CN107326402B - The preparation method of Nitinol - Google Patents
The preparation method of Nitinol Download PDFInfo
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- CN107326402B CN107326402B CN201710597256.9A CN201710597256A CN107326402B CN 107326402 B CN107326402 B CN 107326402B CN 201710597256 A CN201710597256 A CN 201710597256A CN 107326402 B CN107326402 B CN 107326402B
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- nickel
- nitinol
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- fused salt
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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
Abstract
The invention belongs to rare metal refinement technique fields, and in particular to a kind of preparation method of Nitinol.Aiming at the problem that the existing method high production cost for preparing Ni-Ti alloyed powder, being unable to large-scale production; the present invention provides a kind of method that molten-salt electrolysis prepares Nitinol; the following steps are included: using pure titanium, pure nickel as two assistant anodes; metal material is as cathode; it is placed in fused electrolyte and forms electrolytic cell; it with two independent current sources to two anode supplies, is electrolysed, obtains Ni-Ti alloy in cathode codeposition；The 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 process, can directly obtain Ni-Ti alloy powder, which is 400 yuan/kg hereinafter, opposite aerosolization alloyed powder cost has dropped 80%.The method of the present invention production procedure is short, and production cost is low, and product yield is high, has important practical significance.
Description
Technical field
The invention belongs to rare metal refinement technique fields, and in particular to a kind of preparation method of Nitinol.
Background technique
The preparation of Nitinol starts from the 1940s, until 1963, USN's Weapons Laboratory
W.Buehler et al. has found that the NiTi alloy of nearly atomic ratio has shape memory effect, has thus started marmem
Research boom.
With going deep into for research, find its numerous excellent performance, such as: super-elasticity, Gao Biqiang, high fatigue life, high-damping,
The characteristics such as anti-corrosion, wear-resisting, good biocompatibility, thus NiTi alloy can be widely applied to aerospace, medical treatment, building, machinery,
In the engineering fields such as control, electronics.
Main industrial process is fusion casting to NiTi alloy at present.Fusion casting is using titanium sponge as raw material, according to alloy
Ingredient carries out melting with addition of Ni, generallys use electron beam, argon arc, plasma beam smelting equipment and carries out, including stock up, prepare electricity
The processes such as pole, a vacuum consumable smelting, secondary smelting, cogging forging, secondary forging, rolling or extruding, finally obtain bar
Or plate finished product.Since Nitinol is to the strong sensibility of ingredient and processing, the melting and machining control difficulty of Nitinol
Larger, so that technique processing cost is high, the production cycle is long, therefore enterprise enters the threshold value in Nitinol field and mentions significantly
It is high.The recovery rate of NiTi alloy obtained by smelting process only has 30~40%, causes its production cost high, largely limits
It is promoted and applied.Therefore low cost and high performance NiTi alloy new preparation technology is explored to develop as marmem technology
Middle urgent problem.
In recent years, powder metallurgical technique is rapidly developed, powder metallurgy be one kind using metal powder as raw material, through at
The manufacture of type-sintering is that a kind of few cutting or the processing method without cutting, the properties of product of production are equal at the method for metal product
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 the concern by domestic and international researcher.
The process for preparing Ni-Ti alloyed powder more mature at present is gas-atomized powder and rotary electrode method, by Ni-
Ti alloy carries out high temperature melting in melting kettle, is then carrying out gas atomization with high-purity high-pressure inert gas or is using electric rotating
Pole method carries out centrifugal atomizing, and the powder microscopic appearance of acquisition is spherical shape.But the technique is only to meet the small lot that experiment needs
Production, it is yet far from industrialized product.Such alloyed powder market price is 2000 yuan/kg or more, and import powder reaches
4000~8000 yuan/kg, the price is very expensive, and practicability is lower.
Summary of the invention
The technical problem to be solved in the present invention are as follows: the existing method high production cost for preparing Ni-Ti alloyed powder is unable to scale
The problem of metaplasia produces.
The technical solution of present invention solution technical problem are as follows: 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 cathode and forms electrolysis
Slot is electrolysed with two independent current sources to two anode supplies, obtains Ni-Ti alloy in cathode codeposition；The melting
Electrolyte is the mixture of halogenated titanium, nickel halogenide and fused salt.
Wherein, in the preparation method of above-mentioned Nitinol, Ti content >=98wt% of the pure titanium is titanium sponge, titanium
Any one in plate, stud or titanium silk；Ni content >=99.0wt% of the pure nickel, be electrolytic nickel, sponge nickel, nickel plate or
Any one in nickel stick.
Wherein, in the preparation method of above-mentioned Nitinol, the metal material of the cathode be pure nickel, pure titanium, carbon steel or
Any one in stainless steel.
Wherein, in the preparation method of above-mentioned Nitinol, the halogenated titanium is TiFnOr TiCln, 2≤n≤3；Nickel halogenide
For NiF2Or NiCl2；The fused salt is alkali halide or alkaline-earth halide.
Further, in the preparation method of above-mentioned Nitinol, the fused salt be 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 that fused salt is added, 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 when the electrolysis2, preferably
0.8~2.0A/cm2。
Wherein, in the preparation method of above-mentioned Nitinol, Ni―Ti anode current density≤0.3A/cm when 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 when 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 when the electrolysis
Example is 1 ﹕ 1.5~3.
Wherein, in the preparation method of above-mentioned Nitinol, the electrolysis temperature when electrolysis is 670~900 DEG C.
The invention has the benefit that the present invention, which provides a kind of fused salt electrolysis codeposition, prepares Nitinol new process, it can
To directly obtain Ni-Ti alloy powder, which is 400 yuan/kg hereinafter, opposite aerosolization alloyed powder cost
(2000 yuan/kg) have dropped 80%.The method of the present invention only passes through limited process flows such as " electrolytic powder processings-compression moulding-sintering "
It can be obtained fabricated part, opposite applicable industry production technology " stocks up, prepares electrode, is a vacuum consumable smelting, secondary molten
The processes such as refining, cogging forging, secondary forging, rolling or extruding, finally obtain bar or plate finished product ", process flow is substantially contracted
It is short, and entire process flow raw material availability can reach 75~85%, and the recovery rate of Ni-Ti alloy obtained by smelting process only has 30
~40%.Therefore, the method for the present invention production procedure is short, and production cost is low, and product yield is high, has important practical significance.
Figure of description
Fig. 1 show electrolytic cell described in embodiment 1；
Fig. 2 show the product X RD analysis chart that embodiment 1-3 is prepared.
Specific embodiment
The present invention provides a kind of preparation methods of Nitinol, comprising the following steps:
Using pure titanium, pure nickel as two assistant anodes, metal material is placed in fused electrolyte as cathode and forms electrolysis
Slot is electrolysed with two independent current sources to two anode supplies, obtains Ni-Ti alloy in cathode codeposition；The melting
Electrolyte is the mixture of halogenated titanium, nickel halogenide and fused salt.
Wherein, the fused salt is at least one of alkali halide or alkaline-earth halide.
Wherein, the alkali halide is the compound that alkali metal element and halogens are formed, including MgCl2、
CaCl2Or CaF2, the present invention used in alkali halide be at least one therein.
Wherein, in the above-mentioned method for preparing Nitinol, the alkaline-earth halide be LiF, NaF, KF, LiCl,
At least one of NaCl or KCl.
Wherein, the above-mentioned method for preparing Nitinol, the metal material of the cathode are pure nickel, pure titanium, carbon steel or not
Become rusty steel in any one.
In the above-mentioned method for preparing Nitinol, the halogenated titanium is TiFnOr TiCln, wherein 2≤n≤3.With
TiClnFor, indicate there was only TiCl when n=22, indicate there was only TiCl when n=33, the existing TiCl of the expression of 2≤n≤32Also have
TiCl3, it is two kinds of mixture.In the above-mentioned method for preparing Nitinol, the nickel halogenide is NiF2Or NiCl2。
In the above-mentioned method for preparing Nitinol, Ti in the halogenated titanium that fused salt is added, 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 alloying component control is precipitated in cathode, makes Ni―Ti anode only occur to react as shown in formula (1), avoids that (2) occur
(3) it reacts, therefore Ni―Ti anode current density < 0.3A/cm need to be controlled2, 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 overpotential with higher, 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 cathode occurs such as (6) (7) is shown:
Ti3++e→Ti2+ (6)
Ti2++e→Ti (7)
Ni2++2e→Ni (8)
The Ti on cathode3+It is restored by two steps and generates Ti, Ni2+The reduction of one step generates Ni.
At 700 DEG C (vsAg/Ag-), the standard electrode EMF of Ti and Ni are respectively as follows:
It can be seen that the normal potential between Ni and Ti differs 1.08V, reaches same level on potential to the two, then need
Adjust Ti2+Concentration be about Ni2+1011Times, this is obviously unrealistic in actual operation.
Due to being difficult to find co-deposition condition from change concentration conditions merely, so the shadow of kinetic factor must be taken into consideration
It rings.If controlling cathode overpotential with higher, under certain current density, in cathodic reduction concentration polarization occurs for Ni ion
Change, the negative deposition potential for moving on to Ti of current potential, preferentially react under the premise of (8), while reacting (6) (7), at this time Ni from
Son discharges in cathode with Ti ion to meet the requirement of total current simultaneously, can realize that Ni, Ti are co-deposited using this principle.
To realize cathode overpotential with higher, cathode-current density is greater than 0.6A/cm when electrolysis2.It is preferred that 0.8~
2.0A/cm2。
And to guarantee Ti in electrolyten+With Ni2+Ratio keep stablizing, when electrolysis, need to control Ni―Ti anode and nickel anode
Current ratio is 1 ﹕ 1.5~3, according to experimental study, under the power transmission ratio, and Ti in electrolyten+With Ni2+Molar ratio keep
In 1 ﹕ 1.
To guarantee each ion activity in electrolytic process, temperature need to be controlled greater than 670 DEG C, the excessively high equipment of temperature cannot bear and
Economy is also bad, therefore controls more excellent electrolysis temperature at 670~900 DEG C.
Explanation is further explained to a specific embodiment of the invention below in conjunction with embodiment, but is not indicated this
The protection scope of invention is limited in range described in embodiment.
Fused salt as described in the examples is equimolar ratio NaCl-KCl.
Embodiment 1 prepares Nitinol with the method for the present invention
Using titanium sponge, nickel wire as anode, pure titanium rod as cathode, 2wt% is added in equimolar ratio NaCl and KCl
TiCl2And 2.18wt%NiCl2The mixture of composition is that electrolyte forms electrolytic cell, with two independent current sources respectively to two sun
Pole power supply, connection and electrode arrangement are as shown in Fig. 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, 1 ﹕ 1.5 of Ni―Ti anode and nickel anode current strength ratio,
The product for obtaining cathode after electrolysis is washed using dilute hydrochloric acid, obtains product 9.8g, carries out material phase analysis, knot using XRD
Shown in fruit such as Fig. 2 (1-1), as can be known from the results, product is Ni-Ti alloy.
Embodiment 2 prepares Nitinol with the method for the present invention
Using stud, nickel wire as anode, carbon steel rod as cathode, 0.5wt% is added in equimolar ratio NaCl and KCl
TiCl3And 0.55wt%NiCl2The mixture of composition is that electrolyte forms electrolytic cell, with two independent current sources respectively to two sun
Pole power supply, connection and electrode arrangement are as shown in Fig. 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, 1 ﹕ 3 of Ni―Ti anode and nickel anode current strength ratio, electricity
The product for obtaining cathode after solution is washed using dilute hydrochloric acid, obtains product 10.5g, carries out material phase analysis using XRD, as a result
As shown in Fig. 2 (1-2), the results showed that product is Ni-Ti alloy.
Embodiment 3 prepares Nitinol with the method for the present invention
Using pure titanium bits, electrolytic nickel sheet as anode, nickel stick as cathode, it is added in equimolar ratio NaCl and KCl
0.5wt%TiCl3, 1.0wt%TiCl2And 1.64wt%NiCl2The mixture of composition is that electrolyte forms electrolytic cell, with two
For independent current source respectively to two anode supplies, connection and electrode arrangement are as shown in Fig. 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
1 ﹕ 2 of anode current intensity, the product for obtaining cathode after electrolysis are washed using dilute hydrochloric acid, are obtained product 15.1g, are adopted
Material phase analysis is carried out with XRD, as a result as shown in Fig. 2 (1-3), the results showed that product is Ni-Ti alloy.
Table 1 is that three embodiments obtain product chemical component.
The alloyed powder and commercial product impurity content of 1 the method for the present invention of table preparation compare
It can be seen that by the test result of table 1, using the Nitinol powder of the method for the present invention preparation due in technical process
Electrorefining effect, opposite commercial alloys have lower impurity content, and production procedure is simpler, and cost is lower, has
Apparent economic benefit.
Claims (13)
1. the preparation method of Nitinol, which comprises the following steps:
Using pure titanium, pure nickel as two assistant anodes, metal material is placed in fused electrolyte as cathode and forms electrolytic cell,
It with two independent current sources to two anode supplies, is electrolysed, obtains Ni-Ti alloy in cathode codeposition；The melting electricity
The mixture of Xie Zhiwei halogenated titanium, nickel halogenide and fused salt；Ti in the halogenated titanium, nickel halogeniden+With Ni2+Mass ratio be 1 ﹕ 0.5
~1.23；Cathode-current density is 0.8~2.0A/cm when the electrolysis2；Ni―Ti anode current density≤0.3A/ when the electrolysis
cm2；Nickel anode current density >=1.0A/cm when the electrolysis2。
2. the preparation method of Nitinol according to claim 1, it is characterised in that: the Ti content of the pure titanium >=
98wt%, for any one in titanium sponge, titanium plate, stud or titanium silk；Ni content >=99.0wt% of the pure nickel, for electricity
Solve any one in nickel, sponge nickel, nickel plate or nickel stick.
3. the preparation method of Nitinol according to claim 1 or 2, it is characterised in that: the metal material of the cathode
Expect for any one in pure nickel, pure titanium, carbon steel or stainless steel.
4. the preparation method of Nitinol according to claim 1, it is characterised in that: the halogenated titanium is TiFnOr
TiCln, 2≤n≤3；Nickel halogenide is NiF2Or NiCl2；The fused salt is alkali halide or alkaline-earth halide.
5. the preparation method of Nitinol according to claim 2, it is characterised in that: the halogenated titanium is TiFnOr
TiCln, 2≤n≤3；Nickel halogenide is NiF2Or NiCl2；The fused salt is alkali halide or alkaline-earth halide.
6. the preparation method of Nitinol according to claim 3, it is characterised in that: the halogenated titanium is TiFnOr
TiCln, 2≤n≤3；Nickel halogenide is NiF2Or NiCl2；The fused salt is alkali halide or alkaline-earth halide.
7. the preparation method of Nitinol according to claim 1, it is characterised in that: the fused salt be LiF, NaF,
KF、LiCl、NaCl、KCl、MgCl2、CaCl2Or CaF2At least one of.
8. the preparation method of Nitinol according to claim 2, it is characterised in that: the fused salt be LiF, NaF,
KF、LiCl、NaCl、KCl、MgCl2、CaCl2Or CaF2At least one of.
9. the preparation method of Nitinol according to claim 3, it is characterised in that: the fused salt be LiF, NaF,
KF、LiCl、NaCl、KCl、MgCl2、CaCl2Or CaF2At least one of.
10. the preparation method of Nitinol according to claim 4, it is characterised in that: the fused salt be LiF, NaF,
KF、LiCl、NaCl、KCl、MgCl2、CaCl2Or CaF2At least one of.
11. the preparation method of Nitinol according to claim 5, it is characterised in that: the fused salt be LiF, NaF,
KF、LiCl、NaCl、KCl、MgCl2、CaCl2Or CaF2At least one of.
12. the preparation method of Nitinol according to claim 6, it is characterised in that: the fused salt be LiF, NaF,
KF、LiCl、NaCl、KCl、MgCl2、CaCl2Or CaF2At least one of.
13. according to claim 1,2 or any Nitinol of claim 4~12 preparation method, it is characterised in that:
Ni―Ti anode and nickel anode power transmission current strength ratio are 1 ﹕ 1.5~3 when the electrolysis.
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| CN109648082B (en) * | 2019-01-24 | 2021-08-06 | 华南理工大学 | 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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| 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 |
| CN105220182B (en) * | 2015-10-29 | 2017-10-31 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of method for preparing porous titanium valve |
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