CN120243974B - A high-strength 3D printing nickel-titanium-iron shape memory alloy and its preparation method - Google Patents
A high-strength 3D printing nickel-titanium-iron shape memory alloy and its preparation methodInfo
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Abstract
本发明涉及合金增材技术领域，具体涉及一种高强度3D打印镍钛铁形状记忆合金及其制备方法。该合金由该方法制得。该方法包括通过构建热力学数据库，并组合采用凝固模拟以及开源代码库搜寻第二相Ti2Ni相分数和裂纹敏感因子的帕累托最优解集，筛选出合金的目标成分含量；先将目标成分含量的合金成分通过熔炼获得镍钛铁合金铸锭，再通过气雾化法制得镍钛铁预合金粉末，将经过筛分的镍钛铁预合金粉末真空干燥后，得到合金的粉末原料；对粉末原料采用选区激光熔化成形工艺逐层打印制得3D打印镍钛铁形状记忆合金的零件实体。本发明能够制备出相变温度低、力学性能高以及成型好的3D打印镍钛铁形状记忆合金。
The present invention relates to the field of alloy additive technology, and more specifically to a high-strength 3D-printable nickel- titanium-iron shape memory alloy and a preparation method thereof. The alloy is prepared by this method. The method comprises constructing a thermodynamic database and combining solidification simulation with an open-source code library to search for a Pareto optimal solution set for the second-phase Ti₂Ni phase fraction and crack sensitivity factor, thereby screening the target component content of the alloy; first, smelting the alloy components with the target component content to obtain a nickel-titanium-iron alloy ingot; then, a nickel-titanium-iron pre-alloy powder is prepared by gas atomization; the screened nickel-titanium-iron pre-alloy powder is vacuum-dried to obtain a powder raw material of the alloy; and the powder raw material is printed layer by layer using a selective laser melting process to produce a 3D-printed nickel-titanium-iron shape memory alloy part entity. The present invention can produce a 3D-printed nickel-titanium-iron shape memory alloy with a low phase transition temperature, high mechanical properties, and good forming properties.
Description
Technical Field
The invention relates to the technical field of alloy material addition, in particular to a high-strength 3D printing nickel-titanium-iron shape memory alloy and a preparation method thereof.
Background
The nickel-titanium-iron shape memory alloy has the characteristics of low phase transition temperature, excellent mechanical property at room temperature, larger restoring stress at lower temperature and the like. In addition, compared with other low-temperature shape memory alloys, the nickel-titanium-iron shape memory alloy has remarkable advantages in stability and reliability in service in a low-temperature environment. For example, nickel-titanium-iron shape memory alloy pipe joints have found very wide application in aircraft hydraulic piping systems, one of the most typical and successful cases for shape memory alloy applications in the engineering field.
The nickel-titanium based shape memory alloy has machining difficulties, such as material cracking, surface peeling, tearing and other defects in the machining process, due to the high ductility of the nickel-titanium based shape memory alloy and the high work hardening in the machining process. In the laser 3D printing technology which is emerging in recent years, three-dimensional structure information of complex parts is obtained by means of computer-aided design (such as CAD-aided design), and solid parts with complex structures are directly prepared in a layer-by-layer accumulation mode, so that the machining difficulty of nickel-titanium-based shape memory alloy can be effectively solved. The complex structure solid part prepared by the selective laser melting technology has better surface finish and higher geometric accuracy, and is the main 3D printing technology for preparing the nickel-titanium-based shape memory alloy at present.
However, the characteristics of high cooling rate, repeated remelting of alloy, complex thermal history and the like of the selective laser melting technology lead to uneven microstructure of the 3D printing state nickel-titanium shape memory alloy, high residual stress and easy generation of metallurgical defects, thereby influencing the comprehensive performance of the nickel-titanium alloy. In addition, the strong lattice distortion caused by the addition of the third element iron element further increases the solidification cracking tendency of the nickel-titanium shape memory alloy, and deteriorates the formability of the 3D printing nickel-titanium alloy.
At present, the 3D printing nickel-titanium-iron shape memory alloy is usually added with lower iron content (atomic ratio is less than 1 at percent), however, the phase transition temperature of the alloy is higher, and the actual service requirement can not be met. If the 3D printing nickel-titanium-iron shape memory alloy adopts higher iron content (atomic ratio is more than or equal to2 at percent), serious solidification cracking and delamination are easy to occur, the mechanical property is obviously reduced, and even the forming is failed. Therefore, a high-strength 3D printing nickel-titanium-iron shape memory alloy and a preparation method thereof are required to be developed for solving the problems of high phase transition temperature, low mechanical property and poor molding of the existing 3D printing nickel-titanium-iron shape memory alloy.
Disclosure of Invention
The invention aims to provide a high-strength 3D printing nickel-titanium-iron shape memory alloy and a preparation method thereof, and the specific technical scheme is as follows:
in a first aspect, the invention provides a preparation method of a high-strength 3D printing nickel-titanium-iron shape memory alloy, which comprises the following steps:
Step S1, establishing a nickel-titanium-iron ternary system thermodynamic database of a nickel-titanium-rich end according to nickel-titanium-iron system phase balance data in the existing literature, performing solidification simulation on nickel-titanium-iron alloy with a wide alloy component range in the thermodynamic database, acquiring a change relation of second phase fractions and crack sensitivity factors of the nickel-titanium-iron alloy under different component contents by means of a crack sensitivity factor model, searching a pareto optimal solution set of the second phase Ti 2 Ni phase fractions and the crack sensitivity factors by using an open source code library according to the change relation, and further screening to obtain target component contents of the 3D printed nickel-titanium-iron shape memory alloy;
S2, smelting 3D printing nickel-titanium-iron shape memory alloy components with target component content to obtain nickel-titanium-iron alloy cast ingots, preparing nickel-titanium-iron prealloy powder by gas atomization, and vacuum drying the screened nickel-titanium-iron prealloy powder to obtain powder raw materials of the 3D printing nickel-titanium-iron alloy;
And step S3, printing the powder raw materials layer by adopting a selective laser melting forming process to obtain the 3D printing nickel-titanium-iron shape memory alloy part entity.
Optionally, the mass percentage of each component in the wide alloy component range is as follows, 43-50 wt.% of titanium, 0.01-4 wt.% of iron and the balance nickel.
Optionally, the aerosolization method is an electrode-induced aerosolization method.
Optionally, the screened nickel-titanium-iron prealloy powder is nickel-titanium-iron prealloy powder with the particle size of 15-53 mu m and the sphericity of more than 95%.
Optionally, the parameters adopted by the selective laser melting forming process comprise laser power of 80-200W, scanning speed of 300-1000 mm/s, scanning interval of 60-90 mu m, light spot diameter of 40-80 mu m and powder spreading layer thickness of 20-40 mu m;
The selective laser melting forming process adopts a scanning strategy of zoning and interlayer rotation, the width of a laser scanned stripe is 4-6 mm, laser is scanned back and forth in each stripe, an initial included angle of the first layer of laser scanning is set to be 0-60 degrees, specifically 0-57 degrees, the interlayer rotation angle of the laser scanning is 0-90 degrees, specifically 0-45 degrees, 67 degrees or 90 degrees.
Optionally, preheating the substrate to 180-200 ℃ before printing by adopting a selective laser melting forming process on the substrate, and filling inert gas to reduce the oxygen content of the working cabin to below 200 ppm, and keeping the air pressure in the working cabin to be 10-20 mbar higher than the atmospheric pressure.
Optionally, the method further comprises a step S4 of post-treatment, specifically, after the selective laser melting forming process is completed, heating the substrate, stopping introducing inert gas, reducing the gas pressure in a working cabin, cleaning and recovering residual powder after the temperature of the substrate is reduced below 70 ℃, taking out the substrate with the part entity, and separating the part entity from the substrate by wire cutting after the substrate with the printed part is subjected to stress relief annealing.
Optionally, the stress relief annealing comprises heating to 150-200 ℃ at a rate of 5-10 ℃ per minute for stress relief annealing, and air cooling to room temperature after 3-5 h of heat preservation.
Optionally, the step S4 further includes polishing to remove an oxide layer generated on the solid surface of the part after the wire cutting.
In a second aspect, the invention provides a high-strength 3D printing nickel-titanium-iron shape memory alloy, which is prepared by adopting the preparation method of the high-strength 3D printing nickel-titanium-iron shape memory alloy, wherein the target component content of the 3D printing nickel-titanium-iron shape memory alloy comprises 45.4 wt percent by mass of titanium, 2.2 percent by mass of iron wt percent by mass of iron and the balance of nickel.
The application of the technical scheme of the invention has at least the following beneficial effects:
(1) The preparation method of the high-strength 3D printing nickel-titanium-iron shape memory alloy provided by the invention can be used for preparing the 3D printing nickel-titanium-iron shape memory alloy with low phase transition temperature, high mechanical property and good molding. Specifically, in the step S1, the target component content of the 3D printing nickel-titanium-iron shape memory alloy can be efficiently screened out in a wide alloy component range by constructing a thermodynamic database, adopting a solidification simulation and adopting an open source code library to search the pareto optimal solution set of the second phase Ti 2 Ni phase fraction and the crack sensitivity factor, and the 3D printing nickel-titanium-iron shape memory alloy component with the target component content can be prepared into the nickel-titanium-iron shape memory alloy with no crack on the surface, good forming performance, high strength and low phase transition temperature under a wider 3D printing process parameter window through the powder raw material obtained in the step S2. Compared with the mixed powder formed by mechanically mixing the nickel simple substance powder, the titanium simple substance powder and the iron simple substance powder (the iron simple substance powder is easier to oxidize and is easier to introduce impurity oxygen elements), the invention adopts the gas atomization method in the selective laser melting forming process to obtain the nickel-titanium-iron prealloy powder which is more uniform, has better powder fluidity and is not easy to introduce impurities, and can effectively avoid the situation that the alloy cracks in the 3D printing process due to non-uniformity of the powder, impurity inclusion and poor fluidity.
(2) Compared with the traditional nickel-rich low-temperature nickel-titanium shape memory alloy, the target component content of the 3D printing nickel-titanium-iron shape memory alloy provided by the invention limits the mass percent of iron to 2.2 wt percent (namely, the iron atomic ratio in the target component content is 2.1 at percent), the iron element in the content can increase the stability of an austenite phase in the 3D printing nickel-titanium-iron shape memory alloy, the phase transition temperature is obviously reduced, and the relative content of the nickel element and the titanium element is adjusted, so that the alloy solidification path is optimized, the melt channel between crystal grains at the final stage of solidification is reduced, the liquid phase melt backfill is facilitated, the liquid phase supply capability and the lap joint between crystal grains are improved, the hot crack tendency in the alloy solidification process is reduced, and the 3D printing forming performance deterioration caused by the content of the higher iron element is reduced. In addition, the segregation of the brittle Ti 2 Ni phase at the grain boundary can be limited under the content of the target component, and the generation of metallurgical defects (such as hot cracks) is reduced, so that the mechanical property of the 3D printing nickel-titanium-iron alloy is improved. Furthermore, the cost of the iron element is relatively low, and the addition of the iron element with higher content is beneficial to reducing the raw material cost of the 3D printing nickel-titanium-based shape memory alloy.
In addition to the objects, features and advantages described above, the present invention has other objects, features and advantages. The present invention will be described in further detail with reference to the drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 is a graph showing the variation of the fraction of the second phase Ti 2 Ni phase for the 3D printed nickel titanium iron shape memory alloy of example 1 at different titanium and iron contents;
FIG. 2 is a graph showing the variation of crack sensitivity factors for the 3D printed nickel titanium iron shape memory alloy of example 1 at different titanium and iron contents;
FIG. 3 is a compression performance test curve of the 3D printed nickel titanium iron shape memory alloy in example 5;
FIG. 4 is a phase transition curve of the 3D printed nickel titanium iron shape memory alloy of example 5;
FIG. 5 is a tensile property test curve of the 3D printed nickel titanium iron shape memory alloy of example 6;
FIG. 6 is a tensile property test curve of the 3D printed nickel titanium iron shape memory alloy of example 7;
FIG. 7 is a tensile property test curve of the 3D printed nickel titanium iron shape memory alloy of example 8;
FIG. 8 is a tensile property test curve of the 3D printed nickel titanium iron shape memory alloy of example 9;
fig. 9 is a tensile property test curve of the 3D printed nickel titanium iron shape memory alloy of comparative example 1.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
Example 1:
A preparation method of a high-strength 3D printing nickel-titanium-iron shape memory alloy comprises the following steps:
Step S1, establishing a nickel-titanium-iron ternary system thermodynamic database of a nickel-titanium-rich end by adopting a Calphad method according to nickel-titanium-iron system phase balance data in the prior document, adopting Hill-Grignard solidification simulation in Pandat software to carry out solidification simulation on nickel-titanium-iron alloy with a wide alloy component range in the thermodynamic database, acquiring a change relation of a second phase fraction and a crack sensitivity factor of the nickel-titanium-iron alloy under different component contents by means of a Kou crack sensitivity factor model (see the prior document Kou S, A criterion for cracking during resolution, ACTA MATERIALIA; 88:366-74), and adopting an open source code library to search a pareto optimal solution set of the second phase fraction and the crack sensitivity factor (namely, the second phase fraction and the crack sensitivity factor reach the nickel-titanium alloy component content when the pareto is the lowest at the same time), further screening to obtain a target component content of a 3D printed nickel-titanium-iron shape memory alloy, specifically, namely, 45.4. wt, 2.2 and 3D can be used for improving the shape memory defect of the nickel-titanium-iron shape memory alloy under the conditions that the thermal crack sensitivity factor is limited by the Ti 35;
s2, smelting 3D printing nickel-titanium-iron shape memory alloy components with target component content to obtain nickel-titanium-iron alloy cylindrical bar cast ingots, preparing nickel-titanium-iron prealloy powder by gas atomization, and vacuum drying the screened nickel-titanium-iron prealloy powder to obtain powder raw materials of the 3D printing nickel-titanium-iron alloy;
And step S3, printing the powder raw materials layer by adopting a selective laser melting forming process to obtain the 3D printing nickel-titanium-iron shape memory alloy part entity.
The nickel-titanium-iron system phase balance data comprises pure component nickel, pure component titanium, pure component iron, binary nickel-titanium, binary nickel-iron, binary titanium-iron and ternary nickel-titanium-iron phase balance data.
The phase equilibrium data for pure elemental nickel, pure elemental titanium and pure elemental iron are derived from the prior literature Dinsdale A SGTE data for pure elements Calphad 1991;15:317-425.
The phase balance data of binary nickel-titanium system is derived from the prior literature Povoden E, Cirstea D, Lang P, Wojcik T, Kozeschnik E. Thermodynamics of Ti–Ni shape memory alloys. Calphad 2013;41:128-39.
The phase balance data of binary nickel-iron is derived from the prior literature Franke P, Seifert H. The influence of magnetic and chemical ordering on the phase diagram of Cr–Fe–Ni. Calphad 2011;35:148-54.
The phase equilibrium data for binary titanium-iron is derived from the prior literature Guo C, li C, zheng X, du Z, thermodynamic modeling of the Fe-Ti-V system, calphad 2012;38:155-60.
Ternary nickel-titanium-iron phase equilibrium data are derived from the prior literature De Keyzer J, Cacciamani G, Dupin N, Wollants P. Thermodynamic modeling and optimization of the Fe–Ni–Ti system. Calphad 2009;33:109-23.
The mass percentage of each component in the wide alloy component range is as follows, 43-50 wt.% of titanium, 0.01-4 wt.% of iron and the balance nickel.
The nickel-titanium-iron alloy ingot is purchased from Hunan Yuan New Material Co.
The electrode induction gas atomization method can effectively reduce the introduction of impurity elements such as carbon, oxygen and the like, and meets the requirement of low impurity content of alloy powder in an SLM process, and the specific process of the electrode induction gas atomization is as follows:
Firstly, under the protection atmosphere of high-purity argon (more than or equal to 99.99%), controlling the oxygen content in the whole gas atomization process to be lower than 500 ppm, carrying out induction smelting (smelting temperature 1600 ℃ and smelting power 100 kW) on a nickel-titanium-iron alloy cast ingot, then, under the atomization pressure of 6 MPa, crushing a molten nickel-titanium-iron metal melt into small liquid drops through an alumina ceramic tube (nozzle aperture is 3.5 mm) to be quickly solidified into nickel-titanium-iron prealloy powder, and finally, screening and vacuum drying the obtained nickel-titanium-iron prealloy powder to obtain the powder raw material of the 3D printed nickel-titanium-iron alloy. The powder raw materials comprise, by mass, 45.07% of titanium, 2.10% of iron, less than or equal to 0.03% of carbon, less than or equal to 0.08% of oxygen, less than or equal to 0.03% of nitrogen, less than or equal to 0.05% of copper, less than or equal to 0.05% of aluminum, less than or equal to 0.05% of manganese, less than or equal to 0.05% of boron, less than or equal to 0.05% of chromium, the balance of nickel, less than or equal to 0.10% of other elements in total, and other elements except titanium, iron and nickel are impurity elements introduced in the smelting, atomizing and other processes.
The sieved nickel-titanium-iron prealloy powder is nickel-titanium-iron prealloy powder with the particle size of 15-53 mu m and the sphericity of more than 95%.
The selective laser melting forming process comprises the steps of debugging 3D printing equipment, introducing a nickel-titanium-iron alloy three-dimensional slice model into the 3D printing equipment, setting printing process parameters and a laser scanning strategy, preheating a base plate, introducing argon gas to reduce oxygen content in a working cabin, beginning printing to form nickel-titanium-iron shape memory alloy, lowering the base plate by one layer height after finishing printing of one powder layer thickness, spreading nickel-titanium-iron alloy powder of a powder feeding cabin on the base plate again by a scraper, printing the next powder layer, and repeatedly printing the whole part entity layer by layer.
Specifically, the parameters adopted by the selective laser melting forming process comprise 160W of laser power, 1000 mm/s of scanning speed, 80 μm of scanning interval, 60 μm of spot diameter and 30 μm of powder spreading layer thickness;
the selective laser melting forming process adopts a scanning strategy of zoning and interlayer rotation, the width of a laser scanned stripe is 4mm, laser is scanned in each stripe in a reciprocating manner, the initial included angle of the laser scanning of the first layer is set to be 57 degrees, and the interlayer rotation angle of the laser scanning is set to be 67 degrees.
Before printing by adopting a selective laser melting forming process on a substrate, in order to prevent excessive oxygen elements from being introduced and degrading the forming performance of the nickel-titanium-iron alloy, vacuumizing a forming chamber to 10 -3 Pa, and then introducing high-purity argon (99.99%) for atmosphere protection, and repeating the steps for three times. In addition, to prevent warpage and cracking of the bottom of the part, the substrate was preheated to 180 ℃ and the solid bottom of the part was provided with a chamfer having a radius of 1 mm. In the 3D printing forming process, the air pressure in the working cabin is kept to be 10-20 mbar higher than the external atmospheric pressure, and high-purity argon is filled to reduce the oxygen content of the working cabin to below 200 ppm, so that the placing direction of the part entity and the advancing direction of the scraper form an inclination angle of 75 degrees.
And S4, post-processing, namely closing heating the substrate after finishing the selective laser melting forming process, stopping introducing inert gas, reducing the gas pressure in a working cabin, cleaning and recovering residual powder after the temperature of the substrate is reduced to below 70 ℃, taking out the substrate with the part entity, carrying out stress relief annealing on the substrate with a printed part, separating the part entity from the substrate through wire electric discharge cutting, immersing the wire-cut part entity into epoxy resin for embedding and sealing to obtain a sample, and polishing the embedded sample by sequentially using 400-mesh, 600-mesh, 800-mesh, 1200-mesh, 1500-mesh and 2000-mesh silicon carbide sand paper until the surface of the sample is cut with an oxide layer and no obvious scratch, and polishing the sample by using a silicon dioxide fine polishing liquid on a SAPHIR-520 type automatic polishing machine.
The destressing annealing is carried out in a KSL-1200X box furnace at a rate of 5 ℃ per min to 200 ℃ for destressing annealing, and after the heat preservation is carried out for 4 hours, the air cooling is carried out to room temperature.
Example 2:
unlike example 1, the laser power was 80W and the scanning speed was 300 mm/s.
Example 3:
Unlike example 1, the laser power was 200W and the scanning speed was 1000 mm/s.
Example 4:
unlike example 1, the laser power was 140W and the scanning speed was 800 mm/s.
The selected area laser melting forming process parameters (namely 3D printing process parameters) described in examples 1-4 are adopted to respectively prepare 3D printed nickel-titanium-iron shape memory alloy square block-shaped part entities with the dimensions of 8mm multiplied by 8mm (length multiplied by width multiplied by height). The molding quality of each part entity in examples 1 to 4 was measured, and the measurement results are shown in table 1. In table 1, energy density = laser power/(scan speed x scan pitch x layer thickness of the powder bed), in J/mm 3.
In the forming quality detection, the surface crack detection method comprises the steps of firstly polishing the lower bottom surface and the side surface of a 3D printed nickel-titanium-iron shape memory alloy part entity, and then observing the lower bottom surface and the side surface of the part entity by adopting an optical microscope of LEICA DM4500P model, and detecting and recording the surface crack condition of the part entity.
The relative density detection method comprises the steps of firstly, weighing by using an electronic balance of the model MSA324S-000-DU to obtain the dry weight W Drying of a 3D printing nickel-titanium-iron shape memory alloy block part entity, then, completely immersing the part entity in distilled water, weighing the mass W In water of the part entity after the part entity is put into the distilled water, and further, calculating the actual density of the 3D printing nickel-titanium-iron shape memory alloy by adopting the following rho Alloy =ρ Water and its preparation method ×W Drying /（W Drying -W In water ) according to the Archimedes principle, wherein the theoretical density of the 3D printing nickel-titanium-iron shape memory alloy is 6.45 g/cm 3, and finally, dividing the actual density by the theoretical density from the prior literature "Yuan B, Ge J, Chen H, Pan J, Zhang L,Qi X. Printability and microstructure of Fe doped NiTi shape memory alloy fabricated by laser powder bed fusion. Mater Lett 2022;328:133099"; to obtain the relative density of the 3D printing nickel-titanium-iron shape memory alloy block part entity.
The upper surface roughness detection method comprises the following step of scanning the upper surface of a 3D printed nickel-titanium-iron shape memory alloy block-shaped part entity by adopting a ContourGT-K optical profiler to obtain the upper surface roughness of the part entity.
TABLE 1 results of quality measurements of formation under different selected laser melt forming process parameters
As shown in the data of Table 1, the 3D printing nickel-titanium-iron shape memory alloy with no surface cracks and good forming quality can be prepared by adopting the embodiments 1-4. This shows that the target component content of the 3D printing nickel-titanium-iron shape memory alloy screened by the invention can be suitable for a wider 3D printing process parameter window.
Example 5:
The 3D printing process parameters described in example 1 were used to prepare rectangular bulk parts of the nickel-titanium-iron shape memory alloy with dimensions 50mm x 10mm (length x width x height) 3D printed.
The compression performance of the part entity prepared in example 5 was tested by using an Instron 8804 electrohydraulic servo test system, which comprises that firstly, a cylindrical compression sample with a diameter of 8mm and a height of 10mm was processed by wire-cut electrical discharge machining of the part entity prepared in example 5, then, the surface of the cylindrical compression sample was polished to remove the oxide layer generated in the wire-cut process, and further, the cylindrical compression sample was uniaxially compressed at a strain rate of 1.6X10 -4·s-1, and the changes in stress and strain were recorded until the sample broke. The test results are shown in fig. 3. The test method comprises the steps of firstly taking a15 mg sample, taking an empty aluminum crucible as a reference crucible, heating to 100 ℃ from room temperature at a heating rate of 10 ℃ min -1 and preserving heat for 5 minutes, then cooling to-150 ℃ from 100 ℃ at a cooling rate of 10 ℃ min -1 and recording the heat absorption and release condition of the sample in the cooling process, further heating to 100 ℃ from-150 ℃ at a heating rate of 10 ℃ min -1 and recording the heat absorption and release condition of the sample in the heating process, and ending the test. The detection results are shown in FIG. 4.
Referring to FIG. 3, the nickel-titanium-iron shape memory alloy prepared in example 5 has a compressive strength of 2670MPa and a compressive strain of 45%. Compared with the 3D printing nickel-titanium-iron shape memory alloy in the prior literature （Yuan B, Ge J, Zhang L, Chen H, Wei L, Zhou Y, et al. Laser powder bed fusion of NiTiFe shape memory alloy via pre-mixed powder: microstructural evolution, mechanical and functional properties. Rare Metals 2024;43:2300-16）, the compressive strength 2156MPa and the compressive strain 35% of the nickel-titanium-iron shape memory alloy prepared in the example 5 are obviously improved.
Referring to FIG. 4, the nickel-titanium-iron shape memory alloy prepared in example 5 cooled from 100 ℃ to-150 ℃, and the occurrence of martensitic phase transformation was not yet detected in the differential scanning calorimeter test, indicating that the martensitic phase transformation temperature was below-150 ℃. The minimum martensitic transformation initiation temperature of the 3D printed nickel-titanium-iron alloy with the iron addition of 0.52. 0.52 wt% in comparison with the prior art document （Xi R, Jiang H, Li G, Zhang Z, Zhao G, Vanmeensel K. et al. Effect of Fe addition on the microstructure, transformation behaviour and superelasticity of NiTi alloys fabricated by laser powder bed fusion. Virtual Phys Prototyp 2022;18:2126376.） is-50 ℃, indicating that the nickel-titanium-iron shape memory alloy with the iron addition of 2.2. 2.2 wt% in example 5 has a lower martensitic transformation temperature.
The density of the nickel-titanium-iron shape memory alloy prepared in example 5 is 99.2%, the surface roughness is 6.97 μm, and the surface has no cracks.
Example 6:
unlike example 1, the laser power was 180W, the scanning speed was 1000 mm/s, and the laser energy density was 83.3J/mm 3.
Example 7:
the same 3D printing process parameters as in example 1 were used.
Example 8:
unlike example 1, the laser power was 160W, the scanning speed was 900 mm/s, and the laser energy density was 74.1J/mm 3.
The 3D printing process parameters described in examples 6-8 are adopted to prepare 3D printed nickel-titanium-iron shape memory alloy rectangular block-shaped part entities with the dimensions of 50mm multiplied by 10mm (length multiplied by width multiplied by height). The tensile performance of each part entity is tested by adopting an MTS E44.104 electronic universal testing machine, and the testing method comprises the steps of firstly, processing an I-shaped tensile member sample with the length of 15mm, the width of gauge length of 2mm and the thickness of 2mm on each part entity by electric spark wire cutting, then polishing the surface of the I-shaped tensile member sample to remove an oxide layer generated in the online cutting process, and further, uniaxially stretching the I-shaped tensile member sample at the strain rate of 1.6X10 -4·s-1, and recording the change conditions of stress and strain until the sample breaks. The test results are shown in fig. 5-7.
Referring to fig. 5-7, the tensile strength of the 3D printed nickel-titanium-iron shape memory alloy prepared in example 6 is 895MPa, the tensile strength of the 3D printed nickel-titanium-iron shape memory alloy prepared in example 7 is 842MPa, the tensile strength of the 3D printed nickel-titanium-iron shape memory alloy prepared in example 8 is 915MPa, and compared with the tensile strength of the 3D printed nickel-titanium-iron shape memory alloy in the existing literature （Xi R, Jiang H, Li G, Zhang Z, Zhao G, Vanmeensel K. et al. Effect of Fe addition on the microstructure, transformation behaviour and superelasticity of NiTi alloys fabricated by laser powder bed fusion. Virtual Phys Prototyp 2022;18:2126376.）, which is 736 MPa at most, the tensile strength of the 3D printed nickel-titanium-iron shape memory alloy prepared in examples 6-8 adopted in the invention is obviously higher than 736 MPa, and the 3D printed nickel-titanium-iron shape memory alloy has excellent mechanical properties.
In addition, the density of the 3D printed nickel-titanium-iron shape memory alloy prepared in example 6 was 99.6%, the surface roughness was 4.83 μm, and the surface was crack-free. The 3D printed nickel titanium iron shape memory alloy prepared in example 7 had a density of 99.1%, a surface roughness of 6.44 μm, and no surface cracks. The 3D printed nickel titanium iron shape memory alloy prepared in example 6 had a density of 99.5%, a surface roughness of 4.66 μm, and no surface cracks.
Example 9:
Unlike example 1, the laser power was 140W, the scanning speed was 1000 mm/s, and the laser energy density was 58.3J/mm 3.
Comparative example 1:
Unlike example 9, step S3 and step S4 were omitted, and the gas atomization method in step S2 was not employed, and a nickel-titanium-iron alloy cylindrical bar ingot was obtained directly by melting.
Rectangular block shaped part bodies having dimensions of 50mm×10mm (length×width×height) were prepared using the 3D printing process parameters described in example 9 and the ingot casting protocol of comparative example 1, respectively. The tensile performance of each part entity is tested by adopting an MTS E44.104 electronic universal testing machine, and the testing method comprises the steps of firstly, machining each part entity into an I-shaped tensile piece with the length of 15mm, the width of gauge length of 2mm and the thickness of 2mm through electric spark wire cutting, then polishing the surface of the I-shaped tensile piece to remove an oxide layer generated in the wire cutting process, and further uniaxially stretching a sample at the strain rate of 1.6X10 -4·s-1, and recording the change condition of stress and strain until the sample breaks. The test results are shown in fig. 8-9.
Referring to fig. 8-9, the tensile strength of the nickel-titanium-iron alloy formed by adopting the ingot casting scheme of comparative example 1 is 993MPa, and the elongation is 1.15%. The 3D printing nickel-titanium-iron shape memory alloy prepared in example 9 has a density of 99.8%, a surface roughness of 6.59 μm, a tensile strength of 1094 MPa and an elongation of 3.21%. Compared with comparative example 1, the 3D printing nickel-titanium-iron shape memory alloy prepared in example 9 has higher tensile strength, higher elongation and excellent comprehensive mechanical property. Therefore, the 3D printing nickel-titanium-iron shape memory alloy prepared by the invention has good forming property and obviously improved mechanical property.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
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| CN1614056A (en) * | 2004-12-08 | 2005-05-11 | 北京航空航天大学 | Low-phase point-variable high-strength TiNiFe marmem and use as pipe joint thereof |
| CN114669751A (en) * | 2022-04-14 | 2022-06-28 | 中南大学 | A kind of preparation method of crack-free nickel-titanium-copper alloy for additive manufacturing |
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| CN1206382C (en) * | 2003-10-23 | 2005-06-15 | 上海交通大学 | Preparation method of micron-fine-crystal titanium nickel-iron shaped memory alloy block material |
| CN111842888A (en) * | 2020-06-18 | 2020-10-30 | 华中科技大学 | A 4D printing method of nickel-titanium-based ternary shape memory alloy |
| CN113909493B (en) * | 2021-09-09 | 2023-02-17 | 中国地质大学（武汉） | A nickel-titanium alloy and neodymium-iron-boron alloy multi-material and its 4D printing method and application |
| CN114196847B (en) * | 2021-12-16 | 2022-09-02 | 山东大学苏州研究院 | Porous nickel-titanium alloy, preparation method and application thereof, and porous nickel-titanium alloy component |
| CN116809940B (en) * | 2023-08-30 | 2023-11-03 | 吉林大学 | Multi-component shape memory high-entropy alloy for additive manufacturing and preparation method thereof |
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