CN101410329A - 烧结材料、可烧结粉末混合物、制造所述材料的方法及其用途 - Google Patents

烧结材料、可烧结粉末混合物、制造所述材料的方法及其用途 Download PDF

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CN101410329A
CN101410329A CNA2007800105088A CN200780010508A CN101410329A CN 101410329 A CN101410329 A CN 101410329A CN A2007800105088 A CNA2007800105088 A CN A2007800105088A CN 200780010508 A CN200780010508 A CN 200780010508A CN 101410329 A CN101410329 A CN 101410329A
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transition metal
weight
diboride
phase
sintering
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H·塞勒
C·施马尔茨里德
F·瓦尔迈尔
G·维克托
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ESK Ceramics GmbH and Co KG
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ESK Ceramics GmbH and Co KG
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Abstract

本发明涉及烧结材料，其基于过渡金属二硼化物，并包含：a)主相，其具有90－99重量％的细粒状过渡金属二硼化物、或包含至少两种过渡金属二硼化物的过渡金属二硼化物混晶、或这种二硼化物混晶的混合物、或这种二硼化物混晶与一种或多种过渡金属二硼化物的混合物，所述过渡金属选自周期表的副族IV至VI，b)第二相，其具有1－5重量％的微粒碳化硼和/或碳化硅，和c)任选地，作为第三相，最多 5重量％的非连续的晶界相。本发明还涉及用于制造这种烧结材料的粉状可烧结混合物、优选通过无压烧结制造这种烧结材料的方法、和该烧结材料作为防熔融盐和金属、特别是含冰晶石的熔融材料的防腐材料的用途。

Description

烧结材料、可烧结粉末混合物、制造所述材料的方法及其用途
技术领域
本发明涉及基于过渡金属二硼化物的烧结材料、用于制造这种烧结材料的粉状可烧结混合物、制造这种烧结材料的方法和该烧结材料的用途，用作防盐和金属熔体、特别是含冰晶石的熔体的防腐材料，用于制造耐受含冰晶石的熔体的热电偶保护管，用作电极保护材料、电极材料或生产Al所用的熔融电解中的槽衬护材料，以及用作滑动触点、焊接电极和腐蚀栓(erodierstifte)的电极材料。
背景技术
二硼化钛具有许多有利性质，例如3225℃的高熔点、26-32GPa[HV]的高硬度、在室温的优异电导率和良好的耐化学性。
二硼化钛的主要缺点是其可烧结性差。这种差的可烧结性部分可归因于由于制造方法(通过用碳高温还原二氧化钛和氧化硼，或通过金属氧化物在碳和/或碳化硼作用下的还原，被称作碳化硼法)而存在于常用二硼化钛粉末中的杂质，特别是TiO2形式的氧杂质。这种氧杂质通过提高表面扩散而促进了烧结过程中晶粒和孔隙生长。
现有技术
烧结二硼化钛材料可以通过热压法制造。例如，通过在高于1800℃的烧结温度和＞20MPa的压力单轴热压，已经实现了超过理论密度的95％的密度，且热压材料通常具有大于20微米的颗粒大小。但是，热压法的缺点在于，只能由此制造简单的形状，而不能通过该方法制造具有复杂几何的主体和部件。
相反，通过无压烧结法可以制造具有更复杂几何的部件。在此，必须添加合适的烧结助剂以获得具有高密度的烧结体。可能的烧结添加剂是，例如，如铁和铁合金的金属。添加少量铁能够获得具有良好机械性质和超过8MPa m1/2的高断裂韧度的致密材料。例如在EP 433856 B1中描述了这样的材料。但是，这些材料的缺点在于，它们由于金属粘合剂相而具有差的耐蚀性，并特别不耐受冰晶石和含冰晶石的熔体。
EP 0073743 B1描述了对铝熔体耐蚀的二硼化钛材料，其通过使用氢化钛和硼作为致密化添加剂的无压烧结法制成。由于这些添加剂明显没有抑制晶粒生长的作用，在所用的最多2200℃的烧结温度形成了非常大的晶粒，从而由于颗粒大小高于临界颗粒大小而造成强度降低、微裂纹生成增多。
本技术领域中已知的是，由于沿晶界的液相渗透，烧结二硼化钛材料的晶界成为耐蚀性方面的薄弱点。
US-A-4,500,643指出，由纯净的细粒状二硼化钛构成的烧结材料可耐受生产Al所用的熔融电解的使用条件，并因此也耐受冰晶石，但即使少量杂质，特别是氧化物和金属，也会造成显著的晶界腐蚀，并因此造成部件的崩解。该美国专利中所述的二硼化钛材料具有10至45体积％的孔隙率，且孔隙彼此相连，因而存在穿透该材料的连续孔隙。由于开放的孔隙，尽管这种材料耐受冰晶石，但它不适用于分离各种介质；特别地，其不适合作为防冰晶石的防腐材料。该材料因此例如也不适用于制造生产Al所用熔融电解的热电偶保护管，并且也不能用作生产Al所用的熔融电解中的阳极保护材料。由于高的孔隙率，该材料也具有不令人满意的机械强度。
发明目的
因此，本发明的目的是提供一种烧结材料，其不仅具有良好的机械性质，还耐盐和金属熔体、特别是含冰晶石的熔体腐蚀。此外，该材料应该具有封闭孔隙以使其有效起到防腐蚀作用。这种烧结材料还应该能够通过简单和廉价的方法制造，该方法还能制造具有复杂几何的成型体。
发明概要
根据本发明，通过如权利要求1所述的基于过渡金属二硼化物的烧结材料、如权利要求9所述的用于制造这种烧结材料的粉状可烧结混合物、如权利要求17和18所述的用于制造这种烧结材料的方法、和如权利要求24-27所述的烧结材料的用途，实现了上述目的。从属权利要求中描述了本申请主题的有利的或特别有用的实施方案。
因此，本发明提供了一种烧结材料，其基于过渡金属二硼化物，并包含：
a)作为主相，90-99重量％的细粒状过渡金属二硼化物、或包含至少两种过渡金属二硼化物的过渡金属二硼化物混晶、或这种二硼化物混晶的混合物、或这种二硼化物混晶与一种或多种过渡金属二硼化物的混合物，其中所述过渡金属选自周期表的副族IV至VI，
b)作为第二相，1-5重量％的微粒碳化硼和/或碳化硅，和
c)任选地，作为第三相，最多5重量％的非连续的含氧晶界相。
本发明进一步提供了用于制造基于过渡金属二硼化物的烧结材料的粉状可烧结混合物，其包含：
1)0.05-2重量％的金属Al和/或Si的形式的Al和/或Si，和/或与该含量对应的量的Al和/或Si化合物，
2)任选地，至少一种选自周期表的副族IV至VI的过渡金属的碳化物和硼化物的组分，
3)0.5-12重量％的硼，
4)0-5重量％的碳化硼和/或碳化硅，
5)0-5重量％的碳和/或碳化合物，在每种情况下均基于元素碳的含量，和
6)余量的至少一种周期表副族IV至VI的过渡金属二硼化物，其与上述组分2)的过渡金属硼化物不同。
本发明进一步提供了制造这种烧结材料的方法，该方法通过任选在添加有机粘合剂和压制助剂的情况下将上述粉状混合物热压、或热等静压成型、或气压烧结、或火花等离子体烧结而制造。
本发明还提供了通过无压烧结制造上述烧结材料的方法，其包括下列步骤：
a)任选在添加有机粘合剂和压制助剂的情况下，将上述粉状混合物与水和/或有机溶剂混合，以制造均匀的粉末悬浮液，
b)由该粉末悬浮液制造粒化的粉末，
c)将所述粒化的粉末压制，以形成具有高密度的生坯，和
d)将所得生坯在减压下或在保护性气体下在1800-2200℃的温度无压烧结。
本发明的烧结材料适合作为防盐和金属熔体、特别是含冰晶石的熔体的防腐材料。
因此，本发明还特别提供了该烧结材料用于制造耐受含冰晶石的熔体的热电偶保护管的用途。
本发明的烧结材料还适合作为电极保护材料、电极材料或生产Al所用的熔融电解中的槽衬护材料，以及作为滑动触点、焊接电极和腐蚀栓的电极材料。
因此，根据本发明，已经表明，通过提供基于过渡金属二硼化物且其基质(主相)包含细粒状过渡金属二硼化物、或过渡金属二硼化物混晶或其组合的烧结致密材料，实现了上述目的。作为第二相，该材料含有充当晶粒生长抑制剂的微粒碳化硼和/或碳化硅。如果适当，该材料可以含有含氧的非连续晶界相作为第三相。主相的混晶的形成具有额外的晶粒生长抑制作用，从而获得了具有良好机械性质的烧结材料。在晶界之间或在晶界的三相点处，可存在残留含量的微粒形式的杂质，例如含氧杂质。本发明的烧结材料对盐和金属熔体(包括含冰晶石的熔体)具有令人惊讶地优异的耐蚀性。
发明详述
如上所述，本发明材料的微结构包含细粒状主相，该主相包含过渡金属二硼化物、或至少两种过渡金属二硼化物的过渡金属二硼化物混晶、或这种二硼化物混晶的混合物、或这种二硼化物混晶与一种或多种过渡金属二硼化物的混合物。存在主要位于晶界处的较小比例的微粒碳化硼和/或碳化硅作为第二相。碳化硼和/或碳化硅另外具有粒子增强作用。此外，可以在该材料的三相点处少量存在含氧的第三相。在此，重要的是，含氧相不形成连续的晶界膜。如果适当，该材料中也可以存在少量的微粒碳和/或微粒硼。此外，当使用Al或Si或其化合物作为烧结助剂时，主相中可以存在少量这些元素。如果存在所述含氧的第三相，其比例优选为最多2.5重量％。
主相优选具有小于20微米、更优选小于10微米的平均颗粒大小。第二相的碳化硼和/或碳化硅优选具有小于20微米、更优选小于5微米的平均粒度。主相的平均颗粒大小和碳化硼和/或碳化硅的平均粒度通过直线截距长度法在蚀刻的抛光切片上进行。
所述副族IV至VI的过渡金属优选选自Ti、Zr、Hf、V、Nb、Ta、Cr、Mo和W。
主相优选为细粒状TiB2、和/或ZrB2、和/或(TiW)B2和/或(Zr，W)B2和/或(Ti，Zr)B2的混晶，更优选为(Ti，W)B2和/或(Zr，W)B2的混晶，包括三元二硼化物(Ti，Zr，W)B2。主相特别优选是混晶(Ti，W)B2或混晶(Zr，W)B2。主相中WB2的比例优选不多于7重量％。
用于制造本发明可烧结材料的本发明粉状可烧结混合物包含下列组分：
1)0.05-2重量％、优选0.2-0.6重量％的Al和/或Si，其为金属Al和/或Si的形式和/或与该含量对应的量的Al和/或Si化合物。优选使用Al或含氧的Al化合物，特别是Al2O3或勃姆石。
2)任选地，优选≥0.25重量％的选自周期表副族IV至VI的过渡金属的碳化物和硼化物的至少一种组分，优选碳化钨。如果适当，也可以使用副族IV至VI的过渡金属本身和这类过渡金属的氧化物作为组分2)。如果使用过渡金属碳化物，它们的比例可以为最多15重量％。
3)0.5-12重量％、优选1-5重量％的单质形式的硼。
4)0-5重量％的碳化硼和/或碳化硅，
5)0-5重量％、优选0.1-1重量％的碳和/或碳化合物作为有机碳载体，在每种情况下基于元素碳的含量。所添加的碳用于减少原材料中作为杂质存在的氧化物或在烧结过程中形成的氧化物。合适的碳化合物的实例是分散炭黑、酚醛树脂和糖。
6)余量的至少一种周期表副族IV至VI的过渡金属二硼化物，其与上述组分2)的过渡金属硼化物不同。如上所述，该过渡金属选自Ti、Zr、Hf、V、Nb、Ta、Cr、Mo和W。组分6)的过渡金属二硼化物优选为TiB2和/或ZrB2，更优选TiB2。
粉状混合物的上述组分优选以非常高的纯度和小的度使用。例如，组分6)的过渡金属二硼化物优选具有不大于4微米、更优选不大于2微米的平均粒度。
本发明的烧结材料可以以本身已知的方式通过上述粉状混合物的热压、热等静压成型或气压烧结或火花等离子体烧结法制造，如果适当，这在添加有机粘合剂和压制助剂的情况下进行。在此，可以使用常规有机粘合剂，如聚乙烯醇(PVA)、水溶性树脂和聚丙烯酸，以及常规压制助剂，如脂肪酸和蜡。
为了制造本发明的烧结材料，将至少一种副族IV至VI的过渡金属二硼化物与其它粉状组分和，如果适当，与有机粘合剂和压制助剂一起，在水和/或有机溶剂中加工，以形成均匀粉末悬浮液。然后将该均匀粉末悬浮液转化成粒化粉末，优选通过喷雾干燥而转化。然后通过热压、或热等静压成型、或气压烧结进一步加工该粒化粉末，以产生烧结材料。
在优选实施方案中，通过无压烧结制造本发明的烧结材料。在此，将如上所述获得的粒化粉末压制，形成具有高密度的生坯。所有常规成型法，如单轴压制、或冷等静压成型、以及挤出、注射成型、粉浆浇铸和加压粉浆浇铸，都可用于此目的。然后通过在减压下或在保护性气体下在1800-2200℃、优选1900-2100℃、更优选大约2000℃的温度将所得生坯无压烧结，转化成烧结材料。
在无压烧结之前，优选在惰性气氛中在低于烧结温度的温度将生坯烘焙，以除去有机粘合剂或压制助剂。
通过无压烧结获得的材料具有理论密度的至少大约94％的密度，优选为理论密度的至少97％的密度。这种密度值确保所存在的任何孔隙都是闭孔。如果需要，可以通过热等静压成型法将烧结材料后致密化，以提高密度和减少闭孔。
粉状原料混合物中的选自周期表副族IV至VI的过渡金属碳化物的组分与添加的硼在烧结过程中反应，形成过渡金属硼化物和碳化硼。所形成的过渡金属硼化物和/或添加的上述组分2)的过渡金属硼化物可以与组分6)的过渡金属二硼化物(例如二硼化钛)形成混晶。这种硼化物混晶的生成具有晶粒生长抑制作用。添加的和生成的(例如由碳化钨和硼生成的)碳化硼同样具有晶粒生长抑制作用。在本发明烧结材料的制造中，重要的是，粉末混合物中存在的氧杂质非常完全地反应，以防止形成连续的含氧晶界薄膜。这通过借助硼和添加的碳和/或碳化合物还原、以及通过减压蒸发来实现。在相对较高的温度，挥发性氧化物可以优选在1600至1700℃的温度除去。
计算原料混合物中的添加的硼和添加的碳和/或碳化合物的量，以使下示还原反应(1)至(3)进行至反应完全：
(1)WC+6B→WB2+B4C
(2)TiO2+4B→TiB2+2BO(g)
(3)2B2O3+7C→B4C+6CO
在上述还原反应(1)中，作为示例，选择WC作为上述组分2)的代表。
Al和/或Si或它们的化合物充当烧结助剂，且所形成的微结构表明了液相烧结过程。
本发明的耐冰晶石的且致密、细粒化的材料适用于磨损应用。本发明的烧结材料也非常适合作为防盐和金属熔体(例如Al和Cu熔体)、特别是含冰晶石的熔体的防腐材料。本发明烧结材料的具体用途是耐受含冰晶石的熔体的热电偶保护管、电极保护材料、电极材料或生产Al所用的熔融电解中的槽衬护材料，以及作为滑动触点、焊接电极和腐蚀栓的电极材料。
附图简述
图1显示了实施例1中所获材料的微结构的光学显微照片；
图2显示了图1的微结构在冰晶石试验后的光学显微照片；
图3显示了实施例2中所获材料的微结构的光学显微照片；
图4显示了图3的微结构在冰晶石试验后的光学显微照片；
图5显示了对比例1中所获材料的微结构的光学显微照片；
图6显示了图5的微结构在冰晶石试验后的光学显微照片；
图7显示了对比例2中所获材料的微结构的光学显微照片；
图8显示了图7的微结构在冰晶石试验后的光学显微照片；
图9显示了对比例3中所获材料的微结构的光学显微照片；
图10显示了图9的微结构在冰晶石试验后的光学显微照片；
图11显示了图1的微结构的代表性区域的明视场透射电子显微照片；
图12显示了与图11的微结构的晶界垂直的明视场透射电子显微照片(左边)，以及沿左图中所示的白线的相关一维谱(右边)。
下列实施例和对比例例证了本发明。为了评估对冰晶石的耐受性，进行下列试验。
冰晶石试验
在封闭碳坩锅中，将样品与完全覆盖该材料的量的纯冰晶石一起加热，并在1000℃保持24小时。然后通过显微术评估表面。
实施例1：
将450克TiB2粉末(d50＝2微米；1.7重量％的氧，0.15重量％的碳，0.077重量％的铁)、30克碳化钨(d50＜1微米)、10克非晶硼(纯度：96.4％，d50＜1微米)、8克B4C(d50＝0.7微米)和2克氧化铝(勃姆石作为原材料)与10克作为粘合剂的平均摩尔质量为1500的聚乙烯醇、20克作为压制助剂的硬脂酸和20克商品糖一起分散在水溶液中，并喷雾干燥。在1200巴将粒状喷雾干燥的材料冷等静压成型以产生生坯。将生坯在减压下以10K/分钟的加热速率加热至2020℃，并在烧结温度保持45分钟。在切断加热能源的情况下在Ar下进行冷却。
所得烧结体的密度为理论密度的98％。
微结构的光学显微照片显示在图1中。
所得微结构包含(Ti，W)B2混晶基质、微粒B4C和微粒硼(见图11中的透射电子显微照片)。
在这种能谱中进行的TEM研究表明，晶界不含氧和其它杂质。此外，在(Ti，W)B2混晶中存在少量铝。
在图11的整个片段上记录的EDX谱仅显示了元素Ti、W、B和Al。没有发现氧。
还在TEM中使用高分辨率谱成像法检查晶界。在整个晶界上进行直线扫描，作为电子损失能量的函数(图12)，扫描结果表明，在晶界处没有氧信号(532eV)，也没有Ti信号转移(456eV)，如果存在含Ti的次生相就会发生这种Ti信号转移。
然后对尺寸为10×10×10mm3的样本进行冰晶石测试，其中将样本在1000℃暴露于冰晶石熔体24小时。然后检查样本的微结构，结果表明，晶界对冰晶石的侵蚀是稳定的(见图2)。
实施例2：
将450克TiB2粉末(d50＝2微米；1.7重量％的氧，0.15重量％的碳，0.077重量％的铁)、30克碳化钨(d50＜1微米)、10克非晶硼(纯度：96.4％，d50＜1微米)、8克B4C(d50＝0.7微米)和2克氧化铝(勃姆石作为原材料)与10克作为粘合剂的平均摩尔质量为1500的聚乙烯醇和20克作为压制助剂的硬脂酸一起分散在水溶液中，并喷雾干燥。在1200巴将粒状喷雾干燥的材料冷等静压成型以产生生坯。将生坯在减压下以10K/分钟的加热速率加热至1650℃，在1650℃下的保持时间为45分钟，然后以10K/分钟将生坯加热至2020℃，并在烧结温度保持45分钟。在切断加热能源的情况下在Ar下进行冷却。
所得烧结体的密度为理论密度的97.8％。
微结构的光学显微照片显示在图3中。
所得微结构包含(Ti，W)B2混晶基质、微粒B4C和微粒硼。
在1650℃的附加加热处理步骤中，通过氧化物的蒸发和还原除去了晶界中的氧杂质。
在冰晶石中的腐蚀试验(在1000℃下24小时)表明没有经由晶界渗透(图4)。
对比例1：
将450克TiB2粉末(d50＝2微米；1.7重量％的氧，0.15重量％的碳，0.077重量％的铁)、30克碳化钨(d50＜1微米)、10克非晶硼(纯度：96.4％，d50＜1微米)、8克B4C(d50＝0.7微米)和2克氧化铝(勃姆石作为原材料)与10克作为粘合剂的平均摩尔质量为1500的聚乙烯醇和20克作为压制助剂的硬脂酸一起分散在水溶液中，并喷雾干燥。在1200巴下将粒状喷雾干燥的材料冷等静压成型以产生生坯。将生坯在减压下以10K/分钟的加热速率加热至2020℃，并在烧结温度保持45分钟。在切断加热能源的情况下在Ar下进行冷却。
所得烧结体的密度为理论密度的97.9％。
微结构的光学显微照片显示在图5中。
所得微结构包含(Ti，W)B2混晶基质、微粒B4C、微粒Ti-Al-B-O相和连续的非晶含氧晶界薄膜。由于形成厚度为大约2纳米的连续的含氧晶界薄膜，该材料在1000℃表现出其晶界被冰晶石熔体渗透。由于晶界腐蚀，发生该材料的严重崩解(图6)。
对比例2：
将450克TiB2粉末(d50＝2微米；1.7重量％的氧，0.15重量％的碳，0.077重量％的铁)、30克碳化钨(d50＜1微米)、15克非晶硼(纯度：96.4％，d50＜1微米)、10克B4C(d50＝0.7微米)和2克氧化铝(勃姆石作为原材料)与10克作为粘合剂的平均摩尔质量为1500的聚乙烯醇和20克作为压制助剂的硬脂酸一起分散在水溶液中，并喷雾干燥。在1200巴将粒状喷雾干燥的材料冷等静压成型以产生生坯。将生坯在减压下以10K/分钟加热至2020℃，并在烧结温度保持45分钟。在切断加热能源的情况下在Ar下进行冷却。
所得烧结体的密度为理论密度的96.9％。
微结构的光学显微照片显示在图7中。
与实施例1和2相比，观察到了与冰晶石熔体接触时经由晶界的腐蚀；形成了对冰晶石不稳定的晶界沉淀物。
实施例3：
热电偶保护管的制造：
将来自实施例1的粒状喷雾干燥材料(堆密度：1.12克/立方厘米，残留湿含量：0.4％，d50＝51微米)冷等静压成型，以制造一端封闭且尺寸为764毫米长和31.5毫米直径的中空管。烧结周期与实施例1中相同。纵向收缩率为16.9％且横向收缩率为20.6％。烧结密度为理论密度的98％。通过在2000℃和1950巴的热等静压成型将烧结的管后致密化。后致密化之后的密度为理论密度的99.3％。
对比例3：(没有Al化合物作为烧结助剂的原料混合物)
将450克TiB2粉末(d50＝2微米；1.7重量％的O，0.15重量％的C，0.077重量％的Fe)、30克WC(d50＜1微米)和20克非晶B(纯度：96.4％，d50＜1微米)与10克作为粘合剂的平均摩尔质量为1500的聚乙烯醇和20克作为压制助剂的硬脂酸一起分散在水溶液中，并喷雾干燥。在1200巴将粒状喷雾干燥的材料冷等静压成型以形成生坯。将生坯在减压下以10K/分钟加热至2170℃，并在烧结温度保持45分钟。在切断加热能源的情况下在Ar下进行冷却。然后在2000℃在1950巴的Ar压力将烧结体后致密化1小时。密度为理论密度的97.9％。
微结构的光学显微照片显示在图9.
所得微结构包含(Ti，W)B2混晶基质和微粒碳化硼，微粒碳化硼部分存在于晶界中，部分存在于混晶粒中。平均晶粒直径为大约100微米。
在此需要较高烧结温度以实现致密化。产生了粗粒微结构。
也对这种材料进行冰晶石试验。与实施例1和2相比，观察到了与冰晶石熔体接触时经由晶界的腐蚀(图10)。该材料不是耐冰晶石的。

Claims (27)

1.烧结材料，其基于过渡金属二硼化物，并包含：
a)作为主相，90-99重量％的细粒状过渡金属二硼化物、或包含至少两种过渡金属二硼化物的过渡金属二硼化物混晶、或这种二硼化物混晶的混合物、或这种二硼化物混晶与一种或多种过渡金属二硼化物的混合物，其中所述过渡金属选自周期表的副族IV至VI，
b)作为第二相，1-5重量％的微粒碳化硼和/或碳化硅，和
c)任选地，作为第三相，最多5重量％的非连续的含氧晶界相。
2.如权利要求1所述的材料，其中主相a)具有小于20微米、优选小于10微米的平均颗粒大小。
3.如权利要求1和/或2所述的材料，其中第二相b)的碳化硼和/或碳化硅具有小于20微米、优选小于5微米的平均粒度。
4.如权利要求1-3至少一项所述的材料，其中第二相b)的比例为1-4重量％。
5.如权利要求1-4至少一项所述的材料，其中第三相c)以最多2.5重量％的比例存在。
6.如权利要求1-5至少一项所述的材料，其中所述副族IV至VI的过渡金属选自Ti、Zr、Hf、V、Nb、Ta、Cr、Mo和W。
7.如权利要求1-6至少一项所述的材料，其中主相a)是细粒状TiB2和/或ZrB2、和/或(TiW)B2和/或(Zr，W)B2和/或(Ti，Zr)B2的混晶，优选为(Ti，W)B2和/或(Zr，W)B2的混晶，更优选为混晶(Ti，W)B2或混晶(Zr，W)B2。
8.如权利要求1-7至少一项所述的材料，其中主相a)中WB2的比例≤7重量％。
9.粉状可烧结混合物，其用于制造基于过渡金属二硼化物的烧结材料，包含：
1)0.05-2重量％的金属Al和/或Si的形式的Al和/或Si，和/或与该含量对应的量的Al和/或Si化合物，
2)任选地，选自周期表副族IV至VI的过渡金属的碳化物和硼化物的至少一种组分，
3)0.5-12重量％的硼，
4)0-5重量％的碳化硼和/或碳化硅，
5)0-5重量％的碳和/或碳化合物，在每种情况下均基于元素碳的含量，和
6)余量的至少一种周期表副族IV至VI的过渡金属二硼化物，其与上述组分2)的过渡金属硼化物不同。
10.如权利要求9所述的混合物，其中组分1)的比例为0.2-0.6重量％。
11.如权利要求9和/或10所述的混合物，其中组分2)的比例为≥0.25重量％。
12.如权利要求9至11至少一项所述的混合物，其中组分6)的过渡金属二硼化物具有≤4微米、优选≤2微米的平均粒度。
13.如权利要求9至12至少一项所述的混合物，其中副族IV至VI的过渡金属选自Ti、Zr、Hf、V、Nb、Ta、Cr、Mo和W。
14.如权利要求9-13至少一项所述的混合物，其中组分2)是碳化钨。
15.如权利要求9-14至少一项所述的混合物，其中组分6)的过渡金属二硼化物是TiB2和/或ZrB2。
16.如权利要求9-15至少一项所述的混合物，其中组分5)的比例为0.1-1重量％。
17.制造如权利要求1-8至少一项所述的烧结材料的方法，通过任选在添加有机粘合剂和压制助剂的情况下将如权利要求9-16至少一项所述的粉状混合物热压、或热等静压成型、或气压烧结、或火花等离子体烧结而制造。
18.通过无压烧结制造如权利要求1-8至少一项所述的烧结材料的方法，其包括下列步骤：
a)任选在添加有机粘合剂和压制助剂的情况下，将如权利要求9-16至少一项所述的粉状混合物与水和/或有机溶剂混合，以制造均匀的粉末悬浮液，
b)由该粉末悬浮液制造粒化的粉末，
c)将所述粒化的粉末压制，以形成具有高密度的生坯，和
d)将所得生坯在减压下或在保护性气体下在1800-2200℃的温度无压烧结。
19.如权利要求18所述的方法，其中步骤b)中的粒化粉末的制造是通过喷雾干燥进行的。
20.如权利要求18和/或19所述的方法，其中步骤c)中的生坯制造是通过单轴压制、冷等静压成型、挤出、注射成型、粉浆浇铸或加压粉浆浇铸进行的。
21.如权利要求18-20至少一项所述的方法，其中在无压烧结之前在惰性气氛中在低于烧结温度的温度将步骤c)中所得的生坯烘焙。
22.如权利要求18-21至少一项所述的方法，其中步骤d)中的无压烧结在1900-2100℃、优选大约2000℃的温度进行。
23.如权利要求18-22至少一项所述的方法，其中通过热等静压成型法将已经通过无压烧结制成的材料后致密化。
24.如权利要求1-8至少一项所述的烧结材料的用途，用作防盐和金属熔体、特别是含冰晶石的熔体的防腐材料。
25.如权利要求1-8至少一项所述的烧结材料的用途，用于制造热电偶保护管、特别是耐受含冰晶石的熔体的热电偶保护管。
26.如权利要求1-8至少一项所述的烧结材料的用途，用作电极保护材料、电极材料或生产Al所用的熔融电解中的槽衬护材料。
27.如权利要求1-8至少一项所述的烧结材料的用途，用作滑动触点、焊接电极和腐蚀栓的电极材料。
CNA2007800105088A 2006-03-24 2007-03-12 烧结材料、可烧结粉末混合物、制造所述材料的方法及其用途 Pending CN101410329A (zh)

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