CN115803467A - 耐热镍基合金及其制品 - Google Patents
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 66
- 239000000956 alloy Substances 0.000 title claims abstract description 66
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 17
- 238000002844 melting Methods 0.000 claims abstract description 25
- 230000008018 melting Effects 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 239000011651 chromium Substances 0.000 claims abstract description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 239000011733 molybdenum Substances 0.000 claims abstract description 7
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 7
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 7
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010937 tungsten Substances 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 239000011575 calcium Substances 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 239000011777 magnesium Substances 0.000 claims abstract description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910052729 chemical element Inorganic materials 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 17
- 239000013078 crystal Substances 0.000 abstract description 15
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
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- 239000002245 particle Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000010309 melting process Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000007713 directional crystallization Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
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- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 238000000265 homogenisation Methods 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
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- 150000004767 nitrides Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
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- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0433—Nickel- or cobalt-based alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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Abstract
本发明涉及冶金领域，即用于选择性激光熔融的耐热镍基合金的生产。该合金含有铬、钴、铝、钨、钼、钽、碳、硼、铼、钌、钇、铈、镧、钕、镁和/或钙、氧和氮，各组分的比例按重量百分比计如下：铬1.6‑2.4，钴3.0‑4.0，铝5.6‑6.2，钨4.6‑5.6，钼1.6‑2.6，钽6.0‑7.8，碳0.12‑0.2，硼0.008‑0.03，铼5.4‑7.4，钌4.0‑6.0，钇0.002‑0.02，铈0.001‑0.02，镧0.002‑0.2，钕0.0005‑0.01，镁和/或钙0.001‑0.009，氧0.0001‑0.002，氮0.0001‑0.002，镍余量。本发明还公开了一种通过在具有给定晶体取向的单晶基材‑晶种上对所公开的合金的金属粉末组合物进行选择性激光熔融而制成的产品。
Description
技术领域
本发明涉及冶金领域，即耐热镍基合金的粉末组合物的生产以及由它们获得的产品，例如，通过选择性激光熔融(SLM)法制造的燃气涡轮发动机涡轮叶片。
背景技术
开发用于生产涡轮叶片的高性能耐热镍基合金是打造具有竞争力的下一代航空燃气涡轮发动机(GTE)的最重要因素之一。
现代航空燃气涡轮发动机的涡轮叶片是通过与铼和钌合金化的耐热镍合金的定向结晶制造的。使用现有工业过程由在定向结晶的非平衡条件下生产的此类合金制成的涡轮叶片的单晶具有树枝状蜂窝结构，并且其特征在于显著的化学和结构相不均匀，这种不均匀无法通过长时间的均匀化热处理来完全消除。应用用于耐热镍合金粉末组合物的激光选择性熔融的方法来生产部件可以大大降低部件材料的偏析不均匀。
从现有技术(EP 2949768A1，2015年12月2日公布，IPC C22C 19/05)中已知耐热镍基合金。它用于部件的粉末组合物的选择性激光熔融。该合金按重量百分比计具有以下化学成分：
前提是满足以下条件：С/B＝10-32；C/Hf＞2；C/Zr＞8；C/Si＞1。
由已知合金制成的粉末组合物的粒度分布为10-100μm，粉末颗粒具有球形形态。在使用选择性激光熔融法和后续的热处理制造产品后，所生产材料中的y'相体积分数为60-70％。
通过选择性激光熔融法获得的合金的一个缺点是，如果使用部件的气压热处理，由于铪、锆和硅的总含量增加(高达0.13％wt.)，可制造性低。通过选择性激光熔融法由已知合金粉末生产的部件材料中铪、锆和硅的总含量增加导致以下结果：它们有助于通过SLM工艺中偏析到零件材料的结构单元的边界来降低熔点。
由2000年6月13日公布的美国专利6,074,602(IPC C22C19/05)得知一种耐热镍基合金(ReneN5合金)，其最初设计用于铸造在高温下长时间运行的燃气涡轮发动机的单晶叶片。该合金按重量百分比计具有以下优选的化学成分：
显微硬度级别为469-480MB的样品是使用选择性激光熔融法从已知合金的粉末组合物在具有晶体取向<001>的单晶晶种上制成的(超合金2016年。TMS.2016年，第104-109页)。该已知合金的缺点是在20-1,200℃的工作温度范围内强度低：
(高温高强度镍基高温合金-数据补充。多伦多镍开发研究所。1995年第393期，第1-19页。)
由2009年8月27日公布的专利RU 2365656(IPCС22С19/05)得知一种耐热镍基合金(ZhS32-VI合金)，其最初设计用于铸造在高温下长时间运行的燃气涡轮发动机的单晶叶片。该合金按重量百分比计具有以下优选的化学成分：
前提是满足以下条件：15.8≤(W+Re+Ta)≤17.5。
这种由选择性激光熔融法制成的合金的缺点是在选择性激光熔融工艺中倾向于形成有害的碳化物相，其中含有低熔点的硅，其排泄物沿着选择性激光熔融产品单晶界和亚晶界定位，并且在随后的高温气压处理过程中不会溶解。结果，在20-1,200℃的工作温度范围内，由该合金在具有晶体取向<001>的单晶晶种上通过选择性激光熔融法制成的粉末组合物强度参数不够高：
(材料科学，2017年，No.11(248)，第19-22页)。
与要求保护的发明最接近的类似物是耐热镍基合金(RU 2402624 C1，2010年10月27日公布，IPCС22С19/05)合金，用于通过定向结晶法制造具有单晶和定向结构的燃气涡轮机叶片。该合金按重量百分比计具有以下化学成分：
另外的研究表明，在1,200℃的工作温度下，通过选择性激光熔融法由原型合金的粉末组合物在具有晶体取向<001>的单晶晶种上制成的原型合金强度不足：
发明内容
所提出发明的技术成果是开发了一种耐热镍基合金，可以使用选择性激光熔融法由该合金获得涡轮叶片，其在20-1,200℃的工作温度范围内具有更高的强度。
所声明的技术成果是在耐热镍基合金中通过按重量百分比计的以下成分比例实现的，该合金含有铬、钴、铝、钨、钼、钽、碳、硼、铼、钌、钇、铈、镧、钕、镁、钙、氧和氮：
本发明还公开了一种产品，该产品通过在具有给定轴向取向<001>的单晶基材上对所公开的耐热镍基合金的金属粉末组合物进行选择性激光熔融而制成。
发明人已经确定，由于在位于γ'-相和γ-固溶体颗粒之间的界面上的材料结构中形成了稀土金属(镧、铈、钕、钇)氧化物和氮化物的纳米级颗粒，以述及的剩余合金元素的种类和比例将氧和氮引入所提出的合金中引起通过选择性激光熔融法获得的合金及其制品的高温(1,200℃)强度增加。
由于在合成材料的轨道结构中形成了含量增加的高度分散(小于0.1μm)的位于晶胞和亚晶粒的体积内并沿着晶胞和亚晶粒的边界的碳硼化物颗粒，所提出的合金中碳和硼的增加也有助于增加合金和使用选择性激光熔融法由该合金制成的产品的强度。
所提出的通过选择性激光熔融法制造的合金中减少的铬、钴、钼以及增加的钨和钽提高了材料的多相γ/γ'结构的热稳定性(提高了基于金属间化合物Ni3(Al,Ta)的γ'相硬化颗粒的固相线和完全溶解的温度-固溶线温度)。因此，在1200℃的工作温度下，γ'-相硬化颗粒的体积分数
在材料及其制品的结构中增加，并且有助于在1200℃的温度下实现更高的强度参数。
具体实施方式
在真空感应炉中进行所提出的合金的三次熔融和原型合金的一次熔融。所提出的合金和原型合金的化学成分在表1中给出。在HERMIGA10/100VI装置中通过气体雾化(用氩气流进行熔体喷涂)从熔融的合金获得合金的粉末组合物。所得粉末的粒度组成为10-50μm。所提出的合金和原型合金粉末的选择性激光熔融过程是根据预定孵化算法在具有轴向晶体取向<001>的特殊单晶基材上以高纯度氩为介质在EOS M 290单元中进行的，并以直径为12mm、长度为60mm的圆柱形坯件形式获得合金的合成制品。此外，用于差热分析研究的样品由这些选择性激光熔融坯件制成，分析结果确定基质γ固溶体中γ'相完全溶解的温度(固溶线温度)Tc.d，在1200℃的工作温度下γ'相硬化颗粒的体积分数
和固相线温度。
根据测得的固溶线和固相线温度，对生产的合金SLM坯料进行后处理，包括真空均质退火(VGO)、热等静压(HIP)、淬火和两阶段老化处理。用于拉伸机械测试的样品(样品长度60mm，工作底座25mm，工作直径5mm)由经过热处理和气压热处理的SLM坯料制成。
在20℃和1,200℃的空气气氛中进行合成合金样品的拉伸试验。基于测试结果确定抗拉强度σ的值。
要求保护的合金的组合物和由该合金制成的产品的性能以及原型合金的性能在表2中给出。
表2表明，所提出的合金及其制品具有更高的固溶线温度值(高36-46℃)以及因此在1200℃的工作温度下更高的γ'-相硬化颗粒的体积分数
(高9.5-11.9％)。另外，表征所提出的合金的相稳定性的ΔE参数值小于临界值，这表明它不易释放有害的TG1U相。ΔE参数由下式确定：
其中Zi、Ai、Ei分别为合金中第i种化学元素的原子浓度、原子质量和价电子数；i为以下化学元素中的任意一种(例如，按元素排列顺序i＝1-Сr、2-Со等，后续为Al,W,Мо,Та,Re,Ru,Ni)；n＝9(上述化学元素的数目)。
发现所提出的合金中铬、钴、铝、钨、钼、钽、铼、钌和镍的优选含量对应于表征镍耐热合金相稳定性的参数ΔЕ的优选值，其在-0.089至-0.058的范围内。
由于氧和氮微合金元素的作用、剩余合金元素的占比的增加以及因此相组成的物理和化学性能、可制造性和稳定性的改善，所提出的合金及其制品在1200℃的温度下的短期强度(抗拉强度)值σB分别比从原型已知的合金及其制品高28％。所提出的合金的技术优势在于提高了固相线温度值，因此能够在更高温度下对产品进行热处理和气压热处理，以便更充分地消除通过选择性激光熔融获得的合金产品的材料结构中的缺陷(微孔、微裂纹)，没有飞边的风险。因此，所提出的耐热镍基合金在1200℃的温度下的短期强度明显超过原型合金。
这使得可以使用所提出的合金通过选择性激光熔融方法生产在高达1200℃的温度下运行的燃气涡轮发动机的涡轮叶片。
Claims (3)
1.一种耐热镍基粉末合金，用于通过选择性激光熔融制造产品，包含铬、钴、铝、钨、钼、钽、碳和硼，其特征在于，还添加了铼、钌、钇、铈、镧、钕、镁、钙、氧和氮，各组分的比例按重量百分比计如下：
2.根据权利要求1所述的合金，其特征在于铬、钴、铝、钨、钼、钽、铼、钌和镍的化学元素含量对应于条件0≥ΔE≥-0.10，其中
其中Zi、Ai、Ei分别为第i种元素的原子浓度、原子质量和价电子数；i–对应于元素(Cr、Co、A1、W、Mo、Ta、Re、Ru、Ni)；n＝9。
3.一种通过选择性激光熔融制造的耐热镍基合金产品，其特征在于，它是在具有预定轴向取向<001>的单晶基材-晶种上通过选择性激光熔融由根据权利要求1所述的合金制成。
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