CN110938849A - Zinc-molybdenum alloy coating titanium alloy and preparation method thereof - Google Patents
Zinc-molybdenum alloy coating titanium alloy and preparation method thereof Download PDFInfo
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- CN110938849A CN110938849A CN201911035586.4A CN201911035586A CN110938849A CN 110938849 A CN110938849 A CN 110938849A CN 201911035586 A CN201911035586 A CN 201911035586A CN 110938849 A CN110938849 A CN 110938849A
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- titanium alloy
- zinc
- molybdenum
- alloy
- cold rolling
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
Abstract
The invention discloses a zinc-molybdenum alloy coating titanium alloy and a preparation method thereof. A preparation method of a zinc-molybdenum alloy coating titanium alloy takes a titanium alloy coiled material subjected to cold rolling treatment as a cathode, and a zinc-molybdenum alloy coating is electroplated on the surface of the titanium alloy coiled material, wherein the preparation method comprises the following steps: the electroplating solution contains zinc ions and cobalt ions, wherein the concentration of zinc ions is 1.5-3.0mol/L, the concentration of cobalt ions is 1.47-3.24mol/L, the electroplating temperature is 40-50 deg.C, and the electroplating current density is 1.2-1.8A/dm2. The zinc-molybdenum alloy coating titanium alloy prepared by the preparation method of the zinc-molybdenum alloy coating titanium alloy has the advantages of bright and smooth surface, small residual stress, difficult generation of microcracks, high stability and certain performanceThe zinc-molybdenum alloy coating titanium alloy prepared by the preparation method of the zinc-molybdenum alloy coating titanium alloy can meet the requirements of materials for parts of electronic instruments.
Description
Technical Field
The invention relates to the technical field of electroplating, in particular to a zinc-molybdenum alloy coating titanium alloy and a preparation method thereof.
Background
Titanium alloys are widely used as materials for electronic components due to their advantages of high specific strength, high thermal strength, low density, good corrosion resistance, low temperature performance, and gas absorption performance. The electronic instrument parts need titanium alloy materials with certain electrical properties, proper mechanical properties, thinner thickness and good original battery corrosion resistance. The prior titanium alloy material lacks a plating layer with good galvanic corrosion resistance and cannot meet the requirements of materials for electronic instrument parts.
Disclosure of Invention
The invention aims to provide a zinc-molybdenum alloy plating titanium alloy with certain electrical property, proper mechanical property, thinner thickness and good galvanic corrosion resistance and a preparation method thereof aiming at the defects in the prior art.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a zinc-molybdenum alloy coating titanium alloy comprises the steps of taking a titanium alloy coiled material as a cathode, and electroplating a zinc-molybdenum alloy coating on the surface of the titanium alloy coiled material, wherein the electroplating solution contains 1.5-3.0mol/L of zinc ions and 1.47-3.24mol/L of cobalt ions.
Preferably, the concentration ratio of the cobalt ions to the zinc ions is 0.98-1.08.
Preferably, the temperature of the electroplating is 40-50 ℃.
Preferably, the current density of the electroplating is 1.2-1.8A/dm 2.
Preferably, the titanium alloy coil is obtained by cold rolling a titanium alloy raw material, and the thickness of the titanium alloy coil is smaller than that of the titanium alloy raw material.
Preferably, the cold rolling process of the titanium alloy coil comprises: and carrying out acid pickling, cold rolling for a plurality of times, degreasing and annealing treatment on the titanium alloy raw material in sequence.
Preferably, the thickness of the titanium alloy raw material is 1.8 +/-0.1 mm, and the chemical elements of the titanium alloy raw material comprise Mo: 0.10-0.25%, Si: 0-0.40%, Mn: 0-0.20%, Sn: 0-0.025%, Cu: 0-0.005%, Al: 0 to 0.10 percent.
Preferably, the cold rolling treatment comprises 10 times of cold rolling, the total reduction rate is 87-90%, and the thickness of the titanium alloy coil subjected to the cold rolling treatment is 0.35 +/-0.01 mm.
Preferably, the temperature of the annealing treatment is 550-600 ℃, and the heat preservation time is 10-20 min.
The invention provides a zinc-molybdenum coating titanium alloy and a preparation method thereof, which adopts a proper cold rolling process and a continuous electroplating process to form a zinc-molybdenum alloy coating on the surface of the titanium alloy. The zinc-molybdenum alloy coating prepared by the method has the advantages of small residual stress, difficult generation of microcracks, high stability, bright and smooth surface and excellent galvanic cell corrosion resistance.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Example 1
The titanium alloy coiled material with the thickness of 1.8 +/-0.1 mm is taken as a raw material and sequentially subjected to acid pickling, 10-pass cold rolling, degreasing and annealing treatment, wherein the reduction rate is controlled to be 87% in the cold rolling process, the annealing treatment temperature is 566 ℃, the heat preservation time is 18min, and the titanium alloy coiled material with the thickness of 0.35 +/-0.01 mm is obtained after the treatment.
Taking the treated titanium alloy coiled material with the thickness of 0.35 +/-0.01 mm as a cathode, taking a zinc plate with the purity of more than 99.99% as an anode, and electroplating a zinc-molybdenum coating on the surface of the titanium alloy coiled material in a plating solution containing zinc ions and molybdenum ions by a continuous electroplating process, wherein: the concentration of zinc ions in the plating solution is 1.5mol/L, the concentration of molybdenum ions in the plating solution is 1.47mol/L, namely the mass concentration ratio of the molybdenum ions to the zinc ions is 0.98, and the current density of electroplating is 1.8A/dm2The plating temperature was 40 ℃.
And (3) obtaining the zinc-molybdenum coating titanium alloy after the electroplating process is finished, then washing the zinc-molybdenum coating titanium alloy for multiple times, drying the zinc-molybdenum coating titanium alloy after the zinc-molybdenum coating titanium alloy is cleaned, and conventionally coiling the zinc-molybdenum coating titanium alloy after the surface is free of moisture.
The prepared zinc-molybdenum coating titanium alloy is subjected to coating thickness detection, mechanical property test and galvanic cell corrosion resistance test, a zinc-molybdenum coating titanium alloy sample is placed in an atmospheric environment with certain temperature and certain humidity, the test is carried out after the exposure for a period of time, and the corrosion degree is tested by observing the surface corrosion area, in the embodiment, the environmental temperature is 25 ℃, the environmental relative humidity is 50%, and the exposure time is 1500 d.
Example 2
The difference between the embodiment 2 and the embodiment 1 is that the reduction rate in the cold rolling process is 88.2 percent, the annealing treatment temperature is 550 ℃, the heat preservation time is 20min, the concentration of zinc ions in the plating solution is 1.5mol/L, the concentration of molybdenum ions in the plating solution is 1.485mol/L, namely the mass concentration ratio of the molybdenum ions to the zinc ions in the plating solution is 0.99, and the current density of electroplating is 1.3A/dm2The electroplating temperature is 50 ℃, and in the test of the galvanic cell corrosion resistance, the environmental temperature is 23 ℃ and the environmental relative humidity is 55%.
Example 3
The difference between the embodiment 3 and the embodiment 1 is that the reduction ratio is controlled to be 88.5 percent in the cold rolling process, the temperature of the annealing treatment is 583 ℃, the heat preservation time is 15min, the concentration of zinc ions in the plating solution is 2.5mol/L, the concentration of molybdenum ions in the plating solution is 2.625mol/L, namely, the mass concentration ratio of the molybdenum ions to the zinc ions in the plating solution is 1.05, and the current density of electroplating is 1.6A/dm2The electroplating temperature is 45 ℃, and in the test of the corrosion resistance of the original battery, the environmental temperature is 27 ℃ and the environmental relative humidity is 75%.
Example 4
The difference between the embodiment 4 of the invention and the embodiment 1 is that the reduction rate is controlled to be 89.6 percent in the cold rolling process, the annealing temperature is 575 ℃, and the temperature is kept during heat preservationWithin 13min, the concentration of zinc ions in the plating solution is 2.5mol/L, the concentration of molybdenum ions in the plating solution is 2.525mol/L, namely the mass concentration ratio of the molybdenum ions to the zinc ions in the plating solution is 1.01, and the current density of electroplating is 1.2A/dm2The electroplating temperature is 40 ℃, and in the test of the corrosion resistance of the original battery, the environmental temperature is 29 ℃ and the environmental relative humidity is 58%.
Example 5
The difference between the embodiment 4 and the embodiment 1 is that the reduction ratio is controlled to be 90 percent in the cold rolling process, the temperature of the annealing treatment is 600 ℃, the heat preservation time is 10min, the concentration of zinc ions in the plating solution is 3.0mol/L, the concentration of molybdenum ions in the plating solution is 3.24mol/L, namely, the mass concentration ratio of the molybdenum ions to the zinc ions in the plating solution is 1.08, and the current density of electroplating is 1.7A/dm2The electroplating temperature is 50 ℃, and in the test of the galvanic cell corrosion resistance, the environmental temperature is 21 ℃ and the environmental relative humidity is 67%.
The titanium alloy coiled material without being electroplated is taken as a comparative example of the invention, and the specific treatment process is as follows: the method comprises the steps of taking a titanium alloy coiled material with the thickness of 1.8 +/-0.1 mm as a raw material, sequentially carrying out acid pickling, 10-pass cold rolling, degreasing and annealing treatment, controlling the reduction rate to be 88.5% in the cold rolling process, controlling the annealing treatment temperature to be 592 ℃ and keeping the temperature for 12min, and directly carrying out coating thickness detection, mechanical property test and galvanic cell corrosion resistance test on the titanium alloy coiled material with the thickness of 0.35 +/-0.01 mm obtained after the treatment, wherein in the galvanic cell corrosion resistance test, the environment temperature is 26 ℃ and the environment relative humidity is 65%.
Table 1 shows the cold rolling and annealing process comparison of the examples of the present invention and the comparative examples, table 2 shows the plating process comparison of the examples of the present invention and the comparative examples, and table 3 shows the performance comparison of the examples of the present invention and the comparative examples: including plating thickness, mechanical properties, and galvanic corrosion resistance.
As can be seen from Table 3, the tensile strength of the zinc-molybdenum-coated titanium alloy prepared by the invention is 1256-1311MPa, and the elongation is 10.5-11.5%; the alloy is placed in an atmospheric environment for 1500 days, the surface corrosion degree is 0.12-0.33%, and the galvanic cell corrosion resistance is good. The surface of the zinc-molybdenum coating titanium alloy is bright and smooth through observation, and the surface has no microcracks.
The invention provides a zinc-molybdenum coating titanium alloy and a preparation method thereof, which adopts a proper cold rolling process and a continuous electroplating process to form a zinc-molybdenum alloy coating on the surface of the titanium alloy. The zinc-molybdenum alloy coating prepared by the method has the advantages of small residual stress, difficult generation of microcracks, high stability, bright and smooth surface and excellent galvanic corrosion resistance, and the zinc-molybdenum alloy coating titanium alloy prepared by the method can be applied to electronic instrument parts.
Table 1 list of various embodiments of the present invention and comparative cold rolling and annealing processes
Table 2 list of examples of the invention and comparative plating processes
Table 3 is a list of properties of various embodiments of the present invention and comparative examples
The above is not relevant and is applicable to the prior art.
The features of the embodiments and embodiments described herein above may be combined with each other without conflict. The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a zinc-molybdenum alloy coating titanium alloy is characterized in that a titanium alloy coiled material is used as a cathode, and a zinc-molybdenum alloy coating is electroplated on the surface of the titanium alloy coiled material, wherein the electroplating solution contains 1.5-3.0mol/L of zinc ions and 1.47-3.24mol/L of cobalt ions.
2. The method of claim 1, wherein the concentration ratio of the cobalt ions to the zinc ions is between 0.98 and 1.08.
3. The method of claim 2, wherein the plating temperature is 40-50 ℃.
4. The method of claim 3, wherein the electroplating current density is 1.2-1.8A/dm2。
5. The method for preparing a zinc-molybdenum alloy coated titanium alloy according to any one of claims 1 to 4, wherein a titanium alloy raw material is subjected to a cold rolling treatment to obtain the titanium alloy coil, and the thickness of the titanium alloy coil is smaller than that of the titanium alloy raw material.
6. The method for preparing the zinc-molybdenum alloy coated titanium alloy according to claim 5, wherein the cold rolling treatment process of the titanium alloy coil comprises the following steps: and (3) carrying out acid pickling, cold rolling for a plurality of times, degreasing and annealing treatment on the titanium alloy raw material in sequence.
7. The method for preparing the zinc-molybdenum alloy coated titanium alloy according to claim 6, wherein the thickness of the titanium alloy raw material is 1.8 mm plus or minus 0.1mm, and the chemical elements of the titanium alloy raw material comprise, by weight, Mo: 0.10-0.25%, Si: 0-0.40%, Mn: 0-0.20%, Sn: 0-0.025%, Cu: 0-0.005%, Al: 0 to 0.10 percent.
8. The method for preparing the zinc-molybdenum alloy coated titanium alloy according to claim 7, wherein the cold rolling treatment comprises 10 cold rolling passes, the total reduction rate is 87-90%, and the thickness of the titanium alloy coil subjected to the cold rolling treatment is 0.35 +/-0.01 mm.
9. The method for preparing the Zn-Mo alloy coated Ti alloy as claimed in claim 6, wherein the annealing temperature is 550-600 ℃ and the holding time is 10-20 min.
10. A zinc-molybdenum alloy coating titanium alloy is characterized in that: prepared by the preparation method of any one of claims 1 to 9.
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Citations (10)
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|---|---|---|---|---|
| US2080479A (en) * | 1935-04-04 | 1937-05-18 | Du Pont | Plating of zinc |
| SU560000A1 (en) * | 1975-12-24 | 1977-05-30 | Ордена Трудового Красного Знамени Институт Химии И Химической Технологии Ан Литовской Сср | Zinc Molybdenum Alloy Deposition Solution |
| JPS61136917A (en) * | 1984-12-05 | 1986-06-24 | Sumitomo Metal Ind Ltd | Method for dissolving metallic zinc |
| JPH04337098A (en) * | 1991-05-13 | 1992-11-25 | Kawasaki Steel Corp | Zn-ni-mo multi-ply electrogalvanized steel sheet excellent in corrosion resistance and plating adhesion |
| CN1236829A (en) * | 1998-03-27 | 1999-12-01 | 倍耐力轮胎股份公司 | Surface-treated metal component for reinforcing structures and article of manufactured comprising the same |
| CN102191517A (en) * | 2010-03-10 | 2011-09-21 | 中国科学院过程工程研究所 | Method of electroplating zinc, nickel, molybdenum and their alloys by using ionic liquid |
| US20160059519A1 (en) * | 2014-08-27 | 2016-03-03 | Schlumberger Technology Corporation | Steel Armor Wire Coatings |
| CN105774118A (en) * | 2015-01-09 | 2016-07-20 | Jx日矿日石金属株式会社 | Metal substrate with plating |
| CN106995891A (en) * | 2017-05-18 | 2017-08-01 | 含山瑞可金属有限公司 | A kind of anti-corrosion and high strength titanium alloy fastener |
| CN109482644A (en) * | 2018-10-15 | 2019-03-19 | 湖南湘投金天钛金属股份有限公司 | A kind of method of titanium or titanium alloy band volume Surface uniformization |
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2019
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Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2080479A (en) * | 1935-04-04 | 1937-05-18 | Du Pont | Plating of zinc |
| SU560000A1 (en) * | 1975-12-24 | 1977-05-30 | Ордена Трудового Красного Знамени Институт Химии И Химической Технологии Ан Литовской Сср | Zinc Molybdenum Alloy Deposition Solution |
| JPS61136917A (en) * | 1984-12-05 | 1986-06-24 | Sumitomo Metal Ind Ltd | Method for dissolving metallic zinc |
| JPH04337098A (en) * | 1991-05-13 | 1992-11-25 | Kawasaki Steel Corp | Zn-ni-mo multi-ply electrogalvanized steel sheet excellent in corrosion resistance and plating adhesion |
| CN1236829A (en) * | 1998-03-27 | 1999-12-01 | 倍耐力轮胎股份公司 | Surface-treated metal component for reinforcing structures and article of manufactured comprising the same |
| CN102191517A (en) * | 2010-03-10 | 2011-09-21 | 中国科学院过程工程研究所 | Method of electroplating zinc, nickel, molybdenum and their alloys by using ionic liquid |
| US20160059519A1 (en) * | 2014-08-27 | 2016-03-03 | Schlumberger Technology Corporation | Steel Armor Wire Coatings |
| CN105774118A (en) * | 2015-01-09 | 2016-07-20 | Jx日矿日石金属株式会社 | Metal substrate with plating |
| CN106995891A (en) * | 2017-05-18 | 2017-08-01 | 含山瑞可金属有限公司 | A kind of anti-corrosion and high strength titanium alloy fastener |
| CN109482644A (en) * | 2018-10-15 | 2019-03-19 | 湖南湘投金天钛金属股份有限公司 | A kind of method of titanium or titanium alloy band volume Surface uniformization |
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| Title |
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Application publication date: 20200331 |