CN107043867B - A kind of preparation method of porous copper-based shape memory alloy - Google Patents
A kind of preparation method of porous copper-based shape memory alloy Download PDFInfo
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- CN107043867B CN107043867B CN201710015114.7A CN201710015114A CN107043867B CN 107043867 B CN107043867 B CN 107043867B CN 201710015114 A CN201710015114 A CN 201710015114A CN 107043867 B CN107043867 B CN 107043867B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
- B22F3/1134—Inorganic fillers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
Abstract
A kind of preparation method of porous copper-based shape memory alloy of the present invention, include the manufacture of porous marmem, with the pure Cu powder of original metal, pure Al powder and pure Mn powder carry out Cu-Al-Mn prealloyed powders made from ingredient as basis material, it is uniformly mixed with the water NaCl particle that decrystallizes again after evenly mixing with dehydrated alcohol, suppress to obtain green compact, NaCl particle will be remained by being placed in 100 DEG C of boiling water through sinter molding in hole thoroughly boils and removes, finally place it in 60 DEG C of baking oven inside holdings 20~30 minutes, being made has through-hole structure, mean porosities are 50~80%, average pore size is the porous copper-based shape memory alloy product of 0.2~1.5mm.The present invention overcomes the low defects of product preparation cost height of the existing technology and production security.
Description
Technical field
Technical solution of the present invention includes the manufacture of porous marmem, specifically a kind of porous copper-based shape
The preparation method of shape memory alloys.
Background technique
Porous marmem has both porous metal material lightweight, high specific strength, high energy-absorbing and marmem shape
The good characteristics such as shape memory effect and pseudoelasticity, simultaneously because the synergistic effect of its multiple damping source and there is abnormal high damping
Performance.Between the past few decades, the research of people focuses primarily upon porous TiNi marmem, although this kind of alloy is comprehensive
Can be excellent, however its fancy price largely defines that it is widely applied.In recent years, since copper-based shape is remembered
Recalling alloy equally has high damping capacity and excellent shape memory function characteristic, in addition its apparent price advantage, people
Also start to study porous copper-based shape memory alloy, and started the preparation side of a variety of porous copper-based shape memory alloys
Method.For example, Inst., of Solid Physics, Chinese Academy of Sciences (Q.Z.Wang, F.S.Han, Z.Y.Gao, et al, Effects of
Macroscopic defects on the damping behavior of CuAlMn shape memory alloy,
J.Alloy.Compd., 2006,425:200-205), Argentina, Chile and Italy scientist (G.Bertolino,
P.A.Larochette,E.M.Castrodeza,et al,Mechanical properties of martensitic Cu–
Zn-Al foams in the pseudoelastic regime, Mater.Lett., 2010,64:1448-1450) successively report
The road melting THROUGH METHOD preparation process of porous copper-based shape memory alloy.However, these techniques that all there is technical difficulty is high,
The selection of pore-creating medium molten is easy to generate intercrystalline fracture and products obtained therefrom size except difficult, matrix damage is big, metal grain is coarse
The deficiencies of being restricted.For this purpose, inventor once discloses porous CuAlMn shape memory alloy in CN102031405B
Preparation method, this method is a kind of method prepared using sintering-precipitation technology to porous copper-based shape memory alloy,
Used basis material be using copper-base alloy powder made from atomization, although overcome prior art there are the shortcomings that,
There are still following drawbacks for it: first is that the higher cost of product preparation, this is because alloyed powder granularity made from atomization is different, and
Being suitble to molding diameter of particle is mainly -100~200 mesh, and alloyed powder is too thick or too thin porous alloy is not easily molded, this is undoubtedly
Largely increase the cost of material preparation；Second is that required pressing pressure is higher in product preparation, and while being sintered, needs hydrogen
Gas atmosphere, this is because the based alloy powder surface CuAl, there are one layer of fine and close oxidation film, the presence of the film is not easy alloyed powder
Calendering formation and sinter molding will solve the problems, such as that this must just increase pressing pressure, and when sintering is equipped with hydrogen reducing.Pressing pressure
Meeting is increased so that hole shape is distorted, and the use of hydrogen can further increase the cost of preparation, reduce the safety of production.
Summary of the invention
The technical problems to be solved by the present invention are: providing a kind of preparation method of porous copper-based shape memory alloy, adopt
With PM technique, it is pre-alloyed that Cu-Al-Mn made from ingredient is carried out with the pure Cu powder of original metal, pure Al powder and pure Mn powder
Powder overcomes the low defect of product preparation cost height and production security of the existing technology as basis material.
The present invention solves technical solution used by the technical problem: a kind of preparation of porous copper-based shape memory alloy
Method carries out Cu-Al- made from ingredient using PM technique with the pure Cu powder of original metal, pure Al powder and pure Mn powder raw material
Mn prealloyed powders are as basis material, the specific steps are as follows:
The first step, the preparation of Cu-Al-Mn prealloyed powders:
It separately weighs the pure Cu powder of raw material, pure Al powder and pure Mn powder and carries out ingredient, wherein pure Al powder accounts for Cu-Al-Mn
The 11.8~12.0% of mixed powder gross mass, pure Mn powder account for the 2.4~2.6% of Cu-Al-Mn mixed powder gross mass, and pure Cu powder is
Matrix, being added and accounting for the stearic acid of Cu-Al-Mn mixed powder gross mass 0.08~0.12% is additive, under protection of argon gas in row
Ball milling 8~12 hours on planetary ball mill, for the ratio of grinding media to material used in ball milling for 10: 1, the revolving speed of ball mill is 300 revs/min,
Thus Cu-Al-Mn prealloyed powders are made；
Second step, the preparation of green compact:
Cu-Al-Mn prealloyed powders made from the first step are uniformly mixed with the dehydrated alcohol for accounting for its quality 6~8%, so
It is uniformly mixed with the water NaCl particle that decrystallizes that average grain diameter is 0.2~1.5mm afterwards, the dosage for the water NaCl particle that decrystallizes is it
The 50~80% of Cu-Al-Mn prealloyed powders and the percent by volume for the water NaCl granulate mixture that decrystallizes are accounted for, this is uniformly mixed
It closes object and is packed into compacting tool set, be unidirectionally forced into 250~320MPa, and pressure maintaining 1~3 minute, green compact are made；
Third step, sinter molding:
Green compact made from second step are placed in sintering furnace, 10~100Pa is evacuated to, are then charged with argon gas, and heat up
It is sintered 2 hours to 600~620 DEG C, is warming up to 785~795 DEG C again later and is sintered 2 hours, be finally warming up to 970~980 DEG C of burnings
It knot 2 hours, cools to room temperature with the furnace, the intermediate product of sinter molding is made；
4th step, porous copper-based shape memory alloy product are made:
By the intermediate product of sinter molding made from third step be placed in 100 DEG C of boiling water will in hole remain NaCl particle it is thorough
Bottom, which is boiled, removes, and then places it in 60 DEG C of baking oven inside holdings 20~30 minutes, and porous copper-based shape memory alloy product is made.
A kind of preparation method of above-mentioned porous copper-based shape memory alloy, the porous C uAlMn shape memory obtained close
Golden product has through-hole structure, and mean porosities are 50~80%, and average pore size is 0.2~1.5mm.
A kind of preparation method of above-mentioned porous copper-based shape memory alloy, the obtained porous CuAlMn shape memory alloy
The product heat treatment following by further progress: obtained porous CuAlMn shape memory alloy is warming up to 850~900 DEG C
And the quenching-in water for putting into room temperature after sixty minutes is kept the temperature, it is then warming up to 320~350 DEG C again with 8~10 DEG C/min of rate
And put into after keeping the temperature 12~18 minutes in the water of room temperature, complete heat treatment.
The preparation method of above-mentioned a kind of porous copper-based shape memory alloy, wherein raw materials used is commercially available, technique
It is well-known in the art with equipment.
The beneficial effects of the present invention are: the present invention has reality following prominent compared with prior art CN102031405B
Matter feature:
(1) basis material used by is different: basis material used by prior art CN102031405B is with atomization
CuAlMn marmem powder made from method, alloyed powder granularity made from atomization is different, and is suitble to molding diameter of particle
Predominantly -100~200 mesh, alloyed powder is too thick or too thin porous alloy is not easily molded, this undoubtedly largely increases material
Expect the cost of preparation；The method of the present invention carries out Cu- made from ingredient with the pure Cu powder of original metal, pure Al powder and pure Mn powder raw material
Al-Mn prealloyed powders greatly reduce production cost as basis material, compared with alloyed powder made from atomization；Prepared
In prealloyed powders, Al phase has only partially been dissolved in Cu phase, and final hard crisp CuAlMn alloy is simultaneously not formed, therefore prealloy
Change powder surface and there is no the fine and close oxide skin(coating)s formed by Al phase, while it still has excellent calendering formation, from
And be conducive to the compacting and sinter molding of green compact.
(2) preparation process of green compact has substantive difference: being prealloy since green compact of the present invention prepare material therefor
Change Cu-Al-Mn powder, by prolonged ball milling, partial size becomes very little, and surface area is very big, easily aoxidizes, if not taking
Measure may even happen that burning, can not be successfully prepared at all so as to cause sample.In response to this problem, the present invention changes existing skill
The technological parameter and operating procedure for the technology that " prepares green compact " described in art CN102031405B, and closed in advance in Cu-Al-Mn obtained
Aurification powder one is out after tank, and first horse back is using the dehydrated alcohol a greater amount of compared with technology described in prior art CN102031405B and in advance
Alloyed powder is uniformly mixed, so that powder surface coats one layer of liquid film, has effectively been completely cut off air, has been made it impossible to aoxidize,
It takes the water NaCl particle that just decrystallizes again with pore creating material after this vital safeguard measure mix, while being given birth in compression moulding
Remaining air between powder is excluded during base as far as possible, prevents in follow-up sintering residual oxygen to the oxygen on prealloyed powders surface
Change, so that the quality of product is higher.Therefore, this step is also that the present inventor specially designs for different raw material
Process, absolutely not can by limited experiment can easy realization, it is creative.
(3) sintering forming process has significant difference: the method for the present invention uses argon gas during the sintering process to protect gas
Body is lower and safer compared with the hydrogen shield atmosphere cost that the atomized alloy powder of prior art CN102031405B uses；This
In inventive method, heat preservation sintering has been carried out before the fusing point of Al first in sintering, thus guarantee that Al phase is more preferably dissolved in Cu,
And exudation will not be melted when sintering at high temperature, heat preservation sintering is carried out before then heating to the fusing point of NaCl, so that metal
Frame it is substantially stationary to resist high temperature when NaCl melt impact, be finally warming up to final temperature and be sintered, the method for the present invention
Three steps heating sintering process make final products be provided with high sintering quality.
(4) the molten method except NaCl particle is different: the present invention in order to by pore creating material NaCl particle it is molten remove it is more thorough, and
By the way of boiling, which is larger to sample impact, and porous sample is needed to have high stability just feasible (institute of the present invention
The stability that porous alloy is made can be substantially better than the porous alloy of prior art CN102031405B technology preparation), but simultaneously
It can will be remained in hole that pore creating material is easily thoroughly molten to be removed by means of the strong convection of boiling water.Therefore, the boiling of pore creating material
It is molten to remove mode, it is the side that inventor specially uses for the specific structural features of porous alloy obtained by the present invention
Method belongs to creative work.
Compared with prior art, the present invention has following marked improvement:
(1) in prior art CN102031405B, atomization make powder charge it is very high, 100KG block alloy make powder charge it is thousands of
Member, and spraying and powder making has certain recovery rate, while gained alloyed powder partial size is different, wherein being suitble to use sintering-precipitation
The powder that method prepares the suitable partial size of porous alloy only accounts for very little ratio, this results in further using the cost of atomized alloy powder
It significantly rises.The present invention using cheap commercially available (no special preparation) Cu, Al, Mn powder, price obviously want it is low very
It is more, therefore product preparation cost substantially reduces.
(2) the method for the present invention uses argon gas for protective gas during the sintering process, produces very safe.
(3) powder metallurgical technique of the method for the present invention and equipment are simple, it is easy to accomplish large-scale production, Porous Cu obtained
Porosity, aperture and the orientation in hole of base marmem product are accurately controlled with distribution, significantly reduce product
Preparation cost, the sintering quality for improving product.Porous copper-based shape memory alloy product made from the method for the present invention has excellent
Good compression energy absorption characteristics and high damping capacity, can be widely applied in national defence, weaponry and industrial production buffer, subtract
It shakes, the numerous areas of noise reduction.
The method of the present invention is also applied for the preparation of other porous copper-based shape memory alloys.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 be using digital camera to porous CuAlMn shape memory alloy sample made from the embodiment of the present invention 2~5 into
Row observes resulting macro morphology photo, in which:
Fig. 1 (a) is that porosity made from embodiment 3 is 65.0%, and average pore size is the porous C uAlMn shape of 0.56mm
The macro morphology photo of memorial alloy；
Fig. 1 (b) is the macro morphology photo of the cross section of sample shown in (a) figure；
Fig. 1 (c) is the macro morphology photo in the vertical section of sample shown in (a) figure；
Fig. 1 (d) is that porosity made from embodiment 2 is 60.3%, and average pore size is the porous C uAlMn shape of 0.56mm
The macro morphology photo of memorial alloy；
Fig. 1 (e) is that porosity made from embodiment 4 is 70.1%, and average pore size is the porous C uAlMn shape of 0.56mm
The macro morphology photo of memorial alloy；
Fig. 1 (f) is that porosity made from embodiment 5 is 65.5%, and average pore size is the porous C uAlMn shape of 0.93mm
The macro morphology photo of memorial alloy；
Fig. 2 is that porosity made from embodiment 3 is 65%, and average pore size is 0.56mm porous CuAlMn shape memory alloy
Furnace is cold and the XRD spectrum and stereoscan photograph of quenching state, in which:
Fig. 2 (a) is XRD spectrum；
Fig. 2 (b) is the cold Sample Scan electromicroscopic photograph of furnace；
Fig. 2 (c) is qtenched sample stereoscan photograph；
Fig. 3 is different porosities and different heat treatment state porous CuAlMn shape memory alloy made from embodiment 2~5
Quasistatic compression stress-strain curve；
Fig. 4 (a) is different porosities and different heat treatment state porous C uAlMn shape memory made from embodiment 2~5
Energy-absorbing ability curve graph in the quasistatic compression performance chart of alloy；
Fig. 4 (b) is different porosities and different heat treatment state porous C uAlMn shape memory made from embodiment 2~5
Energy absorbing efficiency curve graph in the quasistatic compression performance chart of alloy.
Specific embodiment
Embodiment 1
The first step, the preparation of Cu-Al-Mn prealloyed powders:
It separately weighs the pure Cu powder of raw material, pure Al powder and pure Mn powder and carries out ingredient, wherein pure Al powder accounts for Cu-Al-Mn
The 11.8% of mixed powder gross mass, pure Mn powder account for the 2.4% of Cu-Al-Mn mixed powder gross mass, and pure Cu powder is matrix, and addition accounts for
The stearic acid of Cu-Al-Mn mixed powder gross mass 0.08% is additive, under protection of argon gas in ball milling 8 on planetary ball mill
Hour, the ratio of grinding media to material used in ball milling is 10: 1, and the revolving speed of ball mill is 300 revs/min, thus obtained Cu-Al-Mn prealloy
Change powder；
Second step, the preparation of green compact:
Cu-Al-Mn prealloyed powders made from the first step are uniformly mixed with the dehydrated alcohol for accounting for its quality 6%, then
It is uniformly mixed with the water NaCl particle that decrystallizes that average grain diameter is 0.2mm, the dosage for the water NaCl particle that decrystallizes accounts for Cu- for it
Al-Mn prealloyed powders and the 50% of the percent by volume for the water NaCl granulate mixture that decrystallizes, which is packed into
Compacting tool set is unidirectionally forced into 250MPa, and pressure maintaining 1 minute, and green compact are made；
Third step, sinter molding:
Green compact made from second step are placed in sintering furnace, 10Pa is evacuated to, are then charged with argon gas, and be warming up to 600
DEG C sintering 2 hours, be warming up to again later 785 DEG C be sintered 2 hours, be finally warming up to 970 DEG C be sintered 2 hours, cool to room with the furnace
The product of sinter molding is made in temperature；
4th step, porous copper-based shape memory alloy product are made:
The product of sinter molding made from third step, which is placed in 100 DEG C of boiling water, NaCl particle is remained in hole thoroughly boils
It removes, then places it in 60 DEG C of baking oven inside holdings 20 minutes, porous copper-based shape memory alloy product is made；
5th step, the heat treatment of porous copper-based shape memory alloy product:
Porous CuAlMn shape memory alloy made from 4th step is warming up to 850 DEG C and kept the temperature and puts into room temperature after sixty minutes
Quenching-in water, then with 8 DEG C/min of rate be warming up to again 320 DEG C and keep the temperature 12 minutes after put into room temperature water in, it is complete
At heat treatment, the porous CuAlMn shape memory alloy with good comprehensive performance is thus made.
Porous CuAlMn shape memory alloy product made from the present embodiment has through-hole structure, and mean porosities are
50.0%, average pore size 0.2mm.
Embodiment 2
The first step, the preparation of Cu-Al-Mn prealloyed powders:
It separately weighs the pure Cu powder of raw material, pure Al powder and pure Mn powder and carries out ingredient, wherein pure Al powder accounts for Cu-Al-Mn
The 11.9% of mixed powder gross mass, pure Mn powder account for the 2.5% of Cu-Al-Mn mixed powder gross mass, and pure Cu powder is matrix, and addition accounts for
The stearic acid of Cu-Al-Mn mixed powder gross mass 0.1% is additive, under protection of argon gas in ball milling 10 on planetary ball mill
Hour, for the ratio of grinding media to material used in ball milling for 10:1, the revolving speed of ball mill is 300 revs/min, and Cu-Al-Mn prealloy is thus made
Change powder；
Second step, the preparation of green compact:
Cu-Al-Mn prealloyed powders made from the first step are uniformly mixed with the dehydrated alcohol for accounting for its quality 7%, then
It is uniformly mixed with the water NaCl particle that decrystallizes that average grain diameter is 0.56mm, the dosage for the water NaCl particle that decrystallizes accounts for Cu- for it
Al-Mn prealloyed powders and the 60% of the percent by volume for the water NaCl granulate mixture that decrystallizes, which is packed into
Compacting tool set is unidirectionally forced into 280MPa, and pressure maintaining 2 minutes, and green compact are made；
Third step, sinter molding:
Green compact made from second step are placed in sintering furnace, 20Pa is evacuated to, are then charged with argon gas, and be warming up to 600
DEG C sintering 2 hours, be warming up to again later 790 DEG C be sintered 2 hours, be finally warming up to 975 DEG C be sintered 2 hours, cool to room with the furnace
The product of sinter molding is made in temperature；
4th step, porous copper-based shape memory alloy product are made:
The product of sinter molding made from third step, which is placed in 100 DEG C of boiling water, NaCl particle is remained in hole thoroughly boils
It removes, then places it in 60 DEG C of baking oven inside holdings 25 minutes, porous copper-based shape memory alloy product is made；
5th step, the heat treatment of porous copper-based shape memory alloy product:
Porous CuAlMn shape memory alloy made from 4th step is warming up to 850 DEG C and kept the temperature and puts into room temperature after sixty minutes
Quenching-in water, then with 9 DEG C/min of rate be warming up to again 340 DEG C and keep the temperature 15 minutes after put into room temperature water in, it is complete
At heat treatment, the porous CuAlMn shape memory alloy with good comprehensive performance is thus made.
Porous CuAlMn shape memory alloy product made from the present embodiment has through-hole structure, and mean porosities are
60.0%, average pore size 0.56mm.
Fig. 1 (d) display by measurement and calculates, and porosity made from the present embodiment is 60.3%, and average pore size is
The macro morphology photo of the porous CuAlMn shape memory alloy of 0.56mm；
Embodiment 3
Except the dosage for the water NaCl particle that in second step, decrystallizes accounts for Cu-Al-Mn prealloyed powders and the water that decrystallizes for it
Except the 65% of the percent by volume of NaCl granulate mixture, other are the same as embodiment 2.
Porous CuAlMn shape memory alloy product made from the present embodiment has through-hole structure, and mean porosities are
65.0%, average pore size 0.56mm.
Fig. 1 (a) shows that porosity made from the present embodiment is 65.0%, and average pore size is the porous C uAlMn of 0.56mm
The macro morphology photo of marmem；Fig. 1 (b) shows that the macro morphology of the cross section of product made from the present embodiment shines
Piece；Fig. 1 (c) shows the macro morphology photo in the vertical section of product made from the present embodiment；Fig. 2 shows hole made from the present embodiment
Gap rate 65%, average pore size 0.56mm porous CuAlMn shape memory alloy is through furnace is cold and the XRD spectrum of quenching state and scanning electricity
Mirror photo, in which: Fig. 2 (a) is XRD spectrum；Fig. 2 (b) is the cold Sample Scan electromicroscopic photograph of furnace；Fig. 2 (c) is qtenched sample scanning
Electromicroscopic photograph.Furnace cold conditions porous CuAlMn shape memory alloy is decomposed in annealing process due to β phase as seen from Figure 2,
To α and γ occur2Non-martensite phase.And be quenched after processing, porous CuAlMn shape memory alloy is only by martensite
Phase composition.It is met due to non-martensite and deteriorates the comprehensive performance of porous copper-based shape memory alloy, employed in the present invention
Heat treatment can effectively optimize the microstructure of porous CuAlMn shape memory alloy, to be conducive to the raising of its comprehensive performance.
Embodiment 4
Except the dosage for the water NaCl particle that in second step, decrystallizes accounts for Cu-Al-Mn prealloyed powders and the water that decrystallizes for it
Except the 70% of the percent by volume of NaCl granulate mixture, other are the same as embodiment 2.
Porous CuAlMn shape memory alloy product made from the present embodiment has through-hole structure, and mean porosities are
70.0%, average pore size 0.56mm.
Fig. 1 (e) display by measurement and calculates, and porosity made from the present embodiment is 70.1%, and average pore size is
The macro morphology photo of the porous CuAlMn shape memory alloy of 0.56mm.
Embodiment 5
Except in second step, uniformly mixed with the water NaCl particle that decrystallizes that average grain diameter is 0.93mm, decrystallize water NaCl
The dosage of particle accounts for the 65% of Cu-Al-Mn prealloyed powders and the percent by volume for the water NaCl granulate mixture that decrystallizes for it
Except, other are the same as embodiment 2.
Porous CuAlMn shape memory alloy product made from the present embodiment has through-hole structure, and mean porosities are
65.0%, average pore size 0.93mm.
Fig. 1 (f) display by measurement and calculates, and porosity made from the present embodiment is 65.5%, and average pore size is
The macro morphology photo of the porous CuAlMn shape memory alloy of 0.93mm；
Fig. 1 be using digital camera to porous CuAlMn shape memory alloy sample made from the embodiment of the present invention 2~5 into
Row observes resulting macro morphology photo.As Fig. 1 (a)~Fig. 1 (f) it is found that the porous C uAlMn shape as made from embodiment 2~5
Shape memory alloys are the space open cell network structure of three-dimensional perforation, the frame stability of sample, neat in edge, between alloying pellet
Good metallurgical bonding is formd, the hole in porous CuAlMn shape memory alloy product obtained replicates NaCl completely and makes
The graininess pattern of hole agent, and be evenly distributed in the base, to embody higher sintering quality.
Fig. 3 shows that different porosities made from embodiment 2~5 and different heat treatment state porous C uAlMn shape memory close
The quasistatic compression stress-strain curve of gold；
Fig. 4 (a) shows different porosities made from embodiment 2~5 and different heat treatment state porous C uAlMn shape note
Recall the energy-absorbing ability curve graph in the quasistatic compression performance chart of alloy；
Fig. 4 (b) shows different porosities made from embodiment 2~5 and different heat treatment state porous C uAlMn shape note
Recall the energy absorbing efficiency curve graph in the quasistatic compression performance chart of alloy.
Fig. 3, Fig. 4 (a) and Fig. 4's (b) the result shows that: porous CuAlMn shape memory alloy obtained by embodiment 2~5
Product shows certain toughness characteristics during compressive deformation；Curve longer low stress values plasticity platform area shows simultaneously
These products also have good compression energy absorption characteristics in addition to high damping properties.
Embodiment 6
The first step, the preparation of Cu-Al-Mn prealloyed powders:
It separately weighs the pure Cu powder of raw material, pure Al powder and pure Mn powder and carries out ingredient, wherein pure Al powder accounts for Cu-Al-Mn
The 12.0% of mixed powder gross mass, pure Mn powder account for the 2.6% of Cu-Al-Mn mixed powder gross mass, and pure Cu powder is matrix, and addition accounts for
The stearic acid of Cu-Al-Mn mixed powder gross mass 0.12% is additive, under protection of argon gas in ball milling 12 on planetary ball mill
Hour, the ratio of grinding media to material used in ball milling is 10: 1, and the revolving speed of ball mill is 300 revs/min, thus obtained Cu-Al-Mn prealloy
Change powder；
Second step, the preparation of green compact:
Cu-Al-Mn prealloyed powders made from the first step are uniformly mixed with the dehydrated alcohol for accounting for its quality 8%, then
It is uniformly mixed with the water NaCl particle that decrystallizes that average grain diameter is 1.0mm, the dosage for the water NaCl particle that decrystallizes accounts for Cu- for it
Al-Mn prealloyed powders and the 78% of the percent by volume for the water NaCl granulate mixture that decrystallizes, which is packed into
Compacting tool set is unidirectionally forced into 300MPa, and pressure maintaining 2 minutes, and green compact are made；
Third step, sinter molding:
Green compact made from second step are placed in sintering furnace, 60Pa is evacuated to, are then charged with argon gas, and be warming up to 610
DEG C sintering 2 hours, be warming up to again later 790 DEG C be sintered 2 hours, be finally warming up to 980 DEG C be sintered 2 hours, cool to room with the furnace
The product of sinter molding is made in temperature；
4th step, porous copper-based shape memory alloy product are made:
The product of sinter molding made from third step, which is placed in 100 DEG C of boiling water, NaCl particle is remained in hole thoroughly boils
It removes, then places it in 60 DEG C of baking oven inside holdings 25 minutes, porous copper-based shape memory alloy product is made；
5th step, the heat treatment of porous copper-based shape memory alloy product:
Porous CuAlMn shape memory alloy made from 4th step is warming up to 880 DEG C and kept the temperature and puts into room temperature after sixty minutes
Quenching-in water, then with 9 DEG C/min of rate be warming up to again 340 DEG C and keep the temperature 16 minutes after put into room temperature water in, it is complete
At heat treatment, the porous CuAlMn shape memory alloy with good comprehensive performance is thus made.
Porous CuAlMn shape memory alloy product made from the present embodiment has through-hole structure, and mean porosities are
78.0%, average pore size 1.0mm.
Embodiment 7
The first step, the preparation of Cu-Al-Mn prealloyed powders:
It separately weighs the pure Cu powder of raw material, pure Al powder and pure Mn powder and carries out ingredient, wherein pure Al powder accounts for Cu-Al-Mn
The 12.0% of mixed powder gross mass, pure Mn powder account for the 2.6% of Cu-Al-Mn mixed powder gross mass, and pure Cu powder is matrix, and addition accounts for
The stearic acid of Cu-Al-Mn mixed powder gross mass 0.12% is additive, under protection of argon gas in ball milling 12 on planetary ball mill
Hour, the ratio of grinding media to material used in ball milling is 10: 1, and the revolving speed of ball mill is 300 revs/min, thus obtained Cu-Al-Mn prealloy
Change powder；
Second step, the preparation of green compact:
Cu-Al-Mn prealloyed powders made from the first step are uniformly mixed with the dehydrated alcohol for accounting for its quality 8%, then
It is uniformly mixed with the water NaCl particle that decrystallizes that average grain diameter is 1.5mm, the dosage for the water NaCl particle that decrystallizes accounts for Cu- for it
Al-Mn prealloyed powders and the 80% of the percent by volume for the water NaCl granulate mixture that decrystallizes, which is packed into
Compacting tool set is unidirectionally forced into 320MPa, and pressure maintaining 3 minutes, and green compact are made；
Third step, sinter molding:
Green compact made from second step are placed in sintering furnace, 100Pa is evacuated to, are then charged with argon gas, and be warming up to 620
DEG C sintering 2 hours, be warming up to again later 795 DEG C be sintered 2 hours, be finally warming up to 980 DEG C be sintered 2 hours, cool to room with the furnace
The product of sinter molding is made in temperature；
4th step, porous copper-based shape memory alloy product are made:
The product of sinter molding made from third step, which is placed in 100 DEG C of boiling water, NaCl particle is remained in hole thoroughly boils
It removes, then places it in 60 DEG C of baking oven inside holdings 30 minutes, porous copper-based shape memory alloy product is made；
5th step, the heat treatment of porous copper-based shape memory alloy product:
Porous CuAlMn shape memory alloy made from 4th step is warming up to 900 DEG C and kept the temperature and puts into room temperature after sixty minutes
Quenching-in water, then with 10 DEG C/min of rate be warming up to again 350 DEG C and keep the temperature 18 minutes after put into room temperature water in,
Heat treatment is completed, the porous CuAlMn shape memory alloy with good comprehensive performance is thus made.
Porous CuAlMn shape memory alloy product made from the present embodiment has through-hole structure, and mean porosities are
80.0%, average pore size 1.5mm.
In above-described embodiment it is raw materials used be it is commercially available, technique and equipment are well-known in the art.
Claims (2)
1. a kind of preparation method of porous copper-based shape memory alloy, it is characterised in that: PM technique is used, with original gold
Belong to pure Cu powder, pure Al powder and pure Mn powder raw material and carries out Cu-Al-Mn prealloyed powders made from ingredient as basis material, specifically
Steps are as follows:
The first step, the preparation of Cu-Al-Mn prealloyed powders:
It separately weighs the pure Cu powder of raw material, pure Al powder and pure Mn powder and carries out ingredient, wherein pure Al powder accounts for Cu-Al-Mn mixing
The 11.8~12.0% of powder gross mass, pure Mn powder account for the 2.4~2.6% of Cu-Al-Mn mixed powder gross mass, and pure Cu powder is matrix,
Being added and accounting for the stearic acid of Cu-Al-Mn mixed powder gross mass 0.08~0.12% is additive, under protection of argon gas in planetary ball
Ball milling 8~12 hours on grinding machine, for the ratio of grinding media to material used in ball milling for 10: 1, the revolving speed of ball mill is 300 revs/min, is thus made
Obtain Cu-Al-Mn prealloyed powders；
Second step, the preparation of green compact:
Cu-Al-Mn prealloyed powders made from the first step are uniformly mixed with the dehydrated alcohol for accounting for its quality 6~8%, then with
Average grain diameter is that the water NaCl particle that decrystallizes of 0.2~1.5mm uniformly mixes, and is obtained a homogeneous mixture, wherein the water that decrystallizes
The dosage of NaCl particle accounts for Cu-Al-Mn prealloyed powders and the percent by volume for the water NaCl granulate mixture that decrystallizes for it
50~80%, which is packed into compacting tool set, is unidirectionally forced into 250~320MPa, and pressure maintaining 1~3 minute, is made
Green compact；
Third step, sinter molding:
Green compact made from second step are placed in sintering furnace, 10~100Pa is evacuated to, are then charged with argon gas, and be warming up to 600
~620 DEG C are sintered 2 hours, are warming up to 785~795 DEG C again later and are sintered 2 hours, and it is small to be finally warming up to 970~980 DEG C of sintering 2
When, it cools to room temperature with the furnace, the intermediate product of sinter molding is made；
4th step, porous copper-based shape memory alloy product are made:
The intermediate product of sinter molding made from third step, which is placed in 100 DEG C of boiling water, NaCl particle is remained in hole thoroughly boils
It removes, then places it in 60 DEG C of baking oven inside holdings 20~30 minutes, porous copper-based shape memory alloy product, product tool is made
There is through-hole structure, mean porosities are 50~80%, and average pore size is 0.2~1.5mm.
2. a kind of preparation method of porous copper-based shape memory alloy according to claim 1, it is characterised in that: the described 4th
The porous CuAlMn shape memory alloy product obtained heat treatment following by further progress in step: will be obtained porous
CuAlMn marmem product be warming up to 850~900 DEG C and keep the temperature after sixty minutes put into room temperature quenching-in water, then with
8~10 DEG C/min of rate is warming up to 320~350 DEG C again and puts into the water of room temperature after keeping the temperature 12~18 minutes, completes heat
Processing.
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| CN107916348B (en) * | 2017-12-02 | 2019-05-14 | 河北工业大学 | The preparation method of fine grain CuAlMn marmem |
| CN108193140B (en) * | 2017-12-29 | 2020-07-07 | 盐城工学院 | Application of porous iron-based shape memory alloy in field of friction materials |
| CN108359827B (en) * | 2018-02-01 | 2019-08-23 | 上海交通大学 | The preparation method of the porous antiferromagnetic marmem of MnNi |
| CN108504901A (en) * | 2018-04-02 | 2018-09-07 | 苏州诺弘添恒材料科技有限公司 | A kind of preparation method of titanium nickel cobalt memorial alloy body |
| CN108677047A (en) * | 2018-05-19 | 2018-10-19 | 西安科技大学 | A kind of preparation method of porous copper-based shape memory alloy |
| CN109022877B (en) * | 2018-09-11 | 2020-11-20 | 广东美的制冷设备有限公司 | Foam alloy for noise reduction and noise reduction of air conditioner and preparation method and application thereof |
| CN109022876B (en) * | 2018-09-11 | 2020-12-22 | 广东美的制冷设备有限公司 | Foam alloy for noise reduction and noise reduction of air conditioner and preparation method and application thereof |
| CN109277571B (en) * | 2018-09-25 | 2020-11-06 | 中南大学 | Copper-aluminum-manganese alloy/polymer/carbon nanotube damping material and preparation method thereof |
| CN113454252B (en) * | 2019-03-28 | 2022-06-24 | 古河电气工业株式会社 | Copper alloy strip, method for producing same, resistance material for resistor using same, and resistor |
| CN110788340B (en) * | 2019-11-13 | 2021-11-16 | 中南大学 | Preparation method of 4D printing copper-based shape memory alloy and 4D printing copper-based shape memory alloy |
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