self-drying stable dimension hydraulic cement compositions with improved workability

专利摘要:
These are cementitious binder compositions for cementitious products which include a blend of hydraulic cement-based reactive powder, an inorganic flow control agent, and a metal-based dimensional motion stabilizing agent including at least one member of the group. lithium salt and lithium base, and methods for producing cementitious binder compositions.
公开号:BR112019010480A2
申请号:R112019010480
申请日:2017-12-11
公开日:2019-09-10
发明作者:Dubey Ashish；White Paul
申请人:United States Gypsum Co；
IPC主号:

专利说明:

“HYDRAULIC CEMENT COMPOSITIONS WITH STABLE DIMENSION SELF-DESIGNS WITH ENHANCED WORKABILITY”
FIELD OF THE INVENTION [0001] The present invention relates generally to innovative, self-drying, stable-size hydraulic cement compositions that comprise a mixture of reactive powder based on hydraulic cement, an inorganic flow control agent and a metal-based dimensional motion stabilizing agent. In particular, the invention relates, in general, to such cementitious compositions that offer properties that follow exclusive important characteristics: extremely fast surface drying, extremely fast consolidation and development of early resistivity, excellent workability and flow properties, surface drying extremely fast, very low dimensional movement and shrinkage through drying and the ability to incorporate high amounts of water.
BACKGROUND OF THE INVENTION [0002] Perez-Pena Patent Application Publication No. ^Q 2010-0071597 discloses a method for producing a fast-setting light cementitious composition with improved compressibility to products such as slabs. The method mixes fly ash, citric acid alkali metal salt and light aggregate with water. Compositions including fly ash, alkali metal salts of citric acid and light aggregate are also disclosed.
[0003] The US Patent No 4,488,909 to Galer ^Q et al discusses cementitious compositions comprising Portland cement, cement high alumina, calcium sulfate and lime. The cementitious composition includes Portland cement, cement with a high alumina content, calcium sulfate and lime. Pozzolans, such as fly ash, montmorillonite clay, diatomaceous earth and pumicite can be added up to about 25%. The cement composition includes about 14 to 21% by weight of cement with a high alumina content.
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2/97 [0004] Perez-Pena Patent Application Publication No. ^{Q 2010} 2010-0071597 A1 discloses formulations that use fly ash and citric acid alkali metal salts, such as sodium citrate to form concrete mixtures. Hydraulic cement and plaster can be used up to 25% by weight of the formulation, although its use is not preferred. The activated fly ash binders described in the present application can interact with the traditional foaming systems used to insert air and thereby produce light plates.
[0005] Dubey Patent Application Publication 2016-0214897 A1 by Dubey discloses a method for producing geopolymer cementitious binder compositions for cementitious products, such as concrete, pre-melted building fusion elements and panels, mortar, stucco materials for road repairs and other repair materials and the like is revealed. The geopolymer cement compositions of some modalities are produced by mixing a synergistic mixture of thermally activated aluminosilicate mineral, calcium sulfoaluminate cement, calcium sulfate and a chemical activator with water.
[0006] Patent Application Publication No. ^Q US 2016-0194247 A1 by Dubey discloses a method for producing geopolymer cementitious binder compositions for cementitious products, such as concrete, precast mortar building elements and panels and repair materials and the like is revealed. The geopolymer cement compositions of some modalities are produced by mixing a synergistic mixture of thermally activated aluminosilicate mineral, calcium aluminate cement, calcium sulfate and a chemical activator with water.
[0007] The US Patent No. 6641658 of Dubey ^Q discloses a composition for Portland cement concrete base which contains 35 to 90% Portland cement, 0 to 55% of a pozzolan, 5 to 15% cement with a high content of alumina and 1 to 8% calcium sulfate insoluble anhydride form in place of fine-grained plaster (landplaster) / water-soluble plaster for
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3/97 increases the release of heat and decreases the consolidation time despite the use of high amounts of pozzolan, for example, fly ash. The cementitious composition can include light aggregates and fillers, superplasticizers and additives, such as sodium citrate as a reaction retardant.
[0008] Patent No. ^Q US 7,618,490 B2 to Nakashima et al. discloses a spray material comprising one or more of calcium sulfoaluminate, aluminum silicate, calcium hydroxide, a source of fluorine and Portland cement concrete. Calcium sulfate can be added as a plaster of hemihydrate or anhydrous.
[0009] The ^Q US Patent No. 4,655,979 to Nakano et al. reveals a process for producing cellular concrete using calcium silicate-based cement, alkali metal retardant, calcium sulfoaluminate cement (CSA) and an optional calcium sulfate that can be added to the concrete composition.
[0010] Patent Application Publication No. ^Q 2008-0134943 A1 by Godfrey et al. reveals a waste encapsulation material composed of at least one sulfoaluminate salt of an alkaline earth metal with calcium sulphate, and optional inorganic filler, such as blast furnace slag, pulverized fuel ash, fine-divided silica, limestone and organic and inorganic fluidizing agents. Preferably, at least one alkaline earth metal sulfoaluminate salt comprises calcium sulfoaluminate (CSA). A suitable composition can, for example, comprise at least one sulfoaluminate salt of an alkaline earth metal in combination with plaster and pulverized fuel ash (PFA), in which about 86% of the plaster particles have a particle size of less at 76 pm, and approximately 88% of the PFA particles have a particle size of less than 45 pm. An example comprises 75% (70: 30CSA: CaS042H ₂ 0); 25% pulverized fuel ash; water / solids ratio 0.65.
[0011] Patent No. ^Q US 6,730,162 to Li et al. reveals
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4/97 double cementitious compositions that include a first hydraulic composition that has 2.5 to 95% by weight of C4A3S which is a chemical notation where C = CaO, S = SiC> 2, A = AI ₂ O3 (in other words , calcium sulfoalumin) and 2.5 to 95% by weight of a hemihydrate and / or a calcium sulfate anhydride. Sulfoalumin cements or ferroalumin cements are examples of cements that contain C4A3S. They may also include mineral filler additives selected from the group consisting of slag, fly ash, pozzolana, silica root, limestone fines, by-products of industrial lime and waste.
[0012] Published Chinese Order No. CN 101921548 A by Deng et al. reveals a composition of cement sulfoaluminate produced from 90 to 95% by weight of sulfoaluminate clinker and anhydrous plaster, quartz sand, fly ash from waste incineration, hydroxypropyl methylcellulose ether, powder and redispersible glue fiber. Sulfoaluminate clinker and anhydrous plaster meet the cement sulfoaluminate standard, that is, GB20472-2006.
[0013] Published Korean Order No. KR 549958 B1 by Jung et al. reveals a composition of cement alumina, CSA, plaster, calcium citrate and hydroxylcarboxylic acid.
[0014] Published Korean Order No ^Q KR 2009085451 A from Noh, reveals a composition of blast furnace slag, plaster and CSA. Gypsum can have an average particle size of 4 microns or less.
[0015] Published Korean Order n- KR 2009025683 A reveals a waterproof powder material used for concrete and mortar is obtained by spraying cement, anhydrous plaster, silica powder, waterproof powder, fly ash , calcium sulfoaluminate expansion material and inorganic binder.
[0016] The Korean Order Published No. ^Q KR 2010129104 A by Gyu et al. reveals composition to mix injected concrete, comprises (in% by weight): metakaolin (5 to 20), calcium sulfoaluminate (5
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5/97 to 20), anhydrous plaster (20 to 45) and fly ash (30 to 50).
[0017] There is a need for improved cementitious compositions that offer improved fast consolidation and development of early resistivity, workability and flow properties, fast surface drying and little dimensional movement and shrinkage upon drying.
SUMMARY OF THE INVENTION [0018] The present invention provides an ultra-fast and self-drying cementitious composition comprising a reaction product of a mixture of:
[0019] a reactive powder based on hydraulic cement comprising:
[0020] an aluminate cement selected from at least one member of the group consisting of calcium aluminate cement and calcium sulfoaluminate cement in an amount of 25 to 80 parts by weight per 100 parts by weight of the reactive powder based on hydraulic cement;
[0021] Portland cement in an amount of 2.5 to 45 parts by weight for every 100 parts by weight of reactive powder based on hydraulic cement;
[0022] a calcium sulphate selected from the group consisting of calcium sulphate dihydrate, calcium sulphate hemihydrate, anhydrous calcium sulphate and mixtures thereof, with calcium sulphate in an amount of 15 to 45 parts by weight for every 100 parts by weight of hydraulic cement-based reactive powder;
[0023] an inorganic flow control agent in an amount equal to 0.25 to 3.00 parts by weight for every 1.00 parts by weight of reactive powder based on hydraulic cement, and the inorganic flow control comprises at least one member selected from the group consisting of fly ash and calcium carbonate, and in which the average size
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6/97 particle of the calcium carbonate bands of about 10 to 150 microns;
[0024] a metal-based dimensional motion stabilizing agent in an amount equal to 0.50 to 5.00 percent by weight of the hydraulic cement-based reactive powder, the metal-based dimensional motion stabilizing agent being comprises a lithium compound selected from at least one member of the lithium salt and lithium base group, the lithium salt being at least one member of the lithium carbonate, lithium sulphate, lithium nitrate group, lithium nitride and lithium silicate, the base of which is lithium hydroxide;
[0025] a load in a weight ratio between load and reactive powder based on hydraulic cement from 0: 1 to 5.0: 1; and [0026] water in a weight ratio of water to reactive powder based on hydraulic cement of 0.50: 1 to 1.4: 1.
[0027] Preferably, the mixture has an absence of alkali metal hydroxide and an absence of an alkali metal salt other than lithium salt and lithium base.
[0028] If desired, other additives not considered reactive powder based on hydraulic cement, inorganic flow control agent, stabilizing agent of dimensional movement based on metal or filler can be incorporated into the fluid paste and general cementitious composition of the invention. Such other additives can be, for example, water reducing agents, such as superplasticizers, firming agents, firming agents, air insertion agents, foaming agents, wetting agents, shrinkage control agents, viscosity modifying agents (thickeners), polymer powders capable of redispersion of film formation, polymeric dispersions of film formation, pigments, corrosion control agents, mixtures by reducing the alkali-silica reaction, different reinforcing fibers and internal healing agents.
[0029] Self-drying behavior, for
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7/97 effect of the present invention, refers to the material's ability to substantially consume water through chemical reactions in order to obtain a surface that is sufficiently dry and ready for application of adhesives and coatings. The surface drying and self-drying characteristics of a material are measured by pouring a layer approximately 1/4 inch (0.64 cm) thick of the slurry into a shallow plastic tray. ] Then, the self-drying time is characterized as the time when the top surface of the poured slab changes its appearance from a visible wet surface to a hardened surface that is sufficiently dry to allow the application of organic or inorganic adhesives and finish coatings ( such as carpet and other resilient floor coverings) without negatively affecting the short and long term connection between the finishing cover material and the poured slab. The self-drying time usually occurs just after the final consolidation time is reached, typically about 30 to 45 minutes after the final consolidation time.
[0030] The ultra-fast consolidation characteristic of a material, for the purpose of the present invention, refers to a final material consolidation time preferably, less than 180 minutes, more preferably, less than 120 minutes and, more preferably, less than 60 minutes when measured in accordance with the ASTM C191 -13 test procedure.
[0031] The ultra-fast, self-drying cementitious compositions of the present invention can include different fillers and additives including air insertion agents and foaming agents to add air in specific proportions to produce light cement products. Typical compositions can contain air, for example, 0 to 25% by volume or 2 to 25% by volume.
[0032] It was unexpectedly found that a metal salt, such as lithium carbonate when used in addition to a crucial amount in the compositions of the invention, has a positive impact on the reduction and stabilization of dimensional movement both in the short and long term
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8/97 material term. The compositions of the present invention have a maximum shrinkage, preferably less than 0.10%, more preferably less than 0.05% and more preferably equal to or less than 0.00%. When shrinkage due to maximum drying or linear dimensional movement of material is less than 0.00%, it means that the material undergoes a positive net expansion instead of a liquid shrinkage upon drying. The most preferred compositions of the present invention exhibit net positive expansion upon drying and not liquid shrinkage. Shrinkage by drying or linear dimensional movement of the material is typically measured in accordance with the ASTM C1708-13 standard.
[0033] Another important attribute of the compositions of the invention is the fact that they are self-drying, consume large amounts of water in cement hydration reactions, thus causing a material to dry on the surface extremely quickly, as fast as in one hour after mixing and placing the material. This attribute is significant, for example, in flooring applications, where it allows the application of floor adhesives and floor coverings on the hardened and dry material in a short duration after the placement of material.
[0034] Yet another important and exclusive attribute of the compositions of the present invention is the fact that they have the capacity to use and incorporate a large amount of water in chemical reactions without unduly affecting the consolidation time, drying time, early resistivities to compression and dimensional movement behavior during physical and chemical drying, consolidation and hardening processes. This is an unexpected finding since state-of-the-art hydraulic cement compositions are well known for having a negative impact of excessive water on the consolidation behavior, drying characteristics, early compressibility and movement behavior dimensional.
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9/97 [0035] The hydraulic cement powder compositions of the present invention comprise aluminate-based hydraulic cement (or aluminate-based hydraulic cements), Portland cement and calcium sulfate. The self-drying hydraulic compositions of the present invention are obtained with the use of an inorganic flow control agent, which facilitates the functionality of the material and the flow properties in the fresh state of the material. In addition, the self-drying hydraulic compositions of the present invention are obtained with the use of a metal-based dimensional motion stabilizing agent that has a positive influence on the reduction and stabilization of both short and long-term movement of the material.
[0036] The compositions of the present invention are advantageously used for various applications, including, but not limited to, self-leveling undercoat, floor finish, decorative floor finish, insulation fuse, contractable plaster, pourable plaster, plaster mortars repair, road repair plaster, vertical and suspended repair material, cementitious primer and plaster, tile consolidation adhesive, tile grouts, anchor cements and grouts, synthetic tiles and stones, statuary products and panel products pre-cast or poured into place and construction elements.
[0037] As used in this document, "cementitious materials" is defined as aluminate cement, Portland cement, calcium sulfate and any additional cement that may be added to the reactive mixture. The amount of water depends on the need for the individual materials present in the cementitious composition as well as the functionality requirements of the application under consideration.
[0038] The seating of the compositions of the present invention is characterized by initial and final consolidation times, as measured with the use of Vicat specified in the ASTM C19113 test procedure. The final consolidation time also corresponds to the time when a concrete product, for example, a concrete panel, is hard enough
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10/97 to be manipulated.
[0039] As used in this document, the early resistance of the composition is characterized by measuring the resistance to compression after 2 to 5 hours of mixing. In many applications, a relatively higher compressive resistivity can be advantageous for a cementitious material due to the fact that it can withstand greater stress without deformation or excessive failure. Typically, chemical reactions that provide development of resistivity in such compositions will continue for extended periods after the final consolidation time has been reached.
[0040] The compositions of the invention have an absence of alkali metal salt other than lithium salts. Preferably, the compositions of the invention have an absence of alkali metal salt other than lithium carbonate. The compositions of the invention have an absence of alkali metal hydroxide other than lithium hydroxide. Preferably, the compositions of the invention have an absence of alkali metal hydroxide. The compositions of the invention have an absence of an alkali metal citrate. The compositions of the invention have an absence of alkali metal silicate other than lithium silicate. Preferably, the compositions of the invention have an absence of alkali metal silicate.
[0041] The compositions of Patent Application Publication n ^Q US 2016-0214897 A1 and 2016-0194247 A1 were produced by a chemical chemical reaction activator, for example, alkali metal hydroxides, alkali metal silicates or alkali metal citrates with fly ash. In the present invention, fly ash, if present, is a charge and flow control agent. In the present invention, fly ash does not react to form a geopolymer due to the fact that there is no chemical activator in accordance with Patent Application Publications n ^Q US 2016-0214897 A1 and 2016-0194247 A1.
[0042] The composition of the Publication of Request for
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Patent US ^Q 2010-0071597 A1 from Perez-Pena employed an alkali metal salt of citric acid for chemical activation of fly ash. The present invention does not employ.
[0043] The present invention also provides a method for mixing the composition of the invention, reacting the mixture and allowing the mixture to consolidate. Thus, the invention provides a method which comprises:
[0044] producing a mixture by mixing the composition of the invention which comprises:
[0045] reactive powder based on hydraulic cement comprising:
[0046] aluminate cement, [0047] Portland cement, [0048] calcium sulfate, [0049] the inorganic flow control agent;
[0050] the metal-based dimensional motion stabilizing agent;
[0051] the load; and [0052] water;
[0053] react to the mixture; and [0054] allow the mixture to consolidate and harden.
[0055] Other advantages, benefits and aspects of various modalities of the invention are discussed below, are illustrated in the attached Figures and will be understood by those skilled in the art from the more detailed disclosure below. All percentages, ratios and proportions in this document are by weight, unless otherwise specified.
BRIEF DESCRIPTION OF THE DRAWINGS [0056] Figure 1 shows a photograph of a settlement cake for the composition of Mixture 1 investigated in Example 1.
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12/97 [0057] Figure 1A shows the photograph of a settlement cake for the Mixture 2 composition investigated in Example 1.
[0058] Figure 1B shows the linear movement behavior (shrinkage by drying) of the compositions investigated in Example 1.
[0059] Figure 2 shows linear movement (drying shrinkage) of the mixing compositions investigated in Example 2.
[0060] Figures 3, 4 and 5 show photographs of settlement cakes for Mixtures 1, 2, and 3, respectively, of the compositions investigated in Example 5.
[0061] Figure 5A is a plot showing linear movement (drying shrinkage) of the mixing compositions investigated in Example 5.
[0062] Figures 6, 6A and 6B show photographs of settlement cakes for the compositions of Mixtures 1, 2 and 3, respectively, investigated in Example 6.
[0063] Figure 60 shows a linear motion plot (shrinkage by drying) of mix compositions investigated in Example 6 [0064] Figures 7, 7A and 7B show photographs of settlement cakes for Mixtures 1, 2 and 3, respectively, investigated in Example 7.
[0065] Figure 70 shows a linear motion plot (shrinkage by drying) of mixing compositions investigated in Example 7.
[0066] Figures 8A to 8F show photographs of settlement cakes for Mixtures 1 to 6, respectively, for the compositions investigated in Example 8.
[0067] Figure 8G shows the behavior of
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13/97 linear movement of the compositions of the invention investigated in Example 8.
[0068] Figure 9 demonstrates the linear motion behavior of the compositions of the invention investigated in Example 9.
[0069] Figure 10 shows the linear movement behavior of the compositions of the invention investigated in Example 11.
[0070] Figure 11 shows the linear movement behavior of the compositions of the invention investigated in Example 12.
DETAILED DESCRIPTION OF THE INVENTION [0071] The hydraulic cement powder compositions of the present invention comprise aluminate-based hydraulic cement (or aluminate-based hydraulic cements), Portland cement and calcium sulfate. The self-drying hydraulic compositions of the present invention are obtained with the use of an inorganic flow control agent, which facilitates the functionality of the material and the flow properties in the fresh state of the material. In addition, the self-drying hydraulic compositions of the present invention are obtained with the use of a metal-based dimensional motion stabilizing agent that has a positive influence on the reduction and stabilization of both short and long-term movement of the material.
[0072] The main raw materials of the present invention and the quantities of these raw materials in the compositions of the present invention are described below.
COMPOSITIONS OF THE PRESENT INVENTION [0073] The reactive cementitious mixtures of the present invention comprise aluminate-based cement (or aluminate-based cements), Portland cement, calcium sulfate, inorganic flow control agent, base-based dimensional movement agent metal, water and other optional additives.
[0074] Tables 1, 2, and 3 describe the
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14/97 self-drying and fast-setting, hydraulic cement-based compositions of the present invention comprising aluminate-based cement (or aluminate-based cements), Portland cement, calcium sulfate, inorganic flow control agent, dimensional motion stabilizing agent based on metal, water and other optional additives. Tables 1, 2 and 3 show the composition expressed in parts by weight (bpw) of individual or aggregate components. The reactive powder based on hydraulic cement comprises cement based on aluminate (or cement based on aluminate), Portland cement and calcium sulfate.
[0075] In these Tables and throughout this specification, when a component is represented as Weight Ratio between component / Hydraulic Cement Reactive Powder, for example, Weight Ratio between Inorganic Flow Control Agent / Hydraulic Cement Reactive Powder , this means that the component weight is calculated as a ratio to the weight of the Hydraulic Cement Based Reactive Powder. Thus, a Weight Ratio value between Inorganic Flow Control Agent / Hydraulic Cement-Based Reactive Powder equal to 3.00 means that there is Inorganic Flow Control Agent at 300 bpw for every 100 bpw of Reactive Cement Powder. Hydraulic for a total of 400 bpw.
[0076] In these Tables and throughout this specification when a component is represented as a component / Hydraulic Cement Reactive Powder,% by weight, for example, a Dimensional Motion Stabilizing Agent based on Metal / Reactive Cement Powder Hydraulic, 5.00% by weight means that the amount of Metal-based Dimensional Motion Stabilizing Agent is equal to 5% by weight of the amount of Hydraulic Cement Reactive Powder. In other words, there is a Metal-based Dimensional Movement Stabilizing Agent at 5 bpw for every 100 bpw of Hydraulic Cement Reactive Powder for a total of 105 bpw. Reactive Hydraulic Cement Powder is also alternatively referred to as Hydraulic Cement Based Reactive Powder or simply
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Reactive Cement Powder in this application.
Table 1: Compositions based on Hydraulic Cement of Stable Dimension of the Present Invention that comprise Aluminum Cement, Portland cement, Calcium Sulfate, Inorganic Flow Control Agent and Stabilizing Agent of Dimensional Movement based on Metal Feedstock Wide range Preferred range Most Preferred Range Hydraulic Cement-Based Reactive Powder (100 pbw)- Aluminum-Based Cement, pbw *- Portland cement, pbw- Calcium Sulfate, pbw 25 to 802.5 to 45 15 to 45 30 to 755 to 3520 to 40 35 to 707.5 to 2525 to 35 Weight ratio between Inorganic Flow Control Agent / Hydraulic Cement-Based Reactive Powder 0.25 to 3.0 0.5 to 2.0 0.75 to 1.5 Dimensional Motion Stabilizing Agent based on Metal / Reactive Powder Based on Hydraulic Cement,% by weight 0.5 to 5.0 1.0 to 4.0 1.5 to 3.5 Weight ratio between Load / Reactive Powder Based on Hydraulic Cement 0 to 5.0 0.5 to 3.5 1.0 to 2.5 Weight Ratio between Water / Hydraulic Cement-Based Reactive Powder 0.5 to 1.4 0.6 to 1.3 0.7 to 1.2
* Aluminate cement selected from at least one member of the group consisting of calcium aluminate cement and calcium sulfoaluminate cement.
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Table 2: Compositions Based on Hydraulic Cement of Stable Dimension Self-drying Fast Hardening of the Present Invention Comprising Calcium Sulfoaluminate Cement, Calcium Aluminate Cement, Portland Cement, Calcium Sulfate, Inorganic Flow Control Agent and Stabilizing Agent Metal-based Dimensional Movement Feedstock Wide range Preferred range Most Preferred Range Hydraulic Cement-Based Reactive Powder (100 pbw)- Calcium Sulfoaluminate Cement, pbw- Calcium Aluminate Cement, pbw- Portland cement, pbw- Calcium Sulfate, pbw 25 to 752.5 to 452.5 to 45 15 to 45 30 to 705 to 405 to 3520 to 40 35 to 6510a357.5 to 2525 to 35 Weight ratio between Inorganic Flow Control Agent / Hydraulic Cement-Based Reactive Powder 0.25 to 3.00 0.50 to 2.00 0.75 to 1.50 Dimensional Motion Stabilizing Agent based on Metal / Reactive Powder Based on Hydraulic Cement,% by weight 0.50 to 5.00 1.00 to 4.00 1.50 to 3.50 Weight ratio between Load / Reactive Powder Based on Hydraulic Cement 0 to 5.0 0.5 to 3.5 1.0 to 2.5 Weight Ratio between Water / Hydraulic Cement-Based Reactive Powder 0.50 to 1.40 0.60 to 1.30 0.70 to 1.20
TABLE 3: Hydraulic Cement-Based Compositions of Self-Desiccating Stable Dimension of Quick Hardening of the Present Invention Comprising Calcium Sulfoaluminate Cement, Calcium Aluminate Cement, Portland Cement, Calcium Sulfate, Inorganic Flow Control Agent and Stabilizing Agent for Calcium Metal-based Dimensional Movement With Bands for Additional Additives Feedstock Wide range Preferred range Most Preferred Range
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Hydraulic Cement-Based Reactive Powder (100 pbw)- Aluminate cement, pbw *- Portland cement, pbw- Calcium Sulfate, pbw 25 to 802.5 to 4515 to 45 30 to 755 to 3520 to 40 35 to 707.5 to 2525 to 35 Weight ratio between Inorganic Flow Control Agent / Hydraulic Cement-Based Reactive Powder 0.25 to 3.0 0.5 to 2.0 0.75 to 1.5 Dimensional Motion Stabilizing Agent based on Metal / Reactive Powder Based on Hydraulic Cement,% by weight 0.50 to 5.0 1.0 to 4.0 1.50 to 3.5 Weight ratio between Load / Reactive Powder Based on Hydraulic Cement ** 0 to 5.0 0.5 to 3.5 1.0 to 2.5 Organic Rheology Modifier / Hydraulic Cement-Based Reactive Powder,% by weight ** 0.02 to 1 0.04 to 0.75 0.06 to 0.5 Inorganic Viscosity Enhancing Agents / Hydraulic Cement-Based Reactive Powder,% by weight ** 0 to 1 0 to 0.75 0 to 0.5 Superplasticizer / Hydraulic Cement-Based Reactive Powder,% by weight 0.3 to 3.5 0.4 to 2.5 0.5 to 1.5 Defoamer / Hydraulic Cement-Based Reactive Powder,% by weight ** 0 to 2.0 0.25 to 1.5 0.5 to 1.0 Consolidation retarding agent / Hydraulic Cement-Based Reactive Powder,% by weight ** 0 to 2.0 0.10 to 1.5 0.2 to 1.0 Color Pigment / Reactive Powder Based on Hydraulic Cement,% by weight ** 0 to 8.0 0 to 6.0 0 to 4.0 Hydraulic Cement-Based Reactive Air / Powder Insertion Agent,% by weight ** 0 to 1.0 0 to 0.5 0 to 0.25 Organic Film Forming Polymer / Hydraulic Cement-Based Reactive Powder,% by weight ** 0 to 15.0 0 to 10.0 0 to 5.0 Weight ratio between different pozzolans of fly ash / Hydraulic Cement Reactive Powder ** 0 to 1 0 to 1 0 to 1 Weight Ratio between Water / Hydraulic Cement-Based Reactive Powder 0.50 to 1.40 0.60 to 1.30 0.70 to 1.20
* Aluminate cement selected from at least one of calcium aluminate cement and calcium sulfoaluminate cement, more preferably, both calcium aluminate cement and calcium sulfoaluminate cement.
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18/97 ** The ranges for additional additives preferably also apply to TABLE 2 compositions.
[0077] In order to form a binder composition, the Reactive Cement Powder (aluminate cement, Portland cement and calcium sulfate), the Inorganic Flow Control Agent, the Metal-based Dimensional Movement Stabilizing Agent, the charge and the water are mixed to form a cementitious slurry at an initial temperature (temperature during the first minute that the ingredients are all first presented in the mixture) from about 0 ° C to about 50 ° C.
HYDRAULIC CEMENTS [0078] Hydraulic cement for the purpose of the present invention is a cement that undergoes a chemical consolidation reaction when it comes into contact with water (hydration) and that will not only consolidate (cure) under water but will also form a product waterproof.
[0079] Hydraulic cements include, but are not limited to, aluminum silicate cements such as Portland cement, calcium sulfoaluminate cement and calcium aluminate based cement. For the purposes of this specification, calcium sulfate is not considered a hydraulic cement. However, for the purpose of this specification, a reactive powder based on hydraulic cement includes hydraulic cement and calcium sulfate. Pozzolans, if included in the general composition, are not part of the reactive powder based on hydraulic cement. Pozzolans, if included in the general composition, are additional to reactive powder based on hydraulic cement.
ALUMINUM BASED CEMENT [0080] Calcium sulfoaluminate cements and calcium aluminate cements are aluminate-based cements of the present invention. Calcium aluminate cements with the dodecacalcium hepta-aluminate (C12A7) phase as the predominant phase in cement are
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19/97 most preferred calcium aluminate of the present invention. Different classes of calcium aluminate cements can be used individually or can be combined in quantities specified in accordance with the present invention in order to obtain desirable final results. In a preferred embodiment, a combination of calcium sulfoaluminate cement and calcium aluminate cement is used to obtain extremely fast drying and extremely fast curing behavior.
[0081] In general, in the hydraulic cement-based reactive powder of the compositions of the present invention, the aluminate-based cement comprises an aluminate cement selected from at least one member of the calcium aluminate cement group and cement of calcium sulfoaluminate in an amount of 25 to 80 parts by weight for every 100 parts by weight of reactive powder based on hydraulic cement. Preferably, there are 30 to 75 parts by weight of such aluminate cement per 100 parts by weight of the reactive powder based on hydraulic cement. More preferably, there are 30 to 70 parts by weight of this aluminate cement per 100 parts by weight of the reactive powder based on hydraulic cement.
[0082] When the reactive powder based on hydraulic cement comprises calcium sulfoaluminate cement and calcium aluminate cement, in general, there are 25 to 75 parts by weight of calcium sulfoaluminate cement per 100 parts by weight of the reactive powder to base of hydraulic cement and calcium aluminate cement at 2.5 to 45 parts by weight for every 100 parts by weight of reactive powder based on hydraulic cement; preferably, there are 30 to 70 parts by weight calcium sulfoaluminate cement per 100 parts by weight of the reactive powder based on hydraulic cement and 5 to 40 parts by weight calcium aluminate cement per 100 parts by weight of the reactive powder based hydraulic cement; more preferably, there are 35 to 65 parts by weight calcium sulfoaluminate cement per 100 parts by weight of reactive powder based on hydraulic cement and 10 to 35 parts by weight calcium aluminate cement per 100 parts by weight of reactive powder based on hydraulic cement.
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CALCIUM SULFOALUMINATE CEMENT (CSA) [0083] The calcium cement sulfoaluminate forms an ingredient in the compositions of the present invention. Calcium sulfoaluminate (CSA) cements are a different class of calcium aluminate cement (CAC) cement or calcium silicate based hydraulic cements, for example, Portland cement. CSA cements are hydraulic cements based on calcium sulfoaluminate, and not calcium aluminates which are the basis of CAC cement or calcium silicates which are the basis of Portland cement. Calcium sulfoaluminate cements are produced from clinkers that include Ye'elimite (Ca4 (AIO ₂ ) eSO4 or C4A3S) as a primary phase.
[0084] Other primary phases present in the preferred calcium sulfoaluminate cement may include one or more of the following: calcium disilicate (C ₂ S), tetracalcium aluminoferrite (C4AF) and calcium sulfate (CS). The relatively low requirement of low lime content of calcium sulfoaluminate cements compared to Portland cement reduces energy consumption and greenhouse gas emissions from cement production. In fact, calcium sulfoaluminate cements can be manufactured at temperatures of approximately 200 ° C lower than Portland cement, thereby further reducing energy and greenhouse gas emissions. The amount of the Ye'elimite (Ca4 (AIO ₂ ) 6SO4 or C4A3S) phase present in calcium sulfoaluminate cements is preferably about 20 to about 90% by weight, more preferably about 30 to about 75 % by weight, and more preferably, about 40 to about 60% by weight.
[0085] The amount of calcium sulfoaluminate cement in the compositions of the invention is adjustable based on the amount of the active Ye'elimite phase (Ca4 (AIO ₂ ) eSO4 or C4A3S) present in the CSA cement.
CALCIUM ALUMINATE CEMENT [0086] Calcium aluminate cement (CAC) is
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21/97 other type of hydraulic cement that can form a component of the reactive powder blend of the compositions of the invention when a particularly higher compressive resistivity is not required with low-water slurries containing substantial amounts of fly ash.
[0087] Calcium aluminate cement (CAC) is also commonly called aluminous cement or cement with a high alumina content. Calcium aluminate cements have a high aluminum content, about 30 to 45% by weight is preferred. Higher purity calcium aluminate cements are also commercially available in which the alumina content can be in a range as high as about 80% by weight. These high-purity calcium aluminate cements tend to be very expensive compared to other cements. The calcium aluminate cements used in compositions of the invention are crushed into fine pieces to facilitate the entry of aluminates into the aqueous phase so that rapid formation of etringite and other calcium aluminate hydrates can occur. The surface area of the calcium aluminate cement will typically be greater than 3,000 cm ² / g and preferably about 4,000 to about 6,000 cm ² / g, as measured by the Blaine surface area method (ASTM C 204-11) .
[0088] Several manufacturing methods have emerged to produce calcium aluminate cement worldwide. Preferably, the main raw materials used in the manufacture of calcium aluminate cement are bauxite and limestone. A manufacturing method for producing calcium aluminate cement is described as follows. The bauxite ore is first crushed and dried, then crushed with the limestone. Then, a rotary kiln is fed as dry powder comprising bauxite and limestone. A pulverized low ash coal is used as fuel for the oven. The reaction between bauxite and limestone occurs in the oven and the molten product is collected at the bottom end of the oven and is poured into a set passing through the bottom. The molten clinker is quenched with water to form clinker granules which are then transported
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22/97 to a stockpile. This granulate is then crushed to the desired fineness to produce the final cement.
[0089] Typically, several calcium aluminate compounds can be formed during the calcium aluminate cement manufacturing process. The predominant compound formed is often monocalcium aluminate (CaOAkCb, also called CA). The other compounds of calcium aluminate and calcium silicate that are formed can include 12CaO * 7AI ₂ O3 also called C12A7, CaO * 2AI ₂ O3 also called CA ₂ , calcium disilicate (2CaO * SIO ₂ , called C ₂ S ), dicalcium alumina silicate (2CaO · AI ₂ Os · SIO ₂ , called C ₂ AS). Several other compounds that contain a relatively high proportion of iron oxides can also be formed. They include calcium ferrites, such as CaO * Fe ₂ O3 or CF and 2CaO * Fe ₂ O3 or C ₂ F, and calcium aluminoferrites, such as tetracalcium aluminoferrite (4CaO * AI ₂ O3 * Fe ₂ O3 or C4AF), 6CaO * AI ₂ O3 * 2Fe ₂ O3 or CeAF ₂ ) and 6CaO * 2AI ₂ O3 * Fe ₂ O3 or CeA ₂ F). Other minor constituents often present in calcium aluminate cement include magnesia (MgO), titania (TiO ₂ ), sulfates and alkalis.
[0090] Calcium aluminate cements can have one or more phases mentioned above. Calcium aluminate cements that have monocalcium aluminate (CaO * AI ₂ O3 or CA) and / or dodecacalcium hepta-aluminate (12CaO * 7AI ₂ O3 or Ci ₂ A ) As predominant phases are preferred in the present invention. In addition, the calcium aluminate phases may be available in crystalline and / or amorphous form. Ciment Fondu (or HAC Fondu), SECAR 51, and SECAR 71 are some examples of commercially available calcium aluminate cements that have 0 monocalcium aluminate (CA) as the primary cement phase. TERNAL EV and TERNAL EP are examples of commercially available calcium aluminate cement that have dodecacalcium heptaaluminate (12CaO * 7AI ₂ Os or Ci ₂ A ₇ ) as the predominant cement phase. Both TERNAL EV and TERNAL EP that have 0 liver
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23/97 dodecacalcium aluminate (12CaO7AI ₂ 03 or C12A7) as the predominant cement phase, calcium aluminate cement is particularly preferred in the present invention.
[0091] When calcium aluminate (CAC) cements are used in the present invention, they can partially replace calcium sulfoaluminate cement. The amount of calcium aluminate cement substitution in the compositions of the invention is typically up to about 49% by weight of the aggregate weight of the calcium sulfoaluminate cement and calcium aluminate cement.
PORTLAND CEMENT [0092] Portland cement, in the quantities specified in this document, is a crucial ingredient of the present invention. The use of it is crucial in the development of a fast resistance to compression and in reducing the shrinkage behavior of the material. As used herein, “Portland cement” is a hydraulic cement based on calcium silicate. The ASTM C 150-12 standard defines Portland cement as a “hydraulic cement (cement that not only hardens through reaction with water, but also forms a water resistant product) produced by spraying clinkers that essentially consist of hydraulic calcium silicates , which normally contain one or more of the forms of calcium sulphate with an addition between millings ”. As used herein, "clinkers" are nodules (diameters, about 5 to 25 mm [0.2 to about 1.0 inch]) of a synthesized material that are produced when a crude mixture of predetermined composition is heated to high temperature. The different types of Portland cements and other hydraulic cement based Portland cement, as classified in ASTM C150-12, ASTM C595-13 and ASTM C1600-11, can be usefully employed in the present invention. Oil well cements represent yet another class of hydraulic cements, which can be used instead of
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24/97 Portland cements in the fast-setting, self-drying hydraulic cement compositions of the present invention.
[0093] In general, the hydraulic cement-based reactive powder of the compositions of the present invention comprises Portland cement in an amount of 2.5 to 45 parts by weight per 100 parts by weight of the hydraulic cement-based reactive powder; preferably, 5 to 35 parts by weight of Portland cement per 100 parts by weight of the reactive powder based on hydraulic cement; more preferably, 7.5 to 25 parts by weight of Portland cement per 100 parts by weight of the reactive powder based on hydraulic cement.
CALCIUM SULFATE [0094] Calcium sulfate forms yet another critical ingredient in the self-drying, fast-curing compositions of the present invention. Although calcium sulfate, for example, calcium sulfate dihydrate will react with water, it does not form a water resistant product and is not considered as hydraulic cement for the purpose of the present invention. The types of calcium sulfate that are useful in compositions of the invention include calcium sulfate dihydrate, calcium sulfate hemihydrate and anhydrous calcium sulfate (anhydride). These calcium sulphates can be available naturally or can be produced industrially. Calcium sulphates interact synergistically with the other fundamental components, particularly aluminate cements, of the cementitious compositions of the invention and confer several useful properties for the final material including rapid consolidation, dimensional stability and compression resistance.
[0095] Different morphological forms of calcium sulfate can be usefully employed in the present invention. It has been found that the properties of the compositions and composites of the present invention significantly depend on the type of calcium sulfate used based on the chemical composition, particle size, crystal morphology and treatment
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25/97 chemical and thermal. Among other properties, the consolidation behavior, rate of development of resistivity, final compressibility, shrinkage and crack resistance of the compositions of the invention can be adapted by selecting an appropriate source of calcium sulfate in the formulation. Thus, the selection of the type of calcium sulfate used in the compositions of the invention is based on the balance of the desired properties at the end of the application.
[0096] It was found that the particle size and morphology of calcium sulfate significantly influenced the development of early and final resistivities of the cementitious compositions of the invention. In general, it has been found that a smaller particle size of calcium sulfate provides faster development in early resistivity. When it is desirable to have an extremely rapid rate of development of resistivity, the preferred average particle size of calcium sulfate is in a range of about 1 to about 100 microns, more preferably, about 1 to about 50 microns and , even more preferably, about 1 to about 25 microns. In addition, it was also found that calcium sulfates with a finer particle size resulted in less material shrinkage.
[0097] All three forms of calcium sulfate (primarily, hemihydrate, dihydrate and anhydride) are useful. The most soluble form of calcium sulphate is the hemihydrate, followed by the relatively lower form of solubility of the dihydrate and then followed by the relatively insoluble form of the anhydride. All three forms are, in themselves, known to consolidate (form matrices of the chemical form of the dihydrate) in aqueous media under appropriate conditions, and the consolidation times and compressive resistivities of the consolidated forms are known to follow the order their solubility. For example, with equality among other aspects, used alone as the sole consolidation material, hemihydrate normally has the shortest consolidation times
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26/97 and anhydride typically have the longest consolidation times.
[0098] In general, the hydraulic cement-based reactive powder of the compositions of the present invention comprises a calcium sulphate selected from the group consisting of calcium sulphate dihydrate, calcium sulphate hemihydrate, sulphate anhydrous calcium and mixtures thereof, with calcium sulfate in an amount of 15 to 45 parts by weight per 100 parts by weight of reactive powder based on hydraulic cement; preferably, 20 to 40 parts by weight of calcium sulfate for every 100 parts by weight of the reactive powder based on hydraulic cement; more preferably, 25 to 35 parts by weight calcium sulfate per 100 parts by weight of the reactive powder based on hydraulic cement.
INORGANIC FLOW CONTROL AGENT [0099] The inorganic flow control agents of the present invention are inorganic materials that facilitate workability and sufficient flow properties when mixed with other cementitious components of the invention and with water. The inorganic flow control agents of the present invention include at least one member of the group consisting of fly ash and mineral calcium carbonate materials that have ideal particle size distribution. The ideal average particle size of the calcium carbonate employed in the present invention is in a range of about 10 to 150 microns, more preferably, about 15 to 100 microns, and more preferably, about 25 to 75 microns . Fly ash is obtained as a by-product of the coal combustion process. In the present invention, fly ash is a pozzolanic material, but does not react with chemical activators to form a geopolymer. Geopolymeric reactions start quickly. In contrast, pozzolanic reactions start slowly and are long-term chemical reactions. Thus, in the invention, fly ash does not significantly contribute to the material's resistivity during the first weeks after mixing, unlike geopolymers.
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27/97 [0100] Both Class C fly ash and Class F fly ash, according to ASTM C618 (2008), can be usefully employed in the present invention. Fly ash containing a high content of calcium oxide and calcium aluminate (such as Class C fly ash of the ASTM C618 (2008) standard is preferred in the present invention, as explained below.
[0101] Fly ash is a by-product of fine powder formed from the combustion of coal. Electric power plant utility boilers that burn pulverized coal produce most commercially available fly ash. These fly ash consist essentially of glassy spherical particles as well as residues of hematite and magnetite, coal and some crystalline phases during cooling. The structure, composition and properties of fly ash particles depending on the structure and composition of coal and the combustion processes by which fly ash is formed. The ASTM C618 (2008) standard recognizes two main classes of fly ash for use in Class C and Class F concrete. These two classes of fly ash are generally derived from different types of coals that are a result of difference in coal formation processes that occur over geological time periods. Class F fly ash is normally produced from the burning of anthracite or bituminous coal. Class C fly ash is normally produced from lignite or sub-bituminous coal.
[0102] The ASTM C618 (2008) standard primarily differentiates Class C and Class F fly ash according to their pozzolanic properties. Consequently, in the ASTM C618 (2008) standard, the main difference in specification between the Class F fly ash and the Class C fly ash is the lower limit of S1O2 + AI2O3 + Fe20s in the composition. The lower limit of S1O2 + AI2O3 + Fe2Ü3 for Class F fly ash is 70% and for Class C fly ash is 50%. In this way, Class F fly ash has a higher pozzolan content than fly ash of Class F
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Class C. Although not explicitly recognized in the ASTM 0618 (2008) standard, Class C fly ash is preferably high in calcium oxide (lime).
[0103] If desired, Class C fly ash normally has cement properties in addition to pozzolanic properties due to lime (calcium oxide). Class F is rarely cementitious when mixed with water only. The presence of a high calcium oxide content provides Class C fly ash with cement properties which causes the formation of calcium silicate and calcium aluminate hydrates when mixed with water.
[0104] Typically, fly ash comprises Class C fly ash, for example, about 50 to about 100 parts Class C fly ash per 100 parts by weight fly ash, or about 75 parts to about 100 parts gray Class C steering wheel after every 100 gray steering wheel parts.
[0105] In general, the compositions of the present invention comprise the inorganic flow control agent in a weight ratio between the inorganic flow control agent and the reactive powder based on hydraulic cement from 0.25: 1 to 3 , 0: 1, where inorganic flow control comprises at least one member selected from the group consisting of fly ash and calcium carbonate and where the average particle size of calcium carbonate is in a range of about 10 to 150 microns; preferably, the weight ratio between the inorganic flow control agent and the hydraulic cement-based reactive powder is 0.5: 1 to 2.0: 1; more preferably, the weight ratio between the inorganic flow control agent and the reactive powder based on hydraulic cement is 0.75: 1 to 1.5: 1.
DIFFERENT FLYING GRAY POZOLANIC MATERIALS [0106] The invention optionally comprises a pozzolanic material different from fly ash selected from a group consisting of blast furnace slag, thermally activated clays, shales,
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29/97 metakaolin, zeolites, red mud from marl, crushed rock and crushed clay bricks. Preferably, the pozzolanic material has an AI2O3 content greater than about 5% by weight. Typically, clay or loam is used after thermal activation by heat treatment at temperatures from about 600 ° C to about 850 ° C.
[0107] The ASTM C618 (2008) standard defines pozzolanic materials as “siliceous or siliceous and aluminous materials that, by themselves, have little or no cement value, but will react, in a form divided into thin pieces, and in the presence of moisture , with calcium hydroxide at common temperatures to form compounds that have cement properties ”.
[0108] The invention optionally comprises a mineral silicate and aluminosilicate, other than fly ash, which is a pozzolan that has little or no substantial cementing properties alone in an aqueous medium that mineral additives can be included in the compositions of the invention. Various natural and man-made materials have been called pozzolanic materials that have pozzolanic properties. Some examples of pozzolanic materials include smoked silica, pumice, perlite, diatomaceous earth, fine-grained clay, fine-grained slate, fine-grained slate, fine-grained glass, volcanic tuff, brass and rice hull. All of these pozzolanic materials can be used either alone or in combination. Preferably, however, there is an absence of glass.
[0109] In general, the compositions of the present invention comprise pozzolan different from fly ash in a weight ratio of pozzolan and reactive powder based on hydraulic cement from 0: 1 to 1: 1. However, the invention may have an absence of pozzolan or aluminosilicate material other than fly ash.
MOVEMENT STABILIZING AGENT
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METAL-BASED DIMENSIONAL [0110] The metal-based dimensional motion stabilizing agent of the present invention comprises a lithium compound selected from at least one member of the lithium salt and lithium-based group, the salt of which lithium is at least one member of the group of lithium carbonate, lithium sulfate, lithium nitrate, lithium nitride and lithium silicate, where the base is lithium hydroxide. Preferably, the metal-based dimensional motion stabilizing agent of the present invention comprises lithium carbonate. Most preferably, the metal-based dimensional motion stabilizing agent of the present invention comprises 100% lithium carbonate. It was found that the lithium compound, particularly lithium carbonate, when incorporated in addition to a critical amount in the compositions of the present invention has an unexpected positive positive influence on the stabilization of the movement both in the short and long term of the aluminum cementitious composition of the present invention.
[0111] In general, the compositions of the present invention comprise the metal-based dimensional motion stabilizing agent in an amount equal to 0 to 5.0 percent by weight of the hydraulic cement-based reactive powder, the agent being metal-based dimensional motion stabilizer comprises a lithium compound selected from at least lithium salt and lithium base, the lithium salt being at least one of lithium carbonate, lithium sulfate, lithium nitrate , lithium nitride and lithium silicate, the base is lithium hydroxide. Preferably, the amount of the metal-based dimensional motion stabilizing agent is equal to 1.0 to 4.0 weight percent of the hydraulic cement-based reactive powder. Most preferably, the amount of the metal-based dimensional motion stabilizing agent is 1.5 to 3.5 weight percent of the hydraulic cement-based reactive powder. The invention also addresses the fact that the mixture has an absence of alkali metal hydroxide and an absence of metal salt
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31/97 alkali other than lithium carbonate compound. The invention preferably also contemplates the fact that the mixture has an absence of alkali metal hydroxide and an absence of alkali metal salt other than lithium carbonate compound. The invention also contemplates the fact that the mixture has an absence of alkali metal citrate. The invention also contemplates the fact that the mixture has an absence of alkali metal citrate in addition to lithium hydroxide. The invention also contemplates the fact that, preferably, the mixture has an alkali-free hydroxide.
OPTIONAL CONSOLIDATION CONTROL AGENTS [0112] Other chemical consolidation control additives include sodium carbonate, potassium carbonate, calcium nitrate, calcium nitride, calcium formate, calcium acetate, calcium chloride, aluminum sulfate, sodium aluminate, alkanolamines, polyphosphates and the like. These additives when included as part of the formulation can also influence the rheology of the compositions of the invention in addition to affecting the consolidation behavior. The invention also contemplates an absence of these consolidation control agents.
WATER [0113] Another important attribute of the compositions of the present invention is the fact that they have the capacity to incorporate a very high amount of water without negatively impacting the crucial properties of the material, such as consolidation time, quick drying, early resistivity, final strength and dimensional movement due to drying. Even at such high water levels, the preferred compositions of the present invention exhibit consolidation times of less than 1 hour, fast drying behavior in about 1 hour after mixing and installation of the material, early compressive resistivities (2 hours)
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32/97 than 10.34 MPa (1,500 psi) and extremely low dimensional movement due to material drying. In this way, the invention can advantageously use a wide range of water without negatively impacting crucial properties, such as consolidation time, fast drying, early resistivity and dimensional movement due to drying. For use in the field, this is especially an advantage due to the fact that a user can vary the amount of water, but can obtain substantially the same properties of consolidation time, quick drying, early resistivity, final strength and dimensional movement due to drying . Due to the fast drying characteristics of the surface obtained through rapid cement hydration reactions that incorporate a large amount of chemically bonded water, the compositions of the present invention are referred to herein as self-drying. In contrast, conventional Portland cement-based cement compositions have extremely low consolidations and take several hours to consolidate and obtain surface drying characteristics similar to that of the present invention.
[0114] In general, in the compositions of the present invention, the weight ratio between water and reactive powder based on hydraulic cement is 0.5: 1 to 1.4: 1; preferably, the weight ratio between water and reactive powder based on hydraulic cement is 0.6: 1 to 1.3: 1; more preferably, the weight ratio between water and reactive powder based on hydraulic cement is 0.7: 1 to 1.2: 1, and more preferably, the weight ratio between water and reactive powder based on hydraulic cement. is 0.8: 1 to 1.1: 1.
LOADS [0115] Although the mixture of reactive cementitious powder revealed defines the rapid consolidation component of the cementitious composition of the invention, people skilled in the art will understand that other materials can be included in the composition depending on the intended use and application.
[0116] One or more charges, such as fine aggregate,
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33/97 coarse aggregate, inorganic mineral fillers and light fillers can be used as a component in compositions of the invention.
[0117] These charges are not inorganic flow control agents, as described above.
[0118] These charges are not pozzolan.
[0119] Fine aggregates can be added to the compositions of the invention without affecting the properties to increase the yield of the material. An example of fine aggregate is sand, such as silica sand or alumina sand. Sand is defined as an inorganic rock material with an average particle size of less than about 4.75 mm (0.195 inches) and has a crystalline structure. In this document, sand does not include crushed or recycled glass. Crushed or recycled glass has an amorphous structure. Preferably, the compositions of the present invention have an absence of crushed glass particles. Preferably, the compositions of the present invention have an absence of recycled glass particles. Preferably, the compositions of the present invention have an absence of glass particles.
[0120] The sand used in the present invention preferably meets the standard specifications of the ASTM C33-13 standard. Preferably, the sand has an average particle size of 0.1 mm to about 3 mm. More preferably, the sand has an average particle size of 0.2 mm to about 2 mm. Most preferably, the sand in an average particle size is about 0.3 to about 1 mm. Examples of preferred fine sand used in the present invention include QUIKRETE FINE No. 1961 and UNIMIN 5030 which has a predominant size range of US sieve number n ^Q 70 to ^Q 30 (0.2 to 0.6 mm). The fine aggregate used in the present invention meets the ASTM C33-13 standard.
[0121] Inorganic mineral fillers, such as crushed clay, shale, slate, mica and talc can also be used in the present invention.
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34/97 [0122] Light loads have a specific gravity less than about 1.5, preferably less than about 1, more preferably less than about 0.75, and still more preferably, less than about 0.5. In some other preferred compositions of the invention, specific gravity, light charges are less than about 0.3, more preferably less than about 0.2 and more preferably less than about 0.1 . In contrast, organic mineral fillers preferably have a specific gravity above about 2.0. Examples of light payloads include pumice, vermiculite, expanded forms of clay, slate, slate and perlite, slag, expanded slag, ash, glass microspheres, synthetic ceramic microspheres, hollow ceramic microspheres, light polystyrene microspheres, hollow microspheres of plastic, hollow plastic microspheres and the like. Expanded plastic microspheres and hollow plastic spheres when used in the compositions of the invention are employed in a very small amount based on weight, due to their extremely low specific gravity. When light loads are used to reduce material weight, they can be used in a weight ratio between light load and cementitious materials (cementitious reactive powder) from about 0: 1 to about 2: 1, preferably about 0.01: 1 to about 1: 1, preferably about 0.02: 1 to about 0.75: 1. One or more types of fillers can be used in the compositions of the invention.
[0123] Coarse aggregates can also be added to the compositions of the present invention. The coarse aggregate is defined as an inorganic rock material with an average particle size of at least 4.75 mm (0.195 inches), for example, 0.64 to 3.81 cm (1/4 to 1.5 inches). The aggregate larger than 3.81 cm (1.5 inches) can also be used in some applications, for example, concrete flooring. The particle shape and texture of the coarse aggregate used may be angular, may have a rough texture, elongated, round or smooth or a combination thereof. Preferably, the coarse aggregate is
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35/97 produced from minerals such as granite, basalt, quartz, riolite, andesite, tuff, pumice, limestone dolomite, sandstone, marble, cherte, flint, gradevaque, slate and / or gneiss.
[0124] If desired, the compositions of the invention may contain only sand as the added filler. If desired, the invention contains sand and inorganic mineral fillers and / or light filler as the additional fillers. If desired, the invention uses mineral fillers and light inorganic fillers as the additional fillers. If desired, the invention incorporates sand, mineral filler and light inorganic filler as added fillers. If desired, the invention contains only mineral fillers or light inorganic fillers and does not contain sand, fine aggregate or coarse aggregate. Compositions of the invention that contain coarse aggregate, moreover, may include or exclude one of the following charges - sand, light charge and inorganic mineral charge. Still other compositions are substantially free of any added charges.
[0125] In general, the compositions of the present invention comprise the charge in a weight ratio between the reactive powder based on hydraulic cement equal to 0: 1 to 5.0: 1; preferably, the weight ratio between the load and the hydraulic cement-based reactive powder is 0.5: 1 to 3.5: 1; more preferably, the weight ratio between the load and the reactive powder based on hydraulic cement is equal to 1.0: 1 to 2.5: 1.
ORGANIC RHEOLOGY MODIFIER [0126] Organic Rheology Modifiers are biopolymers or Organic Rheology Control Agents from synthetic sources. Some Organic Rheology Modifiers also act as particulate suspending agents in aqueous systems.
[0127] In general, the compositions of the present invention comprise the Organic Rheology Modifier in an amount equal to 0.02 to 1% by weight of the reactive powder based on hydraulic cement; preferably, the Organic Rheology Modifier in an amount equal to 0.04
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36/97 to 0.75% by weight of reactive powder based on hydraulic cement; more preferably, the Organic Rheology Modifier in an amount equal to 0.06 to 0.50% by weight of the reactive powder based on hydraulic cement.
BIOPOLYMERS [0128] Some of these biopolymers are also known as Thickeners or Viscosity Modifiers. Some, such as methyl cellulose, also function as an emulsifier. Naturally occurring biopolymers comprise polysaccharide or amino acid building blocks and are generally soluble in water. Common examples are starch, cellulose, alginate, egg yolk, agar, arrowroot, carrageenan, collagen, gelatin, guar gum, pectin and xanthan gum. Preferred biopolymers include cellulosic ethers and gum-based organic polymers.
[0129] Succinoglycans, diutane gum, guar gum, welan gum, xanthan gums and organic compounds based on cellulose ether are biopolymers that act as hydrocolloids and rheology control agents. Gum-based polymers are selected from the group consisting of galactomannan gums, glucomannan gums, guar gum, locust bean gum, expensive gum, hydroxyethyl guar, hydroxypropyl guar, cellulose, hydroxypropylcellulose, hydroxymethylcellulose, hydroxyethylcellulose and combinations thereof. .
[0130] Examples of preferred organic cellulose-based polymers useful for controlling rheology in the compositions of the present invention include hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), hydroxypropylmethylcellulose (HPMC), methylcellulose (MC ), ethyl cellulose (EC), methyl ethyl cellulose (MEC), carboxymethyl cellulose (CMC), carboxymethyl ethyl cellulose (CMEC) and carboxymethylhydroxyethyl cellulose (CMHEC).
[0131] The biopolymers mentioned above are typically soluble in both hot and / or cold water. These additives also act as water retention agents and, thus, minimize material segregation and leakage in addition to controlling material rheology.
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ORGANIC RHEOLOGY CONTROL AGENTS [0132] In contrast to biopolymers that may be able to control or modify rheology, for the purposes of this specification, Organic Rheology Control Agents are defined as those that come from synthetic sources. Some of these organic rheology control agents are known as thickeners. Acrylic-based polymers for organic rheology control agents are grouped into three general classes: expandable (or soluble) alkali emulsions (ASEs), hydrophobically modified alkali expandable emulsions (HASEs) and hydrophobically modified ethoxylated urethane resins (HEURs) ). HASE polymers are modifications of ASE polymers following an addition of hydrophobic functional groups. They are commonly known as associative thickeners. In the simplest form, an associative thickener is a water-soluble polymer that contains several relatively hydrophobic groups. HEUR polymers also belong to the category of associative thickeners. However, unlike HASEs, HEURs are non-ionic substances and do not depend on alkali to activate the thickener mechanism.
[0133] For example, the rheology modifier ACULYN 22 is an acrylic polymer emulsion soluble in hydrophobically modified anionic alkali (HASE) available from Dow Chemical. HASE polymers are synthesized from an acid / acrylate copolymer backbone and a monomer that connects hydrophobic groups as side chains. The polymer is produced by emulsion polymerization. ACULYN 22 is synthesized from acrylic acid, acrylate esters and a steareth-20 methacrylate ester.
[0134] Both associative and non-associative types of organic and thickening rheology control agents can be usefully employed in the compositions of the invention.
[0135] Organic rheology control agents
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38/97 and the thickeners mentioned above are soluble in both cold and / or hot water. These additives also act as water retention agents and, thus, minimize material segregation and leakage in addition to controlling material rheology.
ORGANIC FILM FORMING POLYMER ADDITIVES [0136] Organic film forming polymers are polymers that produce a physical, continuous and flexible film. They are available as polymeric dispersions or as redispersible powders. Preferred film-forming polymer dispersions are latex powders. The polymer powders which are capable of redispersion to form the preferred film are latex powders. These polymer powders are capable of redispersion in water and produced by spray drying of aqueous polymer dispersions (latex). Polymer powders are typically produced by spray-drying latex dispersions (emulsions). In the field, polymer powders capable of redispersion of film formation are preferred for ease of use.
[0137] Latex is an emulsion polymer. Latex is a water-based polymer dispersion, used widely in industrial applications. Latex is a stable dispersion (colloidal emulsion) of polymer microparticles in an aqueous medium. Thus, it is a suspension / dispersion of polymeric rubber or plastic microparticles in water. Latexes can be natural or synthetic.
[0138] Latex is preferably produced from pure acrylic, styrene rubber, styrene butadiene rubber, styrene acrylic, vinyl acrylic or ethylene vinyl acetate copolymer and, with more preferably, it is a pure acrylic. Preferably, the latex polymer is derived from at least one acrylic monomer selected from the group consisting of acrylic acid, acrylic acid esters, methacrylic acid and methacrylic acid esters. For example, monomers
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39/97 preferably employed in emulsion polymerization include monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, other acrylates, methacrylates and mixtures thereof, acid acrylic, methacrylic acid, styrene, toluene vinyl, vinyl acetate, vinyl esters of carboxylic acids superior to acetic acid, for example, vinyl versatate, acrylonitrile, acrylamide, butadiene, ethylene, vinyl chloride and the like and mixtures thereof. For example, a latex polymer can be a butyl acrylate / methyl methacrylate copolymer or a 2-ethylhexyl acrylate / methyl methacrylate copolymer. Preferably, the latex polymer is additionally derived from one or more monomers selected from the group consisting of styrene, alpha-methyl styrene, vinyl chloride, acrylonitrile, methacrylonitrile, methacrylate urea, vinyl acetate, monocarboxylic acid vinyl ethers branched tertiary, itaconic acid, crotoconic acid, maleic acid, fumaric acid, ethylene and dienes conjugated to C4-C8.
[0139] Ethylene vinyl acetate (VAE) emulsions are based on copolymerization of vinyl acetate and ethylene, in which the vinyl acetate content can be in the range between 60 and 95 percent, and the ethylene content is in a range between 5 and 40 percent of the total formulation. This product should not be confused with ethylene vinyl acetate (EVA) copolymers, with vinyl acetate generally ranging from 10 to 40 percent, and ethylene can vary between 60 and 90 percent of formulation. VAEs are water-based emulsions and these emulsions can be dried to form redispersible powders, while EVAs are solid materials used for hot melt and plastic molding applications.
[0140] The film-forming polymer can be chosen from dispersions of polymeric particles that can include: (meth) acrylics; vinyls; oil-modified polymers; polyesters; polyurethanes; polyamides; chlorinated polyolefins; and mixtures or copolymers thereof, for
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40/97 example, ethylene vinyl acetate. In addition, polymers should typically have a glass transition temperature (Tg) of -40 ° to 70 ° C. The Tg of a polymer is most commonly determined by differential scanning calorimetry (DSC). Tg is the temperature at which there is a sudden increase in specific heat (Cp). This is manifested by a shift in the baseline of the DSC curve. The Interactional Confederation of Thermal Analysis proposes that an evaluation procedure be used to determine Tg. According to this procedure, two regression lines R1 and R2 are applied to the DSC curve: the regression line before the event (R1) and the regression line at the inflection point (R2). These two lines define the glass transition temperature (Tg) as the intersection between R1 and R2. It should be noted that the values for Tg obtained by DSC depend on the heating rate chosen during the experiment. In general, the heating rate used by DSC measurements is 5 ° C / min.
[0141] As preferred polymers may be mentioned: I) pure acrylate copolymers obtainable as the polymerization product of a plurality of acrylic monomers, such as (meth) acrylic acid, (meth) acrylic monomers containing a hydroxyl group, esters of (meth) acrylic acid and (meth) acrylonitrile; li) styrene acrylate copolymers obtainable as the polymerization product of a monomer mixture comprising styrene and / or substituted styrene in an amount of up to 100% by weight, preferably from 30 to 90% by weight and, with more preferably 40 to 80% by weight, based on the total monomers and one or more acrylic monomers; and, such as (meth) acrylic acid, (meth) acrylic monomers containing a hydroxyl group, (meth) acrylic acid and (meth) acrylonitrile esters; and, ill) ethylene vinyl acetate copolymers obtainable as the vinyl acetate polymerization product, ethylene and, optionally, other comonomers.
[0142] Polymers can be prepared and used in bulky powder form: such powders are capable of redispersion in water
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41/97 during the formation of the second component. ACRONAL S 430 P and ACRONAL S 695 P (BASF Aktiengesellschaft) are examples of a suitable commercially redispersible styrene-acrylate powder copolymer.
[0143] Alternatively, the polymers are supplied directly as a dispersion in the water-based medium, the dispersion being then mixed with additional water and other additives. Such dispersions can be supplied using known commercial products such as: STYROPOR P555 (styrene homopolymer available from BASF Aktiengesellschaft); for styrene-butadiene copolymers, LIPATON SB 3040, LIPATON SB 2740 (Polymer Latex GmbH), STYROLUX 684 D (BASF Aktiengesellschaft) and, SYNTHOMER 20W20 (Synthomer Chemie); SYNTHOMER VL 10286 and SYNTHOMER 9024 (styrene / butadiene / acrylonitrile terpolymer, Synthomer Chemie); for styrene acrylate copolymers, ALBERDINGK H 595, ALBERDINGK AS 6002 (both from Alberdingk Boley), RHODOPAS DS 913 (Rhodia, now Solvay), ACRONAL 290D, ACRONAL S 400, ACRONAL DS 5011 (BASF AktiengesellschaftAS 54FNNASFASFAS 54NNN (Wacker Polymer Systems), MOWILITH LDM 6159 (Celanese) and LIPATON AE 4620 (Polymer Latex GmBH); and, B60A (dispersion of pure acrylate available from Rohm & Haas). Other exemplary commercially available latex polymers include: AIRFLEX EF811 (available from Air Products); EPS 2505 (available from EPS / CCA); and, NEOCAR 2300, NEOCAR 820 and NEOCAR 2535 (available from Dow Chemical Co.).
[0144] Alternatively, aqueous dispersions may be provided by polymerizing appropriate monomeric mixtures, as described by PA Lovell, MS El-Aasser (editors), Emulsion Polymerization and Emulsion Polymers, John Wiley and Sons, Chichester, United Kingdom, 1997 no is incorporated into this document as a reference. The monomeric mixture must generally comprise at least one unsaturated monomer selected from the group consisting of:
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42/97 (meth) acrylonitrile; alkyl (meth) acrylate esters; ethers of (meth) acrylic acids; vinyl ethers; and vinyl monomers.
[0145] The alkyl esters of acrylic acid and methacrylic acid are those derived from 01 to 014 alcohols and thus include as non-limiting examples: (meth) methyl acrylate; (met) ethyl acrylate; (met) isopropyl acrylate; (meth) butyl acrylate; (met) isobutyl acrylate; (met) n-pentyl acrylate; (met) neopentyl acrylate; (met) cyclohexyl acrylate; (meth) 2-hexyl acrylate; (meth) 2-ethylhexyl acrylate; (met) isobornyl acrylate; (meth) 2-hydroxyethyl acrylate, (meth) 3-hydroxypropyl acrylate, (meth) 4-hydroxybutyl acrylate and epsilon-caprolactone adducts thereof; and, di (meth) acrylate esters of alkane diols, such as 1,6-hexane diol diacrylate.
[0146] Suitable vinyl ethers include vinyl acetate, vinyl propionate, vinyl versatate and vinyl laurate. Suitable vinyl comonomers include: ethylene compounds; propene; butene; iso-butene; 1,3-butadiene; isoprene; styrene; alpha-methyl styrene; t-butyl styrene; toluene vinyl; divinyl benzene; heterocyclic vinyl; and vinyl halides, such as chloroprene. Preferably, vinyl comonomers include ethylene, styrene, butadiene and isoprene.
[0147] The monomeric mixture may comprise a carbonyl monomer that is a monoolefinically unsaturated monomer that has an aldehyde group or a ketone group. Monoolefinic unsaturation in the carbonyl monomers of the present invention is typically provided by (meth) acrylate, (meth) acrylamide, styryl or vinyl functionalities. Preferably, the carbonyl monomer is selected from the group consisting of: acrolein; methacrolein; vinyl methyl ketone; vinyl ethyl ketone; vinyl isobutyl ketone; vinyl amyl ketone; acetoacetoxy hydroxyalkyl (meth) acrylates esters; diacetonaacrylamide (DAAM); diacetone (meth) acrylamide; formylstirol; (meth) diacetone acrylate; acetonyl acrylate; 2-hydroxypropyl acrylate-acetyl acetate; 1,4-butanediol acrylate acetylacetate; and mixtures
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43/97 of them.
[0148] Examples of suitable homopolymers and film forming copolymers are vinyl acetate homopolymers, vinyl acetate copolymers with ethylene, vinyl acetate copolymers with ethylene and one or more additional vinyl ethers, vinyl acetate copolymers with ethylene and acrylic esters, vinyl acetate copolymers with ethylene and vinyl chloride, styrene-acrylic ester copolymers, styrene-1,3-butadiene copolymers. Preference is given to vinyl acetate homopolymers; copolymers of vinyl acetate with from 1 to 40% by weight of ethylene; copolymers of vinyl acetate with from 1 to 40% by weight of ethylene and from 1 to 50% by weight of one or more additional comonomers of the group consisting of vinyl ethers having from 1 to 15 carbon atoms in the carboxylic acid radical, for example, vinyl propionate, vinyl laurate, vinyl ethers of alpha-branched carboxylic acids that have 9 to 13 carbon atoms; vinyl acetate copolymers, from 1 to 40 wt% ethylene and preferably 1 to 60 wt% acrylic esters of unbranched or branched alcohols having 1 to 15 carbon atoms, in particular n-acrylate butyl or 2-ethylhexyl acrylate; and copolymers comprising from 30 to 75% by weight of vinyl acetate, from 1 to 30% by weight of vinyl laurate or the vinyl ester of an alpha-branched carboxylic acid having 9 to 13 carbon atoms, and 1 to 30% by weight of acrylic esters of unbranched or branched alcohols which have 1 to 15 carbon atoms, in particular, butyl n-acrylate or 2-ethylhexyl acrylate and which additionally comprise 1 to 40% by weight of ethylene; copolymers comprising vinyl acetate, from 1 to 40% by weight of ethylene and from 1 to 60% by weight of vinyl chloride; the polymers may additionally comprise the auxiliary monomers mentioned above in the specified amounts, and the weight percentages in each case add up to 100% by weight.
[0149] In general, the compositions of the present invention comprise the organic film-forming polymer in a
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44/97 quantity equal to 0 to 15.0% by weight of reactive powder based on hydraulic cement; preferably, the organic film-forming polymer in an amount equal to 0 to 10.00% by weight of the hydraulic cement-based reactive powder; more preferably, the organic film-forming polymer in an amount equal to 0 to 5.00% by weight of the reactive powder based on hydraulic cement.
INORGANIC VISCOSITY IMPROVEMENT AGENTS [0150] The cementitious compositions of the invention can optionally include inorganic rheology enhancing agents that belong to the phyllosilicate family. Examples of useful inorganic rheology enhancing agents may include paligorschite, sepiolite, smectites, kaolinites and illite. In particular, useful smectite clays are hectorite, saponite and montmorillonite. Different varieties of bentonite clays, treated both naturally and chemically, can also be used to control the rheology of these compositions. Such additives can also act as water retention agents and thus minimize material segregation and leakage. Inorganic rheology enhancing agents can be added in the absence of the Organic Rheology Modifier or in combination with it.
[0151] In general, the compositions of the present invention comprise the inorganic viscosity enhancing agent in an amount equal to 0 to 1% by weight of the reactive powder based on hydraulic cement; preferably, the inorganic viscosity enhancing agent in an amount equal to 0 to 0.75% by weight of the reactive powder based on hydraulic cement; more preferably, the inorganic viscosity enhancing agent in an amount equal to 0 to 0.50% by weight of the reactive powder based on hydraulic cement.
AIR INSERTION AGENT [0152] Air insertion agents (also known as foaming agents) can be added to the slurry
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45/97 cement of the invention to form air bubbles (foam) in situ. Air insertion agents are preferably surfactants used to purposely trap microscopic air bubbles in concrete. Alternatively, air insertion agents are employed to produce foam externally which is introduced into the mixtures of the compositions of the invention during the mixing operation to reduce the density of the product. Preferably, in order to externally produce the air-entraining agent (also known as a liquid foaming agent), air and water are mixed to foam in a suitable foaming apparatus. A foam stabilizing agent, such as polyvinyl alcohol, can be added to the foam before the foam is added to the cementitious slurry.
[0153] Examples of foaming / air-inserting agents include alkyl sulfonates, alkylbenzol sulfonates and alkyl ether sulfate oligomers, among others. Details of the general formula for these foaming agents can be found in US Patent No. 5643510 ^Q incorporated herein by reference.
[0154] An air insertion agent (foaming agent), such as one according to the standards, as established in the standard ASTM 0260-1 Oa (2010) Standard Specification for Air-Entraining Admixtures for Concrete ”can be employed. Such air insertion agents are well known to those skilled in the art and are described in Kosmatka et al, Design and Control of Concrete Mixtures, Fourteenth Edition, Portland Cement Association, specifically chapter 8 entitled Air Entrained Concrete, (cited in the Publication of ^Q Patent n US 2007/0079733 A1).
[0155] Suitable air insertion agents (foaming agents) include water-soluble salts (usually sodium) of wood resin, vinsol resin, wood pitch, taloleum pitch or gum pitch; non-ionic surfactants (for example, such as those commercially available from BASF under the trade name TRITON X-100); sulfonated hydrocarbons; proteinaceous materials; or fatty acids (for example,
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46/97 fatty acid tal oil) and esters thereof.
[0156] Commercially available air insertion materials include wood vinsol resin, sulfonated hydrocarbons, fatty and resin acids, substituted aliphatic aryl sulfonates, such as suffinated ligine salts and numerous other interfacially active materials that normally take the form of anionic or non-ionic surface active agents (surfactants), sodium abietate, saturated or unsaturated fatty acids and salts thereof, tensioids, alkyl aryl sulfonates, phenol ethoxylates, lignosulfonates, resin soaps, sodium hydroxystearate, sulfate lauryl, ABSs (alkylbenzenesulfonates), LASs (linear alkylbenzenesulfonates), alkanesulphonates, alkyl (phenyl) polyoxyethylene ethers, alkyl sulfate ethers (phenyl) polyoxyethylene ether or salts thereof, polyethylene ethyl phosphate esters (phenyl) or salts thereof, proteinaceous materials, alkenylsulfosuccinates, alpha-olefinsulfonates, a sodium salt of alphaolefin sulfonate or sodium lauryl sulfate or sulfonate and mixtures thereof.
[0157] In general, the compositions of the present invention comprise the air insertion agent in an amount equal to 0 to 1.0% by weight of the reactive powder based on hydraulic cement; preferably, the air insertion agent in an amount equal to 0 to 0.50% by weight of the hydraulic cement-based reactive powder; more preferably, the air insertion agent in an amount equal to 0 to 0.25% by weight of the hydraulic cement-based reactive powder, more preferably, 0 to 0.2% by weight.
[0158] The air insertion agent, when present, is in an amount of 0.01 to 1, preferably 0.01 to 0.5, more preferably, 0.01 to 0.25, more preferably , 0.05 to 0.2% by weight based on the total weight of the reactive powder based on hydraulic cement.
ANTIFOAMING AGENTS [0159] Antifoaming agents can be added to the cementitious compositions of the invention to reduce the amount of trapped air, increase the resistivity of the material, increase the
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47/97 resistivity of bonding the material to other substrates and producing a defect-free surface in applications where the aesthetics of the surfactant is an important criterion. Examples of suitable antifoam agents useful in the compositions of the invention include polyethylene oxides, propoxylated amines, polyethylene, polyethylene glycol, polypropylene glycol, alkoxylates, polyalkoxylate, fatty alcohol alkoxylates, hydrophobic esters, tributyl phosphate, alkyl polyacrylates, silanes, silanes, silanes, silanes , polysiloxanes, polyether siloxanes, acetylenic diols, tetramethyl decinediol, secondary alcohol ethoxylates, silicone oil, hydrophobic silica, oils (mineral oil, vegetable oil, white oil), waxes (paraffin waxes, ester waxes, waxes fatty alcohol), amides, fatty acids, fatty acid polyether derivatives, etc., and mixtures thereof.
[0160] In general, the compositions of the present invention comprise the defoamer in an amount equal to 0 to 2.0% by weight of the reactive powder based on hydraulic cement; preferably, defoamer in an amount equal to 0.25 to 1.50% by weight of the reactive powder based on hydraulic cement; more preferably, defoamer in an amount equal to 0.50 to 1.00% by weight of the reactive powder based on hydraulic cement.
CONSOLIDATION RETARDANTS [0161] Organic compounds, such as hydroxylated carboxylic acids, carbohydrates, sugars and starches are preferred retardants of some compositions of the present invention. Organic acids, such as citric acid, tartaric acid, malic acid, gluconic acid, succinic acid, glycolic acid, malonic acid, butyric acid, malic acid, fumaric acid, formic acid, glutamic acid, pentanoic acid, glutaric acid, gluconic acid , tartonic acid, mucic acid, benzoic trhydroxy acid etc. they are useful as consolidation retardants in properly sized binder cementitious compositions of the invention.
[0162] Sodium gluconate is also useful as
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48/97 organic consolidation retardant in the compositions of the present invention. Organic cellulose-based polymers, such as hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPG), hydroxypropylmethylcellulose (HPMC), ethylcellulose (EC), methylethylcellulose (MEC), carboxymethylcellulose (CMC ), carboxymethylethylcellulose (CMEC), carboxymethylhydroxyethylcellulose (CMHEC) are additional useful retardants in some of the compositions of the present invention.
[0163] These cellulose-based retardants when added to the composition of the invention significantly increase viscosity of the mixture in addition to causing retardation. Preferably, inorganic acid-based retardants, such as borates or boric acid, are not used or not used in significant amounts due to the fact that they impair the reelegia of the mixture, cause excessive efflorescence and reduce the bonding resistance of the material to other substrates.
[0164] In general, the compositions of the present invention comprise the consolidation retarding agent in an amount equal to 0 to 2.0% by weight of the hydraulic cement-based reactive powder; preferably, the consolidation retarding agent in an amount equal to 0.10 to 1.50% by weight of the reactive powder based on hydraulic cement; more preferably, the consolidation retarding agent in an amount equal to 0.20 to 1.00% by weight of the reactive powder based on hydraulic cement.
SUPERPLASTIFIERS [0165] Water reducing agents (superplasticizers) are preferably used in the compositions of the invention. They can be added in dry form or as a solution. Superplasticizers can help reduce the water demand in the mix. Examples of superplasticizers include polyphthalene sulfonates, polyacrylates, polycarboxylates, polyether polycarboxylates, lignosulfonates, melamine sulfonates, caesins and the like. Depending on the type of superplasticizer used, the weight ratio between the superplasticizer (based on dry powder) and the mixture of reactive powder based on hydraulic cement will be
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Preferably 5% by weight or less, preferably 2% by weight or less, preferably about 0.1 to about 1% by weight.
[0166] Superplasticizers based on the polyether polycarboxylate chemistry are the most preferred chemical addition water reduction mixture for the compositions of the invention. Polyether polycarboxylate superplasticizers are most preferred since they facilitate the achievement of the various objectives of the present invention as mentioned above.
[0167] In general, the compositions of the present invention comprise the superplasticizer in an amount equal to 0.3 to 3.5% by weight of the reactive powder based on hydraulic cement; preferably, superplasticizer in an amount equal to 0.40 to 2.50% by weight of the reactive powder based on hydraulic cement; more preferably, superplasticizer in an amount equal to 0.50 to 1.50% by weight of the reactive powder based on hydraulic cement
OPTIONAL MATERIALS [0168] Optional materials and additives can be included in the compositions of the invention. They include at least one member selected from the group consisting of corrosion control agents, wetting agents, efflorescence control agents, distinct fibers, long and continuous fibers and reinforcement, textile reinforcement, polyvinyl alcohol fibers, fibers glass and / or other distinct reinforcement fibers.
[0169] As efflorescence control agents, water-repellent agents, such as silanes, silicones, siloxanes, stearates can be added to the cementitious compositions of the invention to reduce the potential for efflorescence of the material. Selected examples of useful efflorescence suppressing agents include octyltriethoxy silane, potassium methyl siliconate, calcium stearate, butyl stearate, polymer stearates. These efflorescence control agents reduce the transport of water within the hardened material and thus minimize the migration of
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50/97 salts and other soluble chemicals that can potentially cause efflorescence. Excessive efflorescence can cause insufficient aesthetics, material breakage and damage from expansion reactions that occur due to salt build-up and salt hydration, and reduced bond strength with other substrates and surface coatings.
[0170] Different reinforcement fibers of different types can also be included in the compositions of the invention. Screens produced from materials such as polymer-coated glass fibers and polymeric materials, such as polypropylene, polyethylene and nylon can be used to reinforce pre-cast products based on cement depending on their function and application.
[0171] There may also be an absence of one or more of these optional materials.
COLOR PIGMENT [0172] Any color pigment known in the cement technique can be used. Both organic and inorganic color pigments can be used in the compositions of the present invention. Typical color pigments include titanium dioxide and / or black iron oxide (Fe3O4), chromium oxide, zinc oxide, zinc ferrite and carbon black.
[0173] In general, the compositions of the present invention comprise the color pigment in an amount equal to 0 to 8.0% by weight of the reactive powder based on hydraulic cement; preferably, the color pigment in an amount equal to 0 to 6.00% by weight of the reactive powder based on hydraulic cement; more preferably, the color pigment in an amount equal to 0 to 4.00% by weight of the reactive powder based on hydraulic cement. There may also be an absence of pigment.
INITIAL FLUID PASTE TEMPERATURE [0174] In some compositions of the present invention, it is preferable to form the slurry under conditions that provide a reduced initial binder mixture slurry temperature and, more
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51/97 important, slower gelation and final consolidation times of about 10 to about 240 minutes, more preferably, about 60 to about 120 minutes and more preferably, about 30 to about 60 minutes. An initial lower slurry temperature allows a more controlled working time for commercial use of the binder compositions. The initial slurry temperature is preferably approximately equal to the ambient temperature.
[0175] The "initial temperature" is defined as the temperature of the general mixture during the first minute after the cementitious reactive powder and water are all present in the mixture first. Of course, the temperature of the general mixture may vary during that first minute, however, in order to obtain a preferred thermal stability, it will remain within an initial temperature range of about 0 to about 50 ° C, more preferably, a range from an initial temperature of about 10 to about 35 ° C, more preferably, an initial temperature range of about 15 to about 25 ° C, preferably room temperature.
EXAMPLES [0176] In the examples in this document, as mentioned above, the percentages of the formulas for compositions or products are in percentages by weight, unless expressly stated otherwise. The reported measurements, also in approximate quantities, unless expressly stated otherwise, for example, percentages, weights, temperatures, approximate distances or other properties.
[0177] The cement sulfoaluminate used in the examples is FASTROCK 500, available from the GTS Cement Company. AST calcium sulfoaluminate cement FASTROCK 500 is used as a component of reactive cement powder. FASTROCK 500 has an average particle size of about 5 microns with 95% finer particles than about 25 microns. The Blaine fineness measured for the FASTROCK 500 was about 6,780
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52/97 cm ² / g. The oxide composition of FASTROCK 500 has been analyzed and is shown in
TABLE A:
TABLE A
Oxide % by weight in FASTROCK500 % by weight on Class C flywheel Dog 43.78 24.14 SiO ₂ 14.02 36.90 AI2O3 25.23 20.12 FepOa 1.05 5.96 SO ₃ 8.67 1.19 MgO 3.23 5.44 Na ₂ O 1.81 1.73 K2O 0.32 0.52 TiO ₂ 0.76 1.42 P2O51.18 Loss on Ignition 1.58 0.52
[0178] A main phase present in the calcium sulfoaluminate cement FASTROCK 500 employed in the examples includes C4A3S, C2S, C4AF and CS.
[0179] In all examples, unless otherwise stated, fly ash is a Class C fly ash from Campbell Power Plant, West Olive, Ml. This fly ash has an average particle size of about 4 microns. The Blaine fineness measured from the fly ash is about 4,300 cm ² / g. The oxide composition of the Class C fly ash employed in these examples is shown in TABLE A.
[0180] Unless otherwise indicated, the calcium aluminate cement used in some of the examples is TERNAL EV, available from Kerneos Inc. The primary phase of the calcium aluminate in TERNAL EV is C12A7. The other phases in TERNAL EV include CA, C3A, C4AF and
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53/97
C ₂ S. The typical primary oxide composition of TERNAL EV is according to the following: CaO - 47.5 to 50.5% by weight, AI ₂ Os - 33.5 to 37.5% by weight, SiO ₂ - 3.5 to 6.0% by weight and Fe ₂ Os at 6.5 to 9.0% by weight. The typical fineness of TERNAL EV is as follows: particles finer than 2.6 microns are less than 10% by weight and particles thicker than 90 microns are less than 4% by weight.
[0181] Unless stated otherwise, the Portland cement used in some of the examples was ST MARYS CEMENT PORTLAND TYPE III by St Marys Cement. The typical oxide composition of this Portland cement is according to the following: CaO - 61.7% by weight, SiO ₂ 19.9% by weight, AI ₂ Os - 4.9% by weight, Fe ₂ Os - 2, 87% by weight, MgO - 3.7%, SO3 - 3.49% by weight, K ₂ O - 1.21% by weight, Na ₂ O - 0.18% by weight, TIO ₂ 0.27% by weight, Free Lime - 1.1% by weight and Loss on Ignition-1.7% by weight. The Finea Blaine of the cement was 640 m ² / kg.
[0182] Unless otherwise indicated, the calcium carbonate used in some of the examples is KISH KR-2 crushed calcium carbonate available from the KISH Company. The typical primary oxide composition of KISH KR-2 is CaCOs - 98.5% by weight, MgCOs - 0.6% by weight, SIO ₂ - 0.6% by weight, AI ₂ Os - 0.05% by weight , Fe ₂ Os, 0.04% by weight. The typical particle size of KISH KR-2 crushed calcium carbonate is according to the following: particles finer than 250 microns are less than 99.5% by weight, particles finer than 150 microns are less than 95% by weight , particles finer than 75 microns are less than 75% by weight, and particles finer than 45 microns are less than 60% by weight. The median particle size of KISH KR-2 crushed calcium carbonate is between 25 to 35 microns.
[0183] The calcium sulfate hemihydrate included in several of the examples is the USG HYDROCAL C-Base brand calcium sulfate hemihydrate available from the United States Gypsum Company. HYDROCAL C-Base is an alpha morphological form of calcium sulfate hemihydrate that has a block crystal microstructure and low water demand. THE
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USG HYDROCAL C-Base has an average particle size of about 17 microns.
[0184] The fine-grained calcium sulfate dihydrate included in several of the examples is the USG TERRA ALBA F&P trademark of the United States Gypsum Company. The USG TERRA ALBA F&P charge is a high purity calcium sulfate dihydrate with an average particle size of about 13 microns.
[0185] The anhydrous calcium sulfate used in some of the examples is the USG SNOW WHITE charge from the United States Gypsum Company. The USG SNOW WHITE filler is an insoluble form of calcium sulphate anhydride produced by high temperature heat treatment of calcium sulphate, preferably plaster. It has a very low level of humidity chemically combined, preferably about 0.35%. The average particle size of the USG SNOW WHITE charge is about 7 microns.
[0186] The UNI MIN GRANUSIL 5030 sand included in the examples has a particle size as shown in TABLE B:
TABLE B Sieve Size Passage in Percentage (%) of Sand UNIMIN GRANUSIL 5030 0.59 mm (30 Mesh)0.42 mm (40 Mesh) 100 0.170 mm (50 Mesh) 73 0.210 mm (70 Mesh) 22 0.149 mm (100 Mesh) 4 0.105 mm (140 Mesh) 0
[0187] BASF CASTAMENT FS 20 available from BASF is a dispersant that is a polymerization product based on polyethylene glycol by the Construction Polymers Technical Data Sheet, CASTAMENT FS 20, BASF, October 2011 Rev 1. CASTAMENT FS 20 is urn
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55/97 polycarboxylate ether. It is used in some of the examples as a superplasticizer.
[0188] MELFLUX 6681 F available from BASF is a free-flowing, spray-dried powder of a modified polycarboxylic ether. It is used in some of the examples as a superplasticizer.
[0189] MELFLUX 5581 F available from BASF is a free-flowing, spray-dried powder of a modified polycarboxylic ether. It is used in some of the examples as a superplasticizer.
[0190] AXILAT RH 100 XP is a succinoglycan hydrocolloid available from Momentive.
[0191] The color pigment when used in these examples was LANSCO 8330 Synthetic Black Iron Oxide from LANSCO COLORS.
[0192] STARVIS 3003 F is a powder based on a synthetic high molecular weight copolymer from BASF. It is a high performance viscosity enhancing agent for cementitious materials used as an Organic Rheology Modifier.
[0193] Unless otherwise indicated, the defoamer used in the examples was SURFYNOL 500S available from Evonik Corporation.
[0194] The initial consolidation time and the final consolidation time reported in this document were measured using the ASTM C191-13 standard using Vicat needles.
[0195] The comprehensive intensity of the materials, as used in this document, is measured according to the ASTM C109-13 test method by testing the 5.08 cm x 5.08 cm x 5.08 cm (2 inches x 2 inches x 2 inches) for compression failure. The cubes are removed from the brass molds after hardening and cured in plastic bags until sealed until the age for testing. The cubes are tested at the age of about 2 hours, 4 hours, about 24 hours, about 7 days and about
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56/97 of 28 days after the merger. These cubes are tested in compression in the saturated condition immediately after removing them from the water and drying the surface.
[0196] In the examples, the settlement test to determine the workability of the mixture was conducted using a hollow plastic cylinder, 5.08 cm (2 inches) in diameter x 2.54 (1 inch) high. The cylinder was placed on a flat horizontal plastic plate and filled with a mixture of slurry obtained after mixing the material. The upper surface of the cylinder was secreted with a metal knife to obtain a flat surface. Then, the cylinder was lifted allowing the slurry to leave the bottom of the cylinder and diffused out of the plastic plate to form a circular slurry of slurry. Then, the cake diameter was measured in two perpendicular directions and the measurement of the two readings was reported as the settlement of the mixture.
EXAMPLE 1 - FREE CALCIUM ALUMINATE CEMENT COMPOSITIONS AND PORTLAND CEMENT AND THAT UNDERSTAND FINE GRAIN CALCIUM CARBONATE [0197] This example shows the influence of the calcium carbonate particle size on fresh and hardened properties of cement cement compositions aluminate comprising calcium sulfoaluminate cement and calcium sulfate. TABLE 1.1 shows the two mixing compositions investigated in this example. Both mixing compositions were extended with calcium carbonate mineral filler, HUBERCARB M200, which has a median particle size of 15 microns. Both investigated compositions were free of Portland cement. Lithium carbonate was added in a dosage of 0.20% by weight of the cementitious reactive powder (Hydraulic Cement-Based Reactive Powder). Mixture 1 was formulated with calcium sulfate dihydrate, while Mixture 2 contained calcium sulfate hemihydrate. The superplasticizer used in both blends was BASF CASTAMENT FS20.
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TABLE 1.1: Compositions investigated in Example 1 Feedstock Mix 1 Mix 2 Calcium Sulfoaluminate Cement, pbw Calcium Aluminate Cement, pbw Calcium Sulphate Dihydrate, pbw Calcium Sulphate Hemihydrate, pbwPortland cement, pbwTotal Reactive Powder Based on Hydraulic Cement, pbw 66.70.0033.30.000.00100 66.70.000.0033.30.00100 Weight Ratio between calcium carbonate / Hydraulic Cement-Based Reactive PowderWeight ratio between sand / reactive powder based on hydraulic cementLithium carbonate / Hydraulic Cement-Based Reactive Powder,% by weightCitric Acid / Hydraulic Cement-Based Reactive Powder,% by weightAXILAT RH100 XP / Hydraulic Cement-Based Reactive Powder,% by weightSuperplasticizer / Hydraulic Cement-Based Reactive Powder,% by weightDefoamer / Hydraulic Cement-Based Reactive Powder,% by weightWeight ratio between water / reactive powder based on hydraulic cement 0.750.750.200.500.020.500.200.60 0.750.750.200.500.020.500.200.60
SETTING FLUID PASTE AND CONSOLIDATION BEHAVIOR [0198] TABLE 1.2 shows settlement of fluid paste (demonstrating mixing workability) and consolidation behavior of the two compositions investigated in Example 1. TABLE 1.2 shows the measured diameter of the laying cakes in this example . You can
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58/97 note that the diameter of both cakes was relatively small, indicating that the material was viscous and had insufficient workability and flow properties. It should be noted that materials with insufficient workability and flow properties typically produce a settlement cake with a diameter greater than 15.24 cm (6 inches).
[0199] Figures 1 and 1A show settlement cakes for the compositions investigated in Example 1. From the photographs of the settlement cakes, it can be seen that both mixtures were quite viscous. In addition, the mix cake for Mixture 1 developed significant cracking within the first few hours after it was poured.
TABLE 1.2: Workability (Settlement - Cylinder of 5.08 cm (2 ") in diameter and 2.54 cm (1") in height) and Consolidation Time (Vicat) Mixture n ^Q Settlement(centimeters (inches)) Initial Consolidation (min) ConsolidationFinal (min) 1 10.26 cm (4.5 ”) 36 42 2 8.73 cm (3 7/16 ”) 44 48
SELF-HEALING BEHAVIOR [0200] The self-healing behavior of the two compositions was investigated using the ASTM 01708-13 standard. Both mixtures exhibited extremely insufficient self-healing behavior and failed at the very moment of the initial pour.
LINEAR MOVEMENT [0201] Figure 1B shows the linear movement behavior of the compositions investigated in Example 1. The linear movement behavior test was conducted according to ASTM 01708-13 except that the prismatic samples were removed from the mold at the time of consolidation initial, in which the initial specimen length measurement was obtained shortly after removing the specimen from the mold. Length measurements
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59/97 of sample continued until the age of 56 days. This shows that both compositions have shrunk very significantly over the 56 day period. The final shrinkage of Mixture 1 was about 0.33% while the same for Mixture was about 0.20%. This extension of shrinkage is not acceptable in practical applications, as it will be a significant failure and crack in the product.
[0202] Thus, the absence of calcium aluminate cement and Portland cement in the formulation is harmful.
EXAMPLE 2 - INFLUENCE OF PORTLAND CEMENT IN MIXTURE COMPOSITIONS CONTAINING CALCIUM SULPHOALUMINATE [0203] This example shows the influence of the addition of Portland cement on fresh and hardened properties of aluminate cement compositions comprising calcium sulfoaluminate cement and sulphate alumina. calcium. TABLE 2.1 shows the mixing compositions investigated in this example. All mixing compositions were extended with fly ash. Lithium carbonate was added at small dosage rates of 0.31 to 0.33% by weight of the reactive powder based on hydraulic cement. Mixture 1 was free of Portland cement, while Mixtures 2 to 4 contained increasing levels of Portland cement. None of these mixtures contained in calcium aluminate cement. The superplasticizer used in all four blends was BASF CASTAMENT FS20.
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TABLE 2.1: Compositions investigated in Example 2 Feedstock Mixture1 Mixture2 Mixture3 Mixture4 Calcium Sulfoaluminate Cement, pbw 66.7 62.5 58.8 55.6 Calcium Aluminate Cement, pbw 0.00 0.00 0.00 0.00 Calcium sulfate hemihydrate, pbw 0.00 0.00 0.00 0.00 Calcium sulfate dihydrate, pbw 33.3 31.3 29.4 27.8 Portland cement, pbw 0.00 6.3 11.8 16.7 Total Reactive Powder Based on Hydraulic Cement, pbw 100 100 100 100 Weight ratio between fly ash / reactive powder based on hydraulic cement 1.92 1.84 1.78 1.72 Weight ratio between sand / reactive powder based on hydraulic cement 1.25 1.22 1.19 1.17 Lithium Carbonate / Hydraulic Cement-Based Reactive Powder,% by weight 0.33 0.33 0.32 0.31 Citric Acid / Hydraulic Cement-Based Reactive Powder,% by weight 0.25 0.24 0.24 0.23 AXILAT RH100 XP / Reactive Powder BasedHydraulic Cement,% by weight 0.04 0.04 0.04 0.04 Superplasticizer / Hydraulic Cement-Based Reactive Powder,% by weight 0.83 0.81 0.79 0.78 Defoamer / Hydraulic Cement-Based Reactive Powder,% by weight 0.58 0.57 0.56 0.54 Weight Ratio between Water / Reactive PowderHydraulic cement based powder 1,000 0.975 0.953 0.933 SETTLEMENT IN FOLDER FLUID AND
CONSOLIDATION BEHAVIOR [0204] TABLE 2.2 shows the settlement of the slurry (demonstrating mixing workability) and consolidation behavior of the compositions investigated in Example 2. TABLE 2.2
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61/97 shows The measured diameter of the bottom cakes in this example. It can be seen that the measured settlement of the mixtures investigated in this example decreased with increasing Portland cement content. It should be noted that materials with insufficient workability and flow properties typically produce a settlement cake with a diameter greater than 15.24 cm (6 inches). TABLE 2.2 also demonstrates that the initial and final consolidation times of the mix compositions investigated in this example decreased with increasing Portland cement content.
TABLE 2.2: Workability (Settlement - Cylinder of 5.08 cm (2 ") in diameter and 2.54 cm (1") in height) and Consolidation Time (Vicat) Mixture n- Settlement(centimeters (inches)) Initial Consolidation (min) Final Consolidation (min) 1 18.89 cm (7 7/16 ”) 40 52 2 16.11 cm (6 11/32 ”) 33 39 3 13.1 cm (5 5/32 ”) 28 33 4 9.21 cm (3 5/8 ”) 26 29
COMPRESSION RESISTIBILITY BEHAVIOR [0205] Compressive resistance, when measured in these and other examples, was measured in accordance with ASTM 0109-13. TABLE
2.3 shows the behavior of early (4 hours) and final (28 days) compression resistance of the cementitious compositions investigated in this example. The 4-hour compression resistance of the investigated mixtures ranged from 12.07 MPa (1,750 psi) to 13.44 MPa (1,950 psi). Similarly, the 28-day compressive resistivity of the investigated mixtures ranged from 34.13 MPa (4,950 psi) to 38.96 MPa (5,650 psi). Both the 4-hour compressive resistivity and the 28-day compressive resistivity increased with increasing Portland cement content.
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TABLE 2.3: Resistance to Compression (MPa (psi)) Mixture n ^Q 4 hours 28 days 1 12.16 (1,764) 34.28 (4,972) 2 12.98 (1,882) 37.65 (5,460) 3 12.90 (1,871) 39.05 (5,663) 4 13.24 (1,921) 38.78 (5,624)
SELF-HEALING BEHAVIOR [0206] The self-healing behavior of the compositions in this example was investigated using the ASTM C170813 standard. Mixture 1 failed in 15 minutes, while Mixtures 2 and 3 failed in 7.5 minutes from the start of mixing the material. Mixture 4 exhibited extremely poor self-healing behavior and failed instantly when pouring the material. These results demonstrate that the self-healing behavior decreased with increasing Portland cement content.
LINEAR MOVEMENT [0207] Figure 2 shows the linear motion behavior of the compositions investigated in this example. The test was conducted in accordance with ASTM C1708-13 except that the prismatic samples were removed from the mold at the time of initial consolidation, and the initial specimen length measurement was obtained shortly after removing the specimen from the mold. Sample length measurements continued until the age of 56 days. It can be seen that all four mixtures have shrunk, in which the final shrinkage was in a range between 0.07% and 0.11%. It is also important to note that the final shrinkage decreased with an increase in Portland cement content. For example, for Mixture 1, the final shrinkage was about 0.11%, while for Mixture 4 with the highest amount of Portland cement the final shrinkage reduced to 0.07%. Thus, the
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63/97 absence of Portland cement in the formulation is detrimental to performance.
EXAMPLE 3 - INFLUENCE OF CALCIUM ALUMINATE CEMENT ON EARLY RESISTANCE [0208] This example shows the influence of the addition of calcium aluminate cement on fresh and hardened properties of aluminate cement compositions comprising calcium sulfoaluminate cement, Portland cement and calcium sulfate. TABLE 3.1 shows the mixing compositions investigated in this example. Both mixing compositions were extended with fly ash. Lithium carbonate was added at low dosage rates of less than 0.50% by weight of reactive powder based on hydraulic cement. Mixture 1 was free of calcium aluminate cement, while Mixture 2 contained calcium aluminate cement at a dosage rate of 12.8% by weight of hydraulic cement-based reactive powder. The superplasticizer used in Blend 1 was MELFLUX 5581 F from BASF, whereas that in Blend 2 was MELFLUX 6681 F from BASF.
TABLE 3.1: Compositions investigated in Example 3 Feedstock Mix 1 Mix 2 Calcium Sulfoaluminate Cement, pbw 58.8 51.3 Calcium Aluminate Cement, pbw 0.00 12.8 Calcium sulfate dihydrate, pbw 29.4 25.6 Portland cement, pbw 11.8 10.3 Total Reactive Powder Based on Hydraulic Cement, pbw 100 100 Weight ratio between fly ash / reactive powder based on hydraulic cement 1.22 1.12 Weight ratio between sand / reactive powder based on hydraulic cement 1.19 1.14 Lithium Carbonate / Hydraulic Cement-Based Reactive Powder,% by weight 0.48 0.45 Citric Acid / Hydraulic Cement-Based Reactive Powder,% by weight 0.40 0.38 AXILAT RH100 XP / Hydraulic Cement-Based Reactive Powder,% by weight 0.08 0.11 Superplasticizer,% by weight 0.64 1.06 Defoamer / Hydraulic Cement-Based Reactive Powder,% by weight 0.79 0.76 Weight Ratio between Water / Powder Reactive Powder based on hydraulic cement 0.953 0.983
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SETTING FLUID PASTE AND CONSOLIDATION BEHAVIOR [0209] TABLE 3.2 shows settlement of fluid paste (demonstrating mixing workability) and consolidation behavior of the two compositions investigated in Example 3. TABLE 3.2 shows the measured diameter of the laying cakes in this example . It can be seen that the addition of calcium aluminate cement to the remaining components of the invention did not negatively impact the flow behavior of the material. It should be noted that the addition of materials with sufficient workability and flow properties typically produces a settlement cake with a diameter greater than 15.24 cm (6 inches).
[0210] TABLE 3.2 further demonstrates the times of initial and final consolidation of the compositions of the invention decrease with the addition of calcium aluminate cement.
TABLE 3.2: Workability (Settlement - Cylinder of 5.08 cm (2 ") in diameter and 2.54 cm (1") in height) and Consolidation Time (Vicat) Mixture n ^Q Settlement(centimeters (inches)) Initial Consolidation (min) Final Consolidation (min) 1 20.55 cm (8 3/32 ”) 29 38 2 18.57 cm (7 10/32 ”) 26 30
COMPRESSION RESISTIBILITY BEHAVIOR [0211] TABLE 3.3 shows the behavior of early compression resistance (4 hours) of the cementitious compositions investigated in this example. This table shows that the compressive resistance of the material increases with the addition of calcium aluminate cement in the compositions of the invention. For various applications, it is desirable to have a compressive resistivity greater than 13.79 MPa (2,000 psi). This example
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65/97 demonstrated that high early resistivity can be achieved by adding calcium aluminate cement to the raw material components of the remaining invention.
TABLE 3.3: Compression Resistance (MPa (psi)) Mixture n- 4 hours 1 10.56 (1,531) 2 16 (2,321)
EXAMPLE 4 - INFLUENCE OF THE ADDITION OF PORTLAND CEMENT IN THE PRESENCE OF CALCIUM SULFOALUMINATE CEMENT AND CALCIUM ALUMINATE CEMENT [0212] This example shows the influence of the addition of Portland cement on fresh and hardened properties of aluminate cement compositions that comprise cement of cement calcium sulfoaluminate, calcium aluminate cement and calcium sulfate. TABLE 4.1 shows the mixing compositions investigated in this example. All mixing compositions were extended with fly ash. Lithium carbonate was added at high dosage rates greater than 2.00% by weight of the reactive powder based on hydraulic cement. Mixture 1 contained a greater amount of Portland cement (10.3% by weight), while Mixture 4 had the lowest amount of Portland cement (2.8% by weight). The superplasticizer used in these mixtures was MELFLUX 6681 F from BASF.
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TABLE 4.1: Compositions investigated in Example 4 Feedstock Mixture1 Mixture2 Mixture3 Mixture4 Calcium Sulfoaluminate Cement, pbw 51.3 52.6 54.1 55.6 Calcium Aluminate Cement, pbw 12.8 13.2 13.5 13.9 Calcium sulfate hemihydrate, pbw 0.00 0.00 0.00 0.00 Calcium sulfate dihydrate, pbw 25.6 26.3 27.0 27.6 Portland cement, pbw 10.3 7.9 5.4 2.8 Total Reactive Powder Based on Hydraulic Cement, pbw 100 100 100 100 Weight ratio between fly ash / reactive powder based on hydraulic cement 1.12 1.14 1.16 1.18 Weight ratio between sand / reactive powder based on hydraulic cement 1.14 1.15 1.16 1.17 Lithium Carbonate / Hydraulic Cement-Based Reactive Powder,% by weightCitric Acid / Hydraulic Cement-Based Reactive Powder,% by weight 2.27 2.29 2.31 2.33 0.38 0.38 0.39 0.39 AXILAT RH100 XP / Reactive Powder BasedHydraulic Cement,% by weight 0.12 0.12 0.12 0.12 Superplasticizer / Hydraulic Cement-Based Reactive Powder,% by weight 1.06 1.07 1.08 1.09 Defoamer / Reactive Powder Based onHydraulic Cement,% by weight 0.76 0.76 0.77 0.78 Weight Ratio between Water / Powder Reactive Powder based on hydraulic cement 0.908 0.916 0.924 0.933 SETTLEMENT IN FOLDER FLUID AND
CONSOLIDATION BEHAVIOR [0213] TABLE 4.2 shows the settlement of the slurry (demonstrating mixing workability) and consolidation behavior of the compositions investigated in Example 4. TABLE 4.2 shows the measured diameter of the settlement cakes in this example. You can
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67/97 observe that the measured settlement of all mixtures investigated in this example was greater than 15.24 cm (6 inches), thus demonstrating sufficient workability and flow properties.
[0214] TABLE 4.2 also shows the initial and final consolidation times of the mix compositions investigated in this example. The consolidation times of the inventive mixing compositions decreased with an increase in Portland cement content. In this way, the addition of Portland cement achieves faster consolidation in the aluminous compositions of the present invention.
TABLE 4.2: Workability (Settlement - Cylinder of 5.08 cm (2 ") in diameter and 2.54 cm (1") in height) and Consolidation Time (Vicat) Mixture n ^Q Settlement(centimeters (inches)) Initial Consolidation (min) Final Consolidation (min) 1 17.46 cm (6 7/8 ") 46 51 2 17.3 cm (6 13/16 ”) 49 53 3 18.1 cm (7 1/8 ") 57 62 4 18.42 cm (7 1/4 ”) 61 70
SELF-HEALING BEHAVIOR [0215] All mixtures investigated in this example demonstrated excellent self-healing behavior, as measured according to the ASTM 01708-13 standard. Mixture 1 failed in 30 minutes, while Mixtures 2 and 4 failed in 37.5 minutes from the start of mixing the material. A longer self-healing time is useful in many practical applications, as it allows users a longer window of time to work with the material in order to achieve a desirable installation and finish.
COMPRESSION RESISTIBILITY BEHAVIOR [0216] TABLE 4.3 shows the behavior of early (2 hours and 4 hours) and final (2 hours and 28 hours) compressive resistance
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68/97 days) of the cementitious compositions investigated in this example. For the investigated mixtures, the compressive resistivity of 2 hours was greater than 10.34 MPa (1,500 psi) and the compressive resistivity of 4 hours was greater than
13.79 MPa (2,000 psi). In addition, the 28-day compression resistance of the investigated mixtures was greater than 34.13 MPa (4,950 psi). For various applications, it is desirable to have a compressive resistivity greater than 13.79 MPa (1,500 psi). The formulations of the present invention that allow this attribute to be achieved in 2 hours are preferred.
TABLE 4.3: Compression Resistance (MPa (psi)) Mixture n ^Q 2 hours 4 hours 28 days 1 12.36 (1,793) 17.4 (2,524) 34.28 (4,972) 2 11.86 (1,720) 16.23 (2,354) 37.65 (5,460) 3 11.21 (1,626) 15.51 (2,250) 39.05 (5,663) 4 10.36 (1,503) 14.62 (2,120) 38.78 (5,624)
EXAMPLE 5 - INFLUENCE OF LITHIUM CARBONATE DOSAGE IN DIMENSIONAL MOVEMENT [0217] This example shows that the influence of the lithium carbonate addition rate on fresh and hardened properties of aluminate cement compositions comprising calcium sulfoaluminate cement, calcium cement calcium aluminate, Portland cement and calcium sulfate. TABLE 5.1 shows the mixing compositions investigated in this example. All mixing compositions were extended with fly ash. Lithium carbonate was added at dosage rates in the range of 0.68 to 2.27% by weight of reactive powder based on hydraulic cement. The superplasticizer used in these mixtures was MELFLUX 6681 F from BASF. The mixture by adding viscosity enhancement to these mixtures was STARVIS 3003F from BASF.
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TABLE 5.1: Compositions investigated in Example 5 Feedstock Mixture1 Mixture2 Mixture3 Calcium Sulfoaluminate Cement, pbw 51.3 51.3 51.3 Calcium Aluminate Cement, pbw 12.8 12.8 12.8 Calcium sulfate dihydrate, pbw 25.6 25.6 25.6 Portland cement, pbw 10.3 10.3 10.3 Total Reactive Powder Based on Hydraulic Cement, pbw 100 100 100 Weight ratio between fly ash / reactive powder based on hydraulic cement 1.12 1.12 1.12 Weight ratio between sand / reactive powder based on hydraulic cement 1.14 1.14 1.14 Lithium carbonate / Hydraulic Cement-Based Reactive Powder,% by weight 0.68 1.36 2.27 Citric Acid / Hydraulic Cement-Based Reactive Powder,% by weight 0.38 0.38 0.27 AXILAT RH100 XP / Hydraulic Cement-Based Reactive Powder,% by weight 0.11 0.11 0.11 Superplasticizer / Hydraulic Cement-Based Reactive Powder,% by weight 1.06 1.06 1.06 Mixture by Addition of Viscosity Enhancement / Hydraulic Cement-Based Reactive Powder,% by weight 0.00 0.00 0.30 Defoamer / Hydraulic Cement-Based Reactive Powder,% by weight 0.76 0.76 0.76 Sodium Gluconate / Hydraulic Cement-Based Reactive Powder,% by weight 0.30 0.30 0.35 Color Pigment / Reactive Powder Based on Hydraulic Cement,% by weight 0.00 0.00 2.27 Weight ratio between water / reactive powder based on hydraulic cement 0.91 0.91 0.91
FLUID PASTE SETTING AND
CONSOLIDATION BEHAVIOR
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70/97 [0218] TABLE 5.2 shows the settlement of the slurry (demonstrating the mixing workability) and consolidation behavior of the compositions investigated in Example 5. TABLE 5.2 shows the measured diameter of the settlement cakes in this example. It can be seen that the measured settlement of all the mixtures investigated in this example was equal to or greater than 17.78 cm (7 inches), thus demonstrating excellent workability and flow properties.
[0219] TABLE 5.2 also shows the initial and final consolidation times of the mix compositions investigated in this example. It can be seen that the consolidation times of the mixing compositions of the invention were hardly affected by the amount of lithium carbonate in the composition.
[0220] Figures 3, 4 and 5 show photographs of settlement cakes for Mixtures 1, 2, and 3, respectively, of the compositions investigated in Example 5. Photographs of the settlement cakes show that all three mixtures demonstrated workability of sufficient flow properties.
TABLE 5.2: Workability (Settlement - Cylinder of 5.08 cm (2 ") in diameter and 2.54 cm (1") in height) and Consolidation Time (Vicat) Mixture n ^Q Settlement(centimeters (inches)) Initial Consolidation (min) Final Consolidation (min) 1 19.21 cm (7 9/16) 42 46 2 18.42 cm (7 1/4) 45 49 3 17.78 cm (7) 43 48
COMPRESSION RESISTIBILITY BEHAVIOR [0221] TABLE 5.3 shows the early (2 hours and 4 hours) and final (2 hours and 28 days) compression resistivity behavior of the cementitious compositions investigated in this example. To the
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71/97 investigated mixtures, the compressive resistivity of 2 hours was greater than 10.34 MPa (1,500 psi) and the compressive resistivity of 4 hours was greater than
13.79 MPa (2,000 psi). In addition, the 28-day compression resistance of the investigated mixtures was greater than 34.13 MPa (4,500 psi). For various applications, it is desirable to have a compressive resistivity greater than 13.79 MPa (1,500 psi). The compositions disclosed in this document that allow this feature to be achieved in 2 hours are considered to be the preferred compositions of the present invention.
TABLE 5.3: Resistance to Compression (MPa (psi)) Mixture n ^Q 2 hours 4 hours 28 days 1 12.23 (1,774) 15.55 (2,255) 36.07 (5,232) 2 11.82 (1,714) 15.35 (2,227) 36.69 (5,322) 3 12.08 (1,752) 15.84 (2,297) 32.24 (4,676)
SELF-HEALING BEHAVIOR [0222] The self-healing behavior of the compositions in this example was investigated using the standard ASTM C170813. All mixtures showed a minimum self-healing time of 30 minutes. A longer self-healing time is useful in many practical applications, as it allows users a longer window of time to work with the material in order to achieve a desirable installation and finish.
LINEAR MOVEMENT [0223] Figure 5A is a plot showing the Linear motion behavior (drying shrinkage) of the mix compositions investigated in Example 5. The test was conducted according to ASTM C1708-13 except that the prismatic samples were taken of the mold at the time of initial consolidation, and the initial specimen length measurement was obtained shortly after removing the specimen from the mold. Sample length measurements continued until the age of 56 days. This shows that Mixture 1 and Mixture 2 have shrunk, where one
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72/97 final shrinkage was in a range between 0.06% and 0.08%. This also shows that the final shrinkage decreased with an increase in lithium carbonate content. On the other hand, Mixture 3 saw a resulting expansion compared to the original sample length. The influence of lithium carbonate dosage in reducing shrinkage and expansion is an unexpected finding of the present invention. This example teaches that dimensional movement characteristics of the compositions of the invention can be adapted using an appropriate dosage of lithium carbonate. In the present state of the art in calcium aluminate cements, it is known that lithium carbonate acts as a chemical accelerator to accelerate the reaction of calcium aluminates to obtain rapid consolidation and rapid strength. In addition, the present state of the art does not teach the influence of lithium carbonate dosage on the dimensional movement of compositions that comprise aluminate cements. As unexpectedly found in this example, a higher dosage of lithium carbonate caused an increase in material expansion, thereby helping to reduce material shrinkage and overall dimensional movement. In addition, in contrast to what is known in the present state of the art, it has been surprisingly found that the consolidation and development of compression resistivity of the compositions of the present invention is affected by the amount of lithium carbonate present in the formulation. Without submitting to any theory, it is postulated that complex interactions that occur between reactive powder based on hydraulic cement, the inorganic flow control agent and metal based dimensional stabilizing agent in the presence of water use levels, as disclosed in the invention are responsible for the unexpected results observed and described in that example.
EXAMPLE 6 - HIGH DOSAGE INFLUENCE OF LITHIUM CARBONATE IN DIMENSIONAL MOVEMENT OF COMPOSITIONS CONTAINING FLYING ASH [0224] This example shows the influence of the addition of
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73/97 a high rate of lithium carbonate in the fresh and hardened properties of aluminate cement compositions comprising calcium sulfoaluminate cement, calcium aluminate cement, Portland cement and calcium sulfate. TABLE 6.1 shows the mixing compositions investigated in this example. All mixing compositions were extended with fly ash. Lithium carbonate was added at a dosage rate of 2.31% by weight of reactive powder based on hydraulic cement in all three mixtures investigated. The amount of water added in the three mixtures varied with Mixture 1 which has a w / cm ratio of 0.972, Mixture 2 which has a w / cm ratio of 0.904 and Mixture 3 which has a w / cm ratio of 0.833 . The superplasticizer used in these mixtures was MELFLUX 6681 F from BASF. The mixture by adding viscosity enhancement to these mixtures was STARVIS 3003F from BASF.
TABLE 6.1: Compositions investigated in Example 6 Feedstock Mixture1 Mixture2 Mixture3 Calcium Sulfoaluminate Cement, pbw 50.5 50.5 50.5 Calcium Aluminate Cement, pbw 13.2 13.2 13.2 Calcium sulfate dihydrate, pbw 25.3 25.3 25.3 Portland cement, pbw 11.0 11.0 11.0 Total Reactive Powder Based on Hydraulic Cement, pbw 100 100 100 Weight ratio between fly ash / reactive powder based on hydraulic cement 1.10 1.10 1.10 Weight ratio between sand / reactive powder based on hydraulic cement 1.15 1.15 1.15 Lithium Carbonate / Hydraulic Cement-Based Reactive Powder,% by weightCitric Acid / Hydraulic Cement-Based Reactive Powder,% by weight 2.31 2.31 2.31 0.17 0.17 0.17 AXILAT RH100 XP / Hydraulic Cement-Based Reactive Powder,% by weight 0.13 0.13 0.13
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Superplasticizer / Hydraulic Cement-Based Reactive Powder,% by weight 1.05 1.05 1.05 Mixing by Adding Viscosity Enhancement / Cement-Based Reactive Powder 0.32 0.32 0.32 Hydraulic,% by weight Defoamer / Hydraulic Cement-Based Reactive Powder,% by weight 0.76 0.76 0.76 Gluconate Sodium / Hydraulic Cement-Based Reactive Powder,% by weight 0.36 0.36 0.36 Color Pigment / Reactive Powder Based on Hydraulic Cement,% by weight 3.15 3.15 3.15 Weight Ratio between Water / Powder Reactive Powder based on hydraulic cement 0.972 0.903 0.833
SETTING FLUID PASTE AND CONSOLIDATION BEHAVIOR [0225] TABLE 6.2 shows the settlement of fluid paste (demonstrating mixing workability) and consolidation behavior of the compositions investigated in Example 6. Table 6.2 shows the measured diameter of the laying cakes of this example. It can be seen that the measured settlement of all the mixtures investigated in this example was equal to or greater than 15.24 cm (6 inches), thus demonstrating excellent workability and flow properties.
[0226] TABLE 6.2 also shows the initial and final consolidation times of the mix compositions investigated in this example. It can be seen that the consolidation times of the mixing compositions of the invention decreased slightly with the decrease in the water-reactive powder ratio of the material.
[0227] Figure 6, Figure 6A and Figure 6B show photographs of the settlement cakes for the Mixture 1,2 and 3 compositions, respectively, of the invention in Example 6. The photographs of the settlement cakes show that all three mixtures demonstrated
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75/97 workability of sufficient flow properties.
TABLE 6.2: Workability (Settlement - Cylinder of 5.08 cm (2 ") in diameter and 2.54 cm (1") in height) and Consolidation Time (Vicat) Mixture n- Settlement(centimeters (inches)) Initial Consolidation (min) Final Consolidation (min) 1 19.68 (7.75) 43 48 2 18.41 (7.25) 41 45 3 17.14 (6.75) 39 43
SELF-HEALING BEHAVIOR [0228] The self-healing behavior of the compositions in this example was investigated using the ASTM C170813 standard. All mixtures demonstrated a minimum self-healing time of 30 minutes. A longer self-healing time is useful in many practical applications, as it allows users a time window long enough to work with the material in order to achieve a desirable installation and finish.
COMPRESSION RESISTIBILITY BEHAVIOR [0229] TABLE 6.3 shows the early (2 hours and 4 hours) and final (2 hours and 28 days) compressive resistivity behavior of the cementitious compositions investigated in this example. This shows for the investigated mixtures, the compressive resistivity of 2 hours was greater than 10.34 MPa (1,500 psi) and the compressive resistivity of 4 hours was greater than 13.79 MPa (2,000 psi). In addition, the 28-day compression resistance of the investigated mixtures was greater than 34.13 MPa (4,500 psi). For various applications, it is desirable to have a compressive resistivity greater than
13.79 MPa (1,500 psi). The compositions disclosed in this document that allow this feature to be achieved in 2 hours are considered to be the preferred compositions of the present invention.
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TABLE 6.3: Resistance to Compression (MPa (psi)) Mixture n- 2 hours 4 hours 24 hours 28 days 1 10.8 (1,566) 16.61 (2,119) 18.93 (2,746) 28.33 (4,109) 2 12.66 (1,836) 16.91 (2,453) 22.01 (3,193) 30.52 (4,426) 3 15.02 (2,178) 19.84 (2,878) 26.44 (3,835) 34.27 (4,971)
LINEAR MOVEMENT [0230] Figure 60 shows the linear movement behavior (shrinkage by drying) of the compositions of the invention investigated in this example. The test was conducted according to ASTM 0170813 with the exception that the prismatic samples were removed from the mold at the time of initial consolidation, and the initial length measurement was obtained at the time of removing the specimen from the mold. Sample length measurements continued until the age of 56 days. This shows that all three compositions expanded within the first few hours of melting followed by a gradual shrinkage until the age of 56 days. All three compositions demonstrated a net expansion compared to the initial measured length at the time of initial consolidation. The net expansion was in a range of 0.01% to 0.03% for the three compositions investigated in this example. The influence of lithium carbonate dosage on shrinkage reduction and the resulting expansion is an unexpected and exclusive finding of the present invention.
EXAMPLE 7 - HIGH DOSAGE INFLUENCE OF LITHIUM CARBONATE IN THE DIMENSIONAL MOVEMENT OF COMPOSITIONS CONTAINING THICK GRANULATION CALCIUM CARBONATE [0231] This example shows the influence of adding a high lithium carbonate rate on the fresh and hardened properties of cement compositions of aluminate comprising calcium sulfoaluminate cement, calcium aluminate cement, Portland cement and calcium sulfate. TABLE 7.1 shows the investigated mixing compositions
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77/97 in this example. All mixing compositions were extended with the coarse-grained calcium carbonate mineral filler with 65% by weight of the particles passing through 0.044 mm (325 mesh). The amount of calcium carbonate was varied in the three mixtures, as shown in TABLE 7.1. Lithium carbonate was added at high dosage rates in a range between 1.70 and 2.31% by weight of reactive powder based on hydraulic cement in the three mixtures. The superplasticizer used in these mixtures was MELFLUX 6681 F from BASF. The mixture by adding viscosity enhancement to these mixtures was STARVIS 3003F from BASF.
TABLE 7.1: Compositions investigated in Example 7 Feedstock Mix 1 Mix 2 Mix 3 Calcium Sulfoaluminate Cement, pbw 50.5 50.5 50.5 Calcium Aluminate Cement, pbw 13.2 13.2 13.2 Calcium sulfate dihydrate, pbw 25.3 25.3 25.3 Portland cement, pbw 11.0 11.0 11.0 Total Reactive Powder Based on Hydraulic Cement, pbw 100 100 100 Weight Ratio between calcium carbonate / Hydraulic Cement-Based Reactive Powder 1.10 0.82 0.55 Weight ratio between sand / reactive powder based on hydraulic cement 1.15 1.00 0.85 Lithium carbonate / Hydraulic Cement-Based Reactive Powder,% by weight 2.31 2.01 1.70 Citric Acid / Hydraulic Cement-Based Reactive Powder,% by weight 0.17 0.15 0.12 AXILAT RH100 XP / Hydraulic Cement-Based Reactive Powder,% by weight 0.13 0.11 0.09 Superplasticizer / Hydraulic Cement-Based Reactive Powder,% by weight 1.05 0.91 0.78 Mixture by Addition of Viscosity Enhancement / Hydraulic Cement-Based Reactive Powder,% by weight 0.32 0.27 0.23 Defoamer / Hydraulic Cement-Based Reactive Powder,% by weight 0.76 0.66 0.56 Sodium Gluconate / Hydraulic Cement-Based Reactive Powder,% by weight 0.36 0.31 0.26 Color Pigment / Reactive Powder Based on Hydraulic Cement,% by weight 3.15 2.74 2.32 Weight Ratio between Water / Powder Reactive Powder based on hydraulic cement 0.972 0.784 0.666
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SETTING FLUID PASTE AND CONSOLIDATION BEHAVIOR [0232] TABLE 7.2 shows the settlement of fluid paste (demonstrating mixing workability) and consolidation behavior of the compositions investigated in Example 7. TABLE 7.2 shows the measured diameter of the laying cakes of that example. It can be seen that the measured settlement of all the mixtures investigated in this example was equal to or greater than 15.24 cm (6 inches), thus demonstrating excellent workability and flow properties.
[0233] TABLE 7.2 also shows the initial and final consolidation times of the mix compositions investigated in this example. It can be seen that all three mixtures consolidated very quickly despite the amount of calcium carbonate in the composition.
[0234] Figures 7, 7A and 7B show photographs of settlement cakes for the Mixture 1, 2 and 3 compositions, respectively, investigated in Example 7. From the photographs of the settlement cakes, it can be seen that all three mixtures had sufficient workability and flow properties.
TABLE 7.2: Workability (Settlement - Cylinder of 5.08 cm (2 ") in diameter and 2.54 cm (1") in height) and Consolidation Time (Vicat) Mixture n ^Q Settlement(centimeters (inches)) Initial Consolidation (min) Final Consolidation (min) 1 17.94 cm (7 1/16 ") 42 47 2 17.15 cm (6 3/4 ”) 36 40 3 16.67 cm (6 9/16 ") 30 33
SELF-DRYING BEHAVIOR [0235] A layer approximately 0.635 cm (1/4 inch) thick of the slurry was poured into a shallow plastic tray to observe self-drying and drying characteristics.
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79/97 surface of the material. The self-drying time was characterized as the time when the top surface of the poured under-covering slab changed its observable wet appearance to a hardened surface sufficiently dry to allow the application of floor adhesives and floor coverings (such as carpet and others). resilient floor coverings) without negatively affecting the short and long term link between the floor cover and poured under-cover. The self-drying time usually occurred after reaching the final material consolidation time. The self-drying time for Mixture 1 in this example was characterized as 90 minutes. The self-drying time of Mixture 2 was characterized as 72 minutes. The self-drying time of Mixture 3 was characterized as 60 minutes.
SELF-HEALING BEHAVIOR [0236] The self-healing behavior of the compositions in this example was investigated using the ASTM C170813 standard. All mixtures demonstrated a minimum self-healing time of 22.5 minutes. A longer self-healing time is useful in many practical applications, as it allows users a time window long enough to work with the material in order to achieve a desirable installation and finish.
COMPRESSION RESISTIBILITY BEHAVIOR [0237] TABLE 7.3 shows the early (2 hours and 4 hours) and final (2 hours and 28 days) compressive resistance behavior of the cementitious compositions investigated in this example. For the investigated mixtures, the compressive resistivity of 2 hours was greater than 10.34 MPa (1,450 psi) and the compressive resistivity of 4 hours was greater than
13.79 MPa (1,950 psi). For various applications, it is desirable to have a compressive resistivity greater than 13.79 MPa (1,500 psi). The compositions disclosed in this document that allow this feature to be
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TABLE 7.3: Compression Resistance (MPa (psi)) Mixture n ^Q 2 hours 4 hours 24 hours 1 10.19 (1,478) 13.58 (1,969) 18.93 (2,746) 2 12.42 (1,802) 15.98 (2,318) 22.01 (3,193) 3 14.67 (2,127) 18.21 (2,641) 26.44 (3,835)
LINEAR MOVEMENT [0238] Figure 70 shows the linear motion behavior of the compositions of the invention investigated in this example. The test was conducted according to ASTM C1708-13 except that the prismatic samples were removed from the mold at the time of initial consolidation, and the initial length measurement was obtained at the time of removing the specimen from the mold. The sample length measurements continued on a periodic basis after the initial measurement. This shows that all three compositions expanded within the first few hours of melting followed by a gradual shrinkage. All three compositions demonstrated a net expansion compared to the initial measured length at the time of initial consolidation. It can be concluded that the compositions of the present invention that contain coarse-grained calcium carbonate and high amounts of lithium carbonate show resulting expansion in comparison to the initial length at the time of initial consolidation. It should be noted that the influence of lithium carbonate dosage on shrinkage reduction and the resulting expansion is an unexpected and exclusive finding of the present invention.
EXAMPLE 8 - ALUMINUM CEMENT COMPOSITIONS PROPERTIES THAT UNDERSTAND ONLY ONE TYPE OF ALUMINUM CEMENT [0239] This example demonstrates the performance of
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81/97 aluminous cementitious compositions, TABLE 8.1, which comprises either calcium sulfoaluminate cement or calcium aluminate cement. Mixtures 1 to 3 show compositions that comprise calcium sulfoaluminate cement as the only aluminum cement in the mixture. Mixtures 4 to 6 show compositions that comprise calcium aluminate cement as the only aluminum cement in the mixture. In addition, the amount of calcium sulfate in the mixing compositions was varied to determine its influence on overall performance. All mixing compositions were extended with a charge of mineral calcium carbonate, HUBERCARB M200, which has a median particle size of 15 microns. The superplasticizer used in both blends was BASF CASTAMENT FS20. This example used calcium aluminate cement Ciment Fondu available from Kerneos Inc.
TABLE 8.1: Compositions investigated in Example 8 Feedstock Mix 1 Mix 2 Mix 3 Mix 4 Mix 5 Mix 6 Calcium Sulfoaluminate Cement, pbw 62.5 58.8 55.6 0.0 0.0 0.0 Calcium Aluminate Cement, pbw 0.0 0.0 0.0 62.5 58.8 55.6 Calcium sulfate hemihydrate, pbw 18.8 23.5 27.8 18.8 23.5 27.8 Portland cement, pbw 18.8 17.6 16.7 18.8 17.6 16.7 Total Reactive Powder Based on Hydraulic Cement, pbw 100 100 100 100 100 100 Weight Ratio between Calcium Carbonate / Hydraulic Cement-Based Reactive Powder 1.0 1.0 1.0 1.0 1.0 1.0 Weight Ratio between Sand / Reactive Powder Based on Hydraulic Cement 1.0 1.0 1.0 1.0 1.0 1.0 Lithium Carbonate / Hydraulic Cement-Based Reactive Powder,% by weight 0.25 0.25 0.25 0.25 0.25 0.25 Citric Acid / Hydraulic Cement-Based Reactive Powder,% by weight 0.75 0.75 0.75 0.75 0.75 0.75 AXILAT RH100 XP / Hydraulic Cement-Based Reactive Powder,% by weight 0.02 0.02 0.02 0.02 0.02 0.02 Superplasticizer / Hydraulic Cement-Based Reactive Powder,% by weight 0.50 0.50 0.50 0.50 0.50 0.50 Defoamer / Hydraulic Cement-Based Reactive Powder,% by weight 0.25 0.25 0.25 0.25 0.25 0.25 Weight Ratio between Water / Hydraulic Cement-Based Reactive Powder 0.65 0.65 0.65 0.65 0.65 0.65
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FLUID PASTE SETTING BEHAVIOR [0240] TABLE 8.2 shows the settlement of fluid paste (which demonstrates mixing workability) diameter of the compositions investigated in Example 8. It can be seen that all cakes had a relatively small diameter indicating that the material was very viscous with insufficient workability and flow properties. It should be noted that materials with insufficient workability and flow properties typically produce a plunger diameter greater than 15.24 cm (6 inches) in this test.
[0241] Figures 8A (showing Mixture 1), 8B (showing Mixture 2), 8C (showing Mixture 3), 8D (showing Mixture 4), 8E (showing Mixture 5), 8F (showing Mixture 6) shows photographs of settlement cakes for the compositions investigated in Example 8. From the photographs, it can be seen that all settlement cakes were very viscous. In addition, it can be seen that the settlement cakes for Mixtures 4 to 6 that comprise calcium aluminate cement developed crack within the first few hours after they were poured.
TABLE 8.2: Workability (Settlement - Cylinder of 5.08 cm (2 ") in diameter and 2.54 cm (1") in height) Mixture n ^Q Nesting (centimeters (inches)) 1 5.08 (2 ") 2 5.24 (2 1/16 ”) 3 5.24 (2 1/16 ”) 4 10.95 (4 5/16 ”) 5 10.8 (4 1/4 ”) 6 10.32 (4 1/16 ")
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SELF-HEALING BEHAVIOR [0242] The self-healing behavior of the compositions investigated in this example was characterized using the ASTM 01708-13 standard. All compositions exhibited extremely insufficient self-healing behavior and failed at the very moment of the initial spill. Mixtures 1 to 3 were so viscous that they could not be poured into the trays to conduct the self-healing test.
LINEAR MOVEMENT [0243] Figure 8G shows the linear motion behavior of the compositions of the invention investigated in Example 8. The linear motion behavior test was conducted according to ASTM 01708-13 except that the prismatic samples were removed from the mold in time initial consolidation, and the initial specimen length measurement was obtained shortly after removing the specimen from the mold. Sample length measurements continued until the age of about 56 days. Figure 8G shows that none of the compositions showed expansion. All mixtures showed liquid shrinkage, in which the magnitude of final shrinkage was in the range of about 0.08% to 0.12%. This extension of shrinkage is not desirable in many practical applications due to the potential cracking and removal of material bonding from the applied substrates.
EXAMPLE 9 - PROPERTIES OF ALUMINUM CEMENT COMPOSITIONS IN ABSENCE OF PORTLAND CEMENT [0244] This example demonstrates properties of aluminum compositions in the absence of Portland cement. The three mixtures investigated in the example contained only calcium aluminate cement and calcium sulfate as the cementitious materials and in Portland cement, TABLE 9.1. Three different levels of water / reactive cement powder ratios were also investigated in the absence of Portland cement in the mixture. All mixing compositions were extended with calcium carbonate filler
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TABLE 9.1: Compositions investigated in Example 9 Feedstock Mixture1 Mixture2 Mixture3 Calcium Sulfoaluminate Cement, pbw 0.0 0.0 0.0 Calcium Aluminate Cement, pbw 66.7 66.7 66.7 Calcium sulfate hemihydrate, pbw 33.3 33.3 33.3 Portland cement, pbw 0.0 0.0 0.0 Total Reactive Powder Based on Hydraulic Cement, pbw 100 100 100 Weight Ratio between Calcium Carbonate / Hydraulic Cement-Based Reactive Powder 0.75 0.75 0.75 Weight Ratio between Sand / Reactive Powder Based on Hydraulic Cement 0.75 0.75 0.75 Lithium carbonate / Hydraulic Cement-Based Reactive Powder,% by weightCitric Acid / Hydraulic Cement-Based Reactive Powder,% by weight 0.25 0.25 0.25 0.50 0.50 0.50 AXILAT RH100 XP / Hydraulic Cement-Based Reactive Powder,% by weight 0.02 0.02 0.02 Superplasticizer / Hydraulic Cement-Based Reactive Powder,% by weight 0.50 0.50 0.50 Defoamer / Hydraulic Cement-Based Reactive Powder,% by weight 0.25 0.25 0.25 Weight Ratio between Water / Hydraulic Cement-Based Reactive Powder 0.80 0.70 0.60
CONSOLIDATION BEHAVIOR [0245] TABLE 9.2 shows the initial and final consolidation times of the mixtures investigated in this example. It can be seen that all three mixtures had a relatively long consolidation time, in which the final consolidation time exceeds 90 minutes
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TABLE 9.2: Consolidation Time (Vicat) Mixture n ^Q Initial Consolidation (min) Final Consolidation (min) 1 89 107 2 85 99 3 93 108
SELF-HEALING BEHAVIOR [0246] The self-healing behavior of the compositions investigated in this example was measured using the ASTM 01708-13 standard. All three mixtures exhibited extremely poor self-healing behavior and failed at the very moment of the initial spill.
LINEAR MOVEMENT [0247] Figure 9 demonstrates the linear motion behavior of the compositions of the invention investigated in Example 9. The linear motion behavior test was conducted according to ASTM C1708-13 with the exception that the prismatic samples were removed from the mold in time initial consolidation, in which the initial specimen length measurement was obtained shortly after removing the specimen from the mold. Sample length measurements continued until the age of 56 days. None of the compositions showed long-term expansion behavior. All mixtures showed a liquid shrinkage, in which the final shrinkage magnitude was in the range of about 0.13%. This extent of shrinkage is unacceptable in many practical applications due to the potential cracking and removal of material bonding from the applied substrates. This shows that an absence of Portland cement is harmful.
EXAMPLE 10 - PROPERTIES OF ALUMINUM CEMENT COMPOSITIONS THAT UNDERSTAND HIGH AMOUNT OF PORTLAND CEMENT
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86/97 [0248] This example shows the influence of a high amount of Portland cement on aluminous cement compositions, TABLE 10.1. All six mixtures in this example contained Portland cement at 76.9% by weight of the total reactive powder based on hydraulic cement. Mixtures 1 to 3 comprised calcium sulfoaluminate cement as the only aluminum cement in the composition. Mixtures 4 to 6 comprised calcium aluminate cement as the only aluminum cement in the composition. The superplasticizer in all mixtures was BASF MELFLUX 6681 F.
TABLE 10.1: Compositions investigated in Example 10 Feedstock Mixture1 Mixture2 Mixture3 Mixture4 Mixture5 Mix 6 Calcium Sulfoaluminate Cement, pbw 15.4 15.4 15.4 0.0 0.0 0.0 Calcium Aluminate Cement, pbw 0.0 0.0 0.0 15.4 15.4 15.4 Calcium sulfate dihydrate, pbw 7.7 7.7 7.7 7.7 7.7 7.7 Portland cement, pbw 76.9 76.9 76.9 76.9 76.9 76.9 Total Reactive Powder Based on Hydraulic Cement, pbw 100 100 100 100 100 100 Weight Ratio between fly ash / reactive powder based on hydraulic cement 0.23 0.15 0.08 0.23 0.15 0.08 Weight Ratio between Sand / Reactive Powder Based on Hydraulic Cement 1.85 1.73 1.62 1.85 1.73 1.62 Lithium carbonate / Hydraulic Cement-Based Reactive Powder,% by weight 0.31 0.29 0.27 0.31 0.29 0.27 Citric Acid / Hydraulic Cement-Based Reactive Powder,% by weight 0.15 0.14 0.13 0.15 0.14 0.13 AXILAT RH100 XP / Hydraulic Cement-Based Reactive Powder,% by weight 0.062 0.058 0.054 0.062 0.058 0.054 Superplasticizer / Hydraulic Cement-Based Reactive Powder,% by weight 0.31 0.29 0.27 0.31 0.29 0.27 Defoamer / Hydraulic Cement-Based Reactive Powder,% by weight 0.31 0.29 0.27 0.31 0.29 0.27 Gluconate Sodium / Hydraulic Cement-Based Reactive Powder,% by weight 0.12 0.12 0.11 0.12 0.12 0.11 Color Pigment / Reactive Powder Based on Hydraulic Cement,% by weight 1.23 1.15 1.08 1.23 1.15 1.08 Weight Ratio between Water / Hydraulic Cement-Based Reactive Powder 0.74 0.74 0.73 0.89 0.85 0.65
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SETTING BEHAVIOR OF FLUID PASTE [0249] TABLE 10.2 shows the settlement of fluid paste (which demonstrates mixing workability) diameter of the compositions investigated in Example 10. All cakes had a relatively small diameter indicating that the material was very viscous with insufficient workability and flow properties. It should be noted that materials with sufficient workability and flow properties typically produce a settlement cake that has a diameter greater than 15.24 cm (6 inches) in this test.
TABLE 10.2: Workability (Settlement - Cylinder of 5.08 cm (2 ") in diameter and 2.54 cm (1") in height) Mixture n ^Q Nesting (centimeters (inches)) 1 5.72 (2 1/4 ”) 2 6.03 (2 3/8 ”) 3 5.72 (2 1/4 ”) 4 14.76 (5 13/16 ”) 5 13.65 (5 3/8 ”) 6 12.07 (4 3/4 ”)
CONSOLIDATION BEHAVIOR [0250] TABLE 10.3 shows the initial and final consolidation times of the mix compositions investigated in this example that comprise a high amount of Portland cement. It can be seen that all six mixing compositions had a relatively long consolidation time whose final consolidation time exceeded 120 minutes for Mixtures 1 to 3 and exceeded 360 minutes for Mixtures 4 to 6. Thus, it can be concluded that mix aluminous cement compositions that comprise a high amount of Portland cement are relatively low consolidating and are not advantageous in applications where
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TABLE 10.3: Consolidation Time (Vicat) Mixture n ^Q Initial Consolidation (min) Final Consolidation (min) 1 65 107 2 66 99 3 59 108 4 348 > 360 5 349 > 360 6 340 > 360
COMPRESSION RESISTIBILITY BEHAVIOR [0251] TABLE 10.4 shows the early age (4 hours and 24 hours) and the compressive resistance behavior (28 days) of the cementitious compositions investigated in this example. It can be seen that all the investigated mixing compositions developed resistivity extremely slowly. For Mixtures 1 to 3 which comprise calcium sulfoaluminate cement as the only aluminum cement in the composition, the 4-hour compression resistivities were less than 2.76 MPa (400 psi) and the 24-hour resistivities were less than 4, 65 MPa (675 psi). In addition, for Mixtures 4 to 6 which comprise calcium aluminate cement as the only aluminous cement in the composition, the 4-hour compressive resistivities could not be measured due to the extremely low consolidation behavior, whereas the 24-hour resistivities hours were extremely low, below 2.93 MPa (425 psi). These results demonstrate that aluminous cement compositions that comprise the highest amounts of Portland cement and lower amounts of aluminous cements harden at a very slow rate and develop extremely low compression resistance at an early age. Thus, such cementitious compositions are not desirable when rapid development
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89/97 resistance is desirable at an early age. In addition, the final compressive resistivities (28 days) of these mixtures were also relatively low, in a range of 16.55 MPa (2,400 psi) to 24.13 MPa (3500 psi) only.
TABLE 10.4: Resistance to Compression (MPa (psi)) Mixture n- 4 hours 24 hours 28 days 1 2.59 (376) 4.56 (662) 24.21 (3,512) 2 2.12 (308) 3.82 (554) 21.77 (3,157) 3 2 (290) 3.67 (532) 20.35 (2,951) 4 Immeasurable due to slow consolidation 1.2 (174) 19.69 (2,856) 5 Immeasurable due to slow consolidation 1.72 (250) 16.56 (2,402) 6 Immeasurable due to slow consolidation 2.87 (416) 17 (2,466)
[0252] These data show that the presence of too much Portland cement is harmful.
EXAMPLE 11 - PROPERTIES OF ALUMINUM CEMENT COMPOSITIONS THAT UNDERSTAND LITHIUM-BASED SALTS AS A DIMENSIONAL MOVEMENT STABILIZING AGENT [0253] This example shows the performance of the aluminum cement compositions in Table 11.1 of the present invention that have lithium-based salts as a lithium-based salts. dimensional motion stabilizing agent. Mixture 1 included lithium carbonate, Mixtures 2 to 6 included lithium sulfate, as dimensional movement stabilizing agents. The superplasticizer in all mixtures was BASF MELFLUX 6681 F.
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TABLE 11.1: The compositions investigated in Example 11 Feedstock Mixture1 Mixture2 Mixture3 Mixture4 Mixture5 Mixture6 Calcium Sulfoaluminate Cement, pbw 54.3 54.3 54.3 54.3 54.3 54.3 Calcium Aluminate Cement, pbw 13.0 13.0 13.0 13.0 13.0 13.0 Calcium sulfate dihydrate, pbw 21.7 21.7 21.7 21.7 21.7 21.7 Portland cement, pbw 10.9 10.9 10.9 10.9 10.9 10.9 Total Reactive Powder Based on Hydraulic Cement, pbw 100 100 100 100 100 100 Weight Ratio between Calcium Carbonate / Hydraulic Cement-Based Reactive Powder 0.65 0.65 0.65 0.65 0.65 0.65 Weight Ratio between Sand / Reactive Powder Based on Hydraulic Cement 0.91 0.91 0.91 0.91 0.91 0.91 Lithium carbonate / Hydraulic Cement-Based Reactive Powder,% by weight 1.82 0.00 0.00 0.00 0.00 0.00 Lithium Sulphate / Hydraulic Cement-Based Reactive Powder,% by weight 0.00 0.83 1.24 1.82 2.07 2.48 Citric Acid / Hydraulic Cement-Based Reactive Powder,% by weight 0.20 0.20 0.20 0.20 0.20 0.20 AXILAT RH100 XP / Hydraulic Cement-Based Reactive Powder,% by weight 0.074 0.074 0.074 0.074 0.074 0.074 Superplasticizer / Hydraulic Cement-Based Reactive Powder,% by weight 0.83 0.83 0.83 0.83 0.83 0.83 Defoamer / Hydraulic Cement-Based Reactive Powder,% by weight 0.60 0.60 0.60 0.60 0.60 0.60 Gluconate Sodium / Hydraulic Cement-Based Reactive Powder,% by weight 0.31 0.31 0.31 0.31 0.31 0.31 Hydraulic Cement-Based Reactive Pigment / Powder,% by weight 1.65 1.65 1.65 1.65 1.65 1.65 Weight Ratio between Water // Hydraulic Cement-Based Reactive Powder 0.71 0.71 0.71 0.71 0.71 0.71
SETTING BEHAVIOR OF FLUID PASTE [0254] TABLE 11.2 shows the diameter of settlement of the slurry (which demonstrates mixing workability) of the
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91/97 compositions of Example 11. All cakes had a relatively large diameter which demonstrates satisfactory workability and flow behavior. Materials with sufficient workability and flow properties typically produce a settlement cake that has a diameter greater than 15.24 cm (6 inches) in this test.
TABLE 11.2: Workability (Settlement - Cylinder of 5.08 cm (2 ") in diameter and 2.54 cm (1") in height) Mixture n ^Q Nesting (centimeters (inches)) 1 18.89 cm (7 7/16 ”) 2 18.89 cm (7 7/16 ”) 3 18.57 (7 5/16 ”) 4 18.42 cm (7 1/4 ”) 5 18.42 cm (71/4 ") 6 18.26 (7 3/16 ”)
CONSOLIDATION BEHAVIOR [0255] TABLE 11.3 also shows the initial and final consolidation times of the mix compositions investigated in this example. All six mixing compositions had an extremely rapid consolidation whose final consolidation times were less than 40 minutes. All mixing compositions comprising lithium sulfate had a final curing time of less than 30 minutes. All mixtures comprising lithium sulphate demonstrated extremely fast self-drying behavior with a self-drying time of less than one hour.
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TABLE 11.3: Consolidation Time (Vicat) Mixture n- Initial Consolidation (min) Final Consolidation (min) 1 34 39 2 23 27 3 21 23 4 18 20 5 17 19 6 16 19
COMPRESSION RESISTIBILITY BEHAVIOR [0256] TABLE 11.4 shows the compression resistivity behavior of the cementitious compositions investigated in this example. All mixing compositions had extremely fast curing. It should be noted that the compressive resistivity of two hours (2 hours) for all mixing compositions exceeded 15.17 (2,200 psi), while the compressive resistivity of twenty-four hours (24 hours) for all compositions of mixture exceeded 22.06 MPa (3200 psi).
TABLE 11.4: Resistance to Compression (MPa (psi)) Mixture n- 2 hours 24 hours 1 15.23 (2,209) 24.19 (3,508) 2 16.67 (2,418) 23.95 (3,473) 3 17.1 (2,480) 23.69 (3,436) 4 16.31 (2366) 22.99 (3,334) 5 16.02 (2,323) 23.15 (3,357) 6 15.35 (2227) 22.48 (3,261)
LINEAR MOVEMENT [0257] Figure 10 shows the linear motion behavior of the compositions of the invention investigated in Example 11.0
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93/97 linear motion behavior test was conducted according to ASTM C1708-13 except that the prismatic samples were removed from the mold at the initial consolidation time, and the initial specimen length measurement was obtained shortly after removing the specimen from the mold. Sample length measurements were continued until the age of 42 days. It can be seen that the expansion characteristics of the material increased with an increase in the amount of lithium salt in the composition. Some of the mixing compositions demonstrated liquid expansion even at the age of 42 days. Compositions with low dimensional movement and general shrinkage, as shown in this example, are particularly useful when it comes to breaking strength and bond removal.
EXAMPLE 12 - PROPERTIES OF ALUMINUM CEMENT COMPOSITIONS THAT UNDERSTAND DIFFERENT TYPES OF CALCIUM SULPHATES [0258] This example demonstrates properties of aluminous cement compositions of the present invention comprising different types of calcium sulfates - calcium sulfate dihydrate , calcium sulfate hemihydrate and anhydrous calcium sulfate. TABLE 12.1 shows the mixing compositions investigated in this example. Mixture 1 contained calcium sulfate dihydrate, Mixture 2 contained calcium sulfate hemihydrate, while Mixture 3 contained anhydrous calcium sulfate. The superplasticizer in all mixtures was BASF MELFLUX 6681 F.
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TABLE 12.1: Compositions Investigated in Example 12 Feedstock Mixture1 Mixture2 Mixture3 Calcium Sulfoaluminate Cement, pbw 36.8 36.8 36.8 Calcium Aluminate Cement, pbw 13.2 13.2 13.2 Calcium sulfate dihydrate, pbw 18.4 0.0 0.0 Calcium sulfate hemihydrate, pbw 0.0 18.4 0.0 Anhydrous calcium sulphate, pbw 0.0 0.0 18.4 Portland cement, pbw 31.6 31.6 31.6 Total Reactive Powder Based on Hydraulic Cement, pbw 100 100 100 Weight Ratio between Calcium Carbonate / Hydraulic Cement-Based Reactive Powder 1.15 1.15 1.15 Weight Ratio between Sand / Reactive Powder Based on Hydraulic Cement 2.75 2.75 2.75 Lithium carbonate / Hydraulic Cement-Based Reactive Powder,% by weight 0.69 0.69 0.69 Citric Acid / Hydraulic Cement-Based Reactive Powder,% by weight 0.25 0.25 0.25 AXILAT RH100 XP / Hydraulic Cement-Based Reactive Powder,% by weight 0.083 0.083 0.083 Superplasticizer / Hydraulic Cement-Based Reactive Powder,% by weight 0.41 0.41 0.41 Defoamer / Hydraulic Cement-Based Reactive Powder,% by weight 0.50 0.50 0.50 Gluconate Sodium / Hydraulic Cement-Based Reactive Powder,% by weight 0.28 0.28 0.28 Color Pigment / Reactive Powder Based on Hydraulic Cement,% by weight 1.38 1.38 1.38 Weight Ratio between Water / Hydraulic Cement-Based Reactive Powder 0.98 0.98 0.98
FOLDING SETTING BEHAVIOR
FLUID
Petition 870190048047, of 05/22/2019, p. 103/242
95/97 [0259] TABLE 12.2 shows the settlement of the slurry (which demonstrates mixing workability) diameter of the compositions investigated in Example 12. All cakes had a relatively large diameter which demonstrates satisfactory workability and flow behavior. It should be noted that materials with sufficient workability and flow properties typically produce a settlement cake that has a diameter greater than 15.24 cm (6 inches) in this test.
TABLE 12.2: Workability (Settlement - Cylinder of 5.08 cm (2 ") in diameter and 2.54 cm (1") in height) Mixture n ^Q Nesting (centimeters (inches)) 1 16.83 (6 5/8 ") 2 16.51 (6 1/2 ") 3 16.35 (6 7/16 ”)
CONSOLIDATION BEHAVIOR [0260] TABLE 12.3 also shows the initial and final consolidation times of the mix compositions investigated in this example. All six mixing compositions with different types of calcium sulphates achieved a fast consolidation behavior. The compositions with calcium sulphate dihydrate and anhydrous calcium sulphate had particularly rapid consolidation with final consolidation times equal to or less than 60 minutes. In addition, all of the compositions investigated in this example also exhibited extremely fast self-drying behavior. For Mixture 1 and Mixture 3, the surface of the poured material dried in less than an hour and a half after pouring, whereas the same for Mixture 2 occurred in less than two hours after pouring.
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96/97
TABLE 12.3: Consolidation Time (Vicat) Mixture n- Initial Consolidation (min) Final Consolidation (min) 1 55 59 2 92 103 3 52 58
COMPRESSION RESISTIBILITY BEHAVIOR [0261] TABLE 12.4 shows the early age (4 hours and 24 hours) and the compressive resistance behavior (28 days) of the cementitious compositions investigated in this example. All investigated mixtures demonstrated a rapid development of resistivity at an early age. It should be noted that the 4-hour compression resistivity for all mixtures exceeds 11.03 Mpa (1,600 psi), while the 24-hour compression resistivity for all mixtures exceeds 15.17 MPa (2,200 psi). The compression resistance of 28 days for all mixtures exceeded 24.13 Mpa (3,500 psi). Thus, it can be concluded that the aluminous cement compositions of the present invention that comprise different types of calcium sulphates are capable of producing extremely rapid development of hardening and early resistivity.
TABLE 12.4: Compression Resistance (MPa (psi)) Mixture n- 4 hours 24 hours 28 days 1 11.54 (1,659) 15.69 (2,276) 25.22 (3,658) 2 11.05 (1,603) 15.68 (2,274) 25.32 (3,672) 3 11.43 (1,658) 17.22 (2,497) 29.64 (4,343)
LINEAR MOVEMENT [0262] Figure 11 shows the linear motion behavior of the compositions of the invention investigated in Example 12. The
Petition 870190048047, of 05/22/2019, p. 105/242
97/97 linear motion behavior test was conducted according to ASTM C1708-13 except that the prismatic samples were removed from the mold at the initial consolidation time, and the initial specimen length measurement was obtained shortly after removing the specimen from the mold. Sample length measurements continued until the age of 63 days. It should be noted that all of the mixing compositions of the present invention investigated in this example demonstrated expansion characteristics up to the age of 63 days. Compositions with low dimensional movement and expansion characteristics, as shown in this example, are desirable when it comes to breaking strength and general mechanical stability.
[0263] Although the modalities have been described to implement the present invention, persons skilled in the art, to which the present disclosure refers, will understand that modifications and additions can be made to the present invention without departing from the scope of the same.

权利要求:
Claims (10)
[1]
1 = Cementitious composition characterized by the fact that it comprises a reaction product of a mixture of:
a reactive powder based on hydraulic cement comprising:
an aluminate cement selected from at least one member of the group consisting of calcium aluminate cement and calcium sulfoaluminate cement in an amount of 25 to 80 parts by weight per 100 parts by weight of the reactive powder based on hydraulic cement, Portland cement in an amount of 2.5 to 45 parts by weight per 100 parts by weight of reactive powder based on hydraulic cement, a calcium sulfate selected from the group consisting of sulfate dihydrate calcium, calcium sulphate hemihydrate, anhydrous calcium sulphate and mixtures thereof, with calcium sulphate in an amount of 15 to 45 parts by weight for every 100 parts by weight of reactive powder based on hydraulic cement;
an inorganic flow control agent in a weight ratio between the inorganic flow control agent and the reactive powder based on hydraulic cement from 0.25: 1 to 3.0: 1, with Inorganic flow control comprising at least one member selected from the group consisting of fly ash and calcium carbonate and in which average particle size of the calcium carbonate bands of about 10 to 150 microns;
a metal-based dimensional motion stabilizing agent in an amount equal to 0 to 5.0 percent by weight of the hydraulic cement-based reactive powder, the metal-based dimensional motion stabilizing agent comprising a lithium compound selected from at least one member of the lithium salt and lithium base group, with the lithium salt being at least one member of the lithium carbonate, lithium sulphate, lithium nitrate, lithium nitride and silicate group lithium, the base of which is lithium hydroxide;
Petition 870190048047, of 05/22/2019, p. 107/242
[2]
2/4 a load in a weight ratio between load and reactive powder based on hydraulic cement from 0: 1 to 5.0: 1; and water in a weight ratio of water to reactive powder based on hydraulic cement from 0.5: 1 to 1.4: 1.
2. Composition according to claim 1, characterized by the fact that the reactive powder based on hydraulic cement comprises:
aluminate cement at 30 to 70 parts by weight for every 100 parts by weight of reactive powder based on hydraulic cement;
7.5 to 25 parts by weight Portland cement for every 100 parts by weight of reactive powder based on hydraulic cement;
25 to 35 parts by weight calcium sulfate for every 100 parts by weight of reactive powder based on hydraulic cement;
where the weight ratio between the inorganic flow control agent and hydraulic cement-based reactive powder is 0.75: 1 to 1.5: 1;
the amount of the metal-based dimensional motion stabilizing agent is equal to 1.5 to 3.5 weight percent of the hydraulic cement-based reactive powder;
the weight ratio between load and reactive powder based on hydraulic cement is equal to 1.0: 1 to 2.5: 1; and the weight ratio between water and reactive powder based on hydraulic cement is 0.7: 1 to 1.2: 1.
[3]
3. Composition, according to claim 1, characterized by the fact that the reactive powder based on hydraulic cement comprises: calcium suifoaluminate cement at 25 to 75 parts by weight for every 100 parts by weight of reactive powder based on hydraulic cement; and calcium aluminate cement at 2.5 to 45 parts by weight for every 100 parts by weight of reactive powder based on hydraulic cement.
[4]
4 = Composition, according to claim 1,
Petition 870190048047, of 05/22/2019, p. 108/242
3/4 characterized by the fact that it comprises:
an organic rheology modifier in an amount equal to 0.02 to 1% by weight of the reactive powder based on hydraulic cement;
an inorganic viscosity enhancing agent in an amount equal to 0 to 1% by weight of the reactive powder based on hydraulic cement;
a superplasticizer in an amount equal to 0.3 to 3.5% by weight of the reactive powder based on hydraulic cement;
an antifoam in an amount equal to 0 to 2.0% by weight of the reactive powder based on hydraulic cement;
a consolidation retarding agent in an amount equal to 0 to 2.0% by weight of the reactive powder based on hydraulic cement;
a color pigment in an amount equal to 0 to 8.0% by weight of the reactive powder based on hydraulic cement;
an air insertion agent in an amount equal to 0 to 1.0% by weight of the reactive powder based on hydraulic cement;
an organic film-forming polymer in an amount equal to 0 to 15.0% by weight of the reactive powder based on hydraulic cement; and a pozzolan different from fly ash in a weight ratio between pozzolan and reactive powder based on hydraulic cement from 0 to 1.
[5]
Composition according to claim 1, characterized by the fact that the inorganic flow control agent is a fly ash in the absence of calcium carbonate.
[6]
6. Composition, according to claim 1, characterized by the fact that the inorganic flow control is calcium carbonate in the absence of fly ash.
[7]
7 = Composition according to claim 1, characterized by the fact that the mixture has an absence of alkali metal hydroxide and an absence of alkali metal salt other than carbonate
Petition 870190048047, of 05/22/2019, p. 109/242
4/4 lithium.
[8]
8 = Composition according to claim 1, characterized by the fact that the mixture has an absence of alkali metal citrate.
[9]
9. Composition according to claim 1, characterized by the fact that the mixture has an absence of glass.
[10]
10. Method characterized by the fact that it comprises: producing a mixture by mixing the composition according to any one of claims 1 to 9, which comprises:
reactive powder based on hydraulic cement comprising:
aluminate cement, Portland cement, calcium sulfate;
the inorganic flow control agent;
the metal-based dimensional motion stabilizing agent;
load; and water;
react the mixture; and allow the mixture to consolidate.

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法律状态:
2021-07-27| B06W| Patent application suspended after preliminary examination (for patents with searches from other patent authorities) chapter 6.23 patent gazette]|

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2021-10-05| B350| Update of information on the portal [chapter 15.35 patent gazette]|

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2021-12-14| B11B| Dismissal acc. art. 36, par 1 of ipl - no reply within 90 days to fullfil the necessary requirements|

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