CN107326402A - The preparation method of Nitinol - Google Patents

The preparation method of Nitinol Download PDF

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CN107326402A
CN107326402A CN201710597256.9A CN201710597256A CN107326402A CN 107326402 A CN107326402 A CN 107326402A CN 201710597256 A CN201710597256 A CN 201710597256A CN 107326402 A CN107326402 A CN 107326402A
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nitinol
nickel
titanium
preparation
pure
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CN107326402B (en
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邓斌
穆天柱
范亚卓
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Pangang Group Research Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/04—Electrolytic production, recovery or refining of metal powders or porous metal masses from melts

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Abstract

The invention belongs to rare metal refinement technique field, and in particular to a kind of preparation method of Nitinol.Ni Ti alloyed powders are prepared for existing method production cost is high, the problem of be unable to large-scale production, and the present invention provides a kind of method that molten-salt electrolysis prepares Nitinol, comprises the following steps：Using pure titanium, pure nickel as two assistant anodes, metal material is placed in fused electrolyte as negative electrode and constitutes electrolytic cell, with two independent current sources to two anode supplies, is electrolysed, and Ni Ti alloys are obtained in cathode codeposition；Described fused electrolyte is the mixture of halogenated titanium, nickel halogenide and fused salt.The present invention provides a kind of fused salt electrolysis codeposition and prepares Nitinol new technology, can directly obtain Ni Ti alloy powders, and the alloy powder production cost is 400 yuan/below kg, and 80% is have dropped with respect to aerosolization alloyed powder cost.The inventive method production procedure is short, and production cost is low, and product yield is high, has important practical significance.

Description

The preparation method of Nitinol
Technical field
The invention belongs to rare metal refinement technique field, and in particular to a kind of preparation method of Nitinol.
Background technology
The preparation of Nitinol is started from the 1940s, until 1963, USN's Weapons Laboratory W.Buehler et al. is found that the NiTi alloys of nearly atomic ratio have SME, has thus started marmem Research boom.
With going deep into for research, its numerous premium properties is found, such as：Super-elasticity, Gao Biqiang, high fatigue life, high-damping, The characteristic such as anti-corrosion, wear-resisting, good biocompatibility, thus NiTi alloys can be widely applied to Aero-Space, medical treatment, building, machinery, In the engineering fields such as control, electronics.
NiTi alloys industrial process main at present is fusion casting.Fusion casting is using titanium sponge as raw material, according to alloy Composition carries out melting with addition of Ni, is generally carried out using electron beam, argon arc, beam-plasma smelting equipment, including is got the raw materials ready, prepares electricity The processes such as pole, vacuum consumable smelting, secondary smelting, cogging forging, secondary forging, rolling or extruding, finally give bar Or sheet material finished product.Because Nitinol is to composition and the strong sensitiveness of processing, melting and the machining control difficulty of Nitinol It is larger so that the technique high processing costs, the production cycle is long, thus enterprise enter Nitinol field threshold value carry significantly It is high.The recovery rate of NiTi alloys only has 30~40% obtained by smelting process, causes its production cost high, largely limits Its popularization and application.Therefore inexpensive, high performance NiTi alloys new preparation technology is explored as marmem technology to develop Middle urgent problem.
In recent years, powder metallurgical technique is rapidly developed, powder metallurgy be one kind using metal dust as raw material, through into The method that type-sintering is manufactured into metallic article, is a kind of few cutting or the processing method without cutting, and the properties of product of production are equal It is even, the production cost of titanium alloy can be effectively reduced, and have in terms of production porous material, complex-shaped, small parts Its original advantage.Therefore paid close attention to by domestic and international researcher.
The process for preparing Ni-Ti alloyed powders of more maturation is gas-atomized powder and rotary electrode method at present, by Ni- Ti alloys carry out high temperature melting in melting kettle, are then carrying out gas atomization with high-purity high-pressure inert gas or are using electric rotating Pole method carries out centrifugal atomizing, and the powder microscopic appearance of acquisition is spherical.But the technique is only for the small lot of satisfaction experiment needs Production, it is yet far from industrialized product.Such alloyed powder market price is 2000 yuan/more than kg, and import powder reaches 4000~8000 yuan/kg, price is sufficiently expensive, and practicality is relatively low.
The content of the invention
The technical problem to be solved in the present invention is：The existing method production cost for preparing Ni-Ti alloyed powders is high, be unable to scale The problem of metaplasia is produced.
The present invention solve technical problem technical scheme be：A kind of preparation method of Nitinol is provided.This method includes Following steps：
Using pure titanium, pure nickel as two assistant anodes, metal material is placed in fused electrolyte as negative electrode and constitutes electrolysis Groove, with two independent current sources to two anode supplies, is electrolysed, Ni-Ti alloys is obtained in cathode codeposition；Described melting Electrolyte is the mixture of halogenated titanium, nickel halogenide and fused salt.
Wherein, in the preparation method of above-mentioned Nitinol, Ti contents >=98wt% of described pure titanium, is titanium sponge, titanium Plate, titanium rod or titanium silk in any one；Ni contents >=99.0wt% of described pure nickel, be electrolytic nickel, sponge nickel, nickel plate or Any one in nickel rod.
Wherein, in the preparation method of above-mentioned Nitinol, the metal material of described negative electrode is pure nickel, pure titanium, carbon steel or Any one in stainless steel.
Wherein, in the preparation method of above-mentioned Nitinol, described halogenated titanium is TiFnOr TiCln, 2≤n≤3；Nickel halogenide For NiF2Or NiCl2；Described fused salt is alkali halide or alkaline-earth halide.
Further, in the preparation method of above-mentioned Nitinol, described fused salt is LiF, NaF, KF, LiCl, NaCl, KCl、MgCl2、CaCl2Or CaF2At least one of.
Wherein, in the preparation method of above-mentioned Nitinol, Ti in the halogenated titanium for adding fused salt, nickel halogeniden+With Ni2+ Mass ratio be 1 ﹕ 0.5~1.23.
Wherein, in the preparation method of above-mentioned Nitinol, cathode-current density >=0.6A/cm during the electrolysis2, it is preferably 0.8~2.0A/cm2。
Wherein, in the preparation method of above-mentioned Nitinol, Ni―Ti anode current density≤0.3A/cm during the electrolysis2；It is preferred that For≤0.1A/cm2。
Wherein, in the preparation method of above-mentioned Nitinol, nickel anode current density >=1.0A/cm during the electrolysis2；It is preferred that For 1.2~2.0A/cm2。
Wherein, in the preparation method of above-mentioned Nitinol, Ni―Ti anode and nickel anode power transmission current strength ratio during the electrolysis Example is 1 ﹕ 1.5~3.
Wherein, in the preparation method of above-mentioned Nitinol, the electrolysis temperature during electrolysis is 670~900 DEG C.
Beneficial effects of the present invention are：The present invention provides a kind of fused salt electrolysis codeposition and prepares Nitinol new technology, can To directly obtain Ni-Ti alloy powders, the alloy powder production cost is 400 yuan/below kg, with respect to aerosolization alloyed powder cost (2000 yuan/kg) have dropped 80%.The inventive method only passes through limited technological processes such as " electrolytic powder processings-compressing-sintering " Fabricated part can be obtained, with respect to applicable industry production technology " get the raw materials ready, prepare electrode, it is vacuum consumable smelting, secondary molten The processes such as refining, cogging forging, secondary forging, rolling or extruding, finally give bar or sheet material finished product ", technological process is significantly contracted It is short, and whole technological process raw material availability can reach 75~85%, and the recovery rate of Ni-Ti alloys only has 30 obtained by smelting process ~40%.Therefore, the inventive method production procedure is short, and production cost is low, and product yield is high, has important practical significance.
Figure of description
Fig. 1 show the electrolytic cell described in embodiment 1；
Fig. 2 show the product X RD analysis charts that embodiment 1-3 is prepared.
Embodiment
The invention provides a kind of preparation method of Nitinol, comprise the following steps：
Using pure titanium, pure nickel as two assistant anodes, metal material is placed in fused electrolyte as negative electrode and constitutes electrolysis Groove, with two independent current sources to two anode supplies, is electrolysed, Ni-Ti alloys is obtained in cathode codeposition；Described melting Electrolyte is the mixture of halogenated titanium, nickel halogenide and fused salt.
Wherein, described fused salt is at least one of alkali halide or alkaline-earth halide.
Wherein, the compound that described alkali halide is formed for alkali metal with halogens, including MgCl2、 CaCl2Or CaF2, the alkali halide used in the present invention is at least one therein.
Wherein, in the above-mentioned method for preparing Nitinol, described alkaline-earth halide is LiF, NaF, KF, LiCl, At least one of NaCl or KCl.
Wherein, the above-mentioned method for preparing Nitinol, the metal material of described negative electrode is pure nickel, pure titanium, carbon steel or not Become rusty steel in any one.
In the above-mentioned method for preparing Nitinol, described halogenated titanium is TiFnOr TiCln, wherein, 2≤n≤3.With TiClnExemplified by, only TiCl is represented during n=22, only TiCl is represented during n=33, 2≤n≤3 represent existing TiCl2Also have TiCl3, it is two kinds of mixture.In the above-mentioned method for preparing Nitinol, described nickel halogenide is NiF2Or NiCl2。
In the above-mentioned method for preparing Nitinol, Ti in the halogenated titanium for adding fused salt, nickel halogeniden+With Ni2+Quality Than for 1 ﹕ 0.5~1.23.
In the above-mentioned method for preparing Nitinol, the electrochemical reaction that the Ni―Ti anode may occur such as (1) (2) (3) is shown：
Ti-2e → Ti2+ (1)
Ti2+- e → Ti3+ (2)
Ti-3e → Ti3+ (3)
For the benefit of negative electrode separates out alloying component control, makes Ni―Ti anode only occur to react as shown in formula (1), it is to avoid to occur (2) (3) react, therefore Ni―Ti anode current density need to be controlled<0.3A/cm2, preferred scope<0.1A/cm2。
In the above-mentioned method for preparing Nitinol, the electrochemical reaction that the nickel anode occurs such as (4) (5) is shown：
Ti2+- e → Ti3+ (4)
Ni-2e → Ni2+ (5)
Due to Ti in electrolyte2+Presence, nickel anode react (5) it is more difficult, it is ensured that nickel is smoothly extracted into electricity Xie Zhi, need to control nickel anode to have higher overpotential, therefore need to control nickel anode current density>1.0A/cm2, preferred scope 1.2~2.0A/cm2。
In the above-mentioned method for preparing Nitinol, the electrochemical reaction that the negative electrode occurs such as (6) (7) is shown：
Ti3++e→Ti2+ (6)
Ti2++e→Ti (7)
Ni2++2e→Ni (8)
The Ti on negative electrode3+Pass through the reduction generation of two steps Ti, Ni2+One step reduction generation Ni.
At 700 DEG C (vsAg/Ag-), Ti and Ni standard electrode EMF are respectively：
It can be seen that the normal potential between Ni and Ti differs 1.08V, same level is reached on potential to both, then is needed Adjust Ti2+Concentration be about Ni2+1011Times, this is obviously unrealistic in practical operation.
Due to merely from change concentration conditions it is difficult to co-deposition condition be found, so must take into consideration the shadow of kinetic factor Ring.If controlling negative electrode to have higher overpotential, under certain current density, in cathodic reduction concentration polarization occurs for Ni ions Change, the negative deposition potential for moving on to Ti of current potential, preferentially react on the premise of (8), while react (6) (7), now Ni from Son discharges to meet the requirement of total current simultaneously with Ti ions in negative electrode, can realize that Ni, Ti are co-deposited using this principle.
To realize that negative electrode has higher overpotential, cathode-current density is more than 0.6A/cm during electrolysis2.It is preferred that 0.8~ 2.0A/cm2。
And to ensure Ti in electrolyten+With Ni2+Ratio keep stable, Ni―Ti anode and nickel anode need to be controlled during electrolysis Current ratio is 1 ﹕ 1.5~3, according to experimental study, under the power transmission ratio, Ti in electrolyten+With Ni2+Molar ratio keep In 1 ﹕ 1.
For ensure electrolytic process in each ion activity, need to control temperature be more than 670 DEG C, the too high equipment of temperature can not bear and Economy is not also good, therefore controls more excellent electrolysis temperature at 670~900 DEG C.
Explanation is further explained to the embodiment of the present invention below in conjunction with embodiment, but is not indicated that this The protection domain of invention is limited in described in embodiment in scope.
Fused salt described in embodiment compares NaCl-KCl for equimolar.
Embodiment 1 prepares Nitinol with the inventive method
Using titanium sponge, nickel wire as anode, pure titanium rod as negative electrode, equimolar in NaCl and KCl than adding 2wt% TiCl2And 2.18wt%NiCl2The mixture of composition is that electrolyte constitutes electrolytic cell, with two independent current sources respectively to two sun Pole powers, and connection and electrode arrangement are as shown in Figure 1.Control Ni―Ti anode current density 0.1A/cm2, cathode-current density 2.0A/cm2, nickel anode current density 2.0A/cm2, 670 DEG C of electrolysis temperature, Ni―Ti anode and the ﹕ 1.5 of nickel anode current strength ratio 1, The product that electrolysis obtains negative electrode after terminating is washed using watery hydrochloric acid, obtains product 9.8g, and material phase analysis, knot are carried out using XRD Fruit is as shown in Fig. 2 (1-1), as can be known from the results, and product is Ni-Ti alloys.
Embodiment 2 prepares Nitinol with the inventive method
Using titanium rod, nickel wire as anode, carbon steel rod as negative electrode, equimolar in NaCl and KCl than adding 0.5wt% TiCl3And 0.55wt%NiCl2The mixture of composition is that electrolyte constitutes electrolytic cell, with two independent current sources respectively to two sun Pole powers, and connection and electrode arrangement are as shown in Figure 1.Control Ni―Ti anode current density 0.05A/cm2, cathode-current density 0.8A/cm2, nickel anode current density 1.2A/cm2, 900 DEG C of electrolysis temperature, Ni―Ti anode and the ﹕ 3 of nickel anode current strength ratio 1, electricity The product that solution obtains negative electrode after terminating is washed using watery hydrochloric acid, obtains product 10.5g, carries out material phase analysis using XRD, as a result As shown in Fig. 2 (1-2), it is Ni-Ti alloys as a result to show product.
Embodiment 3 prepares Nitinol with the inventive method
Using pure titanium bits, electrolytic nickel sheet as anode, nickel rod as negative electrode, equimolar in NaCl and KCl than adding 0.5wt%TiCl3, 1.0wt%TiCl2And 1.64wt%NiCl2The mixture of composition is that electrolyte constitutes electrolytic cell, with two Independent current source is respectively to two anode supplies, and connection and electrode arrangement are as shown in Figure 1.Control Ni―Ti anode current density 0.1A/cm2, cathode-current density 1.0A/cm2, nickel anode current density 1.5A/cm2, 800 DEG C of electrolysis temperature, Ni―Ti anode and nickel The ﹕ 2 of anode current intensity 1, the product that electrolysis obtains negative electrode after terminating is washed using watery hydrochloric acid, is obtained product 15.1g, is adopted Material phase analysis is carried out with XRD, as a result as shown in Fig. 2 (1-3), it is Ni-Ti alloys as a result to show product.
Table 1 is that three embodiments obtain product chemical composition.
Alloyed powder prepared by the inventive method of table 1 is contrasted with commercially available prod impurity content
It can be seen that by the result of the test of table 1, the Nitinol powder prepared using the inventive method is due in technical process Electrorefining effect, has lower impurity content with respect to commercial alloys, and production procedure is simpler, and cost is lower, has Obvious economic benefit.

Claims (10)

1. the preparation method of Nitinol, it is characterised in that comprise the following steps：
Using pure titanium, pure nickel as two assistant anodes, metal material is placed in fused electrolyte as negative electrode and constitutes electrolytic cell, With two independent current sources to two anode supplies, it is electrolysed, Ni-Ti alloys is obtained in cathode codeposition；Described melting electricity Solution matter is the mixture of halogenated titanium, nickel halogenide and fused salt.
2. the preparation method of Nitinol according to claim 1, it is characterised in that：The Ti contents of described pure titanium >= 98wt%, is any one in titanium sponge, titanium plate, titanium rod or titanium silk；Ni contents >=99.0wt% of described pure nickel, is electricity Solve any one in nickel, sponge nickel, nickel plate or nickel rod.
3. the preparation method of Nitinol according to claim 1 or 2, it is characterised in that：The metal material of described negative electrode Expect for any one in pure nickel, pure titanium, carbon steel or stainless steel.
4. the preparation method of the Nitinol according to any one of claims 1 to 3, it is characterised in that：Described halogenated titanium For TiFnOr TiCln, 2≤n≤3；Nickel halogenide is NiF2Or NiCl2；Described fused salt is alkali halide or alkaline-earth metal halogen Compound.
5. according to the preparation method of any described Nitinol of Claims 1 to 4, it is characterised in that：Described fused salt is LiF、NaF、KF、LiCl、NaCl、KCl、MgCl2、CaCl2Or CaF2At least one of.
6. according to the preparation method of any described Nitinol of Claims 1 to 5, it is characterised in that：The addition fused salt Ti in halogenated titanium, nickel halogeniden+With Ni2+Mass ratio be 1 ﹕ 0.5~1.23.
7. according to the preparation method of any described Nitinol of claim 1~6, it is characterised in that：The negative electrode during electrolysis Current density >=0.6A/cm2。
8. according to the preparation method of any described Nitinol of claim 1~7, it is characterised in that：Titanium sun during the electrolysis Electrode current density≤0.3A/cm2。
9. according to the preparation method of any described Nitinol of claim 1~8, it is characterised in that：Nickel sun during the electrolysis Electrode current density >=1.0A/cm2。
10. according to the preparation method of any described Nitinol of claim 1~9, it is characterised in that：Titanium sun during the electrolysis Pole and nickel anode power transmission current strength ratio are 1 ﹕ 1.5~3.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109082686A (en) * 2018-09-20 2018-12-25 成都先进金属材料产业技术研究院有限公司 Rod-like shape titanium valve and preparation method thereof
US20210394268A1 (en) * 2019-01-24 2021-12-23 South China University Of Technology 4d printing method and application of titanium-nickel shape memory alloy
CN114232034A (en) * 2021-12-24 2022-03-25 朱鸿民 Multi-anode electrolysis preparation method and application of titanium-aluminum-vanadium alloy powder

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1063909A (en) * 1991-02-04 1992-08-26 中国科学院化工冶金研究所 Molten salt electrolysis for producing ti-al alloy powder
US6540902B1 (en) * 2001-09-05 2003-04-01 The United States Of America As Represented By The United States Department Of Energy Direct electrochemical reduction of metal-oxides
CN105220182A (en) * 2015-10-29 2016-01-06 攀钢集团攀枝花钢铁研究院有限公司 A kind of method preparing porous titanium valve
CN105350028A (en) * 2015-11-24 2016-02-24 攀钢集团攀枝花钢铁研究院有限公司 Nitinol powder prepared through molten salt electrolysis and preparing method of nitinol powder

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1063909A (en) * 1991-02-04 1992-08-26 中国科学院化工冶金研究所 Molten salt electrolysis for producing ti-al alloy powder
US6540902B1 (en) * 2001-09-05 2003-04-01 The United States Of America As Represented By The United States Department Of Energy Direct electrochemical reduction of metal-oxides
CN105220182A (en) * 2015-10-29 2016-01-06 攀钢集团攀枝花钢铁研究院有限公司 A kind of method preparing porous titanium valve
CN105350028A (en) * 2015-11-24 2016-02-24 攀钢集团攀枝花钢铁研究院有限公司 Nitinol powder prepared through molten salt electrolysis and preparing method of nitinol powder

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109082686A (en) * 2018-09-20 2018-12-25 成都先进金属材料产业技术研究院有限公司 Rod-like shape titanium valve and preparation method thereof
CN109082686B (en) * 2018-09-20 2020-04-07 成都先进金属材料产业技术研究院有限公司 Rod-shaped titanium powder and preparation method thereof
US20210394268A1 (en) * 2019-01-24 2021-12-23 South China University Of Technology 4d printing method and application of titanium-nickel shape memory alloy
CN114232034A (en) * 2021-12-24 2022-03-25 朱鸿民 Multi-anode electrolysis preparation method and application of titanium-aluminum-vanadium alloy powder

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