CN112299817A - 一种具有釉面装饰的黄河泥沙质发泡陶瓷保温板的制备方法 - Google Patents

一种具有釉面装饰的黄河泥沙质发泡陶瓷保温板的制备方法 Download PDF

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CN112299817A
CN112299817A CN202011217280.3A CN202011217280A CN112299817A CN 112299817 A CN112299817 A CN 112299817A CN 202011217280 A CN202011217280 A CN 202011217280A CN 112299817 A CN112299817 A CN 112299817A
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yellow river
insulation board
mixture
river silt
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张亚祥
徐晓虹
吴建锋
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Wuhan University of Technology WUT
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Abstract

本发明公开了一种具有釉面装饰的黄河泥沙质发泡陶瓷保温板的制备方法，首先以黄河泥沙、粉煤灰、长石和发泡剂为原料，进行混料、成型压制，然后将化妆土混合料布施在所得坯体表面，进行二次成型压制；再将釉料混合料布施在化妆土表面，进行三次成型压制，并放入辊道窑内进行烧制得到具有釉面装饰的发泡陶瓷保温板。本发明所得发泡陶瓷保温板具有质量轻、装饰效果好、保温隔热、防火性能好等优点，并可实现黄河泥沙等工业废弃物的高掺量应用，具有重要的经济和环境效益。

Description

一种具有釉面装饰的黄河泥沙质发泡陶瓷保温板的制备方法
技术领域
本发明属于绿色建筑材料和建筑节能技术领域，具体涉及一种具有釉面装饰的黄河泥沙质发泡陶瓷保温板的制备方法。
背景技术
黄河泥沙是从黄河河床中捞起或积淀在河边的淤泥，是一种数量巨大的固体废弃物，逐年淤积，容易造成河道阻塞、河床抬高和诸多环保问题。治理黄河泥沙已经成为治理黄河的重点和难点，且目前其有效利用率仍然很低。有学者利用黄河泥沙制备清水砖、免烧砖等。如，专利CN 101386521A公开了一种以黄河泥沙为主要原料制备环保陶瓷清水砖的方法；专利CN102765929A公开了一种以黄河泥沙和污泥为主要原料制备超轻陶粒的方法。
发泡陶瓷保温板是以陶土尾矿、陶瓷碎片、河道淤泥等作为主要原料，采用先进的生产工艺和发泡技术经高温焙烧而成的高气孔率的闭孔陶瓷材料，广泛应用于建筑外墙保温、防火隔离带、建筑自保温冷热桥处理等领域。目前，国内外学者主要采用淤泥、耐火粘土尾矿、锂尾矿、粉煤灰、陶瓷砖抛光渣等为主要原料制备发泡陶瓷保温板。如，专利CN102503506A公开了一种以淤泥为主要原料(35～65份)制备发泡陶瓷保温板的方法，烧成温度为1150～1250℃；专利CN 107353032 A公开了一种以耐火粘土尾矿为主要原料(55～75％)制备发泡陶瓷保温板的方法，烧成温度为1100～1300℃；专利CN109678553A公开了一种以锂尾矿为主要原料(60～65％)制备发泡陶瓷保温板的方法，烧成温度为1170～1190℃；专利CN102603357A公开了一种以粉煤灰为主要原料(50～70％)制备发泡陶瓷保温板的方法，烧成温度为1230～1260℃；巴西学者在《Characterization of cellular ceramicsmade by porcelain tile residues》一文中介绍了以抛光瓷渣为主要原料制备发泡陶瓷的方法，烧成温度为1200℃。
本发明以脊性原料黄河泥沙为主要原料在较低烧制温度下制备发泡陶瓷，并通过配方组成设计，在提高发泡陶瓷中固体废弃物的添加量的同时，解决了黄河泥沙可塑性差、难以成型的问题。此外，本发明在发泡陶瓷化妆土和釉料中引入一定含量的黄河泥沙，使发泡陶瓷坯体层、化妆土层和釉层之间的结合更为紧密，得到装饰效果较好的发泡陶瓷保温板。
发明内容
本发明的目的是提供一种利用黄河泥沙制备发泡陶瓷保温板及其釉面装饰的方法，该方法制备的发泡陶瓷保温板具有质量轻、装饰效果好、保温隔热、防火性能好等优点，并可实现黄河泥沙、粉煤灰等固体废弃物的大比例应用，具有重要的经济和环境效益。
为了实现上述目的，本发明的技术方案为：
一种具有釉面装饰的黄河泥沙质发泡陶瓷保温板的制备方法，它包括以下步骤：
1)原料配比与混合；
坯用原料中各组分及其所占质量百分比包括：黄河泥沙70～80％、粉煤灰5～15％、长石10～15％、外加发泡剂0.1～0.3％，按上述配比称料，混料，得到坯体混合料备用；
2)成型；将所得坯体混合料装填入模，进行一次成型压制，然后将化妆土混合料布施在所得坯体表面，进行二次成型压制；再将釉料混合料布施在化妆土表面，进行三次成型压制，得发泡陶瓷保温板素坯；
3)烧成；将所得发泡陶瓷保温板素坯放入辊道窑内，经1060～1160℃烧制，得到具有釉面装饰的黄河泥沙质发泡陶瓷保温板。
上述方案中，所述黄河泥沙中，主要成分及其所占质量百分比包括：SiO2 60～70％、Al2O3 10～15％、Fe2O3 3～5％、CaO 4～8％。
上述方案中，所述粉煤灰的主要成分及其所占质量百分比包括：SiO2 45～50％、Al2O3 25～30％、Fe2O3＜5％。
上述方案中，所述长石为钾长石和钠长石中的一种或两者按任意比例的混合物；发泡剂为碳化硅炭黑、碳化硅、煤粉中的一种或几种。
上述方案中，所述化妆土混合料中各原料按质量百分比包括：黄河泥沙40～50％、钾长石10～15％、钠长石10～15％、高岭土5～15％、氧化锌3～8％、磷灰石5～8％、滑石3～8％、外加发泡剂0.1～0.3％。
上述方案中，所述釉料混合料中各原料按质量百分比包括：熔块65～80％、黄河泥沙15～20％、高岭土5～15％、外掺色料0.1～0.3％(相对其它原料总质量的百分比)、外掺添加剂0.2～0.5％(相对其它原料总质量的百分比)。
上述方案中，所述添加剂为羧甲基纤维素、三聚磷酸钠中的一种或二者混合物；色料可根据装饰要求选用陶瓷呈色剂。
上述方案中，所述发泡剂的粒径为过700目筛，磷灰石、滑石和熔块的粒径为过325～400目筛，其它原料的尺寸大小为过230～325目筛。
上述方案中，步骤2)中所述一次成型压制采用双向加压方式，成型压力为15～25MPa；二次成型压制采用单向加压，成型压力为10～15MPa，保压20～30s；三次成型压制单向加压，成型压力为5～10MPa，保压20～30s。
上述方案中，步骤3)中所述烧成制度具体包括：首先以5～8℃的速率升温至950～1050℃保温10～20min；然后以3～5℃/min的速率升温至烧结温度(1060～1160℃)，保温20～50min。
优选的，所述烧成制度中，当升温至90～110℃、190～210℃和290～310℃时，分别保温30～60min。
经测试，本发明所得泡陶瓷保温板的体积密度≤500Kg/m3，抗压强度≥2.2MPa，显气孔率为≤0.5％、导热系数≤0.04W/(m﹒K)、防火等级为A1级。满足GB/T 33500-2017《外墙外保温泡沫陶瓷》对隔热保温材料的要求。
本发明的原理为：
1)本发明以黄河泥沙和粉煤灰为主要原料，辅以长石的作用，可在较低温度下生成熔体，降低熔体的黏度及表面张力，从而使气体更容易克服熔体的黏滞阻力，易形成孔结构，并且更易实现孔结构调控；同时可有效解决黄河泥沙可塑性差、难以成型的问题，实现发泡陶瓷板中黄河泥沙的高掺量应用；
2)黄河泥沙的主要物相组成为石英、碳酸钙和白云母，在加热过程中，部分石英和白云母与配方组成中的粉煤灰、长石等发生反应，生成钙长石，赋予发泡陶瓷机械强度；同时本发明发泡陶瓷的坯体层、化妆土层和釉层均含添加有相当含量的黄河泥沙，烧制后物相组成相近，从而使三层之间结合紧密，发泡陶瓷性能优良。
与现有技术相比，本发明的有益效果为：
1)隔热保温性能好；本发明以黄河泥沙和粉煤灰为主要原料制备的发泡陶瓷保温板内部结构为微小孤立的闭气孔，大气孔的筋骨上仍为均匀分布的小气孔，从而赋予其优良的隔热保温性能，导热系数≤0.04W/(m﹒K)；
2)黄河泥沙添加量高，装饰效果好；本发明在以黄河泥沙(坯体中添加量可达80％，化妆土和釉料中添加量分别可达50％和20％)为主要原料的发泡陶瓷坯体表面先后布施化妆土和釉料，一次烧成后获得釉面装饰的发泡陶瓷保温板，能直接用于建筑内外墙，并可根据使用环境设计釉面纹饰，装饰效果好。
附图说明
图1为本发明实施例1所得发泡陶瓷保温板的断面SEM形貌图。
具体实施方式
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。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。
以下实施例中，采用的黄河泥沙的成分(各成分所占质量百分数)如下：
Figure BDA0002760807900000031
以下实施例中，采用的粉煤灰中各化学成分及其所占质量百分比包括：SiO247.11％、Al2O3 26.46％、Fe2O3 3.36％；长石中各化学成分及其所占质量百分比包括：SiO266.52％、Al2O3 18.66％、K2O+Na2O 12.81％。
以下实施例中，采用的熔块为淄博钧陶陶瓷材料有限公司提供的熔块2004。
实施例1
一种具有釉面装饰的黄河泥沙质发泡陶瓷保温板的制备方法，包括如下步骤：
1)原料配比与混合
将坯用原料按质量百分比：黄河泥沙70％、粉煤灰15％、钾长石15％、发泡剂炭黑(其它原料总质量的0.1％)，称料，用球磨机混料0.5h，得到坯体混合料备用；
将化妆土用原料按质量百分比：黄河泥沙40％、钾长石15％、钠长石10％、高岭土15％、氧化锌4％、磷灰石8％、滑石8％、外加碳化硅(其它原料总质量的0.1％)，称料，用球磨机混料0.5h，得到化妆土混合料备用；
将釉料混合料按质量百分比：熔块65％、黄河泥沙20％、高岭土15％、镨黄色料(其他原料总质量的0.1％)、羧甲基纤维素(熔块和高岭土总质量的0.2％)，称料，用球磨机混料0.5h，得到釉料混合料备用；
2)成型
将坯体混合料装填入钢模中，采用液压机双向加压，成型压力为15MPa；将化妆土混合料布施在坯体表面，采用液压机单向加压，成型压力为10MPa，保压20s；将釉料混合料布施在化妆土表面，采用液压机单向加压，得到发泡陶瓷保温板素坯，成型压力为5MPa，保压20s；
3)烧成
将发泡陶瓷保温板素坯放入辊道窑内，经1060℃烧成，得到具有釉面装饰的发泡陶瓷保温板。具体烧成制度为：首先以5℃/min的速率升温至950℃保温10min，然后以3℃/min的升温速率升温至1060℃保温30min；其中升温至110℃、210℃和310℃时各保温30min。
经测试，本发明的泡陶瓷保温板的体积密度500Kg/m3，抗压强度4MPa，导热系数0.04W/(m﹒K)、防火等级为A1级。满足GB/T 33500-2017《外墙外保温泡沫陶瓷》对隔热保温材料的要求。
实施例2
一种具有釉面装饰的黄河泥沙质发泡陶瓷保温板的制备方法，包括如下步骤：
1)原料配比与混合
将坯用原料按质量百分比：黄河泥沙75％、粉煤灰15％、钠长石10％、发泡剂碳化硅(其它原料总质量的0.2％)，称料，用球磨机混料1h，得到坯体混合料备用；
将化妆土用原料按质量百分比：黄河泥沙45％、钾长石10％、钠长石15％、高岭土15％、氧化锌5％、磷灰石5％、滑石5％、碳化硅(其它原料总质量的0.2％)，称料，用球磨机混料1h，得到化妆土混合料备用；
将釉料混合料按质量百分比：熔块70％、黄河泥沙20％、高岭土10％、钒锆蓝色料(其他原料总质量的0.2％)、三聚磷酸钠(熔块和高岭土总质量的0.3％)，称料，用球磨机混料1h，得到釉料混合料备用；
2)成型
将坯体混合料装填入钢模中，采用液压机双向加压，成型压力为20MPa。将化妆土混合料布施在坯体表面，采用液压机单向加压，成型压力为10MPa，保压25s；将釉料混合料布施在化妆土表面，采用液压机单向加压，得到发泡陶瓷保温板素坯，成型压力为10MPa，保压25s；
3)烧成
将发泡陶瓷保温板素坯放入辊道窑内，经1100℃烧成，得到具有釉面装饰的发泡陶瓷保温板；具体烧成制度为：首先以6℃/min的速率升温至1000℃保温20min，然后以4℃/min的升温速率升温至1100℃保温40min；其中升温至100℃、200℃和300℃时各保温30min。
经测试，本发明的发泡陶瓷保温板的体积密度460Kg/m3，抗压强度2.8MPa，导热系数0.036W/(m﹒K)、防火等级为A1级。满足GB/T 33500-2017《外墙外保温泡沫陶瓷》对隔热保温材料的要求。
实施例3
一种具有釉面装饰的黄河泥沙质发泡陶瓷保温板的制备方法，包括如下步骤：
1)原料配比与混合
将坯用原料按质量百分比：黄河泥沙80％、粉煤灰10％、钾长石5％、钠长石5％、发泡剂煤粉(其它原料总质量的0.3％)，称料，用球磨机混料1h，得到坯体混合料备用。
将化妆土用原料按质量百分比：黄河泥沙50％、钾长石15％、钠长石10％、高岭土10％、氧化锌5％、磷灰石5％、滑石5％、碳化硅(其它原料总质量的0.3％)，称料，用球磨机混料1h，得到化妆土混合料备用；
将釉料混合料按质量百分比：熔块80％、黄河泥沙15％、高岭土5％、大红色料(其他原料总质量的0.5％)、三聚磷酸钠(熔块和高岭土总质量的0.5％)，称料，用球磨机混料1h，得到釉料混合料备用；
2)成型
将坯体混合料装填入钢模中，采用液压机双向加压，成型压力为25MPa。将化妆土混合料布施在坯体表面，采用液压机单向加压，成型压力为15MPa，保压30s；将釉料混合料布施在化妆土表面，采用液压机单向加压，得到发泡陶瓷保温板素坯，成型压力为10MPa，保压30s；
3)烧成
将发泡陶瓷保温板素坯放入辊道窑内，经1160℃烧成，得到具有釉面装饰的发泡陶瓷保温板；具体烧成制度为：首先以8℃/min的速率升温至1050℃保温20min，然后以5℃/min的升温速率升温至1150℃保温60min；其中升温至90℃、190℃和290℃时各保温50min。
经测试，本发明的发泡陶瓷保温板的体积密度430Kg/m3，抗压强度2.2MPa，导热系数0.035W/(m﹒K)、防火等级为A1级。满足GB/T 33500-2017《外墙外保温泡沫陶瓷》对隔热保温材料的要求。
对比例
一种具有釉面装饰的黄河泥沙质发泡陶瓷保温板的制备方法，包括如下步骤：
1)原料配比与混合
将坯用原料按质量百分比：黄河泥沙70％、粉煤灰15％、钾长石15％、发泡剂炭黑(其它原料总质量的0.1％)，称料，用球磨机混料0.5h，得到坯体混合料备用；
将釉料混合料按质量百分比：熔块65％、黄河泥沙20％、高岭土15％、镨黄色料(其他原料总质量的0.1％)、羧甲基纤维素(熔块和高岭土总质量的0.2％)，称料，用球磨机混料0.5h，得到釉料混合料备用；
将釉料混合料按质量百分比：熔块65％、黄河泥沙20％、高岭土15％、镨黄色料(其他原料总质量的0.1％)、羧甲基纤维素(熔块和高岭土总质量的0.2％)，称料，用球磨机混料0.5h，得到釉料混合料备用；
2)成型
将坯体混合料装填入钢模中，采用液压机双向加压，成型压力为15MPa。将化妆土混合料布施在坯体表面，采用液压机单向加压，成型压力为10MPa，保压20s；将釉料混合料布施在化妆土表面，采用液压机单向加压，得到发泡陶瓷保温板素坯，成型压力为5MPa，保压20s；
3)烧成
将发泡陶瓷保温板素坯放入辊道窑内，以8℃/min的速率升温1150℃，保温30min，得到具有釉面装饰的发泡陶瓷保温板。
经测试，本对比例所得发泡陶瓷保温板表面存在大量开口气孔(孔径3～5mm)，透过气孔可看到坯体内部，抗压强度仅1MPa，不满足使用要求。造成该问题的主要原因是素坯在烧成过程中未在90～110℃、190～210℃、290～310℃、950～1050℃处保温足够时间，一方面，素坯中的水分和有机质未充分挥发和燃烧，导致在快速升温过程中逸出，破坏发泡陶瓷基体；另一方面，黄河泥沙中的碳酸钙和白云母未与配方组成中的粉煤灰、长石等充分反应，发泡陶瓷骨架结构未完全形成，导致强度过低。
上述实施例仅是为了清楚地说明所做的实例，而并非对实施方式的限制。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他不同形式的变化或者变动，这里无需也无法对所有的实施方式予以穷举，因此所引申的显而易见的变化或变动仍处于本发明创造的保护范围之内。

Claims (10)

1.一种具有釉面装饰的黄河泥沙质发泡陶瓷保温板的制备方法，其特征在于，它包括以下步骤：
1)原料配比与混合；
坯用原料中各组分及其所占质量百分比包括：黄河泥沙70～80％、粉煤灰5～15％、长石10～15％、外加发泡剂0.1～0.3％，按上述配比称料，混料，得到坯体混合料备用；
2)成型；将所得坯体混合料装填入模，进行一次成型压制，然后将化妆土混合料布施在所得坯体表面，进行二次成型压制；再将釉料混合料布施在化妆土表面，进行三次成型压制，得发泡陶瓷保温板素坯；
3)烧成；将所得发泡陶瓷保温板素坯放入辊道窑内，经1060～1160℃烧制，得到具有釉面装饰的黄河泥沙质发泡陶瓷保温板。
2.根据权利要求1所述的制备方法，其特征在于，所述黄河泥沙的主要成分及其所占质量百分比包括：SiO2 60～70％、Al2O3 10～15％、Fe2O3 3～5％、CaO 4～8％。
3.根据权利要求1所述的制备方法，其特征在于，所述粉煤灰的主要成分及其所占质量百分比包括：SiO2 45～50％、Al2O3 25～30％、Fe2O3＜5％。
4.根据权利要求1所述的制备方法，其特征在于，所述长石为钾长石和钠长石中的一种或两者按任意比例的混合物；发泡剂为碳化硅炭黑、碳化硅、煤粉中的一种或几种。
5.根据权利要求1所述的制备方法，其特征在于，所述化妆土混合料中各原料按质量百分比包括：黄河泥沙40～50％、钾长石10～15％、钠长石10～15％、高岭土5～15％、氧化锌3～8％、磷灰石5～8％、滑石3～8％、外加发泡剂0.1～0.3％。
6.根据权利要求1所述的制备方法，其特征在于，所述釉料混合料中各原料按质量百分比包括：熔块65～80％、黄河泥沙15～20％、高岭土5～15％、外掺色料0.1～0.3％、外掺添加剂0.2～0.5％。
7.根据权利要求1所述的制备方法，其特征在于，所述添加剂为羧甲基纤维素、三聚磷酸钠中的一种或二者混合物。
8.根据权利要求1所述的制备方法，其特征在于，步骤2)中所述一次成型压制采用双向加压方式，成型压力为15～25MPa；二次成型压制采用单向加压，成型压力为10～15MPa，保压20～30s；三次成型压制单向加压，成型压力为5～10MPa，保压20～30s。
9.根据权利要求1所述的制备方法，其特征在于，步骤3)中所述烧成制度具体包括：首先以5～8℃的速率升温至950～1050℃保温10～20min；然后以3～5℃/min的速率升温至1060～1160℃，保温20～50min。
10.根据权利要求9所述的制备方法，其特征在于，所述烧成制度中，当升温至90～110℃、190～210℃和290～310℃时，分别保温30～60min。
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