CN117417190A - 碳化钨-氮化硅复合材料及其放电等离子烧结方法 - Google Patents
碳化钨-氮化硅复合材料及其放电等离子烧结方法 Download PDFInfo
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- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 26
- 239000010937 tungsten Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000002490 spark plasma sintering Methods 0.000 title abstract description 13
- 230000007704 transition Effects 0.000 claims abstract description 61
- 239000011812 mixed powder Substances 0.000 claims abstract description 60
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 43
- 239000010439 graphite Substances 0.000 claims abstract description 43
- 238000005245 sintering Methods 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 12
- 238000011049 filling Methods 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 238000000498 ball milling Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 12
- 238000007873 sieving Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
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- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 31
- 239000000919 ceramic Substances 0.000 abstract description 16
- 229910045601 alloy Inorganic materials 0.000 abstract description 7
- 239000000956 alloy Substances 0.000 abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 abstract description 5
- 239000010941 cobalt Substances 0.000 abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 62
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000005219 brazing Methods 0.000 description 5
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Abstract
本发明为一种碳化钨‑氮化硅复合材料及其放电等离子烧结方法。包括如下步骤：(1)分别制备氮化硅基、碳化钨基和过渡层混合粉末；氮化硅基混合粉末的组分质量配比为：Si3N492～96wt％、Y2O31～3wt％、MgSiN21～3wt％、Al2O31～3wt％；碳化钨基混合粉末的组分质量配比具体为：WC92～96wt％、Si3N41～4wt％、Y2O31～3wt％、Al2O31～3wt％；过渡层部分由5～10个子层构成；(2)将粉末按照碳化钨基混合粉末‑过渡层混合粉末‑氮化硅基混合粉末依次填入石墨模具中；(3)放入放电等离子烧结炉中进行烧结。本发明采用氮化硅、氧化钇和氧化铝作为烧结助剂来代替金属粘结相钴，使该碳化钨材料的放电等离子烧结温度升高至1650℃，通过梯度变化的过渡层实现两种材料的梯度过渡，采用放电等离子烧结一次烧结连接碳化钨基硬质合金和氮化硅陶瓷。
Description
技术领域
本发明属于复合材料领域，具体涉及一种碳化钨-氮化硅复合材料及其放电等离子烧结方法。
背景技术
氮化硅陶瓷材料在高温下有着优异的力学性能和化学稳定性，被广泛地用于制造各种耐火以及抗腐蚀部件，而碳化钨基硬质合金有着高弹性模量和韧性等良好的室温力学性能被广泛地应用于航天器材、矿山工具以及切削工具等。氮化硅陶瓷和碳化钨基硬质合金分别在高温和低温条件下有着优异的机械性能。因此，制备一种碳化钨-氮化硅复合结构材料，进而实现该材料在高温低温分布不同的环境下的应用，例如液态金属电池密封材料以及切削刀具棒料等。
传统的碳化钨基硬质合金由钴作为金属粘结剂，其烧结温度在1350℃左右，而氮化硅陶瓷的烧结温度在1650℃左右，这就给碳化钨-氮化硅复合结构材料的连接带来了巨大的困难，常规的连接方式为通过AgCuTi钎料实现碳化钨和氮化硅的钎焊连接，但是由于碳化钨和氮化硅的热膨胀系数差异较大，在钎焊过程中容易产生较大的残余应力，进而导致连接强度低甚至连接处开裂的现象。为了避免钎焊带来的这些缺点，人们采用多次放电等离子烧结实现碳化钨-氮化硅复合结构材料的连接，即先在1650℃的温度下烧结出氮化硅材料部分，然后将烧结好的氮化硅部分再次放入石墨模具中，并填入碳化钨粉末，在1350℃下实现碳化钨-氮化硅叠层梯度复合结构材料的烧结连接。这种多次烧结连接的制备工艺不仅浪费能源，生产效率低，而且制备的叠层梯度复合结构材料由于多次烧结使得晶粒过度生长，进而导致制备的材料力学性能差。此外，因为碳化钨和氮化硅热膨胀系数差异大，烧结得到的材料存在较大的残余应力容易出现裂纹等缺陷，无法满足实际生产所需。
发明内容
本发明的目的在于提供一种适用于高温低温分布不同工作环境的碳化钨基硬质合金-氮化硅陶瓷复合结构材料，采用叠层梯度的过渡结构缓解因为热膨胀系数差异大导致的烧结过程中产生的残余应力过大，并且解决该复合结构材料放电等离子烧结难度大且需多次烧结的问题，提供一种碳化钨-氮化硅复合材料及其放电等离子烧结连接方法。
实现本发明目的的技术解决方案为：一种基于放电等离子烧结碳化钨-氮化硅复合材料的方法，包括如下步骤：
步骤(1)：分别制备氮化硅基混合粉末、碳化钨基混合粉末和过渡层混合粉末；氮化硅基混合粉末的组分质量配比为：Si3N492～96wt％、Y2O31～3wt％、MgSiN21～3wt％、Al2O31～3wt％；碳化钨基混合粉末的组分质量配比具体为：WC92～96wt％、Si3N41～4wt％、Y2O31～3wt％、Al2O31～3wt％；过渡层部分由5～10个子层构成，过渡层混合粉末相应的为5～10组，过渡层混合粉末的组分质量配比为xWC+(1-x)Si3N4，其中x取值范围在10～90wt％，x为WC粉末的质量百分比，过渡层的总厚度为5～10mm；
步骤(2)：将制备好的粉末按照碳化钨基混合粉末-过渡层混合粉末-氮化硅基混合粉末依次填入石墨模具中；
步骤(3)：将装填好粉末的模具放入放电等离子烧结炉中进行烧结。
进一步的，步骤(1)中的氮化硅基混合粉末、碳化钨基混合粉末和过渡层混合粉末均采用湿混球磨的方法制备，球磨后的混合粉末真空干燥，真空冷却至室温后过筛。
进一步的，步骤(1)中湿混球磨的介质为无水乙醇，氮化硅球与混合粉末的质量比为8:1，转速为200～250r/min，球磨时间为12～24h。
进一步的，步骤(1)中的“真空干燥，真空冷却至室温后过筛”具体为：将球磨后的混合粉末放入100～120℃真空干燥箱中干燥，真空冷却至室温后研磨，过100目筛。
进一步的，步骤(2)具体为：将石墨模具内壁覆一层石墨纸，将碳化钨基混合粉末填入石墨模具中，将WC含量不同的过渡层混合粉末按照WC含量由高到低依次填入已填有碳化钨基混合粉末的石墨模具中，最后将氮化硅基混合粉末填入石墨模具中。
进一步的，石墨纸的厚度为0.2±0.02mm。
进一步的，步骤(3)烧结具体为：对装填有混合粉末的石墨模具的压头施加30～60MPa压力，以升温速率30～100℃/min升至1600～1700℃，并保温5～10min，然后随炉冷却至室温。
一种碳化钨-氮化硅复合材料，采用上述的方法制备。
本发明与现有技术相比，其显著优点在于：
(1)本发明采用氧化钇、氮化硅和氧化铝作为烧结助剂代替传统碳化钨硬质合金中的钴粘结相，因为在放电等离子烧结过程中钴会在1200℃左右产生液相，从而使得碳化钨硬质合金在1400℃左右完成烧结，而本发明采用的烧结助剂在烧结过程中产生玻璃相的温度为1450℃左右，这就使得该碳化钨材料的烧结温度提升至1650℃左右，同时还保证了所制备的碳化钨材料的力学性能，从而实现了碳化钨—氮化硅复合材料的一次性放电等离子烧结连接，避免了因为碳化钨和氮化硅烧结温度不同而进行多次放电等离子烧结连接导致的连接强度低、材料力学性能差的问题，进一步提高了碳化钨基硬质合金—氮化硅陶瓷复合结构材料力学性能。
(2)本发明制备的碳化钨基硬质合金-氮化硅陶瓷复合结构材料的碳化钨基硬质合金端和氮化硅陶瓷端由多层碳化钨-氮化硅含量梯度变化的复合材料作为过渡层来连接，避免了因为钎焊时两种材料热膨胀系数差异大导致的连接强度低的问题；该材料兼备了碳化钨硬质合金优异的室温力学性能以及氮化硅陶瓷优异的高温力学性能，可适用于高温低温分布不同的工作环境，具有推广价值。
附图说明
图1为制备的碳化钨-氮化硅复合材料示意图，其中，1为95wt％碳化钨层；2为90wt％碳化钨层；3为70wt％碳化钨层；4为50wt％碳化钨层；5为30wt％碳化钨层；6为10wt％碳化钨层；7为氮化硅层；
图2为实例1制得的过渡层部分连接界面的SEM图，其中2为90wt％WC过渡层，3为70wt％WC过渡层，4为50wt％WC过渡层，5为30wt％WC过渡层，6为10wt％WC过渡层。
图3为实例2制得的过渡层部分层间与相邻层之间的维氏硬度与断裂韧性比较图。
具体实施方式
下面结合附图对本发明作进一步详细描述。
实施例1
碳化钨—氮化硅复合材料及放电等离子烧结连接方法，具体为：
(1)按比例称取氮化硅基混合粉末Si3N492wt％、Y2O33wt％、MgSiN23wt％、Al2O32wt％；碳化钨基混合粉末WC95wt％、Si3N43wt％、Y2O31wt％、Al2O31wt％；按xWC+(1-x)Si3N4的比例称取五种WC含量不同的过渡层粉末，其中x＝90wt％、70wt％、50wt％、30wt％、10wt％。将上述七种不同组分的混合粉末分别装入七个聚氨酯球磨罐中，并将球磨罐固定在球磨机上，以无水乙醇为介质用氮化硅球球磨24小时，氮化硅球和混合粉末的质量比为8:1；将球磨后的七种粉料分别在真空120℃下干燥，冷却至室温后研磨并过100目筛。将制备好的七种混合粉末按照“石墨压头-0.2mm厚石墨垫片-碳化钨基混合粉末-90wt％WC过渡层混合粉末-70wt％WC过渡层混合粉末-50wt％WC过渡层混合粉末-30wt％WC过渡层混合粉末-10wt％WC过渡层混合粉末-氮化硅基混合粉末-0.2mm石墨垫片-石墨压头”的顺序依次装入内壁覆有0.2mm石墨纸的石墨模具中。
(2)将上述石墨模具放置在放电等离子烧结炉中，对模具压头施加50MPa的压力，将放电等离子炉炉腔抽真空至40Pa，然后通入氩气至0.06MPa，再抽真空至40Pa，随后充入氩气至0.06MPa。在此氩气气氛下，烧结至1700℃，升温速率为60℃/min，在1700℃下保温保压5min，然后随炉冷却至室温，实现碳化钨基硬质合金—氮化硅陶瓷复合结构材料放电等离子一体化烧结连接。
本实例制得的碳化钨基硬质合金—氮化硅陶瓷复合结构材料过渡层部分的连接界面SEM图见图2，其中2为90wt％WC过渡层，3为70wt％WC过渡层，4为50wt％WC过渡层，5为30wt％WC过渡层，6为10wt％WC过渡层，有SEM图可知过渡层各层之间没有出现任何缺陷或分层，实现了过渡层各层之间的平滑过渡，提高了碳化钨基硬质合金—氮化硅陶瓷复合结构材料连接强度。
实施例2
一种碳化钨基硬质合金—氮化硅陶瓷复合结构材料及放电等离子一体化烧结连接方法，具体为：
(1)按比例称取氮化硅基混合粉末Si3N492wt％、Y2O33wt％、MgSiN23wt％、Al2O32wt％；碳化钨基混合粉末WC94wt％、Si3N43wt％、Y2O31wt％、Al2O32wt％；按xWC+(1-x)Si3N4的比例称取五种WC含量不同的过渡层粉末，其中x＝90wt％、70wt％、50wt％、30wt％、10wt％。将上述七种不同组分的混合粉末分别装入七个聚氨酯球磨罐中，并将球磨罐固定在球磨机上，以无水乙醇为介质用氮化硅球球磨12小时，氮化硅球和混合粉末的质量比为8:1；将球磨后的七种粉料分别在真空120℃下干燥，冷却至室温后研磨并过100目筛。将制备好的七种混合粉末按照“石墨压头-0.2mm厚石墨垫片-碳化钨基混合粉末-90wt％WC过渡层混合粉末-70wt％WC过渡层混合粉末-50wt％WC过渡层混合粉末-30wt％WC过渡层混合粉末-10wt％WC过渡层混合粉末-氮化硅基混合粉末-0.2mm石墨垫片-石墨压头”的顺序依次装入内壁覆有0.2mm石墨纸的石墨模具中。
(2)将上述石墨模具放置在放电等离子烧结炉中，对模具压头施加40MPa的压力，将放电等离子炉炉腔抽真空至40Pa，然后通入氩气至0.06MPa，再抽真空至40Pa，随后充入氩气至0.06MPa。在此氩气气氛下，烧结至1600℃，升温速率为60℃/min，在1600℃下保温保压8min，然后随炉冷却至室温，实现碳化钨—氮化硅复合结构材料放电等离子一体化烧结连接。
本实例制得的碳化钨基硬质合金—氮化硅陶瓷复合结构材料过渡层部分层间与相邻层之间的维氏硬度与断裂韧性比较图见图3，由图可以进一步证明相邻层之间没有出现裂纹或其他任何缺陷，各层之间连接紧密，连接强度高。
实施例3
一种碳化钨基硬质合金—氮化硅陶瓷复合结构材料及放电等离子一体化烧结连接方法，具体为：
(1)按比例称取氮化硅基混合粉末Si3N492wt％、Y2O33wt％、MgSiN23wt％、Al2O32wt％；碳化钨基混合粉末WC95wt％、Si3N43wt％、Y2O31wt％、Al2O31wt％；按xWC+(1-x)Si3N4的比例称取九种WC含量不同的过渡层粉末，其中x＝90wt％、80wt％、70wt％、60wt％、50wt％、40wt％、30wt％、20wt％、10wt％。将上述十一种不同组分的混合粉末分别装入十一个聚氨酯球磨罐中，并将球磨罐固定在球磨机上，以无水乙醇为介质用氮化硅球球磨24小时，氮化硅球和混合粉末的质量比为8:1；将球磨后的七种粉料分别在真空120℃下干燥，冷却至室温后研磨并过100目筛。将制备好的七种混合粉末按照“石墨压头-0.2mm厚石墨垫片-碳化钨基混合粉末-90wt％WC过渡层混合粉末-80wt％WC过渡层混合粉末-70wt％WC过渡层混合粉末-60wt％WC过渡层混合粉末-50wt％WC过渡层混合粉末-40wt％WC过渡层混合粉末-30wt％WC过渡层混合粉末-20wt％WC过渡层混合粉末-10wt％WC过渡层混合粉末-氮化硅基混合粉末-0.2mm石墨垫片-石墨压头”的顺序依次装入内壁覆有0.2mm石墨纸的石墨模具中。
(2)将上述石墨模具放置在放电等离子烧结炉中，对模具压头施加40MPa的压力，将放电等离子炉炉腔抽真空至40Pa，然后通入氩气至0.06MPa，再抽真空至40Pa，随后充入氩气至0.06MPa。在此氩气气氛下，烧结至1650℃，升温速率为60℃/min，在1650℃下保温保压5min，然后随炉冷却至室温，实现碳化钨基硬质合金—氮化硅陶瓷复合结构材料放电等离子一体化烧结连接。
与常规的多次烧结工艺相比，所有实例中的碳化钨基硬质合金-氮化硅陶瓷复合结构材料微观晶粒无明显异常长大，各层结合面之间没有出现裂纹或其他缺陷，各层之间过渡平滑，结合紧密。这说明含有过渡层的复合结构连接很好地解决了碳化钨和氮化硅热膨胀系数差异大导致的连接强度低和连接处开裂的问题。
Claims (8)
1.一种基于放电等离子烧结碳化钨-氮化硅复合材料的方法，其特征在于，包括如下步骤：
步骤(1)：分别制备氮化硅基混合粉末、碳化钨基混合粉末和过渡层混合粉末；氮化硅基混合粉末的组分质量配比为：Si3N492～96wt％、Y2O31～3wt％、MgSiN21～3wt％、Al2O31～3wt％；碳化钨基混合粉末的组分质量配比具体为：WC92～96wt％、Si3N41～4wt％、Y2O31～3wt％、Al2O31～3wt％；过渡层部分由5～10个子层构成，过渡层混合粉末相应的为5～10组，过渡层混合粉末的组分质量配比为xWC+(1-x)Si3N4，其中x取值范围在10～90wt％，x为WC粉末的质量百分比，过渡层的总厚度为5～10mm；
步骤(2)：将制备好的粉末按照碳化钨基混合粉末-过渡层混合粉末-氮化硅基混合粉末依次填入石墨模具中；
步骤(3)：将装填好粉末的模具放入放电等离子烧结炉中进行烧结。
2.根据权利要求1所述的方法，其特征在于，步骤(1)中的氮化硅基混合粉末、碳化钨基混合粉末和过渡层混合粉末均采用湿混球磨的方法制备，球磨后的混合粉末真空干燥，真空冷却至室温后过筛。
3.根据权利要求2所述的方法，其特征在于，步骤(1)中湿混球磨的介质为无水乙醇，氮化硅球与混合粉末的质量比为8:1，转速为200～250r/min，球磨时间为12～24h。
4.根据权利要求3所述的方法，其特征在于，步骤(1)中的“真空干燥，真空冷却至室温后过筛”具体为：将球磨后的混合粉末放入100～120℃真空干燥箱中干燥，真空冷却至室温后研磨，过100目筛。
5.根据权利要求4所述的方法，其特征在于，步骤(2)具体为：将石墨模具内壁覆一层石墨纸，将碳化钨基混合粉末填入石墨模具中，将WC含量不同的过渡层混合粉末按照WC含量由高到低依次填入已填有碳化钨基混合粉末的石墨模具中，最后将氮化硅基混合粉末填入石墨模具中。
6.根据权利要求5所述的方法，其特征在于，石墨纸的厚度为0.2±0.02mm。
7.根据权利要求6所述的方法，其特征在于，步骤(3)烧结具体为：对装填有混合粉末的石墨模具的压头施加30～60MPa压力，以升温速率30～100℃/min升至1600～1700℃，并保温5～10min，然后随炉冷却至室温。
8.一种碳化钨-氮化硅复合材料，其特征在于，采用权利要求1～7任一项所述的方法制备。
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| CN116000301A (zh) * | 2022-12-13 | 2023-04-25 | 南京理工大学 | 一种碳化钨-氮化硅陶瓷复合立铣刀及其制备方法 |
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