CN1075308A - 在氧化物基质上用陶瓷颜料覆盖的硬质颗粒、其生产方法和应用 - Google Patents

在氧化物基质上用陶瓷颜料覆盖的硬质颗粒、其生产方法和应用 Download PDF

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CN1075308A
CN1075308A CN93101512A CN93101512A CN1075308A CN 1075308 A CN1075308 A CN 1075308A CN 93101512 A CN93101512 A CN 93101512A CN 93101512 A CN93101512 A CN 93101512A CN 1075308 A CN1075308 A CN 1075308A
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hard particles
glaze
oxide
covering
application
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鲁道夫·斯特里特马特
兰勒·昆斯
阿尔伯特·克尔伯尔
伯哈德·维鲁斯
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Lonza AG
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Abstract

本发明涉及氧化物基质上的硬质颗粒，特别是刚 玉，它被陶瓷颜料所覆盖，以及该颗粒的生产方法。
本发明的硬质颗粒特别适于在陶瓷釉，例如在陶 瓷地板面砖中用作配色、耐磨和/或防滑的添加剂。

Description

本发明涉及在氧化物基质尤其是刚玉上被颜料所覆盖的硬质颗粒以及它的生产方法。本发明进一步涉及作为配色、耐磨、使表面粗糙成份的颗粒，尤其是在陶瓷釉、搪瓷颜料、油漆物质和涂层物质中的应用。
为了改进力学性能，尤其是耐磨性和防滑跌安全性，经常在高负载的表面上加入硬质颗粒，比如在陶瓷面砖或者说在它的釉上，特别是潮湿房间的地板，比如公共的或私人的浴室、空地、或用相似的负荷能力建造的其它材料例如人造材料或混凝土砖铺设的地面上。为此目的首先加入刚玉颗粒作硬质材料，这与在搪瓷和釉中添入不产生干扰化学反应的非氧化硬质材料如硬金属或碳化硅以及便宜地得到满意的硬度和耐磨性能相矛盾。
通常加工刚玉颗粒的缺点在于配色和表面外观光泽都可能被限制，特别是在居住区和公共建筑的限制很大，这是由于刚玉颗粒的颜色性质，它为白到棕色或灰到蓝色，更特别的刚玉为粉红色到红玉色，并且在煅烧过程中加入到陶瓷釉中时会变色。只有人为限制颜色的种类并且排除所有强的色调，当和釉色显示出基本相同的颜色时，才能得到满意的结果。把釉中的颜料量加大到通常值之上也不会产生什么帮助，因为刚玉颗粒必须符合位于釉表面的目的，且过多的用量会成本昂贵。有可能所希望的表面外观，比如在釉与硬质材料之间不同颜色的斑点，也会大大受到影响。
本发明的任务是提供可在任何着色的釉和其它表面上加入的氧化硬质颗粒，而不会损害印入的颜色，并扩展了可均匀着色的颜色种类，还能产生特定的表面外观，例如弄上斑点、磨毛、杂色、仿大理石花纹及其它的装饰。
本发明的任务可通过权利要求1所述的用陶瓷颜料覆盖的硬质颗粒来解决。
已经发现在氧化物基质上的硬质颗粒带有一种或多种陶瓷颜料和一种胶结剂的外包层是可能的。
用这种方式可以利用硬质颗粒的良好机械性能，从而使利用颗粒的物体的着色不受限制，或一定数量的外观可能不受损害。
在陶瓷用颜料着色后接着是锻烧过程从（无机）氧化物生产的无机化合物（例如金红石、尖晶石、铬铁矿、铝酸盐、铁酸盐）在陶瓷釉中用作颜料组份是可以理解的，且其特征在于不溶于或只微溶于陶瓷釉。
此外，也可根据运用的特定要求来加入无机颜料例如：单相或多相金属氧化物、金属粉等，以及用烧结颜料（Farbfritten）。
在例如B.Rompp，Chemie-Lexikon，9.Auflage，Band  4，1991  G.Thieme  Verlag  Stuttgart或W.Heinz，Silicat-Lexikon，1.Auflage  1985，Akademie-Verlag  Berlin，S.226中有概述。
对于温度不高于约300℃的表面，比如油漆颜料、人造材料表面和混凝土，一般所有的陶瓷颜料都可没问题地使用。特别在把专门用于釉的玻璃养料用于面砖釉上时，发现在硬质颗粒周围有玻璃颜料与釉的熔合，这可以得到部分所希望的混和结果。
在釉中运用无机颜料在特殊情况下须加以检查，以确定在釉烧制时无机颜料的惰性物质的性能。
本发明中作氧化物基质上被覆盖的硬质颗粒的初始材料中加入的物质优选为氧化铝、氧化锆、氧化硅、尖晶石或它们的混合物，也可随之加入通常的杂质和/或添加物，例如稳定剂或烧结助剂。
特别优选的原料是刚玉，最好是熔融或烧结的刚玉。
本发明覆盖的硬质颗粒的大小可为0.03-3mm，较好为0.06-0.5mm，特别好的是如FEPA-Standard  42-D-1984以及43-D-1984所描写的窄颗粒粒径范围。
由于颗粒的大小使之能流动，且无尘、不会聚结，所以该包裹硬质颗粒很易于加工。
因此，该颗粒既可以用干施釉法也可以用已应用的湿施釉法来加入，并可由自动的设备来良好实施并分配用量。
加入的陶瓷颜料占被覆盖前颗粒量的2-20%重量，最好5-10%重量。所用的量取决于颜料的颗粒大小，所希望的色泽强度、颜料层深度以及硬质颗粒的颗粒大小。
在使用较细的颗粒（例如根据FEPA的F220）时，能用常用的釉着色法通过直接加入颜料来得到视觉均匀的颜色痕迹。
但须指出，为了得到与在常用釉着色法中一样的颜色饱和度，运用本发明覆盖的硬质颗粒时应有一少的足够量。例如通过加入占整个干燥釉混合物重量7%的覆盖的刚玉颗粒，该颗粒最大含10%重量，也可0.7%重量的颜料，来得到与把5%重量颜料直接加到同一釉中所得到的同样的颜色饱和度。
因此，釉中的金属组份剧烈下沉而不致在其它颜料组成中因浸渍而被迫沉出（ausweichen）是可能的。
适用于覆盖层的粘结剂原则上是某些粘结剂，它们既能使硬质颗粒也能使颜料得到充分润湿，并形成足够牢固粘结的层，在包裹颗粒预定的应用例如面砖釉的焙烧时，没有干扰的作用。
较好的粘结剂是硅酸、硅酸盐，总是与添加剂（无色玻璃料，单磷酸铝或这些物质的混合物）一起使用或不加添加剂。特别好的是碱金属硅酸盐（“水玻璃”）比如钠水玻璃。
本发明覆盖的硬质颗粒可用简单廉价的方法来生产。为此目的可以例如，首先用粘结剂的溶液或悬浮液来润湿颗粒成覆盖的硬质颗粒，这可例如通过简单的方法在通常的混和器中或用喷洒把运动的颗粒覆盖起来。用作溶液或悬浮液的较好为水或一种其它易蒸发的液体的溶液或者悬浮液。为使颗粒均匀润湿和预定颜料量胶结时，加入不太多的粘结剂溶液或悬浮液是有利且必需的，所需的量取决于颗粒的比表面积或大小、溶液或悬浮液以及颜料的粘度。
随后该被湿润的颗粒与必需量的细粒颜料完全混和，形成均匀的涂层。粘结剂与颜料量的比值较好地为这样选择，即在外面的涂层中无过量的粘结剂，因为否则颗粒很容易会粘结聚结起来。在涂好颜料后，颗粒首先被干燥。进一步的热学处理，在很大程度上取决于包括所希望的应用的温度范围：
为了利用人造材料的表面、混凝土，以及尤其是为了利用在面砖中玻璃料涂覆的刚玉来产生混和作用，至少温度为300℃，
到
最大1200℃，以便如果要求所涂覆的刚玉绝对惰性时应用于面砖。
最后可以解聚和/或过筛，以破坏和/或除去产生的聚结物。
本发明包裹的硬质颗粒的较好应用是加入到陶瓷釉或搪瓷中去，首先此颗粒在那儿提高了耐磨性和表面的粗糙度，并因此降低了滑跌危险性。为此目的，颗粒最好嵌入于釉或搪瓷颜料的表面，这可以通过在煅烧或燃烧过程中在已是沉积物或以粉末状运用的釉或搪瓷料上撒布来实施。此外，当为釉或搪瓷基质和颗粒包层选择不同的色调和/或色泽强度时，加入颗粒也可影响最终釉或搪瓷层的外观，例如可得到无光泽的变化了的结构，或产生斑点和类似的色彩效果。
在这种情况下，根据釉等的透明度，对搪瓷来说，这样做也是有好处的，即在釉料中均匀分散颗粒或如把所述的底釉色首先施涂到基质上然后用釉在其上覆盖那样类似地处理。
尤其有利的是把本发明的覆盖硬质颗粒的陶瓷用于室外区域、潮湿房间和磨损大的地板尤其是公共建筑物和工厂的地板面砖的釉中。
更有利的是把本发明的覆盖硬质颗粒加入人造材料和涂层物质例如地板和墙涂料中，在此也得到耐磨和配色上的好处。
同样有利的是把本发明的包裹硬质颗粒加入至涂层材料以提高其力学的负载强度。
另外，本发明的覆盖的硬质颗粒也可例如加入至人造石材料，混凝土或灰泥中来应用。
下面的实施例更详细地描述了本发明的内容。
实施例1
向1kg刚玉（纯刚玉，k
Figure 93101512X_IMG1
rnung F-120（d50≈110μm））中加入60体积%的钠水玻璃溶液（34.2%重量固体：8%重量Na2O，26.2%重量SiO2，粘度约70mpa.s）和40体积%水的混合物25毫升，并在轮叶混和器（Schaufelmischer）中混和约20分钟。再把100g颜料例如尖晶石类（颗粒大小100%＜63μm）加入至用上述方法均匀润湿的刚玉中，再继续混和20分钟，这样得到的刚玉颗粒在150℃干燥至剩余温度最大为0.1%（在回转干燥器中用周围空气干燥4小时）。干燥后在212μm筛子上筛分，随后筛下的颗粒在1000℃氧化气氛（空气）下于转炉（Drehrohrofen）中煅烧，当中的停留时间为2小时。
冷却后颗粒在一振荡筛上用硬树胶球分散同时在212μm筛分，以分离剩下的聚结物。产品是一种可做面砖的颗粒，具有均匀颜色痕迹的视觉特征。
实施例2
与实施例1类似，每次用10%重量的陶瓷颜料覆盖刚玉颗粒，所用颜料具有下列色彩和组成（重量百分比）：
绿色：Cr2O395%
Al2O33%
SiO22%
棕色：ZnO50%
Fe2O325%
Cr2O325%
蓝色：Co3O420%
Al2O380%
黄色：Pb3O440%
Sb2O340%
ZnO10%
CaO10%
下表表明了通过加入本发明的硬质颗粒，与常用釉着色相比较可能减少的在釉中对环境不利的化合物（重量百分比）含量。
颜色 对环境有害的化合物 在用5％重量颜料（重量百分比＊）直接着色中 在用7％重量本发明的颗粒着色中（重量百分比）
绿 Cr2O3 4.75 0.67
 棕 ZnOCr2O3 2.501.25 0.350.18
蓝 Co3O4 1.00 0.14
黄 Pb3O4Sb2O3ZnO 2.002.000.50 0.280.280.07
＊）规定的5%中的差别是颜料的组成，颜料本身对环境无害。（例如：Al2O3，SiO2，Fe2O3……）

Claims (15)

1、一种在氧化物基质上的硬质颗粒，其特征在于，它含至少一种陶瓷颜料和至少一种粘结剂的覆盖层。
2、如权利要求1所述的覆盖的硬质颗粒，其特征在于初始原料选自氧化铝、氧化锆、氧化硅、尖晶石和这些氧化物的混和物。
3、如权利要求2所述的覆盖硬质颗粒，其特征在于初始原料是刚玉。
4、如权利要求1-3的一项所述的包裹硬质颗粒，其特征在于颗粒大小为0.03-3mm。
5、如权利要求1-4的一项或多项所述的覆盖硬质颗粒，其特征在于在覆盖层颗粒中陶瓷颜料的量为覆盖层颗粒的5-10%重量。
6、如权利要求1-5的一项或多项所述的覆盖层硬质颗粒，其特征在于粘结剂选自硅酸、硅酸盐、无色釉玻璃料、磷酸铝或这些物质的混合物。
7、如权利要求6所述的覆盖的硬质颗粒，其特征在于粘结剂是碱金属硅酸盐。
8、一种生产如权利要求1-7的任一项或多项所述的覆盖硬质颗粒的方法，其特征在于用粘结剂的溶液或悬浮液来润湿被覆盖的硬质颗粒，随后与必需量的细粉状颜料混和并干燥。
9、如权利要求8所述的方法，其特征在于把碱金属硅酸盐的水溶液用作粘结剂溶液。
10、如权利要求8或9所述的方法，其特征在于硬质颗粒的覆盖层在干燥后于300-1200℃温度被硬化或煅烧。
11、一种如权利要求1-7的一项或多项所述的覆盖硬质颗粒的应用，其特征是加入到陶瓷釉或搪瓷中。
12、如权利要求11所述的应用，其特征在于在陶瓷面砖特别是地板面砖的釉面上用作耐磨添加剂和/或用来防滑。
13、如权利要求1-7的一个或多个权利要求所述的被覆盖着的硬质颗粒的应用，其特征在于加入到人造材料或涂层物质中。
14、如权利要求1-7的一个或多个权利要求所述的被覆盖着的颗粒的应用，其特征在于加入到粉刷材料中。
15、如权利要求1-7的一个或多个权利要求所述的包裹颗粒的应用，其特征在于加入到混凝土、人造石或灰泥中。
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PL297717A1 (en) 1993-09-06
NO930518D0 (no) 1993-02-12
EP0555849A2 (de) 1993-08-18
TR26989A (tr) 1994-09-13
LTIP337A (en) 1994-06-15
FI930574A0 (fi) 1993-02-10
JPH05339081A (ja) 1993-12-21

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