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CN111807876A - A kind of antistatic ceramic tile with nanostructure on the surface and preparation method thereof - Google Patents

A kind of antistatic ceramic tile with nanostructure on the surface and preparation method thereof Download PDF

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CN111807876A
CN111807876A CN202010677292.8A CN202010677292A CN111807876A CN 111807876 A CN111807876 A CN 111807876A CN 202010677292 A CN202010677292 A CN 202010677292A CN 111807876 A CN111807876 A CN 111807876A
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ceramic tile
nano
film layer
antistatic
preparation
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叶德林
刘世明
陈然
简润桐
马杰
王亚婕
黄佳奇
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Foshan Sanshuiguanzhu Ceramics Co ltd
Newpearl Ceramics Group Co ltd
Guangdong Summit Ceramics Co Ltd
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Foshan Sanshuiguanzhu Ceramics Co ltd
Newpearl Ceramics Group Co ltd
Guangdong Summit Ceramics Co Ltd
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Priority to CN202010677292.8A priority Critical patent/CN111807876A/en
Publication of CN111807876A publication Critical patent/CN111807876A/en
Priority to PCT/CN2020/133065 priority patent/WO2022011932A1/en
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81Coating or impregnation
    • C04B41/85Coating or impregnation with inorganic materials
    • C04B41/88Metals
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    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C04B41/5116Ag or Au
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    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/53After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone involving the removal of at least part of the materials of the treated article, e.g. etching, drying of hardened concrete
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    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/91After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics involving the removal of part of the materials of the treated articles, e.g. etching
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/90Electrical properties
    • C04B2111/905Anti-static materials

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Abstract

The invention discloses an antistatic ceramic tile with a nano-structure on the surface and a preparation method thereof. The method comprises the following steps: s1, preparing weak acid with certain solubility according to the requirements of the microstructure of the surface of the ceramic tile; s2, uniformly spraying weak acid on the surface of the ceramic tile after grinding and polishing by adopting high-pressure atomization equipment, and modifying the surface microstructure; s3, cleaning and drying the modified ceramic tile surface; s4, preparing a silver particle-doped nano silicon dioxide aqueous solution; s5, coating the nano silicon dioxide water solution doped with silver particles on the surface of the modified ceramic tile by adopting a coating mode to form a film layer and baking the film layer; s6, after baking, cooling to obtain the anti-static ceramic tile; the invention has the characteristics of low difficulty of production technology, easy implementation and high cost performance.

Description

一种表面拥有纳米结构的防静电陶瓷砖及制备方法A kind of antistatic ceramic tile with nanostructure on the surface and preparation method thereof

技术领域technical field

本发明属于工业陶瓷技术领域,具体涉及一种表面拥有纳米结构的防静电陶瓷砖及制备方法。The invention belongs to the technical field of industrial ceramics, and in particular relates to an antistatic ceramic tile with a nanostructure on the surface and a preparation method thereof.

背景技术Background technique

静电是一种普遍存在的现象,在各行业中,特别是具有精密仪器或者特殊环境对静电需要采用防护措施。在装饰材料方面,有采用防静电的装饰板、木材、导电漆等,而在装饰材料中陶瓷材料是占据了相当大比例的,因此制备一种具有防静电的陶瓷也是大家共同努力的方向。Static electricity is a ubiquitous phenomenon. In various industries, especially those with precision instruments or special environments need to take protective measures against static electricity. In terms of decorative materials, there are anti-static decorative boards, wood, conductive paint, etc., and ceramic materials occupy a considerable proportion of decorative materials, so the preparation of an anti-static ceramic is also the direction of our joint efforts.

目前,研究防静电陶瓷的专利有,如CN103614003B提供了一种使用半导体氧化物添加到陶瓷墨水打印到陶瓷表面,达到抗静电的效果;如专利CN102030519B采用氧化锌、氧化锡半导体粉直接与陶瓷坯料球磨混合制备防静电陶瓷;还有专利CN102795893B、CN103113133A等公布的方案都是采用同样的方法;虽然采用的过程不一样,但都是利用了半导体粉可以消除静电这材料性质。目前添加到陶瓷坯料的半导体粉一般采用的是氧化锌、氧化锡或者氧化锑等单一或者复合粉,而且需要添加一定的比例,如专利CN102030519B所介绍的需要添加11%~35%的二氧化锡、1%~9%的三氧化二锑;如专利CN102795893B所述添加二氧化锡30~45%,因此导致成本很高;另外还有通过采用特殊的工艺制备方法,如专利CN103113133A所介绍采用导电浆料包裹陶瓷砖坯粉的方法,虽然减少了半导体粉的用量,但是增加了生产过程的工序和成本,而且提高了生产的技术难度,不易于实施。At present, there are patents on anti-static ceramics, such as CN103614003B, which provides a method of using semiconductor oxides added to ceramic ink to print on the surface of ceramics to achieve antistatic effect; such as patent CN102030519B, which uses zinc oxide and tin oxide semiconductor powder to directly connect with ceramic blanks Antistatic ceramics are prepared by ball milling and mixing; there are also patents CN102795893B, CN103113133A and other published schemes all adopt the same method; although the process is different, they all use semiconductor powder to eliminate static electricity. At present, the semiconductor powders added to the ceramic blanks generally use single or composite powders such as zinc oxide, tin oxide or antimony oxide, and a certain proportion needs to be added. , 1% to 9% of antimony trioxide; as described in patent CN102795893B, 30 to 45% of tin dioxide is added, so the cost is very high; in addition, there is a special process preparation method, such as the introduction of patent CN103113133A using conductive Although the method of wrapping the ceramic brick powder with slurry reduces the amount of semiconductor powder, it increases the process and cost of the production process, and increases the technical difficulty of production, which is not easy to implement.

因此,开发出一种生产技术难度低,易于实施且性价比高的静电陶瓷砖制备方法势在必行Therefore, it is imperative to develop a method for preparing electrostatic ceramic tiles with low production technical difficulty, easy implementation and high cost performance.

发明内容SUMMARY OF THE INVENTION

本发明的目的是提供一种生产技术难度低,易于实施且性价比高的静电陶瓷砖制备方法。The purpose of the present invention is to provide a method for preparing electrostatic ceramic tiles with low technical difficulty in production, easy implementation and high cost performance.

为实现上述发明目的,本发明采取的技术方案如下:In order to realize the above-mentioned purpose of the invention, the technical scheme adopted by the present invention is as follows:

一种表面拥有纳米结构的防静电陶瓷砖的制备方法,包括以下步骤:A preparation method of an antistatic ceramic tile with nanostructures on the surface, comprising the following steps:

S1、根据陶瓷砖表面微观结构的要求,配制弱酸;S1. According to the requirements of the microstructure of the ceramic tile surface, formulate weak acid;

S2、采用高压雾化设备,均匀喷涂弱酸在研磨抛光后的陶瓷砖表面,进行表面微观结构修饰;S2. Use high-pressure atomization equipment to uniformly spray weak acid on the surface of the ceramic tile after grinding and polishing to modify the surface microstructure;

S3、对修饰后的陶瓷砖表面进行清洗、吹干;S3. Clean and dry the surface of the decorated ceramic tile;

S4、制备掺杂银粒子的纳米二氧化硅水溶液;S4, prepare the nano-silicon dioxide aqueous solution doped with silver particles;

S5、采用涂布方式将掺杂银粒子的纳米二氧化硅水溶液涂布在修饰后的陶瓷砖表面形成薄膜层,并烘烤;S5, using the coating method to coat the nano-silica solution doped with silver particles on the surface of the modified ceramic tile to form a thin film layer, and bake;

S6、烘烤结束,冷却,得到防静电陶瓷砖。S6, after the baking is completed, the process is cooled to obtain an anti-static ceramic tile.

作为优选,所述S4中的掺杂银粒子的纳米二氧化硅水溶液,由掺杂银粒子的纳米二氧化硅、水和偶联剂、PH值调节剂组成;Preferably, the nano-silicon dioxide aqueous solution doped with silver particles in the S4 is composed of nano-silica doped with silver particles, water, a coupling agent, and a pH regulator;

其组成按重量百分比为:掺杂银粒子的纳米二氧化硅:20~50%、水:50~80%、偶联剂:1~5%以及PH值调节剂:0.5~1%。Its composition is as follows: nano-silicon dioxide doped with silver particles: 20-50%, water: 50-80%, coupling agent: 1-5% and pH value adjusting agent: 0.5-1%.

作为优选,所述S1中的弱酸采用浓度为5-15%的柠檬酸。Preferably, the weak acid in the S1 is citric acid with a concentration of 5-15%.

作为优选,所述S2中,高压雾化的压力为0.6~0.8MPa,雾化设备的喷嘴直径0.5~1.0mm。Preferably, in the S2, the pressure of the high-pressure atomization is 0.6-0.8 MPa, and the diameter of the nozzle of the atomizing device is 0.5-1.0 mm.

作为优选,所述S5中采用的涂布方式,是用100%润湿饱和的状态下的棉布把纳米二氧化硅水溶液转移到陶瓷砖表面,所述S5中烘烤过程为在150~250℃的温度下,烘烤20~60分钟。Preferably, the coating method used in the S5 is to transfer the nano-silica aqueous solution to the surface of the ceramic tile with a cotton cloth in a state of 100% wetting and saturation, and the baking process in the S5 is at 150-250 ° C. At the same temperature, bake for 20 to 60 minutes.

作为优选,所述纳米二氧化硅的尺寸为50~200nm,所述银粒子的尺寸为2~5nm。Preferably, the size of the nano-silica is 50-200 nm, and the size of the silver particles is 2-5 nm.

作为优选,所述S2中修饰时间为30~120秒。Preferably, the modification time in S2 is 30-120 seconds.

作为优选,所述S2中陶瓷砖表面进行表面微观结构修饰后的粗糙度Ra为0.1~0.5μm。Preferably, the roughness Ra of the surface of the ceramic tile in S2 after the surface microstructure modification is performed is 0.1-0.5 μm.

本发明还公开了一种表面拥有纳米结构的防静电陶瓷砖,包括陶瓷砖以及薄膜层,所述薄膜层设置于陶瓷砖表面,所述薄膜层的接触角为0~10度,所述薄膜层具有超亲水性。The invention also discloses an antistatic ceramic tile with nanostructures on the surface, comprising a ceramic tile and a thin film layer, the thin film layer is arranged on the surface of the ceramic tile, the contact angle of the thin film layer is 0-10 degrees, and the thin film The layer is superhydrophilic.

作为优选,所述薄膜层厚度为1~5μm。Preferably, the thickness of the thin film layer is 1-5 μm.

相对于现有技术,本发明取得了有益的技术效果:Compared with the prior art, the present invention has achieved beneficial technical effects:

1、通过使用弱酸对陶瓷砖表面进行微观结构处理,增加了陶瓷砖表面的比表面积以及凹陷结构,一方面使得陶瓷砖可以更好的接受掺杂银粒子的纳米二氧化硅溶液涂布,另一方面使得陶瓷砖对于空气中的水分子的吸附能力得到提升,从而使得陶瓷砖具有一定的防静电效果,同时通过对陶瓷砖修饰过的表面涂布掺杂银粒子的纳米二氧化硅溶液,再经过特定的温度和时间对表面涂布有掺杂银粒子的纳米二氧化硅溶液的陶瓷砖进行烘烤,使掺杂银粒子的纳米二氧化硅水溶液在陶瓷砖表面形成一层薄膜层,因薄膜层具有超亲水性,能够吸附空气中的水分子,使得陶瓷砖具有较好的防静电效果,而薄膜层中掺杂的纳米级银粒子,会在薄膜层内形成良好的导电网络,从而使陶瓷砖表面电阻下降,积聚的静电会被尽快地释放,从而达到防静电的效果,使得陶瓷砖的防静电能力得到进一步提升;1. By using weak acid to microstructure the surface of the ceramic tile, the specific surface area and the concave structure of the ceramic tile surface are increased. On the one hand, the ceramic tile can better accept the coating of nano-silica solution doped with silver particles, and on the other hand On the one hand, the adsorption capacity of the ceramic tile for water molecules in the air is improved, so that the ceramic tile has a certain anti-static effect. After a specific temperature and time, the ceramic tiles coated with the nano-silica solution doped with silver particles are baked, so that the nano-silica solution doped with silver particles forms a thin film layer on the surface of the ceramic tiles. Because the film layer is super hydrophilic, it can absorb water molecules in the air, making the ceramic tile have a good anti-static effect, and the nano-sized silver particles doped in the film layer will form a good conductive network in the film layer. , so that the surface resistance of the ceramic tile is reduced, and the accumulated static electricity will be released as soon as possible, so as to achieve the effect of anti-static, so that the anti-static ability of the ceramic tile is further improved;

2、无需对常规陶瓷砖的坯体和釉料配方做出改变,而是通过对常规陶瓷砖进行表面微观结构的修饰以及涂布具有防静电效果的薄膜层,在对陶瓷砖整体结构改变较小的前提下使得陶瓷砖具有良好的防静电的效果,本发明的方法简单易行,适用于工业化生产;2. There is no need to change the body and glaze formula of conventional ceramic tiles, but by modifying the surface microstructure of conventional ceramic tiles and coating a thin film layer with anti-static effect, the overall structure of ceramic tiles is relatively changed. The ceramic tile has a good anti-static effect under the small premise, and the method of the invention is simple and easy to implement, and is suitable for industrial production;

3、无需对现有的陶瓷砖生产设备做出调整,节约了因工艺流程升级而产生的设备改造费用,使得防静电瓷砖的生产成本降低,具有较好的经济适用性,有利于提升本发明的适用范围。3. There is no need to adjust the existing ceramic tile production equipment, which saves the equipment renovation cost due to the upgrading of the technological process, reduces the production cost of anti-static ceramic tiles, has better economic applicability, and is conducive to improving the present invention scope of application.

附图说明Description of drawings

图1是本发明实施例1和2的工艺流程简图;Fig. 1 is the process flow diagram of embodiment 1 and 2 of the present invention;

图2是本发明实施例3的工艺流程简图;Fig. 2 is the process flow diagram of embodiment 3 of the present invention;

图3是本发明实施例4的结构剖视图;3 is a structural cross-sectional view of Embodiment 4 of the present invention;

图4是本发明实施例5的结构剖视图。FIG. 4 is a sectional view of the structure of Embodiment 5 of the present invention.

其中,各附图标记所指代的技术特征如下:Among them, the technical features referred to by each reference number are as follows:

1、陶瓷砖;2、薄膜层。1. Ceramic tile; 2. Film layer.

实施例1为本发明公布的一种表面拥有纳米结构的防静电陶瓷砖及制备方法,内容如下Embodiment 1 is a kind of antistatic ceramic tile with nanostructure on the surface and preparation method disclosed by the present invention, the content is as follows

1)优选选用5%溶度的有机柠檬酸,对陶瓷砖1表面进行微观结构修饰;1) preferably select the organic citric acid of 5% solubility, carry out microstructure modification to the surface of ceramic tile 1;

2)弱酸的喷涂方式采用0.7MPa的空气压力,喷嘴直径优选选用0.5mm,喷涂弱酸在陶瓷砖1表面,优选选用120秒的修饰时间,形成微观结构的粗糙度Ra为0.15μm;2) The spraying method of the weak acid adopts an air pressure of 0.7MPa, the diameter of the nozzle is preferably 0.5mm, and the weak acid is sprayed on the surface of the ceramic tile 1, preferably a modification time of 120 seconds is used, and the roughness Ra of the microstructure is 0.15μm;

3)用清水冲洗陶瓷砖1表面,并用自然风吹干表面,直到肉眼看不到明显的液态水;3) Rinse the surface of ceramic tile 1 with clean water, and dry the surface with natural wind until no obvious liquid water can be seen with the naked eye;

4)用100%润湿饱和状态下的棉布将掺杂纳米二氧化硅水溶液涂布在修饰后的陶瓷砖1表面,涂布速度160mm/s,按重量百分比组成优选方案一:4) Coat the surface of the modified ceramic tile 1 with the doped nano-silicon dioxide aqueous solution with a cotton cloth under 100% wetting and saturated state, and the coating speed is 160mm/s, and the preferred scheme 1 is formed by weight percentage:

掺杂银粒子的纳米二氧化硅:25%,其中银粒子尺寸大小为2nm,二氧化硅尺寸大小为50nm、水:69.5%、亲水硅烷偶联剂:5%、PH值调节剂:0.5%酒石酸钾;Nano-silica doped with silver particles: 25%, in which the size of silver particles is 2nm, the size of silica is 50nm, water: 69.5%, hydrophilic silane coupling agent: 5%, PH value adjuster: 0.5 % Potassium tartrate;

5)涂布后的陶瓷砖1再经过一定的温度和时间进行烘干,烘干时间和温度,优选选用温度180度,时间60min,薄膜层2厚度为2μm,接触角为3度;5) The ceramic tile 1 after coating is dried again through a certain temperature and time, and the drying time and temperature are preferably selected at a temperature of 180 degrees, and a time of 60 minutes. The thickness of the film layer 2 is 2 μm, and the contact angle is 3 degrees;

6)烘干结束,冷却,制备出防静电陶瓷砖。6) After drying, cooling is completed to prepare anti-static ceramic tiles.

经过以上方案制备的产品经检验,在温度25℃,相对湿度50-70%的环境中,采用点对点测试表面电阻为5.68×108Ω,符合SJ/T10694-2006国家标准,是一种良好的防静电陶瓷砖。The product prepared by the above scheme has been tested, and the surface resistance is 5.68×108Ω by point-to-point test in an environment with a temperature of 25°C and a relative humidity of 50-70%, which meets the national standard of SJ/T10694-2006 and is a good anti-static Ceramic tiles.

实施例2为本发明公布的一种表面拥有纳米结构的防静电陶瓷砖及制备方法,内容如下Embodiment 2 is a kind of antistatic ceramic tile with nanostructure on the surface and preparation method disclosed by the present invention, the content is as follows

1)根据弱酸的选用方案,优选选用10%溶度的有机柠檬酸,对陶瓷砖1表面进行微观结构修饰;1) According to the selection scheme of weak acid, preferably organic citric acid with a solubility of 10% is selected to carry out microstructure modification on the surface of ceramic tile 1;

2)弱酸的喷涂方式采用0.6-0.8MPa的空气压力,喷嘴直径优选选用0.6mm,喷涂弱酸在陶瓷砖1表面,优选选用90秒的修饰时间,形成微观结构的粗糙度Ra为0.25μm;2) The spraying method of the weak acid adopts an air pressure of 0.6-0.8MPa, the diameter of the nozzle is preferably 0.6mm, and the weak acid is sprayed on the surface of the ceramic tile 1, preferably a modification time of 90 seconds is used, and the roughness Ra of the microstructure is 0.25μm;

3)用清水冲洗陶瓷砖1表面,并用自然风吹干表面,肉眼看不到明显的液态水;3) Rinse the surface of ceramic tile 1 with clean water, and dry the surface with natural wind, no obvious liquid water can be seen with the naked eye;

4)用100%润湿饱和状态下的棉布将掺杂纳米二氧化硅水溶液涂布在修饰后的陶瓷砖1表面,涂布速度140mm/s,按重量百分比组成优选方案二:4) Coat the surface of the modified ceramic tile 1 with the doped nano-silica aqueous solution with the cotton cloth under 100% wetting and saturated state, the coating speed is 140mm/s, and the preferred scheme 2 is formed by weight percentage:

掺杂银粒子的纳米二氧化硅:32%,其中银粒子尺寸大小为3nm,二氧化硅尺寸大小为120nm、水:64.3%、亲水硅烷偶联剂:3%、PH值调节剂:0.7%酒石酸钾;Nano-silica doped with silver particles: 32%, in which the size of silver particles is 3nm, the size of silica is 120nm, water: 64.3%, hydrophilic silane coupling agent: 3%, PH value adjuster: 0.7 % Potassium tartrate;

5)涂布后的陶瓷砖1再经过一定的温度和时间进行烘干,烘干时间和温度,优选选用温度200度,时间35min,薄膜层2厚度为3μm,接触角为4度;5) The ceramic tile 1 after coating is dried again through a certain temperature and time, and the drying time and temperature are preferably selected at a temperature of 200 degrees, and a time of 35 minutes. The thickness of the film layer 2 is 3 μm, and the contact angle is 4 degrees;

6)烘干结束,冷却,制备出防静电陶瓷砖。6) After drying, cooling is completed to prepare anti-static ceramic tiles.

经过以上方案制备的产品经检验,在温度25℃,相对湿度50-70%的环境中,采用点对点测试表面电阻为5.18×108Ω,符合SJ/T10694-2006国家标准,是一种良好的防静电陶瓷砖。The product prepared by the above scheme has been tested, and the surface resistance is 5.18×108Ω by point-to-point test in an environment with a temperature of 25°C and a relative humidity of 50-70%, which meets the national standard of SJ/T10694-2006 and is a good anti-static Ceramic tiles.

实施例3为本发明公布的一种表面拥有纳米结构的防静电陶瓷砖及制备方法,内容如下Embodiment 3 is a kind of antistatic ceramic tile with nanostructure on the surface and preparation method disclosed by the present invention, the content is as follows

1)优选选用15%溶度的有机柠檬酸,对陶瓷砖1表面进行微观结构修饰;1) preferably select the organic citric acid of 15% solubility, carry out microstructure modification to the surface of ceramic tile 1;

2)弱酸的喷涂方式采用0.8MPa的空气压力,喷嘴直径优选选用1.0mm,喷涂弱酸在陶瓷砖1表面,优选选用120秒的修饰时间,形成微观结构的粗糙度Ra为0.4μm;2) The spraying method of the weak acid adopts an air pressure of 0.8MPa, the diameter of the nozzle is preferably 1.0mm, and the weak acid is sprayed on the surface of the ceramic tile 1, preferably a modification time of 120 seconds is used, and the roughness Ra of the formed microstructure is 0.4μm;

3)用清水冲洗陶瓷砖1表面,并用自然风吹干表面,直到肉眼看不到明显的液态水;3) Rinse the surface of ceramic tile 1 with clean water, and dry the surface with natural wind until no obvious liquid water can be seen with the naked eye;

4)用100%润湿饱和状态下的棉布将掺杂纳米二氧化硅水溶液涂布在修饰后的陶瓷砖1表面,涂布速度120mm/s,按重量百分比组成优选方案三:4) Coat the surface of the modified ceramic tile 1 with the doped nano-silicon dioxide aqueous solution with a cotton cloth in a 100% wetting and saturated state, and the coating speed is 120 mm/s, and the preferred solution 3 is formed by weight percentage:

掺杂银粒子的纳米二氧化硅:40%,其中银粒子尺寸大小为5nm,二氧化硅尺寸大小为200nm、水:57.5%、亲水硅烷偶联剂:1.5%、PH值调节剂:1%酒石酸钾;Nano-silica doped with silver particles: 40%, wherein the size of silver particles is 5nm, the size of silica is 200nm, water: 57.5%, hydrophilic silane coupling agent: 1.5%, PH value adjuster: 1 % Potassium tartrate;

5)涂布后的陶瓷砖1再经过一定的温度和时间进行烘干,烘干时间和温度,优选选用温度250度,时间20min,薄膜层2厚度为5μm,接触角为5度;5) The ceramic tile 1 after coating is dried again through a certain temperature and time, and the drying time and temperature are preferably selected at a temperature of 250 degrees, and a time of 20 minutes. The thickness of the film layer 2 is 5 μm, and the contact angle is 5 degrees;

6)烘干结束,冷却,制备出防静电陶瓷砖。6) After drying, cooling is completed to prepare anti-static ceramic tiles.

经过以上方案制备的产品经检验,在温度25℃,相对湿度50-70%的环境中,采用点对点测试表面电阻为4.58×108Ω,符合SJ/T10694-2006国家标准,是一种良好的防静电陶瓷砖。The product prepared by the above scheme has been tested, and the surface resistance is 4.58×108Ω by point-to-point test in an environment with a temperature of 25°C and a relative humidity of 50-70%, which is in line with the national standard of SJ/T10694-2006 and is a good anti-static Ceramic tiles.

实施例4为本发明公布的一种表面拥有纳米结构的防静电陶瓷砖,包括陶瓷砖1以及薄膜层2,薄膜层2仅覆盖陶瓷砖1的上表面。Embodiment 4 is an antistatic ceramic tile with a nanostructure on the surface disclosed in the present invention, comprising a ceramic tile 1 and a thin film layer 2 , and the thin film layer 2 only covers the upper surface of the ceramic tile 1 .

实施例5为本发明公布的一种表面拥有纳米结构的防静电陶瓷砖,包括陶瓷砖1以及薄膜层2,薄膜层2完全覆盖陶瓷砖1的表面。Embodiment 5 is an antistatic ceramic tile with a nanostructure on the surface disclosed in the present invention, comprising a ceramic tile 1 and a thin film layer 2 , and the thin film layer 2 completely covers the surface of the ceramic tile 1 .

为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例对本发明进行进一步详细说明,但本发明要求保护的范围并不局限于下述具体实施例。In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the embodiments, but the claimed scope of the present invention is not limited to the following specific embodiments.

根据上述说明书的揭示和教导,本发明所属领域的技术人员还可以对上述实施方式进行变更和修改。因此,本发明并不局限于上面揭示和描述的具体实施方式,对发明的一些修改和变更也应当落入本发明的权利要求的保护范围内。此外,尽管本说明书中使用了一些特定的术语,但这些术语只是为了方便说明,并不对发明构成任何限制。Based on the disclosure and teaching of the above specification, those skilled in the art to which the present invention pertains can also make changes and modifications to the above embodiments. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and changes to the invention should also fall within the protection scope of the claims of the present invention. In addition, although some specific terms are used in this specification, these terms are only for convenience of description and do not constitute any limitation to the invention.

Claims (10)

1.一种表面拥有纳米结构的防静电陶瓷砖的制备方法,其特征在于,包括以下步骤:1. the preparation method of the antistatic ceramic tile that a surface possesses nanostructure, is characterized in that, comprises the following steps: S1:根据陶瓷砖(1)表面微观结构的要求,配制弱酸;S1: prepare weak acid according to the requirements of the surface microstructure of the ceramic tile (1); S2:采用高压雾化设备,均匀喷涂弱酸在研磨抛光后的陶瓷砖(1)表面,进行表面微观结构修饰;S2: using high-pressure atomization equipment, uniformly spraying weak acid on the surface of the ceramic tile (1) after grinding and polishing, and carrying out surface microstructure modification; S3:对修饰后的陶瓷砖(1)表面进行清洗、吹干;S3: cleaning and drying the surface of the decorated ceramic tile (1); S4:制备掺杂银粒子的纳米二氧化硅水溶液;S4: prepare the nano-silicon dioxide aqueous solution doped with silver particles; S5:采用涂布方式将掺杂银粒子的纳米二氧化硅水溶液涂布在修饰后的陶瓷砖(1)表面形成薄膜层(2),并烘烤;S5: adopt the coating method to coat the nano-silicon dioxide aqueous solution doped with silver particles on the modified ceramic tile (1) surface to form a thin film layer (2), and bake; S6、烘烤结束,冷却,得到防静电陶瓷砖。S6, after the baking is completed, the process is cooled to obtain an anti-static ceramic tile. 2.根据权利要求1所述的一种表面拥有纳米结构的防静电陶瓷砖的制备方法,其特征在于,所述S4中的掺杂银粒子的纳米二氧化硅水溶液,由掺杂银粒子的纳米二氧化硅、水和偶联剂、PH值调节剂组成;2. the preparation method of the antistatic ceramic tile that a kind of surface owns nanostructure according to claim 1, it is characterized in that, the nano-silicon dioxide aqueous solution doped with silver particles in the described S4, by doped silver particles. Nano-silica, water, coupling agent, pH regulator; 其组成按重量百分比为:掺杂银粒子的纳米二氧化硅:20~50%、水:50~80%、偶联剂:1~5%以及PH值调节剂:0.5~1%。Its composition is as follows: nano-silicon dioxide doped with silver particles: 20-50%, water: 50-80%, coupling agent: 1-5% and pH value adjusting agent: 0.5-1%. 3.根据权利要求1所述的一种表面拥有纳米结构的防静电陶瓷砖的制备方法,其特征在于,所述S1中的弱酸采用浓度为5-15%的柠檬酸。3. The preparation method of the antistatic ceramic tile with nanostructures on the surface according to claim 1, wherein the weak acid in the S1 adopts citric acid with a concentration of 5-15%. 4.根据权利要求3所述的一种表面拥有纳米结构的防静电陶瓷砖的制备方法,其特征在于,所述S2中,高压雾化的压力为0.6~0.8MPa,雾化设备的喷嘴直径0.5~1.0mm。4. The method for preparing an antistatic ceramic tile with nanostructures on its surface according to claim 3, wherein in said S2, the pressure of high-pressure atomization is 0.6-0.8 MPa, and the diameter of the nozzle of the atomizing device is 0.6-0.8 MPa. 0.5~1.0mm. 5.根据权利要求1所述的一种表面拥有纳米结构的防静电陶瓷砖的制备方法,其特征在于,所述S5中采用的涂布方式,是用100%润湿饱和的状态下的棉布把纳米二氧化硅水溶液转移到陶瓷砖(1)表面,所述S5中烘烤过程为在150~250℃的温度下,烘烤20~60分钟。5. the preparation method of the antistatic ceramic tile that a kind of surface has nanostructure according to claim 1, is characterized in that, the coating method adopted in described S5, is the cotton cloth under the state of 100% wetting saturation The nano-silicon dioxide aqueous solution is transferred to the surface of the ceramic tile (1), and the baking process in S5 is to bake at a temperature of 150-250° C. for 20-60 minutes. 6.根据权利要求2所述的一种表面拥有纳米结构的防静电陶瓷砖的制备方法,其特征在于,所述纳米二氧化硅的尺寸为50~200nm,所述银粒子的尺寸为2~5nm。6 . The method for preparing an antistatic ceramic tile with nanostructures on the surface according to claim 2 , wherein the size of the nano-silicon dioxide is 50 to 200 nm, and the size of the silver particles is 2 to 200 nm. 7 . 5nm. 7.根据权利要求2所述的一种表面拥有纳米结构的防静电陶瓷砖的制备方法,其特征在于,所述S2中修饰时间为30~120秒。7 . The method for preparing an antistatic ceramic tile with nanostructures on the surface according to claim 2 , wherein the modification time in the S2 is 30 to 120 seconds. 8 . 8.根据权利要求1所述的一种表面拥有纳米结构的防静电陶瓷砖的制备方法,其特征在于,所述S2中陶瓷砖(1)表面进行表面微观结构修饰后的粗糙度Ra为0.1~0.5μm。8. the preparation method of a kind of antistatic ceramic tile with nanostructure on the surface according to claim 1, it is characterized in that, in described S2, the roughness Ra of ceramic tile (1) surface after surface microstructure modification is 0.1 ~0.5 μm. 9.一种根据权利要求1~8任一所述制备方法制得的表面拥有纳米结构的防静电陶瓷砖,包括陶瓷砖(1)以及薄膜层(2),所述薄膜层(2)设置于陶瓷砖(1)表面,其特征在于,所述薄膜层(2)的接触角为0~10度,所述薄膜层(2)具有超亲水性。9. An antistatic ceramic tile with nanostructures on the surface prepared according to any one of the preparation methods of claims 1 to 8, comprising a ceramic tile (1) and a thin film layer (2), wherein the thin film layer (2) is provided with On the surface of the ceramic tile (1), it is characterized in that the contact angle of the thin film layer (2) is 0-10 degrees, and the thin film layer (2) has super hydrophilicity. 10.根据权利要求9所述的一种表面拥有纳米结构的防静电陶瓷砖,其特征在于,所述薄膜层(2)厚度为1~5μm。10 . The antistatic ceramic tile with nanostructures on the surface according to claim 9 , wherein the thin film layer ( 2 ) has a thickness of 1-5 μm. 11 .
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