CN103074650A - Method for preparing Ni-Ti surface tantalum coating with electrodeposition in room temperature molten salts - Google Patents

Method for preparing Ni-Ti surface tantalum coating with electrodeposition in room temperature molten salts Download PDF

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Publication number
CN103074650A
CN103074650A CN2013100170258A CN201310017025A CN103074650A CN 103074650 A CN103074650 A CN 103074650A CN 2013100170258 A CN2013100170258 A CN 2013100170258A CN 201310017025 A CN201310017025 A CN 201310017025A CN 103074650 A CN103074650 A CN 103074650A
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tantalum
tantalum coating
bpy
room temperature
coating
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CN103074650B (en
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徐君莉
张霞
石忠宁
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Northeastern University China
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Northeastern University China
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Abstract

The invention belongs to the preparation of functional material coatings, in particular to a method for preparing a Ni-Ti surface tantalum coating with electrodeposition in room temperature molten salts. The method comprises the following steps: adding any one of bis-trifluroro sulfonic acid imine butyl pyrrole (CF3SO2) 2N-BPy or chlorinated butyl pyrrole BPy-Cl into any one of lithium halide or bis-trifluroro sulfonic acid imine lithium (CF3SO2) 2N-Li, then adding K2TaF7 or TaCl5, providing tantalum sources, and forming electrolyte; an anode material is graphite or metal tantalum, and a cathode material is Ni-Ti alloy; carrying out electrodeposition at the temperature of 10-40 DEG C higher than the liquidus temperature of the electrolyte, wherein the electric current density is 0.005-0.01A/cm<2>; electrolyzing for 3-5 hours to obtain the compact tantalum coating on the cathode surface. The electrodeposition temperature is low, the operation is convenient, and the cost is low. The tantalum coating with uniform components can be obtained by controlling the electric current density.

Description

A kind of room temperature fused salt galvanic deposit prepares the method for Ni-Ti surface tantalum coating
 
Technical field
The invention belongs to a kind of functional materials coating preparation, particularly a kind of room temperature fused salt galvanic deposit prepares the method for Ni-Ti surface tantalum coating.
Background technology
Niti-shaped memorial alloy can be used for making medicine equipment and surgical implant, such as angiocarpy bracket etc.Be a kind of functional materials, have the characteristics such as good biocompatibility, erosion resistance and be widely used in the biomaterial for medical purpose field.But nickel and compound thereof have potential toxicity to human body.Use the Ni-Ti alloy to do the side effect that skeleton fitting piece etc. produces in patient body.Because behind the Ni-Ti biomedical metal material implanting to human body, Ni is dissolved in body fluid in containing the body fluid of various salinities, the one, cause Ni-Ti alloy corrosion to damage, the 2nd, Ni forms metal hydroxides or muriate (such as human plasma) etc. in vivo, these materials cause very big impact to functions such as body immune system, hemopoietic systems, even have sensitization, carcinogenic, mutagenesis etc. and have a strong impact on.
Therefore, the Ni-Ti alloy all needs it is carried out surface modification before use, reduces application risk, can reduce on the one hand nickel ion and discharge, and can improve its biocompatibility on the other hand.The purpose of Ni-Ti shape memory alloy surface modification is to reduce surperficial Ni content, strengthens its solidity to corrosion, suppresses separating out of Ni ion.The method that prevents the corrosion of Ni-Ti shape memory alloy material is to make its surface passivation, forms passive film, reduces Ni and body fluid crevice corrosion.Up to the present, adopted the several different methods such as physical chemistry, electrochemistry, morphology and biological chemistry to the Ultimum Ti modifying surface, as: plated surface tantalum, surface ceramic coat, bioactive coating on surface etc., its purpose is at the Ni-Ti alloy surface and forms passivation protection film, but all have certain shortcoming: (1) plated surface tantalum method is for to plate tantalum at the Ni-Ti sheet alloy, when can improve the X-ray visibility, further improve corrosion resistance and suppress the stripping of Ni ion, improve biocompatibility; But shortcoming is can not or to be difficult to prepare coating at some large depth-to-width ratios, complex-shaped workpiece, device surface; (2) the surface ceramic coat method is to prepare ceramic layer by the whole bag of tricks on the Ni-Ti surface, prepares phosphorous TiO such as sol-gel method 2Film or Ca/P layer (Ca 5(PO 4) 3(OH) and a small amount of α-Ca 2P 2O 7And Ca 3(PO 4) 2Form, can improve its biocompatibility), the standby TiO of surface oxidation legal system 2Film, surfaces nitrided preparation TiN etc.; But shortcoming is TiO 2The erosion resistance of film is less than tantalum film, and tantalum film contacts with body fluid and is not subjected to any corrosion; (3) the bioactive coating on surface method is to adopt surface vacuum vapour deposition C type polyphenylene ethyl, and makes netted stent, implants in the animal blood vessels and carries out experimentation on animals and Study on biocompatibility; But shortcoming is that vaccum gas phase sedimentation method efficient is low, cost is high.
At Ni-Ti alloy surface plating tantalum layer, tantalum layer has and tissue consistency and blood compatibility characteristics, and the bone that can improve the surface as skeleton structure parts web member is induced and strengthened synostosis; Tantalum layer can reduce blood coagulation, vascular smooth muscle cell curing as intravascular stent, and tantalum has good X ray perviousness simultaneously, and is fine to the demonstration that bone develops.
Summary of the invention
For the deficiency that prior art exists, the invention provides the method that a kind of coating quality is uniform and stable, thickness is controlled and with low cost fused salt galvanic deposit prepares Ni-Ti plated surface tantalum layer.
A kind of room temperature fused salt galvanic deposit of the present invention prepares the method for Ni-Ti surface tantalum coating, may further comprise the steps:
(1) preparation ionogen: at lithium halide or two trifluoro sulfimide lithium (CF 3SO 2) 2Add two trifluoro sulfimide butyl pyrroles (CF in any one of N--Li 3SO 2) 2Any one of N-BPy or chlorinated butyl pyrroles BPy-Cl adds K again 2TaF 7Or TaCl 5The tantalum source is provided, forms electrolyte system;
(2) galvanic deposit prepares the tantalum coating: anode material is graphite or metal tantalum, and negative electrode is the Ni-Ti alloy, and 10 ~ 40 ℃ are carried out galvanic deposit on above-mentioned electrolytical liquidus temperature, current density 0.005 ~ 0.01A/cm 2, electrolysis 3 ~ 5h obtains fine and close tantalum coating at cathode surface.
Wherein, described lithium halide is LiCl or LiF;
Described electrolyte ingredient is two trifluoro sulfimide butyl pyrroles (CF of 80 ~ 90% by mass percentage 3SO 2) 2N-BPy, two trifluoro sulfimide lithium (CF of 5 ~ 15% 3SO 2) 2N--Li and 2 ~ 6% K 2TaF 7
Described electrolyte ingredient is 80 ~ 90% chlorinated butyl pyrroles BPy-Cl, 5 ~ 15% lithium halide and 2 ~ 10% TaCl by mass percentage 5
Beneficial effect of the present invention is:
Electrodeposition temperature of the present invention is low, and is easy to operate, with low cost, by the control current density, can obtain the tantalum coating of homogeneous chemical composition.Coatingsurface is smooth smooth, and polished finish just can become product a little, and the adhesivity of resulting tantalum coating and matrix Ni-Ti is good, and the thickness of coating can be well controlled by control electrodeposition time and current density, has the characteristics such as flexibly easy to make.
Description of drawings
Fig. 1 is that the embodiment of the invention 1 is at the tantalum coating picture of Ni-Ti surface preparation.
Embodiment
The present invention will be further described below in conjunction with embodiment.
With two trifluoro sulfimide butyl pyrroles (CF 3SO 2) 2N-BPy is abbreviated as BPyTf 2N, two trifluoro sulfimide lithiums are abbreviated as LiTf 2N.
Embodiment 1
Preparation 80BPyTf 2N-15LiTf 2N-5K 2TaF 7Ionogen; Anode material is graphite, and negative electrode is the Ni-Ti alloy, and 10 ℃ are carried out galvanic deposit, current density 0.005/cm on electrolytical liquidus temperature 2, electrolysis 5 hours obtains fine and close tantalum coating at cathode surface.The coating that this embodiment obtains as shown in Figure 1, wherein black part is divided into tantalum layer, smooth surface is smooth, even compact.
Embodiment 2
Preparation 90BPyTf 2N-8LiTf 2N-2K 2TaF 7Ionogen; Anode material is graphite, and negative electrode is the Ni-Ti alloy, and 20 ℃ are carried out galvanic deposit, current density 0.008/cm on electrolytical liquidus temperature 2, electrolysis 4 hours obtains fine and close tantalum coating at cathode surface.
Embodiment 3
Preparation 89BPyTf 2N-5LiTf 2N-6K 2TaF 7Ionogen; Anode material is metal tantalum, and negative electrode is the Ni-Ti alloy, and 40 ℃ are carried out galvanic deposit, current density 0.01/cm on electrolytical liquidus temperature 2, electrolysis 3 hours obtains fine and close tantalum coating at cathode surface.
Embodiment 4
Preparation 80BPy-Cl-10LiCl-10TaCl 5Ionogen, graphite are anode, and the Ni-Ti alloy is negative electrode, and 10 ℃ are carried out galvanic deposit, current density 0.005/cm on electrolytical liquidus temperature 2, electrolysis 5 hours obtains fine and close tantalum coating at cathode surface.
Embodiment 5
Preparation 90BPy-Cl-5LiCl-5TaCl 5Ionogen, graphite are anode, and the Ni-Ti alloy is negative electrode, and 10 ℃ are carried out galvanic deposit, current density 0.005/cm on electrolytical liquidus temperature 2, electrolysis 5 hours obtains fine and close tantalum coating at cathode surface.
Embodiment 6
Prepare 83 BPy-Cl-15LiCl-2TaCl 5Ionogen, metal tantalum are anode, and the Ni-Ti alloy is negative electrode, and 10 ℃ are carried out galvanic deposit, current density 0.005/cm on the electrolyte primary crystal temperature 2, electrolysis 5 hours obtains fine and close tantalum coating at cathode surface.

Claims (4)

1. a room temperature fused salt galvanic deposit prepares the method for Ni-Ti surface tantalum coating, it is characterized in that may further comprise the steps:
(1) preparation ionogen: at lithium halide or two trifluoro sulfimide lithium (CF 3SO 2) 2Add two trifluoro sulfimide butyl pyrroles (CF in any one of N--Li 3SO 2) 2Any one of N-BPy or chlorinated butyl pyrroles BPy-Cl adds K again 2TaF 7Or TaCl 5The tantalum source is provided, forms electrolyte system;
(2) galvanic deposit prepares the tantalum coating: anode material is graphite or metal tantalum, and negative electrode is the Ni-Ti alloy, and 10 ~ 40 ℃ are carried out galvanic deposit on above-mentioned electrolytical liquidus temperature, current density 0.005 ~ 0.01A/cm 2, electrolysis 3 ~ 5h obtains fine and close tantalum coating at cathode surface.
2. a kind of room temperature fused salt galvanic deposit according to claim 1 prepares the method for Ni-Ti surface tantalum coating, it is characterized in that described lithium halide is LiCl or LiF.
3. a kind of room temperature fused salt galvanic deposit according to claim 1 prepares the method for Ni-Ti surface tantalum coating, it is characterized in that described electrolyte ingredient is two trifluoro sulfimide butyl pyrroles (CF of 80 ~ 90% by mass percentage 3SO 2) 2N-BPy, two trifluoro sulfimide lithium (CF of 5 ~ 15% 3SO 2) 2N--Li and 2 ~ 6% K 2TaF 7
4. a kind of room temperature fused salt galvanic deposit according to claim 1 prepares the method for Ni-Ti surface tantalum coating, it is characterized in that described electrolyte ingredient is 80 ~ 90% chlorinated butyl pyrroles BPy-Cl, 5 ~ 15% lithium halide and 2 ~ 10% TaCl by mass percentage 5
CN201310017025.8A 2013-01-17 2013-01-17 Method for preparing Ni-Ti surface tantalum coating with electrodeposition in room temperature molten salts Expired - Fee Related CN103074650B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103590078A (en) * 2013-11-27 2014-02-19 东北大学 Method for making Mg-Ni-Al alloy film through electrodeposition
CN111826691A (en) * 2020-08-21 2020-10-27 东北大学 Method for preparing zinc-tantalum alloy by using solvated ionic liquid
CN112176372A (en) * 2020-09-27 2021-01-05 东北大学 Method for preparing cobalt-tantalum alloy coating at low temperature by taking cobalt dichloride and tantalum pentachloride as raw materials

Citations (2)

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JP2007070698A (en) * 2005-09-07 2007-03-22 Kyoto Univ Method for electrodepositing metal

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JP2007070698A (en) * 2005-09-07 2007-03-22 Kyoto Univ Method for electrodepositing metal

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103590078A (en) * 2013-11-27 2014-02-19 东北大学 Method for making Mg-Ni-Al alloy film through electrodeposition
CN103590078B (en) * 2013-11-27 2015-11-04 东北大学 The method of Mg-Ni-Al alloy firm is prepared in a kind of galvanic deposit
CN111826691A (en) * 2020-08-21 2020-10-27 东北大学 Method for preparing zinc-tantalum alloy by using solvated ionic liquid
CN111826691B (en) * 2020-08-21 2021-09-21 东北大学 Method for preparing zinc-tantalum alloy by using solvated ionic liquid
CN112176372A (en) * 2020-09-27 2021-01-05 东北大学 Method for preparing cobalt-tantalum alloy coating at low temperature by taking cobalt dichloride and tantalum pentachloride as raw materials
CN112176372B (en) * 2020-09-27 2021-10-15 东北大学 Method for preparing cobalt-tantalum alloy coating at low temperature by taking cobalt dichloride and tantalum pentachloride as raw materials

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