CN1044622C - High Strength Nickel Base Cast Superalloy - Google Patents
High Strength Nickel Base Cast Superalloy Download PDFInfo
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- CN1044622C CN1044622C CN96107076A CN96107076A CN1044622C CN 1044622 C CN1044622 C CN 1044622C CN 96107076 A CN96107076 A CN 96107076A CN 96107076 A CN96107076 A CN 96107076A CN 1044622 C CN1044622 C CN 1044622C
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 20
- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 15
- 239000000956 alloy Substances 0.000 claims abstract description 63
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 62
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 4
- 229910000851 Alloy steel Inorganic materials 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000005266 casting Methods 0.000 description 5
- 230000035939 shock Effects 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 229910000531 Co alloy Inorganic materials 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008236 heating water Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000005495 investment casting Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007528 sand casting Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
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Abstract
本发明属于镍基合金钢领域。特别是适用在高温(1350℃)下使用的高强度耐磨镍基高温合金部件。本发明所提出的镍基高温合金的具体化学成份为(重量%)C0.10～0.40%，Cr25.0～38.0%，Mo≤2.0%，W10.0～18.0%，Hf0.01～3.0%，Al0.01～3.0%，Si≤2.0%，Mn≤2.0%，Fe≤10%，RE≤0.20，其余为镍，本发明合金与现有技术相比较具有成本低，性能好，尤其在高温下使用其性能明显优于现有合金。The invention belongs to the field of nickel-based alloy steel. It is especially suitable for high-strength and wear-resistant nickel-based superalloy parts used at high temperatures (1350°C). The specific chemical composition of the nickel-based superalloy proposed by the present invention is (weight%) C0.10～0.40%, Cr25.0～38.0%, Mo≤2.0%, W10.0～18.0%, Hf0.01～3.0% , Al0.01～3.0%, Si≤2.0%, Mn≤2.0%, Fe≤10%, RE≤0.20, and the rest is nickel. Compared with the prior art, the alloy of the present invention has low cost and good performance, especially at high temperature Under the use of its performance is significantly better than the existing alloy.
Description
本发明属于镍基合金钢领域。特别是适用在高温(1350℃)下使用的高强度耐磨镍基高温合金部件。The invention belongs to the field of nickel-based alloy steel. It is especially suitable for high-strength and wear-resistant nickel-based superalloy parts used at high temperatures (1350°C).
在现代工业中，轧钢厂的大型钢坯加热炉的高强耐热耐磨部件，如推钢式加热炉内的热滑轨和步进粱式加热炉内的耐热垫块等，均采用钴基高温合金材料制造(如UMCo-50,PGUMCo-50合金COBAL 1973.3,P60-66)。但是这类合金由于钴资源的缺乏和价格的昂贵，所以难以大量推广使用。另外，中国专利CN85100649A介绍了一种Ni-Cr-W型铸造镍基高温合金，虽然该合金的成本低于UMCo-50钴基合金，但该合金在高温时仍存在蠕变强度偏低，和抗热冲击性能差等缺点。采用该合金所制造的热滑轨和垫块等部件，由于这些部件在高温重载下难以长期保持足够的高度而往往导致被加热坯料的温度不均匀性，从而严重影响成材的质量。In modern industry, the high-strength heat-resistant and wear-resistant parts of the large billet heating furnace in the rolling mill, such as the thermal slide rail in the pusher heating furnace and the heat-resistant pad in the walking beam heating furnace, etc., are all made of cobalt-based Manufacture of superalloy materials (such as UMCo-50, PGUMCo-50 alloy COBAL 1973.3, P60-66). However, due to the lack of cobalt resources and the high price of such alloys, it is difficult to popularize and use them in large quantities. In addition, Chinese patent CN85100649A introduces a Ni-Cr-W cast nickel-based superalloy. Although the cost of the alloy is lower than that of the UMCo-50 cobalt-based alloy, the alloy still has low creep strength at high temperatures, and Disadvantages such as poor thermal shock resistance. Parts such as thermal slide rails and pads manufactured by using this alloy, because these parts are difficult to maintain a sufficient height for a long time under high temperature and heavy load, often lead to temperature inhomogeneity of the heated blank, which seriously affects the quality of the finished product.
本发明的目的是提出一种具有在高温下有更高的使用性能和材料成本低的高强度耐磨蚀镍基铸造高温合金。The object of the present invention is to propose a high-strength, corrosion-resistant nickel-based cast superalloy with higher performance at high temperatures and low material cost.
根据本发明的目的，同时也考虑到各合金元素的作用，特别是加入Hf和Al在合金中的效果，并为获得能大量固溶其它合金元素的稳定奥氏体基体效果，因此我们所设计的是以镍为基本元素的镍基高温合金，其具体合金成份范围如下(重量％)C0.10～0.40％，Cr 25.0～38.0％，Mo≤2.0％，W10.0～18.0％，Hf 0.01～3.0％，Al 0.01～3.0％，Si≤2.0％，Mn≤2.0％，Fe≤10％，RE≤0.20，其余为Ni。According to the purpose of the present invention, the effect of each alloy element is also considered, especially the effect of adding Hf and Al in the alloy, and in order to obtain the stable austenite matrix effect of a large amount of solid solution of other alloy elements, so we designed It is a nickel-based high-temperature alloy with nickel as the basic element. The specific alloy composition range is as follows (weight%) C0.10-0.40%, Cr 25.0-38.0%, Mo≤2.0%, W10.0-18.0%, Hf 0.01 ～3.0%, Al 0.01～3.0%, Si≤2.0%, Mn≤2.0%, Fe≤10%, RE≤0.20, the rest is Ni.
本发明镍基铸造高温合金的成份设计，是考虑到现有的高温合金中不足之处，通过对合金成份的调整，来得到具有更高性能和经济的镍基铸造高温合金材料。因此在本发明合金成份中考虑到Cr是提高合金抗氧化性的决定元素，其加入量应不少于25％，W、Mo、Hf是重要的固溶强化和碳化物强化元素，特别是W同时具有明显地提高合金的熔点，和抗高温蠕变的双重作用。故W的加入量应在10～18％,W含量过高，合金中则易析出有害相而使材料的强度降低。Mo和W同时加入有综合强化作用，但Mo所形成的氧化物在高温时容易液化，这样可能使合金材料易坑蚀，因此Mo元素含量应限制在较低水平。Hf元素有明显改善合金的显微组织，特别是碳化物的形貌和晶界形态，对提高合金的强度，特别是对合金韧性的改善起着决定性的作用，但考虑到该合金的成本与性能，因此Hf的含量应控制在0.01～3.0％范围内。抗高温氧化性能较差是含高W、Mo合金存在的共同缺点，因此提高Cr含量的同时，还应加入适量的Al，加入适量的Al能起到抑制合金内部氧化的发生，和有助于合金表面形成致密的氧化保护膜，对材料本身起到保护作用，但Al含量过高或过低都会给合金的性能带来坏的作用。因此Al含量应控制在0.01～3.0％范围内。加入碳元素所形成的碳化物是该合金的主要强化手段，当在该合金中存在稳定的一次碳化物时，可使该材料具有优良的高温耐磨性能，但是碳有明显降低合金的固-液相温度，因此在超高温下长期使用的本发明合金，碳含量应限制在0.10～0.40％范围内。虽然加入适量的稀土可提高在低、中温下使用该合金的抗氧化性能，但是在1200℃以上使用，稀土会给该合金的抗氧化性带来不利的效果。所以在本发明合金中的稀土加入量，应根据材料的实际使用温度而限定在≤0.20％以下。加入Si有利于提高合金的耐热性，但若含量超过2％，对合金韧性产生不良影响，Mn是奥氏体组织的稳定化元素，并有将合金中之S固定的作用，当Mn量限制在2％时即可达到充分效果。故Si、Mn含量范围均限在2％以下。加入Fe取代Ni仅出于降低合金成本的考虑，当Fe含量超过10％时将严重损害合金的高温性能，故本发明要求合金中Fe含量越少越好。P和S都是有害杂质，需限制在0.04％以下。The composition design of the nickel-based cast superalloy of the present invention is to obtain a nickel-based cast superalloy material with higher performance and economy by adjusting the composition of the alloy in consideration of the deficiencies of the existing superalloy. Therefore, in the alloy composition of the present invention, it is considered that Cr is the decisive element for improving the oxidation resistance of the alloy, and its addition should not be less than 25%. W, Mo, and Hf are important solid solution strengthening and carbide strengthening elements, especially W At the same time, it has the dual functions of significantly increasing the melting point of the alloy and resisting high temperature creep. Therefore, the amount of W added should be 10-18%. If the W content is too high, harmful phases are easily precipitated in the alloy and the strength of the material is reduced. Adding Mo and W at the same time has a comprehensive strengthening effect, but the oxide formed by Mo is easy to liquefy at high temperature, which may make the alloy material easy to pit, so the content of Mo element should be limited to a low level. The Hf element can significantly improve the microstructure of the alloy, especially the morphology and grain boundary of the carbide, which plays a decisive role in improving the strength of the alloy, especially the improvement of the toughness of the alloy. However, considering the cost and Performance, so the content of Hf should be controlled in the range of 0.01 to 3.0%. Poor high-temperature oxidation resistance is a common shortcoming of high-W and Mo-containing alloys. Therefore, while increasing the Cr content, an appropriate amount of Al should be added. Adding an appropriate amount of Al can inhibit the occurrence of internal oxidation of the alloy and contribute to A dense oxide protective film is formed on the surface of the alloy to protect the material itself, but too high or too low Al content will have a bad effect on the performance of the alloy. Therefore, the Al content should be controlled within the range of 0.01-3.0%. The carbide formed by adding carbon is the main strengthening method of the alloy. When there is a stable primary carbide in the alloy, the material can have excellent high-temperature wear resistance, but carbon can significantly reduce the alloy's solid- Liquidus temperature, so the carbon content of the alloy of the present invention used for a long time at ultra-high temperature should be limited in the range of 0.10-0.40%. Although adding an appropriate amount of rare earth can improve the oxidation resistance of the alloy when used at low and medium temperatures, but when used above 1200 ° C, the rare earth will bring adverse effects on the oxidation resistance of the alloy. Therefore, the amount of rare earth added in the alloy of the present invention should be limited to ≤0.20% according to the actual use temperature of the material. Adding Si is beneficial to improve the heat resistance of the alloy, but if the content exceeds 2%, it will have a bad effect on the toughness of the alloy. Mn is a stabilizing element of the austenite structure and has the effect of fixing S in the alloy. When the amount of Mn Full effect can be achieved when limited to 2%. Therefore, the content of Si and Mn is limited to less than 2%. Adding Fe to replace Ni is only for the consideration of reducing the cost of the alloy. When the Fe content exceeds 10%, the high-temperature performance of the alloy will be seriously damaged. Therefore, the present invention requires that the Fe content in the alloy be as low as possible. Both P and S are harmful impurities, which need to be limited below 0.04%.
本发明镍基铸造高温合金的制造方法可以采用非真空炉或真空炉进行冶炼，铸造可采用砂型铸造或精密铸造方法进行铸造生产，生产方法与现有技术相似，不需要特殊工艺进行生产。本发明镍基合金与现有技术相比较具有成本低，该合金与CN85100649A专利申请的超高温耐磨铸造镍基合金的成本相当，而与PGUMCo-50钴基高温合金相比较成本仅为2/5，但该合金的使用性能，如高温持久性能，抗热冲击性能和抗氧化性能等均显著优于上述对比合金。The manufacturing method of the nickel-based casting superalloy of the present invention can adopt non-vacuum furnace or vacuum furnace for smelting, casting can adopt sand casting or precision casting method for casting production, the production method is similar to the prior art, and no special process is required for production. Compared with the prior art, the nickel-based alloy of the present invention has low cost, and the cost of the alloy is equivalent to that of the ultra-high temperature wear-resistant casting nickel-based alloy of the CN85100649A patent application, and compared with PGUMCo-50 cobalt-based superalloy, the cost is only 2/ 5, but the performance of this alloy, such as high temperature durability, thermal shock resistance and oxidation resistance, etc. are significantly better than the above comparison alloy.
实施例Example
在本发明镍基铸造合金的化学成份范围内，我们冶炼五炉不同含量配比的合金，为了对比方便，我们也冶炼了1炉CN85100649A合金和PGUMCo-50合金，冶炼均采用25Kg真空感应炉冶炼。并精铸成试样，生产工艺相同。表1为本发明合金与对比合金的成份比较，在表中1、2、3、4、5为本发明合金成份，6、7为对比合金成份，表2为本发明合金实施例的持久性能表，表3为1000小时持久强度的比较，表4为抗热冲击性能对比，在表中的数值是产生可见裂纹的加热——水冷循环次数。表5为氧化失重(g/m2h)的对比。上述实验方式是将试样由室温升至1250℃保温24小时后随电炉炉冷至室温，四次循环后比较试样的失重状况。根据上述表的对比结果可看出，本发明合金与对比合金的相比较其性能优于对比合金，尤其在高温情况下使用，其性能明显优于对比合金。Within the chemical composition range of the nickel-based casting alloy of the present invention, we smelted five furnaces of alloys with different content ratios. For the convenience of comparison, we also smelted one furnace of CN85100649A alloy and PGUMCo-50 alloy, all of which were smelted in a 25Kg vacuum induction furnace . And cast into samples, the production process is the same. Table 1 is the composition comparison of the alloy of the present invention and the contrast alloy, in the table 1, 2, 3, 4, 5 are the composition of the alloy of the present invention, 6, 7 are the composition of the contrast alloy, and table 2 is the durability performance of the alloy embodiment of the present invention Table, Table 3 is the comparison of 1000-hour endurance strength, and Table 4 is the comparison of thermal shock resistance. The values in the table are the heating-water cooling cycles that produce visible cracks. Table 5 is the comparison of oxidation weight loss (g/m2h). The above experimental method is to raise the sample from room temperature to 1250°C for 24 hours, then cool it to room temperature with the electric furnace, and compare the weight loss of the sample after four cycles. According to the comparative results of the above table, it can be seen that the performance of the alloy of the present invention is better than that of the comparison alloy, especially when used under high temperature conditions, its performance is obviously better than that of the comparison alloy.
表1本发明与对比合金的化学成分对比
*RE为配入量*RE is the dosage
表2本发明实施例的持久性能
表3本发明与同类合金及钴基合金1000小进持久强度(MPa)对比
表4本发明与对比合金抗热冲击性能对比，表Table 4 The present invention and comparison alloy thermal shock resistance performance contrast, table
数值为产生可见裂纹的加热-水冷循环次数
表5本发明与对比合金氧化失重量(G/m2.h)对比
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96107076A CN1044622C (en) | 1996-07-16 | 1996-07-16 | High Strength Nickel Base Cast Superalloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96107076A CN1044622C (en) | 1996-07-16 | 1996-07-16 | High Strength Nickel Base Cast Superalloy |
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| Publication Number | Publication Date |
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| CN1148097A CN1148097A (en) | 1997-04-23 |
| CN1044622C true CN1044622C (en) | 1999-08-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN96107076A Expired - Fee Related CN1044622C (en) | 1996-07-16 | 1996-07-16 | High Strength Nickel Base Cast Superalloy |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048528C (en) * | 1997-09-12 | 2000-01-19 | 冶金工业部钢铁研究总院 | Nickel base deforming alloy target material for sputtering glass plating |
| JP3916484B2 (en) * | 2002-03-05 | 2007-05-16 | 独立行政法人科学技術振興機構 | Ni alloy heat resistant material excellent in high temperature oxidation resistance and method for producing the same |
| SE528807C2 (en) * | 2004-12-23 | 2007-02-20 | Siemens Ag | Component of a superalloy containing palladium for use in a high temperature environment and use of palladium for resistance to hydrogen embrittlement |
| CN101935770B (en) * | 2010-08-31 | 2012-04-18 | 西安诺博尔稀贵金属材料有限公司 | Method for manufacturing multi-element nickel-based alloy ingot blank containing aluminum and yttrium |
| CN101974708A (en) * | 2010-11-05 | 2011-02-16 | 钢铁研究总院 | Hot erosion resisting directionally solidified nickel-based cast superalloy |
| JP5998325B2 (en) * | 2011-03-29 | 2016-09-28 | 公立大学法人大阪府立大学 | Friction stir processing tool and friction stir processing method using the same |
| CN103436722A (en) * | 2013-07-30 | 2013-12-11 | 青岛新力通工业有限责任公司 | Production method of novel nickel-base furnace tube |
| CN103540803B (en) * | 2013-10-30 | 2016-03-02 | 钢铁研究总院 | A kind of high rigidity is without magnetic nichrome and preparation method thereof |
| CN103706778A (en) * | 2013-12-31 | 2014-04-09 | 大连福岛精密零部件有限公司 | Method for utilizing non-vacuum furnace to produce high temperature alloy parts of Stirling engine |
| CN108467973B (en) * | 2018-06-11 | 2020-04-10 | 江苏银环精密钢管有限公司 | Nickel-chromium-tungsten high-temperature alloy seamless tube for 700 ℃ ultra-supercritical boiler and manufacturing method thereof |
| CN114635059B (en) * | 2022-03-03 | 2023-02-10 | 北京北冶功能材料有限公司 | Ni-Cr-W-based alloy and preparation method thereof |
| CN117026015B (en) * | 2023-07-18 | 2024-02-13 | 大湾区大学(筹) | High-temperature-resistant alloy and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100649A (en) * | 1985-04-01 | 1986-07-30 | 鞍山钢铁公司 | The ultrahigh-temperature abrasion-resistant cast nickel based alloy |
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1996
- 1996-07-16 CN CN96107076A patent/CN1044622C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100649A (en) * | 1985-04-01 | 1986-07-30 | 鞍山钢铁公司 | The ultrahigh-temperature abrasion-resistant cast nickel based alloy |
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| CN1148097A (en) | 1997-04-23 |
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