CN1817510A - Gel mould-injecting formation of nickel-titanium-based shape memory alloy with high porosity - Google Patents
Gel mould-injecting formation of nickel-titanium-based shape memory alloy with high porosity Download PDFInfo
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- CN1817510A CN1817510A CN 200610011525 CN200610011525A CN1817510A CN 1817510 A CN1817510 A CN 1817510A CN 200610011525 CN200610011525 CN 200610011525 CN 200610011525 A CN200610011525 A CN 200610011525A CN 1817510 A CN1817510 A CN 1817510A
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Abstract
An injection moulding method for preparing high-porosity NiTi-based marmem includes such steps as dissolving acrylamide and N,N-methyleno biacrylamide as cross-linking agent in solvent, adding Ni powder and Ti powder to make them be suspended in the solution, adding trigger and catalyst, injecting the slurry into non-porous mould, cross-linking and polymerizing to become 3D recticular polymer gel while in-situ adhering the particles, and solidifying. Its advantages are high porosity, high rate of open pores and uniform distribution of pores.
Description
Technical field
The invention belongs to the powder metallurgy forming technical field, a kind of gel-casting method of nickel-titanium-based shape memory alloy with high porosity particularly is provided.
Background technology
Advantages such as niti-shaped memorial alloy has that intensity height, proportion are low, endurance, corrosion-resistant, wear-resistant, low magnetic, nontoxic, elastic modelling quantity and people's bone photo are near; Simultaneously, Nitinol also has good biocompatibility, and especially the porous nickel-titanium alloy is easy to be fixed by tissue, is comparatively ideal biomedical embedded material, has broad application prospects in medical field.
But, realize that the preparation of high porosity Nitinol is relatively more difficult.Traditional powder metallurgy forming technology is difficult to obtain finished pieces with complex shapes, and porosity is lower; The Nitinol porosity of self propagating high temperature synthetic technology preparation can reach 60%, but hole macroscopic view distributing homogeneity is relatively poor.
Gel casting forming (gelcasting) is invented in early 1990s by people such as U.S. Oak Ridge National Laboratory professors M.A.Janney, is a kind of complicated shape pottery or the metal parts near-net-shape method that receives much attention in recent years.Its advantage is the easy-formation complicated shape, but molding blank density is even, intensity is high, do not need special degreasing process, do not need special degreasing process production large scale goods and goods porosity and aperture controlled.
Summary of the invention
The object of the present invention is to provide a kind of gel-casting method of nickel-titanium-based shape memory alloy with high porosity, adopt gel injection molding and forming technology to realize the production of high porosity, high opening rate, big powder metallurgy niti-shaped memorial alloy of complicated shape base substrate that hole macroscopic view distributing homogeneity is good.
The present invention is with acrylamide organic monomer and N, N-methylene-bisacrylamide crosslinking agent dissolves in solvent and is mixed with certain density premixed liquid, nickel powder, titanium valve are suspended in the concentrate suspension of wherein making low viscosity, high solid loading, add after initator and the catalyst, this concentrate suspension slurry is injected non-porous mould, under certain temperature condition, organic polymer is monomer crosslinked to aggregate into three-dimensional network shaped polymer gel, and makes powder particle original position bonding and solidify to form base substrate.Concrete technology is as follows:
1) nickel powder, titanium valve are mixed, wherein titanium valve is 40～60 atom % of mixture, and ball milling mixed it in 2～36 hours;
2) with acrylamide and N, the N-methylene-bisacrylamide is with mass ratio (2～200): 1 mixes, with the water-soluble solution of making 1～50 quality % stable homogeneous of this mixture;
3) with above-mentioned solution and NiTi mixed powder and dispersant, wherein powder is 10～50 volume % of gained mixture; The dispersant that uses any as in polyacrylamide, polyacrylic acid, the polymethyl acid amide, dispersant dosage accounts for 0.02～1.0% of metal powder material quality;
4) with third step gained compound ball milling 8～48 hours;
5) above-mentioned slurry room temperature froth in vacuum is 10～30 minutes;
6) slurry is injected mould, mold materials is non-hole material glass or metal, rubber, plastics etc.; Heating mould to 40～80 ℃ afterwards, the demoulding after about 30～120 minutes, room temperature vacuum drying 48～72 hours can obtain the NiTi base substrate.
The technology of the present invention is compared with traditional porous nickel-titanium marmem forming technique, and major advantage is as follows:
1) it is even and solid concentration is adjustable to prepare the concentrate suspension composition; Base substrate after drying, originally the position that exists of moisture becomes intrinsic hole, so base substrate can obtain the niti-shaped memorial alloy that high porosity, high opening rate, hole macroscopic view are evenly distributed behind sintering;
2) do not need complex device and mould, do not need special degreasing process, can realize low cost, the high efficiency production of complicated shape niti-shaped memorial alloy;
3) blank strength reaches more than the 30MPa, can carry out machining;
4) base substrate can obtain the be complementary niti-shaped memorial alloy of mechanical property with skeletal tissue behind sintering.
The specific embodiment
Embodiment 1
With 10～100 μ m nickel powders and 10～100 μ m titanium valves is raw material, mixes in 10 hours than 1: 1 (mass ratio 55.07: 44.93) ball milling according to nickel, titanium atom; With 15 gram acrylamides, 1 gram N, the N-methylene-bisacrylamide is dissolved in 100 ml waters, add 670 gram NiTi mixed powders and 5 gram polyacrylic acid dispersant, ball milling final vacuum de-bubble in 48 hours 30 minutes, obtain the slurry of solid volume fraction 50%, after injecting metal die mould is moved into 80 ℃ of insulating box insulations 120 minutes, dry 72 hours of demoulding final vacuum can obtain gel casting forming niti-shaped memorial alloy part base substrate; Base substrate obtains the niti-shaped memorial alloy part behind sintering.
Gel casting forming niti-shaped memorial alloy part porosity by this technology preparation is 40.7%, and percent opening is 91.5%.
Embodiment 2
With 10～100 μ m nickel powders and 10～100 μ m titanium valves is raw material, mixes in 18 hours than 1: 1 (mass ratio 55.07: 44.93) ball milling according to nickel, titanium atom; With 20 gram acrylamides, 6 gram N, the N-methylene-bisacrylamide dissolves in 100 ml waters makes solution, add 450 gram NiTi mixed powders and 10 gram polyacrylamide dispersants, ball milling final vacuum de-bubble in 24 hours 20 minutes makes solid volume fraction and is 40% slurry.The gained slurry is injected glass mold, and 60 ℃ of insulations 120 minutes, slurry was cured as base substrate in the mould, and dry 48 hours of demoulding final vacuum can obtain gel casting forming niti-shaped memorial alloy part base substrate; Base substrate obtains the niti-shaped memorial alloy part behind sintering.
Gel casting forming niti-shaped memorial alloy part porosity by this technology preparation is 53.9%, and percent opening is 91.1%.
Claims (2)
1, a kind of gel-casting method of nickel-titanium-based shape memory alloy with high porosity is characterized in that:
A, nickel powder, titanium valve are mixed, wherein titanium valve is 40～60 atom % of mixture; Ball milling made its even mixing in 2～36 hours;
B, with acrylamide and N, the N-methylene-bisacrylamide is to mix at 2～200: 1 with mass ratio, with the water-soluble solution of making 1～50 quality % stable homogeneous of this mixture;
C, with above-mentioned solution and NiTi mixed powder and dispersant, wherein powder is 10～50 volume % of gained mixture; The dispersant that uses any as in polyacrylamide, polyacrylic acid, the polymethyl acid amide, dispersant dosage accounts for 0.02～1.0% of metal powder material quality;
D, with c step gained compound ball milling 8～48 hours;
E, above-mentioned slurry room temperature froth in vacuum 10～30 minutes;
Slurry is injected mould, heating mould to 40～80 ℃, the demoulding after about 30～120 minutes, room temperature vacuum drying 48～72 hours can obtain the NiTi base substrate.
2, in accordance with the method for claim 1, it is characterized in that: described mold materials is non-hole material glass or metal, rubber, plastics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100115250A CN100389915C (en) | 2006-03-21 | 2006-03-21 | Gel mould-injecting formation of nickel-titanium-based shape memory alloy with high porosity |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100115250A CN100389915C (en) | 2006-03-21 | 2006-03-21 | Gel mould-injecting formation of nickel-titanium-based shape memory alloy with high porosity |
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| CN1817510A true CN1817510A (en) | 2006-08-16 |
| CN100389915C CN100389915C (en) | 2008-05-28 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100455385C (en) * | 2007-01-25 | 2009-01-28 | 哈尔滨工程大学 | Preparation method of micrometer grade NiMnCa magnetic memory alloy grain |
| CN102554228A (en) * | 2012-01-13 | 2012-07-11 | 北京科技大学 | Method for forming ultrathin-wall porous metal pipe fitting |
| CN104801704A (en) * | 2015-03-26 | 2015-07-29 | 成都新柯力化工科技有限公司 | Shape memory alloy material for three-dimensional printing and preparation method of shape memory alloy material |
| CN106735235A (en) * | 2016-11-22 | 2017-05-31 | 中南大学 | A kind of cogelled casting method of gradient porous metal |
| CN113600830A (en) * | 2021-08-30 | 2021-11-05 | 北京工业大学 | Method for hard alloy photoprinting using responsive polymer matrix |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5908588A (en) * | 1998-02-17 | 1999-06-01 | Eastman Kodak Company | Incipient flocculation molding of particulate inorganic materials |
| EP1119429B1 (en) * | 1998-07-29 | 2003-07-02 | Gkss-Forschungszentrum Geesthacht Gmbh | Method for producing components by metallic powder injection moulding |
| KR100320804B1 (en) * | 1999-08-23 | 2002-01-18 | 한기석 | Apparatus and method for manufacturing an artificial porous titanium nickel medulla by using a hot rotational synthesis method |
| RU2190502C2 (en) * | 2000-03-14 | 2002-10-10 | Томский научный центр СО РАН | Method of production of porous material on base of titanium nickelide for medicine |
| KR100508471B1 (en) * | 2002-12-10 | 2005-08-17 | 주식회사 에스엠코퍼레이션 | Method for manufacturing titanium material |
| CN1227085C (en) * | 2003-01-20 | 2005-11-16 | 北京科技大学 | Injection coagution forming technology for metal powder |
-
2006
- 2006-03-21 CN CNB2006100115250A patent/CN100389915C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100455385C (en) * | 2007-01-25 | 2009-01-28 | 哈尔滨工程大学 | Preparation method of micrometer grade NiMnCa magnetic memory alloy grain |
| CN102554228A (en) * | 2012-01-13 | 2012-07-11 | 北京科技大学 | Method for forming ultrathin-wall porous metal pipe fitting |
| CN102554228B (en) * | 2012-01-13 | 2013-11-06 | 北京科技大学 | Method for forming ultrathin-wall porous metal pipe fitting |
| CN104801704A (en) * | 2015-03-26 | 2015-07-29 | 成都新柯力化工科技有限公司 | Shape memory alloy material for three-dimensional printing and preparation method of shape memory alloy material |
| CN104801704B (en) * | 2015-03-26 | 2017-01-25 | 成都新柯力化工科技有限公司 | Shape memory alloy material for three-dimensional printing and preparation method of shape memory alloy material |
| CN106735235A (en) * | 2016-11-22 | 2017-05-31 | 中南大学 | A kind of cogelled casting method of gradient porous metal |
| CN106735235B (en) * | 2016-11-22 | 2019-06-28 | 中南大学 | A kind of cogelled casting method of gradient porous metal |
| CN113600830A (en) * | 2021-08-30 | 2021-11-05 | 北京工业大学 | Method for hard alloy photoprinting using responsive polymer matrix |
| CN113600830B (en) * | 2021-08-30 | 2022-06-21 | 北京工业大学 | Method for hard alloy photoprinting using responsive polymer matrix |
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| CN100389915C (en) | 2008-05-28 |
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