CN116178034B - 一种晶须增韧高熵碳化物复相陶瓷及其制备方法和应用 - Google Patents
一种晶须增韧高熵碳化物复相陶瓷及其制备方法和应用 Download PDFInfo
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 44
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- 238000000498 ball milling Methods 0.000 claims description 10
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- 229910052786 argon Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
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Abstract
本发明属于非氧化物陶瓷基复合材料技术领域，公开了一种晶须增韧高熵碳化物陶瓷及其制备方法和应用。该方法是将高熵碳化物(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C粉体和碳化硅晶须混合后加入Co，制得(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C‑SiCw‑Co混合粉体，压成坯体后在1450～1650℃，压力为30～40MPa，采用放电等离子烧结或热压烧结工艺，制得晶须增韧高熵碳化物复相陶瓷，该复相陶瓷具有更高的断裂韧性和更低的致密化温度；其相对密度大于96％，维氏硬度为22～25GPa，断裂韧性为5～7MPa·m1/2，可应用在制备切削难加工材料或航空航天耐磨零部件中。
Description
技术领域
本发明属于非氧化物陶瓷基复合材料技术领域，更具体地，涉及一种晶须增韧高熵碳化复相物陶瓷及其制备方法和应用。
技术背景
高熵碳化物陶瓷材料具有高熔点、高硬度、高耐磨性和高化学稳定性等优异性能，可应用于航空航天、高速切削刀具、军事装备和核能等领域。相较于传统过渡金属一元碳化物陶瓷材料，高熵碳化物陶瓷具有多样的元素组合和简单的单一相结构，在成分设计上拥有很大的发挥空间，是传统过渡金属一元碳化物陶瓷的理想替代材料。然而，由于高熵碳化物特殊的晶体结构，导致其断裂韧性低于传统的过渡金属一元碳化物陶瓷，限制了其进一步应用。故开发提升高熵碳化物陶瓷断裂韧性的有效手段，成为了现下研究者的研究重点。
目前，通过引入碳化硅晶须作为第二相，高温(2000℃)烧结制备高熵碳化物复相陶瓷可提升高熵碳化物陶瓷的断裂韧性。但由于碳化硅晶须热稳定性较差，在高温下结构易受损伤，甚至分解为碳化硅颗粒，严重削弱了碳化硅晶须的增韧性能，以至于同添加碳化硅颗粒的增韧效果无异。
发明内容
为了解决上述现有技术存在的不足和缺点，本发明的目的在于提供一种晶须增韧高熵碳化物复相陶瓷的制备方法。该方法工艺简单，得到的高熵碳化物复相陶瓷具有致密的结构，且碳化硅晶须未受损伤，极大地提升了高熵碳化物陶瓷的断裂韧性。
本发明的另一目的在于提供上述方法制备得到的晶须增韧高熵碳化物复相陶瓷。
本发明的再一目的在于提供上述晶须增韧高熵碳化物复相陶瓷的应用。
本发明的目的通过下述技术方案来实现：
一种晶须增韧高熵碳化物复相陶瓷的制备方法，包括以下步骤：
S1.将高熵碳化物(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C粉体和碳化硅晶须(SiCw)混合，加入烧结助剂金属Co，制得(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C-SiCw-Co混合粉体；以(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C粉体和碳化硅晶须的总质量为100％计，(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C粉体的质量百分比为90～95wt.％，碳化硅晶须的质量百分比为5～10wt.％；Co的质量百分比为(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C粉体和碳化硅晶须总质量的3～6wt.％；
S2.将(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C-SiCw-Co混合粉体加入无水乙醇，超声搅拌制得浆料；然后将氮化硅介质球加入浆料经辊式球磨机球磨，经干燥、烘干、过筛后装入石墨模具，干压成坯体；
S3.在保护气氛下，将坯体在1450～1650℃，压力为30～40MPa，进行放电等离子烧结，或者将坯体在1450～1650℃，压力为30～40MPa，进行热压烧结，制得晶须增韧高熵碳化物复相陶瓷。
优选地，步骤S1中所述的高熵碳化物(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C粉体的粒径为30nm～1μm；所述的碳化硅晶须的直径为0.5～1μm。
优选地，步骤S2中所述球磨转速为100～300r/min，所述球磨的时间为18～36h；所述干燥的温度为60～80℃，所述干燥的时间为12～24h。
优选地，步骤S3中所述放电等离子烧结程序为：先以100～150℃/min的速率升温至1000～1200℃，开始充氮气或氩气并且开始加压，继续将温度升至1450～1650℃，同时压力升至30～40MPa；升温程序执行完毕后保温保压5～10min；然后以80～100℃/min的速率降温，1000～1200℃泄压完毕，温度降至750～850℃后随炉降温。
优选地，步骤S3中所述热压烧结程序为：先以10～14℃/min的升温速率升温，室温～1000℃开始充氮气或氩气并且开始加压，继续以6～8℃/min的升温速率升温，将温度升至1450～1650℃，同时压力升至30～40MPa；升温程序执行完毕后保温保压0.5～1h；然后以10～12℃/min的速率降温，1000～1200℃泄压完毕，降温至750～850℃后随炉降温。
一种晶须增韧高熵碳化物复相陶瓷，所述晶须增韧高熵碳化物复相陶瓷是由所述的方法制备得到。
优选地，所述晶须增韧高熵碳化物复相陶瓷的相对密度大于96％，维氏硬度为22～25GPa，断裂韧性为5～7MPa·m1/2。
所述的晶须增韧高熵碳化物复相陶瓷在制备切削难加工材料或航空航天耐磨零部件中的应用。
本发明碳化硅晶须是一种具有高度取向的纤维状单晶材料。作为第二相添加在高熵碳化物陶瓷基体中，由于晶须和高熵碳化物的热膨胀系数不同，会在晶须与高熵碳化物的晶粒界面产生残余应力。当高熵碳化物陶瓷受外力作用产生裂纹时，裂纹尖端的应力延伸到晶须与高熵碳化物晶粒的界面后会被此残余应力吸收部分能量，从而阻碍裂纹的扩展，达到提升高熵碳化物陶瓷断裂韧性的作用。而对于碳化硅晶须，其外层由非1:1摩尔比的Si和C组成，造成有大量空位存在(Karasek,K.R.,et al.,Characterization ofRecentSiC Whiskers.2008:A Collection of Papers Presented at the 13th AnnualConference on Composites and Advanced Ceramic Materials,Part 1of 2：CeramicEngineering and Science Proceedings,Volume 10,Issue 7/8)。导致碳化硅晶须在高温下的稳定性欠佳，在高温下易受到损伤甚至分解为碳化硅颗粒。在本发明中，通过添加Co做为烧结助剂，降低了高熵碳化物陶瓷的烧结温度，有效的避免了碳化硅晶须的损伤，使其增韧作用得到了充分发挥。
与现有技术相比，本发明具有以下有益效果：
1.本发明采用了低温液相烧结工艺，通过在高熵碳化物混合粉体加入中碳化硅晶须和助烧结金属Co，降低了温度对碳化硅晶须的影响，较低的烧结温度和碳化硅晶须的引入减小了烧结后高熵碳化物的晶粒尺寸，充分发挥了碳化硅晶须的增韧作用，从而抑制了晶粒长大对陶瓷力学性能的不利影响。
2.本发明采用了低温液相烧结工艺，该工艺简单，致密化温度较低，节约能源。
3.本发明制得的晶须增韧高熵碳化物复相陶瓷具有高韧性和高硬度。
附图说明
图1是实施例3中得到的晶须增韧高熵碳化物复相陶瓷的抛光面显微结构图。
图2是实施例4中得到的晶须增韧高熵碳化物复相陶瓷的断面显微结构图。
具体实施方式
下面结合具体实施例进一步说明本发明的内容，但不应理解为对本发明的限制。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1
1.以质量分数比为95：5的高熵碳化物(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C粉体和碳化硅晶须(SiCw)为原料，以金属Co为烧结助剂(Co的用量为高熵碳化物(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C粉体和碳化硅晶须总质量的6％)配制混合粉体，加入无水乙醇，并超声搅拌1h制得浆料。
2.将浆料在辊式球磨机以无水乙醇为分散剂，Si3N4球为球磨介质，以200r/min转速混料24h，在烘箱80℃干燥24h后，100目过筛，得到混合均匀的(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C-SiCw-Co混合粉体；
3.将(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C-SiCw-Co混合粉体装入石墨模具，放入放电等离子烧结炉，以100℃/min的速率升温至1000℃，开始充氮气并且开始加压，然后升温至1600℃，同时压力升至30MPa，并保温保压10min，保温结束后以100℃/min的速率降温，1000℃泄压完毕，800℃后随炉降温，得到晶须增韧高熵碳化物复相陶瓷。
本实施例制得的晶须增韧高熵碳化物复相陶瓷的相对密度为99％，维氏硬度为25.0GPa，断裂韧性为5.5MPa·m1/2。
实施例2
1.以质量分数比为93：7的高熵碳化物(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C粉体和碳化硅晶须(SiCw)为原料，以金属Co为烧结助剂(Co的用量为高熵碳化物(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C粉体和碳化硅晶须总质量的6％)配制混合粉体，加入无水乙醇，并超声搅拌1h制得浆料。
2.将浆料在辊式球磨机以无水乙醇为分散剂，Si3N4球为球磨介质，以200r/min转速混料24h，在烘箱80℃干燥24h后，100目过筛，得到混合均匀的(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C-SiCw-Co混合粉体；
3.将(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C-SiCw-Co混合粉体装入石墨模具，放入放电等离子烧结炉，以100℃/min的速率升温至1000℃，开始充氩气并且开始加压，然后升温至1600℃，同时压力升至30MPa，并保温保压10min，保温结束后以100℃/min的速率降温，1000℃泄压完毕，800℃后随炉降温，得到晶须增韧高熵碳化物复相陶瓷。
本实施例制得的晶须增韧高熵碳化物复相陶瓷的相对密度为98％，维氏硬度为23.3GPa，断裂韧性为6.1MPa·m1/2。
实施例3
1.以质量分数比为9：1的高熵碳化物(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C粉体和碳化硅晶须(SiCw)为原料，以金属Co为烧结助剂(Co的用量为高熵碳化物(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C粉体和碳化硅晶须总质量的5％)配制混合粉体，加入无水乙醇，并超声搅拌1h制得浆料。
2.将浆料在辊式球磨机以无水乙醇为分散剂，Si3N4球为球磨介质，以200r/min转速混料24h，在烘箱80℃干燥24h后，100目过筛，得到混合均匀的(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C-SiCw-Co混合粉体；
3.将(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C-SiCw-Co混合粉体装入石墨模具，放入放电等离子烧结炉，以100℃/min的速率升温至1000℃，开始充氩气并且开始加压，然后升温至1600℃，同时压力升至30MPa，并保温保压10min，保温结束后以100℃/min的速率降温，1000℃泄压完毕，800℃后随炉降温，得到晶须增韧高熵碳化物复相陶瓷。
本实施例制备得到的晶须增韧高熵碳化物复相陶瓷的相对密度为96％，维氏硬度为22.6GPa，断裂韧性为7.2MPa·m1/2。
图1是实施例3中得到的晶须增韧高熵碳化物复相陶瓷的抛光面显微结构图。从图1中可以看到，晶须的钉扎效应，高熵碳化物晶粒生长不明显，高熵碳化物晶粒的平均尺寸为0.47μm。晶须形貌完整，且未分解为碳化硅颗粒，表明低的烧结温度对晶须具有很好的保护作用。
实施例4
1.以质量分数比为91：9的高熵碳化物(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C粉体和碳化硅晶须(SiCw)为原料，以金属Co为烧结助剂(Co的用量为高熵碳化物(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C粉体和碳化硅晶须总质量的3％)配制混合粉体，加入无水乙醇，并超声搅拌1h制得浆料。
2.将浆料在辊式球磨机以无水乙醇为分散剂，Si3N4球为球磨介质，以200r/min转速混料24h，在烘箱80℃干燥24h后，100目过筛，得到混合均匀的(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C-SiCw-Co混合粉体；
3.将(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C-SiCw-Co混合粉体装入石墨模具，放入热压烧结炉，以10℃/min的速率升温，室温下开始充氩气并且开始加压，升温至1600℃，同时压力升至30MPa，并保温保压1h，保温结束后以10℃/min的速率降温，1000℃泄压完毕，800℃后随炉降温，得到晶须增韧高熵碳化物复相陶瓷。
本实施例制备得到的晶须增韧高熵碳化物复相陶瓷的相对密度达到97％，维氏硬度为22.3GPa，断裂韧性为6.1MPa·m1/2。
图2是实施例4中得到的晶须增韧高熵碳化物复相陶瓷的断面显微结构图。从图2中可以看出，制备的复合陶瓷具有致密的结构，陶瓷的断裂形式为沿晶断裂，且断面上存在较多由晶须拔出后留下的孔洞，这表明陶瓷具有较高的断裂韧性且具有完整形貌的晶须在陶瓷断裂的过程中发挥了作用，提高了陶瓷的断裂韧性。
本发明的晶须增韧高熵碳化物复相陶瓷的相对密度大于96％，维氏硬度为22～25GPa，断裂韧性为5～7MPa·m1/2。该晶须增韧高熵碳化物复相陶瓷应用在制备切削难加工材料或航空航天耐磨零部件中。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合和简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (5)
1.一种晶须增韧高熵碳化物复相陶瓷的制备方法，其特征在于，包括以下步骤：
S1.将高熵碳化物(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C粉体和碳化硅晶须混合，加入烧结助剂金属Co，制得(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C-SiCw-Co混合粉体；以(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C粉体和碳化硅晶须的总质量为100％计，(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C粉体的质量百分比为90～95wt％，碳化硅晶须的质量百分比为5～10wt％；Co的质量百分比为(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C粉体和碳化硅晶须总质量的3～6wt％；所述的高熵碳化物(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C粉体的粒径为30nm～1μm；所述的碳化硅晶须的直径为0.5～1μm；
S2.将(Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C-SiCw-Co混合粉体加入无水乙醇，超声搅拌制得浆料；然后将氮化硅介质球加入浆料经辊式球磨机球磨，经干燥、烘干、过筛后装入石墨模具，干压成坯体；
S3.在保护气氛下，将坯体在1450～1650℃，压力为30～40MPa，进行放电等离子烧结或者热压烧结，制得晶须增韧高熵碳化物复相陶瓷；
所述放电等离子烧结程序为：先以100～150℃/min的速率升温至1000～1200℃，开始充氮气或氩气并且开始加压，继续将温度升至1450～1650℃，同时压力升至30～40MPa；升温程序执行完毕后保温保压5～10min；然后以80～100℃/min的速率降温，1000～1200℃泄压完毕，温度降至750～850℃后随炉降温；
所述热压烧结程序为：先以10～14℃/min的升温速率升温，室温～1000℃开始充氮气或氩气并且开始加压，继续以6～8℃/min的升温速率升温，将温度升至1450～1650℃，同时压力升至30～40MPa；升温程序执行完毕后保温保压0.5～1h；然后以10～12℃/min的速率降温，1000～1200℃泄压完毕，降温至750～850℃后随炉降温。
2.根据权利要求1所述的晶须增韧高熵碳化物复相陶瓷的制备方法，其特征在于，步骤S2中所述球磨转速为100～300r/min，所述球磨的时间为18～36h；所述干燥的温度为60～80℃，所述干燥的时间为12～24h。
3.一种晶须增韧高熵碳化物复相陶瓷，其特征在于，所述晶须增韧高熵碳化物复相陶瓷是由权利要求1或2所述的方法制备得到。
4.根据权利要求3所述的晶须增韧高熵碳化物复相陶瓷，其特征在于，所述晶须增韧高熵碳化物复相陶瓷的相对密度大于96％，维氏硬度为22～25GPa，断裂韧性为5～7MPa·m1 /2。
5.根据权利要求3或4所述的晶须增韧高熵碳化物复相陶瓷在制备切削难加工材料或航空航天耐磨零部件中的应用。
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