CN107500539B - 一种具有释放负离子功能的调湿陶瓷砖及其制备方法 - Google Patents

一种具有释放负离子功能的调湿陶瓷砖及其制备方法 Download PDF

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CN107500539B
CN107500539B CN201710917552.2A CN201710917552A CN107500539B CN 107500539 B CN107500539 B CN 107500539B CN 201710917552 A CN201710917552 A CN 201710917552A CN 107500539 B CN107500539 B CN 107500539B
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柯善军
田维
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GUANGXI OUSHENNUO CERAMIC Co.,Ltd.
Foshan Oceano Ceramics Co Ltd
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Abstract

本发明公开了一种具有释放负离子功能的调湿陶瓷砖，其自下而上包括纳米多孔坯体层、装饰图案层、纳米负离子材料层和低温薄釉层，所述低温薄釉层具有多孔结构或裂纹结构。本发明通过纳米多孔坯体层实现调湿功能，同时通过纳米负离子材料层和低温薄釉层的复合使该陶瓷砖具有优异的负离子释放能力。本发明还公开了该陶瓷砖的制备方法，其制备工艺步骤简单，可控性强，能耗低，生产效率高，有利于大规模工业化生产。

Description

一种具有释放负离子功能的调湿陶瓷砖及其制备方法
技术领域
本发明涉及建筑陶瓷领域，特别涉及功能性陶瓷砖。
背景技术
随着生活水平的提高，人们对建筑装修的要求也逐渐提高，尤其注重室内装修的舒适与健康。因而应运而生出现了一系列具有空气净化功能的建筑陶瓷产品。
具有负离子功能建筑陶瓷可持续不断的释放负离子，达到清新室内空气的效果。中国发明专利CN1587186A公开了一种可释放负离子的健康陶瓷砖生产方法，通过添加3~10%纳米复合负离子粉，1080~1200℃烧成得到具有释放负离子功能的陶瓷砖。由于负离子粉释放负离子的性能随着温度的增加会急剧的降低，因此经高温热处理的负离子陶瓷砖性能不佳，如采用增加负离子粉含量可能造成陶瓷砖放射性超标。
此外，具有调湿功能建材可实现室内湿度维持在人体舒适的范围内，如中国发明专利CN103172401A公开了一种具有调湿功能陶瓷墙面砖及其制备方法，以10~40%的硅藻土作为吸湿原料，1160~1180℃烧成得到。由于硅藻土的天然微孔结构在高温下容易被破坏，因此高温处理后的硅藻土基陶瓷砖吸湿效果较差，且无釉层，装饰效果不佳。如降低烧成温度，陶瓷砖烧结程度差，砖坯易掉粉，且强度低。
中国发明专利CN10343396167A公开了可调湿减害并能释放负离子的多孔建筑装饰材料，包括含有负离子粉的功能釉层和含有调湿材料的多孔坯体层，经830~1050℃烧成得到。但釉层易堵塞多孔坯体的微孔，导致调湿效果下降，且大量的负离子粉包裹在釉层中，并不能起到释放负离子的作用。
发明内容
本发明的目的在于针对上述现有技术的不足，提供一种具有释放负离子功能的调湿陶瓷砖，其兼具良好的释放负离子效果和调湿性能。
本发明所采取的技术方案是：一种具有释放负离子功能的调湿陶瓷砖，其自下而上包括纳米多孔坯体层、装饰图案层、纳米负离子材料层和低温薄釉层，所述低温薄釉层具有多孔结构或裂纹结构。
作为上述方案的进一步改进，所述低温薄釉层按重量百分比计包括如下化学成分：
SiO2 28~45%；
Al2O3 4~8%；
B2O3 9~15%；
Bi2O3 25~45%；
MgO 0.5~1%；
K2O 1~2.5%；
Na2O 0.5~3%；
Li2O 1~2%。
具体地，所述低温薄釉层的化学成分限定，有利于其形成多孔或裂纹结构。
作为上述方案的进一步改进，所述纳米多孔坯体层按原料重量百分比计具有如下组分：
吸湿原料 30~60%；
钾长石 10~35%；
钠长石 10~25%；
球土 8~15%；
二氧化硅凝胶 1~8%；
添加剂 0.2~1%。
具体地，钾长石和钠长石的含量能有效调整坯体粉料的高温熔体粘度，是实现调湿陶瓷砖低温烧成的重要参数，同时较低的烧成温度可有效提高负离子的释放量。其中二氧化硅凝胶作为无机粘结剂，可有效增加坯体层的强度。
作为上述方案的进一步改进，所述吸湿原料选自硅藻土、沸石、海泡石中的至少一种。
作为上述方案的进一步改进，所述添加剂选自羧甲基纤维素、三聚磷酸钠、聚丙烯酸中的至少一种。
作为上述方案的进一步改进，所述纳米负离子材料层中含有电气石粉和稀土。实际上，是利用了稀土对电气石粉进行激活。纳米负离子材料层的制备方法具体为：将微米级的电气石粉和镧系稀土按质量比为1：（0.5~1）配料，加水制备成固含量为30~35%的浆料，将浆料采用高能量密度陶瓷砂磨机进行纳米化研磨，使得浆料粒径细度小于90nm。采用该方法制备纳米负离子材料，使得电气石粉在研磨粉碎过程中发生晶格畸变，从而有效增强其负离子释放能力。
一种如上所述的具有释放负离子功能的调湿陶瓷砖，其包括如下工艺步骤：
1）将纳米多孔坯体各原料组分与水一同置于球磨机中球磨至细度为0.3以下，过筛、除铁、喷粉，得坯体粉料，后将坯体粉料置于压机中压制成型，得纳米多孔坯体层；
2）步骤1）所得纳米多孔坯体层经干燥后，于表面印刷或喷涂上装饰图案层，后将纳米负离子材料喷涂于装饰图案层上，得纳米负离子材料层；
3）将低温薄釉各原料组分混合均匀，施于步骤2）所得纳米负离子材料层上，经烧成窑一次烧成，得半成品；
4）采用表面处理液对步骤3）所得半成品进行表面喷淋处理，水洗，干燥，得成品。
作为上述方案的进一步改进，步骤1）所述坯体粉料的含水率控制在6~15%范围内。具体地，坯体各原料组分的添加量按质量百分比计为所述各原料组分与水的总重量的45~60%，其可有效控制坯体粉料的含水率。其中过筛处理采用250目筛网，其可使坯体粉料的粒径更均一。
作为上述方案的进一步改进，步骤3）所述的烧成温度为750~900℃，保温时间为20~70min。具体地，低温烧成有利于提高纳米负离子材料的负离子释放能力，然而并不是烧成温度越低越好，还需同时考虑坯体的综合性能。本发明意外地发现，当烧成温度在750~900℃时，不仅保证纳米多孔坯体层具有良好的强度，同时纳米负离子材料层释放负离子的能力最强。
作为上述方案的进一步改进，步骤4）所述表面处理液是由摩尔比为2:1的氟化铵与乙酸混合而成的缓冲液。具体地，通过对低温薄釉层的表面处理，可有效提供其调湿性能和释放负离子的效果。
本发明的有益效果是：
（1）本发明通过纳米多孔坯体层实现调湿功能，同时通过纳米负离子材料层和低温薄釉层的复合使该陶瓷砖具有优异的负离子释放能力。
（2）本发明通过钾长石与钠长石的含量调整高温熔体粘度，实现了调湿陶瓷砖的低温烧成，较低的烧成温度对提高负离子发生量具有重要的意义。同时采用二氧化硅凝胶作为无机粘结剂，可有效地增加坯体的强度。
（3）本发明采用高能量密度陶瓷砂磨机机械纳米研磨激活稀土电气石，使电气石在研磨粉碎的过程中，发生晶格畸变，有效增强其负离子的释放量。
（4）本发明的制备工艺步骤简单，可控性强，能耗低，生产效率高，有利于大规模工业化生产。
具体实施方式
下面结合实施例对本发明进行具体描述，以便于所属技术领域的人员对本发明的理解。有必要在此特别指出的是，实施例只是用于对本发明做进一步说明，不能理解为对本发明保护范围的限制，所属领域技术熟练人员，根据上述发明内容对本发明作出的非本质性的改进和调整，应仍属于本发明的保护范围。同时下述所提及的原料未详细说明的，均为市售产品；未详细提及的工艺步骤或制备方法为均为本领域技术人员所知晓的工艺步骤或制备方法。
实施例1
一种具有释放负离子功能的调湿陶瓷砖，其自下而上包括纳米多孔坯体层、装饰图案层、纳米负离子材料层和低温薄釉层，所述低温薄釉层具有多孔结构或裂纹结构。
其中所述纳米多孔坯体层按原料重量百分比计具有如下组分：30%的硅藻土、25%的钾长石、25%的钠长石、11.8%的球土、8%的二氧化硅凝胶、0.2%的聚丙烯酸。
所述纳米负离子材料层为稀土激活的纳米电气石粉层。
所述低温薄釉层按重量百分比计包括如下化学成分：28%的SiO2、8%的Al2O3、13.5%的B2O3、45%的Bi2O3、0.5%的MgO、2.5%的K2O、0.5%的Na2O和2%的Li2O。
制备方法：
1）将纳米多孔坯体各原料组分与水一同置于球磨机中，固含量为45%，球磨至细度为0.3以下，过250目筛网、除铁、喷粉，得含水率为15%的坯体粉料，后将坯体粉料置于压机中压制成型，得纳米多孔坯体层；
2）步骤1）所得纳米多孔坯体层经干燥后，于表面采用丝网印刷的方式印刷上装饰图案层，后将纳米负离子材料喷涂于装饰图案层上，得纳米负离子材料层；
3）将低温薄釉各原料组分混合均匀，施于步骤2）所得纳米负离子材料层上，经烧成窑一次烧成，烧成温度为900℃，保温时间为20min，得半成品；
4）采用摩尔比为2:1的氟化铵与乙酸配制而成的缓冲液作为表面处理液对步骤3）所得半成品进行表面喷淋处理，水洗，干燥，得实施例1成品。
其中步骤2）中的纳米负离子材料由以下方式制备得到：将市售微米级电气石粉和镧系稀土按质量比1:1配料，加水制备成固含量35%的浆料，将浆料采用高能量密度陶瓷砂磨机进行纳米化研磨，使得浆料中粒径细度小于90nm。
实施例2
一种具有释放负离子功能的调湿陶瓷砖，其自下而上包括纳米多孔坯体层、装饰图案层、纳米负离子材料层和低温薄釉层，所述低温薄釉层具有多孔结构或裂纹结构。
其中所述纳米多孔坯体层按原料重量百分比计具有如下组分：60%的沸石、10%的钾长石、13%的钠长石、15%的球土、1%的二氧化硅凝胶、1%的三聚磷酸钠。
所述纳米负离子材料层为稀土激活的纳米电气石粉层。
所述低温薄釉层按重量百分比计包括如下化学成分：45%的SiO2、4%的Al2O3、15%的B2O3、31.5%的Bi2O3、0.5%的MgO、2.5%的K2O、0.5%的Na2O和1%的Li2O。
制备方法：
1）将纳米多孔坯体各原料组分与水一同置于球磨机中，固含量为60%，球磨至细度为0.3以下，过250目筛网、除铁、喷粉，得含水率为6%的坯体粉料，后将坯体粉料置于压机中压制成型，得纳米多孔坯体层；
2）步骤1）所得纳米多孔坯体层经干燥后，于表面采用丝网印刷的方式印刷上装饰图案层，后将纳米负离子材料喷涂于装饰图案层上，得纳米负离子材料层；
3）将低温薄釉各原料组分混合均匀，施于步骤2）所得纳米负离子材料层上，经烧成窑一次烧成，烧成温度为750℃，保温时间为50min，得半成品；
4）采用摩尔比为2:1的氟化铵与乙酸配制而成的缓冲液作为表面处理液对步骤3）所得半成品进行表面喷淋处理，水洗，干燥，得实施例2成品。
其中步骤2）中的纳米负离子材料由以下方式制备得到：将市售微米级电气石粉和镧系稀土按质量比1:0.5配料，加水制备成固含量30%的浆料，将浆料采用高能量密度陶瓷砂磨机进行纳米化研磨，使得浆料中粒径细度小于90nm。
实施例3
一种具有释放负离子功能的调湿陶瓷砖，其自下而上包括纳米多孔坯体层、装饰图案层、纳米负离子材料层和低温薄釉层，所述低温薄釉层具有多孔结构或裂纹结构。
其中所述纳米多孔坯体层按原料重量百分比计具有如下组分：45%的海泡石、35%的钾长石、10%的钠长石、8%的球土、1%的二氧化硅凝胶、1%的羧甲基纤维素。
所述纳米负离子材料层为稀土激活的纳米电气石粉层。
所述低温薄釉层按重量百分比计包括如下化学成分：43.5%的SiO2、8%的Al2O3、15%的B2O3、25%的Bi2O3、1%的MgO、2.5%的K2O、3%的Na2O和2%的Li2O。
制备方法：
1）将纳米多孔坯体各原料组分与水一同置于球磨机中，固含量为55%，球磨至细度为0.3以下，过250目筛网、除铁、喷粉，得含水率为12%的坯体粉料，后将坯体粉料置于压机中压制成型，得纳米多孔坯体层；
2）步骤1）所得纳米多孔坯体层经干燥后，于表面采用丝网印刷的方式印刷上装饰图案层，后将纳米负离子材料喷涂于装饰图案层上，得纳米负离子材料层；
3）将低温薄釉各原料组分混合均匀，施于步骤2）所得纳米负离子材料层上，经烧成窑一次烧成，烧成温度为800℃，保温时间为30min，得半成品；
4）采用摩尔比为2:1的氟化铵与乙酸配制而成的缓冲液作为表面处理液对步骤3）所得半成品进行表面喷淋处理，水洗，干燥，得实施例3成品。
其中步骤2）中的纳米负离子材料由以下方式制备得到：将市售微米级电气石粉和镧系稀土按质量比1:1配料，加水制备成固含量33%的浆料，将浆料采用高能量密度陶瓷砂磨机进行纳米化研磨，使得浆料中粒径细度小于90nm。
实施例4：性能测试
将实施例1~3制备得的成品进行调湿性能及负离子释放性能的测试，其测试结果如下表1所示。
Figure DEST_PATH_IMAGE001
上述实施例为本发明的优选实施例，凡与本发明类似的工艺及所作的等效变化，均应属于本发明的保护范畴。

Claims (6)

1.一种具有释放负离子功能的调湿陶瓷砖，其特征在于：自下而上包括纳米多孔坯体层、装饰图案层、纳米负离子材料层和低温薄釉层，所述低温薄釉层具有多孔结构或裂纹结构；
所述低温薄釉层经表面处理液表面处理，所述表面处理液是由 摩尔比为2:1的氟化铵与乙酸混合而成的缓冲液；
所述纳米多孔坯体层按原料重量百分比计具有如下组分：
吸湿原料 30~60%；
钾长石 10~35%；
钠长石 10~25%；
球土 8~15%；
二氧化硅凝胶 1~8%；
添加剂 0.2~1%；
所述纳米负离子材料层中含有电气石粉和稀土；
所述纳米负离子材料层的制备方法具体为：将微米级的电气石粉和镧系稀土按质量比为1：（0.5～1）配料，加水制备成固含量为30～35%的浆料，将浆料采用高能量密度陶瓷砂磨机进行纳米化研磨，使得浆料粒径细度小于90nm。
2.根据权利要求1所述的一种具有释放负离子功能的调湿陶瓷砖，其特征在于：所述吸湿原料选自硅藻土、沸石、海泡石中的至少一种。
3.根据权利要求1所述的一种具有释放负离子功能的调湿陶瓷砖，其特征在于：所述添加剂选自羧甲基纤维素、三聚磷酸钠、聚丙烯酸中的至少一种。
4.一种如权利要求1~3任一项所述的具有释放负离子功能的调湿陶瓷砖，其特征在于，包括如下工艺步骤：
1）将纳米多孔坯体各原料组分与水一同置于球磨机中球磨至细度为0.3以下，过筛、除铁、喷粉，得坯体粉料，后将坯体粉料置于压机中压制成型，得纳米多孔坯体层；
2）步骤1）所得纳米多孔坯体层经干燥后，于表面印刷或喷涂上装饰图案层，后将纳米负离子材料喷涂于装饰图案层上，得纳米负离子材料层；
3）将低温薄釉各原料组分混合均匀，施于步骤2）所得纳米负离子材料层上，经烧成窑一次烧成，得半成品；
4）采用表面处理液对步骤3）所得半成品进行表面喷淋处理，水洗，干燥，得成品。
5.根据权利要求4所述的一种具有释放负离子功能的调湿陶瓷砖的制备方法，其特征在于：步骤1）所述坯体粉料的含水率控制在6~15%范围内。
6.根据权利要求4所述的一种具有释放负离子功能的调湿陶瓷砖的制备方法，其特征在于：步骤3）所述的烧成温度为750~900℃，保温时间为20~70min。
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