CN110983152A - Fe-Mn-Si-Cr-Ni based shape memory alloy and preparation method thereof - Google Patents
Fe-Mn-Si-Cr-Ni based shape memory alloy and preparation method thereof Download PDFInfo
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- 229910001285 shape-memory alloy Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 88
- 238000005245 sintering Methods 0.000 claims abstract description 50
- 238000000498 ball milling Methods 0.000 claims abstract description 45
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000011812 mixed powder Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
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- 229910052742 iron Inorganic materials 0.000 claims description 13
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- 229910052804 chromium Inorganic materials 0.000 claims description 10
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- 239000002245 particle Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
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- 230000003446 memory effect Effects 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 27
- 238000002490 spark plasma sintering Methods 0.000 description 21
- 239000011572 manganese Substances 0.000 description 20
- 239000010935 stainless steel Substances 0.000 description 16
- 229910001220 stainless steel Inorganic materials 0.000 description 16
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
-
- 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
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- 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
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
-
- 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
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
Abstract
The invention discloses a Fe-Mn-Si-Cr-Ni-based shape memory alloy and a preparation method thereof, belonging to the technical field of composite materials. The raw materials comprise 12-30 wt.% of Mn powder, 3-6 wt.% of Si powder, 0-12 wt.% of Cr powder, 0-6 wt.% of Ni powder and the balance of Fe powder. During preparation, the Fe powder, the Mn powder, the Si powder, the Cr powder and the Ni powder are subjected to ball milling and mixing, then prepressing is carried out, then the prepressed sample is subjected to discharge plasma (SPS) sintering, the sintering pressure is 20-50 MPa, the sintering temperature is 800-1000 ℃, the temperature is kept for 5-60 min, and then the temperature is reduced and the pressure is relieved, so that the Fe-Mn-Si-Cr-Ni-based shape memory alloy is prepared. The Fe-Mn-Si-Cr-Ni-based alloy has good mechanical property and shape memory effect.
Description
Technical Field
The invention belongs to the technical field of composite materials, and relates to a Fe-Mn-Si-Cr-Ni-based shape memory alloy and a preparation method thereof.
Background
At present, the traditional smelting casting process is mostly adopted for preparing the Fe-based shape memory alloy, particularly the five-element Fe-Mn-Si-Cr-Ni shape memory alloy, although the method is simple, the burning loss and volatilization of alloy elements in the smelting process and the refractory property of Si elements often make the components difficult to control, and the plasticity of the alloy is poor and the cold working is difficult due to time-consuming homogenization treatment, cracks caused by cooling shrinkage in the solidification and quenching processes, tempering embrittlement and the like, so that the engineering application of the alloy is limited. The powder metallurgy principle can well avoid the defects, can accurately control the alloy components, reduce component segregation, increase the solid solubility of the alloy elements in the Fe matrix, and simultaneously avoid the formation of oxides, and has lower energy consumption and pollution in the production process. The produced workpiece has high dimensional precision, does not need or rarely needs subsequent machining, saves metal and reduces cost. Mechanical alloying is one of the techniques used to obtain alloy powders, which can produce nanoscale structures and non-equilibrium phases, thereby improving material properties.
Sintering in the powder metallurgy process is a key process and plays a decisive role in the performance and quality of products. At present, some research on sintering processes has been carried out in the literature. The Cu-A1-Ni memory alloy prepared by the method of mechanical alloying and powder metallurgy has the shape memory recovery rate of 63 percent, but the alloy prepared by the method has sintering holes in the sintering process because the powder particles are in mechanical mosaic occlusion, so the memory effect of the alloy is quickly attenuated. How to realize high-density metallurgical bonding between powder bodies of materials prepared by a mechanical alloying method is to overcome the problemBy the reaction on Al2O3Research on dispersion strengthened copper alloy shows that the key to realizing high-density metallurgical bonding is the hot extrusion after vacuum sintering [ Li Wen, Wangmingpu, Tan Wang, and so on]Discussion of the fifth Haixia powder metallurgy technology workshop, 2004.]. Creep and other researches on the preparation of Fe-17Mn-6Si-0.03C iron-based shape memory alloy by a powder metallurgy method show that the suitable pressing pressure of an experimental alloy pressed compact is 400-500 MPa, when the heat preservation time is the same, the atom diffusion capacity is enhanced along with the increase of the sintering temperature, the forming and growing speed of a sintering neck is accelerated, the metallurgical bonding surfaces among particles are increased, the grain components tend to be homogenized, and the pores tend to be reduced and spheroidized. In the sample sintered at 1100 ℃ and 1150 ℃ (the sintering time is 1h), the matrix structure of the alloy is austenite, certain pores and inclusions exist among austenite grains because a powder metallurgy sintered body is usually a porous structure, and after the sample is sintered at 1100 ℃, the distribution of iron, manganese and silicon in the sample is still not uniform, which indicates that the sintering temperature is low. After the sample is sintered at 1150 ℃, crystal grains grow up, and the distribution of iron, manganese and silicon in austenite crystal grains is relatively uniform. The case of the 1200 c sintered sample is substantially close to that at 1150 c. But when the sintering temperature reaches 1250 ℃, the crystal grains in the alloy obviously grow and the performance is also reduced. Therefore, the sintering temperature suitable for the experimental alloy should be 1150-1200 ℃ [ creep flight, stretch frame, bin, and so on]Technical innovation report, 2009(35):101.]。
Spark Plasma Sintering (SPS) has the advantages of fast temperature rise rate, low sintering temperature, short densification time, and the like, and is widely applied to the preparation of various materials, such as pure metals, alloys, intermetallic compounds, ceramic materials and various composite materials. But the research on preparing Fe-Mn-Si-based shape memory alloy by SPS sintering is less, and a general rule is not obtained yet.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a Fe-Mn-Si-Cr-Ni-based shape memory alloy and a preparation method thereof. And (2) performing discharge plasma (SPS) sintering on the mixture of the Fe powder, the Mn powder, the Si powder, the Cr powder and the Ni powder after mixing to prepare the Fe-Mn-Si-Cr-Ni-based shape memory alloy which has good mechanical property and shape memory effect.
The invention adopts the following technical scheme: the Fe-Mn-Si-Cr-Ni based shape memory alloy comprises high-purity Fe, Mn, Si, Cr and Ni element powder, wherein the raw materials of the Fe-Mn-Si-Cr-Ni based shape memory alloy comprise the following chemical components in percentage by mass: 12-30 wt.% of Mn powder, 3-6 wt.% of Si powder, 0-12 wt.% of Cr powder, 0-6 wt.% of Ni powder and the balance of Fe powder.
Preferably, the purity of the Fe powder is more than 99%, and the particle size is 44-149 mu m.
Preferably, the purity of the Mn powder is more than 99.5, and the particle size is 44-149 mu m.
Preferably, the purity of the Si powder is more than 99.999 percent, and the granularity is 37-149 mu m.
Preferably, the Cr powder has a purity of > 99.5% and a particle size of 5 μm.
Preferably, the purity of the Ni powder is more than 99.9%, and the particle size is 1-3 μm.
Preferably, high-purity Fe, Mn, Si, Cr, and Ni element powders are mixed by a mechanical alloying method, and the grain size of the five high-purity Fe, Mn, Si, Cr, and Ni element mixed powders after the mechanical alloying is 150nm or less.
The preparation method of the Fe-Mn-Si-Cr-Ni-based shape memory alloy comprises the following steps:
s1, mixing and ball-milling raw material powder of Fe, Mn, Si, Cr and Ni according to a preset mass percentage, wherein the mass ratio of balls to materials is 10: 1-20: 1, 0.2-0.5 mL of dispersing agent is added into each 10g of raw material powder, the rotating speed is 300-600 r/min, ball-milling is carried out for 20-90 h, intermittent ball-milling is adopted, namely 30min is stopped after each ball-milling is carried out for 60min, and the operation is alternately carried out to prepare fine mixed powder with the particle size of 150 nm.
S2, putting the mixed powder obtained in the step S1 into a pre-pressing machine, pre-pressing for 10-30S at 300-500 MPa, then performing discharge plasma (SPS) sintering on the pre-pressed sample at 20-50 MPa at 800-1000 ℃ for 5-60 min, and then cooling and releasing pressure to obtain the Fe-Mn-Si-Cr-Ni-based shape memory alloy.
Preferably, the dispersing agent is industrial ethanol with analytical purity of more than or equal to 99.7%, and 0.2-0.5 mL of dispersing agent is added into every 10g of raw material powder. Preferably, the ball milling process of step S1 uses milling balls with a diameter of 10 mm.
Preferably, the specific sintering process in step S2 is: the vacuum degree is 10-40 Pa, the temperature is increased from room temperature to 800-1000 ℃ at the heating rate of 10-100 ℃/min, meanwhile, the pressure is slowly applied to the sintered body to 20-50 MPa, and the temperature is kept for 5-60 min. And cooling along with the furnace to obtain a blank.
Has the advantages that: the invention mixes high-purity Fe, Mn, Si, Cr and Ni element powder by a mechanical alloying method and prepares the Fe-Mn-Si-Cr-Ni-based shape memory alloy by Spark Plasma Sintering (SPS). The fine structure and the uniform mixture of Fe, Mn, Si, Cr and Ni element powder are obtained in a solid state by high-energy ball milling, the solid solubility of alloy elements in an iron matrix is increased, a non-equilibrium phase is synthesized, and then an austenite structure with uniform grains is obtained by SPS rapid heating sintering, so that the volatilization of the Mn element in the sintering process is effectively prevented, and the mechanical property and the shape memory effect of the alloy are greatly improved.
Drawings
FIG. 1 is an XRD pattern of Fe-20Mn-6Si-8Cr-5Ni powder after ball milling for various times for examples 1-15.
Detailed Description
The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
Exemplary embodiments, features and performance aspects of the present invention are described in detail below.
In the following examples, the purity of Fe powder is more than 99%, and the particle size is 44-149 μm; the purity of the Mn powder is more than 99.5, and the granularity is 44-149 mu m; the purity of the Si powder is more than 99.999 percent, and the granularity is 37-149 mu m; the purity of Cr powder is more than 99.5 percent, and the granularity is 5 mu m; the purity of the Ni powder is more than 99.9%, and the granularity is 1-3 mu m; the dispersant is industrial ethanol with analytical purity of more than or equal to 99.7 percent.
Example 1
S1, putting raw material powder consisting of Fe-20Mn-6Si-8Cr-5Ni (namely 20 wt.% of Mn powder, 6 wt.% of Si powder, 8 wt.% of Cr powder, 5 wt.% of Ni powder and the balance of Fe powder) in a stainless steel ball milling tank, adding industrial ethanol as a dispersing agent, adding 0.2-0.5 mL of dispersing agent into every 10g of powder, wherein the ball-material ratio is 20:1, a ball milling medium is a 10mm stainless steel ball, repeatedly washing gas in a glove box transition bin, putting the powder into an operation cavity of a ball mill, covering a sealing cover, taking out the powder in a tube under the argon environment, putting the powder into the ball mill, wherein the ball milling rotation speed is 400r/min, and performing intermittent ball milling, namely stopping 30min after each ball milling for 60min, alternately performing ball milling for 50h to prepare alloy powder.
S2, filling the mixed powder obtained in the step S1 into a hard alloy die for prepressing with the prepressing pressure of 400MPa for 20S, then putting the prepressed sample into a graphite die for Spark Plasma (SPS) sintering with the sintering pressure of 40MPa and the sintering temperature of 900 ℃, keeping the temperature for 30min, and then reducing the temperature and releasing the pressure to obtain the Fe-Mn-Si-Cr-Ni-based shape memory alloy.
Example 2
The mixed powder obtained in step S1 of example 1 is filled into a cemented carbide mold for prepressing at 400MPa for 20S, and then the prepressed sample is filled into a graphite mold for Spark Plasma (SPS) sintering at 950 ℃, 10 ℃/min for 30min at 40MPa, 10Pa vacuum, and then cooled for pressure relief to obtain the Fe-Mn-Si-Cr-Ni-based shape memory alloy.
Example 3
The mixed powder obtained in step S1 of example 1 is filled into a cemented carbide mold for prepressing at 400MPa for 20S, and then the prepressed sample is filled into a graphite mold for Spark Plasma (SPS) sintering at 950 ℃, 30 ℃/min for 60min at 40MPa, 20Pa vacuum, and then cooled for pressure relief to obtain the Fe-Mn-Si-Cr-Ni-based shape memory alloy.
Example 4
The mixed powder obtained in step S1 of example 1 is filled into a cemented carbide mold for prepressing at 400MPa for 20S, and then the prepressed sample is filled into a graphite mold for Spark Plasma (SPS) sintering at 1000 ℃, 50 ℃/min for 30min at 40MPa, 30Pa vacuum, and then cooled for pressure relief to obtain the Fe-Mn-Si-Cr-Ni-based shape memory alloy.
Example 5
S1, putting raw material powder consisting of Fe-20Mn-6Si-8Cr-5Ni (namely 20 wt.% of Mn powder, 6 wt.% of Si powder, 8 wt.% of Cr powder, 5 wt.% of Ni powder and the balance of Fe powder) into a stainless steel tank for ball milling, adding industrial ethanol as a dispersing agent, adding 0.5mL of dispersing agent into every 10g of powder, wherein the ball-material ratio is 20:1, the ball milling medium is 10mm of stainless steel balls, repeatedly washing gas in a glove box transition bin, putting the stainless steel balls into an operation cavity of a ball mill, covering a sealing cover, taking out the stainless steel balls into the ball mill under the condition of ensuring that the argon gas in a tube is used, putting the stainless steel balls into the ball mill, performing intermittent ball milling, namely stopping 30min after ball milling for 60min, and performing ball milling for 20h alternately.
S2, filling the mixed powder obtained in the step S1 into a hard alloy die for prepressing, wherein the prepressing pressure is 400MPa and 20S, then putting the prepressed sample into a graphite die for Spark Plasma (SPS) sintering, the sintering pressure is 40MPa, the vacuum degree is 40Pa, the sintering temperature is 950 ℃, the heating rate is 60 ℃/min, the temperature is kept for 30min, and then, the temperature is reduced and the pressure is relieved, so that the Fe-Mn-Si-Cr-Ni-based shape memory alloy is prepared.
Example 6
The mixed powder obtained in step S1 of example 5 is filled into a cemented carbide mold for prepressing at 400MPa for 20S, and then the prepressed sample is filled into a graphite mold for Spark Plasma (SPS) sintering at 1000 ℃ and 30min under 40MPa vacuum degree of 50Pa and at 80 ℃/min for temperature reduction and pressure relief to obtain the Fe-Mn-Si-Cr-Ni-based shape memory alloy.
Example 7
The mixed powder obtained in step S1 of example 5 is filled into a cemented carbide mold for prepressing at 400MPa for 20S, and then the prepressed sample is filled into a graphite mold for Spark Plasma (SPS) sintering at 950 ℃ for 60min at 40MPa, and then the temperature is reduced and the pressure is released to obtain the Fe-Mn-Si-Cr-Ni-based shape memory alloy.
Example 8
S1, putting raw material powder consisting of Fe-20Mn-6Si-8Cr-5Ni (namely 20 wt.% of Mn powder, 6 wt.% of Si powder, 8 wt.% of Cr powder, 5 wt.% of Ni powder and the balance of Fe powder) into a stainless steel ball milling tank, adding industrial ethanol as a dispersing agent, adding 0.2mL of dispersing agent into every 10g of powder, wherein the ball-material ratio is 20:1, the ball milling medium is 10mm of stainless steel balls, repeatedly washing gas in a glove box transition bin, putting the stainless steel balls into an operation cavity of a ball mill, covering a sealing cover with the gas, taking the stainless steel balls out of the tube under the argon environment, putting the stainless steel balls into the ball mill, performing intermittent ball milling at the ball milling speed of 400r/min, namely stopping 30min after each ball milling for 60min, and performing ball milling for 90 hours alternately.
S2, filling the mixed powder obtained in the step S1 into a hard alloy die for prepressing, wherein the prepressing pressure is 400MPa and 20S, then putting the prepressed sample into a graphite die for Spark Plasma (SPS) sintering, the sintering pressure is 40MPa, the vacuum degree is 50Pa, the sintering temperature is 950 ℃, the heating rate is 100 ℃/min, the temperature is kept for 30min, and then, the temperature is reduced and the pressure is relieved, so that the Fe-Mn-Si-Cr-Ni-based shape memory alloy is prepared.
Example 9
The mixed powder obtained in step S1 of example 8 was loaded into a cemented carbide mold and pre-pressed at 400MPa for 20S, and then the pre-pressed sample was loaded into a graphite mold and discharge plasma (SPS) sintered at 1000 ℃, 90 ℃/min for 30min at 40MPa, 40Pa vacuum, and then cooled and decompressed to obtain Fe-Mn-Si-Cr-Ni based shape memory alloy.
Example 10
The mixed powder obtained in step S1 of example 8 was loaded into a cemented carbide mold and pre-pressed at 400MPa for 20S, and then the pre-pressed sample was loaded into a graphite mold and discharge plasma (SPS) sintered at 950 ℃, 80 ℃/min for 60min at 40MPa, 50Pa vacuum, and then cooled and decompressed to obtain Fe-Mn-Si-Cr-Ni based shape memory alloy.
Example 11
The mixed powder obtained in step S1 of example 1 is filled into a cemented carbide mold for prepressing at 500MPa for 20S, and then the prepressed sample is filled into a graphite mold for Spark Plasma (SPS) sintering at 950 ℃, 100 ℃/min for 30min and at 50MPa for vacuum, and then cooled for pressure relief to obtain the Fe-Mn-Si-Cr-Ni-based shape memory alloy.
Example 12
The mixed powder obtained in step S1 of example 5 is filled into a cemented carbide mold for prepressing at 500MPa for 20S, and then the prepressed sample is filled into a graphite mold for Spark Plasma (SPS) sintering at 950 ℃, 70 ℃/min for 30min at 50MPa, 40Pa vacuum, and then cooled for pressure relief to obtain the Fe-Mn-Si-Cr-Ni-based shape memory alloy.
Example 13
The mixed powder obtained in step S1 of example 8 was loaded into a cemented carbide mold and pre-pressed at a pre-pressing pressure of 500MPa for 20S, and then the pre-pressed sample was loaded into a graphite mold and discharge plasma (SPS) sintered at a sintering pressure of 50MPa, a vacuum degree of 50Pa, a sintering temperature of 950 ℃, a heating rate of 90 ℃/min, a holding time of 30min, and then cooled and decompressed to obtain Fe-Mn-Si-Cr-Ni based shape memory alloy.
Example 14
S1, putting raw material powder consisting of Fe-20Mn-6Si-8Cr-5Ni (namely 20 wt.% of Mn powder, 6 wt.% of Si powder, 8 wt.% of Cr powder, 5 wt.% of Ni powder and the balance of Fe powder) into a stainless steel ball milling tank, adding industrial ethanol as a dispersing agent, adding 0.2-0.5 mL of dispersing agent into every 10g of powder, wherein the ball-material ratio is 20:1, a ball milling medium is a 10mm stainless steel ball, repeatedly washing gas in a glove box transition bin, putting the powder into an operation cavity of a ball mill, covering a sealing cover, taking out the powder in a tube under the argon environment, putting the powder into the ball mill, wherein the ball milling rotation speed is 400r/min, and performing intermittent ball milling, namely stopping 30min after each ball milling for 60min, alternately performing ball milling for 2h to prepare alloy powder.
S2, filling the mixed powder obtained in the step S1 into a hard alloy die for prepressing with the prepressing pressure of 400MPa for 20S, then putting the prepressed sample into a graphite die for Spark Plasma (SPS) sintering with the sintering pressure of 40MPa and the sintering temperature of 900 ℃, keeping the temperature for 30min, and then reducing the temperature and releasing the pressure to obtain the Fe-Mn-Si-Cr-Ni-based shape memory alloy.
Example 15
S1, putting raw material powder consisting of Fe-20Mn-6Si-8Cr-5Ni (namely 20 wt.% of Mn powder, 6 wt.% of Si powder, 8 wt.% of Cr powder, 5 wt.% of Ni powder and the balance of Fe powder) in a stainless steel ball milling tank, adding industrial ethanol as a dispersing agent, adding 0.2-0.5 mL of dispersing agent into every 10g of powder, wherein the ball-material ratio is 20:1, a ball milling medium is a 10mm stainless steel ball, repeatedly washing gas in a glove box transition bin, putting the powder into an operation cavity of a ball mill, covering a sealing cover, taking out the powder in a tube under the argon environment, putting the powder into the ball mill, wherein the ball milling rotation speed is 400r/min, and performing intermittent ball milling, namely stopping 30min after each ball milling for 60min, alternately performing ball milling for 70h to prepare alloy powder.
S2, filling the mixed powder obtained in the step S1 into a hard alloy die for prepressing with the prepressing pressure of 400MPa for 20S, then putting the prepressed sample into a graphite die for Spark Plasma (SPS) sintering with the sintering pressure of 40MPa and the sintering temperature of 900 ℃, keeping the temperature for 30min, and then reducing the temperature and releasing the pressure to obtain the Fe-Mn-Si-Cr-Ni-based shape memory alloy.
TABLE 1 EXAMPLES 1-15 Properties of Fe-Mn-Si-Cr-Ni based shape memory alloys
Summary of experimental data:
as can be seen from examples 1, 2 and 4, the density of the composite material increases with the increase in sintering temperature, the hardness increases first and then decreases, the maximum value is obtained at 950 ℃, and the shape memory recovery rate shows the same trend as the hardness. As can be seen from examples 2, 5, 8, 14 and 15, the density of the composite material increases with the increase of the ball milling time, the hardness increases first and then decreases, the maximum value is obtained at 950 ℃, and the shape memory recovery rate shows the same variation trend as the hardness. It is understood from examples 2 to 3, 5 and 7, and 8 and 10 that the density of the composite material decreases and the hardness and the shape memory recovery rate decrease as the number of voids decreases with the increase in the sintering time. It is understood from examples 2 and 11, examples 5 and 12, and examples 8 and 13 that the densification of the composite material increases with increasing pre-pressing pressure and sintering pressure, but the changes in hardness and shape memory recovery are not significant.
FIG. 1 is an XRD pattern of Fe-20Mn-6Si-8Cr-5Ni powder after ball milling for different time in examples 1-15, which is mainly α -bcc phase in the initial stage of ball milling, and the peaks of Fe, Mn, Si, Cr and Ni are obviously reduced or disappeared with the increase of ball milling time, indicating that Mn, Si, Cr and Ni elements are partially or totally dissolved into α -Fe.
It will be apparent to those skilled in the art from this disclosure that many changes and modifications can be made, or equivalents modified, in the embodiments of the invention without departing from the scope of the invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention shall still fall within the protection scope of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.
Claims (10)
1. A Fe-Mn-Si-Cr-Ni based shape memory alloy characterized by: the raw materials comprise the following chemical components in percentage by mass: 12-30 wt.% of Mn powder, 3-6 wt.% of Si powder, 0-12 wt.% of Cr powder, 0-6 wt.% of Ni powder and the balance of Fe powder.
2. The Fe-Mn-Si-Cr-Ni based shape memory alloy of claim 1, wherein: the purity of the Fe powder is more than 99%, and the granularity is 44-149 mu m.
3. The Fe-Mn-Si-Cr-Ni based shape memory alloy of claim 1, wherein: the purity of the Mn powder is more than 99.5, and the granularity is 44-149 mu m.
4. The Fe-Mn-Si-Cr-Ni based shape memory alloy of claim 1, wherein: the purity of the Si powder is more than 99.999 percent, and the granularity is 37-149 mu m.
5. The Fe-Mn-Si-Cr-Ni based shape memory alloy of claim 1, wherein: the purity of the Cr powder is more than 99.5 percent, and the granularity is 5 mu m.
6. The Fe-Mn-Si-Cr-Ni based shape memory alloy of claim 1, wherein: the purity of the Ni powder is more than 99.9%, and the granularity is 1-3 mu m.
7. The Fe-Mn-Si-Cr-Ni based shape memory alloy of claim 1, wherein: after mechanical alloying, the grain size of the mixed powder of Fe, Mn, Si, Cr and Ni elements is 150nm or less.
8. A method of producing an Fe-Mn-Si-Cr-Ni based shape memory alloy as claimed in any one of claims 1 to 7, which comprises the steps of:
s1, mixing and ball-milling raw material powder of Fe, Mn, Si, Cr and Ni according to a preset mass percentage, wherein the mass ratio of balls to materials is 10: 1-20: 1, 0.2-0.5 mL of dispersing agent is added into each 10g of powder, the rotating speed is 300-600 r/min, the ball-milling is carried out for 20-90 h, intermittent ball-milling is adopted, namely 30min is stopped after each ball-milling is carried out for 60min, and the operation is alternately carried out to prepare fine mixed powder with the particle size of 150 nm;
s2, pre-pressing the mixed powder obtained in the step S1 at 300-500 MPa for 10-30S, and then performing discharge plasma (SPS) sintering on the pre-pressed sample at 20-50 MPa and 800-1000 ℃ for 5-60 min to obtain the Fe-Mn-Si-Cr-Ni-based shape memory alloy.
9. The method of making a Fe-Mn-Si-Cr-Ni based shape memory alloy of claim 8, wherein: the dispersing agent is ethanol; the ball milling process of step S1 used balls having a diameter of 10 mm.
10. The method of making a Fe-Mn-Si-Cr-Ni based shape memory alloy of claim 8, wherein: the specific sintering process in step S2 is: applying pressure to the sample to 20-50 MPa, wherein the vacuum degree is 10-40 Pa; heating to 800-1000 ℃ at a heating rate of 10-100 ℃/min, preserving heat for 5-60 min, and cooling along with the furnace.
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