CN107034387A - A kind of low segregation nickel-base high-temperature single crystal alloy of high-strength corrosion and heat resistant - Google Patents
A kind of low segregation nickel-base high-temperature single crystal alloy of high-strength corrosion and heat resistant Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- 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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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract
A kind of low segregation nickel-base high-temperature single crystal alloy of high-strength corrosion and heat resistant.The invention belongs to nickel-base high-temperature single crystal alloy field, specially a kind of rhenium-containing second generation nickel base superalloy.The alloy both has higher mechanical behavior under high temperature, and good hot corrosion resistance is had both again.The high-temperature unit of aircraft engine worked under marine atmosphere is applicable not only to, ground or naval gas turbine high-temperature component is can be also used for.The composition of the alloy is constituted：Co 6.0~10.0%, Cr 7.0~14.0%, W 3.0~6.0%, Mo 0.5~4.0%, Al 2.0~8.0%, Ta 3.0~7.5%, Re 0.5~3.0%, Ti 0~1.5%, Hf 0~0.5%, C 0~0.5%, B 0~0.4%, remaining is Ni.
Description
Technical field
The invention belongs to nickel-base high-temperature single crystal alloy technical field, specially a kind of high-strength heat resistanceheat resistant of the second generation
Corrosion low segregation nickel-base high-temperature single crystal alloy, the alloy is primarily adapted for use in be held under the conditions of High Temperature Hot-corrosion Behaviorof
By the hot-end component of larger stress, the engine working-blade of such as carrier-borne aircraft or gas turbine.
Background technology
Along with continuing to develop for the carrier-borne aircraft worked under marine environment, ground or naval gas turbine,
The performance requirement of its engine material is also being gradually stepped up, and higher mechanical property is not needed only to have,
And require to have both good hot corrosion resistance.The Ni-based list of corrosion and heat resistant of current China independent development
Brilliant high temperature alloy mainly has DD8, DD10 etc., and its intensity belongs to first generation nickel-base high-temperature single crystal alloy
The row of level.However as the continuous improvement of engine and gas turbine inlet temperature, to above-mentioned heat resistanceheat resistant
The elevated temperature strength of corrosion nickel-base high-temperature single crystal alloy generates larger impact and challenge.The country reaches at present
Corrosion and heat resistant class alloy to second generation nickel-base high-temperature single crystal alloy strength level is relatively fewer.
From after 1960s, obvious change does not occur for the element species in high temperature alloy,
Majority is adjusted in original alloying component.Its reason is the raising with alloying level, is closed
The solidifying segregation of gold is further serious, improves the precipitation tendentiousness of TCP phases, reduces the tissue of alloy
Stability, has had a strong impact on mechanical property, environmental performance and processing performance of alloy etc..Therefore, subtract
The solidifying segregation of few high temperature alloy becomes one of key of promotion high temperature alloy development.
It is high in the urgent need to developing a kind of new high-strength corrosion and heat resistant class nickel-based monocrystal based on above-mentioned background
Temperature alloy, while possessing superior thermal corrosive nature, its mechanical property reaches the Ni-based list of the second generation
The row of the level of brilliant high temperature alloy.
The content of the invention
It is an object of the invention to provide a kind of high-strength low segregation nickel-base high-temperature single crystal alloy of corrosion and heat resistant.
The alloy not only meets the requirement of strength design of carrier-borne aircraft or gas turbine engine turbo blade, and
And possess good hot corrosion resistance.
The invention provides a kind of high-strength low segregation nickel-base high-temperature single crystal alloy of corrosion and heat resistant, its feature exists
In the alloying component composition is as follows with weight/mass percentage composition：
Co 6.0~10.0%, Cr 7.0~14.0%, W 3.0~6.0%, Mo 0.5~4.0%, Al 2.0~
8.0%, Ta 3.0~7.5%, Re 0.5~3.0%, Ti 0~1.5%, Hf 0~0.5%, C 0~0.5%,
B 0~0.4%, remaining is Ni.
It is preferred that proportioning be：Co 6.5~9.0%, Cr 8.0~13.5%, W 3.5~5.5%, Mo 0.8~
3.0%, Al 3.0~7.0%, Ta 4.0~7.0%, Re 1.0~2.5%, Ti 0~1.0%, Hf 0~0.3%,
C 0~0.3%, B 0~0.2%, remaining is Ni.
In the low segregation nickel-base high-temperature single crystal alloy of high-strength corrosion and heat resistant that the present invention is provided, the composition of impurity
Following require is met with percentage composition：O≤10ppm, N≤10ppm, S≤10ppm, P≤10ppm.
Alloy of the present invention is named as DD68, and its Design of Chemical Composition is based primarily upon following reason：
Alloy of the present invention contains the solution strengthening elements such as higher W, Mo, Ta, Re, simultaneously
Contain higher corrosion and heat resistant dvielement Cr.
Cr is the key element for determining alloy hot corrosion resistance, therefore necessary in corrosion and heat resistant class alloy
Contain higher Cr.However, too high Cr can increase the precipitation tendentiousness of TCP phases in alloy, drop
Low-alloyed structure stability.So, Cr content is controlled in 7.0~14.0wt.% in this alloy.
Re is maximally effective solution strengthening dvielement in current nickel-base high-temperature single crystal alloy, in order to reduce conjunction
Re contents in the cost and density of gold, alloy are controlled in 0.5~3.0wt.%.On this basis, lead to
The solution strengthening elements such as increase W, Mo, Ta and γ ' phase formation element Al contents are crossed, to ensure alloy
Elevated temperature strength.
Co can reduce the stacking fault energy of γ matrixes, increase the content of γ ' phases, improve the dissolving temperature of γ ' phases
Degree, significantly improves the creep resistance of alloy.In addition, the structure stability to alloy also has improvement.
However, low-alloyed initial melting temperature can drop in too high Co, the present invention by the control of Co contents 6.0~
10.0wt.%.
W and Mo are two kinds of important solution strengthening elements in nickel-base high-temperature single crystal alloy, the two
By improve recrystallization temperature and diffusion activation energy and the heat resistance for significantly improving alloy.But excessive
W and Mo can make to separate out TCP phases in alloy, drop low-alloyed structure stability.In addition, W and
Mo easily forms volatile oxidn under high-temperature oxidation environment, destroys the cause of alloy surface oxide-film
Close property, is there is Na2SO4Environment in, easily trigger acid frit reaction, have a strong impact on the anti-of alloy
Hot corrosion resistance, especially high Mo classes alloy, often occurs catastrophic corrosion.In summary, this conjunction
W, Mo content are controlled as 3.0~6.0wt.% and 0.5~4.0% in gold.
Al is the basic component of γ ' phases in nickel-base high-temperature single crystal alloy, high temperature of its content to alloy
Performance has a major impact, and Al can form the oxide-film of protectiveness at high temperature, ensure alloy
Antioxygenic property.But low-alloyed structure stability can drop in too high Al content, cause harmful phase
Separate out, therefore the Al content in the alloy is controlled in 2.0~8.0wt.%.
Ta be also in nickel-base high-temperature single crystal alloy γ ' phases primarily form one of element, with suppressing γ ' gatherings
Collect the effect grown up, therefore the heat resistance of alloy can be improved, and the castability of alloy can be improved
Can, low-alloyed structure stability is not dropped, therefore higher Ta contents can be added in alloy.However,
Too high Ta can raise the eutectic content in alloy, improve the complexity of heat treatment.Therefore, originally
Ta addition control is 3.0~7.5wt.% in alloy.
Ti atoms can substitute the Al atoms in γ ' phases, form Ni3(Al,Ti).In certain Al content bar
Under part, Ti can promote the precipitation of γ ' phases by reducing Al solubility.In addition, Ti can also improve
The hot corrosion resistance of alloy, reduction Production Practice of Casting Technologies and antioxygenic property.However, higher Ti
(γ+γ ') eutectic can be caused to be difficult to dissolve in single crystal super alloy, low-alloyed structural homogenity, increase is dropped
The difficulty of heat treatment.With reference to above-mentioned each factor, present invention control Ti contents are 0~1.5%.
C, B are two important interdendritic intensified elements in nickel-base high-temperature single crystal alloy, are used as gap element
Element is filled to interdendritic regions, and interdendritic tearing tendency is reduced by slowing down diffusion rate, and
And can also form carbide and boride, large and small angle crystal boundary, Asia in reinforcing single crystal super alloy
Crystal boundary and interdendritic away from.Because the precipitation of carbide and boride consumes a number of TCP phases shape
Into element, therefore, the effect with stable alloy tissue.In addition, C can be reduced in smelting process
The content that aluminium alloy inner oxide is mingled with, improves the degree of purity of alloy, and then improve the castability of alloy.
However, excessive C, B, which are added, can drop low-alloyed initial melting temperature, low-alloyed mechanical property drops, because
This this alloy is controlled in 0~0.5wt.% and 0~0.4wt.% C, B addition respectively.
Effects of the Hf in nickel-base high-temperature single crystal alloy mainly improves the processing performance of alloy, and reduction is closed
The loose tendentiousness of gold, low-alloyed initial melting temperature can drop in excessive Hf, unfavorable to alloy property, because
To the control of Hf additions in 0~0.5wt.% in this this alloy.
The rational proportion of above-mentioned each element is the basis for making alloy of the present invention obtain Good All-around Property.
Alloy of the present invention is cast into the foundry alloy for meeting chemical composition requirement through vacuum induction melting,
Then by apparatus for directional solidification remelting, grow into monocrystalline parts.
For prior art background, the present invention has developed a kind of low segregation nickel-based monocrystal of high-strength corrosion and heat resistant
High temperature alloy, the alloy shows good combination property, can meet or exceed current second
The mechanical property level of generation typical nickel-base high-temperature single crystal alloy, its corrosion and heat resistant ability with generally acknowledging in the world
Trump alloy In738 alloys are suitable.
Advantages of the present invention and beneficial effect are described as follows：
(1) it is to have both excellent the characteristics of alloy of the present invention compared with other existing nickel-base high-temperature single crystal alloys
Good mechanical behavior under high temperature and good hot corrosion resistance.Mechanical property meets or exceeds the second generation
The average level of nickel-base high-temperature single crystal alloy, 1070 DEG C/140MPa lower creep rupture lives reach 170h；900
Hot corrosion resistance is suitable with In738 alloys at DEG C.It can make under high temperature, high stress, corrosive environment
With (such as the high-temperature unit of aircraft engine, ground or the warship combustion gas that are applied to work under marine atmosphere
Turbine high-temperature component etc.).
(2) alloy of the present invention shows good tissue stabilization at 900 DEG C, 1000 DEG C and 1100 DEG C
Property.
Brief description of the drawings
Fig. 1 is nickel-base high-temperature single crystal alloy as cast condition macrostructure of the present invention；
Fig. 2 is nickel-base high-temperature single crystal alloy as cast condition mirco structure of the present invention；
Fig. 3 is nickel-base high-temperature single crystal alloy heat treatment state macrostructure of the present invention；
Fig. 4 is nickel-base high-temperature single crystal alloy heat treatment state mirco structure of the present invention；
Fig. 5 is nickel-base high-temperature single crystal alloy of the present invention and typical second generation nickel-base high-temperature single crystal alloy
The comparison figure of CMSX-4, ReneN5 alloy enduring quality；
Fig. 6 is one of microscopic structure after described 900 DEG C of Long-term Aging 1000h of nickel-base high-temperature single crystal alloy；
Fig. 7 is two of microscopic structure after described 900 DEG C of Long-term Aging 1000h of nickel-base high-temperature single crystal alloy；
Fig. 8 is one of microscopic structure after described 1100 DEG C of Long-term Aging 1000h of nickel-base high-temperature single crystal alloy；
Fig. 9 is two of microscopic structure after described 1100 DEG C of Long-term Aging 1000h of nickel-base high-temperature single crystal alloy；
Figure 10 is the nickel-base high-temperature single crystal alloy and the Ni-based height of other three kinds of typical turbomachine blade materials
The comparison figure of temperature alloy outward appearance after 5h heat erosions；
Figure 11 is the nickel-base high-temperature single crystal alloy and the Ni-based height of other three kinds of typical turbomachine blade materials
The comparison figure of temperature alloy outward appearance after 24h heat erosions.
Embodiment
Below by embodiment, the present invention will be further described：
The present invention adds higher Cr to ensure the hot corrosion resistance of alloy.In order to improve alloy
Temperature capability, adds appropriate Re and higher W, Ta, to improve the solid solution strengthening effect of alloy.
In addition, " trace element " in alloy is reduced as far as possible, to reduce the influence of the segregation in alloy graining process.
The specific preparation method of alloy of the present invention：Chemical composition is met by vacuum induction melting first
It is required that foundry alloy, then prepared on directional solidification furnace needs to carry out it before monocrystalline coupon, use
Heat treatment.
Embodiment 1-6：The chemical composition of nickel-base high-temperature single crystal alloy sample of the present invention is shown in Table 1.
For the ease of contrast, typical second generation nickel-base high-temperature single crystal alloy CMSX-4 is listed in table 1
With the chemical composition of ReneN5 alloys, " remaining " in table 1 to represent remaining percentage, "-" represents no added.
Table 2 is the 2-in-1 golden enduring quality data of the embodiment of the present invention.Fig. 1-4 is the as cast condition group of alloy of the present invention
Knit and heat treatment state tissue.Fig. 5 is the 2-in-1 gold of the embodiment of the present invention and CMSX-4, Rene N5 alloys
Enduring quality compare figure.As can be seen that nickel-base high-temperature single crystal alloy of the present invention is shown at high temperature
Good enduring quality, is on close level with the enduring quality of CMSX-4 and Rene N5 alloys.
1000h is carried out at 900 DEG C and 1100 DEG C respectively to the nickel-base high-temperature single crystal alloy long-term
Timeliness is tested.Fig. 6 and Fig. 8 are respectively the nickel-base high-temperature single crystal alloy at 900 DEG C and 1100 DEG C
γ ' the phase morphologies at the dry place of dendrite after Long-term Aging 1000h.As can be seen that Long-term Aging 1000h at 900 DEG C
γ ' mutually maintains higher square degree afterwards.With the rise of temperature, at 1100 DEG C after Long-term Aging 1000h
γ ' mutually occur in that obvious raft phenomenon.Fig. 7 and Fig. 9 are respectively that the nickel-base high-temperature single crystal alloy exists
900 DEG C separate out situation with the TCP phases after Long-term Aging 1000h at 1100 DEG C.As a result show, 900 DEG C
An extremely individual other TCP phase of appearance after lower Long-term Aging 1000h, and Long-term Aging 1000h at 1100 DEG C
TCP phases are not found in alloy afterwards.In summary, nickel-base high-temperature single crystal alloy of the present invention is 900
DEG C and 1100 DEG C at show good structure stability during Long-term Aging 1000h.
In738 alloys are the generally acknowledged corrosion and heat resistant type nickel base superalloy in current high temperature alloy field, the conjunction
The elevated temperature strength of gold is relatively low；DD6 alloys are the second generation nickel-base high-temperature single crystal alloys of China's independent development,
With higher temperature capability, but its hot corrosion resistance is poor；DZ125L is China's independent development
A kind of high intensity, low-cost type directional solidification class nickel base superalloy, the hot corrosion resistance of the alloy
It is poor.At present, above-mentioned three kinds of high temperature alloys are widely used.Figure 10 and Figure 11 is this
Invent the nickel-base high-temperature single crystal alloy and above-mentioned three kinds of typical turbomachines blade material nickel base superalloy
In 900 DEG C, 75%Na2SO4Macroscopical shape after heat erosion 5h and 24h is distinguished in+25%NaCl salt baths
Looks.As can be seen that after heat erosion 5h, In738 and DD68 alloy surfaces still have certain metal
Gloss, shows good hot corrosion resistance；DD6 alloy corrosion phenomenons are more obvious, no metal
Gloss；DZ125L alloy corrosions are the most serious, and corrosion layer is significantly thickened.After heat erosion 24h, In738
With DD68 alloys to show obvious corrosion layer thickening phenomenon, DD6 alloy corrosions layer is existing large stretch of
Peel off, and DZ125L alloys lose original shape because of seriously corroded.In summary, in this experiment
Under the conditions of, DD68 alloys show the hot corrosion resistance suitable with In738 alloys, are significantly better than
The hot corrosion resistance of DD6 and DZ125L alloys.
The chemical composition (wt.%) of the alloy (embodiment 1-6) of the present invention of table 1
| Alloy | Co | Cr | W | Mo | Al | Ta | Re | Ti | C | B | Hf | Ni |
| Embodiment 1 | 8.3 | 11.4 | 4.8 | 1.1 | 5.6 | 5.2 | 1.8 | — | 0.01 | 0.005 | 0.1 | It is remaining |
| Embodiment 2 | 8.5 | 11.2 | 5.2 | 1.1 | 5.4 | 4.9 | 2.2 | — | 0.014 | 0.008 | 0.1 | It is remaining |
| Embodiment 3 | 8.8 | 12.1 | 4.2 | 1.3 | 5.1 | 4.8 | 2.0 | — | 0.012 | 0.006 | 0.11 | It is remaining |
| Embodiment 4 | 6.8 | 8.5 | 4.2 | 2.8 | 3.8 | 6.4 | 1.5 | — | 0.008 | 0.12 | 0.06 | It is remaining |
| Embodiment 5 | 7.2 | 13.2 | 3.8 | 1.5 | 6.8 | 6.2 | 2.4 | 0.3 | 0.013 | 0.007 | 0.18 | It is remaining |
| Embodiment 6 | 6.7 | 11.8 | 5.1 | 1.7 | 5.5 | 5.3 | 1.7 | 0.8 | 0.012 | 0.005 | 0.14 | It is remaining |
| CMSX-4 | 9.0 | 6.5 | 6 | 0.6 | 5.6 | 6.5 | 3.0 | 0.1 | — | — | 0.1 | It is remaining |
| Rene N5 | 7.5 | 7.0 | 5.0 | 1.5 | 6.2 | 6.5 | 3.0 | — | 0.05 | 0.04 | 0.15 | It is remaining |
The enduring quality of the heat treatment state alloy sample of the embodiment of the present invention 2 is shown in Table 2.
The 2-in-1 golden enduring quality of the embodiment of the present invention of table 2
| Temperature/DEG C | Stress/MPa | Creep rupture life/t | Elongation percentage/% |
| 1070 | 140 | 145.3 | 18.64 |
| 1070 | 140 | 170.5 | 11.52 |
| 1070 | 140 | 113.0 | 25.70 |
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow be familiar with this
The personage of item technology can understand present disclosure and implement according to this, can not limit the present invention with this
Protection domain.Any equivalent change or modification in accordance with the spirit of the invention, should all cover
Within protection scope of the present invention.
Claims (3)
1. a kind of low segregation nickel-base high-temperature single crystal alloy of high-strength corrosion and heat resistant, it is characterised in that the conjunction
The composition of gold is constituted：
Co 6.0~10.0%, Cr 7.0~14.0%, W 3.0~6.0%, Mo 0.5~4.0%, Al 2.0~
8.0%, Ta 3.0~7.5%, Re 0.5~3.0%, Ti 0~1.5%, Hf 0~0.5%, C 0~0.5%,
B 0~0.4%, remaining is Ni.
2. according to the low segregation nickel-base high-temperature single crystal alloy of high-strength corrosion and heat resistant described in claim 1, it is special
Levy and be, the composition composition of the alloy is with mass percent：Co 6.5~9.0%, Cr 8.0~
13.5%, W 3.5~5.5%, Mo 0.8~3.0%, Al 3.0~7.0%, Ta 4.0~7.0%, Re 1.0~
2.5%, Ti 0~1.0%, Hf 0~0.3%, C 0~0.3%, B 0~0.2%, remaining is Ni.
3. according to the low segregation nickel-base high-temperature single crystal alloy of high-strength corrosion and heat resistant described in claim 1 or 2,
It is characterized in that：In the nickel-base high-temperature single crystal alloy, the composition and percentage composition of impurity meet as follows
It is required that：O≤10ppm, N≤10ppm, S≤10ppm, P≤10ppm.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108070741A (en) * | 2017-12-05 | 2018-05-25 | 大连理工大学 | A kind of nickel-base high-temperature single crystal alloy series Nideal4 alloy series and its application |
| CN108588605A (en) * | 2018-05-03 | 2018-09-28 | 西安科技大学 | A kind of heat treatment process of boracic nickel-base high-temperature single crystal alloy |
| CN108677064A (en) * | 2018-06-08 | 2018-10-19 | 南京赛达机械制造有限公司 | A kind of high life high temperature alloy blade of aviation engine and manufacturing method |
| CN110343907A (en) * | 2019-07-17 | 2019-10-18 | 浙江大学 | High-strength casting Ni containing W3Al based high-temperature alloy and preparation method thereof |
| CN112226648A (en) * | 2020-09-08 | 2021-01-15 | 中国科学院金属研究所 | Low-Re low-S heat-corrosion-resistant nickel-based single crystal superalloy |
| CN112981183A (en) * | 2019-12-18 | 2021-06-18 | 通用电气公司 | Nickel-based superalloys having a microstructure comprising a raft-resistant gamma prime phase and articles made therefrom |
| CN112981187A (en) * | 2021-04-25 | 2021-06-18 | 中国航发北京航空材料研究院 | Modified nickel-based single crystal superalloy, modification method for medium-temperature endurance performance of nickel-based single crystal superalloy and application of modified nickel-based single crystal superalloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108070741A (en) * | 2017-12-05 | 2018-05-25 | 大连理工大学 | A kind of nickel-base high-temperature single crystal alloy series Nideal4 alloy series and its application |
| CN108588605A (en) * | 2018-05-03 | 2018-09-28 | 西安科技大学 | A kind of heat treatment process of boracic nickel-base high-temperature single crystal alloy |
| CN108677064A (en) * | 2018-06-08 | 2018-10-19 | 南京赛达机械制造有限公司 | A kind of high life high temperature alloy blade of aviation engine and manufacturing method |
| CN110343907A (en) * | 2019-07-17 | 2019-10-18 | 浙江大学 | High-strength casting Ni containing W3Al based high-temperature alloy and preparation method thereof |
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