Cement-based composition

Abstract

The present invention is directed to a two-component (2K) anhydrous composition comprising a first component (1) comprising calcium aluminate cement; ground granulated blast furnace slag (GGBS); and fumed silica; and a second component (2) comprising calcined bauxite; and fused zirconia-mullite.

Description

[Technical Field]

[0001] The present invention relates to a two-component (2K) cement-based composition. More specifically, the present invention relates to a two-component (2K) composition comprising a first component (1) comprising calcium aluminate cement; blast furnace granulated slag powder (GGBS); and fumed silica; and a second component (2) comprising calcined bauxite; and molten zirconium light. [Background technology]

[0002] The increasing usefulness of cement-based materials as coatings for industrial machinery, industrial equipment, commercial machinery, commercial equipment, and structural materials exposed to high temperatures, sometimes accompanied by exposure to corrosive chemicals and / or abrasive forces, has been found. These hardened or solidified materials can provide a robust composite structure that protects the underlying substrate from such harsh environmental conditions.

[0003] However, several obstacles have been identified to the wider use of cement-based coatings using this method. Firstly, many industrial installations that would otherwise be candidates for such coatings have complex shapes: piping, chutes, hoppers, bunkers, bins, and furnaces can be cited as descriptive examples of complex structures. Such complexity requires dimensional stability in the coating. Secondly, shrinkage during curing of the castable material or applied coating can result in gaps in the cast structure, cracks or unevenness in the coating, and / or mechanical stress in the coated structure. Thirdly, such coating compositions must exhibit adequate adhesion to the substrate in question. Furthermore, the composition must develop strength rapidly in the cast block or applied coating: slow strength development can be disadvantageous, as the castable structure or coated structure may only be usable after the composition has fully cured.

[0004] U.S. Patent No. 5,135,576 (Knut et al.) discloses a composite structure comprising either an outer layer of ceramic material bonded to the internal structure of superconcrete, or an outer structure of superconcrete bonded to an inner layer of ceramic material. The ceramic material is selected from inorganic or metallic products that are subjected to temperatures of at least 540°C during manufacture or use. The superconcrete comprises densely packed inorganic material particles embedded in a hydraulic cement-based matrix, having a strength of at least 70 MPa.

[0005] CN 1618887 A (Hunan University) discloses a fire-resistant, abrasion-resistant inorganic coating prepared from aluminum dihydrogen phosphate, alumina (Al2O3), silicon carbide (SiC) as an adhesive, and a solidifying agent.

[0006] CN 101570650 A (Beijing Tongda Refractory Technologies Co. Ltd) provides a method for manufacturing a wear-resistant flame-retardant coating based on aggregate raw materials selected from plate-shaped alumina, brown alumina, and bauxite chamotte; fine powder materials selected from plate-shaped alumina powder, flint clay powder, α-Al2O3 fine powder, and ceramic powder; binders selected from phosphoric acid solution, solid aluminum dihydrogen phosphate, and clay powder; fused magnesite as a curing agent; and sintering aids selected from sodium borate and sodium hexametaphosphate.

[0007] FR 2943665 (Kerneos) discloses a self-leveling mortar comprising, based on the total weight of the dry mortar, i) 50 to 90% by weight of aggregate (at least 30% by weight of which is synthetic inorganic aluminoslime aggregate containing 30% by weight of alumina); and ii) 10 to 50% by weight of an ettringite binder comprising a calcium aluminate mineral compound containing calcium oxide (C) and aluminum oxide (A) in a molar ratio (C / A) of 1.2 to 2.7 and calcium sulfate. The binder is soluble and binds to one or more amorphous and / or crystalline mineral phases. A wet mortar is obtained by mixing the dry mortar with an amount of water such that the water-to-solids ratio is less than 0.5:1.

[0008] U.S. Patent No. 10,221,096 (Dubey) discloses a method for producing a geopolymer cement binder composition for cement-based products such as concrete, precast building elements, and panels. The geopolymer cement composition is produced by mixing a synergistic mixture of a thermoactivated aluminosilicate mineral, calcium aluminate cement, calcium sulfate, and a chemical activator with water. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] U.S. Patent No. 5,135,576 [Patent Document 2] CN 1618887 A [Patent Document 3] CN 101570650 A [Patent Document 4] FR 2943665 [Patent Document 5] U.S. Patent No. 10,221,096 [Overview of the project] [Problems that the invention aims to solve]

[0010] Considering the above prior disclosure, in the art, there is still a need for the development of cementitious compositions that, upon curing, exhibit physical and chemical stability at high temperatures (e.g., 400 °C or higher) and provide protection from erosion and mechanical resistance under severe environmental conditions. This composition should also be characterized by rapid strength development, good adhesion, and limited shrinkage upon curing.

Means for Solving the Problems

[0011] According to a first embodiment of the present invention, calcium aluminate cement; ground granulated blast-furnace slag (GGBS); and fumed silica a first component (1) comprising: calcined bauxite; and melted zirconium mullite a second component (2) comprising: A two-component (2K) anhydrous composition is provided.

[0012] In many embodiments, the two-component (2K) anhydrous composition is based on the total weight of the non-volatile components in the composition, 15 to 25 wt%, preferably 18 to 23 wt% of the calcium aluminate cement; 15 to 25 wt%, preferably 18 to 23 wt% of the ground granulated blast-furnace slag (GGBS); and 1 to 15 wt%, preferably 3 to 15 wt% of the fumed silica a first component (1) comprising: Based on the total weight of the non-volatile components in the composition, 15 to 35 wt%, preferably 20 to 35 wt% of the calcined bauxite; and 15 to 35 wt%, preferably 20 to 35 wt% of the melted zirconium mullite a second component (2) comprising: is provided.

[0013] In the composition, the weight ratio of calcium aluminate cement to blast furnace slag fine powder is preferably 0.8 to 1.2:1, for example 0.9 to 1.1:1.

[0014] The composition may further contain silicon carbide, which should preferably be present in the composition in an amount of 5 to 20% by weight based on the total weight of the non-volatile components. It is preferred that at least a part of the silicon carbide present in the composition is included in the first component (1).

[0015] In a second embodiment of the present invention, there is provided a curable coating composition comprising the two-component (2K) composition defined above and in the appended claims and water. The coating composition is preferably characterized by a water factor of 0.5 to 1.5, preferably 0.75 to 1.25.

[0016] The present invention also provides a cured product obtained from the coating composition defined above and in the appended claims. When the coating composition cures, it exhibits rapid strength development, negligible shrinkage, and practical adhesion (especially to metal substrates and refractory materials). The coating composition is also considered to provide an inexpensive means for protecting substrates exposed to severe environmental conditions including, but not limited to, high temperatures and abrasion.

Embodiments for Carrying out the Invention

[0017] As used herein, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise.

[0018] The terms "comprising", "including", and "consisting of" as used herein are synonymous with "comprising", "including", "containing", or "consisting of", are inclusive or open-ended, and do not exclude additional unrecited members, elements, or method steps.

[0019] As used herein, the term "consisting of" excludes any unspecified elements, components, members, or steps of the method. For completeness, the term "including" encompasses "consisting of".

[0020] When quantities, concentrations, dimensions, and other parameters are expressed in terms of ranges, preferred ranges, upper limits, lower limits, or preferred upper limits, it should be understood that any range obtained by combining any upper or preferred value with any lower or preferred value is also specifically disclosed in the specification, regardless of whether the obtained range is explicitly mentioned or not.

[0021] Furthermore, according to standard understanding, the weight range expressed as "from 0" specifically includes 0% by weight, and the components defined by the range may or may not be present in the composition.

[0022] The terms “preferred,” “preferred,” “desirably,” and “particularly” are frequently used herein to describe embodiments of the disclosure that may provide particular benefits under certain circumstances. However, the enumeration of one or more preferred, suitable, desirable, or particular embodiments does not imply that other embodiments are unhelpful, nor is it intended to exclude those other embodiments from the scope of the disclosure.

[0023] As used throughout this specification, the words "may" or "may be" are used in a permissive, or potential, sense, rather than a compulsive one.

[0024] In this specification, room temperature is 23°C ± 2°C. In this specification, “ambient conditions” means the temperature and pressure of the environment in which the composition is located, or the environment in which the coating layer or the substrate of the coating layer is located.

[0025] In this specification, a “two-component (2K) composition” is understood to be a composition in which the first component (1) and the second component (2) need to be stored in separate containers due to their (high) reactivity. When the two parts are mixed immediately before application, they usually react and form a bond without additional activation. Higher temperatures, humidity, or a continuous aqueous phase may be applied to promote the reaction between the mixed components.

[0026] The term “anhydrous” is intended herein to mean that the applicable composition, component, or part contains less than 0.25% by weight of water, based on the weight of the mixture, component, or part. The term “essentially not containing” should be interpreted similarly to mean that the relevant composition, component, or part contains less than 0.25% by weight of the element described.

[0027] As used herein, the term "water" is intended to include tap water, spring water, purified water, deionized water, and desalted distilled water. Water is included in the coating composition of the present invention in liquid form. The presence of solid water particles (ice) is undesirable because solid water cannot be recruited to form the hydrates necessary for the development of the strength of the cured coating composition.

[0028] The aforementioned composition is defined by "weight % based on the total weight of all non-volatile components in the composition." For completeness, volatile components are those with an initial boiling point of 250°C or less, measured at a standard atmospheric pressure of 101.3 kPa. Therefore, non-volatile components are those with an initial boiling point exceeding 250°C, measured at a standard atmospheric pressure of 101.3 kPa.

[0029] The “refractory materials” to which the coating compositions of this application may be applied mean materials having a melting point greater than 1500°C. This definition includes refractory materials that are elements such as graphite, boron, silicon, titanium, hafnium, zirconium, molybdenum, niobium, tantalum, and tungsten; as well as refractory materials that are compounds, typically silicides, oxides, borides, or carbides. Examples of refractory compounds include aluminum oxide; aluminum nitride; silicon oxide; magnesium oxide; calcium oxide; zirconium oxide; chromium oxide; silicon carbide; silicon nitride; boron carbide, and boron nitride. The term “refractory material” is also intended to encompass both monolithic materials and molded materials. There is no particular intention to limit the shape of such refractory materials: exemplary shapes include ceramic fibers, blocks, bricks, wedges, tiles, and plates, but more complex shapes are also assumed.

[0030] As used herein, the term “metallic material” means a pure metal, a metallic alloy, or a metallic composite material. Exemplary metals and metallic alloys to which the coating compositions of the present invention may be applied include: aluminum; aluminum alloys; bronze; beryllium; beryllium alloys; chromium; chromium alloys; cobalt; cobalt alloys; copper; copper alloys; gold; iron; iron alloys; steel; magnesium; magnesium alloys; nickel; nickel alloys; lead; lead alloys; tin; tin alloys such as tin-bismuth and tin-lead; zinc; zinc alloys; and superalloys such as International Nickel 100 (IN-100) and International Nickel 718 (IN-718). Typical steels include crucible steel; carbon steel; spring steel; alloy steel; maraging steel; and stainless steels such as austenitic stainless steel, ferritic stainless steel, duplex stainless steel, and martensitic stainless steel. Furthermore, there is no particular intention to limit the shapes of such metallic materials: complex shapes such as pipes, elbows, hoppers, bins, chutes, and furnaces found in industrial equipment are certainly envisioned.

[0031] As used herein, “concrete” means any type of building material containing aggregates embedded in a matrix (cement or binder) that fills the spaces between aggregate particles and binds the aggregate particles together, such as stone, gravel, frosted rock, or sand. Exemplary matrices include Portland cement, mineral mortar, asphalt, and polymer resins. “Concrete” may further include, as reinforcement, organic or silica-based fibers, or metallic wires, cables, or rods.

[0032] For completeness, the term “water coefficient” is used herein to refer to the weight of water used in the coating composition divided by the total weight of the non-volatile components used (w / w).

[0033] As used herein, “curing” means the reaction in which a given composition hardens from a fluid mixture into a solid. Generally, curing as used herein may be carried out by exposure to ambient conditions or by intentional exposure to heat or radiation.

[0034] Unless otherwise specified, the term "particle size" refers to the longest axis of a particle. For a typical spherical particle, the longest axis is the diameter.

[0035] As used herein, the term “average particle size” (D50) means that 50% of the volume of sampled particles is greater than the stated D50 value, and 50% of the volume of sampled particles is less than the stated D50 value. Similarly, the term “D90,” where used, means that 90% of the volume of sampled particles is less than the stated D90 value, and 10% of the volume of sampled particles is greater than the stated D90 value.

[0036] The viscosity of the coating compositions described herein is measured using a Brookfield viscometer under standard conditions of 20°C and 50% relative humidity (RH), unless otherwise specified. The calibration method, spindle type, and rotation speed of the Brookfield viscometer are appropriately selected according to the manufacturer's instructions, depending on the composition being measured.

[0037] The first component of the two-component anhydrous composition (1) Component A of the present invention composition must include the following: i) Calcium aluminate cement; ii) Granulated blast furnace slag powder (GGBS); and iii) Fumed silica.

[0038] i) Calcium aluminate cement The composition of the present invention comprises calcium aluminate cement. Preferably, the composition contains 15 to 25% by weight, preferably 18 to 23% by weight, of the calcium aluminate based on the total weight of the non-volatile components in the composition.

[0039] As used herein, the term "calcium aluminate cement" means cement conforming to the standard EN 14647 Calcium aluminate cement: composition, specifications and conformity criteria. Such cement can be produced by smelting or sintering, as is known in the art, and can be classified within this standard into groups of iron-rich cement and iron-poor cement. So-called iron-free calcium aluminate cement is not included in the provisions of EN 14647.

[0040] Typical iron-rich calcium aluminate cement is produced by a smelting process, has a gray to dark gray color, and can be characterized by its chemical composition by weight of 36-42% Al2O3, 2-6% SiO2, 14-19% Fe2O3, 37-40% CaO, less than 1.5% MgO, and less than 0.4% SO3.

[0041] Calcium aluminate cement with low iron content has a beige to gray color and typically contains 50-55% Al2O3, 2-6% SiO2, 1-3% Fe2O3, 37-40% CaO, less than 1.5% MgO, and less than 0.4% SO3 by weight. Therefore, it is clear that the darker the color of the calcium aluminate cement, the higher the iron content.

[0042] When manufacturing calcium aluminate cement, the following mineral phases are formed depending on the selected ratio of aluminum oxide (A) and calcium oxide (C): i) In calcium aluminate cement with a high iron content, monocalcium aluminate (CA), brown millerite (C4AF), belite (C2S), ghelenite (C2AS), and meienite (C4AF) are formed. 12 A7) and perovskite (CT); and ii) calcium aluminate cement with low iron content, CA, C2AS, CT and C 12 A7.

[0043] The monocalcium aluminate phase (CA) is primarily responsible for the favorable hydraulic properties (especially the initial strength development) of calcium aluminate cement compared to calcium silicate type cement. The CA phase, and C when present, 12 Phase A7 is considered to be the only phase in calcium aluminate cement that reacts rapidly with water. However, while the reactivity of calcium aluminate with water can be said to increase with increasing C / A molar ratio, C 12 If the A7 content is too high, the high hydraulic reactivity may accelerate the premature hardening of calcium aluminate cement.

[0044] The calcium aluminate cement preferred for use in the present invention can be characterized by an aluminum oxide content of preferably 30 to 55% by weight, more preferably 35 to 45% by weight, based on the total weight of the calcium aluminate cement. In another embodiment, the calcium aluminate cement for use in the present invention preferably has calcium monoaluminate (CA) as the main mineral phase. This means that CA is the largest proportion of all the mineral phases present in the calcium aluminate cement, preferably with a CA content of more than 50% by weight based on the total weight of the calcium aluminate cement. In another embodiment, the calcium aluminate cement used in the present invention preferably has a refractoriness of more than 1000 °C, preferably more than 1200 °C.

[0045] Although not intended to limit the present invention, exemplary commercially available calcium aluminate cements include the following: Istra 40 and Istra 50 available from Calucem; Ciment Fondu and Secar 51 available from Kerneos; Electrolandm available from Cementos Molins; and Gorkal 40 and Gorkal 50 available from Gorka. TM 40 and Istra TM 50; Ciment Fondu and Secar TM 51; available from Kerneos; Electrolandm available from Cementos Molins; and Gorkal TM 40 and Gorkal TM 50.

[0046] ii) Ground granulated blast-furnace slag (GGBS) The composition of the present invention comprises ground granulated blast-furnace slag (GGBS). The composition preferably contains 15 to 25% by weight, preferably 18 to 23% by weight, of the ground granulated blast-furnace slag based on the total weight of the non-volatile components in the composition. In another expression of the composition, which is not intended to be mutually exclusive with the above composition, the weight ratio of calcium aluminate cement to ground granulated blast-furnace slag in the composition is preferably 0.8 to 1.2:1, more preferably 0.9 to 1.1:1. It should be noted that these ranges include the ratio 1:1, which represents a very preferred weight ratio herein.

[0047] Granulated blast furnace slag (GGBS) is a by-product derived from waste slag generated during the production of pig iron from iron ore and limestone in blast furnaces. Blast furnace slag, a molten material containing gangue from iron ore, coke combustion residue, limestone, and other additives, "floats" on top of the newly formed pig iron as a skin. The chemical composition of the molten slag can vary considerably depending on the properties of the ore, the composition of the limestone flux, the composition of the coke, and the type of iron being produced.

[0048] Molten slag is granulated by rapid cooling, more specifically by feeding it through a jet of water. The rapidly cooled granulated solid consists of over 90% glass. The granules are then ground into a fine powder to produce GGBS. The blast furnace granulated slag powder is potentially hydrated; that is, it hydrates when exposed to an alkaline environment.

[0049] Typically, granulated blast furnace slag powder has the following composition based on the weight of the slag powder: 30-50 wt% lime (CaO); 28-38 wt% silica (SiO2); 8-23 wt% alumina (Al2O3); 1-17 wt% magnesia (MgO); 1-2.5 wt% sulfur; and 1-3 wt% ferrous oxide and manganese oxide. However, it is known in the art that the potential hydraulic binding force of slag depends on its specific composition. Therefore, in the present invention, it is preferable that the granulated blast furnace slag powder satisfies at least one of the following constituent requirements: i) Silica (SiO2) content of 28-35% by weight, preferably 28-32% by weight; ii) 10-23% by weight, preferably 12-23% by weight of alumina (Al2O3); and iii) A weight ratio of (CaO+MgO+Al2O3) / SiO2 greater than 1.0, preferably greater than 1.5. It should be noted that these requirements are not mutually exclusive. One, two, or three of the requirements may be met.

[0050] Independently or in addition to the above preferred composition, blast furnace granulated slag fine powder is, a) glassiness of at least 92% as measured by infrared absorption spectroscopy; and b) at least 5000 cm 2 Powder content measured in g according to the EN 196-6 aeration method (brain). It is preferable that it has

[0051] It will be recognized that a single blast furnace granulated slag powder source may not satisfy all of the desirable properties. Therefore, it may be necessary to form a mixture of at least two blast furnace granulated slag powder sources so that the mixture possesses the desired properties.

[0052] iii) Fumed Silica The composition comprises fumed silica. Preferably, the composition contains 1 to 15% by weight, more preferably 3 to 15% by weight or 3 to 12% by weight of the fumed silica, based on the total weight of the non-volatile components in the composition. At least a portion of the fumed silica is incorporated into the first component of the composition. However, this does not prevent a portion of the fumed silica from being included in the second component as defined herein.

[0053] Fumed silica is defined as finely divided amorphous silicon dioxide particles produced by high temperatures in an oxygen-hydrogen flame: an exemplary pyrolysis method for producing fumed silica is gas-phase hydrolysis of silicon tetrachloride. For completeness, the fumed silica used in this invention must be untreated and therefore hydrophilic. Treated or hydrophobic fumed silica is considered unsuitable.

[0054] As is generally understood in the art, fumed silica contains aggregates or aggregated clusters of primary particles. Primary particles are the smallest particles visible in high-resolution transmission electron microscope (TEM) images and cannot be further ground: the size of such primary particles ranges from 5 nm to 100 nm. Some primary particles can aggregate at their contact points to form secondary structures: these aggregated structures include both agglutinants and, if present, assemblies. Aggregates are clumps of two or more primary particles that are impossible or extremely difficult to break down using conventional mixing or dispersion equipment: the primary particles of the agglutinants are sintered together. Aggregates, in contrast, consist of two or more loosely bound agglutinants: in assemblies, the aggregated particles can be held together by electrostatic and van der Waals forces and can therefore break down into smaller assemblies and agglutinants when exposed to conventional high-intensity mixing conditions for cement-based compositions or conditions sufficient to produce fumed silica dispersions.

[0055] As used herein, “secondary particles” of fumed silica refer to the final size of aggregated particles. Secondary particles of fumed silica can be measured by dynamic light scattering analysis using instruments such as the Partica LA-950 Particle Size Distribution Analyzer, available from Horiba, Ltd. This method allows for the calculation of the average particle size (D50).

[0056] In the present invention, it is preferable that the fumed silica has an average secondary particle size (D50) of 0.1 μm to 30 μm, for example, 0.1 μm to 10 μm, in a dry state.

[0057] Suitable commercially available hydrophilic fumed silica grades useful in the present invention include: the Aerosil® product line available from Degussa AG, e.g., AEROSIL® 150, AEROSIL® 200 SP, and AEROSIL® 300; the Sipernat® product line available from Degussa AG, e.g., Sipernat® 22LS; and the Cab-o-sil product line from Cabot Corporation.

[0058] Second component (2) of a two-component anhydrous composition Component B of the composition of the present invention must include i) calcined bauxite and ii) molten zirconium lite.

[0059] i) Calcined bauxite The second component of the composition comprises calcined bauxite. It is preferable that the composition contains 15-35% by weight, preferably 20-35% by weight, of the calcined bauxite, based on the total weight of the non-volatile components in the composition. A two-component (2K) anhydrous composition may, for example, contain 20-30% by weight of the calcined bauxite.

[0060] Bauxite itself is an impure form of alumina containing other oxides, such as iron oxide, titania, and silica. As is known in the art, calcined bauxite is produced by sintering higher grade or high-alumina bauxite at high temperatures, such as 80°C to 1600°C, usually in a rotary kiln, round kiln, or shaft kiln. This calcining method removes moisture from the bauxite, giving calcined bauxite its characteristic high alumina content and refractory properties, low iron content, and particle hardness and toughness.

[0061] Without intending to limit the present invention, the calcined bauxite of the present invention may be characterized by having, based on the weight of the calcined bauxite, a) an alumina content of at least 82% by weight, preferably at least 83% by weight; b) a silica (SiO2) content of less than 5% by weight; c) a titanium dioxide content of less than 4.5% by weight; and d) an Fe2O3 content of less than 4.5% by weight. The calcined bauxite may also be characterized by a loss on ignition of less than 0.5% by weight, as measured by the ASTM C114 standard test method for the chemical analysis of hydraulic cement.

[0062] Independent of or in addition to these compositional requirements, the present invention prefers that the particle size of the calcined bauxite, as measured according to ISO 3310-1:2016 Test sieves - Technical requirements and tests - Part 1: Test sieves for metal wire cloths, be less than 35 mesh, preferably in the range of 50 to 500 mesh, for example, 65 to 325 mesh.

[0063] ii) Fused Zirconium Light The second component of the composition comprises molten zirconium lite. It is preferable that the composition contains 15-35% by weight, preferably 20-35% by weight, of the molten zirconium lite, based on the total weight of the non-volatile components in the composition. A two-component (2K) anhydrous composition may, for example, contain 20-30% by weight of the molten zirconium lite.

[0064] As is known in the art, mullite (3Al2O3·2SiO2) is an orthorhombic homogeneous solid solution of alumina in sillimanite and can be produced by heating andalusite, sillimanite, or kyanite. Molten zirconium mullite can be prepared by mixing a predetermined ratio of zirconia and mullite, heating the mixture to a temperature sufficient to melt it, and then cooling it to form a solid. The solid is then crushed to produce particulate molten zirconium mullite. The zirconia is substantially dispersed in the mullite in rod-like and / or lumpy forms, thereby imparting thermal shock resistance and chemical resistance to the material.

[0065] The molten zirconium lite used in the present invention preferably contains 25-45% by weight, for example 30-45% by weight, of zirconia; and 55-75% by weight, for example 55-70% by weight, of molten zirconium lite. An amount of zirconia less than 25% by weight is not sufficient to impart effective chemical resistance and thermal shock resistance to the resulting coating, while an amount exceeding 45% by weight is considered to impart brittleness to the material.

[0066] Independent of or in addition to these compositional requirements, the present invention prefers that the particle size of the fused zirconium light, as measured according to ISO 3310-1:2016 Test sieves - Technical requirements and tests - Part 1: Test sieves for metal wire cloths, be less than 100 mesh, preferably in the range of 120 mesh to 500 mesh.

[0067] silicon carbide A two-component (2K) anhydrous composition may further contain silicon carbide; therefore, the composition may be further characterized by containing 0 to 20% by weight of the silicon carbide based on the total weight of the non-volatile components in the composition. It is preferable that the two-component (2K) anhydrous composition contains 5 to 20% by weight, preferably 15 to 15% by weight of the silicon carbide based on the total weight of the non-volatile components in the composition. The silicon carbide may be incorporated into one or both of the two components of the composition, but it is preferable that at least a portion, preferably most by weight, of the silicon carbide is included in the first component.

[0068] It should be noted that α- or β-silicon carbide polymorphs, either individually or in mixtures thereof, can be used in the compositions of the present invention. However, β-silicon carbide polymorphs are relatively less oxidatively resistant than α-type polymorphs. For this reason, α-type polymorphs are generally preferred over β-type polymorphs, and conveniently, are typically commercially less expensive. In a further preferred embodiment, which is not intended to make the polymorphic forms mutually exclusive, it is preferable that the silicon carbide has a minimum SiC content equivalent to a purity of 98% by weight, more preferably 99% by weight.

[0069] Independent of, or in addition to, the present invention prefers that the particle size of silicon carbide, as measured according to ISO 3310-1:2016 Test sieves - Technical requirements and tests - Part 1: Test sieves for metal wire cloths, be less than 100 mesh, preferably in the range of 200 to 500 mesh.

[0070] A mixture of silicon carbide particles having various average particle sizes is considered usable in this application. This promotes particle packing, thereby reducing porosity and improving the abrasion resistance of the cured composition. However, it is preferable that none of the silicon carbide particles in the composition exceed a size of 5 mm (4 mesh). The presence of such large particles tends to cause sedimentation from the raw material coated composition batch, especially when the vehicle content of the raw material coated composition batch is close to the upper limit of its specified range, resulting in a non-uniform product.

[0071] Auxiliary drugs As used herein, the term “auxiliary agent” means a substance within the scope of the meaning of standard EN 206.1, particularly as defined in section 3.1.22: a product added in small amounts relative to the mass of the composition to alter the properties of the uncured or cured composition (either one or both components of the composition before mixing). Such auxiliary agents may be used in any desired combination and proportion, provided that they do not adversely affect the properties and essential characteristics of the composition. With some exceptions, the composition should not contain auxiliary agents in amounts exceeding 20% ​​by weight, preferably 10% by weight, based on the total weight of the non-volatile components in the composition.

[0072] The composition may contain at least one auxiliary agent selected from the following: plasticizers; superplasticizers; setting retarders such as gluconates, carboxylic acids (citric acid, tartaric acid), boric acid, and alkali metal phosphates; catalysts; hardening accelerators such as nitrates, thiocyanates, and chloride salts; hardening accelerators such as alkali metal carbonates; air-imbuing agents such as sodium lauryl sulfate; shrinkage inhibitors; foam inhibitors or defoamers; leak inhibitors such as calcium stearate; natural pozzolanic compounds such as pumice, truss, santhrin earth, diatomaceous earth, homstone, and chert; synthetic pozzolanic compounds such as calcined and crushed clay (crushed brick), fly ash, silica dust, oil shale ash, and metakaolin; settling inhibitors such as bentonite and attapulgite; inorganic or organic pigments; one or more latexes; rheology modifiers; water-retaining agents such as starch ethers, cellulose ethers, and modified cellulose ethers.

[0073] As is known in the art, “water-reducing agent” means an anti-flocculation organic compound that acts by electrostatic repulsion and / or steric bulk. Examples of water-reducing agents useful in the present invention include, but are not limited to, polycarboxylates; melamine sulfonates; and polynaphthalene sulfonates.

[0074] There is no prejudice to including organic homopolymers and copolymers in cement-based compositions: one or more latexes of such polymers can mitigate the adhesion and physical properties of the composition and the coating obtained therefrom. Non-limiting examples of suitable (co)polymers include: vinyl acetate homopolymers; copolymers of vinyl acetate with at least one further vinyl ester; copolymers of vinyl acetate with ethylene; copolymers of vinyl acetate, ethylene and at least one further vinyl ester; copolymers of vinyl acetate, ethylene and at least one (meth)acrylic acid ester; copolymers of vinyl acetate with (meth)acrylate and other vinyl esters; copolymers of vinyl acetate, ethylene and vinyl chloride; copolymers of vinyl acetate, ethylene and styrene; copolymers of vinyl acetate and acrylate; styrene-acrylic acid ester copolymers; styrene-1,3-butadiene copolymers; and vinyl chloride-ethylene copolymers.

[0075] The following are preferred: vinyl acetate homopolymers; copolymers of vinyl acetate and ethylene; copolymers of vinyl acetate, ethylene and styrene; copolymers of vinyl acetate, ethylene and at least one comonomer selected from the group consisting of vinyl acetate, ethylene and vinyl esters having 1 to 15 carbon atoms in the carboxylic acid group (e.g., vinyl propionate, vinyl laurate and vinyl versaticate); copolymers of vinyl acetate, ethylene and at least one comonomer selected from the group consisting of vinyl acetate, ethylene and (meth)acrylic acid esters of unbranched or branched alcohols having 1 to 15 carbon atoms (e.g., N-butyl acrylate and 2-ethylhexyl acrylate); copolymers of vinyl acetate, vinyl esters having 1 to 15 carbon atoms in the carboxylic acid group and (meth)acrylic acid esters of unbranched or branched alcohols having 1 to 15 carbon atoms; and copolymers of vinyl acetate, ethylene and vinyl chloride.

[0076] Such polymers can be prepared by conventional means available to those skilled in the art, such as emulsion polymerization. Alternatively, such polymers may be provided from commercial sources. For example, see: FX7000 styrene acrylate copolymer available from Elotex; HD 1500 vinyl acetate / vinyl versatate copolymer available from Elotex; and FX2322 vinyl acetate / ethylene copolymer available from Elotex.

[0077] The term "rheological modifier" refers to an organic compound useful for increasing one or more of the viscosity, cohesive force, and shear threshold of a composition. Rheological modifiers may also have an anti-bleeding effect. Examples of rheological modifiers useful in the present invention include modified or unmodified polysaccharides such as dieutan gum, xanthan gum, gellan gum, and wellan gum.

[0078] Methods and Uses When using, the first and second components of the composition as defined above are mixed with water. While not intended to limit the present invention, conventionally, mixing requires dry mixing of at least a portion (preferably most, and sometimes all) of the solid components in a suitable mixer: then, while the mixer is running, water is gradually added to the mixture along with any remaining solid components present. To ensure a homogeneous mixture is obtained, high-intensity mixing using a mixing energy of at least 0.5 kW per 100 kg of component is preferred. The use of a flat-blade mixer may also be beneficial.

[0079] The method of applying the coating composition is one of the factors that determine the total amount of water added and the time for mixing the water with the dry components in relation to the application of the coating composition. However, a further consideration is that if too much water is added, the particulate material may fall from its suspended state, and it is difficult to resuspend this material. In this regard, a water coefficient of 0.5 to 1.5, for example, 0.75 to 1.25, may be cited as preferred in the mixing of the coating composition of the present invention. Independently of or in addition to the water coefficient, it is preferable that the coating composition be characterized by an applied viscosity of less than 100,000 centipoise, for example, 10,000 to 100,000 centipoise.

[0080] According to the broadest embodiment of the present invention, the coating composition is applied to a substrate and then cured in situ. Before application of the coating composition, it is often recommended to pre-treat the relevant surface to remove foreign matter: this step facilitates the subsequent adhesion of the coating composition to the surface, where applicable. Such treatments are known in the art and can be carried out, for example, in one-step or multi-step methods consisting of one or more of the following uses: etching with an acid and optionally an oxidizing agent suitable for the substrate; ultrasonic treatment; plasma treatment including chemical plasma treatment, corona treatment, atmospheric pressure plasma treatment and flame plasma treatment; immersion in an aqueous alkaline degreasing bath; treatment with an aqueous cleaning emulsion; treatment with a cleaning solvent such as carbon tetrachloride or trichloroethylene; and rinsing with water (preferably with deionized or desalineated water). When using an aqueous alkaline degreasing bath, it is preferable to remove any remaining degreasing agent from the surface by rinsing the substrate surface with deionized or desalineated water.

[0081] Next, the coating composition is applied to the surface of a preferably pre-treated substrate by conventional application methods such as brushing, rolling, troweling, floating, pumping, ramming, casting, gunning, and spraying. Gunning and spraying methods can be performed using conventional commercially available equipment, with pressure conditions, nozzle type, conduit (hose) length and diameter selected to avoid equipment clogging and achieve a controlled application pattern.

[0082] While the above method allows for the application of the coating composition in one or multiple steps, it is recommended to apply the composition to a total wet film thickness of 10-100 mm, for example, 25-75 mm or 25-50 mm.

[0083] The curing of the coating composition of the present invention may occur at temperatures from room temperature to 100°C, preferably 30°C to 100°C, and particularly 40°C to 80°C. The appropriate temperature depends on the specific compounds present and the desired curing rate and can be determined in individual cases by those skilled in the art using simple preliminary tests as necessary. Where applicable, the temperature of the mixture produced from each component of the coating composition can be made higher than the mixing temperature and / or application temperature using conventional means, including microwave induction. Alternatively, the coating composition can be applied to a preheated substrate, and this preheating promotes rapid curing of the composition and improved adhesion to the substrate. In exemplary embodiments, the coating composition is applied as a series of thin layers to achieve a desired total thickness, and the substrate is maintained at a temperature of 30 to 100°C during the application of each layer.

[0084] The coating composition of the present invention can be applied to existing structures made of concrete, fire-resistant materials, or metal materials. Furthermore, the coating composition can be used for repair functions, such as repairing equipment where the coating or fire-resistant surface material has shifted or worn away.

[0085] The following examples illustrate the present invention and do not limit its scope. [Examples]

[0086] The following coating compositions were mixed in a dynamic mixer. This mixing procedure began with the addition of combined calcium alumina cement (CAC) and granulated blast furnace slag (in a 1:1 weight ratio) to the mixer, followed by dry mixing of fumed silica, silicon carbide, catalyst, and water-reducing agent. Subsequently, calcined bauxite and molten zirconium lite were added along with enough water to achieve a water coefficient of 1.

[0087] [Table 1]

[0088] The examples were subjected to the following protocol under identical test conditions, thereby enabling comparison of each example.

[0089] Open Time: The open time (in minutes) of a cement-based coating composition is the time during which a tile can be placed within the applied composition and sufficient wetting of the tile by the composition is ensured. The end of the open time is indicated by insufficient wetting of the back of the tile by the composition. Specifically, a 5cm x 5cm ceramic tile was embedded in a cement-based composition by applying a 2kg load for 30 seconds. The tile was removed and the back of the tile was evaluated. The end of the open time was considered to be when less than 50% of the tile's area was covered by the cement-based composition.

[0090] Curing time: In this specification, curing time (hours) is the time required for the cement-based coating composition to harden or solidify to a predetermined coating thickness. This is measured by measuring the speed of ultrasonic waves passing through the sample. As curing progresses, the ultrasonic waves conduct through the sample more quickly. Depending on the cement-based coating composition, the final speed of the ultrasonic waves is approximately 2400 ms. -1 It approached the value of 1200ms. -1 The curing time was compared when the ultrasonic speed reached a certain level.

[0091] Shore D hardness: This is a standardized test consisting of measuring the penetration depth of a specific indenter. In this specification, Shore D hardness was measured by penetration of a durometer indenter into a sample, according to ASTM D2240. As is known in the art, Shore D hardness is a dimensionless quantity that provides a numerical value from 0 to 100, with higher numbers representing harder materials.

[0092] Two-part abrasion: This test method measures the abrasion resistance of materials that are normally subjected to or can be subjected to abrasion / friction wear in actual use. This abrasion resistance was measured according to ASTM-D 5963 Standard test method for rubber properties - abrasion resistance (rotating drum abrasive machine). Specifically, a test piece was moved on the surface of an abrasive sheet attached to a rotating drum, and the volume loss was measured as cubic millimeters (mm). 3 Abrasion resistance was measured by expressing it in units of ). A smaller value for volume loss indicates better abrasion resistance.

[0093] Dry or Scratch Abrasion: This test method is a laboratory procedure for measuring the resistance of a material to scratch abrasion by dry sand / rubber wheel test. This abrasion resistance was measured according to ASTM G-65: Standard Test Method for Abrasion Measurement Using Dry Sand / Rubber Wheel Apparatus. Procedure B was used as specified in this standard test method, with volume loss measured in cubic millimeters (mm). 3 The results of the abrasion test were reported in units of ). Materials with higher abrasion resistance exhibit smaller volume loss.

[0094] Gas Injection Erosion Test: This test method measures material loss due to gas-entrained solid particle impact erosion using a jet nozzle type erosion apparatus. Abrasion resistance was measured according to ASTM-G76: Standard Test Method for Conducting Erosion Tests by Solid Particle Impact Using Gas Jets. Material volume loss was measured in cubic millimeters (mm²). 3 The test results were reported in units of ) units. The higher the corrosion resistance of the material, the smaller the volume loss.

[0095] Abrasion resistance: This test method measures the relative abrasion resistance of a sample under standard conditions at room temperature. This abrasion resistance was measured according to ASTM C 704: Standard test method for abrasion resistance of refractory materials at room temperature. Volume loss is measured in cubic millimeters (mm). 3 The test results were reported in units of ). Materials with higher wear resistance exhibit smaller volume loss.

[0096] Wet abrasion test: This is a high-stress laboratory abrasion test for materials, using an aluminum oxide particle aqueous slurry as the abrasive medium, and a rotating steel wheel that forces abrasion across the entire flat specimen in line contact with the rotating steel wheel immersed in the slurry. This abrasion resistance was measured according to ASTM-B 611S: Standard test method for measuring high-stress abrasion resistance of hard materials. Volume loss is measured in cubic millimeters (mm). 3 The test results were reported in units of ). Materials with higher wear resistance exhibit smaller volume loss.

[0097] Compressive strength: This property of the test specimens in each example, when a compressive load was applied at a relatively low uniform load rate, was measured according to ASTM-D695-02A: Standard test method for compressive properties of rigid plastics. Test results are reported in MPa.

[0098] The results are shown in Table 2 below. [Table 2]

[0099] In consideration of the above description and examples, it will be apparent to those skilled in the art that equivalent modifications can be made without departing from the claims. The initial disclosures of this specification include at least the following aspects: [1] Calcium aluminate cement; Blast furnace granulated slag fine powder (GGBS); and Humed Silica A first component (1) comprising, Calcined bauxite; and Fused Zirconium Light The second component (2) comprises A two-component (2K) anhydrous composition comprising the above. [2] Based on the total weight of non-volatile components in the composition, 15-25% by weight of the calcium aluminate cement; 15-25% by weight of the blast furnace granulated slag fine powder (GGBS); and 1 to 15% by weight of the fumed silica A first component (1) comprising, Based on the total weight of non-volatile components in the composition, 15-35% by weight of the calcined bauxite; and 15-35% by weight of the fused zirconium lite The second component (2) comprises The composition according to [1], comprising the above. [3] The composition according to [1] or [2], wherein the weight ratio of calcium aluminate cement to blast furnace granulated slag fine powder is 0.8 to 1.2:1, preferably 0.9 to 1.1:1. [4] The composition according to any one of [1] to [3], further comprising 5 to 20% by weight of silicon carbide based on the total weight of nonvolatile components in the composition. [5] The composition according to [4], wherein at least a portion of the silicon carbide is contained in the first component (1). [6] The composition according to any one of [1] to [5], wherein the calcium aluminate cement is characterized by an aluminum oxide content of preferably 30 to 55% by weight, more preferably 35 to 45% by weight, based on the total weight of the calcium aluminate cement. [7] The granulated blast furnace slag fine powder is subject to the following conditions: i) 28-35% by weight of silica (SiO2) based on the weight of the slag fine powder. 2 ) content; ii) 10 to 23% by weight of alumina (Al based on the weight of the slag fine powder) 2 O 3 ) Content; and iii) Greater than 1.0 (CaO + MgO + Al 2 O 3 ) / SiO 2 weight ratio A composition according to any one of [1] to [6] that satisfies at least one of the following conditions. [8] Blast furnace granulated slag fine powder is a) Vitreousness measured by infrared absorption spectroscopy with at least 92% accuracy; and b) at least 5000 cm 2 Powderiness measured according to the EN 196-6 standard for air permeation (brain) in / g. A composition according to any one of [1] to [7], having the following: [9] The composition according to any one of [1] to [8], wherein the calcined bauxite has a particle size smaller than 35 mesh, preferably in the range of 50 to 500 mesh, as measured according to ISO 3310-1:2016.

[10] The composition according to any one of [1] to [9], wherein the molten zirconium lite comprises 25 to 45% by weight of zirconia and 55 to 75% by weight of mullite, based on the weight of the molten zirconium lite.

[11] The composition according to any one of [1] to

[10] , wherein the fused zirconium lite has a particle size less than 100 mesh, preferably in the range of 120 mesh to 500 mesh, as measured according to ISO 3310-1:2016.

[12] The composition according to any one of [1] to

[11] , further comprising a water-reducing agent, wherein the water-reducing agent is preferably present in the composition in an amount of 0.3 to 0.8% by weight based on the total weight of the non-volatile components in the composition. A coating composition comprising the composition described in any of [1] to

[12] and water.

[14] The coating composition according to

[13] , characterized by a water coefficient of 0.5 to 1.5, preferably 0.75 to 1.25. A cured product obtained from the coating composition described in

[15] ,

[13] , or

[14] .

[16] Use of the curing reaction product described in

[15] as a coating for concrete, fire-resistant material or metal material.

Claims

1. Calcium aluminumate cement; Granulated blast furnace slag powder (GGBS); and Humed Silica A first component (1) comprising, Calcined bauxite; and Fused Zirconium Light The second component (2) includes A two-component (2K) anhydrous composition comprising the following: The composition further comprises silicon carbide, wherein the silicon carbide is contained only in the first component, in an anhydrous composition.

2. Based on the total weight of non-volatile components in the composition, 15 to 25% by weight of the calcium aluminate cement; 15 to 25% by weight of the granulated blast furnace slag powder (GGBS); and 1 to 15% by weight of the fumed silica A first component (1) comprising, Based on the total weight of non-volatile components in the composition, 15 to 35% by weight of the calcined bauxite; and 15 to 35% by weight of the fused zirconium lite The second component (2) includes The composition according to claim 1, comprising the above.

3. The composition according to claim 1 or 2, wherein the weight ratio of calcium aluminate cement to blast furnace granulated slag fine powder is 0.8 to 1.2:

1.

4. The composition according to any one of claims 1 to 3, comprising 5 to 20% by weight of silicon carbide based on the total weight of nonvolatile components in the composition.

5. The composition according to any one of claims 1 to 4, wherein the calcium aluminate cement is characterized by an aluminum oxide content of 30 to 55% by weight, based on the total weight of the calcium aluminate cement.

6. The granulated blast furnace slag fine powder is produced under the following conditions: i) 28 to 35% by weight of silica (SiO2) based on the weight of the slag fine powder ２ ) content; ii) 10 to 23% by weight of alumina (Al based on the weight of the slag fine powder) ２ O ３ ) Content; and iii) Greater than 1.0 (CaO + MgO + Al ２ O ３ ) / SiO ２ weight ratio A composition according to any one of claims 1 to 5, which satisfies at least one of the following conditions.

7. Blast furnace granulated slag fine powder is a) Vitreousness measured by infrared absorption spectroscopy with at least 92% accuracy; and b) at least 5000 cm ２ Powderiness measured according to the EN 196-6 standard (brain method) in / g. A composition according to any one of claims 1 to 6, having the following characteristics.

8. The composition according to any one of claims 1 to 7, wherein the calcined bauxite has a particle size smaller than 35 mesh, as measured according to ISO 3310-1:2016.

9. The composition according to any one of claims 1 to 8, wherein the fused zirconium lite comprises 25 to 45% by weight of zirconia and 55 to 75% by weight of mullite, based on the weight of the fused zirconium lite.

10. The composition according to any one of claims 1 to 9, wherein the fused zirconium lite has a particle size smaller than 100 mesh, as measured according to ISO 3310-1:2016.

11. The composition according to any one of claims 1 to 10, further comprising a water-reducing agent.

12. A coating composition comprising the composition according to any one of claims 1 to 11 and water.

13. The coating composition according to claim 12, characterized by a water coefficient of 0.5 to 1.

5.

14. A cured product obtained from the coating composition according to claim 12 or 13.

15. Use of the curing reaction product according to claim 14 as a coating for concrete, fire-resistant material, or metal material.

Images