CN1045607A - 一种提高高温合金性能的方法 - Google Patents
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- 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%
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- 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
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- 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
- C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
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- 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
- C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
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Abstract
本发明提供了一种降低合金元素偏析以提高高温合金性能的方法,其特征在于将合金中的含磷量降低至(以重量百分比计算,下同)0.001以下,对于镍基高温合金则将含磷量降到0.0005以下,而对于以锆作晶界强化机制的镍基高温合金来说还应去锆同时适当控制硼,将硅降至0.05以下。在此基础上,还可进一步把现有牌号的镍基高温合金中铝、钛含量再提高1或者把其中的铬含量再提高4。
Description
本发明属于从高温合金中去除材料以改性的方法的技术领域。
高温合金是制造飞机、舰船、工业交通上使用的燃气轮机高温部件的重要材料,近年来在宇航、核反应堆和化学工业等部门也得到了广泛应用。如何改善高温合金的抗氧化、耐腐蚀性能,提高其高温强度和使用温度是一个意义极为重要的研究课题,它一直受到各国冶金学家和设计工程师的重视。从四十年代末期开始高温合金发展很快,然而进入七十年以后在改进合金成分方面的进展就较为缓慢了,这主要是因为存在如下几个问题:
(1)目前的高温合金其成分已极为复杂,再添加合金元素,铸造时在铸件中会出现严重的偏析,如镍基高温合金,当考虑提高其高温强度要求加入更多的铝、钛等强化元素,为改善其抗热腐蚀性能要求加入更多的铬,则将引起有害的脆性相-σ相的出现,而无法使用;
(2)合金元素增多,则合金的初熔温度也会相应地有所降低。如铁镍铬基高温合金其开锻温度由于受合金初熔温度的限制,必须定在1140℃以下。在这样低的锻造温度下,由于合金变形抗力很大,当用上述合金制造燃气轮机涡轮盘时,必须相应地提高锻压设备能力和技术水平,生产成本必将会有所提高;
(3)调整合金成分,往往难于克服高温使用性能指标同加工焊接等工艺性能之间的矛盾。
总之,随着高温合金的发展,合金化程度不断提高,凝固偏析日趋严重,合金的组织结构稳定性降低,工艺性能变坏,阻碍了合金的进一步发展,因此,减少凝固偏析和抑制有害相的析出是一个重大课题。
本发明的发明人在研究高温合金相结构及相变规律的基础上,发现了磷对高温合金的固液间两相区大小、合金元素的偏析及有害相的析出等均有较明显的影响,并对锆、硼等元素在高温合金中的作用也有新的认识。具体地说:
(一)现有的国内外各种牌号的高温合金对于含磷量均未提出特殊的控制指标,即便有偶尔提到含磷量的资料,一般也仅标注其含磷量(以重量百分比计)在0.005~0.1之间。另一方面,纵观国内外学者所报导的关于微量元素(包括杂质)对高温合金性能的影响方面的研究工作,他们也仅讨论过有害的铅、砷、铋、锑、硫、硅和有益的镁、钇、硼、碳等元素,并未注意到磷在高温合金中的作用。
(二)锆过去被看成是晶界强化元素,有利于提高高温合金的性能;但我们发现锆也是使高温合金产生严重偏析的原因之一,而其晶界强化效应事实上却并不明显,在高温“合金”中加锆实属有害无益;故我们在过去以加入锆作强化元素的高温合金中去除锆,结果使合金性能有显著改善。
本发明的目的是要在上述物理冶金学研究的基础上,提出一种有效地提高高温合金的初熔温度、减少合金元素偏析、抑制有害相析出并改善合金工艺性能的方法。
本发明提供了一种用控制合金中的磷含量、硼含量和去除锆来有效地提高高温合金初熔温度、减少偏析、抑制有害相析出并改善合金工艺性能的方法,其特征在于:将现有的高温合金中的含磷量降低(以重量百分数计算,下同)到0.001以下;对于镍基高温合金来说其含磷量应降低到0.0005以下。本发明提供的方法,对于现有的以锆作为晶界强化机制的高温合金来说,除了将含磷量降低到0.0005以下外,其特征在于去除锆。按本发明的方法可以提供出一系列的低偏析高温合金,它们均具有很好的性能,如对于铁镍铬基变型高温合金GH901合金(类似于IN901合金)来说,采用本发明的方法,其初熔温度可从1140℃提高到1260℃,故开锻温度可提高到1190~1225℃,在这一温度下可以方便地采用精密模锻工艺,锻件的持久和拉伸性能不变,但合金料的有效利用率大为提高;对于铸造高温合金来说,在控制有害相析出的前提下,可将现有牌号的合金中的铝、钛的含量再提高1,而合金的抗热腐蚀性能不变,从比较100小时持久强度数据来看,高温力学性能有明显的提高。不仅如此,对于低磷铸造镍基合金来说,也可将其含铬量再提高4,而使合金的抗高温氧化、抗热腐蚀性能有明显的提高。
本发明还提供了按上述提高高温合金性能方法所配制的新合金成份,它们分别是:(1)类似于GH901(IN901)的低偏析铁镍铬基高温合金,其特征在于:把磷含量控制在0.001以下,合金成份为:镍40~45,铬11~14,钼5.0~6.5;铝≤0.3,钛2.8~3.1,硼0.001~0.004;碳0.02~0.06;磷≤0.001;铁余量;(2)类似于K17(IN100)的低偏析镍基高温合金,其特征在于不加锆并把含磷量控制在0.0005以下,合金成份为:铬8.0~10.0;钴8.0~10.0;钨2.0~5.0;钼1.0~3.0;钽2.0~5.0;铝3.5~5.5;钛3.5~5.0;碳0.1~0.22;磷≤0.0005;硼0.003~0.010,硅≤0.05;铁≤0.3;镍余量。(3)一种类似于M40(IN792)低偏析镍基高温合金,其特征在于:(a)不加锆并把磷含量降至0.0005以下,将铝、钛含量提高1,合金成份范围为:铬11.0~14.0;钴8.0~10.0;钨2.0~5.0;钼1.0~3.0;钽2.0~5.0;铝3.8~4.5;钛4.2~5.4;碳0.1~0.22;磷≤0.0005;硼0.003~0.010;硅≤0.05,铁≤0.3;镍余量。(4)一种类似于M38(IN738)的低偏高铝钛的镍基高温合金,其特征在于不加锆并将磷含量降至0.0005以下,相应地把铝、钛含量提高约1,合金成分范围为:铬15.7/16.3;钴8.0/9.0;钨2.4/2.8;铜1.5/2.0;铌0.6/1.1;钽1.5/2.0;铝3.7/5.0;钛3.7/5.0;碳0.1/0.22;磷≤0.0005,硼0.005/0.010;铁≤0.3;硅≤0.65;镍余量。(5)一种类似于M38(IN738)的低偏析高铬镍基合金,其特征在于不加锆并将磷含量降至0.0005以下,相应地把铬含量提高约4,合金的成份范围为:铬18.0~22.0;钴7.5~9.5;钨1.6~4.0;钼2.5-3.0;铌0.3~1.5;铝3.7~5.0;钛3.5~5.0;碳0.08~0.22;磷≤0.0005;硼0.003~0.010;硅≤0.05;铁0.3。
众所周知,对于铸造合金来说,近二十多年以来,各国在推广空冷技术的同时,又在探索定向凝固等新工艺,其中定向凝固新工艺大约可提高铸造高温合金的使用温度近20℃,但是它不仅增加了利用空冷技术的难度,而且其横向性能指标较纵向性能指标低得多,必须要添加价格昂贵的金属铪才能克服这一缺点。采用本发明所提供的方法,不用加铪即可明显提高定向凝固合金的横向性能指标,故更有利于采用定向凝固工艺,使之很容易同空冷技术结合,两者综合起来可使现有牌号的铸造高温合金的使用温度提高100~300℃。另一方面,对于变形高温合金来说,热加工工艺困难是一个老问题,而采用本发明所提供的方法,则可大大改善合金的热加工性能,有利于这一问题的解决。
本发明的方法其实施例如下:首先严格控制原料中的铁和铬的含磷量,如铁和铬中的含磷量较高时,则用湿法冶金法将铁精制成铁粉,并用电解法将铬多次提纯,要求用作原料的铁和铬中磷含量不得超过≤0.0005;其次用真空感应炉将合格原料熔制成合金,最后当作铸造高温合金叶片时,再将合金投入真空感应炉中重熔,其治炼工艺和现有的高温合金冶炼工艺相同。
本发明的方法无论是对于铁镍铬基高温合金(如IN901合金)或者是对于镍基高温合金(如IN100,IN792;IN738)都同样适用。本发明所提供的低偏析高温合金其典型的合金成分与几种现有牌号合金成份列入表1中,从表1中,可明显看出本发明所提供的低偏高温合金的技术特征在于:(1)不加锆;(2)磷含量低于0.001和0.0005,(3)铝、钛含量可提高1,(4)铬含量可提高4。本发明所提供的高温合金其性能如表2、表3、表4和表5所示,表2为GH901(IN901)合金和低偏析GH901合金性能对此数据;可看出低偏析GH901合金室温拉伸性能,持久性能和初熔温度均有明显的提高,表3为M38(IN738)、K17(IN100)合金同低偏析的M38、K17F的100小时持久强度对比数据,可看出偏低析合金性能有明显地提高;表4为M38(IN738)合金同低偏析的M38和M36持久时间(小时)和抗热腐蚀性能的对比资料,可看出低偏析M38和M36对原来的M38合金性能有较大的改善;表5为IN792合金同低偏析IN792合金高温持久时间(小时)对比数据,相比之下低偏析合金比较原合金性能提高得十分显著。
采用本发明所提供的方法不仅可以探索出一系列的新的性能优良的铁基高温合金和镍基高温合金;而更为重要的是,采用本发明的方法在现有的应用很广泛的性能稳定的高温合金的基础上,可以不改变其成份范围就能使合金性能有较大提高。众所周知,发展一种新成分的高温合金往往需要相当长的时间,这主要是需要做长期而系统的性能试验,如高温持久性能试验,蠕变试验,取得十分稳定的性能数据后,方能投入使用。如果能对现有合金成分范围不作大的改变,仅仅通过控制一、两种元素的含量就能明显地提高高温合金的性能,其意义自然十分重大。总之,本发明所提供的一种提高高温合金的方法,简便易行,而效果却又是令人意想不到的良好,故在工业上加以推广后,其经济意义将会是十分巨大的。
表4 低偏析M38、M36合金持久时间
(小时)和抗热腐蚀性能的比较:
表5 低偏析IN-792合金持久时间
(小时)比较
合金 815℃ 982℃
51(kg/mm2) 39(kg/mm2) 15.5(kg/mm2)
IN-792 100 1000 100
低偏析IN-792(M40) 300 2500 300
Claims (11)
1、一种降低合金元素偏析以提高高温合金性能的方法,其特征在于:将合金中的含磷量降低到(以重量百分比计算)0.001以下,其中对于镍基高温合金其含磷量(以重量百分比计算)要降低到0.0005以下。
2、按权利要求1所述的方法,其特征在于,对于以锆作晶界强化机制的高温合金来说去除锆。
3、按权利要求1所述的方法,其特征在于将现有牌号的镍基高温合金中的铝、钛含量(以重量百分比计算)再提高1。
4、按权利要求2所述的方法,其特征在于将现有牌号的镍基高温合金中铝、钛含量(以重量百分比计算)再提高1。
5、按权利要求1所述的方法,其特征在于将现有牌号的镍基高温合金中的铬含量(以重量百分比计算)再提高4。
6、按权利要求2所述的方法,其特征在于将现有牌号镍基高温合金中的铬含量(以重量百分比计算)再提高4。
7、一种按权利要求1所述的方法所提供的类似于GH901(IN901)的低偏析铁镍铬基高温合金(低偏析GH901),其特征在于合金的成分范围为:镍40~45,铬11~14,钼5.0~6.5;铝≤0.3,钛2.8~3.1,硼0.001~0.004;碳0.02~0.06;磷≤0.001;硅≤0.05;铁余量。
8、一种按权利要求1所述的方法所提供的类似于K17(IN100)的低偏析镍基高温合金,其特征在于合金的成分范围(以重量百分比计算)为:铬8.0~10.0;钴8.0~10.0;钨2.0~5.0;钼1.0~3.0;钽2.0~5.0;铝3.5~5.5;钛3.5~5.0;碳0.1~0.22;磷≤0.0005;硼0.003~0.01,硅≤0.05;铁≤0.3;镍余量。
9、一种按权利要求4所述的方法所提供的类似于M40(IN792)的低偏析镍基高温合金,其特征在于合金成分范围(以重量百分比计算)为:铬11.0~14.0;钴8.0~10.0;钨2.0~5.0;钼1.0~3.0;钽2.0~5.0;铝3.8~4.5;钛4.2~5.4;碳0.1~0.22;磷≤0.0005;硼0.003~0.01;硅≤0.05;铁≤0.3;镍余量。
10、一种按权利要求4所述的方法所提供的类似于M38(IN738)的低偏析高铝钛的镍基高温合金,其特征在于合金成分范围(以重量百分比计算)为:铬15.7/16.3;钴8.0/9.0;钨2.4/2.8;铜1.5/2.0;铌0.6/1.1;钽1.5/2.0;铝3.7/5.0;钛3.7/5.0;碳0.1/0.22;磷≤0.0005,硼0.005/0.010;铁≤0.3;硅≤0.05;镍余量
11、一种按权利要求4、5所述的方法所提供的类似于M38(IN738)的低偏析高铬镍基高温合金,其特征在于合金成分范围(以重量百分比计算)为:铬18.0~22.0;钴7.5~9.5;钨1.6~4.0;钼2.0~3.0;铌0.3~1.5;铝3.7~5.0;钛3.5~5.0;碳0.08~0.22;磷≤0.0005;硼0.003~0.01;硅≤0.05;铁≤0.3;镍余量。
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CN110462078A (zh) * | 2017-02-08 | 2019-11-15 | 博格华纳公司 | 用于涡轮增压器部件的新合金 |
CN112534073A (zh) * | 2018-08-02 | 2021-03-19 | 西门子能源环球有限责任两合公司 | 金属复合物 |
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EP0561179A3 (en) * | 1992-03-18 | 1993-11-10 | Westinghouse Electric Corp | Gas turbine blade alloy |
WO1999067435A1 (en) * | 1998-06-23 | 1999-12-29 | Siemens Aktiengesellschaft | Directionally solidified casting with improved transverse stress rupture strength |
US8083990B2 (en) | 2005-11-09 | 2011-12-27 | Japan Science And Technology Agency | Iron-based alloy having shape memory properties and superelasticity and its production method |
JP5232492B2 (ja) | 2008-02-13 | 2013-07-10 | 株式会社日本製鋼所 | 偏析性に優れたNi基超合金 |
JP2014005528A (ja) * | 2012-05-29 | 2014-01-16 | Toshiba Corp | Ni基耐熱合金およびタービン用部品 |
JP2014047371A (ja) * | 2012-08-30 | 2014-03-17 | Hitachi Ltd | Ni基合金と、それを用いたガスタービン動翼兼ガスタービン |
CN112779385A (zh) * | 2020-12-24 | 2021-05-11 | 陕西宏远航空锻造有限责任公司 | Gh901涡轮盘锻件的热处理方法 |
CN114250375A (zh) * | 2021-06-02 | 2022-03-29 | 中航上大高温合金材料股份有限公司 | 一种使用再生料生产gh738合金的方法 |
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CA920394A (en) * | 1965-04-09 | 1973-02-06 | R. Whitney Clyde | Nickel base alloy |
US3667938A (en) * | 1970-05-05 | 1972-06-06 | Special Metals Corp | Nickel base alloy |
GB2075057B (en) * | 1980-05-01 | 1984-03-07 | Rolls Royce | Nickel base superalloy |
EP0045563B1 (en) * | 1980-07-25 | 1984-12-05 | The Secretary of State for Defence in Her Britannic Majesty's Government of the United Kingdom of Great Britain and | Nickel-base alloy for single crystal casting |
GB2106138B (en) * | 1981-09-19 | 1986-03-19 | Rolls Royce | Single-crystal nickel alloy casting |
EP0194391B1 (en) * | 1985-03-13 | 1989-06-21 | General Electric Company | Yttrium and yttrium-silicon bearing nickel-base superalloys especially useful as compatible coatings for advanced superalloys |
EP0214080A3 (en) * | 1985-08-16 | 1987-11-25 | United Technologies Corporation | Reduction of twinning in directional recrystallization of nickel base superalloys |
FR2593830B1 (fr) * | 1986-02-06 | 1988-04-08 | Snecma | Superalliage a matrice a base de nickel notamment elabore en metallurgie des poudres et disque de turbomachine constitue en cet alliage |
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CN110462078A (zh) * | 2017-02-08 | 2019-11-15 | 博格华纳公司 | 用于涡轮增压器部件的新合金 |
US11214852B2 (en) | 2017-02-08 | 2022-01-04 | Borgwarner Inc. | Alloys for turbocharger components |
CN112534073A (zh) * | 2018-08-02 | 2021-03-19 | 西门子能源环球有限责任两合公司 | 金属复合物 |
US11773469B2 (en) | 2018-08-02 | 2023-10-03 | Siemens Energy Global GmbH & Co. KG | Metal composition |
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