CN107188566A - 一种二硼化钛金属陶瓷的制备方法 - Google Patents

一种二硼化钛金属陶瓷的制备方法 Download PDF

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CN107188566A
CN107188566A CN201710510068.8A CN201710510068A CN107188566A CN 107188566 A CN107188566 A CN 107188566A CN 201710510068 A CN201710510068 A CN 201710510068A CN 107188566 A CN107188566 A CN 107188566A
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titanium diboride
preparation
cermet
parts
argon gas
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张永华
许蘅
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Wang Jingshuo
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Changzhou Yee Tong International Trade Co Ltd
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Abstract

本发明公开了一种二硼化钛金属陶瓷的制备方法，属于无机化学材料制备技术领域。本发明首先以二硼化钛，碳化硅，氮化硼，氧化铝，氧化钙，氧化镁和助溶剂为原料，加入无水乙醇后湿法球磨、过筛、干燥，再加入粘结剂，制得混合粉料，再依次经初压和冷等静压成型，得素坯，随后将素坯于氩气保护状态下高温烧结，制得预制体，再以预制体为阴极，高纯石墨棒为阳极，熔盐为电解质，于氩气保护状态下恒温电解，再将阴极产物取出后洗涤、干燥，即得二硼化钛金属陶瓷。本发明所得二硼化钛金属陶瓷致密度高，机械性能优异，具有优良的耐磨性能。

Description

一种二硼化钛金属陶瓷的制备方法
技术领域
本发明公开了一种二硼化钛金属陶瓷的制备方法，属于无机化学材料制备技术领域。
背景技术
二硼化钛（TiB2）是硼和钛最稳定的化合物，为C32型结构，以共价键形式结合，属六方晶系的准金属化合物。二硼化钛具有高熔点、高强度、高硬度和高弹性模量，因此在结构材料中作为硬质相而被广泛应用于切削工具、耐磨构件，金属熔炼坩埚，轻质装甲等。较之其他陶瓷材料，二硼化钛还具有良好的导电性，正是由于这些优良的物理化学性使二硼化钛备受关注。
但是，二硼化钛是脆性材料，单一的二硼化钛韧性很低（3.5MPa·m1/2）。并且，由于二硼化钛具有强的共价键结构和很低的分散系数，使得致密化过程受到限制，在烧结过程中表现出热膨胀的各向异性，因而制备完全密实的二硼化钛陶瓷十分困难，大大限制了其商业应用。
目前常用的脆性材料强化增韧方法中，金属基体增强不仅能够密实材料、增加韧性，同时还能改善二硼化钛的烧结性能。金属的熔点比二硼化钛低，在烧结过程中容易发生熔化，形成金属液相，因此增加了反应物的接触面积，改善了传质效率，而且液相还可以填充气孔，使致密化程度和材料性能提高，但是，由于二硼化钛的烧结性能很差，与多种金属浸润性不良，Fe、Co、Ni是最早被选作二硼化钛液相烧结的添加剂，但是这些过渡金属与二硼化钛反应生成了更加脆硬的金属硼化合物，因此难以获得完全致密，性能良好的二硼化钛金属陶瓷。
除了金属体系的选择，制备方法与致密化技术也是影响材料性能的重要因素。热压烧结是技术较为成熟，应用最为广泛的工艺，但是热压烧结温度较高，耗能耗时，并且制备的材料往往晶粒粗大，难以完全密实，材料性能不够理想；此外热等静压技术也是常用的工艺，它具有压力大，烧结温度较低，材料密实性好的特点，但是设备较为复杂，工业化推广困难。
综上所述，二硼化钛金属陶瓷具有优良的综合性能，应用前景十分广阔，因此，开发新的金属体系、新的制备工艺技术，以弥补因材料自身性质导致的难以实现完全致密化烧结的问题，势在必行。
发明内容
本发明主要解决的技术问题是：针对传统二硼化钛金属陶瓷在制备过程中，难以实现致密化烧结，且所得产品脆性大，韧性较低的问题，提供了一种二硼化钛金属陶瓷的制备方法。
为了解决上述技术问题，本发明所采用的技术方案是：
（1）按重量份数计，依次取60～80份二硼化钛，10～20份碳化硅，20～30份氮化硼，10～20份氧化铝，3～5份氧化钙，4～6份氧化镁，8～10份助溶剂，100～120份无水乙醇，球磨、过筛后干燥，再加入二硼化钛质量10~15%的粘结剂，得混合粉料；
（2）将混合粉料倒入模具中，初压成型后，再经冷等静压成型，得素坯；
（3）将素坯转入真空烧结炉，于氩气保护状态下高温烧结后，随炉冷却至室温，得预制体；
（4）再以预制体为阴极，高纯石墨棒为阳极，熔盐为电解质，于氩气保护状态下恒温电解，再将阴极产物取出后洗涤、干燥，即得二硼化钛金属陶瓷。
步骤（1）所述的助溶剂为硼砂和冰晶石按质量比为0.6：1～0.8：1混合而成。
步骤（1）所述的粘结剂为酚醛树脂2123或酚醛树脂2402中的一种。
步骤（1）所述的过筛为过180～200目筛。
步骤（2）所述的初压成型条件为：于普通压机中，以110～120MPa压力初压成型。
步骤（2）所述的冷等静压成型条件为：于冷等压机中，以260～300MPa压力冷等静压成型。
步骤（3）所述的于氩气保护状态下高温烧结条件为：以60～80mL/min速率向真空烧结炉内通入氩气，在氩气保护状态下，以10～15℃/min速率程序升温至2000～2200℃，保温烧结3～5h。
步骤（4）所述的熔盐为氯化镁、氯化钾或氯化钠中的一种。
步骤（4）所述的恒温电解条件为：于温度为800～900℃，电解电压为3.0～3.5V条件下，恒温电解60～90min。
本发明的有益效果是：
（1）本发明首先通过添加少量氧化钙和氧化镁，在制备过程中，两者可有效抑制二硼化钛晶粒的生长，这是由于氧化钙、氧化镁和二硼化钛的弹性模量及热膨胀系数存在差异，在冷却过程中，产生的残余应变区导致氧化钙和氧化镁颗粒周围微裂纹发生偏转而使产品强韧化，达到增韧的目的；
（2）本发明通过冷等静压配合在氩气保护状态下高温烧结，使产品具有一定的致密度，再通过熔盐电解，一方面，可以减少产品中的氧含量，达到脱氧效果，另一方面，在助溶剂硼砂和冰晶石的辅助下，氧化铝发生熔融电解，产生的铝液渗透进入产品的孔隙中，冷却后使产品致密度进一步提高，实现致密化烧结，且得益于氮化硼的加入，铝和氮化硼在高温下反应，生成氮化铝，提高铝与陶瓷基体的结合强度，金属铝的加入，使产品韧性进一步提升。
具体实施方式
首先按重量份数计，在球磨罐中依次加入60～80份二硼化钛，10～20份碳化硅，20～30份氮化硼，10～20份氧化铝，3～5份氧化钙，4～6份氧化镁，8～10份助溶剂，100～120份无水乙醇，按球料质量比为10：1～20：1加入球磨珠，球磨混合4～6h后，得球磨料，再将球磨料过180～200目筛，得过筛料，并将所得过筛料转入烘箱中，于温度为105～110℃条件下干燥至恒重，得干燥过筛料，再向干燥过筛料中加入二硼化钛质量10～15%的粘结剂，用玻璃棒搅拌混合10～20min，得混合粉料；将所得混合粉料转入钢制模具中，于普通压机中，以110～120MPa压力初压成型，再移入冷等压机中，以260～300MPa压力冷等静压成型，得素坯；再将所得素坯移入真空烧结炉，以60～80mL/min速率向真空烧结炉内通入氩气，在氩气保护状态下，以10～15℃/min速率程序升温至2000～2200℃，保温烧结3～5h后，随炉冷却至室温，出料，得预制体；随后以预制体为阴极，高纯石墨棒为阳极，熔盐为电解质，刚玉容器为电解槽，以10～30mL/min速率向电解槽内通入氩气，在氩气保护状态下，于温度为800～900℃，电解电压为3.0～3.5V条件下，恒温电解60～90min，待电解结束，将阴极产物取出，用去离子水洗涤3～5次后，转入真空干燥箱，于温度为105～110℃条件下干燥至恒重，出料，即得二硼化钛金属陶瓷。所述的助溶剂为硼砂和冰晶石按质量比为0.6：1～0.8：1混合而成。所述的粘结剂为酚醛树脂2123或酚醛树脂2402中的一种。所述的熔盐为氯化镁、氯化钾或氯化钠中的一种。
实例1
首先按重量份数计，在球磨罐中依次加入60份二硼化钛，10份碳化硅，20份氮化硼，10份氧化铝，3份氧化钙，4份氧化镁，8份助溶剂，100份无水乙醇，按球料质量比为10：1加入球磨珠，球磨混合4h后，得球磨料，再将球磨料过180目筛，得过筛料，并将所得过筛料转入烘箱中，于温度为105℃条件下干燥至恒重，得干燥过筛料，再向干燥过筛料中加入二硼化钛质量10%的粘结剂，用玻璃棒搅拌混合10min，得混合粉料；将所得混合粉料转入钢制模具中，于普通压机中，以110MPa压力初压成型，再移入冷等压机中，以260MPa压力冷等静压成型，得素坯；再将所得素坯移入真空烧结炉，以60mL/min速率向真空烧结炉内通入氩气，在氩气保护状态下，以10℃/min速率程序升温至2000℃，保温烧结3h后，随炉冷却至室温，出料，得预制体；随后以预制体为阴极，高纯石墨棒为阳极，熔盐为电解质，刚玉容器为电解槽，以10mL/min速率向电解槽内通入氩气，在氩气保护状态下，于温度为800℃，电解电压为3V条件下，恒温电解60min，待电解结束，将阴极产物取出，用去离子水洗涤3次后，转入真空干燥箱，于温度为105℃条件下干燥至恒重，出料，即得二硼化钛金属陶瓷。所述的助溶剂为硼砂和冰晶石按质量比为0.6：1混合而成。所述的粘结剂为酚醛树脂2123。所述的熔盐为氯化镁。
实例2
首先按重量份数计，在球磨罐中依次加入80份二硼化钛，20份碳化硅，30份氮化硼，20份氧化铝，5份氧化钙，6份氧化镁，10份助溶剂，120份无水乙醇，按球料质量比为20：1加入球磨珠，球磨混合6h后，得球磨料，再将球磨料过200目筛，得过筛料，并将所得过筛料转入烘箱中，于温度为110℃条件下干燥至恒重，得干燥过筛料，再向干燥过筛料中加入二硼化钛质量15%的粘结剂，用玻璃棒搅拌混合20min，得混合粉料；将所得混合粉料转入钢制模具中，于普通压机中，以120MPa压力初压成型，再移入冷等压机中，以300MPa压力冷等静压成型，得素坯；再将所得素坯移入真空烧结炉，以80mL/min速率向真空烧结炉内通入氩气，在氩气保护状态下，以15℃/min速率程序升温至2200℃，保温烧结5h后，随炉冷却至室温，出料，得预制体；随后以预制体为阴极，高纯石墨棒为阳极，熔盐为电解质，刚玉容器为电解槽，以30mL/min速率向电解槽内通入氩气，在氩气保护状态下，于温度为900℃，电解电压为3.5V条件下，恒温电解90min，待电解结束，将阴极产物取出，用去离子水洗涤5次后，转入真空干燥箱，于温度为110℃条件下干燥至恒重，出料，即得二硼化钛金属陶瓷。所述的助溶剂为硼砂和冰晶石按质量比为0.8：1混合而成。所述的粘结剂为酚醛树脂2402。所述的熔盐为氯化钾。
实例3（对比例）
采用传统热压烧结工艺，利用氩气为保护气，在2000℃下制备TiB2-Fe系金属陶瓷。
对实例1至3所得产品相关参数进行检测，并对产品的磨损性能进行检测，磨损性能具体检测方法如下：
材料磨损性能于M-200试验机上进行，产品经立方碳化硼磨料粗磨和320#金相砂纸细磨再抛光而成，摩擦副采用环-块滑动形式接触，在干擦条件下进行试验，转动速度为200r/min，试验载荷为4kg，磨损时间为2h，试验前后产品均用丙酮清洗，烘干后用ES120J-4精密电子天平称量产品的磨损质量损失，精确度为0.0001g。
具体检测结果如表1所示：
表1
实例1 实例2 对比例
密度（g/cm3） 4.88 4.98 4.65
孔隙度（%） 0.6 0.4 2.3
洛氏硬度（HRA） 93.2 93.4 90.3
弯曲强度（MPa） 920 930 550
抗压强度（MPa） 3350 3400 3000
断裂韧性（MPa·m1/2） 7.5 7.8 6.2
杨氏模量（GPa） 465 470 448
磨损量（g） 0.0005 0.0003 0.0423
由上表可知，本发明所得产品致密度较高，机械性能优异，韧性比传统工艺所得产品大有提升，且更耐磨。

Claims (9)

1.一种二硼化钛金属陶瓷的制备方法，其特征在于具体制备步骤为：
（1）按重量份数计，依次取60～80份二硼化钛，10～20份碳化硅，20～30份氮化硼，10～20份氧化铝，3～5份氧化钙，4～6份氧化镁，8～10份助溶剂，100～120份无水乙醇，球磨、过筛后干燥，再加入二硼化钛质量10～15%的粘结剂，得混合粉料；
（2）将混合粉料倒入模具中，初压成型后，再经冷等静压成型，得素坯；
（3）将素坯转入真空烧结炉，于氩气保护状态下高温烧结后，随炉冷却至室温，得预制体；
（4）再以预制体为阴极，高纯石墨棒为阳极，熔盐为电解质，于氩气保护状态下恒温电解，再将阴极产物取出后洗涤、干燥，即得二硼化钛金属陶瓷。
2.根据权利要求1所述的 一种二硼化钛金属陶瓷的制备方法，其特征在于：步骤（1）所述的助溶剂为硼砂和冰晶石按质量比为0.6：1～0.8：1混合而成。
3.根据权利要求1所述的 一种二硼化钛金属陶瓷的制备方法，其特征在于：步骤（1）所述的粘结剂为酚醛树脂2123或酚醛树脂2402中的一种。
4.根据权利要求1所述的 一种二硼化钛金属陶瓷的制备方法，其特征在于：步骤（1）所述的过筛为过180～200目筛。
5.根据权利要求1所述的 一种二硼化钛金属陶瓷的制备方法，其特征在于：步骤（2）所述的初压成型条件为：于普通压机中，以110～120MPa压力初压成型。
6.根据权利要求1所述的 一种二硼化钛金属陶瓷的制备方法，其特征在于：步骤（2）所述的冷等静压成型条件为：于冷等压机中，以260～300MPa压力冷等静压成型。
7.根据权利要求1所述的 一种二硼化钛金属陶瓷的制备方法，其特征在于：步骤（3）所述的于氩气保护状态下高温烧结条件为：以60～80mL/min速率向真空烧结炉内通入氩气，在氩气保护状态下，以10～15℃/min速率程序升温至2000～2200℃，保温烧结3～5h。
8.根据权利要求1所述的 一种二硼化钛金属陶瓷的制备方法，其特征在于：步骤（4）所述的熔盐为氯化镁、氯化钾或氯化钠中的一种。
9.根据权利要求1所述的 一种二硼化钛金属陶瓷的制备方法，其特征在于：步骤（4）所述的恒温电解条件为：于温度为800～900℃，电解电压为3.0～3.5V条件下，恒温电解60～90min。
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