CN108385010A - A kind of cobalt base superalloy and preparation method thereof of low-density, high structure stability - Google Patents
A kind of cobalt base superalloy and preparation method thereof of low-density, high structure stability Download PDFInfo
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- CN108385010A CN108385010A CN201810301030.4A CN201810301030A CN108385010A CN 108385010 A CN108385010 A CN 108385010A CN 201810301030 A CN201810301030 A CN 201810301030A CN 108385010 A CN108385010 A CN 108385010A
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Abstract
A kind of low-density, the novel γ ' of high structure stability mutually strengthen cobalt base superalloy and preparation method, belong to new material design and shipbuilding field.Its chemical composition is by atomic percentage:5 11%Al, 0.01 3%W, 20 35%Ni, 8 18%Cr, 1 6%Mo, 0.01 1% (Y/Ce/La chooses any one kind of them), 0.01 1%Si, 0.01 1%B, 0.01 1%C, 0.01 1%Zr, 0.01 1%Hf, 0 2%Ta, 0 4%Ti, 0 4%Fe, 0 4%Nb, surplus Co.Designed alloying component has carried out rational optimization to W, Mo, Si and Y/La/Ce element, can significantly reduce alloy density, improves alloy high-temp performance;Developed smelting technology can avoid the scaling loss of low melting point element and the fusing non-uniform phenomenon of high-melting-point element, improve the accuracy and uniformity of ingot chemistry;Developed alloy has lower density and higher medium temperature structure property stability, is a kind of excellent deformation cobalt-based high-temperature structural material compared with similar deformation cobalt base superalloy.
Description
Technical field:
The invention belongs to new material design and development field, a kind of low-density, high structure stability γ ' are in particular, provided
Mutually strengthen the ingredient and preparation method thereof of cobalt base superalloy.
Background technology:
Cobalt base superalloy has excellent heat/corrosion resistance, thermal fatigue resistance and weldability compared with nickel base superalloy
Can, it is the material with important application foreground on the hot-end components such as aviation, rocket chamber and guide vane.Especially
Be, γ ' mutually strengthen Co-Al-W based alloys be found to be Development of Novel cobalt base superalloy open new road [Sato J,
Omori T,Oikawa K,et al.Cobalt-base high-temperature alloys[J].Science,2006,
312(5770):90-1]。
The research and development time for mutually strengthening cobalt base superalloy in relation to novel γ ' is shorter, and correlative study is also very limited, research master
It concentrates in influence of the alloying element to cobalt base superalloy structure property, does not form the alloy designations of series, especially
Deformation cobalt base superalloy only has Neumeier seminars of Germany so far and Dye seminars of Britain has carried out correlative study.
Neumeier et al. using cast-method of rolling is prepared for high performance novel deformation cobalt base superalloy, the alloy with it is difficult deform it is Ni-based
High temperature alloy U720Li, which is compared, the hot-working section of bigger, and yield strength is closed in 800 DEG C of temperature or more higher than U720Li
Gold [Neumeier S, Freund L P,M.Novel wroughtγ/γ′cobalt base superalloys
with high strength and improved oxidation resistance[J].Scripta Materialia,
2015,109:104-107];Dye et al. is prepared for novel deformation cobalt base superalloy, the alloy using the method for powder metallurgy
There is similar yield strength with MarM247, even has higher intensity [Knop M, Mulvey after temperature is higher than 750 DEG C
P,Ismail F,et al.A New Polycrystalline Co-Ni Superalloy[J].JOM,2014,66(12):
2495-2501.]。
However, New Co-Al-W the based alloys developed at present so that alloy is close due to containing 5at%~10at%W elements
Spend higher, even higher than 9.0g/cm3, and the density of traditional deformation nickel base superalloy Wasploy is only 8.2g/cm3.It is novel
The higher disadvantage of the density of cobalt base superalloy will be important as limiting it on aviation, rocket engine hot-end component and applying
One of factor.Therefore, the density for reducing novel cobalt base superalloy is the key that realize one of such alloy practical application.It is protecting
Under the premise of demonstrate,proving alloy structure performance stabilization, it is the most effective approach for reducing cobalt base superalloy density rationally to substitute W elements.
Invention content:
The present invention is for the purpose of reducing novel cobalt base superalloy density, by alloying element selection optimization and reasonably
Preparation process formulates, and develops the novel γ ' phases deformation cobalt base superalloy of a kind of low-density, high structure property stability.
The technical scheme is that:
The cobalt base superalloy of a kind of low-density, high structure stability, chemical composition are by atomic percentage:5-11%
Al, 0.01-3%W, 20-35%Ni, 8-18%Cr, 1-6%Mo, 0.01-1% (Y/Ce/La chooses any one kind of them), 0.01-1%Si,
0.01-1%B, 0.01-1%C, 0.01-1%Zr, 0.01-1%Hf, 0-2%Ta, 0-4%Ti, 0-4%Fe, 0-4%Nb, it is remaining
Amount is Co.
The preparation process of the cobalt base superalloy of low-density, high structure stability as described above, including intermediate alloy melting
With alloy melting process, key step is as follows:
(1) the high melting elements, first melting Co-Mo-W-Ta-Nb intermediate alloys such as W, Mo, Ta, Nb are considered, reduces and closes
Golden fusing point, prevents from occurring high-melting-point alloy in fusion process melting insufficient phenomenon.Simultaneously by the less alloying element of content,
Such as:Si, B, C, Zr, Hf, Y/Ce/La etc., are added intermediate alloy together, to increase the uniformity of these Minor elements.
(2) include Ni, Cr, Fe etc. by the alloying element simple substance in addition to Al, Ti element, earthenware is put into togerther with intermediate alloy
In crucible, and oxidizable Al, Ti element is put into hopper, to be added in fusion process.
(3) vaccum sensitive stove is used to carry out melting, when vacuum degree is less than 5 × 10 in stove-2When Pa, starts small-power power transmission and add
Heat excludes the attachment gas on raw material, continues to be evacuated down to 1 × 10-2When Pa, high-power be rapidly heated to 1500 DEG C -1600 is carried out
DEG C, 10 minutes are kept the temperature, temperature is then reduced to 1300 DEG C -1400 DEG C, keeps the temperature 5 minutes, Al, Ti element in hopper is added, connects
It and is rapidly heated at once to 1500 DEG C -1600 DEG C, heat preservation is poured into a mould after 10-15 minutes, is prepared into cobalt base superalloy ingot casting.
Advantages of the present invention:
(1) present invention has considered each element in composition design to novel cobalt base superalloy cost, density, group
The combined influence of performance is knitted, especially to the meticulous selection and optimization of W, Mo, Si and Y/La/Ce element, to the drop of alloy density
Low and high-temperature behavior promotion plays the role of significantly.Specific Consideration is as follows:
Aluminium:Al elements are γ ' phase formation elements, and since the density of Al is relatively low, it is close that the addition of Al can significantly reduce alloy
Degree.Excessively high Al elements are easy to cause β phases and are formed, therefore the content of Al elements is 5-11at%.
Tungsten:W elements are γ ' phases formation element and solution strengthening element, due to W (ρ=19.3g/cm3) density it is larger, W
Alloy density can be significantly greatly increased in the addition of element, therefore the content of W elements is 0.01-3at%.
Nickel:Ni elements are γ ' phase formation elements, and the addition of Ni elements is conducive to expand γ/γ ' two-phase sections, significantly carry
The structure stability of high cobalt base superalloy, therefore the content of Ni elements is 20-35at%.
Chromium:Cr elements are important anti-oxidant and corrosion-resisant alloy element, and the addition of Cr elements can make material be on active service
Condition lower surface forms fine and close chromium-rich oxidation film, and material is prevented further to aoxidize.Excessive Cr elements can lead to γ/γ ' two-phases
Organize it is unstable, and be easy crystal boundary be precipitated σ phases, therefore the content of Cr elements be 8-18at%.
Molybdenum:Mo elements are important solution strengthening element and γ ' phase stable elements, and excessively high Mo elements can cause to be harmful to
The formation of TCP phases, therefore the content of Mo elements is 1-6at%.
Yttrium/lanthanum/cerium:Y/La/Ce elements can purify matrix and crystal boundary, significantly improve alloy mechanics and antioxygenic property, mistake
Height adds above-mentioned element and can form harmful phase and then deteriorate performance, therefore Y, La, Ce element select one of which to add, and content is
0.01-1at%.
Silicon:The addition of Si elements can reduce the thickness of oxide layer, promote the formation of chromium-rich oxidation film, improve inoxidizability
Can, the addition of a large amount of Si elements can reduce alloy γ/γ ' two-phase structures stability, therefore the content of Si elements is 0.01-
1at%.
Boron:B element is important boundary-strengthening element, and segregation enhances grain-boundary strength in crystal boundary, but excessive B element meeting
Excessive boride is formed, weakens the binding force of crystal boundary instead, therefore the content of B element is 0.01-1at%.
Carbon:The equally important boundary-strengthening element of C element, excessive C element can lead to the carbon of crystal boundary formation film-form
Compound deteriorates its mechanical property, therefore the content of C element is 0.01-1at%.
Zirconium:Zr elements are important boundary-strengthening element, have important role for removal objectionable impurities sulphur, phosphorus, but
Excessive Zr elements can deteriorate its mechanical property, therefore the content of Zr elements is 0.01-1at%.
Hafnium:Hf elements are γ ' phase formation elements, and Hf can also play an important role purification crystal boundary, but Hf element prices
Costliness, therefore the content of Hf elements is 0.01-1at%.
Tantalum:Ta elements are important γ ' phase formation elements, can effectively improve the mechanical property of cobalt base superalloy.
Consider the factors such as density, cost, the content of Ta elements is 0-2at%.
Titanium:Ti elements are important γ ' phase formation elements, can effectively improve the mechanical property of cobalt base superalloy.
Excessively high Ti elements can lead to that β phases are formed and hot-working section is substantially reduced, and deteriorate hot-working character.Therefore Ti elements contain
Amount is 0-4at%.
Iron:The addition of Fe elements can effectively reduce cost of alloy and density, but excessive Fe elements can reduce γ/
The precipitation of the stability and TCP phases of γ ' two-phase structures, therefore the content of Fe elements is 0-4at%.
Niobium:Nb elements are γ ' phase formation elements, and the addition of Nb elements can reduce density, but excessive Nb elements can be led
The precipitation of TCP phases is caused, therefore the content of Nb elements is 0-4at%.
(2) smelting technology raw material of the invention is melted according to fusing point sequence, can avoid low-melting-point metal scaling loss and
The problems such as fusing of high-melting-point element is insufficient, and can effectively avoid and occur uneven components, macro in cobalt base superalloy ingot casting
The defects of segregation is serious is seen, the accuracy and uniformity of ingot chemistry are improved.
(3) compared with the similar γ ' of recent report mutually strengthens deformation cobalt-based/nickel base superalloy, alloy of the present invention it is close
Degree reduces 0.2-0.5g/cm3, hot-working section improves 100-150 DEG C, and after 700-900 DEG C of timeliness 1000-3000h
Still maintain stable γ/γ ' two-phase structures.As it can be seen that institute's invention alloy compared with similar deformation cobalt base superalloy, has more
Low density and higher medium temperature structure property stability are a kind of excellent deformation cobalt-based high-temperature structural materials.
Description of the drawings:
Fig. 1 is LAMP-2 cobalt-baseds deformation high temperature alloy of the present invention through solid gas coupling treated γ/γ ' two-phase structures
Fig. 2 is after LAMP-2 cobalt-baseds deformation high temperature alloy solid gas coupling of the present invention is handled, after 750 DEG C of heat exposure 2000h
γ/γ ' two-phase structures
Specific implementation mode
Technical scheme of the present invention is described further with reference to the accompanying drawings and examples.
Embodiment 1:Co-Ni-Cr-Al-W-Mo-Ti-Ta base deformation high temperature alloys
The affecting laws for mutually strengthening cobalt base superalloy structure property to novel γ ' with reference to each element develop new herein
Type Co-Ni-Cr-Al-W-Mo-Ti-Ta base deformation high temperature alloys, specific ingredient are as shown in table 1.In addition to the ingredient in table, LAMP-
1, also include Y in two kinds of alloys of LAMP-2:0.05at%, Si:0.2at%, Zr:0.06at%, Hf:0.1at%.
The preparation process of Co-Ni-Cr-Al-W-Mo-Ti-Ta base deformation high temperature alloys is as follows:
(1) the high melting elements, first melting Co-Mo-W-Ta intermediate alloys such as W, Mo, Ta are considered, alloy melting point is reduced,
Prevent occurring the non-uniform phenomenon of high-melting-point alloy fusing in fusion process, while by the less alloying element of content, such as:Si、
B, C, Zr, Hf, Y etc., are added intermediate alloy together, to increase the uniformity of these Minor elements.
(2) include Ni, Cr etc. by the alloying element simple substance in addition to Al, Ti element, crucible is put into togerther with intermediate alloy
In, and oxidizable Al, Ti element is put into hopper, to be added in fusion process.
(3) vaccum sensitive stove is used to carry out melting, when vacuum degree is less than 5 × 10 in stove-2When Pa, starts small-power power transmission and add
Heat excludes the attachment gas on raw material, continues to be evacuated down to 1 × 10-2When Pa, progress is high-power to be rapidly heated to 1600 DEG C, keeps the temperature
10 minutes, temperature was then reduced to 1400 DEG C, 5 minutes is kept the temperature, Al, Ti element in hopper is added, is then rapidly heated at once
To 1600 DEG C, heat preservation is poured into a mould after ten minutes, is prepared into cobalt base superalloy ingot casting.
Alloy solution treatment air-cooled after 1230 DEG C of heat preservations for 24 hours ,+750 DEG C of heat preservations of 900 DEG C of heat preservation 8h level-ones timeliness
After the processing of 12h secondary time effects, stable γ/γ ' two-phase structures are can get, the volume fractions of γ ' phases is about 55%~65% (such as
Shown in Fig. 1), it is cubic or close cubic, is uniformly distributed in γ phases.Alloy after 750 DEG C of heat exposure 2000h,
Still keep stable γ/γ ' two-phase structures (as shown in Figure 2).The similar γ ' of the alloy and recent report mutually strengthens deformation cobalt-based
High temperature alloy (CoWAlloy2) is compared, and density reduces 0.2-0.5g/cm3, hot-working section deforms nickel base superalloy with difficult
(U720Li) it compares and improves 110-150 DEG C, room temperature hardness is suitable with U720Li alloys (as shown in table 2), is a kind of excellent
Deformation cobalt-based high-temperature structural material.
1 Co-Ni-Cr-Al-W-Mo-Ti-Ta based alloy each element atomic percents of table and density
[CoWAlloy2 alloy data come from:Freund L P,Giese S,Schwimmer D,et al.High
temperature properties and fatigue strength of novel wroughtγ/γ′Co-base
superalloys[J].Journal of Materials Research,2017:1-8.]
2 Co-Ni-Cr-Al-W-Mo-Ti-Ta based alloy room temperature hardness of table and hot-working section
[U720Li alloy data come from:Zhou L Z,Lupinc V,Guo J T.Evolution of
Microstructure and Mechanical Property during Long-Term Aging in Udimet720Li
[J].Journal of Materials Science&Technology,2001,17(6):633-637.]
Embodiment 2:Co-Ni-Cr-Al-W-Mo-Ti-Nb base deformation high temperature alloys
With reference to each element to the affecting laws of novel cobalt base superalloy structure property, New Co-Ni- is developed herein
Cr-Al-W-Mo-Nb base deformation high temperature alloys, specific alloying component are as shown in table 3.In addition to the ingredient in table, two kinds of conjunctions of 3#, 4#
Also include La in gold:0.05at%, Si:0.2at%, B:0.04at%, C:0.05at%, Zr:0.06at%, Hf:
0.1at%.
The preparation process of New Co-Ni-Cr-Al-W-Mo-Ti-Nb base deformation high temperature alloys is as follows:
(1) the high melting elements, first melting Co-Mo-W-Nb intermediate alloys such as W, Mo, Nb are considered, alloy melting point is reduced,
Prevent occurring the non-uniform phenomenon of high-melting-point alloy fusing in fusion process, while by the less alloying element of content, such as:Si、
B, C, Zr, Hf, La etc., are added intermediate alloy together, to increase the uniformity of these Minor elements.
(2) include Ni, Cr etc. by the alloying element simple substance in addition to Al, Ti element, crucible is put into togerther with intermediate alloy
In, and oxidizable Al, Ti element is put into hopper, to be added in fusion process.
(3) vaccum sensitive stove is used to carry out melting, when vacuum degree is less than 5 × 10 in stove-2When Pa, starts small-power power transmission and add
Heat excludes the attachment gas on raw material, continues to be evacuated down to 1 × 10-2When Pa, progress is high-power to be rapidly heated to 1550 DEG C, keeps the temperature
10 minutes, temperature was then reduced to 1350 DEG C, 5 minutes is kept the temperature, Al, Ti element in hopper is added, is then rapidly heated at once
To 1550 DEG C, heat preservation
It pours into a mould after ten minutes, is prepared into cobalt base superalloy ingot casting.
Alloy solution treatment air-cooled after 1230 DEG C keep the temperature 12h ,+700 DEG C of heat preservations of 900 DEG C of heat preservation 4h level-ones timeliness
After the processing of 12h secondary time effects, stable γ/γ ' two-phase structures are can get, the volume fraction of γ ' phases is about 40%-50%,
It is cubic or close cubic, is uniformly distributed in γ phases.Alloy still keeps stabilization after 700 DEG C of heat exposure 2000h
γ/γ ' two-phase structures.The similar γ ' of the alloy and recent report mutually strengthens deformation cobalt base superalloy (CoWAlloy2) phase
Than density reduces 0.3-0.5g/cm3, hot-working section improves compared with hardly possible deformation nickel base superalloy (U720Li)
120-140 DEG C, room temperature hardness is suitable with U720Li alloys (as shown in table 4), is a kind of excellent deformation cobalt-based high-temperature structural wood
Material.
3 Co-Ni-Cr-Al-W-Mo-Ti-Nb based alloy each element atomic percents of table and density
4 Co-Ni-Cr-Al-W-Mo-Ti-Nb based alloy room temperature hardness of table and hot-working section
Embodiment 3:Co-Ni-Cr-Al-W-Mo-Ti-Fe base deformation high temperature alloys
With reference to each element to the affecting laws of novel cobalt base superalloy structure property, New Co-Ni- is developed herein
Cr-Al-W-Mo-Fe base deformation high temperature alloys, specific alloying component are as shown in table 5.In addition to the ingredient in table, also include in alloy
Ce:0.05at%, Si:0.25at%, B:0.06at%, C:0.05at%, Zr:0.04at%, Hf:0.05at%.
The preparation process of Co-Ni-Cr-Al-W-Mo-Ti-Fe base deformation high temperature alloys is as follows:
(1) the high melting elements, first melting Co-Mo-W intermediate alloys such as W, Mo are considered, alloy melting point is reduced, prevents from melting
Occur high-melting-point alloy during refining and melt non-uniform phenomenon, while by the less alloying element of content, such as:Si、B、C、Zr、
Hf, Ce etc., are added intermediate alloy together, to increase the uniformity of these Minor elements.
(2) include Ni, Cr, Fe etc. by the alloying element simple substance in addition to Al, Ti element, earthenware is put into togerther with intermediate alloy
In crucible, and oxidizable Al, Ti element is put into hopper, to be added in fusion process.
(3) vaccum sensitive stove is used to carry out melting, when vacuum degree is less than 5 × 10 in stove-2When Pa, starts small-power power transmission and add
Heat excludes the attachment gas on raw material, continues to be evacuated down to 1 × 10-2When Pa, progress is high-power to be rapidly heated to 1500 DEG C, keeps the temperature
10 minutes, temperature was then reduced to 1300 DEG C, 5 minutes is kept the temperature, Al, Ti element in hopper is added, is then rapidly heated at once
To 1500 DEG C, heat preservation is poured into a mould after 15 minutes, is prepared into cobalt base superalloy ingot casting.
Alloy solution treatment air-cooled after 1220 DEG C keep the temperature 12h ,+700 DEG C of heat preservations of 900 DEG C of heat preservation 4h level-ones timeliness
After the processing of 12h secondary time effects, stable γ/γ ' two-phase structures are can get, the volume fraction of γ ' phases is about 35%~45%,
It is spherical or close cubic, is uniformly distributed in γ phases.Alloy still keeps stabilization after 700 DEG C of heat exposure 2000h
γ/γ ' two-phase structures.The similar γ ' of the alloy and recent report mutually strengthens deformation cobalt base superalloy (CoWAlloy2) phase
Than density reduces about 0.4g/cm3, hot-working section improves 120- compared with hardly possible deformation nickel base superalloy (U720Li)
140 DEG C, room temperature hardness is suitable with U720Li alloys (as shown in table 6), is a kind of excellent deformation cobalt-based high-temperature structural material.
5 Co-Ni-Cr-Al-W-Mo-Ti-Fe based alloy each element atomic percents of table and density
6 Co-Ni-Cr-Al-W-Mo-Ti-Fe based alloy room temperature hardness of table and hot-working section
Claims (2)
1. the cobalt base superalloy of a kind of low-density, high structure stability, it is characterised in that alloy composition presses atomic percent
Number is:5-11%Al, 0.01-3%W, 20-35%Ni, 8-18%Cr, 1-6%Mo, 0.01-1% (Y/Ce/La chooses any one kind of them),
0.01-1%Si, 0.01-1%B, 0.01-1%C, 0.01-1%Zr, 0.01-1%Hf, 0-2%Ta, 0-4%Ti, 0-4%Fe,
0-4%Nb, surplus Co.
2. the preparation method of the cobalt base superalloy of low-density as described in claim 1, high structure stability, it is characterised in that packet
Intermediate alloy melting and alloy melting process are included, preparation process is as follows:
(1) melting Co-Mo-W-Ta-Nb intermediate alloys, reduction alloy melting point prevent occurring high-melting-point conjunction in fusion process first
Gold melts insufficient phenomenon;Simultaneously by the less alloying element of content, Si, B, C, Zr, Hf, Y/Ce/La are added intermediate together
Alloy, to increase the uniformity of these Minor elements;
(2) by addition to Al, Ti element alloying element simple substance Ni, Cr, Fe and intermediate alloy be put into togerther in crucible, and will be easy
Al, Ti element of oxidation are put into hopper, to be added in fusion process;
(3) vaccum sensitive stove is used to carry out melting, when vacuum degree is less than 5 × 10 in stove-2When Pa, start small-power power transmission heating row
Except the attachment gas on raw material, continue to be evacuated down to 1 × 10-2When Pa, progress is high-power to be rapidly heated to 1500 DEG C -1600 DEG C,
Then heat preservation 10 minutes reduces temperature to 1300 DEG C -1400 DEG C, keeps the temperature 5 minutes, Al, Ti element in hopper is added, then stands
It is rapidly heated at quarter to 1500 DEG C -1600 DEG C, heat preservation is poured into a mould after 10-15 minutes, is prepared into cobalt base superalloy ingot casting.
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