer (Mixer K-Lab from Lancaster Products). The samples were cured at room temperature and their compression forces were measured after curing for 3 hours, 6 hours, 1 day, 3 days, 7 days, 15 days, 21 days and 28 days. In these samples, masonry sand was used as a fine aggregate and active silica from Norchem Inc., together with Class F low CaO ash from Brandon Shores Power Stations, Baltimore, Maryland (Separation Technologies) was used as reactive filler in samples 93, 95 , 97 and 99. Active silica from Norchem Inc., along with Limestone Power Station Class F low ash ash, Jewett, Texas (Headwater Resources) were used as reactive filler in samples 94, 96, 98 and 100. Activator solutions were prepared by dissolving active silica from Norchem Inc. in alkaline hydroxide solution with a mass ratio of K2O / Na2O of about 2.2. No superplasticizers were added. The sodium fluoride (NaF) at about 0.25% by weight of the concrete mixture was added as a force enhancer. The composition, W / C, concentration of alkaline hydroxides in activator solution of the additional samples are shown in Table 17. Compressive forces of Samples 93-98 at the times indicated above are shown in Table 18. Table 17. Composition (% by weight), W / C, molar concentration of alkaline hydroxides in activator solution, and compressive strength (psi) from additional GCUAD samples
* SFF = active silica filling; QZ = ground quartz; FAF = Class F ash, Na2O and K20 added as hydroxides and SiO2 added as active silica (eg Fe-Si residue alloy) to prepare activator solutions Table 18. Compressive strength (psi) of samples cured for different times
ND = not determined The content of articles, patents and patent applications, and all other documents and information available electronically or mentioned here, are incorporated by reference in their entirety to the same extent as if each individual publication were specifically and individually indicated to be incorporated by reference. Applicants reserve the right to physically incorporate into this application any and all materials and information from any of these articles, patents and patent applications, or other physical and electronic documents. The methods described here illustratively can be practiced properly in the absence of any element or elements, limitations or limitations that are not specifically described herein. Thus, for example, the terms "comprising", "including," containing ", etc. should be read expansively and without limitation. Furthermore, the terms and expressions used herein were used as terms of description and not of limitation, and not there is an intention, in the use of such terms and expressions, to exclude any equivalents of the characteristics shown and described or their portions. It is recognized that several modifications are possible within the scope of the claimed invention, so it should be understood that, although the present invention has been specifically described by preferred embodiments and optional features, modification and variation of the invention incorporated herein disclosed can be invoked by those skilled in the art, and that such modifications and variations are considered to be within the scope of the present invention. broadly and generically described here. Each of the narrowest species and subgeneric groups that fall within the generic description are also part of the methods. This includes the generic description of methods with a negative condition or limitation removing any subject of the kind, regardless of whether or not the excised material is specifically recited here. Other embodiments are within the following claims. In addition, when the characteristics or aspects of the methods are described in terms of Markush groups, those skilled in the art will recognize that the invention is thus described in terms of any individual member or subgroup of members of the Markush group.

权利要求:
Claims (15)
[0001]
1. Mixture of ultra-high performance geopolymer concrete composite (GCUAD), characterized by the fact that it comprises: (A) a binder comprising one or more selected from the group consisting of reactive aluminosilicate and reactive alkaline earth aluminosilicate; wherein the binder comprises 10 to 50% by weight of the GCUAD mixture; (B) an alkaline activator comprising an aqueous solution of metal hydroxide and metal silicate; (C) one or more aggregates; and (D) one or more fillers with a particle size up to 75 pm, where the combined fill content is up to 35% by weight of a GCUAD mixture; where a type of one or more fillers has a particle size between 0.05 and 1 pm, and is selected from the group consisting of active silica, precipitated silica, ultrafine calcium carbonate, micron alumina, and submicron particles of metal oxides; and in which the other type of one or more fillers has a particle size between 1 and 75 pm, and is selected from the group consisting of ground quartz, zeolite and ground glass.
[0002]
2. GCUAD mixture, according to claim 1, characterized by the fact that the binder comprises one or more reactive aluminosilicate comprising from 0 to 30% by weight of the GCUAD mixture; optionally in which one or more reactive aluminosilicate is selected from the group consisting of kaolin, reactive vitreous aluminosilicates, and Class F ultrafine fly ash; or wherein the binder comprises one or more reactive alkaline earth aluminosilicates comprising 2 to 40% by weight of the GCUAD mixture; optionally in which one or more reactive alkaline earth aluminosilicate is selected from the group consisting of granulated blast furnace slag, vitreous calcium aluminum silicate (VCAS), class C fly ash, and cement kiln dust.
[0003]
3. GCUAD mixture, according to claim 1, characterized by the fact that the binder comprises reactive aluminosilicate and reactive alkaline earth aluminosilicate; optionally in which the reactive aluminosilicate is meta-kaolin and in which the reactive alkaline earth aluminosilicate is granulated blast furnace slag; optionally wherein the reactive aluminosilicate comprises 2 to 15% by weight of the GCUAD mixture; or wherein the reactive alkaline earth aluminum silicate comprises from 8 to 25% by weight of the GCUAD mixture.
[0004]
4. GCUAD mixture, according to claim 1, characterized by the fact that the combined filling content is 2 to 25% by weight of the GCUAD mixture.
[0005]
5. GCUAD mixture according to claim 1, characterized by the fact that one or more aggregates have a particle size between 0.075 and 10 mm, and comprise up to 75% by weight, preferably 30 to 60% by weight, of the mixture GCUAD; optionally in which one or more aggregates are selected from the group consisting of quartz, granite, basalt, gneiss, limestone and calcined bauxite sand.
[0006]
6. GCUAD mixture, according to claim 1, characterized by the fact that one or more aggregates comprise one or more fine aggregates with a particle size between 0.075 and 0.75 mm; or wherein the alkaline activator solution is 10 to 40% by weight, more preferably 15 to 25% by weight, of the GCUAD mixture.
[0007]
7. GCUAD mixture according to claim 1, characterized by the fact that the metal hydroxide comprises sodium hydroxide, potassium hydroxide, or both; or wherein the metal hydroxide comprises 2 to 10% by weight of M-0 of the GCUAD mixture; or wherein the metal silicate comprises sodium silicate, potassium silicate, or both; or wherein the metal silicate comprises 2 to 10% by weight of SiOs in the GCUAD mixture; or wherein the alkaline activator comprises water of 4 to 25% by weight, more preferably 5 to 15% by weight, of the GCUAD mixture.
[0008]
8. GCUAD mixture, according to claim 1, characterized by the fact that it also comprises one or more fibers, comprising up to 15% by weight of the GCUAD mixture; optionally wherein one or more fibers are selected from the group consisting of organic fibers, glass fibers, basalt fibers, carbon fibers, nano fibers, and metal fibers.
[0009]
9. GCUAD mixture, according to claim 1, characterized by the fact that it also comprises one or more resistance enhancers comprising up to 2% by weight of the GCUAD mixture; wherein one or more resistance enhancers are selected from the group consisting of alkaline carbonate, alkaline phosphate, alkaline sulfate, alkaline oxalate and alkaline fluoride.
[0010]
10. GCUAD mixture, according to claim 1, characterized by the fact that it also comprises superplasticizer solids, comprising up to 5% by weight of the GCUAD mixture; or further comprising a setting retarder, which comprises up to 5% by weight of the GCUAD mixture.
[0011]
11. GCUAD mixture, according to claim 1, characterized by the fact that the packing density of all solid components in the GCUAD mixture is at least 0.5 (v / v), preferably at least 0.6 (v / v) v), more preferably at least 0.7 (v / v).
[0012]
12. GCUAD mixture according to claims 1 to 11, characterized by the fact that the GCUAD mixture has a water to geopolymer solids (W / C) ratio between 0.20 and 0.50, and more preferably between 0.30 and 0.45, where the term "geopolymer solids" is defined as the sum of the masses of the respective constituents of the binder, that is, reactive aluminosilicate and / or reactive alkaline earth aluminosilicate, and masses of alkaline oxide and silicon dioxide dissolved in the activator; the W / C ratio is determined by a set of parameters, such as the H2O / M2O molar ratio for metakaolin, if present, H2O mass fraction for reactive alkaline earth aluminosilicate and other reactive aluminosilicate materials other than metakaolin, fraction mass of H2O for reactive fillings, as well as when and when a superplasticizer is applied; if the moisture content of the fine aggregate deviates from 2.5% by weight, the mixture must be corrected for the H2O difference.
[0013]
13. Method of fabricating a mixture of ultra-high performance geopolymer concrete composite (GCUAD), as defined in any one of claims 1 to 12, characterized by the fact that it comprises: a. mixing a dry mixture of GCUAD with an activator solution to form a GCUAD paste; and b. fixing and curing the GCUAD paste to form a GCUAD product; wherein said dry GCUAD mixture comprises a binder of 10 to 50% by weight, the binder comprises one or more selected from the group consisting of reactive aluminosilicate and reactive alkaline earth aluminosilicate, and the activator solution comprises a aqueous solution of metal hydroxide and metal silicate; the dry mixture further comprises one or more aggregates, and one or more fillers; wherein the combined filling content is 2% to 35% by weight of the GCUAD mixture; wherein a type of one or more fillers with a particle size of up to 75 pm has a particle size between 0.05 and 1 pm, and is selected from the group consisting of active silica, precipitated silica, carbonate of ultrafine calcium, micron alumina, and submicron particles of metal oxides; and in which the other type of one or more fillers has a particle size between 1 and 75 pm and is selected from the group consisting of ground quartz, zeolite, and ground glass.
[0014]
14. Method according to claim 13, characterized by the fact that the GCUAD paste has a setting time of 30 minutes to 3 hours.
[0015]
15. Method according to claim 13, characterized by the fact that the handle of the GCUAD paste has a setting temperature between 20 and 90 ° C.

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公开号 | 公开日

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CA2821512A1|2012-06-21|

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MX2013006638A|2014-01-31|

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EP2651846B1|2019-11-27|

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PL2651846T3|2020-06-29|

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US9090508B2|2015-07-28|

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BR112013014685A2|2016-10-04|

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EP2651846A1|2013-10-23|

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US20120152153A1|2012-06-21|

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KR20140010018A|2014-01-23|

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CA2821512C|2017-10-10|

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CN107265937B|2021-06-29|

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JP2013545714A|2013-12-26|

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-06-11| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2019-11-12| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2020-03-10| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2020-07-07| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-09-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/12/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201061457052P| true| 2010-12-17|2010-12-17|

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US61/457,052|2010-12-17|

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PCT/US2011/065649|WO2012083255A1|2010-12-17|2011-12-16|Geopolymer composite for ultra high performance concrete|

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