CN110963793B - 一种仿玉石陶瓷砖及其制备方法 - Google Patents

一种仿玉石陶瓷砖及其制备方法 Download PDF

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CN110963793B
CN110963793B CN201911148804.5A CN201911148804A CN110963793B CN 110963793 B CN110963793 B CN 110963793B CN 201911148804 A CN201911148804 A CN 201911148804A CN 110963793 B CN110963793 B CN 110963793B
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anorthite
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柯善军
蒙臻明
罗飞
马超
朱志超
孙飞野
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Foshan Oceano Ceramics Co Ltd
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Abstract

本发明公开了一种仿玉石陶瓷砖,其透光料按质量百分比计包括如下原料组分:黏土12~20%、钾长石3~5%、钠长石3~7%、钙长石30~50%、硅灰石12~22%、氧化铝5~8%、膨润土1~3%、羧甲基纤维素钠0.1~0.3%、三聚磷酸钠0.1~0.3%,其中钙长石由氧化铝、二氧化硅和方解石按摩尔比为1:2:1混合后经高温固相人工合成。本发明具有高白度和优异的通透性,且具有良好的耐高温性能。本发明还公开了该陶瓷砖的制备方法,其工艺简单,且制备得的仿玉石陶瓷砖砖坯内晶相含量高、强度高,无需布施面釉直接可进行表面渗透装饰,成本低但仿玉石艺术效果显著。

Description

一种仿玉石陶瓷砖及其制备方法
技术领域
本发明涉及建筑陶瓷领域,特别涉及一种仿玉石陶瓷砖。
背景技术
建筑陶瓷作为一种装饰材料具有表面图案丰富美观,耐磨性能好而受到广大消费者的喜爱,随着喷墨打印技术的迅速普及,各式花色的陶瓷砖逐渐进入了人们的视野,如仿皮纹,仿布纹,仿天然大理石,仿玉等一系列的产品,其中仿玉石这类产品对陶瓷砖的制备工艺就提出了较高的要求,玉质产品本身属于一种透光的产品,而传统的陶瓷砖由于晶相,气孔以及杂质等原因,表现出非透明的特性,所以就要对产品的结构进行调整,调整陶瓷砖产品的晶相,改善内部的气孔和减少杂质的影响,从而来提高陶瓷砖的透光性能。
建筑陶瓷砖是一种莫来石相,石英相,玻璃相,气孔以及杂质的复合体,气孔以及杂质的存在会对光线产生散射,当气孔的孔径跟光线的波长相近时,散射作用最强,光损失也最大,传统的无压烧结的方式不可避免的会在陶瓷砖中形成较多气孔,需要通过调整工艺手段减少气孔的数量,与此同时,莫来石的折射率与玻璃相和石英晶相相差较大,光线在经过这些物相的相界面时,大部分光线发生折射和散射,使得光线的传播路线被改变,光强大部分损失,由于上面诸多因素的影响,因此传统的建筑陶瓷是不透光的,想要实现陶瓷砖的透光性能就需要从上述几个因素入手,提高陶瓷砖的透光性能。
现有技术也报道了相关透光陶瓷砖的制备方法,他们解决透光性能的思路是在配方当中加入一些低温砂等矿物原料,提高陶瓷砖当中玻璃相的成分,从而来提高瓷砖的通透性能,这类技术方案存在的主要问题是,瓷砖当中玻璃相的成分越多,耐高温性能也就越差,这样出窑的陶瓷砖产品的砖型也就很难控制,除此之外,玻璃相增大,产品的抗热震性能也会随之下降。专利CN104478419A公开了一种高白透光陶瓷砖及其生产方法,配方中使用了大量的石英,熔块和长石类物质等等,严重影响产品的耐高温性能。专利CN108569893A使用水洗超白砂,烧滑石为主要原料制备了透光陶瓷砖,主要也是运用了一些容易形成低温液相的物质来增加透光性能。由此可见,现有技术无法获得兼具良好耐高温性能和高白透光的仿玉石陶瓷砖。
发明内容
本发明的目的在于针对上述现有技术的不足,提供一种仿玉石陶瓷砖及其制备方法。
本发明所采取的技术方案是:一种仿玉石陶瓷砖,包括透光料,其按质量百分比计包括如下原料组分:黏土12~20%、钾长石3~5%、钠长石3~7%、钙长石30~50%、硅灰石12~22%、氧化铝5~8%、膨润土1~3%、羧甲基纤维素钠0.1~0.3%、三聚磷酸钠0.1~0.3%,其中钙长石由氧化铝、二氧化硅和方解石按摩尔比为1:2:1混合后经高温固相人工合成。
无论是普通的陶瓷砖产品还是透光类陶瓷砖产品,里面都会存在玻璃相和石英晶相,前者是一种高温的无机粘结剂成分,后者是硅酸盐制品高温网络形成体的主要成分,这两种成分是必不可少的。基于透明陶瓷的理论,要尽量的减少光线在相界面的折射损失,以便获得具有较高透光率的制品。具体地,本发明通过调整透光料当中的晶相成分,以钙长石作为晶相,其折射率跟玻璃相和石英晶相相差较近。当采用钙长石作为主晶相时,在光线经过钙长石和玻璃相的相界面时,所发生的折射的损失就较小,从而使得该透光料本身具有高透特性。实际上,本发明的透光料相当于普通陶瓷砖的基料,其以黏土、长石和石英为主要原料组分,通过合理控制各组分配比,使得组成成分点落在钙长石的初晶区,同时引入特定的钙长石作为晶种,诱导合成以钙长石和石英为主要晶相的陶瓷砖,使其不仅具有高透特性,且具有优异的耐高温性能。其中采用特殊的人工合成的钙长石,使得以钙长石作为晶相的可控性更强。
作为上述方案的进一步改进,所述氧化铝的粒径为0.3~0.5μm,二氧化硅的粒径为0.05~0.1μm,方解石的粒径为0.2~0.3μm。具体地,原料粒度过大,反应不完全,合成的钙长石成分不纯;原料粒度过小,合成产物容易结块,不利于分散。
作为上述方案的进一步改进,所述高温固相人工合成的合成温度为1300~1350℃。具体地,合成温度低,产物反应不完全;合成温度高,晶粒容易过度长大,且容易团聚。
作为上述方案的进一步改进,所述透光料的颗粒级配为40目上小于6.2%,100目上80~89.5%,100目下小于7.5%。具体地,本发明通过调整透光料的颗粒级配,提高粉料的容量,再配合后加工工艺,可有效地减少陶瓷砖当中气孔的数量,使陶瓷砖在压制成型过程中该透光料的拱桥效应减小到最低,从而有利于提高生坯的密度和通透性。
作为上述方案的进一步改进,控制透光料中氧化铁和氧化钛的含量之和≤0.3%。铁离子和钛离子均为着色离子,在光线照射下会成为散射中心,导致透光的光色呈现绿色,从而影响美观。而仿玉石陶瓷砖对陶瓷砖透光的呈色色泽要求很高,本发明通过控制原料当中的铁钛含量,改善了该陶瓷砖的仿玉石透光色泽,真正凸显出天然大理石的透光色泽。
一种如上所述的仿玉石陶瓷砖的制备方法,其包括如下工艺步骤:
1)将透光料与多孔二氧化硅混合,得面料混合料;
2)将透光料与色料混合,得底料混合料;
3)于压机上先布底料混合料,再布面料混合料,经压制成型,得通体结构的生坯;
4)生坯经烘干、喷墨打印助渗剂和渗花陶瓷墨水、入窑烧成,得仿玉石陶瓷砖成品。
具体地,多孔二氧化硅与透光料的质量比为98~99:2~1,色料与透光料的质量比根据实际产品的颜色深浅确定。渗花墨水的颜色与色料颜色进行匹配,通过助渗剂调节实现合适的渗透深度。
作为上述方案的进一步改进,步骤1)中所述面料混合料的细度为过250目筛余小于0.8%。具体地,颗粒过细,表面更致密,容易阻碍墨水的渗透通道。
作为上述方案的进一步改进,步骤3)中所述底料混合料与面料混合料按质量份计的布料比例为9:1。具体地,渗花墨水的渗透深度有限,面料层不能太厚,且面料层过厚,成本较高。
作为上述方案的进一步改进,步骤4)中所述入窑烧成的烧成温度为1180~1230℃。具体地,低于该温度范围烧成吸水率过大,高于该温度范围,容易过烧。
本发明的有益效果是:
本发明的透光料以黏土、长石、石英为主要原材料,并引入人工合成的钙长石,使其具有高白度和优异的通透性,且具有良好的耐高温性能。该透光料制备所得陶瓷砖不仅白度高、透光色泽好、仿玉石效果逼真,同时能承受超过1400℃的高温,其砖型良好、整体抗折强度超过40MPa。
本发明的原料当中无需引入如硅酸锆等增白原料,大大降低了该陶瓷砖的内外照指数,是一种环境友好型的产品。
本发明的制备方法工艺简单,且制备得的仿玉石陶瓷砖砖坯内晶相含量高、强度高,无需布施面釉直接可进行表面渗透装饰,成本低但仿玉石艺术效果显著。
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
一种仿玉石陶瓷砖,其透光料按质量百分比计包括:黏土16%、钾长石3%、钠长石3%、钙长石50%、硅灰石22%、氧化铝5%、膨润土0.8%、羧甲基纤维素钠0.1%、三聚磷酸钠0.1%。其中,所述钙长石由粒径为0.3μm的氧化铝、粒径为0.1μm的二氧化硅和粒径为0.2μm的方解石按摩尔比为1:2:1混合后经1350℃高温固相人工合成。同时,控制透光料中氧化铁和氧化钛的含量之和≤0.3%。
制备方法:
1)将原料组分混合,球磨,控制细度为过250目筛余小于0.8%,经喷粉处理,控制其颗粒级配为40目上小于6.2%,100目上80%,100目下小于7.5%,得透光料;
2)将所述透光料与多孔二氧化硅按质量比98:2混合,得面料混合料;
2)将透光料与色料混合,得底料混合料;
3)于压机上先布底料混合料,再布面料混合料,控制底料混合料与面料混合料按质量份计的布料比例为9:1,经3800T压制成型,得通体结构的生坯;
4)生坯经烘干、喷墨打印助渗剂和渗花陶瓷墨水、入窑烧成,烧成温度为1180℃,得实施例1仿玉石陶瓷砖成品。
实施例2
一种仿玉石陶瓷砖,其透光料按质量百分比计包括:黏土22%、钾长石5%、钠长石10%、钙长石39%、硅灰石13%、氧化铝8%、膨润土2.4%、羧甲基纤维素钠0.3%、三聚磷酸钠0.3%。其中,所述钙长石由粒径为0.5μm的氧化铝、粒径为0.05μm的二氧化硅和粒径为0.3μm的方解石按摩尔比为1:2:1混合后经1300℃高温固相人工合成。同时,控制透光料中氧化铁和氧化钛的含量之和≤0.3%。
制备方法:
1)将原料组分混合,球磨,控制细度为过250目筛余小于0.8%,经喷粉处理,控制其颗粒级配为40目上小于6.2%,100目上89.5%,100目下小于7.5%,得透光料;
2)将所述透光料与多孔二氧化硅按质量比99:1混合,得面料混合料;
2)将透光料与色料混合,得底料混合料;
3)于压机上先布底料混合料,再布面料混合料,控制底料混合料与面料混合料按质量份计的布料比例为9:1,经4500T压制成型,得通体结构的生坯;
4)生坯经烘干、喷墨打印助渗剂和渗花陶瓷墨水、入窑烧成,烧成温度为1230℃,得实施例2仿玉石陶瓷砖成品。
实施例3
一种仿玉石陶瓷砖,其透光料按质量百分比计包括:黏土20%、钾长石4%、钠长石7%、钙长石40%、硅灰石20%、氧化铝7%、膨润土1.55%、羧甲基纤维素钠0.3%、三聚磷酸钠0.15%。其中,所述钙长石由粒径为0.4μm的氧化铝、粒径为0.08μm的二氧化硅和粒径为0.25μm的方解石按摩尔比为1:2:1混合后经1320℃高温固相人工合成。同时,控制透光料中氧化铁和氧化钛的含量之和≤0.3%。
制备方法:
1)将原料组分混合,球磨,控制细度为过250目筛余小于0.8%,经喷粉处理,控制其颗粒级配为40目上小于6.2%,100目上85%,100目下小于7.5%,得透光料;
2)将所述透光料与多孔二氧化硅按质量比99:1混合,得面料混合料;
2)将透光料与色料混合,得底料混合料;
3)于压机上先布底料混合料,再布面料混合料,控制底料混合料与面料混合料按质量份计的布料比例为9:1,经4000T压制成型,得通体结构的生坯;
4)生坯经烘干、喷墨打印助渗剂和渗花陶瓷墨水、入窑烧成,烧成温度为1200℃,得实施例3仿玉石陶瓷砖成品。
对比例1
一种仿玉石陶瓷砖,其透光料按质量百分比计包括:黏土16%、钾长石3%、钠长石3%、钙长石50%、硅灰石22%、氧化铝5%、膨润土0.8%、羧甲基纤维素钠0.1%、三聚磷酸钠0.1%。其中,所述钙长石由粒径为0.3μm的氧化铝、粒径为0.1μm的二氧化硅和粒径为0.2μm的方解石按摩尔比为1:3:1混合后经1350℃高温固相人工合成。同时,控制透光料中氧化铁和氧化钛的含量之和≤0.3%。
制备方法:
1)将原料组分混合,球磨,控制细度为过250目筛余小于0.8%,经喷粉处理,控制其颗粒级配为40目上大于8%,100目上70%,100目下大于20%,得透光料;
2)将所述透光料与多孔二氧化硅按质量比90:10混合,得面料混合料;
2)将透光料与色料混合,得底料混合料;
3)于压机上先布底料混合料,再布面料混合料,控制底料混合料与面料混合料按质量份计的布料比例为9:1,经3800T压制成型,得通体结构的生坯;
4)生坯经烘干、喷墨打印助渗剂和渗花陶瓷墨水、入窑烧成,烧成温度为1180℃,得对比例1仿玉石陶瓷砖成品。
对比例2
一种普通石纹透光陶瓷砖,其基料按质量百分比计包括:石英50%、黏土25%、钾钠长石24.8%、羧甲基纤维素钠0.1%、三聚磷酸钠0.1%。制备方法:采用普通陶瓷砖的制备方法得对比例2陶瓷砖成品。
实施例4:性能测试
将实施例1~3所得成品和对比例1~2所得成品以及一款市售的天然玉质石材(四川福来建材有限公司的YS-524产品)分别进行相关性能测试,其测试结果如下表1所示。
表1各实施例和对比例成品相关性能测试结果
测试样品 抗折强度 白度 透光性 耐高温性
实施例1 51Mpa 85 透光
实施例2 55MPa 88 透光
实施例3 53MPa 87 透光
天然玉质石材 30MPa 60 透光
对比例1 42MPa 65 半透光
对比例2 35MPa 30 半透光
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)

1.一种仿玉石陶瓷砖,包括透光料,其特征在于:所述透光料按质量百分比计包括如下原料组分:黏土12~20%、钾长石3~5%、钠长石3~7%、钙长石30~50%、硅灰石12~22%、氧化铝5~8%、膨润土1~3%、羧甲基纤维素钠0.1~0.3%、三聚磷酸钠0.1~0.3%,其中钙长石由氧化铝、二氧化硅和方解石按摩尔比为1:2:1混合后经高温固相人工合成;所述氧化铝的粒径为0.3~0.5μm,二氧化硅的粒径为0.05~0.1μm,方解石的粒径为0.2~0.3μm;所述高温固相人工合成的合成温度为1300~1350℃;所述透光料的颗粒级配为40目上小于6.2%,100目上80~89.5%,100目下小于7.5%。
2.根据权利要求1所述的一种仿玉石陶瓷砖,其特征在于:控制透光料中氧化铁和氧化钛的含量之和≤0.3%。
3.一种如权利要求1或2所述的仿玉石陶瓷砖的制备方法,其特征在于包括如下工艺步骤:
1)将透光料与多孔二氧化硅混合,得面料混合料;
2)将透光料与色料混合,得底料混合料;
3)于压机上先布底料混合料,再布面料混合料,经压制成型,得通体结构的生坯;
4)生坯经烘干、喷墨打印助渗剂和渗花陶瓷墨水、入窑烧成,得仿玉石陶瓷砖成品。
4.根据权利要求3所述的一种仿玉石陶瓷砖的制备方法,其特征在于:步骤1)中所述面料混合料的细度为过250目筛余小于0.8%。
5.根据权利要求3所述的一种仿玉石陶瓷砖的制备方法,其特征在于:步骤3)中所述底料混合料与面料混合料按质量份计的布料比例为9:1。
6.根据权利要求3所述的一种仿玉石陶瓷砖的制备方法,其特征在于:步骤4)中所述入窑烧成的烧成温度为1180~1230℃。
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