CN115961176B - NiTiCu shape memory alloy and 4D printing method and application thereof - Google Patents
NiTiCu shape memory alloy and 4D printing method and application thereof Download PDFInfo
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- 229910001285 shape-memory alloy Inorganic materials 0.000 title claims abstract description 107
- 238000007639 printing Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 41
- 230000007704 transition Effects 0.000 claims abstract description 56
- 230000008569 process Effects 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000011065 in-situ storage Methods 0.000 claims abstract description 13
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 52
- 239000000956 alloy Substances 0.000 claims description 52
- 239000000843 powder Substances 0.000 claims description 46
- 230000008859 change Effects 0.000 claims description 44
- 239000010936 titanium Substances 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 238000002844 melting Methods 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 11
- 230000006698 induction Effects 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 230000006399 behavior Effects 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 230000004927 fusion Effects 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 230000007480 spreading Effects 0.000 claims description 5
- 238000003892 spreading Methods 0.000 claims description 5
- 238000000889 atomisation Methods 0.000 claims description 4
- 238000009689 gas atomisation Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 229910003322 NiCu Inorganic materials 0.000 claims 2
- 229910001000 nickel titanium Inorganic materials 0.000 description 19
- 239000002244 precipitate Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
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- 239000002245 particle Substances 0.000 description 3
- 229910001566 austenite Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 238000013461 design Methods 0.000 description 2
- 229910000734 martensite Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
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- 125000004122 cyclic group Chemical group 0.000 description 1
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Abstract
The invention discloses a NiTiCu shape memory alloy, a 4D printing method and application thereof, wherein the content range of Cu in the NiTiCu shape memory alloy is 5-15 at%, the content range of Ni is 30-50 at%, and the balance is Ti. The NiTiCu shape memory alloy matrix has uniformly distributed nano-scale (15-120 nm) precipitated phase with the density of 2 multiplied by 10 10～4×1011/cm2, and can be widely applied to the fields of driving devices, executing components and the like. The NiTiCu shape memory alloy with complex configuration, narrow phase transition temperature hysteresis and high stability is prepared by a process of combining 4D printing and in-situ heat treatment. After the primary and the repeated thermal cycles, the phase transition temperature hysteresis of the NiTiCu shape memory alloy is less than 15 ℃, and the phase transition temperature variation amplitude is also less than 10%.
Description
Technical Field
The invention belongs to the field of NiTiCu shape memory alloy, 4D printing and laser powder bed melting, and particularly relates to a NiTiCu shape memory alloy, a 4D printing method and application thereof.
Background
Shape memory alloys are functional alloys that can return to their original shape by applying a certain external stimulus (e.g., thermal field, magnetic field, etc.) or unloading a loading stress after being deformed by an external force. NiTi-based shape memory alloys (NiTi, niTiCu, niTiFe, niTiHf, etc.) are the most widely used class of functional metal materials in the engineering field at present. In the 21 st century, niTi-based shape memory alloys as driving and executing elements are gradually realizing innovative applications in the fields of intelligent robots, complex driving devices and executing elements, etc., although B2 austenite in NiTi binary alloysThe driving strain of the B19' martensitic transformation is close to 8%, but the phase transformation temperature hysteresis is wider (25-50 ℃), the sensitivity is low and the response speed is slow when the alloy is used as a driver, and meanwhile, the NiTi binary shape memory alloy has obvious attenuation and poor stability in functional characteristics such as super elasticity after multiple heat/stress cycles. Therefore, the NiTi binary shape memory alloy cannot fully meet the urgent requirements of the driving element on sensitivity, response speed, control precision and durability, and limits the further application of the NiTi binary shape memory alloy in the field of driving elements. In order to improve the sensitivity and response speed of the NiTi binary shape memory alloy driving element, researchers use R phase transition (1-5 ℃) with narrow hysteresis in the NiTi binary shape memory alloy as driving phase transition, however, the strain of the phase transition is only 1%, and the requirement of large driving strain cannot be met. Therefore, it is necessary to find a NiTi-based shape memory alloy with a narrow phase change hysteresis and an appropriate driving strain as a raw material for the driving element. B2 Austenite/>, in NiTiCu shape memory alloyThe B19 martensite is a phase transformation process with narrow hysteresis (8-15 ℃) and drive strain of about 3.5%, and the phase transformation can ensure the drive sensitivity and the response speed and simultaneously give consideration to the drive strain, so that the NiTiCu shape memory alloy is an ideal raw material for a new generation of drive elements.
In general, the NiTi-based shape memory alloy has high response sensitivity, low thermal conductivity and other physical properties, so that the subsequent processing difficulty and the cost of a primary formed part are high. Thus, the conventional process of making NiTi-based shape memory alloy components has relatively simple geometries, such as wires, plates, rods, tubes, etc., which greatly limits their range of applications (prog. Mater. Sci.57 (5) (2012) 911-946). The 4D printing technique is additive manufacturing to produce shape memory alloys that enable controlled variations in the shape, performance and function of the components in both the temporal and spatial dimensions through active design of material properties or structural configurations (mate. Des.122 (2017) 42-79). As a typical metal additive manufacturing process, laser powder bed fusion (Laser powder bed fusion, LPBF) additive manufacturing represents a significant advantage in near net forming components with complex geometries as compared to conventional manufacturing processes. The successful application of LPBF to the NiTi-based shape memory alloy greatly reduces subsequent processing flows and also provides favorable conditions for the direct preparation of the precise and complex NiTi-based shape memory alloy component. Currently, high-density/complex NiTi-based shape memory alloy components such as layered high-damping structures (Scr. Mater.146 (2018) 246-250), porous structures (J. Mater. Res. Technology.15 (2021) 6797-6812), negative Poisson's ratio structures (Acta Mater.105 (2016) 75-83) and the like have been successfully prepared through LPBF processes. Meanwhile, the research result also shows that in the LPBF process, the occurrence of unbalanced rapid solidification and the existence of complex thermal history have a remarkable influence on the phase change behavior (hysteresis and stability) of the NiTi-based shape memory alloy. How to obtain phase transformation behavior meeting specific requirements in additive manufacturing of NiTi-based alloys is a current problem that needs to be addressed.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the primary object of the invention is to provide a NiTiCu shape memory alloy which has the characteristics of narrow phase transition temperature hysteresis and high stability.
The second object of the present invention is to provide a 4D printing preparation method of a nituu shape memory alloy, which prepares the nituu shape memory alloy with narrow phase transition temperature hysteresis and high stability by adopting a 4D printing technology and combining an in-situ heat treatment process, and compared with the traditional casting, severe plastic deformation and other methods, the 4D printing preparation method can realize near-net forming and personalized customization, and improves the utilization rate of materials, thereby saving the cost.
The third object of the present invention is to provide an application of the above-mentioned NiTiCu shape memory alloy, which is mainly in the fields of intelligent robots, complex driving devices, executing components and the like.
The primary purpose of the invention is realized by the following scheme:
A niticeu shape memory alloy comprising the following features:
(1) The composition characteristics are as follows: the range of Cu content in the NiTiCu shape memory alloy is 5-15 at%, the range of Ni content is 30-50 at%, and the balance is Ti;
(2) Microstructure characteristics: the NiTiCu shape memory alloy matrix has a uniformly distributed precipitated phase (FIG. 1);
(3) Phase change behavior characteristics: the phase transition temperature hysteresis of the NiTiCu shape memory alloy with the characteristics (1) and (2) is 3-15 ℃, and the variation range of the phase transition temperature of the NiTiCu shape memory alloy after multiple thermal cycles is 6-10%.
Specifically, in the characteristic (1), the Cu content is regulated according to the phase transition temperature and the phase transition stability required by the NiTiCu shape memory alloy in the use process, and the regulation of the Cu content in the characteristic (1) directly influences the precipitation type and the density of a precipitated phase in the NiTiCu shape memory alloy characteristic (2).
Preferably, the Cu content in the niticeu shape memory alloy in the feature (1) is 5at.%, the Ni content is 43at.%, and the balance is Ti.
Preferably, the Cu content in the niticeu shape memory alloy in the feature (1) is 10at%, the Ni content is 37at%, and the balance is Ti.
Preferably, the Cu content in the niticeu shape memory alloy in the feature (1) is 15at.%, the Ni content is 45at.%, and the balance is Ti.
Preferably, the homogeneously distributed precipitated phase in the feature (2) is Ti 2 (NiCu) or Ti (NiCu) 2, which is 15-120 nm in size and 2×10 10～4×1011/cm2 in density.
The second object of the invention is achieved by the following technical scheme:
A4D printing preparation method of NiTiCu shape memory alloy comprises the following steps:
(1) Pulverizing: mixing and smelting pure nickel, pure titanium and pure copper raw materials to obtain a NiTiCu pre-alloyed raw bar with uniform element distribution, and preparing the NiTiCu pre-alloyed raw bar into NiTiCu alloy powder by an electrode induction smelting gas atomization (EIGA) method;
(2) 4D printing and forming: adopting a process strategy of in-situ heat treatment, and 4D printing and molding the NiTiCu alloy powder obtained in the step (1) by laser powder bed melting (LPBF) equipment to prepare the NiTiCu shape memory alloy;
Preferably, the smelting times in step (1) are 4 to 8 times, and the size of the NiTiCu alloy powder ranges from 15 to 53 mu m (figure 2).
Preferably, the specific process of the electrode induction melting gas atomization (EIGA) in step (1) is: vacuumizing powder making equipment to below 5X 10 -3 Pa, heating the NiTiCu alloy bar with the diameter of 30-50 mm to 1200-1500 ℃ through an induction coil, atomizing the NiTiCu alloy bar through Ar or He inert gas with the atomization pressure of 3-8 MPa, and screening to obtain NiTiCu alloy powder.
Preferably, the Laser Powder Bed Fusion (LPBF) forming apparatus in step (2) includes CONCEPT LASER M, EOS M280/290,SLM Solutions 125/250/280.0/500,RENISHAW 400,BLT-S320, and the like.
Preferably, the specific step of 4D printing and molding in the step (2) is as follows: and (3) performing primary melting on the NiTiCu alloy powder in the step (1) by laser powder bed melting (LPBF) forming equipment under the technological parameters of 70-150W of laser power, 80-200 mm/s of scanning speed, 30 mu m of powder spreading layer thickness and 100 mu m of scanning interval, and performing in-situ heat treatment on the primary melting pass by adopting the technological parameters of 90-120W of laser power, 1000-1400 mm/s of scanning speed and 100 mu m of scanning interval to obtain the NiTiCu shape memory alloy.
The third object of the present invention is achieved by the following technique:
the NiTiCu shape memory alloy is applied to the fields of intelligent robots, complex driving devices, executive components and the like.
The principle of the invention is as follows:
The NiTiCu shape memory alloy with narrow phase change hysteresis and high stability is obtained by the methods of alloy element content design, matrix precipitation phase characteristic regulation and the like. Meanwhile, the invention successfully obtains the 4D printing NiTiCu shape memory alloy with narrow and stable phase change temperature lag through 4D printing process parameter regulation (in-situ heat treatment) based on the urgent requirements of the intelligent robot, the complex driving device, the executive component and other fields on the NiTiCu driving element with narrow and stable phase change lag, and provides basis for the industrialized application of the NiTiCu driving element with complex configuration, narrow and stable phase change temperature lag. The NiTiCu shape memory alloy with narrow phase transition temperature lag and high stability is prepared by combining a 4D printing technology with an in-situ heat treatment process, and the NiTiCu shape memory alloy shows narrow phase transition temperature lag and stable phase transition temperature in the process of repeated cyclic heat action, and is shown in figure 3.
Compared with the prior art, the invention has the following advantages and effects:
(1) The range of Cu content in the NiTiCu shape memory alloy with narrow phase transition temperature hysteresis and high stability is 5-15 at%, the range of Ni content is 30-50 at%, and the balance is Ti. The NiTiCu shape memory alloy matrix has a uniformly distributed nano-precipitated phase (Ti 2 (NiCu) or Ti (NiCu) 2). Meanwhile, the phase transition temperature hysteresis of the NiTiCu shape memory alloy is less than 15 ℃, and the variation amplitude of the phase transition temperature of the NiTiCu shape memory alloy after multiple heat cycles is less than 10%;
(2) The invention adopts 4D printing technology to realize the formation of NiTiCu shape memory alloy with narrow phase change lag and high stability, and compared with the traditional casting, severe plastic deformation and other methods, the invention can prepare complex shape parts, meets the customization requirement, and realizes the application of the NiTiCu shape memory alloy in the fields of intelligent robots, complex driving devices, executive components and the like;
(3) According to the invention, the NiTiCu shape memory alloy with narrow phase transition temperature hysteresis and high stability can be prepared by adopting a 4D printing technology and an in-situ heat treatment process, near-net forming and personalized customization can be realized, and the utilization rate of materials is improved, so that the cost is saved.
Drawings
FIG. 1 is a microstructure view of a transmission electron microscope of a nano-precipitate phase in a NiTiCu shape memory alloy matrix of example 1;
FIG. 2 is a diagram of the morphology of NiTiCu alloy powder of example 1;
FIG. 3 is a graph of phase change behavior of NiTiCu shape memory alloy during the 1 st st (first cycle), 10 th (tenth cycle), and 50 th (fifty-th cycle) thermal cycles.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
Example 1
1. The microstructure characteristics of the NiTiCu shape memory alloy with narrow phase transition temperature hysteresis and high stability are as follows:
The NiTiCu shape memory alloy contains 5at.% Cu, 43at.% Ni and 52at.% Ti, and the matrix is uniformly distributed with Ti 2 (NiCu) precipitate phases with a size of 10nm, and the density of the precipitate phases is 8×10 10/cm2～4×1011/cm2, namely 8×10 10～4×1011 precipitate phases per square centimeter.
2. The 4D printing preparation method of the NiTiCu shape memory alloy with narrow phase transition temperature lag and high stability comprises the following steps:
(1) And (3) carrying out mixed smelting on pure nickel (with the proportion of 43at percent), pure titanium (with the proportion of 52at percent) and pure copper (with the proportion of 5at percent) bars for 6 times to obtain NiTiCu prealloyed original bars with uniform element distribution, vacuumizing powder making equipment to 4X 10 -3 Pa, heating the NiTiCu alloy bars with the diameter of 40mm to 1400 ℃ through an induction coil, atomizing the NiTiCu alloy bars through Ar inert gas with the atomizing pressure of 6MPa, and screening to obtain alloy powder with the particle size of 15-53 mu m.
(2) 4D printing and forming: the alloy powder in the step (1) is melted (LPBF) by an EOS M280 laser powder bed to form NiTiCu shape memory alloy, specifically, in the 4D printing preparation process, the laser power of 150W, the laser scanning speed of 200mm/s, the powder spreading layer thickness of 30 mu M, the process parameters of 100 mu M of scanning interval are adopted to carry out primary melting on the NiTiCu alloy powder, and then the process parameters of 90W, the laser scanning speed of 1000mm/s and the scanning interval of 100 mu M are adopted to carry out in-situ heat treatment on the primary melting pass to obtain a 4D printing NiTiCu alloy sample 1; meanwhile, the NiTiCu alloy powder is subjected to fusion forming by adopting the technological parameters of 150W laser power, 200mm/s laser scanning speed, 30 mu m powder paving layer thickness and 100 mu m scanning interval, so as to obtain a 4D printing NiTiCu alloy sample 2.
3. 4D printing has the phase change behavior characteristics of NiTiCu shape memory alloy with narrow phase change temperature hysteresis and high stability: for sample 1 of 4D printed niticeu alloy, the phase transition temperature hysteresis of 4D printed niticeu shape memory alloy was 3 ℃ during the primary thermal cycle; after 10 times of thermal cycles, the phase transition temperature hysteresis of the NiTiCu shape memory alloy is 5.5 ℃, and the variation amplitude of the phase transition temperature is 6%; after 50 thermal cycles, the phase transition temperature hysteresis of the NiTiCu shape memory alloy is 6 ℃, and the change amplitude of the phase transition temperature is 8%. For the 4D printed niticeu alloy sample 2, the phase transition temperature hysteresis of the 4D printed niticeu shape memory alloy was 6 ℃ during the primary thermal cycle; after 10 times of thermal cycles, the phase transition temperature hysteresis of the NiTiCu shape memory alloy is 8.5 ℃, and the change amplitude of the phase transition temperature is 12%; after 50 thermal cycles, the phase transition temperature hysteresis of the NiTiCu shape memory alloy is 10 ℃, and the change amplitude of the phase transition temperature is 16%. As reported in the literature, as a phase change hysteresis (J.Manuf.Process.77 (2022) 539-550 and J.Allys Compd.885 (2021) 160971) at 30-40 ℃ in a 4D printed NiTi shape memory alloy, a phase change temperature change (Mater. Des.208 (2021) 109935) at 8-15 ℃ after 10 thermal cycles was found, the NiTiCu alloy of the present invention had a narrow phase change temperature hysteresis and high phase change temperature stability (prog. Mater. Sci.50 (5) (2005) 511-678 and prog. Mater. Sci.83 (2016) 630-663).
Example 2
1. The microstructure characteristics of the NiTiCu shape memory alloy with narrow phase transition temperature hysteresis and high stability are as follows:
The NiTiCu shape memory alloy contains Cu 10 at%, ni 37 at%, ti 53 at%, and Ti 2 (NiCu) precipitate phase of 80nm in density of 2×10 10/cm2～9×1010/cm2, i.e. 2×10 10～9×1010 precipitate phases per square centimeter.
2. The 4D printing preparation method of the NiTiCu shape memory alloy with narrow phase transition temperature hysteresis and high stability comprises the following steps:
(1) Pure nickel (with the proportion of 37 at.%), pure titanium (with the proportion of 53 at.%) and pure copper (with the proportion of 10 at.%) are mixed and smelted for 8 times to obtain NiTiCu prealloy original bars with uniform element distribution, powder making equipment is vacuumized to 3.5 multiplied by 10 -3 Pa, niTiCu alloy bars with the diameter of 30mm are heated to 1200 ℃ through an induction coil, the NiTiCu alloy bars are atomized through He inert gas with the atomization pressure of 3MPa, and alloy powder with the particle size of 15-53 mu m is obtained through screening.
(2) 4D printing and forming: and (3) melting (LPBF) the alloy powder in the step (1) through a CONCEPT LASER M laser powder bed to form the NiTiCu shape memory alloy. Specifically, in the 4D printing preparation process, technological parameters of laser power 70W, laser scanning speed 80mm/s, powder spreading layer thickness of 30 mu m and scanning interval of 100 mu m are adopted to carry out primary melting on NiTiCu alloy powder, and then technological parameters of laser power 120W, laser scanning speed 1400mm/s and scanning interval of 100 mu m are adopted to carry out in-situ heat treatment on primary melting pass, so as to obtain a 4D printing NiTiCu alloy sample 1; meanwhile, the NiTiCu alloy powder is subjected to fusion forming by adopting the technological parameters of laser power 70W, laser scanning speed 80mm/s, powder spreading layer thickness 30 mu m and scanning interval 100 mu m, so as to obtain a 4D printing NiTiCu alloy sample 2.
3. Phase change behavior characteristics of NiTiCu shape memory alloy with narrow phase change temperature hysteresis and high stability prepared by 4D printing: for the 4D printed NiTiCu alloy sample 1, the phase transition temperature hysteresis of the NiTiCu shape memory alloy is 7.5 ℃ in the primary thermal cycle process, the phase transition temperature hysteresis of the NiTiCu shape memory alloy is 8 ℃ after 10 thermal cycles, and the change amplitude of the phase transition temperature is 6%; after 50 thermal cycles, the phase transition temperature hysteresis of the NiTiCu shape memory alloy is 9 ℃, and the change amplitude of the phase transition temperature is 8%. For the 4D printed NiTiCu alloy sample 2, the phase transition temperature hysteresis of the NiTiCu shape memory alloy is 9 ℃ in the primary thermal cycle process, and after 10 thermal cycles, the phase transition temperature hysteresis of the NiTiCu shape memory alloy is 11 ℃, and the change amplitude of the phase transition temperature is 13%; after 50 thermal cycles, the phase transition temperature hysteresis of the NiTiCu shape memory alloy is 14.5 ℃ and the change amplitude of the phase transition temperature is 17%. As reported in the literature, as a phase change hysteresis (J.Manuf.Process.77 (2022) 539-550 and J.Allys Compd.885 (2021) 160971) at 30-40 ℃ in a 4D printed NiTi shape memory alloy, a phase change temperature change (Mater. Des.208 (2021) 109935) at 8-15 ℃ after 10 thermal cycles was found, the NiTiCu alloy of the present invention had a narrow phase change temperature hysteresis and high phase change temperature stability (prog. Mater. Sci.50 (5) (2005) 511-678 and prog. Mater. Sci.83 (2016) 630-663).
Example 3
1. The microstructure characteristics of the NiTiCu shape memory alloy with narrow phase transition temperature hysteresis and high stability are as follows:
The NiTiCu shape memory alloy contains 15at.% Cu, 45at.% Ni and 40at.% Ti, and Ti (NiCu) 2 precipitate phases with the size of 80-150nm are uniformly distributed in the matrix, and the density range of the precipitate phases is 2×10 10/cm2～3.5×1010/cm2, namely 2×10 10～3.5×1010 precipitate phases per square centimeter.
2. The 4D printing preparation method of the NiTiCu shape memory alloy with narrow phase change hysteresis and high stability comprises the following steps:
(1) Pure nickel (accounting for 45 at.%), pure titanium (accounting for 40 at.%) and pure copper (accounting for 15 at.%) are mixed and smelted for 6 times to obtain NiTiCu prealloy original bars with uniform element distribution, powder making equipment is vacuumized to 3X 10 -3 Pa, niTiCu alloy bars with the diameter of 50mm are heated to 1500 ℃ through an induction coil, the NiTiCu alloy bars are atomized through Ar inert gas with the atomization pressure of 8MPa, and alloy powder with the particle size of 15-53 mu m is obtained through screening.
(2) 4D printing and forming: and (3) melting (LPBF) the NiTiCu alloy powder in the step (1) through a RENISHAW-400 laser powder bed to form the NiTiCu shape memory alloy. In the 4D printing preparation process, a process strategy of in-situ heat treatment is selected, namely, the process parameters of 100W laser power, 160mm/s laser scanning speed, 30 mu m powder paving layer thickness and 100 mu m scanning interval are adopted to carry out primary melting on NiTiCu alloy powder, and then the process parameters of 105W laser power, 1200mm/s laser scanning speed and 100 mu m scanning interval are adopted to carry out in-situ heat treatment on primary melting pass, so as to obtain a 4D printing NiTiCu alloy sample 1; meanwhile, the NiTiCu alloy powder is subjected to fusion forming by adopting the technological parameters of 100W laser power, 160mm/s laser scanning speed, 30 mu m powder paving layer thickness and 100 mu m scanning interval, so that a 4D printing NiTiCu alloy sample 2 is obtained.
3. Phase change behavior characteristics of NiTiCu shape memory alloy with narrow phase change temperature hysteresis and high stability prepared by 4D printing: for the 4D printing NiTiCu alloy sample 1, the phase transition temperature hysteresis of the NiTiCu shape memory alloy is 12 ℃ in the primary thermal cycle process, and after 10 thermal cycles, the phase transition temperature hysteresis of the NiTiCu shape memory alloy is 14 ℃, and the change amplitude of the phase transition temperature is 8%; after 50 thermal cycles, the phase transition temperature hysteresis of the NiTiCu shape memory alloy is 15 ℃, and the change amplitude of the phase transition temperature is 10%. For the 4D printed NiTiCu alloy sample 2, the phase transition temperature hysteresis of the NiTiCu shape memory alloy is 16 ℃ in the primary thermal cycle process, and after 10 thermal cycles, the phase transition temperature hysteresis of the NiTiCu shape memory alloy is 18 ℃ and the change amplitude of the phase transition temperature is 17%; after 50 thermal cycles, the phase transition temperature hysteresis of the NiTiCu shape memory alloy is 23 ℃, and the change amplitude of the phase transition temperature is 22%. As reported in the literature, as a phase change hysteresis (J.Manuf.Process.77 (2022) 539-550 and J.Allys Compd.885 (2021) 160971) at 30-40 ℃ in a 4D printed NiTi shape memory alloy, a phase change temperature change (Mater. Des.208 (2021) 109935) at 8-15 ℃ after 10 thermal cycles was found, the NiTiCu alloy of the present invention had a narrow phase change temperature hysteresis and high phase change temperature stability (prog. Mater. Sci.50 (5) (2005) 511-678 and prog. Mater. Sci.83 (2016) 630-663).
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (6)
1. A niticeu shape memory alloy characterized by comprising the following characteristics:
(1) The composition characteristics are as follows: the range of Cu content in the NiTiCu shape memory alloy is 5-15 at%, the range of Ni content is 30-50 at%, and the balance is Ti;
(2) Microstructure characteristics: the NiTiCu shape memory alloy matrix has a uniformly distributed precipitated phase;
(3) Phase change behavior characteristics: the phase transition temperature hysteresis of the NiTiCu shape memory alloy with the characteristics (1) and (2) is 3-15 ℃, and the phase transition temperature change amplitude of the NiTiCu shape memory alloy after 50 thermal cycles is 6-10%;
The uniformly distributed precipitated phase in the feature (2) is Ti 2 (NiCu) or Ti (NiCu) 2, the size of which is 15-120 nm, and the density of which is 2 multiplied by 10 10~4×1011/cm2.
2. The niticeu shape memory alloy of claim 1, wherein the Cu content of the niticeu shape memory alloy in the feature (1) is 5 at%, the Ni content is 43 at%, and the balance is Ti.
3. A 4D printing preparation method of a niticeu shape memory alloy according to any one of claims 1 to 2, characterized by comprising the steps of:
(1) Pulverizing: mixing and smelting pure nickel, pure titanium and pure copper raw materials to obtain a NiTiCu pre-alloyed raw bar with uniform element distribution, and preparing the NiTiCu pre-alloyed raw bar into NiTiCu alloy powder by an electrode induction smelting gas atomization method;
(2) 4D printing and forming: adopting a process strategy of in-situ heat treatment, and printing and forming the NiTiCu alloy powder obtained in the step (1) by using laser powder bed fusion forming equipment 4D to prepare NiTiCu shape memory alloy;
The specific steps of 4D printing and forming in the step (2) are as follows: and (3) performing primary melting on the NiTiCu alloy powder in the step (1) by using laser powder bed melting forming equipment under the technological parameters of 70-150W of laser power, 80-200 mm/s of scanning speed, 30 mu m of powder spreading layer thickness and 100 mu m of scanning interval, and performing in-situ heat treatment on the primary melting pass by using the technological parameters of 90-120W of laser power, 1000-1400 mm/s of scanning speed and 100 mu m of scanning interval to obtain the NiTiCu shape memory alloy.
4. The method for preparing a NiTiCu shape memory alloy by 4D printing according to claim 3, wherein the smelting time in the step (1) is 4-8 times, and the size of NiTiCu alloy powder is 15-53 μm.
5. The method for preparing the NiTiCu shape memory alloy by 4D printing according to claim 3, wherein the specific process of the electrode induction melting gas atomization method in the step (1) is as follows: vacuumizing powder making equipment to below 5X 10 -3 Pa, heating the NiTiCu alloy bar with the diameter of 30-50 mm to 1200-1500 ℃ through an induction coil, atomizing the NiTiCu alloy through Ar or He inert gas with the atomization pressure of 3-8 MPa, and screening to obtain NiTiCu alloy powder.
6. Use of a niticeu shape memory alloy according to any of claims 1 to 2 in the field of intelligent robots, complex driving devices and actuators.
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| CN106591627A (en) * | 2016-12-31 | 2017-04-26 | 镇江市丹徒区硕源材料科技有限公司 | High-strength shape memory alloy and preparing method and application thereof |
| CN111842888A (en) * | 2020-06-18 | 2020-10-30 | 华中科技大学 | 4D printing method of nickel titanium based ternary shape memory alloy |
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| CN106591627A (en) * | 2016-12-31 | 2017-04-26 | 镇江市丹徒区硕源材料科技有限公司 | High-strength shape memory alloy and preparing method and application thereof |
| CN111842888A (en) * | 2020-06-18 | 2020-10-30 | 华中科技大学 | 4D printing method of nickel titanium based ternary shape memory alloy |
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| Title |
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| Investigations on phase transformation and mechanical characteristics of laser additive manufactured TiNiCu shape memory alloy structures;S.Shiva等;《Journal of Materials Processing Technology》;第238卷;第142-151页 * |
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