CN113999013A - 一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法 - Google Patents

一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法 Download PDF

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CN113999013A
CN113999013A CN202111293798.XA CN202111293798A CN113999013A CN 113999013 A CN113999013 A CN 113999013A CN 202111293798 A CN202111293798 A CN 202111293798A CN 113999013 A CN113999013 A CN 113999013A
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carbonitride
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魏博鑫
张孟孟
李学问
房文斌
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Harbin University of Science and Technology
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Abstract

一种反应热压烧结法低温制备碳氮化物‑硅化物固溶体复相陶瓷的方法。本发明属于复相陶瓷材料领域。本发明的目的是为了解决现有复相陶瓷的烧结性和高温性能差的技术问题。方法：步骤1：将碳化物粉体、碳氮化物粉体和硅粉体混合，球磨，得到复合粉体；步骤2：将步骤1得到的复合粉体进行烧结，得到碳氮化物‑硅化物固溶体复相陶瓷。本发明选择能够发生固相交换的第四副族碳化物和碳氮化物，充分利用原始粉末在烧结过程中固相反应及其固溶耦合协同过程，可形成阴阳离子双重固溶体或分相固溶体，与传统手段相比本发明能够降低烧结温度300℃～500℃。且较低的烧结温度保证了经此方法制备的材料具有细小平均晶粒尺寸，并使得其强度和硬度均得到显著提升。

Description

一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相 陶瓷的方法
技术领域
本发明属于复相陶瓷材料领域，具体涉及一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法。
背景技术
第四副族金属碳化物(MC,如TiC,ZrC,HfC)具有优异的物理和化学性能，如高熔点、高硬度、高模量，良好的耐磨性、抗腐蚀性和抗热震性。然而，由于MC具有强共价键和低扩散系数，并且在烧结过程中缺乏液相传质，只能利用固相扩散进行传质，因此在不使用烧结助剂情况下，想要在低温(<2000℃)下制备出具有较高的相对致密度(>98％)的MC几乎不可能实现，因此导致其使用受到限制。
近年来，人们已经做出许多努力来提高第四副族金属碳化物陶瓷的可烧结性，但是引入不同的添加剂会损伤材料固有性能，且烧结材料依然常出现获得的微观结构与性能不理想、自身烧结温度高，以及高温性能差等问题，因此面对日益迫切的高性能需求，制备出优异的钛副族复相固溶体陶瓷对于复合材料领域具有重要意义。
发明内容
本发明的目的是为了解决现有复相陶瓷的烧结性和高温性能差的技术问题，而提供一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法。
本发明的一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法按以下步骤进行：
步骤1：将碳化物粉体、碳氮化物粉体和硅粉体混合，球磨，得到复合粉体；
步骤2：将步骤1得到的复合粉体进行烧结，所述烧结的具体过程为：在真空条件下，以15℃/min～25℃/min的升温速率匀速升温，当温度达到1200～1500℃时以2MPa/min～4MPa/min的速度进行加压，当温度达到1400～1700℃，压力达到25MPa～35MPa后停止升温和加压，并在该温度和压力下保温保压50min～70min，得到碳氮化物-硅化物固溶体复相陶瓷。
进一步限定，步骤1中所述碳化物粉体为碳化钛粉体、碳化锆粉体或碳化铪粉体。
进一步限定，步骤1中所述碳氮化物粉体为碳氮化钛粉体、碳氮化锆粉体或碳氮化铪粉体。
进一步限定，步骤1中所述碳化物粉体的粒径为0.10μm～0.35μm。
进一步限定，步骤1中所述碳氮化物粉体的粒径为0.10μm～0.30μm。
进一步限定，步骤1中所述硅粉体的粒径为2.0μm～5.0μm。
进一步限定，步骤1中所述球磨的磨球为硬质合金，球料比为(5～50):1，球磨转速为200rpm～300rpm，球磨时间为5h～30h。
进一步限定，步骤1中所述复合粉体(以摩尔百分含量为100％计)中碳化物粉体的摩尔质量分数为45％～91％，碳氮化物粉体的摩尔质量分数为4％～48％，硅粉体的摩尔质量分数为5％～20％。
进一步限定，步骤2中所述烧结的具体过程为：在真空条件下，以20℃/min的升温速率匀速升温，当温度达到1300℃时以3MPa/min的速度进行加压，当温度达到1500℃，压力达到30MPa后停止升温和加压，并在该温度和压力下保温保压60min。
进一步限定，步骤2中所述烧结的具体过程为：在真空条件下，以20℃/min的升温速率匀速升温，当温度达到1400℃时以3MPa/min的速度进行加压，当温度达到1600℃，压力达到30MPa后停止升温和加压，并在该温度和压力下保温保压60min。
本发明与现有技术相比具有的显著效果：
1)本发明选择能够发生固相交换的第四副族碳化物和碳氮化物，充分利用原始粉末在烧结过程中固相反应及其固溶耦合协同过程，可形成阴阳离子双重固溶体(如(Zr,Ti)(C,N))或分相固溶体(如(Zr,Ti)(C,N)+(Ti,Zr)(C,N))；
2)本发明通过加入的硅单质在烧结过程中使基体中产生C空位，促进物质扩散并降低临界剪切应力，且Si在烧结过程中形成液相增强物质传输并促进物质间的相互反应；
3)本发明的制备方法将原始粉末采用行星式高能球磨工艺进行研磨制备复合粉体，增加粉体颗粒的比表面积，降低反应活化能并起到细化晶粒的作用。
4)本发明的方法与传统手段相比，能够降低烧结温度300℃～500℃。且较低的烧结温度保证了经此方法制备的材料具有细小平均晶粒尺寸，并使得其强度和硬度均得到显著提升。
附图说明
图1为实施例1的碳氮化物-硅化物固溶体复相陶瓷的XRD图谱；
图2为实施例1的碳氮化物-硅化物固溶体复相陶瓷的断口SEM照片；
图3为图2中A处的元素含量图；
图4为图2中B处的元素含量图；
图5为实施例1的碳氮化物-硅化物固溶体复相陶瓷的断口EDS面扫照片；
图6为实施例5的碳氮化物-硅化物固溶体复相陶瓷的XRD图谱；
图7为实施例5的碳氮化物-硅化物固溶体复相陶瓷的断口SEM照片；
图8为图7中C处的元素含量图；
图9为图7中D处的元素含量图；
图10为实施例5的碳氮化物-硅化物固溶体复相陶瓷的断口EDS面扫照片。
具体实施方式
实施例1：本实施例的一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法按以下步骤进行：
步骤1：将碳化锆粉体、碳氮化钛粉体和硅粉体按摩尔比为81:9:10混合，使用行星式高能球磨机进行球磨，磨球为硬质合金，球料比为30:1，球磨转速为250rpm，球磨时间为24h，得到复合粉体；所述碳化物粉体的平均粒径为0.25μm，所述碳氮化物粉体的平均粒径为0.23μm，所述硅粉体的平均粒径为2.8μm；
步骤2：将步骤1得到的复合粉体进行烧结，所述烧结的具体过程为：在真空条件下，以20℃/min的升温速率匀速升温，当温度达到1300℃时以3MPa/min的速度进行加压，当温度达到1500℃，压力达到30MPa后停止升温和加压，并在该温度和压力下保温保压60min，得到(Zr,Ti)(C,N)-SiC固溶体复相陶瓷。
实施例2：本实施例的一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法按以下步骤进行：
步骤1：将碳化锆粉体、碳氮化钛粉体和硅粉体按摩尔比为72:8:20混合，使用行星式高能球磨机进行球磨，磨球为硬质合金，球料比为30:1，球磨转速为250rpm，球磨时间为24h，得到复合粉体；所述碳化物粉体的平均粒径为0.25μm，所述碳氮化物粉体的平均粒径为0.23μm，所述硅粉体的平均粒径为2.8μm；
步骤2：将步骤1得到的复合粉体进行烧结，所述烧结的具体过程为：在真空条件下，以20℃/min的升温速率匀速升温，当温度达到1300℃时以3MPa/min的速度进行加压，当温度达到1500℃，压力达到30MPa后停止升温和加压，并在该温度和压力下保温保压60min，得到对(Zr,Ti)(C,N)-SiC-ZrSi固溶体复相陶瓷。
实施例3：本实施例的一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法按以下步骤进行：
步骤1：将碳化锆粉体、碳氮化钛粉体和硅粉体按摩尔比为90.25:4.75:5混合，使用行星式高能球磨机进行球磨，磨球为硬质合金，球料比为30:1，球磨转速为250rpm，球磨时间为24h，得到复合粉体；所述碳化物粉体的平均粒径为0.25μm，所述碳氮化物粉体的平均粒径为0.23μm，所述硅粉体的平均粒径为2.8μm；
步骤2：将步骤1得到的复合粉体进行烧结，所述烧结的具体过程为：在真空条件下，以20℃/min的升温速率匀速升温，当温度达到1300℃时以3MPa/min的速度进行加压，当温度达到1500℃，压力达到30MPa后停止升温和加压，并在该温度和压力下保温保压60min，得到(Zr,Ti)(C,N)-SiC-ZrSi固溶体复相陶瓷。
实施例4：本实施例的一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法按以下步骤进行：
步骤1：将碳化锆粉体、碳氮化钛粉体和硅粉体按摩尔比为85.5:4.5:10混合，使用行星式高能球磨机进行球磨，磨球为硬质合金，球料比为30:1，球磨转速为250rpm，球磨时间为24h，得到复合粉体；所述碳化物粉体的平均粒径为0.25μm，所述碳氮化物粉体的平均粒径为0.23μm，所述硅粉体的平均粒径为2.8μm；
步骤2：将步骤1得到的复合粉体进行烧结，所述烧结的具体过程为：在真空条件下，以20℃/min的升温速率匀速升温，当温度达到1300℃时以3MPa/min的速度进行加压，当温度达到1500℃，压力达到30MPa后停止升温和加压，并在该温度和压力下保温保压60min，得到(Zr,Ti)(C,N)-SiC-ZrSi固溶体复相陶瓷。
实施例5：本实施例的一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法按以下步骤进行：
步骤1：将碳化锆粉体、碳氮化钛粉体和硅粉体按摩尔比为47.5:47.5:5混合，使用行星式高能球磨机进行球磨，磨球为硬质合金，球料比为30:1，球磨转速为250rpm，球磨时间为24h，得到复合粉体；所述碳化物粉体的平均粒径为0.25μm，所述碳氮化物粉体的平均粒径为0.23μm，所述硅粉体的平均粒径为2.8μm；
步骤2：将步骤1得到的复合粉体进行烧结，所述烧结的具体过程为：在真空条件下，以20℃/min的升温速率匀速升温，当温度达到1300℃时以3MPa/min的速度进行加压，当温度达到1500℃，压力达到30MPa后停止升温和加压，并在该温度和压力下保温保压60min，得到(Zr,Ti)(C,N)-(Ti,Zr)(C,N)-SiC固溶体复相陶瓷。
实施例6：本实施例的一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法按以下步骤进行：
步骤1：将碳化锆粉体、碳氮化钛粉体和硅粉体按摩尔比为45:45:10混合，使用行星式高能球磨机进行球磨，磨球为硬质合金，球料比为30:1，球磨转速为250rpm，球磨时间为24h，得到复合粉体；所述碳化物粉体的平均粒径为0.25μm，所述碳氮化物粉体的平均粒径为0.23μm，所述硅粉体的平均粒径为2.8μm；
步骤2：将步骤1得到的复合粉体进行烧结，所述烧结的具体过程为：在真空条件下，以20℃/min的升温速率匀速升温，当温度达到1300℃时以3MPa/min的速度进行加压，当温度达到1500℃，压力达到30MPa后停止升温和加压，并在该温度和压力下保温保压60min，得到(Zr,Ti)(C,N)-(Ti,Zr)(C,N)-SiC固溶体复相陶瓷。
实施例7：本实施例的一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法按以下步骤进行：
步骤1：将碳化钛粉体、碳氮化锆粉体和硅粉体按摩尔比为47.5:47.5:5混合，使用行星式高能球磨机进行球磨，磨球为硬质合金，球料比为30:1，球磨转速为250rpm，球磨时间为24h，得到复合粉体；所述碳化物粉体的平均粒径为0.23μm，所述碳氮化物粉体的平均粒径为0.26μm，所述硅粉体的平均粒径为2.8μm；
步骤2：将步骤1得到的复合粉体进行烧结，所述烧结的具体过程为：在真空条件下，以20℃/min的升温速率匀速升温，当温度达到1500℃时以3MPa/min的速度进行加压，当温度达到1700℃，压力达到30MPa后停止升温和加压，并在该温度和压力下保温保压60min，得到(Ti,Zr)(C,N)-(Zr,Ti)(C,N)-SiC固溶体复相陶瓷。
实施例8：本实施例的一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法按以下步骤进行：
步骤1：将碳化钛粉体、碳氮化锆粉体和硅粉体按摩尔比为45:45:10混合，使用行星式高能球磨机进行球磨，磨球为硬质合金，球料比为30:1，球磨转速为250rpm，球磨时间为24h，得到复合粉体；所述碳化物粉体的平均粒径为0.23μm，所述碳氮化物粉体的平均粒径为0.26μm，所述硅粉体的平均粒径为2.8μm；
步骤2：将步骤1得到的复合粉体进行烧结，所述烧结的具体过程为：在真空条件下，以20℃/min的升温速率匀速升温，当温度达到1400℃时以3MPa/min的速度进行加压，当温度达到1600℃，压力达到30MPa后停止升温和加压，并在该温度和压力下保温保压60min，得到(Ti,Zr)(C,N)-(Zr,Ti)(C,N)-SiC固溶体复相陶瓷。
实施例9：本实施例的一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法按以下步骤进行：
步骤1：将碳化钛粉体、碳氮化锆粉体和硅粉体按摩尔比为81:9:10混合，使用行星式高能球磨机进行球磨，磨球为硬质合金，球料比为30:1，球磨转速为250rpm，球磨时间为24h，得到复合粉体；所述碳化物粉体的平均粒径为0.23μm，所述碳氮化物粉体的平均粒径为0.26μm，所述硅粉体的平均粒径为2.8μm；
步骤2：将步骤1得到的复合粉体进行烧结，所述烧结的具体过程为：在真空条件下，以20℃/min的升温速率匀速升温，当温度达到1400℃时以3MPa/min的速度进行加压，当温度达到1600℃，压力达到30MPa后停止升温和加压，并在该温度和压力下保温保压60min，得到(Ti,Zr)(C,N)-SiC固溶体复相陶瓷。
检测试验：
(一)对实施例1-9所得固溶体复相陶瓷进行力学性能表征，使用尺寸为2×4×20mm3的试样，在跨距为16mm、压头速度为0.5mm/min的Instron-5500机器上，通过三点弯曲实验测量弯曲强度。结果表明如表1所示。
(二)维氏硬度使用维氏硬度计进行测试，载荷为9.8N，保压时间为10s。结果表明如表1所示。
(三)固溶体复相陶瓷的实际密度(ρ实)采用阿基米德排水法测定，理论密度(ρ理)采用混合物法则计算，固溶体复相陶瓷的相对致密度为实际密度与理论密度之比。结果表明如表1所示。
表1实施例1-9样品性能检测数据
抗弯强度(MPa) 硬度(GPa) 相对致密度(％)
实施例1 436±35 21.03±0.8 98.99
实施例2 458±19 20.89±0.75 99.74
实施例3 522±20 19.56±0.74 98.50
实施例4 454±4 21.3±0.46 99.02
实施例5 422±33 24.51±0.69 99.89
实施例6 435±28 22.37±0.49 98.96
实施例7 446±17 23.58±0.62 98.88
实施例8 460±23 22.64±0.57 99.34
实施例9 449±25 19.82±0.65 99.42

Claims (10)

1.一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法，其特征在于，该方法按以下步骤进行：
步骤1：将碳化物粉体、碳氮化物粉体和硅粉体混合，球磨，得到复合粉体；
步骤2：将步骤1得到的复合粉体进行烧结，所述烧结的具体过程为：在真空条件下，以15℃/min～25℃/min的升温速率匀速升温，当温度达到1200～1500℃时以2MPa/min～4MPa/min的速度进行加压，当温度达到1400～1700℃，压力达到25MPa～35MPa后停止升温和加压，并在该温度和压力下保温保压50min～70min，得到碳氮化物-硅化物固溶体复相陶瓷。
2.根据权利要求1所述的一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法，其特征在于，步骤1中所述碳化物粉体为碳化钛粉体、碳化锆粉体或碳化铪粉体。
3.根据权利要求1所述的一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法，其特征在于，步骤1中所述碳氮化物粉体为碳氮化钛粉体、碳氮化锆粉体或碳氮化铪粉体。
4.根据权利要求1所述的一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法，其特征在于，步骤1中所述碳化物粉体的粒径为0.10μm～0.35μm。
5.根据权利要求1所述的一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法，其特征在于，步骤1中所述碳氮化物粉体的粒径为0.10μm～0.30μm。
6.根据权利要求1所述的一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法，其特征在于，步骤1中所述硅粉体的粒径为2.0μm～5.0μm。
7.根据权利要求1所述的一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法，其特征在于，步骤1中所述球磨的磨球为硬质合金，球料比为(5～50):1，球磨转速为200rpm～300rpm，球磨时间为5h～30h。
8.根据权利要求1所述的一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法，其特征在于，步骤1中所述复合粉体中碳化物粉体的摩尔质量分数为45％～91％，碳氮化物粉体的摩尔质量分数为4％～48％，硅粉体的摩尔质量分数为5％～20％。
9.根据权利要求1所述的一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法，其特征在于，步骤2中所述烧结的具体过程为：在真空条件下，以20℃/min的升温速率匀速升温，当温度达到1300℃时以3MPa/min的速度进行加压，当温度达到1500℃，压力达到30MPa后停止升温和加压，并在该温度和压力下保温保压60min。
10.根据权利要求1所述的一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法，其特征在于，步骤2中所述烧结的具体过程为：在真空条件下，以20℃/min的升温速率匀速升温，当温度达到1400℃时以3MPa/min的速度进行加压，当温度达到1600℃，压力达到30MPa后停止升温和加压，并在该温度和压力下保温保压60min。
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