WO2021092985A1 - 一种自清洁户外用人造石板及其制备方法 - Google Patents

一种自清洁户外用人造石板及其制备方法 Download PDF

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Publication number
WO2021092985A1
WO2021092985A1 PCT/CN2019/119776 CN2019119776W WO2021092985A1 WO 2021092985 A1 WO2021092985 A1 WO 2021092985A1 CN 2019119776 W CN2019119776 W CN 2019119776W WO 2021092985 A1 WO2021092985 A1 WO 2021092985A1
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Prior art keywords
self
cleaning
parts
powder
artificial stone
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PCT/CN2019/119776
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English (en)
French (fr)
Inventor
刘福财
肖敏
汪鹏飞
黎浩
黄贺明
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广东盖特奇新材料科技有限公司
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Publication of WO2021092985A1 publication Critical patent/WO2021092985A1/zh

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Classifications

    • 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
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1055—Coating or impregnating with inorganic materials
    • C04B20/1077—Cements, e.g. waterglass
    • 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
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/2038—Resistance against physical degradation
    • C04B2111/2061—Materials containing photocatalysts, e.g. TiO2, for avoiding staining by air pollutants or the like
    • 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
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/27—Water resistance, i.e. waterproof or water-repellent 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
    • C04B2111/54—Substitutes for natural stone, artistic materials or the like
    • C04B2111/542—Artificial natural stone

Definitions

  • the invention relates to the technical field of artificial stone, and more specifically, to a self-cleaning artificial stone slab for outdoor use and a preparation method thereof.
  • artificial slate has high strength, high flame retardancy, high weather resistance, high acid and alkali resistance, wide color options, realistic imitation stone effect, and good decorative effect. , Suitable for factory production, convenient construction, etc., making it a decorative material for interior and exterior walls of various high-end buildings today.
  • Titanium dioxide is a semiconductor material with good chemical stability, photocatalytic activity and superhydrophilicity. It is safe and non-toxic, and has a low cost. It has been widely used, such as white pigments and porcelain glazes, vehicle decorations , Building surface cooling, food additives, brighteners, etc. Titanium dioxide has good photocatalytic activity and light-induced super-hydrophilicity under sunlight. It has the functions of self-cleaning, antibacterial, disinfection, air and water purification, and has been put into use in many industries such as construction, transportation, and new energy. .
  • the application number is 201910572001.6 and the invention name is a real stone paint with good anti-fouling and self-cleaning ability and its preparation method.
  • titanium dioxide nanosheets are used to prepare real stone paint with good anti-fouling and self-cleaning ability, but real stone paint It is a resin matrix, which is prone to aging and other phenomena, has poor interface adhesion with the slate, and is prone to peeling.
  • titanium dioxide directly used in building boards.
  • Self-cleaning artificial stone slab for outdoor use is a new type of inorganic decorative board developed in response to the shortcomings of the above-mentioned traditional outdoor decorative board. It has good volume stability, good self-cleaning performance, low shrinkage, no warpage and deformation, extremely low water absorption, and durability. It has good performance, good mechanical properties, good decorative effect, good stain resistance and waterproof performance. It can be widely used in outdoor architectural decoration. This product has broad market application prospects and will lead the development direction of inorganic decorative panels in the future.
  • the present invention overcomes at least one of the shortcomings described in the prior art and provides a product with good volume stability, good self-cleaning performance, low shrinkage, no warpage and deformation in use, extremely low water absorption, and durability.
  • the present invention adopts the following technical solutions:
  • a self-cleaning artificial stone slab for outdoor use prefabricated from ultra-high-performance mineral powder with a compressive strength of 100-150 MPa.
  • the ultra-high-performance mineral powder includes the following raw material components in parts by weight: mineral active powder 80-100 parts of body, 8-13 parts of titanium dioxide, 150-220 parts of self-cleaning aggregate, 4-8 parts of nano-silica, 0.5-2 parts of water repellent, 10-15 parts of water, 2 ⁇ water reducing agent 4 parts, 4-10 parts of pigment.
  • the mineral active powder is mainly composed of cement of 42.5 or more mixed with one or more of silica fume, mineral powder, glass beads, and zeolite powder, and the mass ratio of the mineral active powder components is cement : Silica fume: Mineral powder: Glass beads: Zeolite powder is 1:0.05 ⁇ 0.2:0.5 ⁇ 1:0 ⁇ 0.3:0 ⁇ 0.2.
  • the titanium dioxide is anatase titanium dioxide with a particle size of 10 to 1000 nm.
  • it uses its photocatalytic function to completely oxidize and degrade most organic pollutants into harmless inorganic small molecules such as water and carbon dioxide.
  • it takes advantage of its photo-induced super-hydrophilicity to take the inorganic contaminants on the surface of the artificial stone away from the surface of the artificial stone under the rain, and keep the surface of the artificial stone as clean as new.
  • the self-cleaning aggregate is one or a combination of zeolite or ceramsite with a particle size of 20-70 mesh and porous structure and soaked in silica fume, nano-titanium dioxide, cement, bead powder, quartz after cleaning. It is obtained from a self-cleaning photocatalytic suspension slurry formed by stone powder, dispersant, retarding water reducing agent, water, and thickening agent.
  • the porous structure of the aggregate can increase the surface area of the adsorbed titanium dioxide and improve the self-cleaning performance of the artificial stone slab.
  • the mass ratio of cement, microsilica powder, nano titanium dioxide, microbead powder, quartz stone powder, dispersant, retarding type water reducing agent, water, and thickening agent in the self-cleaning photocatalytic suspension slurry is 1:0.05 ⁇ 0.15: 0.05 ⁇ 0.10: 0.10 ⁇ 0.20: 0.05 ⁇ 0.15: 0.003 ⁇ 0.006: 0.005 ⁇ 0.02: 0.25 ⁇ 0.4: 0.0001 ⁇ 0.0003, control the slurry concentration at 75 ⁇ 85%, and the slurry fluidity at 250 ⁇ 300mm.
  • the particle size of the nano-silica is 5-100 nm, which can improve the wear resistance, impermeability and waterproof performance of the artificial stone slab in the present invention.
  • the water-repellent agent is polysiloxane or organic silicon, which plays a waterproof role in the present invention and improves the waterproof performance of the self-cleaning outdoor artificial stone slab.
  • the preparation method of the self-cleaning outdoor artificial stone slab includes the following steps:
  • step S2 Add all the mineral active powder, nano silica, water repellent, pigment and 40wt% water to the premixed aggregate obtained in step S1 and stir for 1 to 2 minutes;
  • step S3 Add all the water reducing agent and the remaining 60% by weight of water to the pre-wet mixture obtained in step S2, and fully stir for 7-9 minutes to obtain the mixture for use;
  • step S5 Cover the mixture in the panel mold in step S4 with an isolation moisturizing film, and then put it into a vacuum press for vacuum exhaust and simultaneous vibration compression;
  • step S6 The board pressed in step S5 is cured at 40°C for 6-8 hours, and then heated to 80-90°C for 12-16 hours to obtain a rough board;
  • step S7 Remove the isolating and moisture-retaining film from the blank board obtained in step S6, scrape the bottom, fix the thickness, and polish to obtain a self-cleaning outdoor artificial stone slab.
  • step S3 the viber consistency of the stirring mixture material is 5-30 s; the initial setting time after stirring and mixing is not less than 60 minutes.
  • step S5 the vacuuming time is not less than 60s, and the pressing time is not less than 120s; 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 S6 the humidity is maintained above 75% during the high-temperature curing process.
  • the present invention has the following beneficial effects:
  • the self-cleaning outdoor artificial stone slab according to the present invention has good volume stability, good self-cleaning performance, low shrinkage, no warpage and deformation, extremely low water absorption, good durability, good mechanical properties, and good decorative effects , Good stain resistance and waterproof performance, compressive strength of 100-150 MPa, electric flux less than 100 Coulomb, etc.
  • the self-cleaning outdoor artificial slate of the present invention has a wide range of raw materials, can realize industrialized production, has high production efficiency, is a green energy-saving and environmentally friendly product, and has economic and social benefits.
  • vacuum degassing is used to improve the compactness of the ultra-high toughness concrete inorganic decorative board, so that the surface of the ultra-high toughness concrete inorganic decorative board is free of pores after being polished and polished. Improve the decorative effect.
  • the self-cleaning outdoor artificial stone slab according to the present invention adopts porous aggregates, which can increase the surface area of the titanium dioxide carrier, and can expose more titanium dioxide to the surface after polishing and improve the self-cleaning performance of the artificial stone slab.
  • a self-cleaning artificial stone slab for outdoor use prefabricated from ultra-high-performance mineral powder with a compressive strength of 100-150 MPa.
  • the ultra-high-performance mineral powder includes the following raw material components in parts by weight: mineral active powder 80 parts of body, 8 parts of titanium dioxide, 150 parts of self-cleaning aggregate, 4 parts of nano-silica, 0.5 parts of water repellent, 10 parts of water, 2 parts of water reducing agent, 4 parts of pigments.
  • the mineral active powder is mainly composed of cement above 42.5 and mixed with silica fume, mineral powder, glass beads, and zeolite powder.
  • the mass ratio of the mineral active powder components is cement: silica fume: mineral powder: glass beads: zeolite powder It is 1:0.125:0.75:0.15:0.1.
  • the titanium dioxide is anatase titanium dioxide with a particle size of 10 to 1000 nm.
  • it uses its photocatalytic function to completely oxidize and degrade most organic pollutants into harmless inorganic small molecules such as water and carbon dioxide.
  • it uses Its light-induced super-hydrophilicity will take the inorganic contaminants on the artificial stone surface away from the artificial stone slab surface under rain washing, and keep the artificial stone slab surface clean as new.
  • the self-cleaning aggregate is one or a combination of zeolite or ceramsite with a particle size of 20-70 mesh porous structure and soaked in micro silica powder, nano titanium dioxide, cement, microbead powder, quartz stone powder after cleaning , Dispersant, retarding type water reducer, water, thickener formed by self-cleaning photocatalytic suspension slurry system.
  • the porous structure of the aggregate can increase the surface area of the adsorbed titanium dioxide and improve the self-cleaning performance of the artificial stone slab.
  • the mass ratio of cement, microsilica powder, nano titanium dioxide, microbead powder, quartz stone powder, dispersant, retarding type water reducing agent, water, and thickening agent in the self-cleaning photocatalytic suspension slurry is 1:0.05 : 0.05: 0.10: 0.05: 0.003: 0.005: 0.25: 0.0001, control the slurry concentration at 75-85%, and the slurry fluidity at 250-300mm.
  • the silicon dioxide content of the microsilica powder is not less than 85%, the activity index is greater than 100%, and the average particle diameter is 0.18um; the nanometer titanium dioxide is anatase crystal type with an average particle diameter of 0.13um; the cement requires 42.5 Grade or above; the activity index of the microbead powder is greater than 75%, and the fineness is greater than 300 mesh; the fineness of the quartz stone powder is greater than 800 mesh, and the silicon dioxide content is 93%; the water reducing rate of the retarding type water reducing agent is greater than 30%, the retarding time is 2 to 4 hours; the dispersant is one or more of sodium hexametaphosphate, polyacrylic acid, sodium dodecylbenzene sulfonate, etc.; the thickener is methyl fiber Vegetarian.
  • the test piece made of the self-cleaning photocatalytic suspension slurry has a 28-day compressive strength of not less than 80 MPa, a tensile strength of not less than 3.5 MPa, and a water absorption rate of less than 1%.
  • the particle size of the nano-silica is 5-100 nm, which can improve the wear resistance, impermeability and waterproof performance of the artificial stone slab in the present invention.
  • the water-repellent agent is polysiloxane or organic silicon, which plays a waterproof role in the present invention and improves the waterproof performance of the self-cleaning outdoor artificial stone slab.
  • the preparation method of the self-cleaning outdoor artificial stone slab includes the following steps:
  • step S2 Add all the mineral active powder, nano silica, water repellent, pigment and 40wt% water to the premixed aggregate obtained in step S1 and stir for 1 to 2 minutes;
  • step S3 Add all the water reducing agent and the remaining 60wt% of the water to the pre-wet mixture obtained in step S2, fully stir for 7-9 minutes, and the viber consistency test of the mixture material will be within 5-30s.
  • the setting time is not less than 60 minutes, and the mixture is obtained for use;
  • step S5. Cover the insulating moisturizing film on the mixture in the panel mold of step S4, and then put it into a vacuum press for vacuum exhaust and vibration pressing at the same time.
  • the vacuuming time is not less than 60s, and the pressing time is not less than 120s.
  • the 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 S6 The board pressed in step S5 is cured at 40°C for 6-8 hours, and then heated to 80-90°C for 12-16 hours to obtain a blank board, and the humidity is maintained above 75% during high-temperature curing;
  • step S7 Remove the isolating and moisture-retaining film from the blank board obtained in step S6, scrape the bottom, fix the thickness, and polish to obtain a self-cleaning outdoor artificial stone slab.
  • the ultra-high-performance mineral powder includes the following raw material components in parts by weight: 100 parts of mineral active powder, 13 parts of titanium dioxide, 220 parts of self-cleaning aggregate, 8 parts of nano silica, 2 parts of water repellent, 15 parts of water, 4 parts of water reducing agent, 10 parts of pigment.
  • the ultra-high-performance mineral powder includes the following raw material components in parts by weight: 85 parts by weight of mineral active powder, 9.5 parts by titanium dioxide, 170 parts by self-cleaning aggregate, 5 parts by nano silica, 0.9 parts by water repellent, 11 parts of water, 2.5 parts of water reducing agent, 5.5 parts of pigment.
  • the ultra-high-performance mineral powder includes the following raw material components in parts by weight: 95 parts of mineral active powder, 11.5 parts of titanium dioxide, 200 parts of self-cleaning aggregates, 7 parts of nano silica, 1.6 parts of water repellent, 14 parts of water, 3.5 parts of water reducing agent, 8.5 parts of pigment.
  • the mineral active powder is mainly composed of cement of 42.5 or more mixed with silica fume and mineral powder, and the mass ratio of the components of the mineral active powder is cement: silica fume: mineral powder of 1:0.05:0.5.
  • the mass ratio of cement, microsilica powder, nano titanium dioxide, microbead powder, quartz stone powder, dispersant, retarding type water reducing agent, water, and thickening agent in the self-cleaning photocatalytic suspension slurry is 1:0.15 : 0.10: 0.20: 0.15: 0.006: 0.02: 0.4: 0.0003.
  • the ultra-high performance mineral powder includes the following raw material components in parts by weight: 90 parts of mineral active powder, 10.5 parts of titanium dioxide, 185 parts of self-cleaning aggregates, 6 parts of nano silica, 1.25 parts of water repellent, 12.5 parts of water, 3 parts of water reducing agent, 7 parts of pigment.
  • the mineral active powder is mainly composed of cement above 42.5 and mixed with silica fume, mineral powder, glass beads, and zeolite powder.
  • the mass ratio of the mineral active powder components is cement: silica fume: mineral powder: glass beads: zeolite powder It is 1:0.2:1:0.3:0.2.
  • the mass ratio of cement, microsilica powder, nano titanium dioxide, microbead powder, quartz stone powder, dispersant, retarding type water reducing agent, water, and thickening agent in the self-cleaning photocatalytic suspension slurry is 1:1 : 0.075: 0.15: 0.10: 0.0045: 0.0125: 0.325: 0.0002.
  • step S5 Except that no vacuum exhaust is performed in step S5, the other conditions are the same as in embodiment 1.
  • comparative example 1 60 parts of mineral active powder, compared with example 1, both compressive strength and light-induced superhydrophilicity decreased more, and the photocatalytic activity decreased less; comparative example 2 titanium dioxide 3 parts, Compared with Example 1, the compressive strength is basically unchanged, and the light-induced superhydrophilicity and photocatalytic activity are both reduced. Comparative Example 3 uses machine-made sand for the self-cleaning aggregate. Compared with Example 1, the compressive strength is basically the same. In contrast, the light-induced superhydrophilicity and photocatalytic activity decreased significantly; Comparative Example 4 did not perform vacuum degassing. Compared with Example 1, both the compressive strength and light-induced superhydrophilicity decreased significantly, and the photocatalytic activity decreased significantly.
  • Comparative Example 5 does not use pH 2 ⁇ 4 acetic acid solution to clean the surface weathering or corrosives for 3-5 minutes in the cleaning process.
  • the compressive strength is slightly decreased, and the light-induced superhydrophilicity is decreased more.
  • the photocatalytic activity decreases less;
  • the pH value of the aggregate surface in Comparative Example 6 is lower than 10, compared with Example 1, the compressive strength is slightly decreased, the photo-induced superhydrophilicity decreases more, and the photocatalytic activity decreases less ;
  • the slurry concentration of the self-cleaning photocatalytic suspension slurry is less than 75%, and the slurry fluidity is less than 250mm.
  • Example 1 Compared with Example 1, the compressive strength is slightly reduced, and the light-induced superhydrophilicity and photocatalytic activity In Comparative Example 8, the self-cleaning photocatalytic suspension slurry was replaced with nano-titanium dioxide dispersion. Compared with Example 1, the compressive strength decreased slightly, and the light-induced superhydrophilicity and photocatalytic activity decreased significantly.
  • the types of mineral active powder, titanium dioxide, and aggregate selected in the present invention are the best; the porous structure of the aggregate can increase the surface area of the titanium dioxide carrier and increase the content of titanium dioxide exposed on the surface, thereby improving the artificial stone slab Self-cleaning performance; vacuum defoaming can improve the compactness of the decorative panel, thereby improving the mechanical properties, stain resistance, waterproof performance, and self-cleaning performance of the decorative panel.

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
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Abstract

一种自清洁户外用人造石板及其制备方法，所述自清洁户外人造石板由抗压强度100～150兆帕的超高性能矿物粉体预制而成，所述超高性能矿物粉体包括以下重量份数的原料组分：矿物活性粉体80～100份、二氧化钛8～13份、自清洁型骨料150～220份、纳米二氧化硅4～8份、憎水剂0.5～2份、水10～15份、减水剂2～4份、颜料4～10份。所述人造石板体积稳定性好、自清洁性能好、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，表面耐污性能好，整体综合成本造价低，适合推广使用。

Description

一种自清洁户外用人造石板及其制备方法 技术领域
本发明涉及人造石技术领域，更具体地，涉及一种自清洁户外用人造石板及其制备方法。
背景技术
随着材料制造技术及设备、人们审美及对质量要求的升级，人造石板具有高强度、高阻燃、高耐候、高耐酸碱性能、颜色可选性广、仿石材效果逼真、装饰效果好、适于工厂化生产、施工便利等优点，使其成为当今各种高档建筑物的内外墙装饰材料。
随着工业经济的发展，工业废气、汽车尾气、雾霾等污染接踵而来，建筑户外用人造石装饰板不可避免受到污染，这些污染物很容易在人造石板表面形成很强的附着力，仅靠雨水的冲刷已很难将其冲刷干净。而且由于重力作用及雨水的冲刷作用力，会将污染物向下推拉，在板面形成条状的污染物痕迹，严重地影响
板面外观装饰效果和建筑物的美观度。在现有的条件下只能依靠“蜘蛛人”人工定期进行清理，消耗大量清洁剂，特别是高层建筑幕墙的清理给“蜘蛛人”的人身安全造成威胁，造成整个社会资源的浪费。
二氧化钛是一种半导体材料，具有良好的化学稳定性、光催化活性和超亲水性，并且安全无毒，成本较低，得到了广泛的应用，例如用作白色颜料和瓷器釉料、车辆装饰、建筑表面降温、食品添加剂、增白剂等。二氧化钛在太阳光的照射下具有很好的光催化活性和光诱导超亲水性，具有自清洁、抗菌，消毒，净化空气和水源等作用，已经在建筑、交通、新能源等多个行业投入使用。申请号为201910572001.6、发明名称为一种具有良好抗污自清洁能力的真石漆及其制备方法的中国发明申请中，采用二氧化钛纳米片制备了具有良好抗污自清洁能力的真石漆，但是真石漆为树脂基体，容易出现老化等现象，与石板的界面粘结力较差，容易出现剥落现象。而二氧化钛在建筑板材方面直接使用的实际应用较少。
因此，研究一种集自清洁功能、装饰效果好、耐久性好、仿石材效果逼真于一体的新型无机装饰板材是建筑装饰材料行业的发展方向。
自清洁户外用人造石板就是针对上述传统户外用装饰板的不足而研发的新型无机装饰板材，其体积稳定性好、自清洁性能好、低收缩、使用不翘曲变形，吸水率极低、耐久性性能好、力学性能好、装饰效果好、耐污防水性能好，可广泛应用于户外建筑装饰，该产品具有广阔的市场应用前景，将引领未来无机装饰板材的发展方向。
发明内容
有鉴于此，本发明为克服上述现有技术所述的至少一种不足，提供一种体积稳定性好、自清洁性能好、低收缩、使用不翘曲变形、吸水率极低、耐久性性能好、力学性能好、装饰效果好、耐污防水性能好的自清洁户外用人造石板及其制备方法，解决传统户外装饰板材易受户外有机物和灰尘污染后不易清洗的问题。
为了解决上述存在的技术问题，本发明采用下述技术方案：
一种自清洁户外用人造石板，由抗压强度100～150兆帕的超高性能矿物粉体预制而成，所述超高性能矿物粉体包括以下重量份数的原料组分：矿物活性粉体80～100份、二氧化钛8～13份、自清洁型骨料150～220份、纳米二氧化硅4～8份、憎水剂0.5～2份、水10～15份、减水剂2～4份、颜料4～10份。
进一步地，所述矿物活性粉体以42.5以上水泥为主体掺加硅灰、矿粉、玻璃微珠、沸石粉中的一种或几种活性粉体，矿物活性粉体成分的质量比是水泥：硅灰：矿粉：玻璃微珠：沸石粉为1:0.05～0.2:0.5～1:0～0.3:0～0.2。
进一步地，所述二氧化钛为粒径10～1000nm的锐钛型二氧化钛，一方面利用其光催化功能，将绝大部分有机污染物完全氧化并降解为水和二氧化碳等无害的无机小分子，另一方面利用其光致超亲水性，在雨水冲刷下将人造石表面的无机污染物带离人造石板表面，保持人造石板表面清洁如新。
进一步地，所述自清洁型骨料为粒径20～70目多孔结构的沸石或陶粒中的一种或两种组合清洗后浸泡于微硅粉、纳米二氧化钛、水泥、微珠粉、石英石粉体、分散剂、缓凝型减水剂、水、增稠剂形成的自清洁光催化悬浮浆体制得。骨料的多孔结构，可以提高吸附二氧化钛的表面积，提高人造石板的自清洁性能。所述自清洁光催化悬浮浆体中水泥、微硅粉、纳米二氧化钛、微珠粉、石英石粉体、分散剂、缓凝型减水剂、水、增稠剂的质量比为1：0.05～0.15：0.05～0.10：0.10～0.20：0.05～0.15：0.003～0.006：0.005～0.02：0.25～0.4：0.0001～0.0003，控制浆体浓度在75～85％，浆体流动度在250～300mm。多孔结构的沸石或陶粒清洗后使其表面pH值不低于10再浸泡于自清洁光催化悬浮浆体，使多孔骨料表面与自清洁光催化悬浮浆体亲和力更好，并能发挥碱激发作用，提高多孔骨料与水化产物的界面粘结强度。清洗过程中，先用水冲洗除去泥及泥块等杂物直至排出清澈的水，再用pH值2～4醋酸溶液清洗表面风化物或腐蚀物，最后用pH值10～12氢氧化钠溶液或氢氧化钾溶液浸泡控制表面pH值不低于10。
进一步地，所述纳米二氧化硅的粒径为5～100nm，在本发明中可以提高人造石板的耐磨、抗渗、防水性能。
进一步地，所述憎水剂为聚硅氧烷或有机硅，在本发明中起防水作用，提高自清洁户外人造石板的防水性能。
上述自清洁户外用人造石板的制备方法，包括以下步骤：
S1.按配比计算各原材料用量，将全部二氧化钛、自清洁型骨料先预混2～4分钟；
S2.将全部矿物活性粉体、纳米二氧化硅、憎水剂、颜料和40wt％的水加入步骤S1所得预混骨料中搅拌1～2分钟；
S3.将全部减水剂和剩余60wt％的水加入到步骤S2所得预湿的混合料中，充分搅拌7～9分钟，得到混合物，备用；
S4.准备好面板模具，依据厚度计算并称取步骤S3备好的混合料均匀布料在面板模具内；
S5.在步骤S4面板模具内的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；
S6.将步骤S5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；
S7.将步骤S6得到的毛坯板取掉隔离保湿膜进行刮底、定厚、抛光，得到自清洁户外用人造石板。
进一步地，步骤S3中，搅拌混合物材料的维勃稠度为5～30s；搅拌混合后初凝凝结时间不小于60分钟。
进一步地，步骤S5中，抽真空时间不少于60s，压制时间不少于120s；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。步骤S6中，高温固化过程保持湿度在75％以上。
本发明与现有技术相比较有如下有益效果：
(1)本发明涉及的自清洁户外用人造石板具有体积稳定性好、自清洁性能好、低收缩、使用不翘曲变形，吸水率极低、耐久性性能好、力学性能好、装饰效果好、耐污防水性能好、抗压强度100-150兆帕、电通量小于100库仑等特点。
(2)本发明涉及的自清洁户外用人造石板制备方法中模具耗用量少，模具周转周期短，解决传统装饰混凝土板模具耗用量多、费用高的问题。
(3)本发明涉及的自清洁户外用人造石板的原材料来源广泛，可实现工业化生产，生产效率高，属于绿色节能环保产品，具有经济社会效益。
(4)本发明涉及的自清洁户外用人造石板制备方法中，采用真空脱泡，提高超高韧性混凝土无机装饰板的致密性，使超高韧性混凝土无机装饰板打磨、抛光后表面无气孔，提高装饰效果。
(5)本发明涉及的自清洁户外用人造石板采用多孔骨料，可以提高二氧化钛载体的表面积，打磨抛光后可以让更多的二氧化钛裸露在表面，提高人造石板的自清洁性能。
具体实施方式
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
一种自清洁户外用人造石板，由抗压强度100～150兆帕的超高性能矿物粉体预制而成，所述超高性能矿物粉体包括以下重量份数的原料组分：矿物活性粉体80份、二氧化钛8份、自清洁型骨料150份、纳米二氧化硅4份、憎水剂0.5份、水10份、减水剂2份、颜料4份。
所述矿物活性粉体以42.5以上水泥为主体掺加硅灰、矿粉、玻璃微珠、沸石粉，矿物活性粉体成分的质量比是水泥：硅灰：矿粉：玻璃微珠：沸石粉为1:0.125:0.75:0.15:0.1。
所述二氧化钛为粒径10～1000nm的锐钛型二氧化钛，一方面利用其光催化功能，将绝大部分有机污染物完全氧化并降解为水和二氧化碳等无害的无机小分子，另一方面利用其光致超亲水性，在雨水冲刷下将人造石表面的无机污染物带离人造石板表面，保持人造石板表面清洁如新。
所述自清洁型骨料为粒径20～70目多孔结构的沸石或陶粒中的一种或两种组合清洗后浸泡于微硅粉、纳米二氧化钛、水泥、微珠粉、石英石粉体、分散剂、缓凝型减水剂、水、增稠剂形成的自清洁光催化悬浮浆体制得。骨料的多孔结构，可以提高吸附二氧化钛的表面积，提高人造石板的自清洁性能。所述自清洁光催化悬浮浆体中水泥、微硅粉、纳米二氧化钛、微珠粉、石英石粉体、分散剂、缓凝型减水剂、水、增稠剂的质量比为1：0.05：0.05：0.10：0.05：0.003：0.005：0.25：0.0001，控制浆体浓度在75～85％，浆体流动度在250～300mm。所述微硅粉的二氧化硅含量不小于85％，活性指数大于100％，平均颗粒直径为0.18um；所述纳米二氧化钛为锐钛晶体型，平均颗粒直径为0.13um；所述水泥要求42.5等级以上；所述微珠粉活性指数大于75％，细度大于300目；所述石英石粉细度在800目以上，二氧化硅含量93％；所述缓凝型减水剂减水率大于30％，缓凝时间为2～4小时；所述分散剂为六偏磷酸钠、聚丙烯酸、十二烷基苯磺酸钠等的一种或几种；所述增稠剂为甲基纤维素。所述自清洁光催化悬浮浆体制成试件28天抗压强度不低于80兆帕，抗拉强度不低于3.5兆帕，吸水率低于1％。多孔结构的沸石或陶粒清洗后使其表面pH值不低于10再浸泡于自清洁光催化悬浮浆体，使多孔骨料表面与自清洁光催化悬浮浆体亲和力更好，并能发挥碱激发作用，提高多孔骨料与水化产物的界面粘结强度。清洗过程中，先用水冲洗除去泥及泥块等杂物直至排出清澈的水，再用pH值2～4醋酸溶液清洗表面风化物或腐蚀物，最后用pH值10～12氢氧化钠溶液或氢氧化钾溶液浸泡控制表面pH值不低于10。
所述纳米二氧化硅的粒径为5～100nm，在本发明中可以提高人造石板的耐磨、抗渗、防水性能。
所述憎水剂为聚硅氧烷或有机硅，在本发明中起防水作用，提高自清洁户外人造石板的防水性能。
上述自清洁户外用人造石板的制备方法，包括以下步骤：
S1.按配比计算各原材料用量，将全部二氧化钛、自清洁型骨料先预混2～4分钟；
S2.将全部矿物活性粉体、纳米二氧化硅、憎水剂、颜料和40wt％的水加入步骤S1所得预混骨料中搅拌1～2分钟；
S3.将全部减水剂和剩余60wt％的水加入到步骤S2所得预湿的混合料中，充分搅拌7～9分钟，搅拌混合物材料工作度维勃稠度测试在5～30s，搅拌混合后初凝凝结时间不小于60分钟，得到混合物，备用；
S4.准备好面板模具，依据厚度计算并称取步骤S3备好的混合料均匀布料在面板模具内；
S5.在步骤S4面板模具内的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60s，压制时间不少于120s，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；
S6.将步骤S5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，高温固化过程保持湿度在75％以上；
S7.将步骤S6得到的毛坯板取掉隔离保湿膜进行刮底、定厚、抛光，得到自清洁户外用人造石板。
实施例2
除超高性能矿物粉体的配方不同外，其他条件同实施例1。
所述超高性能矿物粉体包括以下重量份数的原料组分：矿物活性粉体100份、二氧化钛13份、自清洁型骨料220份、纳米二氧化硅8份、憎水剂2份、水15份、减水剂4份、颜料10份。
实施例3
除超高性能矿物粉体的配方不同外，其他条件同实施例1。
所述超高性能矿物粉体包括以下重量份数的原料组分：矿物活性粉体85份、二氧化钛9.5份、自清洁型骨料170份、纳米二氧化硅5份、憎水剂0.9份、水11份、减水剂2.5份、颜料5.5份。
实施例4
除超高性能矿物粉体的配方不同外，其他条件同实施例1。
所述超高性能矿物粉体包括以下重量份数的原料组分：矿物活性粉体95份、二氧化钛11.5份、自清洁型骨料200份、纳米二氧化硅7份、憎水剂1.6份、水14份、减水剂3.5份、颜料8.5份。所述矿物活性粉体以42.5以上水泥为主体掺加硅灰、矿粉，矿物活性粉体成分的质量比是水泥：硅灰：矿粉为1：0.05：0.5。所述自清洁光催化悬浮浆体中水泥、微硅粉、纳米二氧化钛、微珠粉、石英石粉体、分散剂、缓凝型减水剂、水、增稠剂的质量比为1：0.15：0.10：0.20：0.15：0.006：0.02：0.4：0.0003。
实施例5
除超高性能矿物粉体的配方不同外，其他条件同实施例1。
所述超高性能矿物粉体包括以下重量份数的原料组分：矿物活性粉体90份、二氧化钛10.5份、自清洁型骨料185份、纳米二氧化硅6份、憎水剂1.25份、水12.5份、减水剂3份、颜料7份。所述矿物活性粉体以42.5以上水泥为主体掺加硅灰、矿粉、玻璃微珠、沸石粉，矿物活性粉体成分的质量比是水泥：硅灰：矿粉：玻璃微珠：沸石粉为1:0.2:1:0.3:0.2。所述自清洁光催化悬浮浆体中水泥、微硅粉、纳米二氧化钛、微珠粉、石英石粉体、分散剂、缓凝型减水剂、水、增稠剂的质量比为1：1：0.075：0.15：0.10：0.0045：0.0125：0.325：0.0002。
对比例1
除了矿物活性粉体60份外，其他条件同实施例1。
对比例2
除了二氧化钛3份外，其他条件同实施例1。
对比例3
除了自清洁型骨料采用机制砂外，其他条件同实施例1。
对比例4
除了步骤S5中没有进行真空排气外，其他条件同实施例1。
对比例5
除用于制备自清洁型骨料的多孔结构的沸石或陶粒的清洗过程中不用pH值2～4醋酸溶液清洗表面风化物或腐蚀物外，其他条件同实施例1。
对比例6
除用于制备自清洁型骨料的多孔结构的沸石或陶粒清洗后表面pH值低于10外，其他条件同实施例1。
对比例7
除自清洁光催化悬浮浆体的浆体浓度低于75％，浆体流动度小于250mm外，其他条件 同实施例1。
对比例8
除自清洁光催化悬浮浆体替换为纳米二氧化钛分散液外，其他条件同实施例1。
对以上实施例1～5、对比例1～8所制备的自清洁人造石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自清洁人造石板性能检测结果
Figure PCTCN2019119776-appb-000001
从表1来看，对比例1矿物活性粉体60份，与实施例1对比，抗压强度和光诱导超亲 水性均下降较多，光催化活性下降较少；对比例2二氧化钛3份，与实施例1对比，抗压强度基本没变化，光诱导超亲水性和光催化活性均下降较多；对比例3自清洁型骨料采用机制砂，与实施例1对比，抗压强度基本没变化，光诱导超亲水性和光催化活性均下降较多；对比例4没有进行真空脱泡，与实施例1对比，抗压强度和光诱导超亲水性均下降较多，光催化活性下降较少；对比例5清洗过程中不用pH值2～4醋酸溶液清洗表面风化物或腐蚀物3-5分钟，与实施例1对比，抗压强度略有下降，光诱导超亲水性下降较多，光催化活性下降较少；对比例6中骨料表面pH值低于10，与实施例1对比，抗压强度略有下降，光诱导超亲水性下降较多，光催化活性下降较少；对比例7中自清洁光催化悬浮浆体的浆体浓度低于75％，浆体流动度小于250mm，与实施例1对比，抗压强度略有下降，光诱导超亲水性和光催化活性均下降较多；对比例8中自清洁光催化悬浮浆体替换为纳米二氧化钛分散液，与实施例1对比，抗压强度略有下降，光诱导超亲水性和光催化活性均下降较多。通过大量试验，在本发明所选取的矿物活性粉体、二氧化钛、骨料种类为最优；多孔结构的骨料可以增加二氧化钛载体的表面积，使露在表面的二氧化钛含量增加，从而提高人造石板的自清洁性能；真空脱泡可以提高装饰板致密性，从而提高装饰板的力学性能、耐污防水性能、自清洁性能。
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. 一种自清洁户外用人造石板，其特征在于，所述自清洁户外人造石板由抗压强度100～150兆帕的超高性能矿物粉体预制而成，所述超高性能矿物粉体包括以下重量份数的原料组分：矿物活性粉体80～100份、二氧化钛8～13份、自清洁型骨料150～220份、纳米二氧化硅4～8份、憎水剂0.5～2份、水10～15份、减水剂2～4份、颜料4～10份。
  2. 根据权利要求1所述的一种自清洁户外用人造石板，其特征在于，所述矿物活性粉体以42.5以上水泥为主体掺加硅灰、矿粉、玻璃微珠、沸石粉中的一种或几种活性粉体，矿物活性粉体成分的质量比是水泥：硅灰：矿粉：玻璃微珠：沸石粉为1:0.05～0.2:0.5～1:0～0.3:0～0.2。
  3. 根据权利要求1所述的一种自清洁户外用人造石板，其特征在于，所述二氧化钛为粒径10～1000nm的锐钛型二氧化钛。
  4. 根据权利要求1所述的一种自清洁户外用人造石板，其特征在于，所述自清洁型骨料为粒径20～70目多孔结构的沸石或陶粒中的一种或两种组合清洗后浸泡于微硅粉、纳米二氧化钛、水泥、微珠粉、石英石粉体、分散剂、缓凝型减水剂、水、增稠剂形成的自清洁光催化悬浮浆体制得，所述自清洁光催化悬浮浆体中水泥、微硅粉、纳米二氧化钛、微珠粉、石英石粉体、分散剂、缓凝型减水剂、水、增稠剂的质量比为1：0.05～0.15：0.05～0.10：0.10～0.20：0.05～0.15：0.003～0.006：0.005～0.02：0.25～0.4：0.0001～0.0003。
  5. 根据权利要求1所述的一种自清洁户外用人造石板，其特征在于，所述纳米二氧化硅的粒径为5～100nm。
  6. 根据权利要求1所述的一种自清洁户外用人造石板，其特征在于，所述憎水剂为聚硅氧烷或有机硅。
  7. 一种如权利要求1～6任一项所述的自清洁户外用人造石板的制备方法，其特征在于，包括以下步骤：
    S1.按配比计算各原材料用量，将全部二氧化钛、自清洁型骨料先预混2～4分钟；
    S2.将全部矿物活性粉体、纳米二氧化硅、憎水剂、颜料和40wt％的水加入步骤S1所得预混骨料中搅拌1～2分钟；
    S3.将全部减水剂和剩余60wt％的水加入到步骤S2所得预湿的混合料中，充分搅拌7～9分钟，得到混合物，备用；
    S4.准备好面板模具，依据厚度计算并称取步骤S3备好的混合料均匀布料在面板模具内；
    S5.在步骤S4面板模具内的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；
    S6.将步骤S5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；
    S7.将步骤S6得到的毛坯板取掉隔离保湿膜进行刮底、定厚、抛光，得到自清洁户外用人造石板。
  8. 根据权利要求7所述自清洁户外用人造石板的制备方法，其特征在于，步骤S3中，搅拌混合物材料的维勃稠度为5～30s；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所述自清洁户外用人造石板的制备方法，其特征在于，步骤S5中，抽真空时间不少于60s，压制时间不少于120s；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所述自清洁户外用人造石板的制备方法，其特征在于，步骤S6中，高温固化过程保持湿度在75％以上。
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