CN104364221A - 耐火陶瓷配料及由其形成的砖块 - Google Patents

耐火陶瓷配料及由其形成的砖块 Download PDF

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CN104364221A
CN104364221A CN201380031359.9A CN201380031359A CN104364221A CN 104364221 A CN104364221 A CN 104364221A CN 201380031359 A CN201380031359 A CN 201380031359A CN 104364221 A CN104364221 A CN 104364221A
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H·哈姆特
S·格希尔
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Abstract

本发明涉及一种耐火陶瓷配料及由其形成的耐火陶瓷砖块。

Description

耐火陶瓷配料及由其形成的砖块
本发明涉及一种耐火陶瓷配料，还涉及由其形成的耐火陶瓷砖块。
耐火陶瓷产品分为不同类型，例如碱性产品和非碱性产品。本发明只涉及碱性产品，即配料和砖块，其碱性基材由烧结氧化镁和/或熔融氧化镁组成。
由DE 44 03 869 C2和DE 198 59 372 C1已知各类的配料和砖块。除了碱性基材，已知产品包括尖晶石(铁铝尖晶石、锰尖晶石、锰铁尖晶石)。
已经发现，通过结合碱性基材和上述尖晶石，可以获得烧制产品的有益机械性能。特别是，改进(降低)烧制成型体的延展性(脆性)，在一些情况下改进耐腐蚀性，特别是耐碱腐蚀性。
需要指出的是，现阶段还不能完全理解在相应部分的烧制过程中的反应和烧结机理，尽管多种发现提出，在单个配料组分之间不发生完全的、致密的烧结，这意味着烧制部分还表现出一定程度的“弹性”(挠性)。换句话说，尽管在烧制时配料组分参与物理-化学相互作用，但是该产品仍然比单个配料组分具有更少脆性，并且整体上“更弹性”。
尽管在工业上前述耐火产品已经成功多年并且用于例如回转水泥窑的衬里，但是，仍存在进一步改进的需求，特别是关于烧制产品的耐热性。例如，在硅酸二钙-铝酸钙-尖晶石-方镁石系统中的不变点是仅约1325℃。
本发明的一个目的是提供一种碱性耐火陶瓷配料，由其形成的耐火成型部件除了具有有益的结构弹性外还具有高耐火性，该耐火性由高于1400℃的不变点确定。该烧制产品应优选还表现出特别良好的耐腐蚀性。
本发明区别于现有技术中指出的采用尖晶石与方镁石基材结合的路线。已经发现尖晶石的Al2O3含量对于降低烧制产品的耐热性是至关重要的。这在与配料组分CaO结合时尤其适用。尽管采用贫钙基材可以降低全部配料的CaO含量，但是当在使用过程中回收氧化钙时，这一问题仍然存在。例如，在水泥熟料生产中所用的回转窑就是这种情况。
大量测试表明，可以通过完全不同的配料组分，即选自包括碳化硅、碳氧化硅、碳氮氧化硅、氮化硅的组中的配料组分来消除这些缺陷。
如果，随着加入传统粘结剂例如木质素磺酸盐(例如，相对于全部配料的加入量为至多4质量％)，由所述配料压制并烧制(尤其在从1400℃至1600℃的温度范围)砖块，在依据本发明的产品中，在碱性(MgO)基材和粒状骨料之间只存在部分烧结桥接，其中特别形成以下矿物相：MgSiO3、Mg2SiO4、SiO2。在这种情况下，通过在(氧化)高温过程中SiC的氧化形成SiO2。在大多数情况下，SiO2与MgO反应并形成顽辉石。由于顽辉石在MgO旁并不稳定，邻近于此形成了镁橄榄石，其与碱性基材直接键合。
在测试中，已可能观察到最多一半的粒状骨料的表面与周围的碱性耐火基材烧结。在很多情况中，在烧制后，粒状骨料甚至松散地位于碱性基质中，换言之，在单独的骨料颗粒和碱性基质材料之间完全不存在固定连接。除了氧化镁，镁橄榄石也可能出现在骨料颗粒的直接环境中。可以通过对抛光截面的显微观测手段来了解粒状骨料与周围碱性耐火基材的烧结程度；结果表明了晶粒周边与周围的碱性基材烧结最多超过其长度的一半。
就这方面而言，根据本发明的耐火陶瓷产品的结构不同于现有技术中包含尖晶石的砖块的结构图。采用这种新产品，至少获得已知尖晶石产品表现出的延展性特征值。
相对于现有技术的这种状态，依据本发明的产品特性为具有明显更高的不变点，该不变点比具有铁铝尖晶石和/或锰尖晶石和/或锰铁尖晶石的产品的不变点一般高至少100℃，通常高大于200℃。耐火性也相应高。
在最普通的实施方案中，本发明包括具有以下组分的耐火陶瓷配料：
-75至98质量％的至少一种选自烧结氧化镁、熔融氧化镁的碱性基材，
-2至25质量％的至少一种选自碳化硅、氮化硅、碳氧化硅、碳氮氧化硅的粒状骨料，
-至多5质量％的其它成分，
-其中每个质量数据均是相对于全部配料。
通过以下变化可以最优化前述性能，只要没有明确排除，这些变化可以单独实现或者与另一变化相结合实施：
-采用的碱性基材中，＜125μm的粉末部分的比例在＞10和＜40质量％范围内(相对于全部配料)，
-采用的碱性基材中，＞1mm颗粒部分的比例为＞35质量％(相对于全部配料)，
-采用的粒状骨料的颗粒范围为＞125μm和＜3mm，其中下限也可以是＞0.5mm，且上限也可以是＜2mm，
-降低全部配料中粒状骨料的比例至2至10质量％的量，
-选择碱性基材，其本身包括至少95质量％的MgO，其中该比例优选甚至更高，例如超过97质量％，或者超过98.5质量％，
-调节骨料和碱性基材的粒径，使得碱性粒状基材(即除去＜125μm的粉末部分的碱性基材)的d90值高于粒状骨料的d90值，
-采用具有铁含量的碱性基材，以Fe2O3来测量，铁含量相对于碱性基材为小于0.6质量％，其中该比例应尽可能小，例如＜0.3质量％，
-选择碱性基体组分，使得其不含有或者相对于全部配料只含有少量(在每种情况下＜0.3质量％)的氧化铬和/或氧化铝，
-该骨料材料还应当尽可能纯，以便获得最佳的所需效果，其中优选相对于在全部配料中的骨料的质量百分比，骨料的杂成分尤其为＜5质量％。
由此，依据本发明的配料特别包括两种不同颗粒部分的配料组分(碱性基材、粒状骨料)，其中已经证明优选为碱性基材具有粉末部分(＜125μm)含量，而粒状骨料在该粉末范围外的颗粒部分中(以上，即在较粗颗粒中)应当是非常主要的存在(优选至少90％)。
除了主要由所用原料带来的少量杂质外，依据本发明的产品只包含氧化物CaO、MgO和SiO2(除了骨料中的碳化物和/或氮化物外)。所用碱性组分的CaO/SiO2比例相对高，且优选至少2，特别优选＞3、＞4或＞5。由此可获得比1700℃明显更高的不变点。
与硅连接的碳化物或氮化物也导致高CaO/SiO2比。这在关于烧制产品的腐蚀性要求方面也有益处。
当采用碳化硅在氧化高温过程时，可发生碳化硅的部分氧化，其导致更低的CaO/SiO2比。以这种方式，可带来增加的烧结，这在原则上是不期望的，因为其会增加脆性。
然而，在这种程度上，依据本发明的配料可以通过调整烧制时的炉内气氛来调整烧制产品的特定延展性。
最终，本发明使得烧制产品用碳浸润，例如沥青。这对于依据现有技术(具有铁铝尖晶石、锰铁尖晶石或锰尖晶石形式的尖晶石添加剂)的产品是不可能的，因为尖晶石包含铁或锰的氧化物，在实施温度下，这些铁或锰的氧化物将被浸润材料还原。这将导致浸润材料被氧化，并由此变得至少部分失效。相反，依据本发明的产品适于这类碳浸润，特别因为在实际实施方案中其已经包含碳化物物质(粒状骨料)。
为了制造依据本发明的陶瓷成型部件，配料中加入了粘结剂。可加入配料的粘结剂，例如，比例在1至4质量％的范围内，还特别优选比例在2至3质量％的范围内，每一个比例都是相对于100质量％的全部配料(因此，粘结剂的比例是被加入100质量％的配料)。
该依据本发明的耐火陶瓷成型部件在其最普通的实施方案中具有以下特征，每个特征都是在室温下确定的：
-产自上述种类的配料，
-之后压制成成型部件，
-接着在1400℃和1600℃之间的温度烧制，
-其中最多一半的粒状骨料与周围碱性基材烧结。
该砖块可以具有以下性能特征：
-弹性模量：＜60GPa
-断裂功：＞200Nm
-标称缺口抗张强度：＜9MPa
-特征长度：＞250mm
-不变点：＞1700℃。
弹性模量(E-模量)可以特别依据以下参考文献资料来确定：G Robben，BBollen，A Brebels，J van Humbeeck，O van der Biest：″Impulse excitation apparatus tomeasure resonant frequencies，elastic module and internal friction at room and hightemperature″，Review of Scientific Instruments，Vol.68，pp 4511-4515(1997)。
断裂功、标称缺口抗张强度及特征长度可以特别依据以下参考文献资料来确定：Harmuth H.，Manhart Ch.，Auer Th.，Gruber D.：″Fracture MechanicalCharacterisation of Refractories and Application for Assessment and Simulation of theThermal Shock Behaviour″，CFI Ceramic Forum International，Vol.84，No.9，pp E80-E86(2007)。
不变点可以特别由该砖块中存在的矿物相的相图来确定。
该砖块可以优选用于工业窑炉例如用于水泥熟料生产的回转窑中，也可以用于钢铁工业。
本发明的更多特征来自从属权利要求的特征及其它申请文件。
以下根据多个示例性实施方案的协助，从更详尽的细节角度阐述本发明。
四种不同耐火陶瓷配料详细列在下述表1中，其中配料S-1、S-2和S-3表示了依据本发明的配料的示例性实施方案，而配料S-0表示了并非依据本发明的对比配料的组成。其中所有配料的比例数据都是依据不同组分相对于对应的全部配料的100质量％计算的(质量％)。
配料组分 S-0 S-1 S-2 S-3
烧结氧化镁(颗粒部分3至5mm) 15.0 15.0 15.0 15.0
烧结氧化镁(颗粒部分1至＜3mm) 40.0 37.0 36.0 34.0
烧结氧化镁(颗粒部分0.125至＜1mm) 15.7 13.9 13.1 12.2
烧结氧化镁(粉末部分＜125μm) 29.3 29.1 28.9 28.8
碳化硅(颗粒部分0.5至1.7mm) 0 5 7 10
表1
在每种情况下采用依据表1的配料组分制造依据本发明的砖块的制备方法如下所示：
-混合配料组分与粘结剂，即相对于100质量％的全部配料，作为粘结剂的液态木质素磺酸盐为2.5质量％，
-采用140MPa的压力压制标准砖块(230×85×114mm)，
-在空气中于1400℃烧制该砖块8小时。
根据表1的配料制造的砖块的数据和性能特征如表2所示。在此，采用对应配料的标记(S-0、S-1、S-2、S-3)表示由该配料制造的每种砖块。
此外，为了比较的目的，基于碱性基材制造的四个其它耐火砖块的数据和性能特征列在表2中，这些砖块每一个都不是采用依据本发明的配料制造的。具体的，砖块A-D是以下类型的砖块：
A：基于具有94质量％MgO和6质量％Fe2O3的烧结氧化镁的烧制氧化镁砖块。
B：基于具有97质量％MgO、2质量％SiO2、0.6质量％CaO和0.4质量％Al2O3+Fe2O3+MnO的烧结氧化镁的烧制氧化镁砖块。
C：基于具有89.5质量％MgO和10.5质量％Al2O3的烧结氧化镁的烧制氧化镁-尖晶石砖块。
D：基于具有91.8质量％MgO、3.4质量％Al2O3、3.8质量％Fe2O3、0.7质量％CaO和0.3质量％SiO2的烧结氧化镁的烧制氧化镁-铁铝尖晶石砖块。
*1：在1400℃烧制；*2：在1500℃烧制
表2
在砖块S-0、S-1、S-2和S-3中所用的烧结氧化镁具有＞97质量％的MgO含量。所用的碳化硅具有大约95质量％的纯度。
表中所示性能值依据以下方法测定：
-弹性模量：依据前述″Review of Scientific Instruments″(1997)中参考文献的资料。示例性实施方案中弹性模量是在RFDA(谐振频率和阻尼分析仪)(由IMCE n.v.，Slingerweg 52，B-3600Genk制造)协助下测定的。
-断裂功、标称缺口抗张强度和特征长度：采用依据前述″CFI Ceramic ForumInternational″(2007)中参考文献的楔形劈裂试验的实施和评估方法来测定。
权利要求书(按照条约第19条的修改)
1.一种耐火陶瓷配料，具有如下组分：
a)75至98质量％的至少一种选自烧结氧化镁、熔融氧化镁的碱性基材，
b)2至25质量％的至少一种选自碳化硅、氮化硅、碳氧化硅、碳氮氧化硅的粒状骨料，
c)至多5质量％的其它成分，
以上每种均是相对于全部配料，其中
d)该碱性基材中存在相对于全部配料比例在＞10至＜40质量％范围内的＜125μm的粉末部分，及
e)该粒状骨料中存在＞125μm和＜2mm的颗粒部分。
2.依据权利要求1所述的耐火陶瓷配料，其碱性基材中存在相对于全部配料比例在＞35质量％范围内的＞1mm的颗粒部分。
3.依据权利要求1所述的耐火陶瓷配料，其粒状骨料中存在＞0.5mm和＜2mm的颗粒部分。
4.依据权利要求1所述的耐火陶瓷配料，其粒状骨料相对于全部配料的量为2-10质量％。
5.依据权利要求1所述的耐火陶瓷配料，其碱性基材包括至少95质量％的MgO。
6.依据权利要求1所述的耐火陶瓷配料，其除粉末部分外的碱性粒状基材的d90值高于粒状骨料的d90值。
7.依据权利要求1所述的耐火陶瓷配料，其中碱性基材具有以Fe2O3测量的相对于碱性基材小于0.6质量％的铁含量。
8.依据权利要求1所述的耐火陶瓷配料，其包含相对于全部配料为小于0.3质量％的氧化铝。
9.依据权利要求1所述的耐火陶瓷配料，其包含相对于全部配料为小于0.3质量％的氧化铬。
10.依据权利要求1所述的耐火陶瓷配料，其粒状骨料包含相对于全部配料中的骨料质量百分比最大为5质量％的其它成分。
11.一种耐火陶瓷砖块，其由如权利要求1所述的配料通过压制和在1400℃和1600℃之间烧制制成，其中最多一半的所述粒状骨料与周围碱性基材烧结。
12.依据权利要求11所述的耐火陶瓷砖块，具有如下性能参数中的至少一种：
a)弹性模量：＜60GPa
b)断裂功：＞200N/m
c)标称缺口抗张强度：＜9MPa
d)特征长度：＞250mm
e)不变点：＞1700℃。

Claims (14)

1.一种耐火陶瓷配料，具有如下组分：
a)75至98质量％的至少一种选自烧结氧化镁、熔融氧化镁的碱性基材，
b)2至25质量％的至少一种选自碳化硅、氮化硅、碳氧化硅、碳氮氧化硅的粒状骨料，
c)至多5质量％的其它成分，
以上每种均是相对于全部配料。
2.依据权利要求1所述的耐火陶瓷配料，其碱性基材中存在相对于全部配料比例在＞10至＜40质量％范围内的＜125μm的粉末部分。
3.依据权利要求1所述的耐火陶瓷配料，其碱性基材中存在相对于全部配料比例在＞35质量％范围内的＞1mm的颗粒部分。
4.依据权利要求1所述的耐火陶瓷配料，其粒状骨料中存在＞125μm和＜3mm的颗粒部分。
5.依据权利要求1所述的耐火陶瓷配料，其粒状骨料中存在＞0.5mm和＜2mm的颗粒部分。
6.依据权利要求1所述的耐火陶瓷配料，其粒状骨料相对于全部配料的量为2-10质量％。
7.依据权利要求1所述的耐火陶瓷配料，其碱性基材包括至少95质量％的MgO。
8.依据权利要求1所述的耐火陶瓷配料，其中除粉末部分外的碱性粒状基材的d90值高于粒状骨料的d90值。
9.依据权利要求1所述的耐火陶瓷配料，其碱性基材具有以Fe2O3测量的相对于碱性基材小于0.6质量％的铁含量。
10.依据权利要求1所述的耐火陶瓷配料，其包含相对于全部配料为小于0.3质量％的氧化铝。
11.依据权利要求1所述的耐火陶瓷配料，其包含相对于全部配料为小于0.3质量％的氧化铬。
12.依据权利要求1所述的耐火陶瓷配料，其粒状骨料包含相对于全部配料中的骨料质量百分比最大为5质量％的其它成分。
13.一种耐火陶瓷砖块，其由如权利要求1所述的配料通过压制和在1400℃和1600℃之间烧制制成，其中最多一半的所述粒状骨料与周围碱性基材烧结。
14.依据权利要求13所述的耐火陶瓷砖块，具有如下性能参数中的至少一种：
a)弹性模量：＜60GPa
b)断裂功：＞200N/m
c)标称缺口抗张强度：＜9MPa
d)特征长度：＞250mm
e)不变点：＞1700℃。
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