NiTiHf high temperature shape memory alloy with two-way shape memory effect, and 4D printing method and application thereof

Patent metadata

Field	Value
Publication number	US-12370602-B2
Application number	US-202217976902-A
Country	US
Kind code	B2
Filing date	Oct 31, 2022
Priority date	Jun 24, 2022
Publication date	Jul 29, 2025
Grant date	Jul 29, 2025

Abstract

The invention belongs to the technical field of shape memory alloys and additive manufacturing, and discloses a NiTiHf high temperature shape memory alloy with two-way shape memory effect and a 4D printing method and application thereof. The 4D printing method includes alloy powder processing, model building and substrate preheating, and 4D printing forming. The present invention patent is based on the design concept of reducing thermal gradient and the environmental friendly concept of clean production. It adopts substrate preheating combined with low laser power and low scanning speed laser powder bed fusion technology or low preheating temperature electron beam powder bed fusion technology to improve the formed alloy. The lattice compatibility with the NiTi substrate reduces the residual stress of the formed sample, and produces no cracks, no obvious holes, density ≥99%, high phase transformation temperature, excellent tensile mechanical properties and two-way shape memory effect.

First claim

The invention claimed is:

1. A 4D printing method of NiTiHf high temperature shape memory alloy comprising:
(1) powder processing: preparing and vacuum smelting high-purity titanium, high-purity nickel and high-purity crystalline hafnium according to a selected atomic percentage to obtain NiTiHf alloy rods, preparing NiTiHf alloy powder by an electrode induction-melting gas atomization method or a plasma rotating electrode atomization method, and sieving to obtain NiTiHf alloy powder with a selected size range;
(2) constructing a model and preheating a substrate: building a three-dimensional model of structural parts to be prepared, completing a slicing process and generating a print file; the substrate is a NiTi alloy substrate and preheating the NiTi alloy substrate;
(3) forming by 4D printing: forming a NiTiHf high temperature shape memory alloy with a two-way shape memory effect by utilizing the NiTiHf alloy powder sieved in step (1) through a laser powder bed fusion 4D printing additive manufacturing with a laser power of 45 to 100 W and a scanning speed of 100 to 200 mm/s, or by an electron beam powder bed fusion 4D printing additive manufacturing with a substrate preheat temperature of 300 to 500° C.;
wherein in step (3), a size of NiTiHf alloy powder suitable for the electron beam powder bed fusion 4D printing additive manufacturing is 50 to 120 m.

2. The 4D printing method of NiTiHf high temperature shape memory alloy according to claim 1 , wherein the selected atomic percentage of the NiTiHf alloy rods in step (1) is: Ni 50.1 to 52.5 at. %, Hf 19.0 to 22.5 at. %, and a remaining is Ti.

3. The 4D printing method of NiTiHf high temperature shape memory alloy according to claim 1 , wherein the electrode induction-melting gas atomization method in step (1) is as follows:
heating the NiTiHf alloy rods to between 1450 to 1750° C. by an electrode induction;
obtaining the NiTiHf alloy powder by atomizing the NiTiHf alloy rods with high-purity argon gas, an atomization pressure is 2.5 to 4.5 MPa, a supplemental gas pressure is 0.05 to 0.2 MPa, the atomizing gas temperature is 30 to 45° C., a melting power is 15 to 25 kW, and an entire environment is protected by argon.

4. The 4D printing method of NiTiHf high temperature shape memory alloy according to claim 1 , wherein the plasma rotating electrode atomization method in step (1) is:
melting the NiTiHf alloy rods by a high temperature plasma arc, obtaining the NiTiHf alloy powder by atomizing the melted NiTiHf alloy rods, a rotating speed of an electrode rod is 18000 to 24000 r/min, a plasma arc current intensity is 1500 to 2000 A, a feed rate is 0.8 to 1.2 mm/s, high-purity argon is used as an atomizing medium.

5. The 4D printing method of NiTiHf high temperature shape memory alloy according to claim 1 , wherein in step (3), a size of NiTiHf alloy powder suitable for the laser powder bed fusion 4D printing additive manufacturing is 15 to 75 μm, a preheating temperature of the substrate is 150 to 350° C.

6. The 4D printing method of NiTiHf high temperature shape memory alloy according to claim 1 , wherein process conditions of the laser powder bed fusion 4D printing additive manufacturing in step (3) are: a laser scanning spacing of 60 to 100 μm, a powder layer thickness of 20 to 50 μm, and a scanning strategy of 67° to 90° rotation between layers.

7. The 4D printing method of NiTiHf high temperature shape memory alloy according to claim 1 , wherein process conditions of the electron beam powder bed fusion 4D printing additive manufacturing in step (3) are: an accelerating voltage of 60 to 80 kV, a scanning current 15 of 25 mA, a scanning spacing 150 to 250 μm, a powder layer thickness of 50 to 100 μm, a scanning rate 800 to 1300 mm/s, and a scanning strategy of 67° to 90° rotation between layers.

Assignees

• Univ South China Tech
• Guangdong Huayi Plumbing Fittings Ind Co Ltd

Inventors

• Yang Chao
• Ma Hongwei
• Ding Yanfei
• Cai Weisi
• Yu Xiao

Classifications

• C22C30/00

  Alloys containing less than 50% by weight of each constituent · CPC title

• C22C1/02

  by melting {(C22C1/1036 takes precedence)} · CPC title

• B22F2009/0836

  with electric or magnetic field or induction · CPC title

• B22F9/082

  atomising using a fluid (using centrifugal force B22F9/10) · CPC title

• B22F10/366

  Scanning parameters, e.g. hatch distance or scanning strategy · CPC title