WO2021012310A1 - 一种高韧性无机复合人造石材面板及其制备方法 - Google Patents

一种高韧性无机复合人造石材面板及其制备方法 Download PDF

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WO2021012310A1
WO2021012310A1 PCT/CN2019/099202 CN2019099202W WO2021012310A1 WO 2021012310 A1 WO2021012310 A1 WO 2021012310A1 CN 2019099202 W CN2019099202 W CN 2019099202W WO 2021012310 A1 WO2021012310 A1 WO 2021012310A1
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artificial stone
parts
inorganic composite
toughening
composite artificial
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PCT/CN2019/099202
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English (en)
French (fr)
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刘福财
肖敏
李斌
郑增勇
黄贺明
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黄贺明
刘福财
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Publication of WO2021012310A1 publication Critical patent/WO2021012310A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/52—Producing shaped prefabricated articles from the material specially adapted for producing articles from mixtures containing fibres, e.g. asbestos cement
    • B28B1/523—Producing shaped prefabricated articles from the material specially adapted for producing articles from mixtures containing fibres, e.g. asbestos cement containing metal fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B3/00—Producing shaped articles from the material by using presses; Presses specially adapted therefor
    • B28B3/006—Pressing by atmospheric pressure, as a result of vacuum generation or by gas or liquid pressure acting directly upon the material, e.g. jets of compressed air
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B3/00—Producing shaped articles from the material by using presses; Presses specially adapted therefor
    • B28B3/02—Producing shaped articles from the material by using presses; Presses specially adapted therefor wherein a ram exerts pressure on the material in a moulding space; Ram heads of special form
    • B28B3/022—Producing shaped articles from the material by using presses; Presses specially adapted therefor wherein a ram exerts pressure on the material in a moulding space; Ram heads of special form combined with vibrating or jolting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B13/00—Layered products comprising a a layer of water-setting substance, e.g. concrete, plaster, asbestos cement, or like builders' material
    • B32B13/02—Layered products comprising a a layer of water-setting substance, e.g. concrete, plaster, asbestos cement, or like builders' material with fibres or particles being present as additives in the layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B13/00—Layered products comprising a a layer of water-setting substance, e.g. concrete, plaster, asbestos cement, or like builders' material
    • B32B13/04—Layered products comprising a a layer of water-setting substance, e.g. concrete, plaster, asbestos cement, or like builders' material comprising such water setting substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B32B37/1018—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure using only vacuum
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B32B37/1045—Intermittent pressing, e.g. by oscillating or reciprocating motion of the pressing means
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/06—Quartz; Sand
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/06—Quartz; Sand
    • C04B14/068—Specific natural sands, e.g. sea -, beach -, dune - or desert sand
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/38—Fibrous materials; Whiskers
    • C04B14/48—Metal
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2623—Polyvinylalcohols; Polyvinylacetates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/103—Metal fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/028—Treatment by energy or chemical effects using vibration, e.g. sonic or ultrasonic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
    • B32B2315/06—Concrete
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2318/00—Mineral based
    • B32B2318/04—Stone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2607/00—Walls, panels
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302—Water reducers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00008—Obtaining or using nanotechnology related materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00612—Uses not provided for elsewhere in C04B2111/00 as one or more layers of a layered structure
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/54—Substitutes for natural stone, artistic materials or the like
    • C04B2111/542—Artificial natural stone

Definitions

  • the invention relates to the technical field of processing artificial stone materials, and more specifically, to a high-toughness inorganic composite artificial stone panel and a preparation method thereof.
  • Traditional artificial stone is mainly composed of resin organic artificial stone and a small amount of inorganic artificial stone.
  • Resin artificial stone mainly has the disadvantages of large thermal deformation, easy drum deformation and cracking, aging deformation, discoloration, reduced strength due to ultraviolet radiation and temperature, unpleasant gas, non-degradable combustion, and short service life.
  • the new inorganic artificial stone panels are currently mainly traditional cement-based terrazzo products, with low compressive strength, poor hardness, poor bending strength, strong brittleness, easy brittle fracture, high overall water absorption, stain resistance and chemical resistance Poor, it is difficult to achieve the performance of natural stone, the panel is easy to break, and it is not safe to use.
  • the inorganic artificial stone itself has a brittle structure and is resistant to bending and breakage.
  • Most of the artificial stone panel structure is a single-layer structure. When the structure is subjected to external force, the bottom directly cracks and causes brittle fracture. The structure is low in ductility and the product is directly damaged, so there is a structure A metal mesh or fiber mesh reinforcement structure (such as CN106630805A) is added in the middle to improve it. However, when the surface is compressed, the brittle surface at the bottom is still bent and deformed and brittle cracking occurs.
  • the present invention overcomes the shortcomings of existing traditional inorganic artificial stone technology products such as insufficient compressive performance, poor bending strength and toughness, and high water absorption, and provides a high strength, pollution resistance, high toughness, long service life, and durability. Aging, economical and reasonable multilayer composite structure of high toughness inorganic composite artificial stone panel.
  • the present invention adopts the following technical solutions:
  • a high-toughness inorganic composite artificial stone panel comprising a surface layer, an intermediate metal fiber toughening layer and a base toughening layer.
  • the surface layer includes the following raw material components in parts by weight: quartz sand 40-70, quartz powder 10-30, inorganic activity Powder 20 ⁇ 45, pigment 0.5 ⁇ 4, water reducing agent 0.3 ⁇ 1, water 3 ⁇ 10;
  • the middle metal fiber toughening layer includes the following raw material components in parts by weight: inorganic active powder 40 ⁇ 60, sand 45 ⁇ 65.
  • the quartz sand has a fineness modulus of 2.0-3.0, a silica content of 93% or more, no impurities and weathering, and a rough hardness of 7 or more.
  • the quartz powder has a fineness of 600 mesh or more, a silica content of 93% or more, and a rough stone hardness of 7 or more.
  • the core function of the quartz powder in the present invention is to improve the wear resistance and scratch resistance of the gelled powder hydration product on the surface of the artificial stone after mixing except for the aggregate, and to improve the surface density performance.
  • the inorganic active powder is mainly pure white Portland cement with a strength grade of 42.5 or higher, mixed with one of white silica fume, mineral powder, nano calcium oxide, nano silica silica, and sintered high white kaolin powder Or several active powders.
  • the color of the active powder is single white, the whiteness index is more than 80, and the activity index detection is more than 100%, which ensures the strength of the material and also ensures good stability of subsequent toning.
  • the ratio of cement to other active powders is 1:0.2 ⁇ 0.6.
  • the pigment is an inorganic pigment of various colors.
  • the water reducing agent does not have the color of metal ions, the concentration is not more than 20%, the water reducing rate is more than 20%, and the retarding time is 0.5 to 1 hour.
  • the sand is one or more of river sand, machine-made sand, and quartz sand. It is required to be free of mud and mud, free of organic shellfish, and the material's solidity quality loss is not more than 8%, and the maximum particle diameter Not more than 2.5 mm, and the fineness modulus is less than 3.0 and greater than 2.0.
  • the metal fiber includes one or more of metal fibers with a diameter ranging from 0.1 mm to 0.2 mm, an aspect ratio from 50 to 150, and a tensile strength greater than 1000 MPa.
  • the toughening agent is one or more of latexes such as polyvinyl alcohol glue or acrylamide glue.
  • the overall thickness of the panel is 15-50 mm
  • the thickness of the surface layer is 3-5 mm
  • the thickness of the base layer is 3-5 mm.
  • Another object of the present invention is to provide a method for preparing the above-mentioned high-toughness inorganic composite artificial stone panel, which includes the following steps:
  • step S2 the base toughening layer mixture in the panel mold is covered with an isolation moisturizing film, and then placed in a vacuum press for vacuum exhaust and simultaneous vibration compression;
  • step S3 The board pressed in step S3 is cured at 40°C for 6-8 hours, and then heated to 80-90°C for 12-16 hours after demolding to obtain a rough board;
  • step S5. Remove the isolating and moisturizing film from the blank board obtained in step S4, scrape the bottom, fix the thickness, and polish to obtain a high-toughness inorganic composite artificial stone panel.
  • step S1 the time of stirring and mixing is not less than 10 minutes, the Vib consistency test time of the working performance of the stirring material is 5-30 seconds, and the initial setting time after stirring and mixing is not less than 60 minutes.
  • step S3 the vacuuming time is not less than 60 seconds, and the pressing time is not less than 120 seconds; the vacuum pressure is -0.07 to -0.1 MPa, the pressure load of the press is not less than 1 MPa, and the pressure is not less than 5000 kN.
  • step S4 the humidity is maintained above 75% during the high temperature curing process.
  • This process uses a layered continuous cloth method to focus on compression so that the materials between the layers have a certain cross-bite to solve the phenomenon of pressure separation of the interface bonding strength.
  • the pressure is increased for the traditional inorganic stone manufacturing vacuum process, and the vacuum is shortened. Time, improve the density and production efficiency of artificial stone, reduce the water absorption rate of the layout, through adjusting the temperature and moisturizing staged curing not only improve the efficiency of the early mold use, but also make the volume of the artificial stone panel more stable, and completely overcome the shrinkage performance and ensure the strength Consistency and stability.
  • the high-toughness composite artificial stone panel of the present invention has the advantages of high strength, high bending resistance, low brittleness, impact resistance, crack resistance, good seismic performance, etc., and has stable volume and low shrinkage. , Use no warpage deformation, very low water absorption, good durability, no aging and other problems, strong bonding between layers, high structural safety, good ductility, no instant brittle fracture, and can be used as a load-bearing structure.
  • the surface has good stain resistance, a wide range of material sources, and the overall overall cost is low, which is suitable for popularization.
  • Figure 1 is a schematic diagram of the structure of a high-toughness inorganic composite artificial stone panel.
  • a high-toughness inorganic composite artificial stone panel with an overall thickness (t1+t2+t3) of 15-50mm including a surface layer with a thickness t1 of 3-5mm, an intermediate metal fiber toughened layer and a thickness t3 of 3 ⁇ 5mm base toughening layer
  • the surface layer includes the following raw materials in parts by weight: quartz sand 40, quartz powder 10, inorganic active powder 20, pigment 0.5, water reducing agent 0.3, water 3; intermediate metal fiber toughening
  • the layer includes the following raw material components in parts by weight: inorganic active powder 40, sand 45, water reducing agent 0.8, water 6, and metal fiber 4
  • the base toughening layer includes the following raw materials in parts by weight: inorganic active powder 30. Quartz sand 30, quartz powder 15, water reducing agent 0.5, water 4, toughening agent 0.8.
  • the fineness modulus of the quartz sand is 2.3 (the fineness modulus of the quartz sand can be between 2.0 and 3.0, and 2.3 is selected in this embodiment), the silica content is above 93%, no impurities, weathering, and rough hardness Above 7.
  • the quartz powder has a fineness of 600 mesh or more, a silica content of 93% or more, and a rough stone hardness of 7 or more.
  • the inorganic active powder is P.O42.5 white cement as the main body and mixed with white silica fume (here can be mixed with white silica fume, mineral powder, nano calcium oxide, nano silica silica, and sintered high white kaolin powder. Kinds or several active powders).
  • the pigments are inorganic pigments of various colors.
  • the water reducing agent does not have the color of metal ions, the concentration is not more than 20%, the water reducing rate is more than 20%, and the retarding time is 0.5 to 1 hour.
  • the sand is river sand (it can be one or more of river sand, machine-made sand, and quartz sand), and it is required to be free of mud and mud, free of organic shellfish, and the material's solidity quality loss is not more than 8%,
  • the maximum particle diameter is not more than 2.5 mm, and the fineness modulus is 2.6.
  • the metal fiber has a diameter of 0.1mm, a length-to-diameter ratio of 100, and a metal fiber with a tensile strength greater than 1000MPa (may be one of the metal fibers with a diameter range of 0.1-0.2mm, an aspect ratio of 50-150, and a tensile strength greater than 1000MPa.
  • a metal fiber with a tensile strength greater than 1000MPa may be one of the metal fibers with a diameter range of 0.1-0.2mm, an aspect ratio of 50-150, and a tensile strength greater than 1000MPa.
  • the toughening agent is polyvinyl alcohol glue and acrylamide glue.
  • the high-toughness inorganic composite artificial stone panel is prepared according to the following steps:
  • step S2 the base toughening layer mixture in the panel mold is covered with an isolation moisturizing film, and then placed in a vacuum press for vacuum exhaust and simultaneous vibration pressing.
  • the vacuuming time is not less than 60 seconds, and the pressing time is not less than 60 seconds. Less than 120 seconds;
  • the vacuum pressure is -0.07 ⁇ -0.1MPa, the pressure load of the press is not less than 1MPa, and the pressure is not less than 5000kN;
  • step S3 The pressed board in step S3 is cured at 40°C for 6-8 hours, and after demolding, it is heated to 80-90°C and cured for 12-16 hours to obtain a blank board, and the humidity is maintained above 75% during high-temperature curing;
  • step S5. Remove the isolating and moisturizing film from the blank board obtained in step S4, scrape the bottom, fix the thickness, and polish to obtain a high-toughness inorganic composite artificial stone panel.
  • Example 1 Except that the formulation of the high-toughness inorganic composite artificial stone panel is different, the other conditions are the same as in Example 1.
  • a high-toughness inorganic composite artificial stone panel including the following parts by weight of raw materials: the surface layer includes the following parts by weight of each raw material component: quartz sand 70, quartz powder 30, inorganic active powder 45, pigment 4, water reducing agent 1 , Water 10;
  • the intermediate metal fiber toughening layer includes the following parts by weight of each raw material component: inorganic active powder 60, sand 65, water reducing agent 1.5, water 14, metal fiber 8;
  • the base toughening layer includes the following parts by weight Each raw material component: inorganic active powder 50, quartz sand 55, quartz powder 20, water reducing agent 1.2, water 8, toughening agent 2.5.
  • Example 1 Except that the formulation of the high-toughness inorganic composite artificial stone panel is different, the other conditions are the same as in Example 1.
  • a high-toughness inorganic composite artificial stone panel comprising the following parts by weight of raw materials: the surface layer includes the following parts by weight of each raw material component: quartz sand 50, quartz powder 15, inorganic active powder 27, pigment 1.5, water reducing agent 0.5 , Water 4.5;
  • the intermediate metal fiber toughening layer includes the following parts by weight of each raw material component: inorganic active powder 45, sand 50, water reducing agent 0.9, water 8, metal fiber 5;
  • the base toughening layer includes the following parts by weight Each raw material component: inorganic active powder 35, quartz sand 36, quartz powder 16, water reducing agent 0.65, water 5, toughening agent 1.2.
  • Example 1 Except that the formulation of the high-toughness inorganic composite artificial stone panel is different, the other conditions are the same as in Example 1.
  • a high-toughness inorganic composite artificial stone panel including the following parts by weight of raw materials: the surface layer includes the following parts by weight of each raw material component: quartz sand 60, quartz powder 25, inorganic active powder 38, pigment 3, water reducing agent 0.8 , Water 8.5; the intermediate metal fiber toughening layer includes the following parts by weight of each raw material component: inorganic active powder 55, sand 60, water reducing agent 1.4, water 12, metal fiber 7; the base toughening layer includes the following parts by weight Each raw material component: inorganic active powder 45, quartz sand 49, quartz powder 19, water reducing agent 1.05, water 7, toughening agent 2.1.
  • Example 1 Except that the formulation of the high-toughness inorganic composite artificial stone panel is different, the other conditions are the same as in Example 1.
  • a high-toughness inorganic composite artificial stone panel comprising the following parts by weight of raw materials: the surface layer includes the following parts by weight of each raw material component: quartz sand 55, quartz powder 20, inorganic active powder 32, pigment 2.3, water reducing agent 0.65 , Water 6.5; the intermediate metal fiber toughening layer includes the following parts by weight of each raw material component: inorganic active powder 50, sand 55, water reducing agent 1.2, water 10, metal fiber 6; the base toughening layer includes the following parts by weight Each raw material component: inorganic active powder 40, quartz sand 42.5, quartz powder 17.5, water reducing agent 0.85, water 6, toughening agent 1.65.
  • Example 1 Except that the base layer does not contain a toughening agent, the others are the same as in Example 1.
  • the base layer of Comparative Example 1 does not contain a toughening agent. Compared with Example 1, the compressive strength, bending strength, and impact resistance are all decreased, while the Mohs hardness, wear resistance and stain resistance are basically unchanged
  • the middle layer of Comparative Example 2 does not contain metal fibers. Compared with Example 1, the compressive strength, bending strength, and impact resistance are all decreased, and the Mohs hardness, wear resistance, and stain resistance are basically unchanged; Comparative Example 3 ordinary resin Compared with Example 1, the artificial stone has reduced compressive strength, bending strength, impact resistance, Mohs hardness, wear resistance, and stain resistance.

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Abstract

一种高韧性无机复合人造石材面板及其制备方法，所述面板包括表层、中间金属纤维增韧层和基底增韧层，表层包括如下重量份的各原料组分：石英砂40～70、石英粉10～30、无机活性粉体20～45、颜料0.5～4、减水剂0.3～1、水3～10；中间金属纤维增韧层包括如下重量份的各原料组分：无机活性粉体40～60、砂45～65、减水剂0.8～1.5、水6～14、金属纤维4～8；基底增韧层包括如下重量份的各原料组分：无机活性粉体30～50、石英砂30～55、石英粉15～20、减水剂0.5～1.2、水4～8、增韧剂0.8～2.5。

Description

一种高韧性无机复合人造石材面板及其制备方法 技术领域
本发明涉及加工类人造石材技术领域，更具体地，涉及一种高韧性无机复合人造石材面板及其制备方法。
背景技术
随着国家对生态环境保护的加强，天然石矿山开采受严格控制。另一方面中国的基础建设，如机场、地铁站、高铁站，商业广场、会馆中心仍在继续，大量基础建设对人造石材面板材料也有大量的需求,替代天然石的人造石具有广阔的市场前景。
传统人造石主要由树脂类有机人造石和少量无机人造石组成。树脂类人造石主要存在受热变形较大，易鼓变形开裂，受紫外线辐射及温度影响老化变形、变色、强度降低，燃烧有难闻气体及不可降解、使用寿命短等缺点，现已经逐步受到环保限制使用；新型无机人造石材面板目前主要是传统水泥基水磨石类产品，抗压强度低、硬度差、抗弯曲强度差，脆性强，容易脆断、整体吸水率高、抗污及耐化学性能能力差，很难达到天然石材的性能，面板很容易折断，使用不安全。
目前无机人造石本身为脆性结构、抗弯易折断，人造石面板结构大部分为单层结构，结构受外力作用过程中，底部直接开裂产生脆断，结构延性低，产品直接破坏，因此有结构局部中间加金属网或纤维网增强结构(类如CN106630805A)进行改良，但由于表面受压时，底部脆性面依旧弯曲变形产生脆性开裂，尽管延展变形增大时增强网起到一定抗拉作用减缓裂纹开展作用，随着强度增大裂纹穿透纤维网继续扩展，因此结构也会不断破坏，不能有效克服结构破损断裂状况；也有结构采用了面层加直接纤维基体层结合形成增韧板手段来克服了面层受压变形开裂问题(类如CN109354468A)，但由于引入纤维基体层对于人造石面板加工过程中，底部刮平过程中形成表面纤维露出及纤维通道孔，因此造成了面板结构吸水性能的大幅度提升，如果是金属纤维极容易出现锈蚀破损及金属锈蚀污染现象，同时如果是其他类纤维表面吸水率会大幅度提升，降低面板力学以及耐久性能。
发明内容
有鉴于此，本发明为克服现有传统无机人造石技术产品抗压性能不足、抗弯曲强度及韧性差、吸水率高等缺陷，提供一种强度高、耐污染、韧性高、使用寿命长、耐老化、经济合理的多层复合结构的高韧性无机复合人造石材面板。
为了解决上述存在的技术问题，本发明采用下述技术方案：
一种高韧性无机复合人造石材面板，包括表层、中间金属纤维增韧层和基底增韧层，表层包 括如下重量份的各原料组分：石英砂40～70、石英粉10～30、无机活性粉体20～45、颜料0.5～4、减水剂0.3～1、水3～10；中间金属纤维增韧层包括如下重量份的各原料组分：无机活性粉体40～60、砂45～65、减水剂0.8～1.5、水6～14、金属纤维4～8；基底增韧层包括如下重量份的各原料组分：无机活性粉体30～50、石英砂30～55、石英粉15～20、减水剂0.5～1.2、水4～8、增韧剂0.8～2.5。
进一步地，所述石英砂细度模数在2.0～3.0之间、二氧化硅含量在93％以上、无杂质及风化、原石硬度在7以上。
进一步地，所述石英粉细度为600目以上、二氧化硅含量在93％以上、原石硬度在7以上。本发明中石英粉的核心作用在于提升混合后人造石材表面除骨料外的胶凝粉体水化产物的耐磨以及耐划伤性能，提高表面致密度性能。
进一步地，所述无机活性粉体以强度等级为42.5以上纯白色硅酸盐水泥为主体掺加白色硅粉、矿粉、纳米氧化钙、纳米硅氧化硅、烧结高白高岭土粉中的一种或几种活性粉体。该活性粉体颜色单一为白色，白度指标超过80以上，活性指数检测大于100％，保证材料强度同时更保证后续调色具有良好的稳定性。水泥与其他活性粉体比例为1：0.2～0.6。
进一步地，所述颜料为无机类各色颜料。
进一步地，所述减水剂不具备金属离子颜色且浓度不大于20％、减水率大于20％、缓凝时间0.5～1小时。
进一步地，所述砂是河沙、机制砂、石英砂中的一种或几种，要求不含泥及泥块、不含有机物贝壳类，材料坚固性质量损失不大于8％，最大颗粒直径不大于2.5毫米，细度模数小于3.0大于2.0。
进一步地，金属纤维包括直径范围0.1～0.2mm、长径比50～150、抗拉强度大于1000MPa的金属纤维中的一种或几种。
进一步地，所述增韧剂为聚乙烯醇胶水或丙烯酰胺胶水等乳胶液中的一种或几种。
进一步地，所述面板的整体厚度为15～50mm，表层的厚度为3～5mm，基底层的厚度为3～5mm。
本发明的另一个目的在于提供上述高韧性无机复合人造石材面板的制备方法，包括如下步骤：
S1.将用于表层、中间金属纤维增韧层、基底增韧层的原料分别按比例搅拌混合均匀得到各层混合料，备用；
S2.准备好面板模具，依据厚度计算并称取步骤S1备好的表层混合料均匀布料在面板模具内，然后依据厚度计算并称取步骤S1配好的中间金属纤维增韧层混合料均匀布料在面板模具内 的表层混合料上，再依据厚度计算并称取步骤S1配好的基底增韧层混合料均匀布料在面板模具内的中间金属纤维增韧层混合料上；
S3.在步骤S2面板模具内的基底增韧层混合料上覆上隔离保湿膜，然后放入真空压机进行抽真空排气并同时震动压制；
S4.将步骤S3压制好的板在40℃下固化6～8小时，脱模后再升温至80～90℃固化12～16小时得到毛坯板；
S5.将步骤S4得到的毛坯板取掉隔离保湿膜进行刮底、定厚、抛光，得到高韧性无机复合人造石材面板。
进一步地，步骤S1中，搅拌混合的时间分别不少于10分钟，搅拌材料工作性能的维勃稠度测试时间为5～30秒，搅拌混合后初凝凝结时间不小于60分钟。
进一步地，步骤S3中，抽真空时间不少于60秒，压制时间不少于120秒；真空压力为-0.07～-0.1MPa，压机压强荷载不小于1MPa，压力不小于5000kN。
进一步地，步骤S4中，高温固化过程保持湿度在75％以上。
本工艺通过分层连续布料方式集中进行压制让层与层之间物料有一定的相互交叉咬合解决界面粘结强度受压分离现象，针对传统无机石制造真空工艺提升了压制压力，缩短了抽真空时间，提升人造石材密实度与制作效率，降低了版面吸水率，通过调整温度及保湿分阶段固化不但提升前期模具使用效率，同时使得人造石材面板体积更加稳定，后续完全克服收缩性能，保证强度的一致性稳定。
本发明与现有技术相比较有如下有益效果：本发明所述高韧性复合人造石材面板具有高强度、高抗弯曲、低脆性、耐冲击、抗裂、抗震性能好等优点，体积稳定低收缩、使用不翘曲变形，吸水率极低、耐久性性能好，不存在老化等问题，层与层之间结合牢固，结构安全度高，延性好不会产生瞬间脆断，可做承载力结构，表面耐污性能好，材料来源广泛，整体综合成本造价低，适合推广使用。
附图说明
图1是高韧性无机复合人造石材面板的结构示意图。
附图标记说明：表层100，中间金属纤维增韧层200，基底增韧层300。
具体实施方式
附图仅用于示例性说明，不能理解为对本发明的限制；为了更好说明本实施例，附图某些部件会有省略、放大或缩小，并不代表实际产品的尺寸；对于本领域技术人员来说，附图中某些公知结构及其说明可能省略是可以理解的；附图中描述位置关系的用于仅用于示例性说明，不能理解为对本发明的限制。下面结合具体实施例对本发明做进一步详细说明。
实施例1
如图1所示，一种高韧性无机复合人造石材面板，整体厚度(t1+t2+t3)为15～50mm，包括厚度t1为3～5mm的表层、中间金属纤维增韧层和厚度t3为3～5mm的基底增韧层，表层包括如下重量份的各原料组分：石英砂40、石英粉10、无机活性粉体20、颜料0.5、减水剂0.3、水3；中间金属纤维增韧层包括如下重量份的各原料组分：无机活性粉体40、砂45、减水剂0.8、水6、金属纤维4；基底增韧层包括如下重量份的各原料组分：无机活性粉体30、石英砂30、石英粉15、减水剂0.5、水4、增韧剂0.8。
其中，所述石英砂细度模数为2.3(石英砂细度模数可以在2.0～3.0之间，本实施例选用2.3)、二氧化硅含量在93％以上、无杂质及风化、原石硬度在7以上。
所述石英粉细度为600目以上、二氧化硅含量在93％以上、原石硬度在7以上。
所述无机活性粉体为P.O42.5白水泥为主体掺加白色硅粉(这里可以掺加白色硅粉、矿粉、纳米氧化钙、纳米硅氧化硅、烧结高白高岭土粉中的一种或几种活性粉体)。
所述颜料为无机类各色颜料。
所述减水剂不具备金属离子颜色且浓度不大于20％、减水率大于20％、缓凝时间0.5～1小时。
所述砂是河沙(可以是河沙、机制砂、石英砂中的一种或几种)，要求不含泥及泥块、不含有机物贝壳类，材料坚固性质量损失不大于8％，最大颗粒直径不大于2.5毫米，细度模数2.6。
金属纤维直径为0.1mm、长径比100、抗拉强度大于1000MPa的金属纤维(可以是直径范围0.1～0.2mm、长径比50～150、抗拉强度大于1000MPa的金属纤维中的一种或几种金属纤维)。
所述增韧剂为聚乙烯醇胶水和丙烯酰胺胶水。
所述高韧性无机复合人造石材面板按照以下步骤制得：
S1.将用于表层、中间金属纤维增韧层、基底增韧层的原料分别按比例搅拌混合均匀，搅拌混合的时间分别不少于10分钟，搅拌材料工作性能的维勃稠度测试时间为5～30秒，搅拌混合后初凝凝结时间不小于60分钟，得到各层混合料，备用；
S2.准备好面板模具，依据厚度计算并称取步骤S1备好的表层混合料均匀布料在面板模具内，然后依据厚度计算并称取步骤S1配好的中间金属纤维增韧层混合料均匀布料在面板模具内的表层混合料上，再依据厚度计算并称取步骤S1配好的基底增韧层混合料均匀布料在面板模具内的中间增韧层混合料上；
S3.在步骤S2面板模具内的基底增韧层混合料上覆上隔离保湿膜，然后放入真空压机进行抽 真空排气并同时震动压制，抽真空时间不少于60秒，压制时间不少于120秒；真空压力为-0.07～-0.1MPa，压机压强荷载不小于1MPa，压力不小于5000kN；
S4.将步骤S3压制好的板在40℃下固化6～8小时，脱模后再升温至80～90℃固化12～16小时得到毛坯板，高温固化过程保持湿度在75％以上；
S5.将步骤S4得到的毛坯板取掉隔离保湿膜进行刮底、定厚、抛光，得到高韧性无机复合人造石材面板。
实施例2
除高韧性无机复合人造石材面板的配方不同外，其他条件同实施例1。
一种高韧性无机复合人造石材面板，包括以下重量份数的原料：表层包括如下重量份的各原料组分：石英砂70、石英粉30、无机活性粉体45、颜料4、减水剂1、水10；中间金属纤维增韧层包括如下重量份的各原料组分：无机活性粉体60、砂65、减水剂1.5、水14、金属纤维8；基底增韧层包括如下重量份的各原料组分：无机活性粉体50、石英砂55、石英粉20、减水剂1.2、水8、增韧剂2.5。
实施例3
除高韧性无机复合人造石材面板的配方不同外，其他条件同实施例1。
一种高韧性无机复合人造石材面板，包括以下重量份数的原料：表层包括如下重量份的各原料组分：石英砂50、石英粉15、无机活性粉体27、颜料1.5、减水剂0.5、水4.5；中间金属纤维增韧层包括如下重量份的各原料组分：无机活性粉体45、砂50、减水剂0.9、水8、金属纤维5；基底增韧层包括如下重量份的各原料组分：无机活性粉体35、石英砂36、石英粉16、减水剂0.65、水5、增韧剂1.2。
实施例4
除高韧性无机复合人造石材面板的配方不同外，其他条件同实施例1。
一种高韧性无机复合人造石材面板，包括以下重量份数的原料：表层包括如下重量份的各原料组分：石英砂60、石英粉25、无机活性粉体38、颜料3、减水剂0.8、水8.5；中间金属纤维增韧层包括如下重量份的各原料组分：无机活性粉体55、砂60、减水剂1.4、水12、金属纤维7；基底增韧层包括如下重量份的各原料组分：无机活性粉体45、石英砂49、石英粉19、减水剂1.05、水7、增韧剂2.1。
实施例5
除高韧性无机复合人造石材面板的配方不同外，其他条件同实施例1。
一种高韧性无机复合人造石材面板，包括以下重量份数的原料：表层包括如下重量份的各原料组分：石英砂55、石英粉20、无机活性粉体32、颜料2.3、减水剂0.65、水6.5；中 间金属纤维增韧层包括如下重量份的各原料组分：无机活性粉体50、砂55、减水剂1.2、水10、金属纤维6；基底增韧层包括如下重量份的各原料组分：无机活性粉体40、石英砂42.5、石英粉17.5、减水剂0.85、水6、增韧剂1.65。
对比例1
除基底层不含增韧剂外，其他同实施例1。
对比例2
除中间增韧层不含金属纤维外，其他同实施例1。
对比例3
普通树脂人造石材。
对以上实施案例1～5、对比案例1～3所制备的高韧性无机复合人造石材面板制作成标准试件进行性能测试，测试结果如表1所示：
表1无机装饰板性能检测结果
Figure PCTCN2019099202-appb-000001
从表1来看，对比例1基底层不含增韧剂，与实施例1对比，压缩强度、抗弯强度、抗冲击性能均下降，莫氏硬度、耐磨性能、耐污性能基本没变化；对比例2中间层不含金属纤维，与实施例1对比，压缩强度、抗弯强度、抗冲击性能均下降，莫氏硬度、耐磨性能、耐污性能基本没变化；对比例3普通树脂人造石材，与实施例1对比，压缩强度、抗弯强度、抗冲击性能、莫氏硬度、耐磨性能、耐污性能均下降。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精 神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (10)

  1. 一种高韧性无机复合人造石材面板，其特征在于，包括表层、中间金属纤维增韧层和基底增韧层，表层包括如下重量份的各原料组分：石英砂40～70、石英粉10～30、无机活性粉体20～45、颜料0.5～4、减水剂0.3～1、水3～10；中间金属纤维增韧层包括如下重量份的各原料组分：无机活性粉体40～60、砂45～65、减水剂0.8～1.5、水6～14、金属纤维4～8；基底增韧层包括如下重量份的各原料组分：无机活性粉体30～50、石英砂30～55、石英粉15～20、减水剂0.5～1.2、水4～8、增韧剂0.8～2.5。
  2. 根据权利要求1所述的高韧性无机复合人造石材面板，其特征在于，所述无机活性粉体以强度等级为42.5以上纯白色硅酸盐水泥为主体掺加白色硅粉、矿粉、纳米氧化钙、纳米硅氧化硅、烧结高白高岭土粉中的一种或几种活性粉体。
  3. 根据权利要求1所述的高韧性无机复合人造石材面板，其特征在于，所述石英砂细度模数在2.0～3.0之间、二氧化硅含量在93％以上、原石硬度在7以上；所述石英粉细度为600目以上、二氧化硅含量在93％以上、原石硬度在7以上。
  4. 根据权利要求1所述的高韧性无机复合人造石材面板，其特征在于，所述砂是河沙、机制砂、石英砂中的一种或几种。
  5. 根据权利要求1所述的高韧性无机复合人造石材面板，其特征在于，所述增韧剂包括聚乙烯醇胶水、丙烯酰胺胶水中的一种或几种。
  6. 根据权利要求1所述的高韧性无机复合人造石材面板，其特征在于，所述面板的整体厚度为15～50mm，表层的厚度为3～5mm，基底层的厚度为3～5mm。
  7. 根据权利要求1～6任一项所述高韧性无机复合人造石材面板的制备方法，其特征在于，包括如下步骤：
    S1.将用于表层、中间金属纤维增韧层、基底增韧层的原料分别按比例搅拌混合均匀得到各层混合料，备用；
    S2.准备好面板模具，依据厚度计算并称取步骤S1备好的表层混合料均匀布料在面板模具内，然后依据厚度计算并称取步骤S1配好的中间金属纤维增韧层混合料均匀布料在面板模具内的表层混合料上，再依据厚度计算并称取步骤S1配好的基底增韧层混合料均匀布料在面板模具内的中间金属增韧层混合料上；
    S3.在步骤S2面板模具内的基底增韧层混合料上覆上隔离保湿膜，然后放入真空压机进行抽真空排气并同时震动压制；
    S4.将步骤S3压制好的板在40℃下固化6～8小时，再升温至80～90℃固化12～16小时得到毛坯板；
    S5.将步骤S4得到的毛坯板取掉隔离保湿膜进行刮底、定厚、抛光，得到高韧性无机复合人 造石材面板。
  8. 根据权利要求7所述高韧性无机复合人造石材面板的制备方法，其特征在于，步骤S1中搅拌混合的时间分别不少于10分钟，搅拌材料工作性能的维勃稠度测试时间为5～30秒；搅拌混合后初凝凝结时间不小于60分钟。
  9. 根据权利要求7所述高韧性无机复合人造石材面板的制备方法，其特征在于，步骤S3中，抽真空时间不少于60秒，压制时间不少于120秒；真空压力为-0.07～-0.1MPa，压机压强荷载不小于1MPa，压力不小于5000kN。
  10. 根据权利要求7所述高韧性无机复合人造石材面板的制备方法，其特征在于，步骤S4中，高温固化过程保持湿度在75％以上。
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