CN101068758B - 基于碳化硅与氮化硅粘合剂的烧结耐火砖 - Google Patents

基于碳化硅与氮化硅粘合剂的烧结耐火砖 Download PDF

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CN101068758B
CN101068758B CN2005800409436A CN200580040943A CN101068758B CN 101068758 B CN101068758 B CN 101068758B CN 2005800409436 A CN2005800409436 A CN 2005800409436A CN 200580040943 A CN200580040943 A CN 200580040943A CN 101068758 B CN101068758 B CN 101068758B
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refractory block
block according
sintered refractory
boron
sintered
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CN101068758A (zh
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埃里克·乔戈
奥利弗·马古因
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Saint Gobain Centre de Recherche et dEtudes Europeen SAS
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Abstract

一种基于碳化硅(SiC)与氮化硅(Si3N4)粘合剂的烧结耐火砖，具体应用于制造铝电解槽，其特点是该烧结耐火砖包括以重量百分比计算的至少0.05％的硼和/或0.05％至1.2％的钙。

Description

基于碳化硅与氮化硅粘合剂的烧结耐火砖
技术领域
本发明涉及特别是用于制造铝电解槽的新型烧结耐火砖及其制造方法，和本发明涉及一种包括上述耐火砖的电解槽。
背景技术
如图1所示，通过电解在基于熔融冰晶石的电解质溶液10中的溶解的氧化铝，可以以工业规模生产铝金属2。按照惯例，电解质溶液10装于一电解槽12内。电解槽12包括侧壁14和底部16。底部16由耐火底砖17、阴极24以及位于较低部分的绝缘块组成。侧壁14由金属外壳20环绕的侧部耐火砖18构成。
侧部耐火砖18的尺寸可以不同。现有的侧部耐火砖超过30×100×100mm(毫米)，并可达到120×300×300mm。
耐火砖18的成分可基于碳(石墨和/或无烟煤)。典型地，用于耐火砖18的灰泥是耐火水泥21，设置在耐火砖间以及耐火砖和金属外壳20间。电解槽12包括至少一个阳极22和至少一个阴极24。设置阳极22和阴极24使其可以接触到熔融的金属电解质，阴极24通常被设置在靠近底部16。
当给电极22和24通上电时，在电解质溶液10中发生电解反应，在电解槽内形成铝的电解液，该电解液沉积在阴极上。
在焦耳效应下，通过电解质溶液10的高电流还会引起热量释放。通过电解槽12的侧壁14排出该热量会使固化的冰晶石层26沉积在耐火砖18的内表面27上。该层称为“自衬里(self-lining)”层。
耐火砖18必须保护金属外壳20并允许充分散热，以确保熔融的电解质溶液10内的温度稳定。特别是，避免达到超过固化的冰晶石的自衬里层26再次液化而使电解槽四周迅速腐蚀的温度是至关重要的。此外，耐火砖18经常暴露于腐蚀性环境(极热的液态金属、下部为熔融的冰晶石、上部为腐蚀性气体)中，并承受高温、高热量和机械应力。
为了满足这些需求，已经知道基于碳化硅颗粒的耐火砖一般具有令人满意的耐腐蚀性。通常，碳化硅颗粒在1600℃至约2000℃的温度范围烧结。还知道，在极高的温度(2150℃)下烧结细粒碳化硅颗粒时，可以加入硼和碳。但是，碳化硅极其难于烧结并且/或者其造价极其昂贵。此外，特别是由于在烧制时大量收缩，烧结碳化硅耐火砖的烧结形式是受到限制的。
还知道，基于致密烧结碳化硅颗粒的耐火砖只有不到1％的B4C和C，例如Hexolloy
Figure S05840943620070531D000021
然而，目前这类耐火砖极为昂贵。
最后，已经知道基于碳化硅(SiC)的耐火砖由氮化硅(Si3N4)填质粘结。用于这种耐火砖的粘合剂在七十年代末开发，并在例如美国US-A-2752258号专利中描述。与碳耐火砖相比，这种耐火砖提高了在抗氧化性、机械强度(腐蚀)和导热性之间的兼顾性。当在磁场作用下电解质溶液移动时，该电解质溶液可能会给电解槽底部造成很大的磨损，这种耐火砖在耐磨性方面的改善特别有利于电解槽的底部。
在氮气氛中烧制碳化硅和硅的混合物，该碳化硅和硅的混合物与来自氮气氛中的氮反应性烧结，得到上述耐火砖。
为获得有效的容积并方便疏散热量，研究工作一直集中在减小这种耐火砖的厚度上。然而，不能减小厚度而不影响电解槽的使用寿命。因此，必须同时提高耐火砖的抗氧化性以及其对来自冰晶石电解液的腐蚀的抵抗性。耐火砖的应力更大时更有这种必要。尤其是，现在使用的电解槽的电流超过200,000安培，因此，必须从中大量散热，氧化气体大量产生，自衬里层可能变得不稳定。
因此，需要一种基于碳化硅(SiC)与氮化物(Si3N4)粘合剂的新型耐火砖，该耐火砖能有效并持久地抵抗在铝电解槽中、尤其是在铝电解槽侧壁上可能产生的热应力和/或化学应力。
发明内容
本发明的目的在于满足上述需要。
根据本发明，采用如下所述达到上述目的。一种基于碳化硅(SiC)与氮化硅(Si3N4)粘合剂的烧结耐火砖，具体应用于制造铝电解槽，该烧结耐火砖的显著特点在于其包括总含量以重量百分比计算在0.05％至1.5％之间、优选为1.2％的钙和硼。优选地，该烧结耐火砖包括至少0.05％、优选为至少0.3％且更加优选为至少0.5％的硼和/或在0.05％至1.2％之间的钙。
出人意料的是，发明人发现对于铝电解槽的应用，硼和/或钙的存在提供了性能上的实质性进步，尤其在抗氧化性、对来自冰晶石电解液的腐蚀的抵抗性及氧化条件下尺寸的稳定性上。
本发明的耐火砖还表现出一项或多项以下优选特征：
·以重量百分比计算，该耐火砖包括小于3％的硼；
·以重量百分比计算，在全部的β型和α型的氮化硅(Si3N4)中，β型氮化硅(Si3N4)至少占40％，优选至少占60％，更加优选为至少占80％；
·以重量百分比计算，Si2ON2的含量小于5％，优选为小于2％；
·该耐火砖的孔隙率优选为10％或10％以上；以及
·硼不是TiB2形式，因为TiB2形式的钛在氧化气氛中接触熔融的冰晶石时会不稳定，此外，TiB2相对于铝也不稳定。
同样优选地，Si3N4/SiC的重量比例在5％至45％之间，优选为在10％至20％之间，也就是说，Si3N4/SiC的重量比例在0.05至0.45之间，优选为在0.1至0.2之间。
优选地，Si3N4/SiC的比例小于0.3并且/或者超过0.05。此外，氮化硅含量以重量百分比计算优选为11％或11％以上。
本发明还提供了一种包括侧壁的电解槽，所述侧壁包括多种耐火砖，至少一种所述耐火砖是根据本发明所述的耐火砖。优选地，形成本发明的电解槽的侧壁的所有耐火砖是估计本发明所述的耐火砖。
最后，本发明提供一种制造根据本发明的耐火砖的方法，包括以下连续步骤：
a)准备包括颗粒混合物的炉料，该颗粒混合物包括碳化硅颗粒和至少一种硼和/或钙的化合物，作为选择，在上述颗粒混合物中加入粘合剂；
b)在模具内使上述炉料成形；
c)对模具内的炉料进行压模，形成预成坯；
d)对上述预成坯进行脱模；
e)在优选为空气或湿度可控气氛中，干燥上述预成坯；以及
f)在温度范围为1100℃至1700℃的氮还原气氛中烧制上述预成坯。
发明人发现，在该配方中加入硼和/或钙，获得的基于碳化硅(SiC)与氮化硅(Si3N4)粘合剂的烧结耐火砖的性能提高。具体的说，对来自含氟物和熔融的冰晶石的腐蚀的抵抗性提高。
本发明的方法还具有以下优选特征中的一项或多项：
·上述硼和/或钙的化合物中含有硼；
·以一预定量加入上述硼和/或钙的化合物，使得在步骤f)末获得根据本发明所述的耐火砖，具体的说，使得该耐火砖包括以重量百分比计算至少0.05％、优选为至少0.3％、更优选为至少0.5％的硼和/或小于3％的硼；
·上述硼和/或钙的化合物不含氧，也就是说，加入“非氧化物形式”的上述硼和/或钙的化合物；
·上述硼的化合物选自由含有硼的氧化物、碳化物、氮化物、氟化物和金属合金形成的组，具体的说，选自B4C、CaB6、H3BO3和BN，优选为选自B4C和CaB6，更优选的上述硼的化合物是CaB6；
·上述钙的化合物选自由含有钙的氧化物、碳化物、氮化物、氟化物和金属合金形成的组，优选为选自CaB6、CaSi、CaSiO3和CaCO3；
·以一预定量加入上述钙的化合物，使得在步骤f)末获得的耐火砖中，钙的含量以重量百分比计算在0.05％至1.2％之间。
在以下的说明书和附图中，本发明的其它特征和优点表现的更为明显。
附图说明
图1是电解槽沿主要中间平面的横截面的示意图；
图2是不同耐火砖根据美国ASTMC863标准在900℃进行实验时，随氧化作用时间增加，其体积增加百分比的变化曲线。
具体实施方式
除非另有说明，本说明书中所有的百分比为重量百分比。
当一种颗粒被描述为“基于”一种成分，则指上述颗粒包括重量超过50％的该成分。
只要在初始炉料中加入至少一种不含氧的硼的化合物，就可以使用已知的耐火砖的制造方法来制造根据本发明所述的耐火砖。
优选的，该使用的方法包括以下步骤：
a)准备包括颗粒混合物的炉料，该颗粒混合物包括碳化硅颗粒和至少一种硼和/或钙的化合物，在上述颗粒混合物中加入粘合剂；
b)在模具内使上述炉料成形；
c)对模具内的炉料进行压模，形成预成坯；
d)对上述预成坯进行脱模；
e)在优选为空气或湿度可控气氛中，干燥上述预成坯，使用现有的工艺规程制造预成坯；以及
f)在温度范围为1100℃至1700℃的氮还原气氛中烧制上述预成坯，并干燥该预成坯。
在步骤a)中，优选的，该颗粒混合物包括以重量百分比计算的30％至90％的耐火颗粒，其中至少90％的该耐火颗粒的尺寸在50μm(微米)至5mm(毫米)之间，和10％至60％的至少一种耐火粉末，其中至少90％的该耐火粉末的颗粒直径小于200μm。有利的是，上述颗粒度分布可使耐火砖具有最佳粘合力。
在该混合物的最大湿度低于7％、优选低于5％的条件下，可以以颗粒形式或其它任何形式补充硼。
粘合剂的作用是使颗粒混合物结成块状物，该块状物足够刚硬可以在步骤e)前保持其形状。粘合剂的选择取决于所需的形状。因为该粘合剂，所述的块状物便于按照模具壁采取厚度不同的层状形式形成耐火砖。
可以使用任何已知的粘合剂或已知粘合剂的混合物。该粘合剂优选为“暂时性”粘合剂，也就是说，在耐火砖的干燥和烧制步骤中，该粘合剂会全部或部分消失。更加优选的，至少一种该暂时性粘合剂是改性淀粉衍生物的溶液、糊精或木纤维质衍生物的水溶液、处理剂溶液，例如聚乙烯醇、酚醛树脂或另一环氧型树脂、糠醇或它们的混合物。更加优选的，该暂时性粘合剂的量占炉料颗粒混合物重量的0.5％至7％。
颗粒混合物和粘合剂中可加入现有技术中用于制造烧结耐火砖的压制添加剂。上述添加剂包括增塑剂，例如改性淀粉或聚乙二醇，和润滑剂，例如可溶性油或硬脂酸衍生物。这种添加剂的量与现有技术中制造基于碳化硅(SiC)与氮化硅(Si3N4)粘合剂的烧结耐火砖时所使用的该添加剂的量相同。
持续混合该炉料直到获得充分均匀的物质。
在步骤b)中，炉料成形并置于模具中。
在接下来的压实或“压制”步骤c)中，通过在炉料的上表面施加压力压缩模具中物质，使其转换成能被烧结的预成坯。合适的单位压力在300kg/cm2(千克/平方厘米)至600kg/cm2之间。优选的，进行单轴或均衡压制，例如使用液压机。有利的是，在压制之前进行手动或气动和/或振动夯实操作。
接下来，对该预成坯进行脱模(步骤d))，然后进行干燥(步骤e))。该预成坯可以在适度的高温进行干燥。优选的，该预成坯在110℃至200℃的温度范围进行干燥。根据预成坯的形式，常规的干燥时间在10小时至一星期，直到该预成坯中残留的水分含量小于O.5％。
烧制干燥后的预成坯(步骤f))。烧制周期在约为3至15天的冷却到冷冻之间，该烧制周期取决于耐火砖的材料以及尺寸和形状。根据本发明，为通过反应性烧结形成氮化物，烧制在氮中进行，其中氮化物表现为颗粒的陶瓷的粘合剂。优选在1100℃至1700℃的温度范围进行烧制循环。烧制过程中，氮与炉料的颗粒混合物中的某些成分反应，形成氮化硅填质，该填质能使上述炉料的颗粒粘合，特别是使碳化硅颗粒粘合。这样就制成了一整体式的耐火砖。
在下面以非限制性说明方式提供的各种试验中，作为添加剂(B4C、CaB6和CaSiO3)使用的粉末的颗粒尺寸小于45pm。其在初始组成中的含量在表1说明。
金属性的硅也以表1说明的比例加入。
由圣戈班陶瓷材料公司出售的不同粒度级的“黑色”或“耐火”碳化硅也被应用。这种材料主要由α型碳化硅组成，并且具有以重量计算平均为98.5％的碳化硅化学成分。
表1还示出了为表征本发明产品与参考产品(类产品)相比较而进行的各种试验的结果。所有的测量在样品的核心进行。
·产品的氮(N)含量使用LECO(LECO TC 436 DR；LECO CS 300)型分析器测量。给定值为重量百分数。
·产品的硼(B)和钙(Ca)含量采用X射线荧光光谱测定法测量。给定值为重量百分数。
·氧化试验按照美国材料实验协会(ASTM)C863标准进行。为再现铝电解槽的耐火砖所经历的氧化条件，样品(通常其尺寸为25×25×120mm)经过在900℃的饱和水蒸气气氛中至少100小时的试验。氧化产生由氮化硅和碳
化物转化成二氧化硅而导致的质量增加(“Om”值，以百分比给定)和/或体积增加(“Ov”，以百分比给定)。因此，质量增加和体积增加成为氧化程度的指标。当两种材料的氧化指标至少相差1％(平均超过3个测试样品)时，该两种材料被认为是不同的材料。
·由于被反应的氧化产物堵塞而导致的开放孔隙率的变化也是一种可以确定氧化程度的测量方式。开放孔隙率按国际ISO5017标准测量(“PO-Ox”值，以百分比给定)。
·耐腐蚀性试验确定已经经过氧化试验的、横截面为25mm×25mm的样品的性能。在熔融的冰晶石电解液中，这些样品在1030℃保持22小时，然后测量其腐蚀长度，也就是，其因腐蚀而减少的长度。“Ic”值以百分比规定了测试样品的腐蚀长度和参考样品的腐蚀长度的比例。“Ic”值越低，耐腐蚀性越好。
·耐火产品中存在的晶相由X射线衍射法确定。主要地，已发现存在氮化硅Si3N4和氧氮化物相Si2ON2。表1中说明了这些相以重量百分比计算的量。补充物是SiC。
本发明的产品的表观比重在2.4至2.7之间。参考产品的表观比重为2.6。
氮化硅可以是α型或β型。α型氮化硅表现为紊乱的氮化硅纤维形式，而β型氮化硅为形状不同的氮化硅颗粒形式。
由申请人在过去几年中进行的分析表明，β型氮化硅因其较低的比表面积，其对快速燃烧的敏感度小于α型氮化硅。在快速燃烧过程中，氮化硅被氧化并产生被熔融的冰晶石“消耗”的硅。这样，这些反应导致孔的孔隙率和连通性增加，便于腐蚀性材料渗透。因此，促进β型氮化硅的形成有利于提高对来自熔融的冰晶石的腐蚀的抵抗性。
然而，已知，β型氮化硅相的增加通常伴随氮氧化物相Si2ON2的增加。
然而，与氮化硅(无论哪种氮化硅)相比，氮氧化硅，象残留的硅及具有氧化铝杂质的硅铝氧氮物一样，通常在氮化过程中产生，耐冰晶石的性那能较差，是不希望的物相。因此，限制其量是有益的。
发明人发现，向初始炉料中加入硼和/或钙，优选以不含氧的形式，有利于在碳化硅与氮化物粘合剂的氮化过程中，在不会增加有害的Si2ON2氮氧化物相的情况下，刺激向β型氮化硅转化。下面表1说明这一发现。
因而，根据本发明，优选以非氧化物形式加入硼的化合物。有利的是，在不会大量增加Si2ON2氮氧化物相的情况下，这种加入物使转化的氮化硅几乎全部为β型氮化硅。
表1
Figure S05840943620070531D000081
表1说明加入硼和/或钙能提高由碳化硅与Si3N4基粘合剂成的耐火材料的耐腐蚀性。
表1说明加入硼和/或钙能有益于提高β型Si3N4的比例。然而，如在例14和例15中所见，只有加入非氧化物形式的硼和/或钙，才能将氮氧化硅Si2ON2的量限制在接近于或低于参考产品中的氮氧化硅Si2ON2的量值。
表1说明当最终产品中硼的量不为零时，开放孔隙率提高：只有例14、例15和例16的开放孔隙率大于的参考产品的孔隙率。因此，优选的，该产品含有0.05％至3％的硼。
此外，表1表明，初始炉料中硼化合物的存在，有益于催化氮化反应(提高本发明产品中氮的量)。
发明人不希望受到理论的限制，部分解释了耐腐蚀性，即氧化降解稳定性的提高。如表1中所说明的以及如图2中所示的，本发明产品的抗氧化性被提高。
表1表明，本发明的产品由于氧化而产生的体积变化非常有限，此外，当加入结合硼的钙时，其氧化后的质量增加有限。因此，加入CaB6、尤其以0.5％至2％的量加入CaB6是有益的。
图2显示了当试验延长到500小时时抗氧化性的变化。证实并强调了本发明产品相对于参考产品的进步。
表1表明，即使加入少量的硼和/或钙对耐腐蚀性也有影响。而且，还表现为，以重量百分比计算加入最少量为0.8％的硼和/或钙能产生基本为最大的耐腐蚀性。
优选地，初始炉料中以重量百分比计算的CaB6在0.5％以上。
向初始炉料中加入B4C表现出的效果与B4C的含量低于0.2％时的效果基本相同。B4C的含量在0.6％时获得增强的效果。
显然，本发明不仅局限于通过非限制性说明实例所说明和描述的实现方式。
发明人还观察到，以非氧化物形式加入硼，更具体的说，加入CaB6或B4C，也在对本发明产品的致密性没有显著影响的同时，有助于提高其热扩散率。这显然对促进热传递非常重要。
此外，已发现，本发明的产品不包含针状Si3N4，包括本发明的产品的表面上也不包含针状Si3N4。
本发明的产品的氧化性说明，可以设想其在除电解槽以外的其它方面上的应用。

Claims (23)

1.一种烧结耐火砖，具体应用于制造铝电解槽，由包括以下连续步骤的方法制得：
a)准备包括颗粒混合物的炉料，该颗粒混合物包括碳化硅颗粒和至少一种硼的化合物，作为选择，在上述颗粒混合物中加入粘合剂；所述的硼的化合物选自硼的氧化物、碳化物、氮化物、氟化物和CaB6；
b)在模具内使上述炉料成形；
c)对模具内的炉料进行压模，形成预成坯；
d)对上述预成坯进行脱模；
e)干燥上述预成坯；以及
f)在温度范围为1100℃至1700℃的氮还原气氛中烧制上述预成坯以形成氮化硅粘合剂；
其特征在于，该耐火砖包括0.05％至1.5％的硼，Si3N4/SiC的重量比例在0.05至0.45的范围内。
2.根据权利要求1所述的烧结耐火砖，其特征在于，硼的重量百分比在0.05％至1.2％的范围内。
3.根据权利要求1所述的烧结耐火砖，其特征在于，Si3N4/SiC的重量比例在0.1至0.2的范围内。
4.根据权利要求1所述的烧结耐火砖，其特征在于，在全部β型氮化硅和α型氮化硅中，以重量百分比计算，β型氮化硅至少占40％。
5.根据权利要求4所述的烧结耐火砖，其特征在于，在全部β型氮化硅和α法型氮化硅中，以重量百分比计算，β型氮化硅至少占80％。
6.根据权利要求1所述的烧结耐火砖，其特征在于，以重量百分比计算，Si2ON2的量小于5％。
7.根据权利要求6所述的烧结耐火砖，其特征在于，以重量百分比计算，Si2ON2的量小于2％。
8.根据权利要求1所述的烧结耐火砖，其特征在于，以重量百分比计算，Si3N4含量为11％或11％以上。
9.根据权利要求1所述的烧结耐火砖，其特征在于，孔隙率为10％或10％以上。
10.根据权利要求1所述的烧结耐火砖，其特征在于，包括一硼和钙的混合物，硼和钙的总量在0.05％至1.5％的范围内。
11.根据权利要求10所述的烧结耐火砖，其特征在于，钙的重量百分比在0.05％至1.2％的范围内。
12.根据权利要求11所述的烧结耐火砖，其特征在于，在全部β型氮化硅和α型氮化硅中，以重量百分比计算，β型氮化硅至少占80％。
13.根据权利要求2所述的烧结耐火砖，其特征在于，以重量百分比计算，Si2ON2的量小于5％。
14.根据权利要求13所述的烧结耐火砖，其特征在于，Si3N4/SiC的重量比例在0.1至0.2的范围内。
15.根据权利要求14所述的烧结耐火砖，其特征在于，在全部β型氮化硅和α法型氮化硅中，以重量百分比计算，β型氮化硅至少占80％。
16.根据权利要求1所述的烧结耐火砖，其特征在于，以重量百分比计算，包括至少0.3％的硼。
17.根据权利要求1所述的烧结耐火砖，其特征在于，通过碳化硅和硅的混合物，与来自氮气氛中的氮反应性烧结获得。
18.根据权利要求1至17之一的权利要求所述的烧结耐火砖，其特征在于，所述的硼的化合物选自B4C、CaB6、H3BO3和BN。
19.根据权利要求18所述的烧结耐火砖，其特征在于，所述的硼的化合物选自B4C和CaB6。
20.根据权利要求19所述的烧结耐火砖，其特征在于，所述的硼的化合物是CaB6。
21.根据权利要求1所述的烧结耐火砖，其特征在于，所述的硼的化合物不含氧。
22.根据权利要求1所述的烧结耐火砖，其特征在于，所述的颗粒混合物包括一钙的化合物，其选自钙的氧化物、碳化物、氮化物、氟化物和金属合金。
23.一种电解槽，具有包括多种耐火砖的侧壁，其特征在于，所述耐火砖中的至少一种是根据权利要求1至22中任一项所述的耐火砖。
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