CN108277535B - A kind of copper aluminium manganese base single crystal alloy - Google Patents
A kind of copper aluminium manganese base single crystal alloy Download PDFInfo
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- CN108277535B CN108277535B CN201810022365.2A CN201810022365A CN108277535B CN 108277535 B CN108277535 B CN 108277535B CN 201810022365 A CN201810022365 A CN 201810022365A CN 108277535 B CN108277535 B CN 108277535B
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/52—Alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/01—Alloys based on copper with aluminium as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/05—Alloys based on copper with manganese as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/02—Single-crystal growth directly from the solid state by thermal treatment, e.g. strain annealing
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Abstract
The invention discloses a kind of copper aluminium manganese base single crystal alloys, with the other super large grain structure of Centimeter Level, it is obtained after 800~950 DEG C of single phase region carries out the annealing of 1~30h by the cast alloy of polycrystalline structure, the cast alloy includes following weight percentage components: copper 70~82%, aluminium 10~16%, manganese 5~12%, optional metal 0.2~3%.For aluminium content between 10%~16%, obtained single crystal alloy has the Heusler-L2 of high-sequential in the present invention1(Cu2AlMn) structure, in addition, the addition of optional metal causes alloy that phenomenon of phase separation occurs in the present invention, therefore in addition to L2 in alloy1Outside phase, there is also the precipitated phases of the very tiny optional metallic element of richness, and the presence of this kind of precipitated phase is that alloy is promoted to form super large crystal grain deciding factor in high-temperature heat treatment.
Description
Technical field
The invention belongs to metal single crystal technical field of alloy, and in particular to a kind of copper aluminium manganese base single crystal alloy.
Background technique
Single crystal alloy usually has mechanics more more excellent than polycrystalline alloy and functional characteristic, therefore has wide application
Prospect.Metal material is all polycrystalline structure, bulk single crystal alloy by traditional heat treatment process (melting, solidification, annealing)
It can only could often be obtained by some special equipment and technique, such as directional solidification processes (1, Otsuka, K., Wayman,
C.M., Nakai, K., Sakamoto, H.&Shimizu, K.Superelasticity effects and stress-
Induced martensitic transformations in Cu-Al-Ni alloys.Acta Metall.24,207-
226,1976；2, Saburi, T., Inada, Y., Nenno, S.&Hori, N.Stress-induced martensitic
Transformations in Cu-Zn-Al and Cu-Zn-Ga alloys.J.Phys.43,633-638,1982；3,
Kato, H., Dutkiewicz, J.& Miura, S.Superelasticity and shape memory effect in Cu-
23at.%Al-7at.%Mn alloy single crystals.Acta Metall.Mater:42,1359-1365,1994；
4, Kato, H., Ozu, T., Hashimoto, S., Miura, S.Cyclic stress-strain response of
Superelastic Cu-Al-Mn alloy single crystals.Mater.Sci.Eng.A.264,245-253,1999；
5、The reorientation of the 2H martensite phase in Cu-A1-Mn shape memory
Single crystal alloy.Mater.Sci.Eng.A.481-482,526-531,2008).Some metal materials are passing through
Abnormal grain growth phenomenon can occur when macroscopic deformation after annealing or dynamic recrystallization, it is hereby achieved that monocrystal material, still
These methods are only capable of obtaining the sheet material of some simple shapes or wire rod (1, Goss, N.P.New development in
electrical strip steels characterized by fine grain structure approaching the
Properties of a single crystal.Trans.ASM 23,511-531,1934；2, Humphreys, F.J.&
Hatherly, M.in Recrystallization and related annealing phenomena (Elsevier,
Oxford, ed.2,2004；3, Padilha, A.F., Plaut, R.L.& Rios, P.R.Annealing of cold-worked
Austenitic stainless steels.ISIJ Int.43,135-143,2003；4, Ciulik, J.&Taleff,
E.M.Dynamic abnormal grain growth:A new method to produce single
Crystal.Scr.Mater.61,895-898,2009), and process is more complicated, technique is cumbersome, and it is at high cost, and cannot obtain
The monocrystal material of bulk is obtained, therefore is unfavorable for practical application.
The Omori et al. of Japan has found a kind of copper aluminium manganese ternary-alloy material, composition range be (mass ratio) 7.8%~
8.8% aluminium, 7.2%~14.3% manganese, surplus are copper (1, Omori, T.et al.Abnormal grain growth
Induced by cyclic heat treatment.Science 341,1500-1502,2013；2, Kusama, T., et
Al.Ultra-large single crystals by abnormal grain growth.Nat.Comm.8,354- (1-9),
2017).This kind of alloy material needs not move through macroscopic deformation, can be obtained super large grain structure by tens of thermal cycles,
Its Thermal Cycling are as follows: cast alloy carries out the heat treatment that homogenizes in 900 DEG C of single phase regions of high temperature first, then that alloy is slow
Then cooling (cooling velocity is 0.5 DEG C/min~3.3 DEG C/min) (rises to 500 DEG C, 740 DEG C or 760 DEG C in slow heating
Warm speed is 10 DEG C/min) to 900 DEG C of isothermal treatment for short time, it is quenched after carrying out tens of secondary cycle heat treatments according to above-mentioned technique.But
Not only time-consuming but also technique is extremely cumbersome for above-mentioned circle heat treatment, very strict to temperature rate requirement, is unfavorable for reality
The production application on border.
Up to the present, metal single crystal alloy application and it is few, be concentrated mainly on the fields such as aerospace, this is mainly
Because of metal single crystal alloy, especially bulk single crystal alloy just can get only by special installation and process materials, production effect
Rate is low and its is expensive.Therefore the metal alloy compositions that exploitation can be obtained bulk monocrystalline by simple process have very
Important theory significance and boundless application prospect.
Summary of the invention
It is an object of the invention to overcome prior art defect, a kind of copper aluminium manganese base single crystal alloy is provided.
Technical scheme is as follows:
A kind of copper aluminium manganese base single crystal alloy has the other super large grain structure of Centimeter Level, by the as cast condition of polycrystalline structure
Alloy obtains after 800~950 DEG C of single phase region carries out the annealing of 1~30h, which includes following weight percent
Component: copper 70~82%, aluminium 10~16%, manganese 5~12%, optional metal 0.2~3%,
Wherein, above-mentioned optional metal and copper is there are liquid phase two-phase laminated flow, its own with body-centered cubic structure or can with manganese,
Aluminium forms body-centered cubic structure, and can make alloy that body-centred cubic phenomenon of phase separation occur.
In a preferred embodiment of the invention, the cast alloy by forming following weight percentage components:
Copper 70~82%, aluminium 10~16%, manganese 5~12%, optional metal 0.2~3%.
In a preferred embodiment of the invention, the cast alloy includes following weight percentage components: copper
75~80.5%, aluminium 10~14%, manganese 6~12%, optional metal 0.2~3%.
It is further preferred that the cast alloy by forming following weight percentage components: copper 75~80.5%, aluminium 10
~14%, manganese 6~12%, optional metal 0.2~3%.
In a preferred embodiment of the invention, the optional metal be molybdenum, tungsten, vanadium or chromium,
When optional metal is molybdenum, weight percent of the optional metal in the cast alloy is 0.2~3%；
When optional metal is tungsten, weight percent of the optional metal in the cast alloy is 0.2~1%；
When optional metal is vanadium, weight percent of the optional metal in the cast alloy is 0.2~1%；
When optional metal is chromium, weight percent of the optional metal in the cast alloy is 0.2~1%.
In a preferred embodiment of the invention, the temperature of the annealing is 800~900 DEG C.
In a preferred embodiment of the invention, the time of the annealing is 3~30h.
The beneficial effects of the present invention are:
1, the copper aluminium manganese ternary alloy three-partalloy that in the prior art, Omori et al. is reported since aluminium content is 7.8%~8.8%,
Therefore obtained single crystal alloy is unordered body-centered cubic (A2) structure, aluminium content is obtained between 10%~16% in the present invention
Single crystal alloy has the Heusler--L2 of high-sequential1(Cu2AlMn) structure, in addition, the addition of optional metal is led in the present invention
Cause alloy that phenomenon of phase separation occurs, therefore in addition to L2 in alloy1Outside phase, there is also the precipitations of the very tiny optional metallic element of richness
Phase (its size is between more than ten nanometers to more than ten microns), the presence of this kind of precipitated phase are to promote alloy shape in high-temperature heat treatment
At super large crystal grain deciding factor.
2, the copper aluminium manganese ternary alloy three-partalloy that in the prior art, Omori et al. is reported has to pass through tens of thermal cycles
Super large grain structure can be obtained, and of the invention it is only necessary to cast alloy with the quaternary copper aluminium manganese-base alloy mutually separated
Carrying out primary annealing can be obtained super large grain structure.Therefore copper aluminium manganese base single crystal alloy preparation process of the invention is extremely simple,
It is very easy to realize, there is extraordinary application prospect.
Detailed description of the invention
Fig. 1 be the embodiment of the present invention 1 in cast alloy and 900 DEG C heat treatment for 24 hours after it is obtained have super large crystal grain
Alloy photo.
Fig. 2 be the embodiment of the present invention 2 in cast alloy and 850 DEG C heat treatment for 24 hours after it is obtained have super large crystal grain
Alloy photo.
Fig. 3 be the embodiment of the present invention 4 in cast alloy and 900 DEG C heat treatment for 24 hours after it is obtained have super large crystal grain
Alloy photo.
Fig. 4 be the embodiment of the present invention 6 in cast alloy and 900 DEG C heat treatment for 24 hours after it is obtained have super large crystal grain
Alloy photo.
Fig. 5 be the embodiment of the present invention 8 in cast alloy and 900 DEG C heat treatment for 24 hours after it is obtained have super large crystal grain
Alloy photo.
Fig. 6 is the micro-organization chart of the cast alloy in the embodiment of the present invention 2.Wherein alloy is by Heusler-L21
(Cu2AlMn), A2 (Mo) precipitated phase and γ of very tiny rich Mo1(Cu9Al4) phase composition.
Specific embodiment
Technical solution of the present invention is further explained and described below by way of specific embodiment combination attached drawing.
All alloys all have a common heterogeneous microstructure in the present invention, i.e., all include by phenomenon of phase separation institute
Caused Heusler-L21(Cu2AlMn the tiny precipitated phase of)+the 4th kind of alloying element of richness.
Embodiment 1
Copper, aluminium, manganese, molybdenum raw material are pressed into copper 76% respectively, the mass percent of aluminium 13%, manganese 10%, molybdenum 1% is matched
Material, then carries out melting for alloy, obtains cast alloy after alloy is cooling.Then cast alloy is annealed at 900 DEG C
Processing, annealing time are to quench afterwards for 24 hours, obtain the alloy material with super large grain structure, result is as shown in Figure 1, can be straight
Obtain about 4cm bulk monocrystalline.
Embodiment 2
Copper, aluminium, manganese, molybdenum raw material are pressed into copper 79.8%, aluminium 14%, manganese 6%, the mass percent of molybdenum 0.2% respectively
Then alloy is carried out melting by ingredient, obtain cast alloy as shown in FIG. 6 after alloy is cooling.Then cast alloy is existed
850 DEG C are made annealing treatment, and annealing time is to quench afterwards for 24 hours, obtain the alloy material with super large grain structure, result is such as
Shown in Fig. 2, wherein available is more than the bulk monocrystalline of 2cm.
Embodiment 3
Copper, aluminium, manganese, molybdenum raw material are pressed into copper 75% respectively, the mass percent of aluminium 10%, manganese 12%, molybdenum 3% is matched
Material, then carries out melting for alloy, obtains cast alloy after alloy is cooling.Then cast alloy is annealed at 850 DEG C
Processing, annealing time are to quench afterwards for 24 hours, obtain the alloy material with super large grain structure, wherein available is more than the block of 2cm
Material monocrystalline.
Embodiment 4
Copper, aluminium, manganese, tungsten raw metal are pressed into copper 77% respectively, aluminium 13%, manganese 9%, the mass percent ingredient of tungsten 1%,
Then alloy is subjected to melting, obtains cast alloy after alloy is cooling.Then cast alloy is carried out at annealing at 900 DEG C
Reason, annealing time are to quench afterwards for 24 hours, obtain the alloy material with super large grain structure, result is as shown in figure 3, wherein may be used
Acquisition is more than the bulk monocrystalline of 2cm.
Embodiment 5
Copper, aluminium, manganese, tungsten raw metal are pressed into copper 75.5%, aluminium 14%, manganese 10%, the mass percent of tungsten 0.5% respectively
Then alloy is carried out melting by ingredient, obtain cast alloy after alloy is cooling.Then cast alloy is moved back at 900 DEG C
Fire processing, annealing time quench after being 12h, obtain the alloy material with super large grain structure, wherein can get is more than 2cm's
Bulk monocrystalline.
Embodiment 6
Copper, aluminium, manganese, vanadium metal raw material are pressed into copper 76.3%, aluminium 14%, manganese 9%, the mass percent of vanadium 0.7% respectively
Then alloy is carried out melting by ingredient, obtain cast alloy after alloy is cooling.Then cast alloy is moved back at 900 DEG C
Fire processing, annealing time be quench afterwards for 24 hours, obtain have super large grain structure alloy material, result as shown in figure 4, its
In can get be more than 2cm bulk monocrystalline.
Embodiment 7
Copper, aluminium, manganese, vanadium metal raw material are pressed into copper 79% respectively, aluminium 12%, manganese 8%, the mass percent ingredient of vanadium 1%,
Then alloy is subjected to melting, obtains cast alloy after alloy is cooling.Then cast alloy is carried out at annealing at 800 DEG C
Reason, annealing time quench after being 30h, obtain the alloy material with super large grain structure, wherein available is more than the bulk of 2cm
Monocrystalline.
Embodiment 8
Copper, aluminium, manganese, chromium raw metal are pressed into copper 80.5%, aluminium 12%, manganese 7%, the mass percent of chromium 0.5% respectively
Then alloy is carried out melting by ingredient, obtain cast alloy after alloy is cooling.Then cast alloy is moved back at 900 DEG C
Fire processing, annealing time quench after being 3h, obtain the alloy material with super large grain structure, result is as shown in figure 5, wherein
It can get the bulk monocrystalline of about 1cm.
Embodiment 9
Copper, aluminium, manganese, chromium raw metal are pressed into copper 78% respectively, aluminium 13%, manganese 8%, the mass percent ingredient of chromium 1%,
Then alloy is subjected to melting, obtains cast alloy after alloy is cooling.Then cast alloy is carried out at annealing at 850 DEG C
Reason, annealing time are to quench afterwards for 24 hours, obtain the alloy material with super large grain structure, wherein available is more than the bulk of 1cm
Monocrystalline.
The foregoing is only a preferred embodiment of the present invention, the range that the present invention that therefore, it cannot be limited according to is implemented, i.e.,
Equivalent changes and modifications made in accordance with the scope of the invention and the contents of the specification should still be within the scope of the present invention.
Claims (7)
1. a kind of copper aluminium manganese base single crystal alloy, it is characterised in that: there is the other super large grain structure of Centimeter Level, by polycrystalline knot
The cast alloy of structure is quenched after 800 ~ 950 DEG C of single phase region carries out the annealing of 1 ~ 30h and is obtained, which includes as follows
The component of weight percent: copper 70 ~ 82%, aluminium 10 ~ 16%, manganese 5 ~ 12%, the 4th kind of alloying element 0.2 ~ 3%, the 4th kind of alloy member
Element is molybdenum, tungsten, vanadium or chromium；
Wherein, above-mentioned 4th kind of alloying element and copper is there are liquid phase two-phase laminated flow, its own is with body-centered cubic structure or can be with
Manganese, aluminium form body-centered cubic structure, and can make alloy that body-centred cubic phenomenon of phase separation occur.
2. a kind of copper aluminium manganese base single crystal alloy as described in claim 1, it is characterised in that: the cast alloy is by as follows
The group of weight percent is grouped as: copper 70 ~ 82%, aluminium 10 ~ 16%, manganese 5 ~ 12%, the 4th kind of alloying element 0.2 ~ 3%.
3. a kind of copper aluminium manganese base single crystal alloy as described in claim 1, it is characterised in that: the cast alloy includes such as
The component of lower weight percent: copper 75 ~ 80.5%, aluminium 10 ~ 14%, manganese 6 ~ 12%, the 4th kind of alloying element 0.2 ~ 3%.
4. a kind of copper aluminium manganese base single crystal alloy as claimed in claim 3, it is characterised in that: the cast alloy is by as follows
The group of weight percent is grouped as: copper 75 ~ 80.5%, aluminium 10 ~ 14%, manganese 6 ~ 12%, the 4th kind of alloying element 0.2 ~ 3%.
5. a kind of copper aluminium manganese base single crystal alloy as described in any claim in Claims 1-4, it is characterised in that:
When the 4th kind of alloying element is molybdenum, the 4th kind of weight percent of the alloying element in the cast alloy is 0.2 ~ 3%；
When the 4th kind of alloying element is tungsten, the 4th kind of weight percent of the alloying element in the cast alloy be 0.2 ~
1%；
When the 4th kind of alloying element is vanadium, the 4th kind of weight percent of the alloying element in the cast alloy be 0.2 ~
1%；
When the 4th kind of alloying element is chromium, the 4th kind of weight percent of the alloying element in the cast alloy be 0.2 ~
1%。
6. a kind of copper aluminium manganese base single crystal alloy as described in any claim in Claims 1-4, it is characterised in that:
The temperature of the annealing is 800 ~ 900 DEG C.
7. a kind of copper aluminium manganese base single crystal alloy as described in any claim in Claims 1-4, it is characterised in that:
The time of the annealing is 3 ~ 30h.
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| CN109593986B (en) * | 2018-12-24 | 2020-03-06 | 厦门大学 | Copper-zinc-aluminum-iron single crystal alloy material |
| CN111187941B (en) * | 2020-02-10 | 2021-11-05 | 江西理工大学 | High-strength high-toughness copper alloy material and preparation method thereof |
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| CN101473056A (en) * | 2006-06-23 | 2009-07-01 | 日本碍子株式会社 | Copper-based rolled alloy and method for producing the same |
| CN106148757A (en) * | 2015-04-20 | 2016-11-23 | 沈阳万龙源冶金新材料科技有限公司 | One Albatra metal |
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| CN101473056A (en) * | 2006-06-23 | 2009-07-01 | 日本碍子株式会社 | Copper-based rolled alloy and method for producing the same |
| CN106148757A (en) * | 2015-04-20 | 2016-11-23 | 沈阳万龙源冶金新材料科技有限公司 | One Albatra metal |
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