CN115124350A - 一种应用于高温环境下的陶瓷复合材料的制备工艺 - Google Patents
一种应用于高温环境下的陶瓷复合材料的制备工艺 Download PDFInfo
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- 229910007948 ZrB2 Inorganic materials 0.000 claims abstract description 45
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000843 powder Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- ZTXONRUJVYXVTJ-UHFFFAOYSA-N chromium copper Chemical compound [Cr][Cu][Cr] ZTXONRUJVYXVTJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 20
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- 239000011651 chromium Substances 0.000 description 3
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- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 3
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Abstract
本发明涉及ZrB2基高温陶瓷制备技术领域，且公开了一种应用于高温环境下的陶瓷复合材料的制备工艺，包括如下步骤：在微米粒径的二硼化锆ZrB2粒子上生成纳米粒径的铬铜复合团簇粒子，将其在真空下煅烧并在煅烧过程中采用氢气还原，得到二硼化锆ZrB2‑铬铜团簇粒子包覆型复合粉体，采用放电等离子体烧结的方法，制备应用于高温环境下的二硼化锆ZrB2‑铬铜团簇粒子包覆型陶瓷复合材料，其断裂韧性达到了5.84‑6.27MPa·m1/2，并且取得了降低二硼化锆ZrB2粒子烧结温度、促进致密化、具备优异抗高温氧化性的有益技术效果。
Description
技术领域
本发明涉及ZrB2基高温陶瓷制备技术领域，具体为一种应用于高温环境下的陶瓷复合材料的制备工艺。
背景技术
由于ZrB2中极强的共价键结构和低原子扩散率，且在制备过程中无液相和气相传质途径，因此通常需要在极高的温度、长时间保温和施加压力的条件下才能烧结得到单相致密的ZrB2块体材料。除了ZrB2的本征因素外，减小粉末颗粒尺寸、提高粉体纯度以及降低氧含量均可促进ZrB2陶瓷材料的致密化过程。另外，在ZrB2中加入烧结助剂，不仅可以促进材料的烧结致密，而且还能提升制备得到ZrB2基超高温陶瓷的力学和抗氧化性能。
目前，ZrB2中添加的烧结助剂可以分为以下几类：1)金属粉末，如Fe、Ni、Cr等，在高温烧结时发生熔化形成液相填充陶瓷粉体之间的空隙，从而促进材料致密化；2)非金属粉末，如C、B等，可通过消除ZrB2粉末表面的杂质来促进材料烧结致密；3)陶瓷粉末，如B4C、Si3N4[、AlN、ZrN、HfN、SiC等，这类烧结助剂的致密化作用机理主要有：与ZrB2表面杂质反应净化晶界、生成低熔点产物以及自身软化变形等。
发明内容
(一)解决的技术问题
针对ZrB2陶瓷存在的烧结致密性差、塑韧性较低、易高温氧化的不足，本发明提供一种应用于高温环境下的陶瓷复合材料的制备工艺。
(二)技术方案
为实现上述目的，本发明提供如下技术方案：
一种应用于高温环境下的陶瓷复合材料的制备工艺，包括以下步骤：
步骤S1，在微米粒径的二硼化锆ZrB2粒子上生成纳米粒径的铬铜复合团簇粒子，将其在真空下煅烧并在煅烧过程中采用氢气还原，得到二硼化锆ZrB2-铬铜团簇粒子包覆型复合粉体；
步骤S2，以二硼化锆ZrB2-铬铜团簇粒子包覆型复合粉体为原料，采用放电等离子体烧结的方法，制备可以应用于高温环境下的二硼化锆ZrB2-铬铜团簇粒子包覆型陶瓷复合材料。
优选的，所述步骤S1，二硼化锆ZrB2粒子的粒径≥1um且≤15um；铬铜复合团簇粒子的粒径≥10nm且≤50nm。
优选的，所述步骤S1，在微米粒径的二硼化锆ZrB2粒子上生成纳米粒径的铬铜复合团簇粒子，其在350-380℃下真空煅烧1-2h，在620-680℃下采用氢气还原1-3h，得到二硼化锆ZrB2-铬铜团簇粒子包覆型复合粉体。
优选的，所述步骤S2，放电等离子烧结工艺参数为：初始压强为8-15MPa，在真空下增加压力到18-20MPa，在1680-1750℃、18-20MPa的真空条件下保温7-15min。
(三)有益的技术效果
与现有技术相比，本发明具备以下有益的技术效果：
在粒径≥1um且≤15um的二硼化锆ZrB2粒子上生成粒径≥10nm且≤50nm的铬铜复合团簇粒子，将其在真空下煅烧并采用氢气还原，得到二硼化锆ZrB2-铬铜团簇粒子包覆型复合粉体，其以二硼化锆ZrB2粒子为内核、以铬铜团簇粒子为外壳；
以二硼化锆ZrB2-铬铜团簇粒子包覆型复合粉体为原料，采用放电等离子体烧结的方法，制备可以应用于高温环境下的二硼化锆ZrB2-铬铜团簇粒子包覆型陶瓷复合材料，其断裂韧性达到了5.84-6.27MPa·m1/2；
在二硼化锆ZrB2-铬铜团簇粒子核壳包覆型陶瓷复合材料中，铬-铜复合团簇粒子(铬熔点1907℃、铜1083℃)在常温下，既有较优的塑韧性，又能保持较高的强度，在高于铜的熔化温度1083℃的高温下，铜熔化成液态，能够显现出塑韧性，可以进入二硼化锆ZrB2粒子的空洞中帮助传质，起到降低二硼化锆ZrB2粒子烧结温度、促进致密化的作用；
并且当氧扩散至材料表面时，可以形成了Cr2O3钝化物保护膜，阻挡氧离子向二硼化锆ZrB2粒子扩散，对二硼化锆ZrB2粒子起到保护作用，使其具备优异的抗高温氧化性。
具体实施方式
实施例1：
二硼化锆ZrB2-铬铜团簇粒子包覆型复合粉体的制备：
将3.2gCrCl3分散于由100mL蒸馏水中，搅拌下由恒压漏斗以30滴/min的速率滴入100mL溶解有4.5g硼氢化钠的蒸馏水溶液，向上述溶液中加入1gCuSO4、10g酒石酸钾钠、10g乙二胺四乙酸和5mg2，2-联吡啶，调节pH至10，升温至60℃后恒温水浴加热，在搅拌下向该溶液中加入5g平均粒径1-2um的二硼化锆ZrB2粒子和5mgPdCl2，在60℃下回流6h，在平均粒径1-2um的二硼化锆ZrB2粒子上生成粒径≥10nm且≤50nm的铬-铜复合团簇粒子，在整个过程中一直通入氮气，经过滤、洗涤，真空烘干之后在360℃下真空煅烧1h，在650℃下采用氢气还原2h，得到二硼化锆ZrB2-铬铜团簇粒子包覆型复合粉体；
以二硼化锆ZrB2-铬铜团簇粒子包覆型复合粉体为原料，采用放电等离子体烧结的方法，以三高石墨为放电等离子烧结模具，烧结出直径为2cm、长度为7cm的圆柱形二硼化锆ZrB2-铬铜团簇粒子包覆型陶瓷复合材料，放电等离子烧结工艺参数为：初始压强为10MPa，在真空下增加压力到20MPa，先以80℃/min的速率升高到1600℃，再以50℃/min的速率升高到1720℃，之后在1720℃、20MPa的真空条件下保温10min，之后降温。
实施例2：
二硼化锆ZrB2-铬铜团簇粒子包覆型复合粉体的制备：
将2.5gCrCl3分散于由100mL蒸馏水中，搅拌下由恒压漏斗以30滴/min的速率滴入100mL溶解有3g硼氢化钠的蒸馏水溶液，向上述溶液中加入0.8gCuSO4、8g酒石酸钾钠、8g乙二胺四乙酸和5mg2，2-联吡啶，调节pH至10，升温至50℃后恒温水浴加热，在搅拌下向该溶液中加入5g平均粒径3-5um的二硼化锆ZrB2粒子和5mgPdCl2，在50℃下回流8h，在平均粒径3-5um的二硼化锆ZrB2粒子上生成粒径≥10nm且≤50nm的铬-铜复合团簇粒子，在整个过程中一直通入氮气，经过滤、洗涤，真空烘干，之后在350℃下真空煅烧1h，在620℃下采用氢气还原1h，得到二硼化锆ZrB2-铬铜团簇粒子包覆型复合粉体；
以二硼化锆ZrB2-铬铜团簇粒子包覆型复合粉体为原料，压制成型后，采用放电等离子体烧结的方法，以三高石墨为放电等离子烧结模具，烧结出直径为2cm、长度为7cm的圆柱形二硼化锆ZrB2-铬铜团簇粒子包覆型陶瓷复合材料，放电等离子烧结工艺参数为：初始压强为8MPa，在真空下增加压力到20MPa，先以80℃/min的速率升高到1560℃，再以50℃/min的速率升高到1680℃，之后在1680℃、20MPa的真空条件下保温15min，之后降温。
实施例3：
二硼化锆ZrB2-铬铜团簇粒子包覆型复合粉体的制备：
将4gCrCl3分散于由100mL蒸馏水中，搅拌下由恒压漏斗以30滴/min的速率滴入100mL溶解有8g硼氢化钠的蒸馏水溶液，向上述溶液中加入1.5gCuSO4、15g酒石酸钾钠、15g乙二胺四乙酸和10mg2，2-联吡啶，调节pH至10，升温至80℃后恒温水浴加热，在搅拌下向该溶液中加入5g平均粒径15um的二硼化锆ZrB2粒子和10mgPdCl2，在80℃下回流4h，在平均粒径15um的二硼化锆ZrB2粒子上生成粒径≥10nm且≤50nm的铬-铜复合团簇粒子，在整个过程中一直通入氮气，经过滤、洗涤，真空烘干之后在380℃下真空煅烧2h，在680℃下采用氢气还原3h，得到二硼化锆ZrB2-铬铜团簇粒子包覆型复合粉体；
以二硼化锆ZrB2-铬铜团簇粒子包覆型复合粉体为原料，压制成型后，采用放电等离子体烧结的方法，以三高石墨为放电等离子烧结模具，烧结出直径为2cm、长度为7cm的圆柱形二硼化锆ZrB2-铬铜团簇粒子包覆型陶瓷复合材料，放电等离子烧结工艺参数为：初始压强为15MPa，在真空下增加压力到18MPa，先以80℃/min的速率升高到1650℃，再以50℃/min的速率升高到1750℃，之后在1750℃、18MPa的真空条件下保温7min，之后降温。
对比例1：
以平均粒径1-2um的二硼化锆ZrB2粒子为原料，压制成型后，采用放电等离子体烧结的方法，以三高石墨为放电等离子烧结模具，烧结出直径为2cm、长度为7cm的圆柱形二硼化锆ZrB2陶瓷材料，放电等离子烧结工艺参数为：初始压强为10MPa，在真空下增加压力到20MPa，先以80℃/min的速率升高到1600℃，再以50℃/min的速率升高到1720℃，之后在1720℃、20MPa的真空条件下保温10min，之后降温。
性能测试：
一、根据GB/T6569-2006，在WDW-5型微机控制电子万能试验机上采用三点弯曲法测定弯曲强度；
二、根据GB/T23806-2009，在电子万能试验机上进行断裂韧性测试；
三、利用432SVD型显微硬度计测试维氏硬度；
上述测试结果见下表1；
表1
Claims (4)
1.一种应用于高温环境下的陶瓷复合材料的制备工艺，其特征在于，包括以下步骤：
步骤S1，在微米粒径的二硼化锆ZrB2粒子上生成纳米粒径的铬铜复合团簇粒子，将其在真空下煅烧并在煅烧过程中采用氢气还原，得到二硼化锆ZrB2-铬铜团簇粒子包覆型复合粉体；
步骤S2，以二硼化锆ZrB2-铬铜团簇粒子包覆型复合粉体为原料，采用放电等离子体烧结的方法，制备可以应用于高温环境下的二硼化锆ZrB2-铬铜团簇粒子包覆型陶瓷复合材料。
2.根据权利要求1所述的一种应用于高温环境下的陶瓷复合材料的制备工艺，其特征在于，所述步骤S1，二硼化锆ZrB2粒子的粒径≥1um且≤15um；铬铜复合团簇粒子的粒径≥10nm且≤50nm。
3.根据权利要求1所述的一种应用于高温环境下的陶瓷复合材料的制备工艺，其特征在于，所述步骤S1，在微米粒径的二硼化锆ZrB2粒子上生成纳米粒径的铬铜复合团簇粒子，其在350-380℃下真空煅烧1-2h，在620-680℃下采用氢气还原1-3h，得到二硼化锆ZrB2-铬铜团簇粒子包覆型复合粉体。
4.根据权利要求1所述的一种应用于高温环境下的陶瓷复合材料的制备工艺，其特征在于，所述步骤S2，放电等离子烧结工艺参数为：初始压强为8-15MPa，在真空下增加压力到18-20MPa，在1680-1750℃、18-20MPa的真空条件下保温7-15min。
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