CN116253569B - 一种利用自蔓延辅助固溶体掺杂技术制备(Hf,Ta)B2-MoSi2阻氧涂层的方法 - Google Patents
一种利用自蔓延辅助固溶体掺杂技术制备(Hf,Ta)B2-MoSi2阻氧涂层的方法 Download PDFInfo
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- 229910016006 MoSi Inorganic materials 0.000 title claims abstract description 110
- 238000000576 coating method Methods 0.000 title claims abstract description 108
- 239000011248 coating agent Substances 0.000 title claims abstract description 102
- 229910052735 hafnium Inorganic materials 0.000 title claims abstract description 98
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 65
- 239000001301 oxygen Substances 0.000 title claims abstract description 65
- 239000006104 solid solution Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000005516 engineering process Methods 0.000 title claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 92
- 238000005245 sintering Methods 0.000 claims abstract description 49
- 230000004888 barrier function Effects 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 23
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052796 boron Inorganic materials 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 13
- 239000010439 graphite Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 13
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 12
- 238000011049 filling Methods 0.000 claims abstract description 10
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011812 mixed powder Substances 0.000 claims abstract description 10
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005303 weighing Methods 0.000 claims abstract description 5
- 238000005498 polishing Methods 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims description 16
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
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- 229910018557 Si O Inorganic materials 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 6
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
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- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种利用自蔓延辅助固溶体掺杂技术制备(Hf,Ta)B2‑MoSi2阻氧涂层的方法,包括称取钽、铪、硼单质粉原料,通过自蔓延反应制备(Hf,Ta)B2固溶粉体;按配比称取(Hf,Ta)B2固溶粉体与商业粉MoSi2并进行二维混料;将混合粉体填充进石墨模具中,并均匀包裹清洗好的碳材料基体,放入放电等离子烧结炉中进行烧结;烧结完毕打磨后得到(Hf,Ta)B2‑MoSi2阻氧涂层;本发明克服了现有(Hf,Ta)B2‑MoSi2阻氧涂层制备方法存在的原料粉反应温度高、保温时间长、涂层制备复杂、制备周期长,阻氧防护温区有待提高等问题,具有瞬时点然自蔓延反应的特点,以及降低反应温度、缩短反应时间、简化涂层整体制备流程等优势,并可有效提高(Hf,Ta)B2‑MoSi2粉体的烧结活性,促进阻氧涂层致密化烧结,具有提升阻氧涂层的抗氧化性能的效果。
Description
技术领域
本发明涉及石墨材料抗氧化防护领域,具体是一种利用自蔓延辅助固溶体掺杂技术制备(Hf,Ta)B2-MoSi2阻氧涂层的方法。
背景技术
随着航空航天领域与高新技术产业的飞速发展,高温结构材料的需求日益增加,碳材料因其低密度、低热膨胀系数、优异的抗热震性和优异的高温力学性能而广泛应用于航空和航天工业。然而,碳材料对氧元素高度敏感,当工作环境为高于400℃的有氧环境时,石墨材料因自身剧烈的氧化活性,与空气中的氧气和水都可以发生反应生成CO或CO2气体,导致其极易被氧化腐蚀,而且随着温度的升高,氧化侵蚀速率也越快,严重影响其在高温条件下的使用。因此,改善石墨材料的超高温抗氧化性能成为近年来的研究热点。
涂层技术的基本原理是在石墨基体上制备一层超高温抗氧化涂层,通过涂层实现基体与氧气隔绝,达到阻挡氧气渗入的效果,进而实现石墨材料的高温稳定性。此方法对基体影响相较于基体改性法小,不会牺牲石墨材料本身优异的性能,从而达到抗氧化的目的,而且涂层的结构、组分可根据不同工作环境需求而进行设计,应用范围广泛,因而成为近年来抗氧化研究的关注点。因此,开发可靠的外部抗氧化涂层技术对于充分利用碳材料的潜力至关重要。
由于HfB2和MoSi2具有高熔点、高热导率、优异的抗氧化性和化学稳定性的特点,HfB2-MoSi2阻氧涂层显示出优异的石墨基保护潜力。如任宣儒等人(任宣儒,王炜光,孙科,胡昱雯,徐磊华,冯培忠.液相烧结法制备MoSi2改性HfB2-SiC超高温陶瓷抗氧化涂层[J].新型炭材料,2022,37(03):603-614.)公开了一种采用MoSi2与HfB2改性增强阻氧涂层抗氧化性能的方法,证明了MoSi2、HfB2等材料改性后的涂层在1500℃高温下具有良好的阻氧性能。但MoSi2、HfB2等单相材料改性阻氧涂层在高于1500℃温域后抗氧化效果将急剧衰减。然而,随着石墨材料的高温防护要求的提升,1500℃的防护温度已不能满足部分应用需求,亟需针对更高温度的抗氧化防护提出挑战。
固溶硼化物作为一种优异的改性材料,发挥了固溶元素的“协同作用”,可以进一步的促进改性的效果。基于固溶硼化物的掺杂改性作用,有望满足石墨材料在高于1500℃温域的防护需求。许亮等人(许亮,张岩,谭大旺,郭伟明,江泽斌.溶TaB2对HfB2-SiC陶瓷材料的组织结构与力学性能的影响[J].人工晶体学报,2019,48(12):2303-2307.)公开了一种(Hf,Ta)B2-SiC固溶掺杂粉体材料的制备方法,证明了固溶(Hf,Ta)B2-SiC材料的改性优势。然而该种方法采用传统硼热还原方法,反应温度高(1600℃),保温时间长(1h),这极大程度上造成能源浪费,且在一定程度上复杂了阻氧涂层的整体制备流程,延长了整体制备周期。此外,常规硼热还原方法得到的粉体活性较低,不利于后续涂层致密化制备,这势必影响阻氧涂层的抗氧化效果。
发明内容
为解决上述技术问题,本发明提供的技术方案为:本发明提供的(Hf,Ta)B2-MoSi2阻氧涂层的方法的制备方法,其按照以下步骤进行:
(1)以钽、铪、硼单质粉为原料,按摩尔配比混合、研磨,得到混合前驱粉体;
(2)将复合前驱粉体于压片机中压片,取出坯体放入自蔓延反应炉中,连接好钨丝电源并抽真空;
(3)开启钨丝电源点火,待反应完毕后取出产物并研磨,得到(Hf,Ta)B2固溶粉体;
(4)按1:1摩尔配比称取(Hf,Ta)B2固溶粉体与商业粉MoSi2并进行二维混料,混合后得到(Hf,Ta)B2-MoSi2混合粉体;
(5)将(Hf,Ta)B2-MoSi2混合粉体填充进石墨模具中,并均匀包裹清洗好的碳材料基体,放入放电等离子烧结炉中进行烧结;
(6)烧结完毕后,取出产物,打磨后得到(Hf,Ta)B2-MoSi2阻氧涂层。
上述方法中,合成后得到的(Hf,Ta)B2-MoSi2阻氧涂层的化学组成为:(Hf1-xTax)B2-MoSi2(x=0.01~0.04),其特征为:Hf与Ta元素以固溶体的形式存在于(Hf,Ta)B2中;
优选地,步骤(1)中所述的(Hf,Ta)B2-MoSi2阻氧涂层的制备方法,所述的钽、铪、硼单质粉为原料的按摩尔配比范围为(99:1:200)~(96:4:200);
优选地,步骤(2)中所述的(Hf,Ta)B2-MoSi2阻氧涂层的制备方法,所述将自蔓延反应炉抽真空,真空范围:50~80Pa;
优选地,步骤(4)中所述的(Hf,Ta)B2-MoSi2阻氧涂层的制备方法,所述将(Hf,Ta)B2固溶粉体与商业粉MoSi2进行二维混料,混料条件为:混料时间30~60min,转速50~200r/min;
本发明与现有技术相比的优点在于:
1、本发明采用利用自蔓延辅助固溶掺杂技术制备(Hf,Ta)B2-MoSi2阻氧涂层,既保留了固溶掺杂技术的优势,保证了涂层固溶掺杂改性效果,增强了阻氧涂层内部组织弥散结构,满足了石墨材料在高于1500℃温域的防护需求;也发挥了自蔓延技术辅助的优势,可以瞬时快速制备固溶(Hf,Ta)B2-MoSi2粉体,降低了固溶硼化物的反应温度与缩短保温时间,达到了缩短阻氧涂层制备周期的效果。
2、作为一种有效的制备方法,本发明的(Hf,Ta)B2-MoSi2阻氧涂层利用了自蔓延辅助固溶掺杂技术技术,克服了传统MoSi2、HfB2等单相材料改性阻氧涂层在高于1500℃温域的抗氧化效果急剧衰减问题,具有提升阻氧涂层工作温度、延长服役时间等优势;同时,克服了传统硼热还原制备固溶硼化物粉体时存在的反应温度高、保温时间长,以及复杂涂层制备流程、延长涂层制备周期等问题,无需长时间高温反应,具有瞬时快速自燃烧的特点,以及简化涂层制备流程、缩短涂层制备周期等优势;
3、采用本方法,(Hf,Ta)B2-MoSi2粉体无需长时间高温反应,点然即可瞬时自蔓延反应,比传统硼热还原方法的反应温度降低了约1600℃,反应时间缩短了约1h,且有效简化了(Hf,Ta)B2-MoSi2阻氧涂层的制备工艺,缩短阻氧涂层制备周期;而且可有效提高(Hf,Ta)B2-MoSi2粉体的烧结活性,促进阻氧涂层致密化烧结,具有提升阻氧涂层的抗氧化性能的效果。
总之,本发明克服了现有(Hf,Ta)B2-MoSi2阻氧涂层制备方法存在的原料粉反应温度高、保温时间长,以及涂层制备复杂、制备周期长,阻氧防护温区有待提高等问题,具有瞬时点然自蔓延反应的特点,以及降低反应温度、缩短反应时间、简化涂层整体制备流程等优势,并可有效提高(Hf,Ta)B2-MoSi2粉体的烧结活性,促进阻氧涂层致密化烧结,具有提升阻氧涂层的抗氧化性能的效果。
附图说明
图1为本发明的工艺流程图。
图2为本发明实施例1~4得到的(Hf,Ta)B2固溶粉体的X射线衍射物相分析结果。
图3为本发明实施例1得到的(Hf,Ta)B2-MoSi2涂层的扫描电镜断面结果。
图4为本发明实施例2得到的(Hf,Ta)B2-MoSi2涂层的扫描电镜断面结果。
图5为本发明实施例3得到的(Hf,Ta)B2-MoSi2涂层的扫描电镜断面结果。
图6为本发明实施例4得到的(Hf,Ta)B2-MoSi2涂层的扫描电镜断面结果。
图7为本发明实施例1得到的(Hf,Ta)B2-MoSi2涂层的扫描电镜表面结果。
图8为本发明实施例2得到的(Hf,Ta)B2-MoSi2涂层的扫描电镜表面结果。
图9为本发明实施例3得到的(Hf,Ta)B2-MoSi2涂层的扫描电镜表面结果。
图10为本发明实施例4得到的(Hf,Ta)B2-MoSi2涂层的扫描电镜表面结果。
图11为本发明实施例1得到的(Hf,Ta)B2-MoSi2涂层经1700℃高温氧化后的扫描电镜表面结果。
图12为本发明实施例2得到的(Hf,Ta)B2-MoSi2涂层经1700℃高温氧化后的扫描电镜表面结果。
图13为本发明实施例3得到的(Hf,Ta)B2-MoSi2涂层经1700℃高温氧化后的扫描电镜表面结果。
图14为本发明实施例4得到的(Hf,Ta)B2-MoSi2涂层经1700℃高温氧化后的扫描电镜表面结果。
图15为本发明实施例1~4得到的(Hf,Ta)B2-MoSi2涂层经1700℃高温氧化后的氧化增重曲线。
图16为本发明对比例2得到的自蔓延粉HfB2-MoSi2涂层的扫描电镜断面结果。
图17为本发明对比例3得到的商业粉HfB2-TaB2-MoSi2涂层的扫描电镜断面结果。
图18为本发明对比例2得到的自蔓延粉HfB2-MoSi2涂层的扫描电镜表面结果。
图19为本发明对比例3得到的商业粉HfB2-TaB2-MoSi2涂层的扫描电镜表面结果。
图20为本发明对比例1得到的自蔓延粉(Hf95Ta5)B2-MoSi2涂层经1700℃高温氧化后的扫描电镜表面结果。
图21为本发明对比例2得到的自蔓延粉HfB2-MoSi2涂层经1700℃高温氧化后的扫描电镜表面结果。
图22为本发明对比例3得到的商业粉HfB2-TaB2-MoSi2涂层经1700℃高温氧化后的扫描电镜表面结果。
图23为本发明对比例1~3得到的涂层经1700℃高温氧化后的氧化增重曲线。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。通常在此处附图中描述和示出的本发明实施例的组件可以以各种不同的配置来布置和设计。
实施例1:
本实施例中利用自蔓延辅助固溶掺杂技术制备(Hf1-xTax)B2-MoSi2(x=0.01)阻氧涂层的方法,按照以下步骤进行:
(1)以钽、铪、硼单质粉为原料,按摩尔配比99:1:200混合、研磨,得到混合前驱粉体;
(2)将混合前驱粉体于压片机中,以直径16mm、压强200Mpa的条件压片,取出坯体放入自蔓延反应炉中,连接好钨丝电源并抽真空,真空度50Pa;
(3)开启钨丝电源点火,点然后坯体开始自蔓延燃烧反应,待反应完毕后取出产物并于研钵中研磨15min,得到(Hf,Ta)B2固溶粉体;
(4)按1:1摩尔配比称取(Hf,Ta)B2固溶粉体与商业粉MoSi2共2.5g,进行二维混料,混料时间30min,转速50r/min,混合后得到(Hf,Ta)B2-MoSi2混合粉体;
(5)将(Hf,Ta)B2-MoSi2混合粉体填充进石墨模具中,并均匀包裹清洗好的碳材料基体,放入放电等离子烧结炉中按照烧结温度:1500℃、保温时间5min、施加压力3.5kN的烧结工艺进行烧结;
(6)烧结完毕后,取出产物,打磨后得到(Hf99Ta1)B2-MoSi2阻氧涂层。
本实施例所得(Hf,Ta)B2-MoSi2阻氧涂层中固溶粉体的物象结构如图2所示,阻氧涂层氧化前断面扫描结果、氧化前表面扫描结果以及氧化后表面扫描结果分别如图3、图7以及图11所示,经1700℃高温氧化后的氧化增重曲线如图15所示,氧化后增重结果如表1所示,可以看出:实施例1中所得(Hf,Ta)B2-MoSi2阻氧涂层结构致密,表面完整,氧化后表面形成具有固溶体氧化物弥散分布的致密Si-O玻璃膜,且在1700℃高温增重较少,表现出较为优异的阻氧防护效果。
实施例2:
本实施例中利用自蔓延辅助固溶掺杂技术制备(Hf1-xTax)B2-MoSi2(x=0.02)阻氧涂层的方法,按照以下步骤进行:
(1)以钽、铪、硼单质粉为原料,按摩尔配比98:2:200混合、研磨,得到混合前驱粉体;
(2)将混合前驱粉体于压片机中,以直径16mm、压强200Mpa的条件压片,取出坯体放入自蔓延反应炉中,连接好钨丝电源并抽真空,真空度60Pa;
(3)开启钨丝电源点火,点然后坯体开始自蔓延燃烧反应,待反应完毕后取出产物并于研钵中研磨15min,得到(Hf,Ta)B2固溶粉体;
(4)按1:1摩尔配比称取(Hf,Ta)B2固溶粉体与商业粉MoSi2共2.5g,进行二维混料,混料时间40min,转速100r/min,混合后得到(Hf,Ta)B2-MoSi2混合粉体;
(5)将(Hf,Ta)B2-MoSi2混合粉体填充进石墨模具中,并均匀包裹清洗好的碳材料基体,放入放电等离子烧结炉中按照烧结温度:1500℃、保温时间5min、施加压力3.5kN的烧结工艺进行烧结;
(6)烧结完毕后,取出产物,打磨后得到(Hf98Ta2)B2-MoSi2阻氧涂层。
本实施例所得(Hf,Ta)B2-MoSi2阻氧涂层中固溶粉体的物象结构如图2所示,阻氧涂层氧化前断面扫描结果、氧化前表面扫描结果以及氧化后表面扫描结果分别如图4、图8以及图12所示,经1700℃高温氧化后的氧化增重曲线如图15所示,氧化后增重结果如表1所示,可以看出:实施例2中所得(Hf,Ta)B2-MoSi2阻氧涂层结构致密,表面完整,氧化后表面形成具有固溶体氧化物弥散分布的致密Si-O玻璃膜,且在1700℃高温增重较少,表现出较为优异的阻氧防护效果。
实施例3:
本实施例中利用自蔓延辅助固溶掺杂技术制备(Hf1-xTax)B2-MoSi2(x=0.03)阻氧涂层的方法,按照以下步骤进行:
(1)以钽、铪、硼单质粉为原料,按摩尔配比97:3:200混合、研磨,得到混合前驱粉体;
(2)将混合前驱粉体于压片机中,以直径16mm、压强200Mpa的条件压片,取出坯体放入自蔓延反应炉中,连接好钨丝电源并抽真空,真空度70Pa;
(3)开启钨丝电源点火,点然后坯体开始自蔓延燃烧反应,待反应完毕后取出产物并于研钵中研磨15min,得到(Hf,Ta)B2固溶粉体;
(4)按1:1摩尔配比称取(Hf,Ta)B2固溶粉体与商业粉MoSi2共2.5g,进行二维混料,混料时间50min,转速150r/min,混合后得到(Hf,Ta)B2-MoSi2混合粉体;
(5)将(Hf,Ta)B2-MoSi2混合粉体填充进石墨模具中,并均匀包裹清洗好的碳材料基体,放入放电等离子烧结炉中按照烧结温度:1500℃、保温时间5min、施加压力3.5kN的烧结工艺进行烧结;
(6)烧结完毕后,取出产物,打磨后得到(Hf97Ta3)B2-MoSi2阻氧涂层。
本实施例所得(Hf,Ta)B2-MoSi2阻氧涂层中固溶粉体的物象结构如图2所示,阻氧涂层氧化前断面扫描结果、氧化前表面扫描结果以及氧化后表面扫描结果分别如图5、图9以及图13所示,经1700℃高温氧化后的氧化增重曲线如图15所示,氧化后增重结果如表1所示,可以看出:实施例3中所得(Hf,Ta)B2-MoSi2阻氧涂层结构致密,表面完整,氧化后表面形成具有固溶体氧化物弥散分布的致密Si-O玻璃膜,且在1700℃高温下具有极少的增重,表现出优异的阻氧防护效果。
实施例4:
本实施例中利用自蔓延辅助固溶掺杂技术制备(Hf1-xTax)B2-MoSi2(x=0.04)阻氧涂层的方法,按照以下步骤进行:
(1)以钽、铪、硼单质粉为原料,按摩尔配比96:4:200混合、研磨,得到混合前驱粉体;
(2)将混合前驱粉体于压片机中,以直径16mm、压强200Mpa的条件压片,取出坯体放入自蔓延反应炉中,连接好钨丝电源并抽真空,真空度80Pa;
(3)开启钨丝电源点火,点然后坯体开始自蔓延燃烧反应,待反应完毕后取出产物并于研钵中研磨15min,得到(Hf,Ta)B2固溶粉体;
(4)按1:1摩尔配比称取(Hf,Ta)B2固溶粉体与商业粉MoSi2共2.5g,进行二维混料,混料时间60min,转速200r/min,混合后得到(Hf,Ta)B2-MoSi2混合粉体;
(5)将(Hf,Ta)B2-MoSi2混合粉体填充进石墨模具中,并均匀包裹清洗好的碳材料基体,放入放电等离子烧结炉中按照烧结温度:1500℃、保温时间5min、施加压力3.5kN的烧结工艺进行烧结;
(6)烧结完毕后,取出产物,打磨后得到(Hf96Ta4)B2-MoSi2阻氧涂层。
本实施例所得(Hf,Ta)B2-MoSi2阻氧涂层中固溶粉体的物象结构如图2所示,阻氧涂层氧化前断面扫描结果、氧化前表面扫描结果以及氧化后表面扫描结果分别如图6、图10以及图14所示,经1700℃高温氧化后的氧化增重曲线如图15所示,氧化后增重结果如表1所示,可以看出:实施例4中所得(Hf,Ta)B2-MoSi2阻氧涂层结构致密,表面完整,氧化后表面形成具有固溶体氧化物弥散分布的致密Si-O玻璃膜,且在1700℃高温增重较少,表现出较为优异的阻氧防护效果。
对比例1:
本对比例中利用自蔓延辅助固溶掺杂技术制备(Hf95Ta5)B2-MoSi2阻氧涂层的方法,按照以下步骤进行:
(1)以钽、铪、硼单质粉为原料,按摩尔配比95:5:200混合、研磨,得到混合前驱粉体;
(2)将混合前驱粉体于压片机中,以直径16mm、压强200Mpa的条件压片,取出坯体放入自蔓延反应炉中,连接好钨丝电源并抽真空,真空度70Pa;
(3)开启钨丝电源点火,点然后坯体开始自蔓延燃烧反应,待反应完毕后取出产物并于研钵中研磨15min,得到(Hf,Ta)B2固溶粉体;
(4)按1:1摩尔配比称取(Hf,Ta)B2固溶粉体与商业粉MoSi2共2.5g,进行二维混料,混料时间50min,转速150r/min,混合后得到(Hf,Ta)B2-MoSi2混合粉体;
(5)将(Hf,Ta)B2-MoSi2混合粉体填充进石墨模具中,并均匀包裹清洗好的碳材料基体,放入放电等离子烧结炉中按照烧结温度:1500℃、保温时间5min、施加压力3.5kN的烧结工艺进行烧结;
(6)烧结完毕后,取出产物,打磨后得到(Hf95Ta5)B2-MoSi2阻氧涂层。
本对比例所得(Hf,Ta)B2-MoSi2阻氧涂层经1700℃高温氧化后的表面扫描结果以及氧化增重曲线分别如图6、图23所示,氧化后增重结果如表1所示,可以看出:对比例1中所得(Hf,Ta)B2-MoSi2阻氧涂层经1700℃高温氧化后仍能保持较为致密的结构,表面完整,但氧化后表面形成的氧化物团聚严重,未呈现明显弥散分布,有潜在剥落风险。虽然该对比例下的样品仍保持有相对完整的玻璃膜,但较于实施例3,由于固溶元素添加过量,对比例1在1700℃高温下的氧化增重有所增加,阻氧特性有所劣化,进而凸显出实施例3的优选配比。尽管如此,对比例1仍然表现一定的防护效果。
对比例2
本对比例中利用自蔓延方法制备HfB2-MoSi2阻氧涂层的方法,按照以下步骤进行:
(1)以铪、硼单质粉为原料,按摩尔配比100:200混合、研磨,得到混合前驱粉体;
(2)将混合前驱粉体于压片机中,以直径16mm、压强200Mpa的条件压片,取出坯体放入自蔓延反应炉中,连接好钨丝电源并抽真空,真空度70Pa;
(3)开启钨丝电源点火,点然后坯体开始自蔓延燃烧反应,待反应完毕后取出产物并于研钵中研磨15min,得到HfB2粉体;
(4)按1:1摩尔配比称取HfB2粉体与商业粉MoSi2共2.5g,进行二维混料,混料时间50min,转速150r/min,混合后得到HfB2-MoSi2混合粉体;
(5)将HfB2-MoSi2混合粉体填充进石墨模具中,并均匀包裹清洗好的碳材料基体,放入放电等离子烧结炉中按照烧结温度:1500℃、保温时间5min、施加压力3.5kN的烧结工艺进行烧结;
本对比例所得HfB2-MoSi2阻氧涂层氧化前断面扫描结果、氧化前表面扫描结果以及氧化后表面扫描结果分别如图17、图19以及图21所示,经1700℃高温氧化后的氧化增重曲线如图23所示,氧化后增重结果如表1所示,可以看出:对比例2中所得自蔓延HfB2-MoSi2阻氧涂层结构较为致密,表面较为完整,但存在部分孔洞。氧化后表面也能形成具有固溶体氧化物弥散分布的致密Si-O玻璃膜,但过渡金属元素(如Hf)氧化物具有偏析现象,未能在表面有效弥散,且氧化增重均高于实施例1~4,阻氧防护效果欠佳。通过对比实施例3,可进一步凸显出本发明自蔓延辅助固溶体掺杂技术的优势与必要性。
对比例3
本对比例中利用商业粉制备HfB2-TaB2-MoSi2阻氧涂层的方法,按照以下步骤进行:
(1)选用商业粉HfB2、TaB2与MoSi2,按95:5:100摩尔配比称称取原料,并进行二维混料,混料时间50min,转速150r/min,混合后得到HfB2-TaB2-MoSi2混合粉体;
(2)将HfB2-TaB2-MoSi2混合粉体填充进石墨模具中,并均匀包裹清洗好的碳材料基体,放入放电等离子烧结炉中按照烧结温度:1500℃、保温时间5min、施加压力3.5kN的烧结工艺进行烧结;
本对比例所得商业粉HfB2-TaB2-MoSi2阻氧涂层氧化前断面扫描结果、氧化前表面扫描结果以及氧化后表面扫描结果分别如图18、图20以及图22所示,经1700℃高温氧化后的氧化增重曲线如图23所示,氧化后增重结果如表1所示,可以看出:对比例3中所得商业粉HfB2-TaB2-MoSi2阻氧涂层结构致密,表面完整,氧化后表面形成具有固溶体氧化物弥散分布的致密Si-O玻璃膜,但表面氧化物颗粒枝晶化现象,过渡金属元素(如Hf、Ta)存在部分偏析,过渡金属氧化物未能在表面有效固溶与弥散,且氧化增重高于实施例3,阻氧防护效果欠佳。通过与实施例3、对比例1结合比对,可进一步凸显出本发明自蔓延辅助固溶体掺杂技术的优势与必要性。
表1氧化后增重结果
以上对本发明及其实施方式进行了描述,这种描述没有限制性,附图中所示的也只是本发明的实施方式之一,实际的结构并不局限于此。总而言之,如果本领域的普通技术人员受其启示,在不脱离本发明创造宗旨的情况下,不经创造性的设计出与该技术方案相似的结构方式及实施例,均应属于本发明的保护范围。
Claims (2)
1.一种利用自蔓延辅助固溶体掺杂技术制备(Hf,Ta)B2-MoSi2阻氧涂层的方法,其特征在于,包括以下步骤:
(1)以钽、铪、硼单质粉为原料,按摩尔配比混合、研磨,得到混合前驱粉体;
(2)将混合前驱粉体于压片机中压片,取出坯体放入自蔓延反应炉中,连接好钨丝电源并抽真空,其中,真空范围:50~80Pa;
(3)开启钨丝电源点火,待反应完毕后取出产物并研磨,得到(Hf,Ta)B2固溶粉体;
(4)按1:1摩尔配比称取(Hf,Ta)B2固溶粉体与商业粉MoSi2并进行二维混料,混合后得到(Hf,Ta)B2-MoSi2混合粉体;
(5)将(Hf,Ta)B2-MoSi2混合粉体填充进石墨模具中,并均匀包裹清洗好的碳材料基体,放入放电等离子烧结炉中进行烧结;
(6)烧结完毕后,取出产物,打磨后得到(Hf,Ta)B2-MoSi2阻氧涂层;
合成后得到的(Hf,Ta)B2-MoSi2阻氧涂层的化学组成为:(Hf1-x Ta x )B2-MoSi2 (x=0.01~0.04),其中,Hf与Ta元素以固溶体的形式存在于(Hf,Ta)B2中。
2.根据权利要求1所述的一种利用自蔓延辅助固溶体掺杂技术制备(Hf,Ta)B2-MoSi2阻氧涂层的方法,其特征是,所述将(Hf,Ta)B2固溶粉体与商业粉MoSi2进行二维混料,混料条件为:混料时间30~60min,转速50~200r/min。
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