CN101977872A - 耐火陶瓷制品和所属的模制件 - Google Patents

耐火陶瓷制品和所属的模制件 Download PDF

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CN101977872A
CN101977872A CN2009801092116A CN200980109211A CN101977872A CN 101977872 A CN101977872 A CN 101977872A CN 2009801092116 A CN2009801092116 A CN 2009801092116A CN 200980109211 A CN200980109211 A CN 200980109211A CN 101977872 A CN101977872 A CN 101977872A
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R·尼利卡
M-A·米勒
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Abstract

本发明涉及耐火陶瓷制品以及使用该制品制造的模制件。

Description

耐火陶瓷制品和所属的模制件
本发明涉及耐火陶瓷制品以及用该制品制造的模制件。
基于氧化镁(MgO)的耐火陶瓷材料以及由此制造的坯料和模制件用来衬砌高温机组，例如钢铁工业、有色金属工业(非铁工业)用的工业窑炉，同样已知用来衬砌煅烧矿物原料的窑炉。
或多或少纯的MgO制品的缺点是耐温度交变性较差。在这方面，已知有许多不同的措施，来改善基础模制件即基于MgO的模制件的机械特性值。属于这方面的有含有尖晶石添加剂如铁尖晶石的MgO制品(DE 4403869)。相应的产品已基本上得到证明是有效的。然而，高温强度有时还不够高。
在MgO制品中掺加铬铁矿有缺点：在耐火材料的按规定的应用中可能形成有毒的铬酸盐。
本发明的任务在于，提出一种基于MgO的断裂机械特性良好的耐火陶瓷制品。
本发明基于下列考虑：在基于MgO的，亦即带有方镁石主要结构相的耐火陶瓷模制件中，结合有具有本质不同的特性的第二结构相，以在承受机械负载时在结构中获得裂纹分支并以此提高断裂能量。
在系统的探索中，作为这种适当的第二相发现一种耐火陶瓷制品，其95质量％以上由MgO和锆酸钙组成，并从熔融物获得。
为了制造这种产品，在电炉(例如电弧炉)中共同熔化MgO原料(例如，烧结氧化镁或熔融氧化镁)、钙载体(例如，煅烧石灰)以及二氧化锆(ZrO2)。选择原料成分中的质量份额，使得方镁石和锆酸钙在熔化过程中的反应之后处于平衡。例如，MgO的比例可为50至60质量％，氧化钙的比例可为10至18质量％，而ZrO2的比例可为25至35质量％。
通过原料成分一起熔融并随后结晶而产生MgO和锆酸钙结构相，它们彼此交互生长，就是说，相互至少部分地三维包围。这种组织结构的特征在于贯穿结构(英文：蠕状的交互生长(myrmekitic intergrowths)；贯穿组织(penetration textures))，其他详情参见专业书籍Paul Ramdohr博士的″The Ore Minerals And Their Intergrowths(矿石矿物及其相互生长)″，Pergamon Press，Akademie-Verlag GmbH，New York，1969，109-127。相应的公开附此作参考。
这种制品在进一步加工(粉碎)之后可作为填充组分(颗粒)与相应粒度的烧结或熔融氧化镁以及诸如临时粘结剂等常用添加剂一起，加工成耐火陶瓷模制件。
由凝固的熔融物形成的耐火陶瓷制品(下文称作熔凝颗粒)在其最一般的实施方式中含有≥95质量％的MgO和锆酸钙组分，而基于MgO的耐火陶瓷模制件在其最一般的实施方式中的特征在于上述类型产品的比例在3和30质量％之间。
按照一个实施方式，熔凝颗粒具有＞质量15％的MgO比例。按照另一个实施方式，锆酸钙的质量份额＞30％。
按照相应的初步试验，熔凝颗粒中的MgO比例在45和65质量％之间，以及锆酸钙比例在35和55质量％之间生产比较有利。
重要的是，为了不危及熔凝颗粒的高熔点以及由此达到的有利的高温强度，诸如Al2O3、SiO2、TiO2或Fe2O3等副成分(作为氧化物给出和计算)要保持尽可能低，在任何情况下总计≤5质量％，其中按照一个实施方式氧化铝含量应＜2质量％，按照另一个实施方式SiO2含量应该＜1质量％。
由于这种添加剂从熔体制得，其开敞孔隙率相对较小，按照一个实施方式＜8％(按体积计)。
在耐火陶瓷模制件中由熔凝颗粒形成的结构相的比例可以在上述极限值(3至30质量％)以内限制为＞5且＜20质量％。
按照一个实施方式，由于MgO结构基质，该模制件的至少95质量％由方镁石和锆酸钙结构相构成。
在经煅烧的耐火陶瓷模制件中熔融材料各个结构相也彼此三维交互生长，即相互包围(围绕)。这对于模制件断裂机械特性有重要影响。若熔凝颗粒受到裂纹影响，则裂纹以特征方式穿过颗粒发展。这时，裂纹在界面上顺着MgO的解理性走向锆酸钙，并在另一方向上离开锆酸钙。在MgO上再一次出现时，裂纹再次偏向MgO的解理性方向。这样往往出现分阶形成的齿状裂缝侧面。
MgO(方镁石)和锆酸钙的高熔点导致明显超过2000°的高不变点，因此导致良好的高温强度值。
后面的实施例表示按照本发明的产品与传统的MgO模制件(砖)比较的断裂机械数据。这涉及具体的试验值，可以看出带有一定比例的本发明熔凝颗粒的耐火陶瓷模制件与纯MgO制品相比可以如何改善断裂机械特性的基本趋势。
由从属权项的特征以及其它申请材料可以看出本发明的其他特征。其包括选择熔凝颗粒的适当粒度，例如0.3至3mm，特别是0.5至2mm，和MgO基质组分(＜5mm，以及＜3mm，其中细颗粒部分＜100μm)。MgO+锆酸钙的比例还可以≥97质量％。另外，模制件的开敞孔隙率可为＜20％(按体积计)，还可为＜15％(按体积计)。
在后面的示例中，使用由凝固的熔融物构成的陶瓷制品(熔凝颗粒)，它含有MgO约52质量％和锆酸钙约46质量％，其余杂质如Al2O3，SiO2，TiO2，Fe2O3。
Figure BPA00001235495400031
为了制造相应的模制件，分别加入聚乙烯醇(20％溶液)，相对于100％(按质量计)MgO-基质组分计其量为2.5％(按质量计)，压成模制件并在1750℃下煅烧。
楔形间隙试验的结果(表示为断裂能量，J/m2)用曲线图示于图1，其中垂直位移σv[mm]相对于垂直荷载Fv[N]作图。曲线图上的数字与上表中示例的命名法一致。由此可以看出，通过在批料中加入熔凝颗粒，砖的单位断裂能量显著提高。
1)按照DIN EN 993-1测定
2)按照DIN EN 993-1测定
3)按照DIN-EN 993-7测定
4)按照WO2005/085155A1测定

Claims (14)

1.由凝固的熔融物形成的耐火陶瓷制品，其≥95质量％由MgO和锆酸钙构成。
2.按照权利要求1的制品，其≥97质量％由MgO和锆酸钙构成。
3.按照权利要求1的制品，其MgO比例＞15质量％。
4.按照权利要求1的制品，其锆酸钙比例＞30质量％。
5.按照权利要求1的制品，其MgO比例在45和65质量％之间，锆酸钙比例在35和55质量％之间。
6.按照权利要求1的制品，其Al2O3含量＜2质量％。
7.按照权利要求1的制品，其SiO2含量＜1质量％。
8.按照权利要求1的制品，其开敞孔隙率＜8体积％。
9.基质基于MgO并且含有3-30质量％的权利要求1至8中任一项的产品的耐火陶瓷模制件。
10.含5-20质量％的权利要求1至8中任一项的产品的耐火陶瓷模制件。
11.按照权利要求9的模制件，其＞95质量％由方镁石和锆酸钙结构相组成。
12.按照权利要求9的模制件，其＞97质量％由方镁石和锆酸钙结构相组成。
13.按照权利要求9的模制件，其中所述制品具有贯穿结构。
14.按照权利要求9的模制件，其开敞孔隙率＜20体积％。
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AR071320A1 (es) 2010-06-09
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