CN101410347A - 烧结耐磨硼化物材料、制备所述材料的可烧结粉末混合物、所述材料的制备方法及其用途 - Google Patents
烧结耐磨硼化物材料、制备所述材料的可烧结粉末混合物、所述材料的制备方法及其用途 Download PDFInfo
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Abstract
本发明提供一种烧结耐磨材料，其基于过渡金属二硼化物并包含a)作为主相，80－98.8重量％的细粒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，其中过渡金属选自周期表的IV－VI副族，b)作为第二相，0.2－5重量的％连续、含氧晶粒间界相和c)作为第三相，1－15重量％的颗粒碳化硼和/或碳化硅。本发明另外涉及用于制备这种烧结材料的粉状可烧结混合物、优选通过无压烧结制备该烧结材料的方法、以及该烧结材料用于制造在一般机械工程、特别是化学设备工程中的耐磨部件的用途。
Description
技术领域
本发明涉及一种基于过渡金属二硼化物的烧结耐磨材料，用于制备这种烧结材料的粉状可烧结混合物、这种烧结材料的制备方法以及该烧结材料的用途，其用于制造一般设备构造体，特别是制造化学设备构造体中的耐磨部件，用于制造切削机以及非切削操作和成形用的工具，以及用作滑动接点、焊接电极和侵蚀钉(Erodierstifte)用的电极材料。
发明背景
二硼化钛具有许多有利的性能，如3225℃的高熔点，26-32GPa[HV]的高硬度，室温下的优异导电性和良好耐化学性。
二硼化钛的主要缺点在于其可烧结性差。可烧结性差部分可归因于杂质，特别是TiO2形式的氧杂质，其由于制备方法的原因而存在于通常使用的二硼化钛粉末中，所述制备方法或者是将二氧化钛和氧化硼碳热(carbothermische)还原或者是通过碳和/或碳化硼将金属氧化物还原(即碳化硼法)。这种氧杂质在烧结过程中通过增加表面扩散而增加了颗粒和孔的生长。
现有技术
烧结的二硼化钛材料可以通过热压法制备。例如，通过在1800℃以上烧结温度和＞20Mpa压力下的单轴热压制获得了超过理论密度的95％的密度，该热压材料典型地具有大于20μm的粒度。然而，热压法具有如下缺点：由此只可以产生简单几何形状体，而通过该方法不能产生复杂几何形状体或组件。
相反，通过无压烧结法可以产生具有更加复杂几何形状的组件。在此，为了得到具有高密度的烧结体，必须添加合适的烧结助剂。例如，可能的烧结添加剂为金属如铁和铁合金。添加少量的铁能够得到具有良好机械性和超过8MPa m1/2断裂韧性的致密材料。例如，这种材料描述于EP 433856B1中。然而，这些具有金属粘结相的材料(其还可以称为金属陶瓷)具有以下缺点：它们因为金属粘结相而对空气或氧气具有差的耐蚀性，特别是它们不耐酸和碱。由于这些材料对酸和碱的反应性，它们不能用于化学设备构造体。
US-A-5,108,670描述了一种烧结二硼化钛材料的制备方法，该材料具有改善的韧性且不含金属粘结相。为了制备该烧结材料，将二硼化钛与最多10重量％的二硼化铬混合，将该混合物压入模中并随后在微波炉中的由Y2O3颗粒组成的粉末床中烧结，以便Y2O3随后与TiB2反应并形成钇-钛氧化物相，产生具有氧化第二相的TiB2材料。尽管通过该材料获得大约6MPa·m1/2的较高断裂韧性，但它具有如下缺点：获得了不超过18GPa的硬度，这对于耐磨用途是非常低的。此外，在粉末床中的烧结方法不适于制造大体积的部件和具有较厚壁的部件，因为不能达到均匀分布。
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如高硬度、高强度和高韧性，也耐氧化和耐腐蚀，特别是对于酸和碱，并且如果需要，它在高温下也具有良好的机械性。这种烧结材料还应该能够通过简单且便宜且还能够制造具有复杂几何形状的成形体的方法制备。
发明概述
根据本发明，上述目的通过如权利要求1所述的基于过渡金属二硼化物的烧结耐磨材料、如权利要求8所述的用于制备这种烧结材料的粉状可烧结混合物、如权利要求15和16所述的这种烧结材料的制备方法以及如权利要求22-26所述的该烧结材料的用途来实现。本申请主题的有利或特别有用的实施方案描述在从属权利要求中。
因此本发明提供一种烧结耐磨材料，其基于过渡金属二硼化物并包含
a)作为主相，80-98.8重量％的细粒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，其中过渡金属选自周期表的IV-VI副族，
b)作为第二相，0.2-5重量％的连续、含氧晶粒间界相和
c)作为第三相，1-15重量％的颗粒碳化硼和/或碳化硅。
本发明另外提供一种用于制备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％的作为金属Al和/或Si的Al和/或Si，和/或其量相当于所述含量的Al和/或Si化合物，
2)任选地至少一种选自周期表IV-VI副族过渡金属的碳化物和硼化物的组分，
3)0.5-19重量％的硼，
4)0-15重量％的碳化硼和/或碳化硅和
5)作为余量，至少一种周期表IV-VI副族的过渡金属二硼化物，其不同于以上组分2)的过渡金属硼化物。
本发明另外提供这种烧结材料的制备方法，其通过将如上所述粉状混合物热压制或热等静压成型或气体加压烧结或火花等离子体烧结，其中任选地添加有机粘结剂和压制助剂。
本发明同样提供一种通过无压烧结制备如上所述烧结材料的方法，其包括步骤：
a)将如上所述粉状混合物与水和/或有机溶剂混合，任选地添加有机粘结剂和压制助剂，从而产生均匀的粉末悬浮液，
b)从该粉末悬浮液产生粒化的粉末，
c)压制粒化的粉末从而形成具有高密度的生坯和
d)在1800-2200℃的温度，在减压下或保护气下将得到的生坯无压烧结。
本发明的烧结材料适于制造耐磨部件，该耐磨部件用在一般设备构造体中、特别是由于其对酸和碱的耐蚀性而用在化学设备构造体中、热力设备构造体中、造纸机中、研磨工艺中和磨损保护中。
本发明同样提供了该烧结材料的用途，其用于制造切削机以及非切削操作和成形、成型工艺和偏转辊用的工具。
另外的用途涉及制造喷水和喷砂的喷嘴。
本发明的烧结材料同样适用作滑动接点、焊接电极和侵蚀钉用的电极材料。
根据本发明，由此表明上述目的是通过提供一种烧结、耐磨的致密材料而实现，该材料基于过渡金属二硼化物并且其基体(主相)包含细粒过渡金属二硼化物或过渡金属二硼化物混晶或其组合。作为第二相，该材料含有薄的连续晶粒间界膜形式的含氧、连续晶粒间界相。在三相点，可以存在较大量或较大范围的含氧第二相。作为第三相，该材料含有充当晶粒生长抑制剂的颗粒碳化硼和/或碳化硅。主相的混晶形成具有另外的晶粒生长抑制作用，因此得到具有良好机械性的烧结材料。本发明的烧结材料对于酸和碱具有令人惊讶地显著耐蚀性，同时保持很好的机械性。
发明详述
如上所述，本发明材料的微观结构包含细粒主相，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。作为第二相，存在低厚度(例如大约2nm)的连续含氧晶粒间界膜。在三相点，可以存在较大量或较大范围的含氧第二相。主要位于晶粒间界的小部分颗粒碳化硼和/或碳化硅作为第三相存在。碳化硼和/或碳化硅另外具有颗粒强化作用。任选地，在材料中还可以存在少量颗粒碳和/或颗粒硼。此外，当Al或Si或其化合物用作烧结助剂时，这些元素可以少量存在于主相中。含氧第二相的比例优选最多2.5重量％。
主相的平均晶粒大小优选小于20μm，更优选小于10μm。第三相的碳化硼和/或碳化硅的平均粒度优选小于20μm，更优选小于5μm，并且第三相的比例为1-15重量％，优选1-4重量％。
主相的平均晶粒大小和碳化硼和/或碳化硅的平均粒度通过在蚀刻的抛光片上的线性截距长度法来测定。
IV-VI副族的过渡金属优选选自Ti、Zr、Hf、V、Nb、Ta、Cr、Mo和W。
主相优选是细粒TiB2和/或ZrB2和/或混晶(TiW)B2和/或(Zr，W)B2和/或(Ti，Zr)B2，更优选是混晶(Ti，W)B2和/或(Zr，W)B2，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。
用于制备根据本发明的可烧结材料的本发明的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％的作为金属Al和/或Si的Al和/或Si，和/或其量相当于所述含量的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％的至少一种选自周期表IV-VI副族的过渡金属碳化物和硼化物的组分，优选碳化钨。任选地，IV-VI副族过渡金属自身和这些过渡金属的氧化物也可以用作组分2)。
3)0.5-19重量％，优选1-5重量％的元素形式的硼。
4)0-15重量％，优选0.5-5重量％的碳化硼和/或碳化硅。
5)作为余量，至少一种周期表IV-VI副族的过渡金属二硼化物，其不同于以上组分2)的过渡金属硼化物。如上所述，过渡金属选自Ti、Zr、Hf、V、Nb、Ta、Cr、Mo和W。组分5)的过渡金属二硼化物优选为TiB2和/或ZrB2，更优选为TiB2。
上述粉状混合物组分优选以极高纯度和小粒度使用。例如，组分5)的过渡金属二硼化物的平均粒度优选不超过4μm，更优选不超过2μm。
本发明的烧结材料可以以本身已知的方式来制备，其通过将如上所述粉状混合物热压制、热等静压成型、气体加压烧结或火花等离子体烧结，其中任选地添加有机粘结剂和压制助剂。在此，可以使用常用的有机粘结剂如聚乙烯醇(PVA)、水溶性树脂和聚丙烯酸以及常用的压制助剂如脂肪酸和蜡。
为了制备本发明的烧结材料，在水中和/或有机溶剂中将至少一种IV-VI副族的过渡金属二硼化物连同其它粉状组分以及任选的有机粘结剂和压制助剂一起处理，从而形成均匀粉末悬浮液。然后将均匀粉末悬浮液转化成粒化粉末，优选通过喷雾干燥进行。然后可以进一步通过热压制或热等静压成型该处理粒化粉末，从而产生烧结材料。
在一个优选实施方案中，本发明的烧结材料通过无压烧结制备。在此，压制如上所述得到的粒化粉末，从而形成具有高密度的生坯。为此，可以使用所有常用的成形工艺，如单轴压制或冷等静压成型以及挤出、注塑、滑移浇铸和加压滑移浇铸。然后通过在1800-2200℃，优选1900-2100℃，更优选大约2000℃的温度，在减压下或保护气下的无压烧结将得到的生坯转化成烧结材料。
优选在无压烧结之前，在低于烧结温度的温度下，在惰性环境中烘焙生坯，以便除去有机粘结剂或压制助剂。
通过无压烧结得到的材料的密度为理论密度的至少大约94％，优选密度为理论密度的至少97％。该密度值确保任何存在的孔隙率为闭合孔隙率。如果需要的话，可以通过热等静压成型使烧结材料后致密化，从而增加密度并较少闭合孔隙率。
选自周期表IV-VI副族的过渡金属碳化物的粉状起始混合物组分在烧结过程中与添加的硼反应，从而形成过渡金属硼化物和碳化硼。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5)的过渡金属二硼化物(例如二硼化钛)形成混晶。该硼化物混晶形成具有晶粒生长抑制作用。添加的和形成的(例如从碳化钨和硼形成的)碳化硼同样具有晶粒生长抑制作用。
Al和/或Si或其化合物作为烧结助剂并且形成的微观结构表明液相烧结过程。
本发明的烧结材料显著地适于制造耐磨部件，该耐磨部件用在一般设备构造体，特别是化学设备构造体，热力设备构造体中，用于造纸机中，研磨工艺中和磨擦保护中。本发明烧结材料的特定用途为切削机以及非切削操作和成形、成型工艺和偏转辊用的工具。它还适用于制造喷水或喷砂的喷嘴以及用作滑动接点、焊接电极和侵蚀钉用的电极材料。
附图简要说明
图1显示了在实施例1中得到的材料的微观结构的光学显微照片；
图2显示了在实施例2中得到的烧结材料的微观结构的光学显微照片；
图3显示了图1微观结构的典型区域的亮场透射电子显微镜照片；
图3b和3c显示了对应于图3a的EELS光谱，其显示了含氧第二相的被检区的定性元素组成；
图4a显示了图1微观结构的典型区域的典型(Ti，W)B2-(Ti，W)B2晶粒间界的亮场透射电子显微镜照片；
图4b显示了通过EFTEM(能量过滤透射电镜法)测定的对应于图4a的氧分布；
图4c显示了沿着图4b中绘制的线的氧的行扫描；和
图5显示了在对比例1中得到的烧结材料的微观结构的光学显微照片；
下列实施例和对比例1说明本发明。
实施例1
将450g TiB2粉末(d50＝2μm；1.7重量％的氧，0.15重量％的碳，0.077重量％的Fe)、30g碳化钨(d50＜1μm)、10g无定形硼(纯度：96.4％，d50＜1μm)、8g碳化硼粉末(d50＝0.7μm)和2g Al2O3(勃姆石作为起始材料)连同10g平均摩尔质量为1500的作为粘结剂的聚乙烯醇和20g作为压制助剂的硬脂酸分散在水溶液中并喷雾干燥。在1000巴下单轴压制粒状喷雾干燥材料从而得到生坯。碳化的生坯的总含氧量为2.7％。在减压下以10K/min将生坯加热到2020℃，并在该烧结温度下保持45分钟。关掉热源，在氩气下进行冷却。
得到的样品的烧结密度为理论密度的98％。
微观结构的光学显微照片显示在图1中。
得到的微观结构包含(Ti，W)B2混晶基体、细碎的颗粒B4C、Ti-Al-B-O相，该相主要存在于三相点(图3a、b和c，EELS光谱)下并且是大约2nm厚的连续含氧无定形的晶粒间界膜(图4a，b和c，EFTEM)。
烧结体的硬度为2500(HKO.1)，断裂韧性通过SEVNB法来测定并且为5.3MPa·m1/2，E模量为560GPa和通过4点法测量的挠曲强度为500MPa。
实施例2
将450g TiB2粉末(d50＝2μm；1.7重量％的氧，0.15重量％的碳，0.077重量％的Fe)、30g WC(d50＜1μm)、10g无定形硼(纯度：96.4％，d50＜1μm)、8g B4C(d50＝0.7μm)和2g Al2O3(勃姆石作为起始材料)连同10g平均摩尔质量为1500的作为粘结剂的聚乙烯醇和20g作为压制助剂的硬脂酸分散在水溶液中并喷雾干燥。在1200巴下对粒状喷雾干燥材料进行冷等静压成型从而得到生坯。碳化的生坯的总含氧量为2.7％。在减压下以10K/min将生坯加热到2060℃，并在该烧结温度下保持45分钟。关掉热源，在氩气下进行冷却。
得到的样品的烧结密度为理论密度的98.7％。
微观结构的光学显微照片显示在图2中。
得到的微观结构包含(Ti，W)B2混晶基体、细碎的颗粒B4C、Ti-Al-B-O相，该相主要存在于三相点并且是大约2nm厚的连续含氧无定形的晶粒间界膜。
实施例3
将436g TiB2粉末(d50＝2μm；1.7重量％的氧，0.15重量％的碳，0.077重量％的Fe)、44g WC(d50＜1μm)、18g无定形硼(纯度：96.4％，d50＜1μm)和2g Al2O3(勃姆石作为起始材料)连同10g平均摩尔质量为1500的作为粘结剂的聚乙烯醇和20g作为压制助剂的硬脂酸分散在水溶液中并喷雾干燥。在1200巴下对粒状喷雾干燥材料进行冷等静压成型从而得到生坯。以10K/min将生坯加热到2020℃，并在该烧结温度下保持45分钟。关掉热源，在氩气下进行冷却。
实施例4：
在氩气下，通过在2000℃和1950巴下的热等静压成型使实施例1的烧结体后致密化，保持60分钟。得到的样品的密度为理论密度的99.1％。
在100℃下1摩尔的HCl中，使如实施例4描述所制得的材料样品进行耐腐蚀试验。样品大小为20×3×4mm。使样品暴露于腐蚀介质90分钟。此后，腐蚀速率为1.51μg/mm2·h。
为了比较，还在对比样品上进行该测试，所述对比样品由含0.5体积％的Fe-Cr-Ni粘结相的烧结TiB2材料制得。在具有如上相同大小的样品上测定的腐蚀速率为5.26μg/mm2·h，这样来自实施例4的本发明材料的腐蚀速率减少了4/5。
对比例1：(不使用Al化合物作为烧结助剂的起始混合物)
将450g TiB2粉末(d50＝2μm；1.7重量％的氧，0.15重量％的碳，0.077重量％的Fe)、30g WC(d50＜1μm)、20g无定形硼(纯度：96.4％，d50＜1m)连同10g平均摩尔质量为1500的作为粘结剂的聚乙烯醇和20g作为压制助剂的硬脂酸分散在水溶液中并喷雾干燥。在1200巴下对粒状喷雾干燥材料进行冷等静压成型从而得到生坯。在减压下以10K/min将生坯加热到2170℃，并在该烧结温度下保持45分钟。关掉热源，在氩气下进行冷却。随后在1950巴的氩气压力下在2000℃下使烧结体进行后致密化一小时。密度为理论密度的97.9％。
微观结构的光学显微照片显示在图5中。
得到的微观结构包含(Ti，W)B2混晶基体和颗粒碳化硼，颗粒碳化硼部分存在于晶粒间界中和部分存在于混晶晶粒中。平均晶粒直径为大约100μm。在此需要较高的烧结温度，从而达到闭合孔隙率。得到粗晶微观结构。
Claims (26)
1、一种烧结耐磨材料，其基于过渡金属二硼化物并包含
a)作为主相，80-98.8重量％的细粒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，其中过渡金属选自周期表的IV-VI副族，
b)作为第二相，0.2-5重量％的连续、含氧晶粒间界相和
c)作为第三相，1-15重量％的颗粒碳化硼和/或碳化硅。
2、如权利要求1所述的材料，其中主相a)的平均晶粒大小为小于20μm，优选小于10μm。
3、如权利要求1和/或2所述的材料，其中第三相c)的碳化硼和/或碳化硅的平均粒度小于20μm，优选小于5μm。
4、如权利要求1-3至少一项所述的材料，其中第三相c)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，其中第二相b)的存在比例为最多2.5重量％。
6、如权利要求1-5至少一项所述的材料，其中IV-VI副族的过渡金属选自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TiB2和/或ZrB2和/或混晶(TiW)B2和/或(Zr，W)B2和/或(Ti，Zr)B2，优选是混晶(Ti，W)B2和/或(Zr，W)B2，更优选是混晶(Ti，W)B2或混晶(Zr，W)B2。
8、一种用于制备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％的作为金属Al和/或Si的Al和/或Si，和/或其量相当于所述含量的Al和/或Si化合物，
2)任选地至少一种选自周期表IV-VI副族过渡金属的碳化物和硼化物的组分，
3)0.5-19重量％，优选1-5重量％的硼，
4)0-15重量％，优选0.5-5重量％的碳化硼和/或碳化硅和
5)作为余量，至少一种周期表IV-VI副族的过渡金属二硼化物，其不同于以上组分2)的过渡金属硼化物。
9、如权利要求8所述的混合物，其中组分1)的比例为0.2-0.6重量％。
10、如权利要求8和/或9所述的混合物，其中组分2)的比例为≥0.25重量％。
11、如权利要求8-10至少一项所述的混合物，其中组分5)的过渡金属二硼化物的平均粒度为≤4μm，优选≤2μm。
12、如权利要求8-11至少一项所述的混合物，其中IV-VI副族的过渡金属选自Ti、Zr、Hf、V、Nb、Ta、Cr、Mo和W。
13、如权利要求8-12至少一项所述的混合物，其中组分2)为碳化钨。
14、如权利要求8-13至少一项所述的混合物，其中组分5)的过渡金属二硼化物为TiB2和/或ZrB2。
15、一种制备如权利要求1-7至少一项所述的烧结材料的方法，其包括将如权利要求8-14至少一项所述的粉状混合物热压制或热等静压成型或气体加压烧结或火花等离子体烧结，其中任选地添加有机粘结剂和压制助剂。
16、一种通过无压烧结制备如权利要求1-7至少一项所述的烧结材料的方法，其包括步骤：
a)将如权利要求9-14至少一项所述的粉状混合物与水和/或有机溶剂混合，任选地添加有机粘结剂和压制助剂，从而产生均匀的粉末悬浮液，
b)从该粉末悬浮液产生粒化的粉末，
c)压制粒化的粉末从而形成具有高密度的生坯和
d)在1800-2200℃的温度，在减压下或保护气下将得到的生坯无压烧结。
17、如权利要求16所述的方法，其中步骤b)中的粒化粉末的产生通过喷雾干燥进行。
18、如权利要求16或17所述的方法，其中步骤c)中的生坯的产生通过单轴压制、冷等静压成型、挤出、注塑、滑移浇铸或加压滑移浇铸进行。
19、如权利要求16-18至少一项所述的方法，其中在无压烧结之前，在低于烧结温度的温度下在惰性环境中烘焙步骤c)中得到的生坯。
20、如权利要求16-19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℃的温度下进行。
21、如权利要求16-20至少一项所述的方法，其中通过热等静压成型使通过无压烧结产生的材料后致密化。
22、如权利要求1-7至少一项所述的烧结材料的用途，其用于制造一般设备构造体中、特别是化学设备构造体中、热力设备构造体中、造纸机中、研磨工艺中和磨擦保护中的耐磨部件。
23、如权利要求1-7至少一项所述的烧结材料的用途，其用于制造切削机用的工具。
24、如权利要求1-7至少一项所述的烧结材料的用途，其用于制造非切削操作和成形、成型工艺和偏转辊用的工具。
25、如权利要求1-7至少一项所述的烧结材料的用途，其用于制造喷水或喷砂喷嘴。
26、如权利要求1-7至少一项所述的烧结材料的用途，其用作滑动接点、焊接电极和侵蚀钉的电极材料。
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|---|---|---|---|---|
| JPH0610106B2 (ja) * | 1985-06-14 | 1994-02-09 | 旭硝子株式会社 | 導電性可変ＺｒＢ２質複合焼結体 |
| JPH0627036B2 (ja) * | 1988-06-22 | 1994-04-13 | 日本鋼管株式会社 | 高強度高靭性ＴｉＢ▲下２▼セラミックス |
| JPH0674177B2 (ja) * | 1990-09-21 | 1994-09-21 | 工業技術院長 | ホウ化チタン／炭化ケイ素複合セラミックスの高強度化法 |
| JPH05319935A (ja) * | 1991-10-29 | 1993-12-03 | Mitsubishi Heavy Ind Ltd | ＴｉＢ２ セラミックス焼結体 |
| DE4319460A1 (de) * | 1993-06-11 | 1994-12-15 | Kempten Elektroschmelz Gmbh | Verbundwerkstoffe auf der Basis von Borcarbid, Titandiborid und elementarem Kohlenstoff sowie Verfahren zu ihrer Herstellung |
| US5449646A (en) * | 1994-07-29 | 1995-09-12 | Dow Corning Corporation | Preparation of high density zirconium diboride ceramics with preceramic polymer binders |
| JPH09100165A (ja) * | 1995-10-03 | 1997-04-15 | Mitsubishi Materials Corp | 硼化物セラミックス及びその製造方法 |
| DE102006013729A1 (de) * | 2006-03-24 | 2007-10-04 | Esk Ceramics Gmbh & Co. Kg | Gesinterter Werkstoff, sinterfähige Pulvermischung, Verfahren zur Herstellung des Werkstoffs und dessen Verwendung |
-
2006
- 2006-03-24 DE DE102006013746A patent/DE102006013746A1/de not_active Withdrawn
-
2007
- 2007-03-12 US US12/225,473 patent/US20090105062A1/en not_active Abandoned
- 2007-03-12 WO PCT/EP2007/002160 patent/WO2007110149A1/de active Application Filing
- 2007-03-12 CN CNA2007800106042A patent/CN101410347A/zh active Pending
- 2007-03-12 EP EP07723199A patent/EP1999087A1/de not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102869807A (zh) * | 2010-05-04 | 2013-01-09 | 攀时欧洲公司 | 二硼化钛靶子 |
| CN102869807B (zh) * | 2010-05-04 | 2015-12-16 | 攀时欧洲公司 | 二硼化钛靶子 |
| CN109133937A (zh) * | 2018-08-08 | 2019-01-04 | 天津德天助非晶纳米科技有限公司 | 三元硼化物及其制备方法和应用 |
| CN109133937B (zh) * | 2018-08-08 | 2021-05-25 | 天津德天助非晶纳米科技有限公司 | 三元硼化物及其制备方法和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20090105062A1 (en) | 2009-04-23 |
| DE102006013746A1 (de) | 2007-09-27 |
| EP1999087A1 (de) | 2008-12-10 |
| WO2007110149A1 (de) | 2007-10-04 |
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