CN101356136A - 防火模制品或材料及其生产方法 - Google Patents

防火模制品或材料及其生产方法 Download PDF

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CN101356136A
CN101356136A CNA2006800404884A CN200680040488A CN101356136A CN 101356136 A CN101356136 A CN 101356136A CN A2006800404884 A CNA2006800404884 A CN A2006800404884A CN 200680040488 A CN200680040488 A CN 200680040488A CN 101356136 A CN101356136 A CN 101356136A
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Prior art keywords
carbon
mixture
molded articles
oxide
titanium
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C·G·阿内齐里斯
J·胡巴尔科瓦
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Technische Universitaet Bergakademie Freiberg
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Technische Universitaet Bergakademie Freiberg
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Abstract

本发明涉及防火模制品或材料，还涉及在氧化镁、氧化铝、氧化锆莫来石、二氧化锆、镁铝尖晶石、铝矾土、氧化钇、碳化硅、氮化硅或氮化硼产品，或例如压制碳粘结砖、碳粘结滑动板或碳粘结浸入式喷嘴或浇铸含碳和/或碳粘结产品或碳粘结塞的碳粘结产品的混合物中获得高强度粘结相的方法，其具有改善的机械、热学和化学性能。防火模制品或材料的粘结基体包含碳化钛相和/或碳氮化钛相。防火模制品或材料由基于碳化混合物的氧化的和/或非氧化的和/或含碳的防火颗粒和粘合剂组成，其中加入细颗粒二氧化钛、钛铁矿、FeTiO3、CaTiO3、MgTiO3、BaTiO3或它们的混合物，或还加入一种或多种元素金属颗粒。

Description

防火模制品或材料及其生产方法
本发明涉及防火模制品或材料，还涉及在氧化镁、氧化铝、氧化锆莫来石、二氧化锆、镁铝尖晶石、铝矾土、氧化钇、碳化硅、氮化硅、氮化硼产品中或在例如压制碳粘结砖、碳粘结滑动板或碳粘结浸入式喷嘴或铸造的含碳和/或碳粘结产品或碳粘结塞的碳粘结产品混合物中，获得高强度粘结相的方法，这些产品具有改善的机械、热学和化学性能。本发明的方法也能用于生产没有碳添加剂的防火产品。
碳粘结产品在冶金转炉炉身中广泛应用为内衬，例如转炉中的碳粘结氧化镁砖，或关键部件，例如浸入式喷嘴或滑动板或塞或在连续铸造区域中的浇注槽。碳粘结防火产品也用于传输容器中的鼓风炉区域，例如钢水包，或在化学工业或废物再生工业中用作耐温管道，或在水泥工业中用作内衬材料。酚醛树脂类如酚醛树脂A或线形酚醛清漆，合成煤焦油如carbores，或天然煤焦油或沥青，优选作为粘合剂。金属添加剂，例如Si或Al或Mg优选地用于优化含碳产品的抗氧化性。
德国公开专利申请DE19954893A1公开了氧化性能改善的碳粘结产品。通过将选自易还原的过渡元素化合物的催化活性物质，尤其是铜、铬、镍或铁的茂金属或金属苯甲酸盐(metallobenzoates)或金属环烷酸盐(metallonaphthenates)加入到合成树脂组分中，在1000℃产生出结晶的高度石墨化的碳，有助于改善化学性能。
在Akria Jamaguchi等人发表于J.Amer.Ceram.Society的“Effect ofrefractory oxides on the oxidation of graphite and amorphous carbon”中，在没有粘合剂的情况下，石墨和无定形碳与Al2O3、MgO、TiO2和ZrO2混合在一起，并用热分析的方法检测它们直到1000℃的“放热反应曲线图”(exothermy)。
自90年代以来，从通过CVD(化学气相沉积)法得到的金属工具上的涂层知道TiCN相具有突出的侵蚀、腐蚀、磨损和氧化性能(“Bandstructures of substoichiometric titanium nirtrides and carbonitrides：spectroscopical and theoretical inverstigations”，M.Guemmaz，G.Moraitis，J.Phys：Condens.Matter 9(1997)8453-8463)。然而，直到那时也没有考虑到使用这种钛化合物生产防火模制品。然而对于在应用温度高，尤其是在高于1500℃应用防火模制品的使用者，为了延长高应力防火产品的使用年限，努力进一步改善机械、热学和化学性能是值得的。
DE19935251A1公开了使用含TiO2微粒材料作为防火产品的添加剂，其中将含TiO2材料加入到骨料和粘合剂的混合物中。在这种情况下，结晶态TiO2保留在产品中。当被液态炉渣渗透或熔化时，TiO2部份溶解并反应形成氮化钛或碳氮化钛。该反应不仅影响这种防火产品的稳定性，而且影响接触这种产品的炉渣或熔融物。
EP1275626A1公开了碳粘结防火材料，该材料由5-85重量％的碳、5-15重量％的氧化铝或氧化铝和其它材料的混合物、5-15重量％的金属硅、5-20重量％的Ti、TiN、TiCN和/或TiC制成。将粘合剂加入该起始混合物中，接着将混合物捏合、成型且压制形成模制品，随后在1250℃烧制。不考虑Ti添加剂价格昂贵的事实，结晶的Ti添加剂仍保留在防火材料中。
本发明的目的是制造有或没有碳添加剂的防火模制品或材料，其具有热塑变形性，且还具有改善的热机械性能和氧化性能，及高强度的粘结相。
本发明的目的是通过防火模制品或材料实现的，该防火模制品或材料是基于氧化的和/或非氧化的和/或含碳的防火颗粒和粘合剂的碳化混合物，该混合物中加入了细颗粒的二氧化钛或钛铁矿或FeTiO3或CaTiO3或MgTiO3或BaTiO3或它们的混合物，或还加入一种或多种元素金属颗粒，且其中粘结基体中含有碳化钛相和/或碳氮化钛相。
细粒的二氧化钛或钛铁矿或FeTiO3或CaTiO3或MgTiO3或BaTiO3或额外的一种或多种元素金属颗粒的加入，导致本发明的防火模制品或材料为具有碳化钛相和/或碳氮化钛相的高强度的粘结基体。除碳化钛相和/或碳氮化钛相之外，如果还加入另外的一种或多种元素金属颗粒，该粘结基体还含有结晶的金属碳化物和/或金属碳氧化物(metaloxicarbides)。与现有技术相比，碳化钛相和/或碳氮化钛相，和有加入金属时的金属碳化物和/或金属碳氧化物，使得本发明的防火模制品或材料在高温使用时稳定。
所述一种或多种金属颗粒选自Al、Si、Ti、Mg、Fe、Mo和/或W。除直接加入到粘合剂中之外，这些颗粒也能加入到防火颗粒和粘合剂的混合物中。
氧化的防火颗粒由氧化镁或氧化铝或氧化锆莫来石或二氧化锆或镁铝尖晶石或铝矾土或氧化钇或这些氧化物的混合物组成。
非氧化的防火颗粒由碳化硅或氮化硅或氮化硼或它们的混合物组成。
含碳的防火颗粒由石墨和/或炭黑组成。
在本发明的有益的实施方式中，防火模制品或材料的组成是基于氧化镁和粘合剂的碳化混合物，其中加入了细颗粒二氧化钛和单质铝，在高达1000℃的碳化温度下，它们的粘结基体包含碳化钛相和/或碳氮化钛相，以及碳化钛(TiC)、碳化铝(Al4C3)和碳化铝钛(Al2Ti4C)和碳氧化铝(Al2OC)。在高于1500℃的更高的碳化温度下，粘结相包含稳定的、结晶化的碳化钛和碳化铝相。
本发明的防火模制品或材料是由氧化的和/或非氧化的和/或含碳的防火颗粒和基于合成树脂和/或沥青和/或合成煤焦油和/或天然煤焦油的粘合剂的混合物制成的。在这种情况下粘合剂中加入细颗粒的二氧化钛或钛铁矿或FeTiO3或CaTiO3或MgTiO3或BaTiO3、或还加入一种或多种元素金属颗粒，根据加入的金属，混合物在粘结基体中原位生成碳化钛相和/或碳氮化钛相和/或金属碳化物和/或金属碳氧化物和/或更多的碳化物和/或碳氧化物的温度下碳化。
如果在粘合剂中单独加入二氧化钛，碳化温度高于1200℃。进一步地在更高的温度下或在操作温度应用过程中进一步形成碳化钛相和/或碳氮化钛相。
在加TiO2或不加TiO2的条件下，如果在粘合剂中加入钛铁矿和/或FeTiO3和/或CaTiO3和/或MgTiO3和/或BaTiO3，那么碳化温度低于1200℃，优选低于1000℃。
在本发明的有益的实施方式中，选自Al、Si、Ti、Y、Mg、Fe、Mo或W的一种或多种元素金属颗粒加入到混合物和/或粘合剂中。为了制造具有碳化钛相和/或碳氮化钛相的粘结基体，碳化温度低于1200℃。
氧化的防火颗粒由氧化镁或氧化铝或氧化锆莫来石或二氧化锆或镁铝尖晶石或铝矾土或氧化钇或这些氧化物的混合物组成。
非氧化的防火颗粒由碳化硅或氮化硅或氮化硼或它们的混合物组成。
含碳的防火颗粒由石墨和/或炭黑组成。
细颗粒的二氧化钛和/或钛铁矿和/或FeTiO3和/或CaTiO3和/或MgTiO3和/或BaTiO3以2重量％的最大量，优选以0.3至1.5重量％加入到粘合剂中。
相对于使用的混合物，加入最大量为3重量％的，优选1至2重量％的单质金属。
根据本发明，细颗粒的二氧化钛(TiO2)或细颗粒的含钛原料、或细颗粒的有或无基于Al、Mg、Si、Ti、Fe、Y的金属或它们的混合物的含钛材料，加入到基于合成树脂、沥青或合成煤焦油或天然煤焦油或它们的混合物的粘合剂中，并进一步与不同组份的含或不含炭黑的石墨以及与如MgO或Al2O3或ZrO2的防火氧化物，在集中混合器中混合，并通过加或不加水、增塑剂和水泥的压制方法或铸造方法转换成产品。根据本发明，在高达1000℃下碳化后或在1300至1500℃之间的碳化过程后，产品获得粘结相，其具有突出的机械、热学和化学性能。钛铁矿、FeTiO3、CaTiO3、MgTiO3和BaTiO3作为含钛原料或含钛材料。优选铁钛矿或钛铁矿既能在1000℃以下反应产生石墨又能反应产生粘结相中的碳化钛和/或碳氮化钛。
仅向粘合剂中加入细粒的二氧化钛和/或钛铁矿和/或FeTiO3和/或CaTiO3和/或MgTiO3和/或BaTiO3，和额外的一种或多种元素金属颗粒，导致根据本发明生产的防火模制品或材料为高强度粘结基体，其具有碳化钛相和/或碳氮化钛相，或在加入金属的情况下还具有另外的金属碳化物和/或金属碳氧化物。与现有技术相比，粘结基体中原位生成的碳化钛相和/或碳氮化钛相和/或金属碳化物和/或金属碳氧化物改善了高温下使用的本发明防火模制品或材料的机械、热学和化学性能。另外，它们提高了蠕变稳定性。
就防火产品来说，在结构中粘结相的连接最不牢固。根据本发明、根据被提及的方法，通过将这些添加剂添加在粘合剂中和在粘结基体中形成这些相，粘结相被增强。根据本发明，这些产生的相在更高的碳化温度或应用温度下也仍保持结晶态。在高于1500℃的更高的碳化温度下形成稳定、结晶的碳化钛和金属碳化物相。
二氧化钛和/或钛铁矿和/或FeTiO3和/或CaTiO3和/或MgTiO3和/或BaTiO3的颗粒尺寸小于5μm，优选小于2μm。
加入的金属的颗粒尺寸在5至150μm之间。
在本发明方法的有益的实施方式中，防火模制品或材料是基于氧化镁和粘合剂的混合物制备的，混合物中加入细颗粒的二氧化钛和单质铝，在高达1000℃下碳化。这种方法制备的模制品或材料在粘结基体中包含碳化钛相和/或碳氮化钛相及碳化钛(TiC)、碳化铝(Al4C3)和碳化铝钛(Al2Ti4C)和碳氧化铝(Al2OC)。
本发明的示范性实施方式详细描述如下：
本发明有益的机械、热学和化学性能基于冶金学应用的转炉中的碳粘结氧化镁产品得以证实。直径50mm和高50mm的圆柱实验室样品由三种混合物以120MPa的压力通过单方向压制而成。混合物列于表1。
在本发明的混合物2(表1)中，单加入TiO2不加金属在应用温度高于1300℃下粘结相中伴随少量未反应的TiO2形成碳氮化钛(TiC0.7N0.3)。与只加入铝的合成树脂粘结产品相比，根据本发明，从1500℃开始，粘结相中只存在碳氮化钛(TiCN)，其赋予碳粘结产品显著更高的抗氧化性、机械强度和抗热震性。
在本发明的混合物3(表1)中，加入TiO2和铝金属，在高于1000℃的温度下，形成碳化钛(TiC)、碳化铝(Al4C3)和碳化铝钛(Al2Ti4C)和碳氧化铝(Al2OC)。根据本发明在更高的温度下，尤其是在1500℃下粘结相主要由碳化铝和碳化钛组成。与只加含铝添加剂的合成树脂粘结产品相比，粘结基体中的这两相从1000℃已经开始赋予碳粘结产品显著更高的抗氧化性、机械强度和抗热震性。
混合物1是现有技术的对比混合物。
表1：混合物1、2和3的组成。
Figure A20068004048800091
Figure A20068004048800101
表2是，在1000℃下碳化后，在氧气氛中于1200℃下氧化测试3小时后的开口孔隙率、冷压强度和氧化深度。
表2：混合物1、2和3的性能。
  混合物1   混合物2   混合物3
  开口孔隙率(体积％)   13.04   13.1   11.3
  冷压强度(MPa)   22   23   32
  氧化深度(mm)   8-10   2-3   1-2
混合物2和3具有显著较小的氧化深度，且混合物3还具有突出的强度。由于在较高温度下于粘结基体中突出形成的非常一致的碳化钛相和碳氮化钛相，粘结剂中添加有二氧化钛的混合物2和3的机械、热学和化学性能在高于1500℃的应用温度下尤其进一步得以增强。与碳化铝相相比，取决于防火系统，由于碳氮化钛相的显著较高的抗氧化性和稳定性，单添加二氧化钛能赋予防火产品显著的优点。
图1是有TiCN相的非线性碳化混合物2的REM(扫描电子显微镜)照片。原位生成的TiCN的颗粒尺寸处于纳米范围。这也赋予粘结相高强度，因此增强了机械和热力学性能。
图2是在1000℃下碳化，并于1200℃下在空气中抗氧化测试3小时后的MgO-C碳粘结产品，(从左至右)基于没有添加剂、有Al添加剂的、有TiO2添加剂的及有Al和TiO2添加剂的线形酚醛清漆粘合剂的MgO-C产品。单添加TiO2降低了脱碳/氧化深度。添加TiO2和Al的结合进一步增强了抗氧化性。基本没有可见的脱碳迹象。
图3和图4是添加有Al和TiO2的混合物3的粘结基体的断裂表面的REM(扫描电子显微镜)照片。由碳化铝、碳氧化铝和碳化钛形成的哑铃状结构赋予防火产品突出的热力-机械性能，包括抗氧化性和抗侵蚀性。

Claims (15)

1.基于氧化的和/或非氧化的和/或含碳的防火颗粒和粘合剂的碳化混合物的防火模制品或材料，其中加入了细颗粒的二氧化钛或钛铁矿或FeTiO3或CaTiO3或MgTiO3或BaTiO3或它们的混合物，或还加入一种或多种元素金属颗粒，且其中粘结基体包含碳化钛相和/或碳氮化钛相。
2.根据权利要求1的防火模制品或材料，其特征在于一种或多种元素金属颗粒选自Al、Si、Ti、Mg、Fe、Mo和/或W，且粘结基体进一步包含金属碳化物和/或金属碳氧化物。
3.根据权利要求1或2的防火模制品或材料，其特征在于氧化的防火颗粒由氧化镁或氧化铝或氧化锆莫来石或二氧化锆或镁铝尖晶石或铝矾土或氧化钇或这些氧化物的混合物组成，非氧化的防火颗粒由碳化硅或氮化硅或氮化硼或它们的混合物组成，含碳的防火颗粒由石墨和/或炭黑组成。
4.由具有基于合成树脂和/或沥青和/或合成煤焦油和/或天然煤焦油的粘合剂与氧化的和/或非氧化的和/或含碳的防火颗粒的混合物制备防火模制品或材料的方法，其特征在于，向粘合剂中加入细颗粒的二氧化钛和/或钛铁矿和/或FeTiO3和/或CaTiO3和/或MgTiO3和/或BaTiO3，其中将该混合物在粘结基体中产生碳化钛相和/或碳氮化钛相的温度下碳化。
5.根据权利要求4所述的方法，其特征在于单独添加TiO2时的碳化温度高于1200℃。
6.根据权利要求4所述的方法，其特征在于在有TiO2或无TiO2时加入钛铁矿和/或FeTiO3和/或CaTiO3和/或MgTiO3和/或BaTiO3时的碳化温度低于1200℃。
7.根据权利要求4所述的方法，其特征在于向所述混合物和/或粘合剂中还加入一种或多种选自Al、Si、Ti、Y、Mg、Fe、Mo和/或W的元素金属颗粒，将该混合物在高达1000℃下碳化，其中粘结基体中产生碳化钛相和/或碳氮化钛相和金属碳化物和/或金属碳氧化物。
8.根据权利要求4-7中任一项的方法，其特征在于氧化的防火颗粒是氧化镁、氧化铝、氧化锆莫来石、二氧化锆、镁铝尖晶石、铝矾土或氧化钇或这些氧化物的混合物，非氧化的防火颗粒是碳化硅、氮化硅、氮化硼或它们的混合物，含碳防火颗粒由石墨和/或炭黑组成。
9.根据权利要求4-8中任一项的方法，其特征在于细颗粒的二氧化钛和/或钛铁矿和/或FeTiO3和/或CaTiO3和/或MgTiO3和/或BaTiO3，以2重量％的最大量加入到粘合剂中。
10.根据权利要求4-9中任一项的方法，其特征在于一种或多种元素金属颗粒以相对于混合物的3重量％的最大量加入到粘合剂或混合物中。
11.根据权利要求4-10中任一项的方法，其特征在于为了生产模制品，在碳化前成型和压制该混合物。
12.根据权利要求4-11中任一项的方法，其特征在于二氧化钛和/或钛铁矿和/或FeTiO3和/或CaTiO3和/或MgTiO3和/或BaTiO3的颗粒尺寸小于5μm。
13.根据权利要求4-12中任一项的方法，其特征在于加入的金属的颗粒尺寸是5μm至150μm。
14.根据权利要求1至3的防火模制品或防火材料用于碳粘结产品或含碳产品的用途。
15.根据权利要求14的用途，其特征在于碳粘结产品是压制的碳粘结砖、碳粘结滑动板或碳粘结浸入式喷嘴或浇铸含碳产品或碳粘结塞。
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