CN101921114A - 具有面心立方结构的高纯度TiB陶瓷粉末及其制备方法 - Google Patents

具有面心立方结构的高纯度TiB陶瓷粉末及其制备方法 Download PDF

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CN101921114A
CN101921114A CN 201010281267 CN201010281267A CN101921114A CN 101921114 A CN101921114 A CN 101921114A CN 201010281267 CN201010281267 CN 201010281267 CN 201010281267 A CN201010281267 A CN 201010281267A CN 101921114 A CN101921114 A CN 101921114A
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胡建东
董鲜峰
陶思托
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Abstract

本发明涉及一种具有面心立方结构的高纯度TiB陶瓷粉末及其制备方法。TiB陶瓷粉末是由Ti元素和B元素组成的化合物，化学式为TiB，化学组分为40～60％Ti和40～60％B元素，原子比例和化学组分相同；在低于熔点温度时，它为固体粉末状态，具有晶体结构，原子按面心立方点阵方式排列，即TiB晶体由面心立方晶胞组成，面心立方晶胞的特征是当原子以面心平移时，可以得到周围环境完全相同的原子。所述的TiB陶瓷粉末的制备方法包括：压制压坯、配制固体渗剂、压坯装盒、烧结和制粉五步。其特点是工艺简单，成本低，质量容易控制，适合工业化生产。

Description

具有面心立方结构的高纯度TiB陶瓷粉末及其制备方法
技术领域
本发明涉及一种陶瓷粉末材料及其制备方法，属于工程材料领域。
背景技术
陶瓷是一种重要而特殊的工程材料，具有耐高温、耐腐蚀、耐磨损和特殊功能等特点，是特殊场合必须使用的材料。陶瓷是由金属元素和非金属元素形成的化合物。通常称氧和金属形成的化合物为氧化物陶瓷，其中常见的有Al2O3和CeO2等。还有一类陶瓷是由金属和非氧元素形成的陶瓷，常见的有SiC、SiN，MoSi2、TiN和TiC等，它们被归结为非氧化物陶瓷。这类陶瓷在耐高温、耐腐蚀和耐磨损方面表现出非常优良的性能。其中氮化硅SiN的强度可达700MP；硬度1800Kg/mm2。
金属和硼元素形成的化合物属于非氧化物陶瓷。它们包括二硼化钛(TiB 2)、一硼化铁(FeB)、一硼化铬(CrB)、一硼化钼(MoB)、一硼化钽(TaB)、二硼化磁zirconium boride(ZrB 2)和二硼化铪hafnium boride(HfB 2)等.这些陶瓷熔点和硬度高，耐磨性好，但是很难制成纯粉末材料。零件的成形成本高。钛-硼体系化合物理论上有Ti2B，TiB，Ti3B4和TiB2等。但在Ti-B相涂上给出的只有TiB2和TiB，对它们的研究较多。TiB2具有六方晶体结构；TiB具有正交晶体结构。TiB2有粉末材料存在，但TiB尚无粉末状态材料。
发明内容
TiB2和TiB是Ti-B体系中二种重要化合物。TiB2具有六方晶体结构，TiB具有正交晶体结构。TiB2有粉末产品，而TiB还没用粉末产品。后者是以原位生成的方式在复合材料中获得的，与基体材料伴生存在，可明显改善材料的性能。目前尚无可靠方法制备正交结构TiB，更没有关于面心立方结构TiB的报道。本发明的目的是提出与以上不同的具有面心立方结构的高纯度TiB陶瓷粉末及其制备方法，填补Ti-B系陶瓷粉末材料空白，为功能陶瓷市场添加新品种。
本发明的上述目的通过以下技术方案实现，结合附图说明如下：
本发明的一种具有面心立方结构的高纯度TiB陶瓷粉末，是由Ti元素和B元素组成的化合物，化学式为TiB，化学组分为40～60％Ti和40～60％B元素，原子比例和化学组分相同；在低于熔点温度时，它为固体粉末状态，具有晶体结构，原子按面心立方点阵方式排列， 即TiB晶体由面心立方晶胞组成，面心立方晶胞的特征是当原子以面心平移时，可以得到周围环境完全相同的原子。
所述的一种具有面心立方结构的高纯度TiB陶瓷粉末的制备方法，具体步骤如下：
步骤一，压制压坯
用压力机压制压坯：先把Ti粉装入模具里，然后对粉末施压制成压坯，密度为理论密度的50％～90％；
步骤二，配制固体渗剂
固体渗剂的成分是5～10％B4C，20～80％SiC％，5～8％KBF4，8～12％Mn-铁和0～30％木炭；或者是以硼铁取代Mn-铁，以硼砂取代碳化硼B4C，按同样成分配制成的固体渗剂；
步骤三，压坯装盒
准备好料盒，先用按步骤二配制的固体渗剂铺底，把压坯放在中间，四周及上面充填固体渗剂，其上面放置另外一快压坯，如果多个压坯同时烧结，以同样方式用固体渗剂将第二块压坯包围，盖上盖板用黄泥封好缝隙等待烧结，使用的固体渗剂和压坯总重量的比例大约为7～10∶1；固体渗剂为颗粒状；或者是以未经压制的Ti粉取代Ti压坯作为原料直接按以上方式装盒”；
步骤四，烧结
把装好的料盒放在电阻炉内烧结，烧结温度为700～1200C，时间为2～6小时，不用保护气氛；
步骤五，制粉
待料盒充分冷却后，打开盖板，把烧结的压坯取出，经轻微碾压后便获得了具有面心立方结构的高纯度TiB陶瓷粉末，其颗粒度和原始Ti粉颗粒度基本相同，纯度可以达到95％以上。
现有正交晶体结构TiB通常在复合材料中原位生成，或是通过热压烧结制成的纯度较高的块体材料。正交TiB材料的制备方法有：1，固相反应合成法，它是以Ti和TiB2粉末为原材料，经混合后压制成压坯，对压坯进行烧结获。产物通常含剩余Ti或TiB2。2，气-固反应法，它是通过碳氢气体(hydrocarbon)和Ti粉末反应。3，自蔓延高温烧结合成(SHS)，它是一种典型通过自身放热达到高温实现固相合成工艺。4，火花等离子体烧结(SPS)，它的原理和SHS相同只是反应的开始是通过等离子体来点燃的。产物成分难控制。
用以上方法制的复合材料通常含剩余钛或二硼化钛，降低了材料性能。目前合成的含TiB较多的复合材料是含有80％TiB和20％钛金属的复合材料。
本发明使用固体渗剂和Ti粉制备TiB，在料合内用固体渗剂包围Ti粉，在高温加热时固体渗剂可以产生活性硼原子，由活性硼原子和Ti原子发生化学反应生产TiB粉末，其化学反应有：
4BF3+3SiC+4O2＝2BF2+B2O3+2SiF4↑+SiO2+2CO↑    (1)
B4C+2KF+SiC+4O2＝[B]+BF2↑+B2O3+K2SiO3+2CO↑  (2)
2B4C+2BF3+5O2＝[B]+BF2↑+B2O3+2CO2↑          (3)
活性硼原子可以按下式获得：
3BF2＝[B]+2BF3↑                               (4)
B2O3和BF3或SiC按下式反应生成活性[B]原子和BF2：
2B2O3+2BF3＝3B2O2+2F2                          (5)
3B2O2＝2B2O3+2[B]                              (6)
4B2O3+6SiC+6BF3＝11[B]+3BF2+3SiO2+3SiF4+6CO↑  (7)
制成纯TiB粉末的机理是活性[B]原子向Ti压坯或Ti粉扩散，与Ti原子结合生产TiB。由于Ti压坯含有大量孔隙，[B]原子很容易从表面向心部扩散。在温度足够高和保温时间足够长时可以保证整个Ti压坯完全变成TiB。方法的基本原理是通过活性B原子逐渐向Ti压坯扩散，形成TiB粉末块体，这是有别于其他方法的创新之处。
TiB粉末颗粒的最终尺寸取决于原始Ti粉尺寸。
面心立方TiB粉末的制备方法
粉末制备是通过如图6所示的工艺路线来完成的。
图6TiB粉末制备工艺路线
由图6可见，TiB粉末制备工艺方法包括5个步骤。
第一步是准备Ti粉末材料。用于制备TiB粉末的Ti粉为市场销售的Ti粉，粒度为-200目或其它规格；纯度为大于95％或更纯。
第二步是把Ti粉压制成压坯，压坯密度为理论密度的50％～90％。压坯用常规粉末冶金方法制备。
第三步是把Ti粉末压坯装入料盒，在料盒内用固体渗剂把压坯材料包围起来(如图7所示)。固体渗剂的成分是5～10％B4C，20～80％SiC％，5～8％KBF4，8～12％Mn-铁和0～30％木炭；或者是以硼铁取代Mn-铁，以硼砂取代碳化硼(B4C)，按同样成分配制成的固体渗剂。
具体工艺方法(见图7)是先把固体渗剂铺(1)放在料盒(2)的底部，然后把压坯(3)放在固体渗剂上，随后把压坯材料包围起来，它们之间用固体渗剂隔离，在压坯材料周围也添加固体渗剂，在压坯上部也添加渗剂，把压坯包围在固体渗剂之中。最后把盒盖或称盖板(4)盖在料盒上，用黄泥或石墨纸封严以避免盒内反应气氛外溢和外部空气进入盒内。
第四步是把装好的料盒放置在无保护气氛的电阻炉中进行加热，加热温度是700～1200C，保温时间是2～6小时。。
Ti压坯烧结后呈蓬松团块状，轻微粉碎后成为TiB粉末，具有图3所示的形貌。
第五步是把蓬松团块粉碎成粉末。
本发明的技术效果：
本发明制备的TiB粉末不同于现有正交TiB粉末，而是一种具有面心立方结构(f.c.c.)的新型TiB陶瓷粉末。在检索文献中未见报道，在市场也没有见到类似产品。采用的方法简单、可靠、成本低和容易实现，材料性能好。
附图说明
图1TiB粉末照片。
图2TiB粉末的X-射线图，符合面心立方结构(X-射线衍射卡No.06-0641)
图3面心立方TiB扫描电镜照片
图4TEM显微像，显示TiB颗粒形貌，尺寸小于100nm。
图5TiB颗粒的电子衍射图。
图6TiB粉末制备工艺路线。
图7材料装箱示意。
图中：1.固体出渗剂2.盒盖3.料盒4.压坯
具体实施方式
下面结合实例具体说明本发明的具有面心立方结构的高纯度TiB陶瓷粉末及其制备方法。
本发明说书的一种具有面心立方结构的高纯度TiB陶瓷粉末，是由Ti元素和B元素组成的化合物，化学式为TiB，化学组分为40～60％Ti和40～60％B元素，原子比例和化学组分相同；在低于熔点温度时，它为固体粉末状态，具有晶体结构，原子按面心立方点阵方式排列，即TiB晶体由面心立方晶胞组成，面心立方晶胞的特征是当原子以面心平移时，可以得到周围环境完全相同的原子。
一种用于上述的具有面心立方结构的高纯度TiB陶瓷粉末的制备方法，
具体步骤如下：
1、压制压坯
用常规粉末冶金方法在模具里把Ti粉压制成形，获得压坯，压制力为100MPa左右。压坯重量由膜腔体积决定，其密度为理论密度的50％～90％。
2、配制固体渗剂
配制固体渗剂，其成分为5～10％B4C，20～80％SiC％，5～8％KBF4，8～12％Mn-铁和0～30％木炭；或者是以硼铁取代Mn-铁，以硼砂取代碳化硼(B4C)。
3、把压坯装进料盒
在料盒里把压坯用固体渗剂包围起来，固体渗剂和压坯的重量比约为7～10∶1。最终Ti压坯和固体渗剂在盒内的布置情况见图7。需要注意的是每个压坯必须用固体渗剂隔开。最后用黄泥或石墨纸封住盖板的缝隙。用Ti粉取代Ti粉压坯也能获得同样效果。
4、烧结
把装好的料盒放置在无保护气氛的电阻炉中进行加热烧结，获得TiB烧结体。加热温度是700-1200C左右，时间是2～6小时。
5、制粉
把烧结体从盒中取出，将其粉碎便获得TiB粉末。
以下是该方法的具体实施例：
第一步压制压坯
用压力机压制压坯，具体方法是先把Ti粉装入模具里，然后对粉末施压制成压制。在这个例子里，我们压坯的直径为6厘米，高4厘米，孔隙度为50％，压坯重量为80克。
第二步配制固体渗剂
成分20％渗碳剂，5％B4C，60％SiC，5％KBF4和10％Mn-铁％配制100公斤固体渗剂。配置方法为称量20公斤渗碳剂；5公斤B4C：60公斤SiC：5公KBF4和10公斤Mn-铁。以上原材料均为粉末状态，颗粒度为80～200目。把这些称量好的粉末装入混料机，经4～8小时混合后取出备用。其中渗碳剂的制备方法同上。混料方式为干混。
第三步装盒
按图7示意的情况装盒。料盒直径为16厘米，高14厘米，由低碳钢焊接而成。先用固体渗剂铺底，把压坯放在中间，四周及上面充填固体渗剂。其上面放置另外一快压坯，以同样方式用固体渗剂将第二块压坯包围。盖上盖板用黄泥封好缝隙等待烧结。使用的固体渗剂和压坯总重量的比例大约是5∶1。
第四步烧结
把装好的料盒放在电阻炉内烧结，加热温度为850C，保温2小时，不用保护气氛。
第五步制粉
待料盒充分冷却后，打开盖板，把烧结的压坯取出，经轻微碾压后便获得了TiB粉末材料，其颗粒度和原始Ti粉颗粒度基本相同，纯度可以达到95％以上。
采用以上配方时，以硼砂取代B4C，以硼铁取代Mn铁，即按20％渗碳剂，5％硼砂，60％SiC，5％KBF4和10％硼铁配制固体渗剂时也能获得同样的效果。
用以上方法制备的材料的性能如下：
1、面心立方TiB粉末形貌
图1显示合成的面立方TiB粉末。
由图1可见面心立方TiB粉末是颗粒度细小的粉末材料，颜色为褐色或咖啡色。
2，面心立方TiB电阻率
利用4端子法测定的面心立方TiB粉末电阻率为15×10-7Ωm，表明面心立方TiB粉末具有良好的导电性，是导电陶瓷材料。
3，面心立方TiB的电极性能
把TiB粉末压制成压坯，在1200C烧结4小时，真空保护，制成片状样品，其尺寸是直径10mm，厚度1.3mm。以Mg为阴极，以浸NaCl水溶液的棉布为电解质，以TiB片或其它金属作为阳极，测试电池的输出电压和功率。电池结构为：
Mg(阴极)//浸NaCl水溶液的棉布(电解质)//TiB(阳极)
表1显示实验结果。由表中数据可见，TiB具有最好的导电性。在燃料电池方面的效果有待进一步确认。
表1TiB和其它阳极材料电性能测试数据
  阳极   TiB   TiB2   LiNiO2   Ag   Fe   Cu   Al
  输出电压/V   1.58   1.27   1.53   1.45   0.73   1.38   0.92
  电流密度/mA/cm2   57.5   7.5   15   12.5   8   25   4.75
  功率密度/mW/cm2   90.85   9.52   22.95   18.12   5.58   34.5   4.32
*以上数据的测试是在室温进行的。
4、低温电阻
测试试样直径10毫米，厚1.3毫米。在1200C真空烧结4小时制成。用美国产keithley，2000型万用表(精度6位半)测试电阻特性。试样在室温的电阻值是70～75欧姆，在液氮中的电阻值为零。这一现象表明TiB可能存在低温超导特性。其具体性能指标有待进一步确认。
5、X-射线晶体结构测量
图2显示TiB粉末的x-衍射图。图2衍射图的标定结果显示在表2。
表2面心立方TiB粉末X-射线衍射峰的标定结果
  峰位置   1   2   3   4   5
  2-Theta测量值   36.529   42.479   61.736   74.050   77.934
  2-Theta标准值   36.649   42.611   61.797   73.995   77.923
  晶面指数   111   200   220   311   222
由晶面指数可知，合成TiB粉末材料的晶体结构为面心立方结构(f.c.c.)。
6、面心立方TiB粉末形貌的扫描电子显微镜(SEM)观察
图3是面心立方TiB材料的扫描电子显微镜照片。由照片可见TiB颗粒粘结在一起，形成集团，每个集团之间松散连接或者是被孔隙隔离。TiB颗粒呈片状，片的边缘不规则，沿某个方向择优突出。说明TiB颗粒在形核和长大时延某晶体学方向择优生长。
7、透射电子显微镜(TEM)晶体结构测量和形貌观察
把TiB粉末放在酒精溶液中在超声波中震动5分钟后，TiB集团被粉碎成粉末，由碳支持膜铜网把分散后的粉末捞起，制成透射电子显微镜样品。图4显示透射电镜观测到的TiB粉末形貌；颗粒尺寸小于100nm，形貌呈非等轴状。图5显示这些颗粒的电子衍射图。电子衍射图由一系列同心衍射成。
Fig.4TEM显微像，显示TiB颗粒形貌，尺寸小于100nm
Fig.5TiB颗粒的电子衍射图
对这些衍射环进行了标定。结果列于表3。
表3电子衍射图的标定结果
Figure BDA0000026244630000071
表中R分别代表衍射环的半径；d代表晶格常数；N#为各晶面指数平方和，即N＝h2+k2+l2。由标定结果可见TiB粉末颗粒的晶体结构符合面心立方结构，与x-射线衍射测定的结果一致。
8、其它性能
表4列出了面心立方TiB粉末的一些物理和机械性能。
表4面心立方TiB粉末的物理和机械性能
  纯度   ≥95％
  熔点   2200℃
  颜色   褐色
  分子式   TiB
[0113] 
  晶体结构   立方结构
  活性   在氢氟酸、硫酸、盐酸和硝酸中不发生反应
  粉末颗粒尺寸/nm   100-1500
  硬度/Hv   1000
  电阻率/Ωm   ×10-7
X-射线衍射和电子衍射测定TiB粉末具有面心立方晶体结构。TiB粉末的熔点为2200C，硬度Hv 1000，颜色为褐色。纯度在95％以上。和氢氟酸、硫酸、盐酸和硝酸基本不发生反应。
面心立方TiB粉末应用价值
主要应用有用：
1、作为导电陶瓷材料。可以制作真空镀膜导电蒸发舟和高温电热元件等。
2、可用其制造陶瓷精加工刀具、拉丝模、挤压模、喷砂嘴、高温密封元件等。
3、添加在各种金属基体中，制备金属基复合材料。可作为多元复合材料的重要组元，与TiC，TiN，SiC等材料制成陶瓷复合材料，用于各种耐高温部件及功能部件，如高温坩埚、引擎部件等。也可用其制作装甲防护材料。
4、可以作为铝电解槽阴极涂层材料。使铝电解槽的耗电量降低，电解槽寿命延长。
5、可作为金属表面熔覆材料，在金属表面制成耐高温、抗腐蚀涂层。
6、可以作为电池电极(包括燃料电池)和超导材料。

Claims (2)

1.一种具有面心立方结构的高纯度TiB陶瓷粉末，其特征在于，是由Ti元素和B元素组成的化合物，化学式为TiB，化学组分为40～60％Ti和40～60％B元素，原子比例和化学组分相同；在低于熔点温度时，它为固体粉末状态，具有晶体结构，原子按面心立方点阵方式排列，即TiB晶体由面心立方晶胞组成，面心立方晶胞的特征是当原子以面心平移时，可以得到周围环境完全相同的原子。
2.用于权利要求1所述的一种具有面心立方结构的高纯度TiB陶瓷粉末的制备方法，其特征在于，具体步骤如下：
步骤一，压制压坯
用压力机压制压坯：先把Ti粉装入模具里，然后对粉末施压制成压坯，密度为理论密度的50％～90％；
步骤二，配制固体渗剂
固体渗剂的成分是5～10％B4C，20～80％SiC％，5～8％KBF4，8～12％Mn-铁和0～30％木炭；或者是以硼铁取代Mn-铁，以硼砂取代碳化硼B4C，按同样成分配制成的固体渗剂；
步骤三，压坯装盒
准备好料盒，先用按步骤二配制的固体渗剂铺底，把压坯放在中间，四周及上面充填固体渗剂，其上面放置另外一快压坯，如果多个压坯同时烧结，以同样方式用固体渗剂将第二块压坯包围，盖上盖板用黄泥封好缝隙等待烧结，使用的固体渗剂和压坯总重量的比例大约为7～10∶1；固体渗剂为颗粒状；或者是以未经压制的Ti粉取代Ti压坯作为原料直接按以上方式装盒”；
步骤四，烧结
把装好的料盒放在电阻炉内烧结，烧结温度为700～1200C，时间为2～6小时，不用保护气氛；
步骤五，制粉
待料盒充分冷却后，打开盖板，把烧结的压坯取出，经轻微碾压后便获得了具有面心立方结构的高纯度TiB陶瓷粉末，其颗粒度和原始Ti粉颗粒度基本相同，纯度可以达到95％以上。
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WO2012034362A1 (zh) * 2010-09-15 2012-03-22 吉林大学 具有面心立方结构的高纯度Ti(B，N)陶瓷粉末及其制备方法
CN102632261A (zh) * 2012-04-26 2012-08-15 株洲精工硬质合金有限公司 一种金属陶瓷刀具及其制备方法
CN103302266A (zh) * 2013-06-03 2013-09-18 江苏蓝日超硬钢材料有限公司 一种自蔓延合成TiB2颗粒增强铜基表面复合材料的制备方法及一种复合铜铸件
CN109704354A (zh) * 2019-03-07 2019-05-03 吉林大学 一种单一相纳米立方一硼化钛的高温高压制备方法
CN111377458A (zh) * 2020-04-18 2020-07-07 蒋央芳 一种超细硼化铁的制备方法

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WO2012034362A1 (zh) * 2010-09-15 2012-03-22 吉林大学 具有面心立方结构的高纯度Ti(B，N)陶瓷粉末及其制备方法
CN102632261A (zh) * 2012-04-26 2012-08-15 株洲精工硬质合金有限公司 一种金属陶瓷刀具及其制备方法
CN102632261B (zh) * 2012-04-26 2013-10-23 株洲精工硬质合金有限公司 一种金属陶瓷刀具及其制备方法
CN103302266A (zh) * 2013-06-03 2013-09-18 江苏蓝日超硬钢材料有限公司 一种自蔓延合成TiB2颗粒增强铜基表面复合材料的制备方法及一种复合铜铸件
CN109704354A (zh) * 2019-03-07 2019-05-03 吉林大学 一种单一相纳米立方一硼化钛的高温高压制备方法
CN109704354B (zh) * 2019-03-07 2021-12-21 吉林大学 一种单一相纳米立方一硼化钛的高温高压制备方法
CN111377458A (zh) * 2020-04-18 2020-07-07 蒋央芳 一种超细硼化铁的制备方法

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