WO2020151476A1 - 一种钛镍形状记忆合金的4d打印方法及应用 - Google Patents

一种钛镍形状记忆合金的4d打印方法及应用 Download PDF

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WO2020151476A1
WO2020151476A1 PCT/CN2020/070204 CN2020070204W WO2020151476A1 WO 2020151476 A1 WO2020151476 A1 WO 2020151476A1 CN 2020070204 W CN2020070204 W CN 2020070204W WO 2020151476 A1 WO2020151476 A1 WO 2020151476A1
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titanium
nickel
shape memory
powder
memory alloy
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杨超
卢海洲
马宏伟
李元元
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South China University of Technology SCUT
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    • C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
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    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20—Direct sintering or melting
    • B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
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    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • B22F2009/0836—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with electric or magnetic field or induction
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/08—Non-ferrous metals or alloys
    • B23K2103/14—Titanium or alloys thereof
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    • Y02P10/25—Process efficiency

Definitions

  • the invention belongs to the technical field of shape memory alloy preparation, and specifically relates to a 4D printing method and application of a titanium nickel shape memory alloy.
  • titanium-nickel shape memory alloys have excellent biocompatibility and are widely used in biomedical applications such as dentition correction wires, spinal orthopedic rods, intramedullary needles/nails, angioplasty rings, and surgical micro forceps. field.
  • biomedical applications such as dentition correction wires, spinal orthopedic rods, intramedullary needles/nails, angioplasty rings, and surgical micro forceps. field.
  • using its excellent shape memory effect and super elasticity it is widely used in pipe joints, pipe fixing, spring drive devices, temperature controllers, temperature sensor triggers and other fields; using its high damping performance, it is widely used in vibration control Components, cone dampers and other fields; using its excellent corrosion resistance, it has application prospects in the chemical industry, ship parts and other fields.
  • 4D printing is an additive manufacturing technology for smart materials.
  • the “D” in 4D printing refers to the dimensions of time, space, etc., that is, driven by external fields such as temperature and stress, the shape, performance, or function of the smart component responds quickly with time and space changes according to the pre-design, and realizes the integration of structure and function Design. Therefore, the 4D printing technology proposed by the present invention is to realize the selective laser melting (SLM) forming of titanium-nickel alloy powder.
  • SLM selective laser melting
  • SLM technology can directly melt the metal powder under the heat of the laser beam according to the three-dimensional data model, and solidify it into metal parts with good metallurgical bonding and high precision. It is especially suitable for thin walls, complex cavities, internal runners, etc. The manufacture of complex thin-walled precision components that are difficult to achieve with traditional processing technology.
  • the SLM technology has a high cooling rate during the solidification of molten powder, which includes a wide range of non-equilibrium solidification phenomena during the cooling process, which can refine the crystal grains and improve the solid solubility, thereby making the formed parts fine and compact, and the composition is uniform , Excellent performance.
  • SLM technology can also reduce the capital investment in mold design. It only takes about 20% of the cost of the traditional manufacturing process and about 10% of the time to manufacture the required parts, which greatly improves production efficiency.
  • the energy suitable for additive manufacturing of titanium-nickel alloys is usually 50-100J/mm 3. Relatively low, the optimal tensile properties of the additively manufactured titanium-nickel alloy are 606MPa tensile strength and 6.8% elongation; the targeted alloy system is Ni 50.1 Ti 49.9 (Reference 2: Mater.Sci.Eng .A724(2018)220-230), the optimal shape memory performance of the additively manufactured titanium-nickel alloy is the recovery angle of 20°; the alloy system targeted is Ni 50.9 Ti 49.1 (Reference 3: Sci.Rep.7(2017) 46707). In view of this, it is necessary to explore a method of using additive manufacturing technology to prepare high-performance titanium-nickel shape memory alloys to expand the industrial application of titanium-nickel alloys.
  • the primary purpose of the present invention is to provide a 4D printing method for titanium nickel shape memory alloys.
  • the method has fast manufacturing speed, short production cycle, mass production, personalized manufacturing, and remote control, and is especially suitable for thin-walled, special-shaped, and complex-structure products.
  • it effectively solves the problems encountered by traditional technology, makes its production more environmentally friendly and more efficient, and greatly accelerates its application.
  • the present invention provides a new process path for preparing ultra-high performance titanium nickel alloy.
  • Another object of the present invention is to provide a titanium nickel shape memory alloy prepared by the above method.
  • Another object of the present invention is to provide the above-mentioned titanium-nickel shape memory alloy in the preparation of spectacle frames, orthodontic wires, compression plates, spinal orthopedic rods, driving devices, actuators, complex dampers, corrosion-resistant equipment, intelligent control Applications in temperature devices, self-expanding trusses, self-expanding communication satellite components, and variant aircraft components.
  • a 4D printing method of titanium-nickel shape memory alloy includes the following steps:
  • Pulverizing mixing and smelting pure titanium and pure nickel to obtain titanium-nickel alloy rods, and then obtain alloy powders by rotating electrode atomization method, and sieving the powders to obtain particles with a particle size of 15-53 ⁇ m Titanium nickel alloy powder;
  • the titanium-nickel alloy powder after the surface modification treatment in step (2) is formed by selective laser melting (SLM) to obtain a titanium-nickel shape memory alloy.
  • SLM selective laser melting
  • the atomic percentage elemental composition of the titanium-nickel alloy bar in step (1) is: Ti 44-55 at.%, and the balance is Ni.
  • the specific steps of the rotating electrode atomization method in step (1) are as follows: the titanium-nickel alloy bar is heated to between 1250 and 1500°C through electrode induction by the electrode induction gas atomization powder making equipment; Argon atomizes the rod to obtain alloy powder, and the pressure during the atomization is controlled between 2.5 and 8 MPa.
  • the conditions for the surface modification in step (2) are: no ball milling medium is added, the protective atmosphere is 0.15-0.2MPa high-purity argon, the discharge voltage is controlled at 130 ⁇ 5V, the current is controlled at 1.2-2A, and the motor
  • the rotating speed is 600 ⁇ 1200r/min, the duration of each discharge treatment is 1h ⁇ 2h, the interval between two adjacent discharge treatments is 30min, and the number of discharge treatments is 6-10 times.
  • the energy density used is much higher than the commonly used low values currently reported in the literature.
  • a titanium-nickel shape memory alloy prepared by the above method the phase composition of the titanium-nickel shape memory alloy consists of a B2 austenite phase with a CsCl type structure, a B19' martensite phase with a monoclinic structure and Ti 2 Ni precipitation Phase composition; its microstructure includes nano-scale cellular crystals and micron-sized dendrites, and the cellular crystals and dendrites are alternately distributed in layers. Its microstructure is different from the reported observed square grains, lamellar martensite, fine grains, and S-shaped grains (Reference 1, Reference 2, Reference 4: Mater.Charact.94(2014) ) 189-202. Reference 5: Acta Mater. 144 (2016) 552-560.).
  • the grain boundaries are composed of discontinuous Ti 2 Ni precipitates with a size of 20 to 180 nm, and there are a large number of nano twins inside; for micron-sized dendrites, there are internal
  • the high density of dislocations and the dispersed Ti 2 Ni nanoparticle phase, the size of the nanoparticle phase is 5-30nm.
  • titanium-nickel shape memory alloy is used in the preparation of spectacle frames, dentition correction wires, compression bone plates, spinal orthopedic rods, driving devices, executive components, complex dampers, corrosion-resistant equipment, intelligent temperature control devices, self-expanding trusses, Expand applications in communication satellite components and variant aircraft components.
  • the principle of the present invention is: the present invention introduces the discharge plasma into the alloy powder by performing surface modification treatment on the titanium nickel alloy powder, so that the mechanical force and the plasma effect synergistically promote the refinement and activation of the powder.
  • the role of plasma is mainly divided into two aspects: (1) the thermal effect of the plasma; (2) the high-energy electron bombardment effect.
  • the electron temperature of the plasma can be as high as 10 4 K.
  • the high-speed and high-temperature pulse electrons impact the surface of the material, increasing the thermal stress and strain on the surface of the powder, leading to the phenomenon of "thermal explosion" of the material; in addition, the particles in the plasma It has high activity.
  • the coupling of plasma and mechanical vibration can greatly accelerate the surface modification of the titanium-nickel alloy powder, significantly reduce the reaction activation energy, greatly increase the activity of the titanium-nickel alloy powder and enhance the compound synthesis ability, promote the diffusion of atoms or ions, and induce low-temperature reactions.
  • the interaction between the titanium-nickel alloy powder and the laser in the subsequent 4D printing forming process is improved, so that the titanium-nickel alloy powder melts faster, and the nucleation speed also increases, resulting in a unique ultra-high performance structure.
  • titanium-nickel shape memory alloy is an intermetallic compound with low thermal conductivity and high thermal stress, it is easy to cause cracking.
  • low energy density 50J/mm 3 ⁇ 100J/mm 3
  • high energy density is used for forming
  • dense and high-performance titanium-nickel alloys There are certain difficulties in dense and high-performance titanium-nickel alloys.
  • the processed titanium-nickel alloy powder of the present invention can be formed at an energy density of 150J/mm 3 ⁇ E ⁇ 300J/mm 3 , and the prepared titanium-nickel alloy has a density of ⁇ 99.5%, and its strength and elongation are significantly higher than those of existing
  • the reported titanium-nickel alloy formed by SLM technology; the shape memory performance of the titanium-nickel alloy prepared at the same time is also far better than the current literature reports.
  • the present invention adopts 4D printing forming process to prepare titanium-nickel shape memory alloy. According to the designed three-dimensional model, it can complete the forming of complex-shaped titanium-nickel alloy parts, realize the rapid manufacturing of complex-structured titanium-nickel alloy parts, and can greatly expand the titanium-nickel alloy Applications in medical, sanitary, aerospace and other fields.
  • Fig. 1 is a scanning electron microscope image of a titanium-nickel alloy prepared by 4D printing in Example 1 ((a) and (b) in the figure show different magnifications and regions).
  • Example 2 is a transmission electron microscope image of the titanium-nickel alloy prepared by 4D printing in Example 1 ((a), (b), (c) in the figure show different magnifications and regions).
  • Figure 3 is a scanning electron microscope image of the titanium-nickel alloy prepared by 4D printing in Example 2 ((a) and (b) in the figure show different magnifications and areas).
  • Example 4 is a transmission electron microscope image of the titanium-nickel alloy prepared by 4D printing in Example 2 ((a), (b), (c) in the figure show different magnifications and regions).
  • Flour milling The ingredients are prepared according to the following titanium-nickel atomic ratio: Ti 50.6at.%, Ni49.4at.%.
  • the titanium-nickel alloy bar is smelted under vacuum conditions.
  • Use AMC-EIGA-50 powder milling equipment to heat the bar to 1350°C, atomize the bar under 4.5MPa argon pressure, collect the obtained original powder, perform screening treatment, and control the particle size of the target powder. In the range of 15 ⁇ 53 ⁇ m.
  • the specific forming steps are as follows: construct a three-dimensional model of the structural parts to be prepared, input the constructed three-dimensional model into Magics 15.01 for layered processing; import the data file into the SLM forming equipment, set the process parameters and save the settings, seal the forming chamber, and use a vacuum pump to The forming chamber is evacuated to a vacuum of 6 ⁇ 10 -2 Pa, and then high-purity protective argon gas is flushed to ensure that the oxygen content in the forming chamber is always below 200 ppm during the laser forming process; a powder spreading device is used to spread the thickness of the substrate evenly in advance 30 ⁇ m titanium-nickel alloy powder, and the excess powder is sent to the recovery tank, and then collected and reused.
  • the laser melts the pre-laid alloy powder according to the set process parameters, and then the formed substrate is lowered by a distance of the powder thickness (30 ⁇ m), and then the powder of the same thickness is preset on the melting layer , Laser melting again.
  • the above steps are repeated until the predetermined size and shape of the alloy block are reached, and the formed part is cut from the formed substrate to obtain a formed alloy sample.
  • the surface of the titanium-nickel alloy sample formed in this embodiment was polished, and its density was measured by the Archimedes drainage method, and the tensile performance was tested in accordance with the international standard (Chinese GB/T 228-2002).
  • the results show that the density of the titanium-nickel alloy prepared by the 4D printing technology in this example is 99.5%, which is composed of the B2 austenite phase of the CsCl type structure, the B19′ martensite phase of the monoclinic structure and the Ti 2 Ni precipitation Phase composition, the microstructure presents alternate distribution of micron-scale dendrites and nano-scale cellular crystals ( Figure 1).
  • the grain boundaries of nanoscale cellular crystals consist of discontinuous Ti 2 with a diameter of 20-30 nm and a length of 20-100 nm.
  • Ni precipitated phase composition and there are a large number of nano twins inside (Figure 2); for micron-sized dendrites, there are high-density dislocations and dispersed Ti 2 Ni nano-particle phase, the size of the nano-particle phase 5-20nm, the microstructure obtained in the present invention is completely different from the reported observed square grains, flaky martensite, fine grains, and S-shaped grains, etc. (Reference 1, Reference 2, Reference Reference 4, Reference 5).
  • the tensile strength of 4D printed titanium-nickel alloy is 778MPa and the elongation is 7.2%, which is much higher than the tensile strength of Ni 50.1 Ti 49.9 alloy 606MPa and the elongation of 6.8% (Reference 2); the length of 4D printed titanium-nickel alloy
  • the bending angle of the sheet specimen is 180°, the shape memory effect can be restored completely, and the recovery rate is 100%; when the bending angle of the long sheet specimen is 261°, the shape memory effect of the long sheet specimen can be restored to 232° and the recovery rate 90%; the shape memory performance is much higher than the recovery angle of the shape memory performance of Ni 50.9 Ti 49.1 alloy by 20° (Reference 3).
  • the superelastic strain reaches 5.8% in the austenite state, and the strain recovery rate exceeds 90%.
  • Flour milling The ingredients are prepared according to the following titanium-nickel atomic ratio: Ti 49.5at.%, Ni50.5at.%.
  • the titanium-nickel alloy bar is smelted under vacuum conditions.
  • Use AMC-EIGA-50 powder milling equipment to heat the bar to 1400°C, atomize the bar under 3MPa argon pressure, collect the obtained original powder, perform screening treatment, and control the particle size of the target powder to 15 ⁇ 53 ⁇ m range.
  • the surface of the titanium-nickel alloy sample formed in this embodiment was polished, and its density was measured by the Archimedes drainage method, and the tensile performance was tested in accordance with the international standard (Chinese GB/T 228-2002).
  • the results show that the density of the 4D printed titanium-nickel alloy in this example is 99.6%, composed of B2 austenite phase with CsCl type structure, B19′ martensite phase with monoclinic structure and Ti 2 Ni precipitation phase, and the microstructure presents Micron-scale dendrites and nano-scale cellular crystals are alternately distributed (Figure 3).
  • the grain boundaries of nano-scale cellular crystals are composed of discontinuous Ti 2 Ni precipitates with a diameter of 25-35 nm and a length of 25-150 nm.
  • nano twins there are a large number of nano twins inside; for micron-sized dendrites, there are high-density dislocations and a dispersed Ti 2 Ni nano-particle phase inside.
  • the size of the nano-particle phase is 10-20 nm ( Figure 4).
  • the microstructure obtained in the invention is completely different from the reported observed square grains, lamellar martensite, fine grains, and S-shaped grains, etc. (Reference 1, Reference 2, Reference 4, Reference 5 ).
  • the tensile strength of 4D printed titanium-nickel alloy is 708MPa and the elongation is 7.0%, which is much higher than the tensile strength of Ni 50.1 Ti 49.9 alloy 606MPa and the elongation of 6.8% (Reference 2); 4D printed titanium-nickel alloy long piece
  • the bending angle of the shape sample is 162°, the shape can be completely restored through the shape memory effect, the recovery rate is 100%, and the shape memory performance is much higher than the shape memory performance of Ni 50.9 Ti 49.1 alloy.
  • the recovery angle of 20° (Reference 3) . In the austenite state, its superelastic strain reaches 5.5%, and the strain recovery rate exceeds 90%.
  • Flour milling The ingredients are prepared according to the following titanium-nickel atomic ratio: Ti 44at.%, Ni 56at.%.
  • the titanium-nickel alloy bar is smelted under vacuum conditions.
  • Use AMC-EIGA-50 powder milling equipment to heat the bar to 1250°C, atomize the bar under 2.5MPa argon pressure, collect the obtained original powder, and perform screening treatment to control the particle size of the target powder. In the range of 15 ⁇ 53 ⁇ m.
  • the surface of the titanium-nickel alloy sample formed in this embodiment was polished, and its density was measured by the Archimedes drainage method, and the tensile performance was tested in accordance with the international standard (Chinese GB/T 228-2002).
  • the results show that the density of the titanium-nickel alloy prepared by 4D printing technology in this example is 99.6%, which is composed of B2 austenite phase with CsCl type structure, B19′ martensite phase with monoclinic structure and Ti 2 Ni precipitation Phase composition, the microstructure presents alternate distribution of micron-scale dendrites and nano-scale cellular crystals.
  • the grain boundaries of nano-scale cellular crystals are composed of discontinuous Ti 2 Ni precipitates with a diameter of 20-30 nm and a length of 50-180 nm.
  • microstructure obtained in the present invention is completely different from the reported observed square grains, flaky martensite, fine grains, and S-shaped grains, etc. (Reference 1, Reference 2, Reference 4, Reference 5.).
  • the tensile strength of 4D printed titanium-nickel alloy is 728MPa and the elongation is 7.3%, which is much higher than the tensile strength of Ni 50.1 Ti 49.9 alloy 606MPa and the elongation of 6.8% (Reference 2); the length of 4D printed titanium-nickel alloy
  • the bending angle of the sheet sample is 158°, the shape memory effect can be completely restored, and the recovery rate is 100%; the shape memory performance is much higher than the shape memory performance of Ni 50.9 Ti 49.1 alloy, the recovery angle of 20° (Reference 3) .
  • the strain recovery rate exceeds 90%.
  • Flour milling The ingredients are prepared according to the following atomic ratio of titanium to nickel: Ti 55at.%, Ni 45at.%.
  • the titanium-nickel alloy bar is smelted under vacuum conditions.
  • Use AMC-EIGA-50 powder milling equipment to heat the bar to 1500°C, atomize the bar under 8MPa argon pressure, collect the obtained original powder, perform screening treatment, and control the particle size of the target powder to 15 ⁇ 53 ⁇ m range.
  • the surface of the titanium-nickel alloy sample formed in this embodiment was polished, and its density was measured by the Archimedes drainage method, and the tensile performance was tested in accordance with the international standard (Chinese GB/T 228-2002).
  • the results show that the density of the titanium-nickel alloy prepared by 4D printing technology in this example is 99.6%, which is composed of B2 austenite phase with CsCl type structure, B19′ martensite phase with monoclinic structure and Ti 2 Ni precipitation Phase composition, the microstructure presents alternate distribution of micron-scale dendrites and nano-scale cellular crystals.
  • the grain boundaries of nano-scale cellular crystals are composed of discontinuous Ti 2 Ni precipitates with a diameter of 30-40nm and a length of 40-180nm.
  • microstructure obtained in the present invention is completely different from the reported observed square grains, flaky martensite, fine grains, and S-shaped grains, etc. (Reference 1, Reference 2, Reference 4, Reference 5.).
  • the tensile strength of 4D printed titanium-nickel alloy is 758MPa and the elongation rate is 7.1%, which is much higher than the tensile strength of Ni 50.1 Ti 49.9 alloy 606MPa and the elongation rate of 6.8% (Reference 2); the length of 4D printed titanium-nickel alloy
  • the bending angle of the sheet specimen is 163°, the shape memory effect can be completely restored, and the recovery rate is 100%; the shape memory performance is much higher than the shape memory performance of Ni 50.9 Ti 49.1 alloy, the recovery angle of 20° (Reference 3) .
  • the strain recovery rate exceeds 90%.

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Abstract

一种钛镍形状记忆合金的4D打印方法、钛镍形状记忆合金及其应用。将纯钛和纯镍进行配料、熔炼，得到钛镍合金棒材，然后通过旋转电极雾化法制取合金粉末，对粉末进行筛分处理，获得粒径为15～53μm的钛镍合金粉末；将所得钛镍合金粉末置于放电等离子体辅助球磨机中进行放电处理，对粉末进行表面改性，最后通过SLM成形，得到钛镍形状记忆合金。钛镍形状记忆合金的相组成由CsCl型结构的B2奥氏体相、单斜结构的B19'马氏体相和Ti 2Ni沉淀相组成；其微观结构包括纳米级的胞状晶和微米尺寸的树枝晶，且胞状晶和树枝晶呈现层状交替分布。具有独特的组织结构、近全致密、超高性能的特点。

Description

一种钛镍形状记忆合金的4D打印方法及应用 技术领域
本发明属于形状记忆合金制备技术领域，具体涉及一种钛镍形状记忆合金的4D打印方法及应用。
背景技术
在众多的形状记忆合金中，钛镍形状记忆合金具有优异的生物相容性，广泛应用于牙列矫正丝、脊柱矫形棒、髓内针/钉、血管成形环和手术用微型钳子等生物医疗领域。同时，利用其优良的形状记忆效应和超弹性，广泛应用于管路接头、管路固定、弹簧驱动装置、温度控制器、温度传感器触发器等领域；利用其高阻尼性能，广泛应用于振动控制构件、锥形阻尼器等领域；利用其优良的耐腐蚀性能，在化工、船舶零件等领域存在应用前景。
然而，对于钛镍形状记忆合金而言，采用传统工艺(熔炼铸造法、热等静压、粉末冶金法等)制备存在着较多的问题：(1)相变温度对其化学成分很敏感，在熔炼铸造中会引入杂质元素(如C、N、O等)，影响其形状记忆性能；(2)钛镍记忆合金的加工性能差，降低了生产效率；(3)记忆合金的传统生产工艺成本较高，使得最终产品价格昂贵，不利于广泛使用。此外对于精密复杂钛镍合金零件，譬如多孔结构、驱动器等等，采用传统工艺存在无法成形或成形成本高等问题。因此，探索新的钛镍合金成形工艺，在不降低其性能的同时拓展其应用领域，成为急需解决的问题。
4D打印是对智能材料的增材制造制备技术。4D打印多出的“D”是指时间、空间等维度，即在温度、应力等外场驱动下，智能构件的形状、性能或功能按预先设计随时间、空间变化而快速响应，实现结构功能一体化设计。因而，本 发明提出的4D打印技术即是实现对钛镍合金粉末的选区激光熔化(Selective Laser Melting，SLM)成形。
SLM技术能按照三维数据模型直接将金属粉末在激光束的热作用下完全熔化，并凝固成形为具有良好冶金结合和较高精度的金属零件，特别适合薄壁、内腔复杂、内流道等传统加工技术难以实现的复杂薄壁精密构件的制造。同时，SLM技术熔融粉末凝固过程中具有高的冷却速率，在冷却过程中包含大范围的非平衡凝固现象，从而可细化晶粒，提高固溶度，进而使得成形件组织细小致密、成分均匀、性能优异。SLM技术还可以降低模具设计的资金投入，仅需传统制造工艺20％左右的成本和10％左右的时间即可制造出所需制件，大大提高生产效率。
目前，利用SLM技术制备出高性能的钛镍合金及其零部件的成功案例鲜有报道。其制备难度包括：(1)钛镍合金机加工困难；(2)其相组成复杂，包括B2奥氏体相、B19’马氏体相、R相以及沉淀相等，且这些相热传导率低，不利于4D打印成形；(3)4D打印过程中存在一对矛盾，需要足够高的能量彻底熔化金属粉末以获得近全致密的块状材料，同时需要足够低的能量输入尽可能降低熔池与粉体间的温度梯度和残余应力以避免裂纹化倾向。在关于钛镍合金增材制造的研究中报道中(参考文献1：Prog.Mater.Sci.83(2016)630-663)，适用于钛镍合金增材制造的能量通常为50-100J/mm 3，相对偏低，增材制造的钛镍合金最优拉伸性能为606MPa的拉伸强度和6.8％的延伸率；针对的合金体系为Ni 50.1Ti 49.9(参考文献2：Mater.Sci.Eng.A724(2018)220-230)，增材制造的钛镍合金最优形状记忆性能为回复角20°；针对的合金体系为Ni 50.9Ti 49.1(参考文献3：Sci.Rep.7(2017)46707)。有鉴于此，有必要探索出一种运用增材制造技术制备高性能钛镍形状记忆合金的方法，以拓展钛镍合金的产业化应用领域。
发明内容
为了解决目前无法通过4D打印技术成形高性能钛镍合金及其零件的现状， 本发明的首要目的在于提供一种钛镍形状记忆合金的4D打印方法。该方法制造速度快，生产周期短，可批量生产，也可个性化制造，还可远程操控，尤其适用于薄壁、异型、结构复杂的产品。同时有效地解决传统工艺遇到的问题，使其生产更加环保、更高效，大幅加快其应用步伐。此外，本发明为制备超高性能钛镍合金提供了一种新的工艺路径。
本发明的另一目的在于提供一种通过上述方法制备得到的钛镍形状记忆合金。
本发明的再一目的在于提供上述钛镍形状记忆合金在制备眼镜框、牙列矫正丝、加压接骨板、脊柱矫形棒、驱动装置、执行元器件、复杂阻尼器、耐腐蚀设备、智能控温器件、自展开桁架、自展开通讯卫星零部件、变体航空器零部件等中的应用。
本发明目的通过以下技术方案实现：
一种钛镍形状记忆合金的4D打印方法，包括如下步骤：
(1)制粉：将纯钛和纯镍进行配料、熔炼，得到钛镍合金棒材，然后通过旋转电极雾化法制取合金粉末，对粉末进行筛分处理，获得粒径为15～53μm的钛镍合金粉末；
(2)粉末改性：将步骤(1)所得钛镍合金粉末置于放电等离子体辅助球磨机中进行放电处理，对粉末进行表面改性；
(3)4D打印成形：将步骤(2)表面改性处理后的钛镍合金粉末通过选区激光熔化(SLM)成形，得到钛镍形状记忆合金。
优选地，步骤(1)中所述钛镍合金棒材的原子百分比元素组成为：Ti44～55at.％，余量为Ni。
优选地，步骤(1)中所述旋转电极雾化法的具体步骤如下：通过电极感应气雾化制粉设备将钛镍合金棒材通过电极感应加热到1250～1500℃之间；通过高纯氩气雾化棒材得到合金粉末，雾化过程压力控制在2.5～8MPa之间。
优选地，步骤(2)中所述表面改性的条件为：不加入球磨介质，保护气氛 为0.15～0.2MPa高纯氩气，放电电压控制在130±5V，电流控制在1.2～2A，电机转速600～1200r/min，每次放电处理持续时间为1h～2h，相邻两次放电处理的间隔为30min，放电处理次数为6～10次。
优选地，步骤(3)中所述SLM成形的条件为：激光功率P≥60W，激光扫描速度ν≤200mm/s，激光扫描间距h＝60～100μm，铺粉层厚t＝30～60μm，且能量输入密度E(E＝P/ν×h×t)介于150J/mm 3≤E≤300J/mm 3。采用的能量密度远远高于目前文献报道的常用低值。
一种钛镍形状记忆合金，通过上述方法制备得到；所述钛镍形状记忆合金的相组成由CsCl型结构的B2奥氏体相、单斜结构的B19′马氏体相和Ti 2Ni沉淀相组成；其微观结构包括纳米级的胞状晶和微米尺寸的树枝晶，且胞状晶和树枝晶呈现层状交替分布。其微观结构不同于已报道的观察到的方形晶粒、片状马氏体、细晶、和S形晶粒等(参考文献1、参考文献2、参考文献4：Mater.Charact.94(2014)189-202.参考文献5：Acta Mater.144(2018)552-560.)。对于纳米级的胞状晶而言，其晶界由不连续的、尺寸为20～180nm的Ti 2Ni沉淀相组成，同时内部存在大量纳米孪晶；对于微米尺寸的树枝晶而言，其内部存在高密度的位错以及弥散分布的Ti 2Ni纳米颗粒相，纳米颗粒相的尺寸为5～30nm。
上述钛镍形状记忆合金在制备眼镜框、牙列矫正丝、加压接骨板、脊柱矫形棒、驱动装置、执行元器件、复杂阻尼器、耐腐蚀设备、智能控温器件、自展开桁架、自展开通讯卫星零部件、变体航空器零部件等中的应用。
本发明原理为：本发明通过对钛镍合金粉末进行表面改性处理，将放电等离子体引入到合金粉末中，使机械力作用和等离子体作用协同促进粉末的组织细化、活性激活等。等离子体的作用主要分为两方面：(1)等离子体的热效应；(2)高能电子轰击效应。等离子体的电子温度可高达10 4K，高速高温的脉冲电子冲击材料表面，增加粉体表面微区的热应力、应变，导致材料的“热爆”现象；此外由于等离子体中的物质微粒都具有高活性，吸附沉积在粉体表面后引起材料表面高能活化，提高粉体原子的扩散能力，放电诱发自蔓延反应等机 制。通过等离子体和机械震动耦合，可以大大加速钛镍合金粉末表面的改性，明显降低反应活化能、极大提高钛镍合金粉末活性和增强化合物合成能力，促进原子或离子扩散，诱发低温反应，从而提高了钛镍合金粉末在随后4D打印成形过程中与激光的交互作用，使得钛镍合金粉末熔化速度更快，形核速度也随之增大，得到独特的超高性能组织结构。
本发明的制备方法及所得到的产物具有如下优点及有益效果：
(1)由于钛镍形状记忆合金属于金属间化合物，热传导率低，热应力大易导致开裂，目前通常采用低能量密度(50J/mm 3～100J/mm 3)成形，故采用高能量密度成形致密高性能的钛镍合金存在一定的难度。而本发明经处理后的钛镍合金粉末可在150J/mm 3≤E≤300J/mm 3能量密度下成型，制备的钛镍合金的致密度≥99.5％，强度和延伸率明显远高于已报道的SLM技术成形的钛镍合金；同时制备的钛镍合金的形状记忆性能也远优于目前文献报道情况。
(2)本发明采用4D打印成形工艺制备钛镍形状记忆合金，根据设计的三维模型可以完成复杂形状钛镍合金零件的成形，实现复杂结构钛镍合金零件的快速制造，可以大大拓展钛镍合金在医疗、卫浴、航空航天等领域的应用。
附图说明
图1为实施例1中4D打印制备成型的钛镍合金的扫描电镜图(图中(a)、(b)显示不同放大倍数及区域)。
图2为实施例1中4D打印制备成型的钛镍合金的透射电镜图(图中(a)、(b)、(c)显示不同放大倍数及区域)。
图3为实施例2中4D打印制备成型的钛镍合金的扫描电镜图(图中(a)、(b)显示不同放大倍数及区域)。
图4为实施例2中4D打印制备成型的钛镍合金的透射电镜图(图中(a)、(b)、(c)显示不同放大倍数及区域)。
具体实施方式
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
(1)制粉。按照下述钛镍原子比进行配料：Ti 50.6at.％，Ni49.4at.％。在真空条件下熔炼出钛镍合金棒材。运用AMC-EIGA-50制粉设备将棒材加热到1350℃，在4.5MPa氩气气压下，将棒材进行雾化，收集所得到的原始粉末，进行筛选处理，控制目标粉末的粒径在15～53μm范围内。
(2)粉末改性。将钛镍合金粉末在真空手套箱内装入不锈钢球磨罐(球磨罐内不加入不锈钢球或其他球磨介质)；取出不锈钢罐，向真空罐体中冲入高纯氩气(0.15～0.2MPa)；将不锈钢罐置于Plasma-BM-S型等离子体球磨机进行放电处理。控制参数为：电压125V，电流控制在1.4A，电极转速800r/min，每次放电处理持续时间为1h，相邻两次放电处理的间隔为30min，放电处理次数为6次。
(3)4D打印成形。运用SLM成形设备(型号Concept Laser M2)对放电处理后粉末进行4D打印成形，工艺参数为：激光功率P＝70W，激光扫描速度ν＝105mm/s，激光扫描间距h＝100μm，铺粉层厚t＝30μm，能量输入密度E＝P/ν×h×t＝222J/mm 3。具体成型步骤为：构建所需制备结构零件的三维模型，将构建的三维模型输入Magics 15.01进行分层处理；将数据文件导入SLM成形设备，设置工艺参数并保存设置，密封成形室，用真空泵将成形室内抽至真空度为6×10 -2Pa，之后冲入高纯保护氩气，保证激光成形过程中成形室内氧含量始终低于200ppm；用铺粉装置在基板上预先均匀铺置厚度为30μm的钛镍合金粉末，并将多余的粉末送入回收缸中，之后收集重复使用。激光器根据设计的切片形状和激光扫描策略，按照设置的工艺参数，熔化预先铺设的合金粉末，随后成形基板下降一个铺粉厚度(30μm)的距离，再在熔化层上重新预置相同 厚度的粉末，再次激光熔化。重复上述步骤，直到达到预先设定的合金块体尺寸和形状，将成形件从成形基板上切割下来，得到成形的合金试样。
将本实施例成形的钛镍合金试样表面磨光，通过阿基米德排水法测其致密度，按照国际标准(Chinese GB/T 228-2002)进行拉伸性能测试。结果表明，本实施例中通过4D打印技术制备得到的钛镍合金的致密度为99.5％，由CsCl型结构的B2奥氏体相、单斜结构的B19′马氏体相和Ti 2Ni沉淀相组成，微观结构呈现出微米级树枝晶和纳米级胞状晶层状交替分布(图1)，纳米级胞状晶的晶界由不连续的、直径20-30nm，长度为20-100nm的Ti 2Ni沉淀相组成，同时内部存在大量纳米孪晶(图2)；对于微米尺寸的树枝晶而言，其内部存在高密度的位错以及弥散分布的Ti 2Ni纳米颗粒相，纳米颗粒相的尺寸为5-20nm，本发明中获得的微观结构完全不同于已报道的观察到的方形晶粒、片状马氏体、细晶、和S形晶粒等(参考文献1、参考文献2、参考文献4、参考文献5)。4D打印钛镍合金的拉伸强度为778MPa、延伸率为7.2％，远高于Ni 50.1Ti 49.9合金606MPa的拉伸强度和6.8％的延伸率(参考文献2)；4D打印钛镍合金的长片状试样弯曲角度为180°时，形状记忆效应其形状能够完全恢复、回复率为100％；长片状试样弯曲角度为261°时，形状记忆效应其形状能够恢复232°、回复率为90％；形状记忆性能远高于Ni 50.9Ti 49.1合金形状记忆性能的回复角20°(参考文献3)。另外，在奥氏体状态下其超弹性应变达到5.8％，应变回复率超过90％。
实施例2
(1)制粉。按照下述钛镍原子比进行配料：Ti 49.5at.％，Ni50.5at.％。在真空条件下熔炼出钛镍合金棒材。运用AMC-EIGA-50制粉设备将棒材加热到1400℃，在3MPa氩气气压下，将棒材进行雾化，收集所得到的原始粉末，进行筛选处理，控制目标粉末的粒径在15～53μm范围内。
(2)粉末改性。将钛镍合金粉末在真空手套箱内装入不锈钢球磨罐(球磨 罐内不加入不锈钢球或其他球磨介质)；取出不锈钢罐，向真空罐体中冲入高纯氩气(0.15～0.2MPa)；将不锈钢罐置于Plasma-BM-S型等离子体球磨机进行放电处理。控制参数为：电压135V，电流控制在1.7A，电极转速1000r/min，每次放电处理持续时间为1.2h，相邻两次放电处理的间隔为30min，放电处理次数为8次。
(3)4D打印成形。运用SLM成形设备(型号Concept Laser M2)对放电处理后粉末进行4D打印成形，具体成型步骤同实施例1。工艺参数为：激光功率P＝70W，激光扫描速度ν＝80mm/s，激光扫描间距h＝100μm，铺粉层厚t＝30μm，能量输入密度E＝P/ν×h×t＝292J/mm 3。
将本实施例成形的钛镍合金试样表面磨光，通过阿基米德排水法测其致密度，按照国际标准(Chinese GB/T 228-2002)进行拉伸性能测试。结果表明，本实施例4D打印钛镍合金的致密度为99.6％，由CsCl型结构的B2奥氏体相、单斜结构的B19′马氏体相和Ti 2Ni沉淀相组成，微观结构呈现出微米级树枝晶和纳米级胞状晶层状交替分布(图3)，纳米级胞状晶的晶界由不连续的、直径25-35nm，长度为25-150nm的Ti 2Ni沉淀相组成，同时内部存在大量纳米孪晶；对于微米尺寸的树枝晶而言，其内部存在高密度的位错以及弥散分布的Ti 2Ni纳米颗粒相，纳米颗粒相的尺寸为10-20nm(图4)，本发明中获得的微观结构完全不同于已报道的观察到的方形晶粒、片状马氏体、细晶、和S形晶粒等(参考文献1、参考文献2、参考文献4、参考文献5)。4D打印钛镍合金的拉伸强度为708MPa、延伸率为7.0％，远高于Ni 50.1Ti 49.9合金606MPa的拉伸强度和6.8％的延伸率(参考文献2)；4D打印钛镍合金长片状试样弯曲角度为162°时，通过形状记忆效应其形状能够完全恢复、回复率为100％，形状记忆性能远高于Ni 50.9Ti 49.1合金形状记忆性能的回复角20°(参考文献3)。在奥氏体状态下其超弹性应变达到5.5％，应变回复率超过90％。
实施例3
(1)制粉。按照下述钛镍原子比进行配料：Ti 44at.％，Ni 56at.％。在真空条件下熔炼出钛镍合金棒材。运用AMC-EIGA-50制粉设备将棒材加热到1250℃，在2.5MPa氩气气压下，将棒材进行雾化，收集所得到的原始粉末，进行筛选处理，控制目标粉末的粒径在15～53μm范围内。
(2)粉末改性。将钛镍合金粉末在真空手套箱内装入不锈钢球磨罐(球磨罐内不加入不锈钢球或其他球磨介质)；取出不锈钢罐，向真空罐体中冲入高纯氩气(0.15～0.2MPa)；将不锈钢罐置于Plasma-BM-S型等离子体球磨机进行放电处理。控制参数为：电压125V，电流控制在1.2A，电极转速1200r/min，每次放电处理持续时间为2h，相邻两次放电处理的间隔为30min，放电处理次数为10次。
(3)4D打印成形。运用SLM成形设备(型号Concept Laser M2)对放电处理后粉末进行4D打印成形，具体成型步骤同实施例1。工艺参数为：激光功率P＝70W，激光扫描速度ν＝120mm/s，激光扫描间距h＝100μm，铺粉层厚t＝30μm，能量输入密度E＝P/ν×h×t＝194J/mm 3。
将本实施例成形的钛镍合金试样表面磨光，通过阿基米德排水法测其致密度，按照国际标准(Chinese GB/T 228-2002)进行拉伸性能测试。结果表明，本实施例中通过4D打印技术制备得到的钛镍合金的致密度为99.6％，由CsCl型结构的B2奥氏体相、单斜结构的B19′马氏体相和Ti 2Ni沉淀相组成，微观结构呈现出微米级树枝晶和纳米级胞状晶层状交替分布，纳米级胞状晶的晶界由不连续的、直径20-30nm，长度为50-180nm的Ti 2Ni沉淀相组成，同时内部存在大量纳米孪晶；对于微米尺寸的树枝晶而言，其内部存在高密度的位错以及弥散分布的Ti 2Ni纳米颗粒相，纳米颗粒相的尺寸为5-20nm。本发明中获得的微观结构完全不同于已报道的观察到的方形晶粒、片状马氏体、细晶、和S形晶粒等(参考文献1、参考文献2、参考文献4、参考文献5.)。4D打印钛镍合金的拉伸强度为728MPa、延伸率为7.3％，远高于Ni 50.1Ti 49.9合金606MPa的拉伸强度和6.8％的延伸率(参考文献2)；4D打印钛镍合金的长片状试样弯曲角 度为158°时，形状记忆效应其形状能够完全恢复、回复率为100％；形状记忆性能远高于Ni 50.9Ti 49.1合金形状记忆性能的回复角20°(参考文献3)。在奥氏体状态下其超弹性应变达到5.3％，应变回复率超过90％。
实施例4
(1)制粉。按照下述钛镍原子比进行配料：Ti 55at.％，Ni 45at.％。在真空条件下熔炼出钛镍合金棒材。运用AMC-EIGA-50制粉设备将棒材加热到1500℃，在8MPa氩气气压下，将棒材进行雾化，收集所得到的原始粉末，进行筛选处理，控制目标粉末的粒径在15～53μm范围内。
(2)粉末改性。将钛镍合金粉末在真空手套箱内装入不锈钢球磨罐(球磨罐内不加入不锈钢球或其他球磨介质)；取出不锈钢罐，向真空罐体中冲入高纯氩气(0.15～0.2MPa)；将不锈钢罐置于Plasma-BM-S型等离子体球磨机进行放电处理。控制参数为：电压125V，电流控制在2A，电极转速600r/min，每次放电处理持续时间为1h，相邻两次放电处理的间隔为30min，放电处理次数为6次。
(3)4D打印成形。运用SLM成形设备(型号Concept Laser M2)对放电处理后粉末进行4D打印成形，具体成型步骤同实施例1。工艺参数为：激光功率P＝70W，激光扫描速度ν＝150mm/s，激光扫描间距h＝100μm，铺粉层厚t＝30μm，能量输入密度E＝P/ν×h×t＝155J/mm 3。
将本实施例成形的钛镍合金试样表面磨光，通过阿基米德排水法测其致密度，按照国际标准(Chinese GB/T 228-2002)进行拉伸性能测试。结果表明，本实施例中通过4D打印技术制备得到的钛镍合金的致密度为99.6％，由CsCl型结构的B2奥氏体相、单斜结构的B19′马氏体相和Ti 2Ni沉淀相组成，微观结构呈现出微米级树枝晶和纳米级胞状晶层状交替分布，纳米级胞状晶的晶界由不连续的、直径30-40nm，长度为40-180nm的Ti 2Ni沉淀相组成，同时内部存在大量纳米孪晶；对于微米尺寸的树枝晶而言，其内部存在高密度的位错以及 弥散分布的Ti 2Ni纳米颗粒相，纳米颗粒相的尺寸为5-30nm。本发明中获得的微观结构完全不同于已报道的观察到的方形晶粒、片状马氏体、细晶、和S形晶粒等(参考文献1、参考文献2、参考文献4、参考文献5.)。4D打印钛镍合金的拉伸强度为758MPa、延伸率为7.1％，远高于Ni 50.1Ti 49.9合金606MPa的拉伸强度和6.8％的延伸率(参考文献2)；4D打印钛镍合金的长片状试样弯曲角度为163°时，形状记忆效应其形状能够完全恢复、回复率为100％；形状记忆性能远高于Ni 50.9Ti 49.1合金形状记忆性能的回复角20°(参考文献3)。在奥氏体状态下其超弹性应变达到5.6％，应变回复率超过90％。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (8)

  1. 一种钛镍形状记忆合金的4D打印方法，其特征在于包括如下步骤：
    (1)制粉：将纯钛和纯镍进行配料、熔炼，得到钛镍合金棒材，然后通过旋转电极雾化法制取合金粉末，对粉末进行筛分处理，获得粒径为15～53μm的钛镍合金粉末；
    (2)粉末改性：将步骤(1)所得钛镍合金粉末置于放电等离子体辅助球磨机中进行放电处理，对粉末进行表面改性；
    (3)4D打印成形：将步骤(2)表面改性处理后的钛镍合金粉末通过SLM成形，得到钛镍形状记忆合金。
  2. 根据权利要求1所述的一种钛镍形状记忆合金的4D打印方法，其特征在于：步骤(1)中所述钛镍合金棒材的原子百分比元素组成为：Ti44～55at.％，余量为Ni。
  3. 根据权利要求1所述的一种钛镍形状记忆合金的4D打印方法，其特征在于步骤(1)中所述旋转电极雾化法的具体步骤如下：通过电极感应气雾化制粉设备将钛镍合金棒材通过电极感应加热到1250～1500℃之间；通过高纯氩气雾化棒材得到合金粉末，雾化过程压力控制在2.5～8MPa之间。
  4. 根据权利要求1所述的一种钛镍形状记忆合金的4D打印方法，其特征在于步骤(2)中所述表面改性的条件为：不加入球磨介质，保护气氛为0.15～0.2MPa高纯氩气，放电电压控制在130±5V，电流控制在1.2～2A，电机转速600～1200r/min，每次放电处理持续时间为1h～2h，相邻两次放电处理的间隔为30min，放电处理次数为6～10次。
  5. 根据权利要求1所述的一种钛镍形状记忆合金的4D打印方法，其特征在于步骤(3)中所述SLM成形的条件为：激光功率P≥60W，激光扫描速度ν≤200mm/s，激光扫描间距h＝60～100μm，铺粉层厚t＝30～60μm，且能量输入密度E介于150J/mm 3≤E≤300J/mm 3。
  6. 一种钛镍形状记忆合金，其特征在于：通过权利要求1～5任一项所述的方法制备得到；所述钛镍形状记忆合金的相组成由CsCl型结构的B2奥氏体相、单斜结构的B19′马氏体相和Ti 2Ni沉淀相组成；其微观结构包括纳米级的胞状晶和微米尺寸的树枝晶，且胞状晶和树枝晶呈现层状交替分布。
  7. 根据权利要求6所述的一种钛镍形状记忆合金，其特征在于：对于纳米级的胞状晶而言，其晶界由不连续的、尺寸为20～180nm的Ti 2Ni沉淀相组成，同时内部存在大量纳米孪晶；对于微米尺寸的树枝晶而言，其内部存在高密度的位错以及弥散分布的Ti 2Ni纳米颗粒相，纳米颗粒相的尺寸为5～30nm。
  8. 权利要求6或7所述的一种钛镍形状记忆合金在制备眼镜框、牙列矫正丝、加压接骨板、脊柱矫形棒、驱动装置、执行元器件、复杂阻尼器、耐腐蚀设备、智能控温器件、自展开桁架、自展开通讯卫星零部件、变体航空器零部件中的应用。
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CN109648082B (zh) * 2019-01-24 2021-08-06 华南理工大学 一种钛镍形状记忆合金的4d打印方法及应用
CN110090954B (zh) * 2019-04-24 2020-11-06 中国石油大学(北京) 一种增材制造NiTi形状记忆合金及其制备方法
US11648729B2 (en) 2019-06-03 2023-05-16 The Boeing Company Additive manufacturing powder particle, method for treating the additive manufacturing powder particle, and method for additive manufacturing
CN112296335B (zh) * 2019-07-23 2022-06-07 暨南大学 一种激光选区熔化成形块体纳米孪晶铜基复合材料的方法
CN110465662B (zh) 2019-08-09 2021-01-19 华南理工大学 一种原位调控镍钛合金功能特性的4d打印方法及应用
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110055891A (ko) * 2009-11-20 2011-05-26 한국생산기술연구원 마이크로 입자의 표면에 나노 입자를 증착시키기 위한 혼합 분말 제조장치 및 이를 이용하여 제조되는 혼합 분말
CN104116578A (zh) * 2014-07-18 2014-10-29 西安交通大学 一种4d打印成型人工血管支架的方法
CN104325136A (zh) * 2014-11-26 2015-02-04 康凯 一种金属粉末及其制备方法和应用
CN105522161A (zh) * 2015-12-25 2016-04-27 中国科学院重庆绿色智能技术研究院 一种3d打印用细粒径球形粉末的快速规模化制备方法
CN105642905A (zh) * 2016-03-23 2016-06-08 龙岩紫荆创新研究院 一种镍基合金球形粉末的等离子体制备方法
CN108145172A (zh) * 2016-12-05 2018-06-12 无锡辛德华瑞粉末新材料科技有限公司 一种4d打印专用金属粉末的制备方法
CN109022920A (zh) * 2018-08-30 2018-12-18 中南大学 一种无裂纹的4d打印钛镍形状记忆合金及其制备方法
CN109648082A (zh) * 2019-01-24 2019-04-19 华南理工大学 一种钛镍形状记忆合金的4d打印方法及应用

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6149742A (en) * 1998-05-26 2000-11-21 Lockheed Martin Corporation Process for conditioning shape memory alloys
JP2012107262A (ja) * 2009-03-12 2012-06-07 Yoshimi Seisakusho:Kk 形状記憶合金製部材の製造方法及び形状記憶合金製部材を利用したアクチュエータ
EP2461900A4 (en) * 2009-08-07 2017-08-02 Innovative Processing Technologies Inc. Methods and systems for processing materials, including shape memory materials
CN103949637A (zh) * 2014-05-09 2014-07-30 张百成 一种基于选择性激光熔化技术的钛镍记忆合金加工方法
KR102322229B1 (ko) * 2014-05-13 2021-11-05 더 유니버시티 오브 유타 리서치 파운데이션 실질적으로 구형인 금속 분말의 제조
JP6348233B2 (ja) * 2014-12-24 2018-06-27 華南理工大学 粉体の高エネルギー球入破砕における冷プラズマ放電支援の応用方法および装置
US10662513B2 (en) * 2016-07-26 2020-05-26 Verkko Biomedical, LLC Dynamic, non-homogenous shape memory alloys
CA3031191A1 (en) * 2016-08-18 2018-02-22 Arconic Inc. Tailored metal powder feedstocks for facilitating preferential recovery after additive manufacturing
CN106825594B (zh) * 2017-02-08 2018-12-14 中航迈特粉冶科技（北京）有限公司 一种3d打印用球形钛镍形状记忆合金粉末的制备方法
CN107022692B (zh) * 2017-03-30 2019-10-18 华南理工大学 一种放电等离子体辅助球磨制备Cu-Sn-Bi轴承合金的方法
CN107326402B (zh) * 2017-07-20 2019-04-02 攀钢集团研究院有限公司 镍钛合金的制备方法
CN108044109A (zh) * 2017-12-21 2018-05-18 西安欧中材料科技有限公司 用于增材制造的医用镍钛合金粉末的制备方法
CN208960995U (zh) * 2018-09-29 2019-06-11 宁波众远新材料科技有限公司 一种3d打印金属粉体材料制造设备
CN109128205A (zh) * 2018-09-29 2019-01-04 宁波众远新材料科技有限公司 一种3d打印金属粉体材料制造设备及方法
JP7157702B2 (ja) * 2019-05-29 2022-10-20 株式会社古河テクノマテリアル ＮｉＴｉ系合金材料、ＮｉＴｉ系合金材料の製造方法およびＮｉＴｉ系合金材料からなる線材または管材
US20220055891A1 (en) * 2020-08-20 2022-02-24 U.S. Army Combat Capabilities Development Command, Army Research Laboratory Phase change micro shutter array grid and method

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110055891A (ko) * 2009-11-20 2011-05-26 한국생산기술연구원 마이크로 입자의 표면에 나노 입자를 증착시키기 위한 혼합 분말 제조장치 및 이를 이용하여 제조되는 혼합 분말
CN104116578A (zh) * 2014-07-18 2014-10-29 西安交通大学 一种4d打印成型人工血管支架的方法
CN104325136A (zh) * 2014-11-26 2015-02-04 康凯 一种金属粉末及其制备方法和应用
CN105522161A (zh) * 2015-12-25 2016-04-27 中国科学院重庆绿色智能技术研究院 一种3d打印用细粒径球形粉末的快速规模化制备方法
CN105642905A (zh) * 2016-03-23 2016-06-08 龙岩紫荆创新研究院 一种镍基合金球形粉末的等离子体制备方法
CN108145172A (zh) * 2016-12-05 2018-06-12 无锡辛德华瑞粉末新材料科技有限公司 一种4d打印专用金属粉末的制备方法
CN109022920A (zh) * 2018-08-30 2018-12-18 中南大学 一种无裂纹的4d打印钛镍形状记忆合金及其制备方法
CN109648082A (zh) * 2019-01-24 2019-04-19 华南理工大学 一种钛镍形状记忆合金的4d打印方法及应用

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112676576A (zh) * 2020-12-21 2021-04-20 中北大学 一种化学梯度Cr-Fe-Ni组元合金的SLM成形方法
CN114836654A (zh) * 2022-04-08 2022-08-02 华南理工大学 一种等原子比镍钛合金单程形状记忆效应的高效训练方法
CN115971490A (zh) * 2022-12-12 2023-04-18 中南大学 一种抗菌多孔钛镍合金的制备方法及其产品
CN117564298A (zh) * 2023-10-07 2024-02-20 华南理工大学 一种宽温域形状记忆复合材料及其4d打印制备方法
CN118430701A (zh) * 2024-07-03 2024-08-02 吉林大学 基于机器学习的选择性激光熔化NiTi合金相变温度预测方法
CN119122971A (zh) * 2024-08-06 2024-12-13 中国石油大学(北京) 镍钛合金缓冲吸能点阵结构及其制备方法

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