CN109822095A - Shape memory alloy particles enhance Cu-base composites and preparation method - Google Patents
Shape memory alloy particles enhance Cu-base composites and preparation method Download PDFInfo
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Abstract
The present invention provides a kind of shape memory alloy particles enhancing Cu-base composites and preparation method, is prepared from the following steps step 1: the shape memory alloy particles and copper powder particle of selection micron order < 100 μm;Step 2: by shape memory alloy particles and mixed-powder is obtained in copper powder particle mechanical mixture 20~80 minutes;Step 3: mixed-powder is placed in graphite jig and obtains shape memory alloy particles enhancing Cu-base composites using discharge plasma sintering process.Shape memory alloy particles enhancing Cu-base composites intensity compared with fine copper of the invention is significantly improved, while keeping and large plastometric set similar in fine copper;Shape memory alloy particles, which enhance Cu-base composites, has martensitic traoformation characteristic;The preparation method of shape memory alloy particles enhancing Cu-base composites has the advantages that sintering time is short, sintering temperature is low, sintering process can pressurize compared with pressureless sintering method, can be substantially reduced interfacial reaction and improve production efficiency.
Description
Technical field
The present invention relates to a kind of composite material and preparation method more particularly to a kind of enhancing of shape memory alloy particles are copper-based
Composite material and preparation method.
Background technique
Marmem (Shape memory alloy, SMA) has unique shape memory effect and super-elasticity,
The every field such as aerospace, instrument, temperature control, medical treatment, artificial satellite have a wide range of applications.Wherein using NiTi alloy as representative
Marmem due to good shape memory effect, super-elasticity, mechanical performance and corrosion resistance, always in shape
Shape memory alloys occupy leading position in field.In cooling and temperature-rise period thermo elastic martensite phase occurs respectively for NiTi alloy
Become (austenite → martensite) and reverse transformation (martensite → austenite), this is alloy shape memory effect and hyperelastic base
Plinth, martensite and austenite have different elasticity modulus, intensity and hardness, this is the application of same material at different temperatures
Provide the flexibility in design.By heating the shape note that martensite → austenite reverse transformation is realized occurs for NiTi alloy at present
Recalling effect still is such main functional characteristic of alloy.But since phase transition process is controlled by temperature, NiTi alloy is caused to ring
The frequency answered is low (~Hz), is unfavorable for practical application.In addition, such alloy is expensive, application cost is high and difficulty of processing
Greatly, therefore researchers at home and abroad propose matrix material NiTi alloy is low with some application costs, easy to process, thermal conductivity is good
Material progress is compound, is solved these problems by preparing the method for composite material.
In previous report, the composite material of NiTi alloy wire and resin gets the attention and studies, research hair
Existing, since resin matrix and NiTi alloy interface are combined into physical bond, interface cohesion is poor, influences to a certain extent
The transmitting of stress and strain between NiTi alloy and matrix, furthermore the thermal conductivity of resin is poor, so that material can not be effectively improved
The response frequency of material.Compared with resin, certain chemical reaction can occur for metallic matrix and NiTi alloy, and interface cohesion more holds
Easy-regulating.Therefore, metal material is prepared metal-base composites as matrix is that current NiTi alloy composite materials develop
One important directions.Have at present and NiTi alloy wire and aluminium alloy, magnesium alloy or titanium alloy-based bluk recombination are prepared into composite wood
The report of material, the results showed that certain interfacial reaction can occur with metallic matrix for NiTi alloy, to improve the stress at interface
It is transmitted with strain, improves the performance of composite material.But due to preparing composite material using NiTi alloy wire, lead to composite wood
There are strong anisotropy for material.If asked using the anisotropic that NiTi particle preparation composite material can effectively solve material
Topic, the report of NiTi particulate composite is less at present, the predominantly metallic aluminium that matrix is selected.Compared with aluminium, copper has more preferable
Thermal conductivity, conductivity and processing performance.Therefore the present invention proposes NiTi particle and metallic copper is compound, using powder metallurgic method
Composite material is prepared, the heating conduction and processing performance of composite material are improved by copper, utilizes NiTi particle enhanced copper matrix
Mechanical strength, while assigning composite material martensitic traoformation characteristic.We used pressureless sintering method (cold pressing+high temperature sintering) in the past
It is prepared for magnetic memorial alloy Particles/Cu composite material, the study found that the method is since sintering temperature is high, sintering time is long, burns
Can not pressurize during knot, cause magnetic memorial alloy particle and basal body interface strong reaction, composite material mesoporous hole defect compared with
The problems such as more.Therefore the present invention is proposed using sintering temperature is low, sintering time is short, sintering process can apply stressed electric discharge etc.
Gas ions sintering method (SPS) prepares NiTi granule reinforced copper base composite material.
Summary of the invention
The purpose of the invention is to provide a kind of shape memory with martensitic traoformation characteristic, high intensity and big plasticity
Alloying pellet enhances Cu-base composites and preparation method.
The object of the present invention is achieved like this:
A kind of shape memory alloy particles enhancing Cu-base composites, are prepared from the following steps:
Step 1: the shape memory alloy particles and copper powder particle of selection micron order < 100 μm;
Step 2: by shape memory alloy particles and mixed-powder is obtained in copper powder particle mechanical mixture 20~80 minutes;
Step 3: mixed-powder is placed in graphite jig and obtains marmem using discharge plasma sintering process
Granule reinforced copper base composite material.
The invention also includes features some in this way:
1. the mass fraction of the shape memory alloy particles is 10~60%;
2. the marmem is NiTi alloy, the shape memory alloy particles and copper powder particle are atomization molding
Spherical;
3. the reaction temperature of the discharge plasma sintering process is 700~850 DEG C, pressure is 40~60MPa, time
Wie5~10min.
A kind of preparation method of shape memory alloy particles enhancing Cu-base composites, includes the following steps:
Step 1: the shape memory alloy particles and copper powder particle of selection micron order < 100 μm;
Step 2: by shape memory alloy particles and mixed-powder is obtained in copper powder particle mechanical mixture 20~80 minutes;
Step 3: mixed-powder is placed in graphite jig and obtains marmem using discharge plasma sintering process
Granule reinforced copper base composite material.
The mass fraction of the shape memory alloy particles is 10~60%;
The marmem is NiTi alloy, and the shape memory alloy particles and copper powder particle are that atomization is molding
Spheric granules;
The reaction temperature of the discharge plasma sintering process is 700~850 DEG C, pressure is 40~60MPa, time Wie5
~10min.
Compared with prior art, the beneficial effects of the present invention are:
(1) shape memory alloy particles of the invention enhancing Cu-base composites intensity compared with fine copper is significantly mentioned
Height, while keeping and large plastometric set similar in fine copper.
(2) shape memory alloy particles of the invention enhancing Cu-base composites have martensitic traoformation characteristic.
(3) preparation method of shape memory alloy particles of the invention enhancing Cu-base composites is compared with pressureless sintering method
Have the advantages that sintering time is short, sintering temperature is low, sintering process can pressurize, interfacial reaction can be substantially reduced and improve life
Produce efficiency.
Detailed description of the invention
Fig. 1 is the preparation of NiTi particle/Cu composite material and performance characterization schematic diagram;
Fig. 2 is different content NiTi particle/Cu composite material stereoscan photograph: (a) being sintered pure Cu, (b) 20% content
Composite material, (c) 30% content composite material, (d) 40% content composite material, (e) 40% content composite material (corrosion NiTi
Particle), (f) 40% content composite material (corrosion Cu matrix);
Fig. 3 is different content NiTi particle/Cu composite material (20%, 30% and 40%) and NiTi particle room temperature XRD
Diffracting spectrum;
Fig. 4 is that different content NiTi particle/Cu composite material (20%, 30% and 40%) and the compression stress-of pure Cu are answered
Varied curve;
Fig. 5 is different content NiTi particle/Cu composite material (20%, 30% and 40%) and NiTi particle DSC curve.
Specific embodiment
Present invention is further described in detail with specific embodiment with reference to the accompanying drawing.
A kind of shape memory alloy particles enhancing Cu-base composites and preparation method, (1) select micron order (< 100 μm)
Shape memory alloy particles and copper powder particle;(2) mass fraction of shape memory alloy particles is selected as 10~60%;(3) will
Shape memory alloy particles and 20~80min of copper powder particle mechanical mixture;(4) uniformly mixed powder is placed in graphite jig
It is sintered 5~10min under 700~850 DEG C, 40~60MPa using the method that discharge plasma is sintered, obtains shape memory conjunction
Gold particle enhances Cu-base composites;The marmem selected in the step (1) is NiTi alloy;The step (1)
The shape memory alloy particles and copper powder particle of middle selection are to be atomized molding spheric granules;Composite material in the step (4)
Preparation process be discharge plasma sintering process;The enhancing of shape memory alloy particles obtained in the step (4) is copper-based multiple
Condensation material has martensitic traoformation characteristic.
The purpose of the present invention is to provide a kind of, and the shape memory with martensitic traoformation characteristic, high intensity and big plasticity closes
Gold particle enhances Cu-base composites.The shape memory alloy particles that a kind of sintering temperature is low, sintering time is short are also provided simultaneously
Enhance the preparation method of Cu-base composites.
(1) atomization spherical shape Cu powder of the particle size less than 50 microns is selected;
(2) atomization spherical Ni of the particle size less than 100 microns is selected50Ti50Powder;
(3) Cu powder is mixed 30 minutes with NiTi particle using high speed vibration ball mill (1400 revs/min of revolving speed) and is obtained
Mixed-powder, the mass fraction of NiTi particle are respectively 20%, 30% and 40%;
(4) mixed-powder of Cu powder and NiTi particle is placed in graphite jig, using discharge plasma sintering furnace in
800 DEG C, 40MPa be sintered 5min under vacuum conditions, obtain NiTi particle/Cu composite material.In order to be sintered pure Cu bulk into
Row comparison prepares Cu bulk using identical sintering method.Composite material preparation flow is as shown in Figure 1.
(5) microstructure picture of pure Cu and NiTi particle/Cu composite material, such as Fig. 2 are sintered by scanning electron microscopic observation
It is shown.The tissue of the composite material of pure Cu and 20%, 30%, 40% after wherein Fig. 2 (a), (b), (c), (d) are respectively polished shines
Piece.Since the corrosive liquid of NiTi with Cu microscopic structure imaging is different, we are to NiTi and Cu in same composite material
Matrix is utilized respectively hydrofluoric acid nitric acid solution and iron chloride ethanol solution is corroded, and Fig. 2 (e), (f) are respectively 40% composite wood
Microstructure picture in material after NiTi particle and Cu matrix corrosion.From Fig. 2 (a) as can be seen that the Cu prepared using SPS sintering
The microscopic structure of bulk is finer and close, the Cu bulk that sintering pore quantity is prepared before being considerably less than using pressureless sintering method.From
Fig. 2 (b), (c), (d) are distributed in Cu matrix in which can be seen that dark NiTi spheric granules more disperse, with NiTi
Grain content increases, and still more uniformly, local agglomeration tendency is smaller for distribution of particles.From Fig. 2 (e) it can be found that NiTi particle passes through
It can be observed that partial martensite lath structure, illustrating NiTi particle, there are partial martensite phases in room temperature after excessive erosion.Fig. 2
It (f) is the microphoto after corrosion Cu matrix, there it can be seen that NiTi particle microscopic structure is unobvious, but can be obvious
Observe the grain structure and crystal boundary of Cu matrix.In addition, it is observed that NiTi particle and Cu matrix are sent out from two photos
Given birth to interfacial reaction, interfacial reaction layer is as shown by arrows in figure, there it can be seen that NiTi particle had occurred with Cu matrix it is weaker
Interfacial reaction, the performance of NiTi particle will not be destroyed, shown through low temperature, SPS sintering method can be controlled effectively in short-term
Interfacial reaction between grain and matrix.
(6) using the object phase composition of X-ray diffractometer test composite material, as shown in figure 3, sintering is given in figure simultaneously
The diffracting spectrum of Cu bulk, NiTi particle and different content composite material, it can be seen from the figure that composite material mainly by Cu and
The diffraction maximum of NiTi particle forms, and the diffraction maximum of interfacial reaction phase is not observed, illustrates that the content of interfacial reaction phase is lower, this
It is consistent with the SEM of front observation result.
(7) using the compressive stress strain curve of universal electrical Material Testing Machine test composite material, as shown in figure 4, pure
Cu has big plasticity in compression process, and being compressed into flake will not be broken.After NiTi Particles dispersed, with
NiTi granule content increases, and the yield strength and elasticity modulus of composite material significantly improve, this is mainly NiTi particle to Cu base
Caused by the invigoration effect of body.Compression verification discovery, for 20% and 30% content composite material, does not also send out in compression process
Raw fracture shows the big plasticity similar with pure Cu, but when content increases to 40%, composite material occurs after flexible deformation
Stress bust is observed that crackle from compression sample, but further there is no along initial for composite material in loading procedure
Crackle continues extension and is broken, but continuous plastic deformation occurs with load is continued, therefore analyze, and initial crack generation can
The part reunion occurred after capable of improving with NiTi granule content is related, preferentially cracks in local reunion position, but crackle
Obstruction in expansion process by other diffusing particles continues to show to contain with low in loading procedure to can not continue to extend
Measure the similar plastic deformation of composite material.Therefore, it can be obtained after NiTi particle and Cu matrix are compound and have both high-intensitive and big modeling
The composite material of property.
(8) the martensitic traoformation row of differential scanning calorimetric analysis instrument test different content composite material and NiTi particle is utilized
For as shown in Figure 5.It can be seen from the figure that NiTi particle has multistep martensitic traoformation feature, and reverse transformation shows as a step
Phase transformation.With Cu it is compound after, the martensitic phase of material, which becomes apparent, to die down, and this is mainly due to NiTi granule contents in composite material
Few, phase transformation peak caused by latent heat of phase change is smaller dies down.In addition, composite material only shows a step geneva compared with NiTi particle
Body phase transformation and reverse transformation, and phase transition temperature reduces, and this may be related with constraint of the Cu matrix to NiTi particle transformation behavior, Cu
The constraint of matrix causes particle that martensitic traoformation occurs in the composite to become difficult, so as to cause phase transition temperature reduction.
In summary: the present invention is to provide a kind of shape memory alloy particles enhancing Cu-base composites and preparation sides
Method.(1) micron order (< 100 μm) shape memory alloy particles and copper powder particle are selected;(2) quality of shape memory alloy particles
Score is selected as 10~60%;(3) by shape memory alloy particles and copper powder particle mechanical mixture 20~80 minutes;(4) it will mix
Uniform powder is closed to be placed in graphite jig using the method for discharge plasma sintering under 700~850 DEG C, 40~60MPa
It is sintered 5~10min, obtains shape memory alloy particles enhancing Cu-base composites.Cu-base composites of the invention have horse
Family name's body phase-change characteristic, good intensity and ductility, the preparation process of the composite material is high-efficient, favorable repeatability, is suitble to criticize
Amount production.
Claims (10)
1. a kind of shape memory alloy particles enhance Cu-base composites, characterized in that be prepared from the following steps:
Step 1: the shape memory alloy particles and copper powder particle of selection micron order < 100 μm;
Step 2: by shape memory alloy particles and mixed-powder is obtained in copper powder particle mechanical mixture 20~80 minutes;
Step 3: mixed-powder is placed in graphite jig and obtains shape memory alloy particles using discharge plasma sintering process
Enhance Cu-base composites.
2. shape memory alloy particles according to claim 1 enhance Cu-base composites, characterized in that the shape note
The mass fraction for recalling alloying pellet is 10~60%.
3. shape memory alloy particles according to claim 1 or 2 enhance Cu-base composites, characterized in that the shape
Shape memory alloys are NiTi alloy, and the shape memory alloy particles and copper powder particle are to be atomized molding spheric granules.
4. shape memory alloy particles according to claim 1 or 2 enhance Cu-base composites, characterized in that described to put
The reaction temperature of electro-plasma sintering process is 700~850 DEG C, pressure is 40~60MPa, time Wie5~10min.
5. shape memory alloy particles according to claim 3 enhance Cu-base composites, characterized in that described electric discharge etc.
The reaction temperature of gas ions sintering process is 700~850 DEG C, pressure is 40~60MPa, time Wie5~10min.
6. a kind of preparation method of shape memory alloy particles enhancing Cu-base composites, characterized in that include the following steps:
Step 1: the shape memory alloy particles and copper powder particle of selection micron order < 100 μm;
Step 2: by shape memory alloy particles and mixed-powder is obtained in copper powder particle mechanical mixture 20~80 minutes;
Step 3: mixed-powder is placed in graphite jig and obtains shape memory alloy particles using discharge plasma sintering process
Enhance Cu-base composites.
7. the preparation method of shape memory alloy particles enhancing Cu-base composites according to claim 6, characterized in that
The mass fraction of the shape memory alloy particles is 10~60%.
8. shape memory alloy particles according to claim 6 or 7 enhance Cu-base composites, characterized in that the shape
Shape memory alloys are NiTi alloy, and the shape memory alloy particles and copper powder particle are to be atomized molding spheric granules.
9. shape memory alloy particles according to claim 6 or 7 enhance Cu-base composites, characterized in that described to put
The reaction temperature of electro-plasma sintering process is 700~850 DEG C, pressure is 40~60MPa, time Wie5~10min.
10. shape memory alloy particles according to claim 8 enhance Cu-base composites, characterized in that the electric discharge
The reaction temperature of plasma sintering method is 700~850 DEG C, pressure is 40~60MPa, time Wie5~10min.
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Cited By (5)
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CN110499437A (en) * | 2019-09-25 | 2019-11-26 | 哈尔滨工程大学 | A kind of nickel manganese gallium/carbon/carbon-copper composite material and preparation method |
CN112176217A (en) * | 2020-10-28 | 2021-01-05 | 江西勇骏实业有限公司 | High-strength copper alloy and preparation method thereof |
CN112760511A (en) * | 2020-12-24 | 2021-05-07 | 先导薄膜材料(广东)有限公司 | Preparation method of titanium-nickel-palladium alloy |
WO2023226166A1 (en) * | 2022-05-23 | 2023-11-30 | 上海交通大学 | Preparation method for aluminum-based composite material reinforced with shape memory ceramic and having adjustable austenite content |
CN118207483A (en) * | 2024-04-30 | 2024-06-18 | 广州航海学院 | Fe-Mn-Si based memory alloy material, preparation method and application |
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CN110499437A (en) * | 2019-09-25 | 2019-11-26 | 哈尔滨工程大学 | A kind of nickel manganese gallium/carbon/carbon-copper composite material and preparation method |
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WO2023226166A1 (en) * | 2022-05-23 | 2023-11-30 | 上海交通大学 | Preparation method for aluminum-based composite material reinforced with shape memory ceramic and having adjustable austenite content |
CN118207483A (en) * | 2024-04-30 | 2024-06-18 | 广州航海学院 | Fe-Mn-Si based memory alloy material, preparation method and application |
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