CN110714141B - Method for improving shape memory effect of cobalt-nickel base alloy - Google Patents
Method for improving shape memory effect of cobalt-nickel base alloy Download PDFInfo
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- CN110714141B CN110714141B CN201911078269.0A CN201911078269A CN110714141B CN 110714141 B CN110714141 B CN 110714141B CN 201911078269 A CN201911078269 A CN 201911078269A CN 110714141 B CN110714141 B CN 110714141B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
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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
- C22F1/006—Resulting in heat recoverable alloys with a memory effect
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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
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
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Abstract
The invention discloses a method for improving the shape memory effect of a cobalt-nickel base alloy, belonging to the field of shape memory alloys. The cobalt-nickel base alloy contains Co, Ni and Si elements, and the weight percentage of each element in the alloy is as follows: 12-32% of Ni, 4-8% of Si, 0-0.2% of C, 0-0.2% of N, and the balance of Co and inevitable impurities. The method comprises the following specific steps: (1) firstly, processing a cobalt-nickel base alloy at 1100-1300 ℃ for 10 minutes-5 hours, and then quenching the cobalt-nickel base alloy into a liquid cooling medium; (2) then, the cobalt-nickel base alloy is put above L12And (3) separating out the structural phase at the upper limit temperature not higher than 1000 ℃ for 10 seconds to 30 minutes, and then cooling the structural phase to room temperature or quenching the structural phase into a liquid cooling medium. The method can obviously improve the shape memory effect of the cobalt-nickel base alloy and has simple treatment process.
Description
Technical Field
The invention relates to the field of shape memory alloys, in particular to a method for improving the shape memory effect of a cobalt-nickel-based alloy.
Background
The shape memory alloy has wide application prospect in the fields of aerospace, mechanical and chemical engineering, biomedical treatment and the like due to the unique shape memory effect. The shape memory effect of cobalt-nickel based shape memory alloys results from the transformation of a face-centered cubic parent phase into a close-packed hexagonal martensitic phase and its inverse. In addition, the face-centered cubic parent phase and the close-packed hexagonal martensite in the alloy are ferromagnetic, so that the alloy is expected to be a bifunctional alloy with magnetism and shape memory effect. However, the shape memory effect of cobalt-nickel based Alloys in solid solution state is poor and the maximum recoverable strain is below 4.5% (Materials Science and Engineering A, 2006, 438-. Furthermore, training (Materials Science and Engineering A, 2014, 618: 41-45), high temperature pre-deformation (metals and Materials transformations A, 2015, 46: 1550-. Meanwhile, the methods have deformation processes, increase the preparation cost and are not suitable for processing complex parts. Therefore, how to improve the shape memory effect of cobalt-nickel based alloys is a problem to be solved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for improving the shape memory effect of a cobalt-nickel-based alloy.
The cobalt-nickel base alloy contains Co, Ni and Si elements, and the weight percentage of each element in the alloy is as follows: 12-32% of Ni, 4-8% of Si, 0-0.2% of C, 0-0.2% of N, and the balance of Co and inevitable impurities. The specific steps for improving the shape memory effect of the cobalt-nickel base alloy comprise: (1) firstly, processing the cobalt-nickel base alloy at 1100-1300 ℃ for 10 minutes-5 hours, and then quenching the cobalt-nickel base alloy into a liquid cooling medium. At temperatures below 1000 deg.C, the cobalt-nickel based alloy will have L12Structural phases precipitate which significantly worsen the shape memory effect of cobalt-nickel based alloys. Accordingly, the quenching in the above treatment process is to suppress L1 in the cooling process after the high temperature treatment2And (4) separating out a structural phase. In addition, the high density of stacking faults is beneficial to improving the shape memory effect of the cobalt-nickel based alloy. Thus, another purpose of quenching is to introduce a high density of stacking faults and dislocations in preparation for subsequent heat treatment. (2) Then, the cobalt-nickel base alloy is put above L12And (3) separating out the structural phase at the upper limit temperature not higher than 1000 ℃ for 10 seconds to 30 minutes, and then cooling the structural phase to room temperature or quenching the structural phase into a liquid cooling medium. The above treatment process has three purposes: one is to eliminate L1 in which precipitation could not be suppressed in step (1)2A structural phase; the other is to use the step (1)The introduced high-density dislocation is decomposed into stacking faults, and the density of the stacking faults is further improved; the number of stacking faults tends to decrease significantly after higher temperature and longer treatment, and therefore a final objective of the above treatment process is to avoid a decrease in stacking fault density while allowing dislocations to decompose completely into stacking faults.
In order to obtain the optimal shape memory effect, the cobalt-nickel base alloy comprises the following elements in percentage by weight: 15-27% of Ni, 5-6% of Si, and the balance of Co and inevitable impurities; the specific steps are preferably as follows: (1) firstly, the cobalt-nickel base alloy is preferably treated at 1200-1250 ℃ for 1-3 hours, and the treatment process is more favorable for introducing high-density stacking faults and dislocation; (2) then, the cobalt-nickel base alloy is preferably higher than L12The upper limit temperature of structural phase precipitation is not higher than 900 ℃ and the treatment lasts for 1-5 minutes; the liquid cooling medium is water or saline water or liquid metal, wherein the temperature of the liquid metal is not higher than 200 ℃; l12The upper limit temperature of structural phase precipitation is preferably lower than 750 ℃, and at the moment, the L1 can be effectively avoided due to the fact that the atomic diffusion speed is remarkably reduced2And (4) separating out a structural phase.
The invention has the following advantages: (1) the shape memory effect of the cobalt-nickel base alloy can be obviously improved, and the effect is obvious; (2) the preparation process can be completed by simple conventional equipment; (3) compared with high-temperature pre-deformation, training and thermal mechanical treatment, the method is simple, has no deformation processing process, reduces the cost and is suitable for parts with complex shapes.
Detailed Description
The present invention will be further described with reference to the following examples. It should be noted that the examples given are not to be construed as limiting the scope of the invention, and that those skilled in the art, on the basis of the above teachings, will be able to make numerous insubstantial modifications and adaptations of the invention without departing from its scope.
The cobalt-nickel based alloys selected in comparative examples 1 to 5 and examples 1 to 7 have the following elements in weight percent: 19.9% of Ni, 5.9% of Si, and the balance of Co and inevitable impurities. L1 in the alloy2The upper precipitation temperature of the structural phase was 650 ℃. Thus, inNo L1 in the alloy when processed at a temperature higher than 650 DEG C2Structural phase precipitated and pre-existing L12The structural phase will also dissolve. And (3) characterizing the shape memory effect of the alloy by adopting a bending deformation method. Comparative examples 1 and 2 show that: after treatment at 1200 ℃, L1 is formed by air cooling2Structural phases precipitated, whereas water cooling did not provide L12And (4) structural phase precipitation. At this time, the former had a significantly lower shape recovery rate of 5.6% deformation at room temperature than the latter. This indicates L12Structural phase precipitation will deteriorate the shape memory effect of the alloy. Comparative examples 3 and 4 show that: after 1200 ℃ water cooling treatment in the step (1), the mixture is cooled at 600 ℃ (lower than L1)2Upper limit of the precipitation temperature of the structural phase) may be treated with L12Structural phases are precipitated which will lead to a significant deterioration of the shape memory effect of the alloy. Examples 1 to 7 show that: after 1200 ℃ water cooling treatment in the step (1), the mixture is cooled to 700 ℃ (higher than L1)2The upper limit precipitation temperature of the structural phase) to 1000 ℃ can obviously improve the shape recovery rate of the alloy, and particularly, the alloy is treated at 800-1000 ℃ for 30 seconds to 5 minutes. Comparative example 5 illustrates that: at 800 ℃ although without L12Structural phases are separated out, but too long a treatment time leads to a significant reduction in the number of stacking faults, at which point the desired shape memory effect cannot be achieved. In addition, the maximum recoverable strain of example 3 at room temperature deformation can reach 5.1%, which is significantly higher than the maximum recoverable strain of the existing cobalt-nickel based alloy. In summary, the results in table 1 clearly show that the present invention can significantly improve the shape memory effect of cobalt-nickel based alloys.
TABLE 1 treatment methods and Presence/absence of L1 for comparative examples 1 to 5 and examples 1 to 72Structural phase and shape recovery
The cobalt-nickel based alloys selected in comparative examples 6 to 8 and examples 8 to 14 have the following elements in weight percent: 23.9% of Ni, 5.6% of Si, and the balance of Co and inevitable impurities. L1 in the alloy2The upper precipitation temperature of the structural phase was 710 ℃. Therefore, L1 is not existed in the alloy when the temperature is higher than 710 DEG C2Structural phases are precipitated, andpreexisting L12The structural phase will also dissolve. And (3) characterizing the shape memory effect of the alloy by adopting a bending deformation method. Comparative examples 6 and 7 show that: after treatment at 1200 ℃, L1 is formed by air cooling2Structural phases precipitated, whereas water cooling did not provide L12And (4) structural phase precipitation. At this time, the former had a significantly lower shape recovery rate of 5.6% deformation at room temperature than the latter. This indicates L12Structural phase precipitation will deteriorate the shape memory effect of the alloy. Comparative example 8 shows that: after 1200 ℃ water cooling treatment in the step (1), the mixture is cooled at 600 ℃ (lower than L1)2Upper limit of the precipitation temperature of the structural phase) is treated with L12Structural phases are precipitated which will lead to a significant deterioration of the shape memory effect of the alloy. Examples 8 to 14 show that: after 1200 ℃ water cooling treatment in the step (1), the mixture is cooled to 750 ℃ (higher than L1)2The upper limit precipitation temperature of the structural phase) to 1000 ℃ can obviously improve the shape recovery rate of the alloy, and particularly, the alloy is treated for 1 minute at 800 ℃; after the alloy is treated at 800 ℃ for 1 minute, the shape recovery rate of the alloy can be effectively improved by adopting liquid metal cooling at 100 ℃ rather than water cooling. In addition, the maximum recoverable strain of example 9 can reach 5.0% when deformed at room temperature, and can reach 7.1% when deformed at liquid nitrogen temperature, which is significantly higher than the maximum recoverable strain of the existing cobalt-nickel-based alloy. In summary, the results in Table 2 clearly show that the present invention significantly improves the shape memory effect of cobalt-nickel based alloys.
TABLE 2 treatment methods and Presence/absence of L1 for comparative examples 6 to 8 and examples 8 to 142Structural phase and shape recovery
Claims (7)
1. The method for improving the shape memory effect of the cobalt-nickel-based alloy is characterized in that the cobalt-nickel-based alloy contains Co, Ni and Si elements, and the weight percentage of each element in the alloy is as follows: 12-32% of Ni, 4-8% of Si, 0-0.2% of C, 0-0.2% of N, and the balance of Co and inevitable impurities; the method comprises the following specific steps: (1) firstly, processing the cobalt-nickel base alloy at 1100-1300 ℃ for 10 minutes-5 hours, and then quenchingFiring into a liquid cooling medium; (2) then, the cobalt-nickel base alloy is put above L12And (3) separating out the structural phase at the upper limit temperature not higher than 1000 ℃ for 10 seconds to 30 minutes, and then cooling the structural phase to room temperature or quenching the structural phase into a liquid cooling medium.
2. The method for improving the shape memory effect of the cobalt-nickel based alloy according to claim 1, wherein the weight percentage of each element in the cobalt-nickel based alloy is as follows: 15-27% of Ni, 5-6% of Si, and the balance of Co and inevitable impurities.
3. The method of claim 1, wherein (1) the cobalt-nickel based alloy is first treated at 1200-1250 ℃ for 1-3 hours.
4. The method of claim 1, wherein (2) the cobalt-nickel based alloy is then placed above L12The upper limit temperature of the structural phase precipitation is not higher than 900 ℃ and the treatment lasts for 1-5 minutes.
5. The method of claim 1, wherein the liquid cooling medium is water or brine or a liquid metal.
6. A method for improving shape memory effect of Co-Ni based alloy according to claim 1 or 4 wherein L12The upper limit temperature of structural phase precipitation is lower than 750 ℃.
7. A method for improving shape memory effect of cobalt nickel based alloys according to claim 5 wherein the temperature of the liquid metal is not higher than 200 ℃.
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Citations (5)
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| EP0519311A1 (en) * | 1991-06-19 | 1992-12-23 | Krupp Industrietechnik Gmbh | Shape memory alloy iron-nickel-cobalt-titanium, and process for producing this alloy |
| CN104018054A (en) * | 2014-06-17 | 2014-09-03 | 东南大学 | Rare earth magnetic material with controlled deformation of magnetic field and preparation method thereof |
| WO2016118213A2 (en) * | 2014-11-06 | 2016-07-28 | Rensselaer Polytechnic Institute | Grain boundary engineering of polycrystalline shape memory alloys by phase manipulation for enhanced mechanical ductility and application fatigue life |
| CN105861861A (en) * | 2016-04-05 | 2016-08-17 | 南京工程学院 | Memory alloy driven by magnetic field to deform and preparing method of memory alloy |
| CN109097610A (en) * | 2018-08-01 | 2018-12-28 | 河海大学 | It is a kind of with the magnetic memorial alloy and preparation method thereof strained greatly |
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Patent Citations (5)
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|---|---|---|---|---|
| EP0519311A1 (en) * | 1991-06-19 | 1992-12-23 | Krupp Industrietechnik Gmbh | Shape memory alloy iron-nickel-cobalt-titanium, and process for producing this alloy |
| CN104018054A (en) * | 2014-06-17 | 2014-09-03 | 东南大学 | Rare earth magnetic material with controlled deformation of magnetic field and preparation method thereof |
| WO2016118213A2 (en) * | 2014-11-06 | 2016-07-28 | Rensselaer Polytechnic Institute | Grain boundary engineering of polycrystalline shape memory alloys by phase manipulation for enhanced mechanical ductility and application fatigue life |
| CN105861861A (en) * | 2016-04-05 | 2016-08-17 | 南京工程学院 | Memory alloy driven by magnetic field to deform and preparing method of memory alloy |
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