CN110372394A - 一种高塑性高弹性氮化硼致密陶瓷及其制备方法 - Google Patents

一种高塑性高弹性氮化硼致密陶瓷及其制备方法 Download PDF

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CN110372394A
CN110372394A CN201910791250.4A CN201910791250A CN110372394A CN 110372394 A CN110372394 A CN 110372394A CN 201910791250 A CN201910791250 A CN 201910791250A CN 110372394 A CN110372394 A CN 110372394A
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boron nitride
sintering
preparation
compact
ductility
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CN110372394B (zh
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赵智胜
张洋
武英举
张爽爽
胡文涛
于栋利
何巨龙
徐波
柳忠元
田永君
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Yanshan University
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Abstract

本发明涉及一种高塑性高弹性氮化硼致密陶瓷及其制备方法，制备方法包括以下步骤：A）装料：称量一定质量的洋葱结构的球形氮化硼纳米粉体，预压成型，将预压成型后的预压坯放入烧结模具；B）烧结：将步骤A）中的预压坯连同烧结模具一起放入放电等离子烧结设备或者热压烧结设备中烧结；C）出料：待设备内温度自然冷却至室温后取出模具，退模获得高塑性高弹性氮化硼致密陶瓷块体。本发明通过烧结洋葱结构的球形氮化硼纳米粉体，获得高强度高塑性的氮化硼陶瓷。

Description

一种高塑性高弹性氮化硼致密陶瓷及其制备方法
技术领域
本发明涉及塑性陶瓷制备技术领域，尤其是一种高塑性高弹性氮化硼致密陶瓷及其制备方法。
背景技术
不同于金属，陶瓷是脆性材料，在室温下没有塑性，仅具有很小的弹性形变。当超过弹性极限时(通常弹性极限形变小于1％)，陶瓷中的裂纹将迅速扩展，瞬间破坏整个陶瓷体，从而阻碍了陶瓷在工程中的众多应用。六方氮化硼(hBN)陶瓷作为陶瓷材料的一种，其具有高热导率、低介电系数、优良润滑性、耐腐蚀、高的热稳定性以及优异的抗热震性等，在冶金、电子、化工、航空等领域有着非常广阔的应用，但强度低、弹性低、无塑性同样限制了其应用。
六方氮化硼的晶体结构类似于石墨，层内硼原子与氮原子以sp2共价键方式连接，相邻层间则以较弱的范德华力连接。这种层状的晶体结构导致了六方氮化硼很差的烧结特性以及在外力作用下的滑移变形，因此传统烧结工艺获得的高纯六方氮化硼陶瓷强度都较低，一般都低于130MPa，同时弹性应变也较小(小于1％)，并且没有发现塑性形变，如申请号为201410422994.6的中国专利申请一种无压烧结高纯氮化硼陶瓷的方法，通过该方法制备出的六方氮化硼陶瓷机械性能也较差，其实施例1中获得的六方氮化硼陶瓷其室温抗折强度仅为30.7MPa，维氏硬度仅0.08GPa，断裂韧性为0.69MPa·m1/2；通过添加烧结助剂(例如：B2O3、Al2O3、ZrO2、CaO、SiAlON、Si3N4、AlN、SiC、YAG、Y2SiO5、莫来石等)得到的含烧结助剂的复合陶瓷材料，虽然其强度有了一定的提高，但往往会导致六方氮化硼陶瓷的热导率、抗热震性和介电等性能的降低，并且其弹性也没有显著得到提高，同样没有塑性发现，如申请号为201510683710.3的一种氮化硅/六方氮化硼纳米复相陶瓷的制备方法，申请号为201410833418.0的一种纳米级六方氮化硼/二氧化硅复相陶瓷材料的制备方法。
发明内容
本发明需要解决的技术问题是提供一种高塑性高弹性氮化硼致密陶瓷及其制备方法，该方法通过烧结洋葱结构的球形氮化硼纳米粉体，获得高强度高塑性的氮化硼陶瓷。
为解决上述技术问题，本发明所采用的技术方案是：
一种高塑性高弹性氮化硼致密陶瓷及其制备方法，制备方法包括以下步骤：
A)装料：称量一定质量的洋葱结构的球形氮化硼纳米粉体，预压成型，将预压成型后的预压坯放入烧结模具；
B)烧结：将步骤A)中的预压坯连同烧结模具一起放入放电等离子烧结设备或者热压烧结设备中烧结；
C)出料：待设备内温度自然冷却至室温后取出模具，退模获得高塑性高弹性氮化硼致密陶瓷块体。
本发明的技术方案的进一步改进在于：步骤A)中烧结模具为石墨模具，石墨模具外围使用碳毡包裹。
本发明的技术方案的进一步改进在于：步骤A)中预压成型为双向施加压力，施加压力大小为2MPa～5MPa，保压时间1min～5min。
本发明的技术方案的进一步改进在于：步骤A)中所使用的原料为洋葱结构的球形氮化硼纳米粉体，其粒径在10nm到1000nm。
本发明的技术方案的进一步改进在于：步骤B)中烧结步骤为抽真空至真空度高于1×10-1Pa后升压至烧结压力，待烧结压力稳定后升温至烧结温度，高温烧结后关闭加热程序并卸压。
本发明的技术方案的进一步改进在于：步骤B)中施加的烧结压力大小为30MPa～50MPa，烧结温度为1600℃～2000℃，保温时间为1min～30min。
本发明的技术方案的进一步改进在于：步骤B)中烧结方式为放电等离子烧结或者是热压烧结。
本发明的技术方案的进一步改进在于：步骤B)升温的速率为20℃/min～100℃/min。
本申请还提供了所述的制备方法所制备的高塑性高弹性氮化硼致密陶瓷，压缩强度不低于400MPa，室温总压缩应变不低于9％，室温塑性应变不低于4％，弹性应变不低于5％。
由于采用了上述技术方案，本发明取得的技术进步是：
本发明一种高塑性高弹性氮化硼致密陶瓷及其制备方法，该方法通过烧结洋葱结构的球形氮化硼纳米粉体，获得高强度高塑性的氮化硼陶瓷。
使用洋葱结构的球形氮化硼纳米粉体，一方面球形氮化硼纳米粉体较层片状六方氮化硼粉体具有更好的流动性，促进烧结过程中的填隙，有利于在较低温度下获得致密烧结体；另一方面洋葱结构的氮化硼内部含有大量褶皱，在受压缩过程中容易形成sp3键，增加了烧结体的强度。
预压成型为双向施加压力，双向实施压力能够使处于预压成型模具内的洋葱结构的球形氮化硼纳米粉体双向受力，降低了预压坯上下压力梯度，避免单向施压而导致的上下压力梯度过大，而使预压坯上下密度相差较大，进而影响烧结后块体的整体致密度，双向施加压力也能使粉体被压缩的更致密，利于后续预压坯的烧结。
石墨模具外围使用碳毡包裹，碳毡将石墨模具中间的缝隙围住，能够减小石墨模具中的热量扩散，减小石墨模具内部的温度梯度，从而避免烧结体显微组织结构以及力学性能的不均匀。
烧结压力设定为30MPa～50MPa，在此压力范围内，既能够保证在较低温度下即可获得致密的烧结体，施加压力较小，降低了工业成本，易于实现工业批量生产，同时该压力范围可以控制洋葱结构的球形氮化硼纳米粉体的相变速度，防止晶粒长大过快。
附图说明
图1(a)是本发明实施例1制备产物的室温单轴压缩加载卸载应力-应变曲线；图1(b)是本发明实施例1制备产物维氏硬度随载荷变化图；图1(c)是本发明实施例1制备产物X射线衍射图；
图2(a)是本发明实施例2制备产物的室温单轴压缩加载卸载应力-应变曲线；图2(b)是本发明实施例2制备产物维氏硬度随载荷变化图；
图3(a)是本发明实施例3制备产物的室温单轴压缩加载卸载应力-应变曲线；图3(b)是本发明实施例3制备产物维氏硬度随载荷变化图；图3(c)是本发明实施例3制备产物X射线衍射图；
图4(a)是本发明实施例4制备产物的室温单轴压缩加载卸载应力-应变曲线；图4(b)是本发明实施例4制备产物维氏硬度随载荷变化图；
图5(a)是本发明实施例1～5所用洋葱结构球形氮化硼纳米粉末形貌图，图5(b)是本发明实施例1～5所用洋葱结构球形氮化硼纳米粉末电子显微镜结构图。
具体实施方式
下面结合实施例对本发明做进一步详细说明：
实施例1
本实施例一种高塑性高弹性氮化硼致密陶瓷的制备方法包括以下步骤：
A)装料：称量7g的洋葱结构的球形氮化硼纳米粉体，洋葱结构的球形氮化硼纳米粉体为粒径在10nm到1000nm，预压成型，预压成型为双向施加压力，将洋葱结构的球形氮化硼纳米粉体置于预压成型模具内，施加压力大小为5MPa，保压时间1min，预压成型模具为内径为20mm的圆形不锈钢模具，将预压成型后的预压坯放入烧结模具，烧结模具为石墨模具，石墨模具外围使用碳毡包裹；
B)烧结：将步骤A)中的预压坯连同烧结模具一起放入放电等离子烧结设备烧结，烧结方式为放电等离子烧结，烧结步骤为抽真空至真空度为1×10-1Pa后升压至烧结压力，烧结压力大小为50MPa，待烧结压力稳定后升温至烧结温度，升温的速率为100℃/min，烧结温度为1600℃，保温时间为5min，高温烧结后关闭加热程序并卸压；其中烧结步骤中不抽真空也可以升压至烧结压力，但预压坯中含有一定量的气孔，其中水蒸气、氢气、氧气能借助溶解和扩散过程从封闭气孔中逸出，一氧化碳、二氧化碳和氮气等由于溶解度较低，不易从封闭气孔中逸出，预压坯置于真空条件下，真空度越高，气体越能从封闭气孔中逸出，能提高最终制备产物的致密度，但真空度越高，需要抽真空的时间也越长，增加生产成本，本发明的实施例均抽真空至真空度为1×10-1Pa后升压；
本实施例中使用的放电等离子烧结设备是住友石炭矿业株式会社的SPS-3.20MK-IV，而后续实施例中使用的热压烧结设备为日本富士电波工业公司的HIGH-MULTI-5000；
C)出料：待设备内温度自然冷却至室温后取出模具，退模获得高塑性高弹性氮化硼致密陶瓷块体。
本发明测试制备产物高塑性高弹塑性氮化硼致密陶瓷块体的压缩强度和塑性应变使用材料力学性能试验机，在室温下对测试样品进行各项性能测试，测试样品为圆柱体，测试样柱尺寸为直径3mm，高度4.5mm，材料力学性能试验机加载应变速率为1×10-5－1×10-2，硬度的测试使用测试显微硬度计为德国KB PrüftechnikGmbH公司生产的KB-5BVZ，测试制备产物强度高塑性氮化硼陶瓷块体时采用维氏压头，载荷20g～500g，保压30s,通过不同测量载荷下硬度拟合出硬度渐近线,即测试样品硬度为渐近线指示硬度。
如图1(a)所示实施例1制备产物的单轴压缩加载卸载应力-应变曲线，压缩强度为620MPa，应力应变曲线具有明显的非线性特征，其中塑性形变为8％，弹性应变为5％，总压缩应变为13％；如图1(b)制备产物维氏硬度为1.04GPa；
如图1(c)所示本发明实施例1制备产物的X射线衍射图，实施例1获得的烧结体在结构上没有完全石墨化，具有类六方氮化硼结构；对本实施例1的制备产物通过阿基米德排水法测定其烧结体密度为2.10g/cm3，经计算测量密度相对于其的理论密度的相对密度为96％。
实施例2
本实施例的一种高塑性高弹性氮化硼致密陶瓷的制备方法，其工艺步骤与实施例1相近，与实施例1相差别的具体工艺参数参见表1中实施例2列所示。
如图2(a)所示的实施例2制备产物的单轴压缩加载卸载应力-应变曲线，压缩强度为614MPa，应力应变曲线具有明显的非线性特征，其中塑性形变为6.3％，弹性应变为4.9％，总压缩应变为11.2％；如图2(b)所示,制备产物维氏硬度为0.91GPa；本发明实施例2制备产物具有与实施例1相似的晶体结构；对本实施例2的制备产物通过阿基米德排水法测定其烧结体密度为2.09g/cm3，经计算测量密度相对于其的理论密度的相对密度为95.4％。
实施例3
本实施例的一种高塑性高弹性氮化硼致密陶瓷的制备方法，其工艺步骤与实施例1相近，与实施例1相差别的具体工艺参数参见表1中实施例3列所示。
如图3(a)所示实施例3制备产物的单轴压缩加载卸载应力-应变曲线，压缩强度为501MPa，应力应变曲线具有明显的非线性特征，其中塑性形变为4.8％，弹性应变为4.8％，总压缩应变为9.6％；如图3(b)制备产物维氏硬度为0.81GPa；如图3(c)所示本发明实施例3制备产物的X射线衍射图，实施例3获得制备产物具有与实施例1类似的未完全石墨化的类六方氮化硼结构；对本实施例1的制备产物通过阿基米德排水法测定其烧结体密度为2.07g/cm3，经计算测量密度相对于其的理论密度的相对密度为95％。
实施例4
本实施例的一种高塑性高弹性氮化硼致密陶瓷的制备方法，其工艺步骤与实施例1相近，与实施例1相差别的具体工艺参数参见表1中实施例4列所示。
如图4(a)所示的实施例4制备产物的单轴压缩加载卸载应力-应变曲线，压缩强度为460MPa，应力应变曲线具有明显的非线性特征，其中塑性形变为4％，弹性应变为5.1％，总压缩应变为9.1％；如图2(b)所示,制备产物维氏硬度为0.75GPa；本发明实施例4制备产物具有与实施例1相似的晶体结构；对本实施例4的制备产物通过阿基米德排水法测定其烧结体密度为2.07g/cm3，经计算测量密度相对于其的理论密度的相对密度为95％。
表1实施例1～4高塑性高弹性氮化硼致密陶瓷的制备方法参数对照表
表2实施例1～4高塑性高弹性氮化硼致密陶瓷性能结果对照表

Claims (9)

1.一种高塑性高弹性氮化硼致密陶瓷的制备方法，其特征在于：制备方法包括以下步骤：
A）装料：称量一定质量的洋葱结构的球形氮化硼纳米粉体，预压成型，将预压成型后的预压坯放入烧结模具；
B）烧结：将步骤A）中的预压坯连同烧结模具一起放入放电等离子烧结设备或者热压烧结设备中烧结；
C）出料：待设备内温度自然冷却至室温后取出模具，退模获得高塑性高弹性氮化硼致密陶瓷块体。
2.根据权利要求1所述的一种高塑性高弹性氮化硼致密陶瓷的制备方法，其特征在于：步骤A）中烧结模具为石墨模具，石墨模具外围使用碳毡包裹。
3.根据权利要求1所述的一种高塑性高弹性氮化硼致密陶瓷的制备方法，其特征在于：步骤A）中预压成型为双向施加压力，施加压力大小为2MPa~5MPa，保压时间1min~5min。
4.根据权利要求1所述的一种高塑性高弹性氮化硼致密陶瓷的制备方法，其特征在于：步骤A）中所使用的原料为洋葱结构的球形氮化硼纳米粉体，其粒径在10nm到1000 nm。
5.根据权利要求1所述的一种高塑性高弹性氮化硼致密陶瓷的制备方法，其特征在于：步骤B）中烧结步骤为抽真空至真空度高于1×10-1Pa后升压至烧结压力，待烧结压力稳定后升温至烧结温度，高温烧结后关闭加热程序并卸压。
6.根据权利要求5所述的一种高塑性高弹性氮化硼致密陶瓷的制备方法，其特征在于：步骤B）中施加的烧结压力大小为30MPa~50MPa，烧结温度为1600℃~2000℃，保温时间为1min~30min。
7.根据权利要求1所述的一种高塑性高弹性氮化硼致密陶瓷的制备方法，其特征在于：步骤B）中烧结方式为放电等离子烧结或者是热压烧结。
8.根据权利要求1所述的一种高塑性高弹性氮化硼致密陶瓷的制备方法，其特征在于：步骤B）升温的速率为20℃/min~100℃/min。
9.权利要求1~8任一项所述的制备方法所制备的高塑性高弹性氮化硼致密陶瓷，其特征在于：压缩强度不低于400MPa，室温总压缩应变不低于9%，室温塑性应变不低于4%，弹性应变不低于5%。
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