CN105331941B - One kind is in copper, copper alloy, zinc and zinc alloy surface differential arc oxidation method - Google Patents
One kind is in copper, copper alloy, zinc and zinc alloy surface differential arc oxidation method Download PDFInfo
- Publication number
- CN105331941B CN105331941B CN201510647800.7A CN201510647800A CN105331941B CN 105331941 B CN105331941 B CN 105331941B CN 201510647800 A CN201510647800 A CN 201510647800A CN 105331941 B CN105331941 B CN 105331941B
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- Prior art keywords
- zinc
- copper
- arc oxidation
- aluminium film
- alloy
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5846—Reactive treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/024—Anodisation under pulsed or modulated current or potential
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium 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
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
Abstract
The invention discloses one kind in copper, copper alloy, zinc and zinc alloy surface differential arc oxidation method, this method first prepares aluminium film with magnetron sputtering method in copper, copper alloy, zinc or zinc alloy surface, the aluminium film is handled with micro-arc oxidation again, obtains alumina ceramic membrane.Non- valve metal after magnetron sputtering is handled carries out the alumina ceramic membrane that differential arc oxidation obtains again, and wearability improves more than 10 times, and corrosion resistance also greatly enhances；Solves the technical problem for the ceramic membrane poor performance that non-valve metal can not use micro-arc oxidation to prepare ceramic membrane or preparation.
Description
Technical field
The present invention relates to one kind in copper, copper alloy, zinc and zinc alloy surface differential arc oxidation method, belongs to electrochemical field.
Background technology
It is well known that only valve metal（Aluminium, magnesium, zirconium, titanium etc.）Differential arc oxidation processing could be directly carried out on surface, and
The non-valve metal such as copper, iron, zinc directly can not carry out differential arc oxidation, it is necessary to carry out after-treatment on surface, but most of secondary place
The features such as differential arc oxidation film layer carried out again after reason can all come across matrix attachment loosely, and film layer wears no resistance.
Because Cu-base composites have very high conduction, heat conductivility, it is expected to be used in requirement and have both high conductance
With wearability field, in actual applications Cu-base composites often to enter line slip with various materials as conducting element and connect
Touch, it is the major issue to merit attention that the abrasion of material, which includes composite itself and the abrasion with mating plate, and it is directly affected
To the whole normal work for sliding electric contact-system, so these parts often require that material with high electrical conductivity, heat conduction
While property, also to possess excellent wearability, therefore, further investigation tool be carried out to the friction and wear behavior of such composite
There are important theory and realistic meaning.Equally, it is also required to further for zinc and zinc alloy material, its wear-resisting and decay resistance
Improve.
The content of the invention
Present invention solves the technical problem that it is, by the method for differential arc oxidation in copper, copper alloy, zinc and zinc alloy surface system
Standby alumina ceramic membrane, improve the wearability and corrosion resistance of these metals.
The technical scheme is that, there is provided it is a kind of in copper, copper alloy, zinc and zinc alloy surface differential arc oxidation method, elder generation
With magnetron sputtering method copper, copper alloy, zinc or zinc alloy surface prepare aluminium film, then with micro-arc oxidation to the aluminium film at
Reason, obtains alumina ceramic membrane.
Further, the thickness of the aluminium film is 6-200 microns.
Further, the thickness of the aluminium film is 40-60 microns.
Further, the design parameter of the micro-arc oxidation is：To prepare copper, copper alloy, zinc or zinc after having aluminium film
Alloy makees anode, and steel plate makees negative electrode；The concentration of electrolyte is 10-70g/L, 20-30 DEG C of temperature；Power parameter is arranged to：Positive electricity
Flow for 2-10A/dm2, negative current 1-9A/dm2, positive negative duty is 10%-30%, frequency 1000-3000Hz.
Further, the electrolyte is 12-60g/L aluminate, phosphate or silicate and 1-5g/L hydroxide
Potassium forms.
Further, the aluminate, phosphate and silicate are sodium salt.
The table of the differential arc oxidization technique rising in recent years very strong as the adhesive force in matrix surface growth in situ
Face treatment technology, the effect highly significant in terms of the wear-resisting and rotproofness of aluminium alloy and its zircaloy is improved, but copper, zinc and its conjunction
Gold can not carry out conventional differential arc oxidation processing.
One layer of aluminium film is plated in copper, zinc and its alloy surface before differential arc oxidation, film plating process is a lot, there is spraying, hot dipping
Cross, but the film of these methods plating and matrix adhesive force be not firm, even if to the wear-resisting of copper, zinc or its alloy after differential arc oxidation
Property, the raising also unobvious of corrosion resistance.
Magnetron sputtering of the present invention is as a kind of method of sputter coating, film and the matrix adhesive force jail of sputtering
The advantages of leaning on, and sputtered film thickness can be controlled, it is very strong that one layer of adhesive force can be obtained after differential arc oxidation is handled
Alumina ceramic membrane, it can greatly strengthen the wearability of film layer.
The first differential arc oxidation again after matrix surface sputters one layer of pure aluminium film of the method for the magnetron sputtering first that we use
Method can greatly strengthen the anti-wear performance of non-valve metal, can largely extend the service life of material, save
Material.
In order to improve film performance, we devise following technical scheme, comprise the following steps that：
1st, copper, copper alloy, zinc or kirsite sample are polished with 60# to 5000# SiC sand paper respectively, then uses polishing cloth
Polishing, and with alcohol, deionized water rinsing.
2nd, the copper after polishing, copper alloy, zinc or kirsite sample are carried out magnetron sputtering, one layer can be sputtered as requested
6 to 200 microns of fine aluminium film, according to the film layer of which kind of specifically used thickness of purposes.
3rd, the sample after magnetron sputtering is sealed with epoxy resin, exposes the area for being coated with aluminium film.
4th, electrolyte is prepared：Aluminate（12-60g/L）And potassium hydroxide（Mixed liquor 1-5g/L).Electrolyte is placed
Electrolyte temperature is kept to exist in circulating cooling groove（20-30）℃.
The 5th, mao power source parameter is set, positive current is（2-10）A/dm2, negative current is arranged to（1-9）A/dm2, it is positive and negative
Dutycycle is arranged to 10%-30%, and frequency maintains（1000-3000）Hz.
6th, copper, copper alloy, zinc or kirsite sample are done anode, steel plate does negative electrode, turns on the power reaction（4-10）min.
7th, sample is taken out, is rinsed with clear water, then with deionized water rinsing, drying.Now just copper, iron, zinc and its
Alloy surface forms the wear-resisting alumina ceramic membrane of a floor height.
The invention has the advantages that the copper, copper alloy, zinc or kirsite after magnetron sputtering is handled carry out the differential of the arc again
Obtained alumina ceramic membrane is aoxidized, wearability improves more than 10 times, and corrosion resistance also greatly enhances；Solve copper,
Copper alloy, zinc and kirsite can not be asked using the technology for the ceramic membrane poor performance that micro-arc oxidation prepares ceramic membrane or preparation
Topic.
Brief description of the drawings
The Brass sample and the brass base of comparative example 1 that Fig. 1 expressions embodiment 1 obtains are respectively under 50N and 10N load
The Wear track depth comparison diagram formed after friction 30min.
Fig. 2 represent the brass base of the obtained Brass sample of embodiment 1 and comparative example 1 respectively 3.5% NaCl electrolyte
In polarization curve comparison diagram.
Embodiment
Separately below by taking copper, copper alloy, zinc and kirsite as an example, differential arc oxidation processing is carried out, the technology of the present invention is imitated
Fruit is described further.
Embodiment 1：The fine aluminium film for forming one layer of 40 microns after brass polishing by magnetron sputtering, by epoxy
After resin seal, brass is placed on concentration and added for 32g/L sodium aluminates in 1g potassium hydroxide, setting electrolytic parameter is positive current
0.6A/cm2Negative current is 0.5A/cm2, positive negative duty is 20%, frequency 1000Hz.Done with sputtering brass after fine aluminium film
Anode, steel plate do negative electrode, react 5min, it is possible to form one layer of fine and close abradability aluminium oxide ceramics film in brass surfaces, obtain
Brass sample.
The Brass sample that embodiment 1 is obtained carries out wearability and corrosion resistance test, and its main tester is as follows：
TT260 carries out layer calibrator：Beijing Time Zhifeng Science Co., Ltd.It can be used to measure the thickness of film layer；
MIS800 type ion beam magnetron sputtering composite coating equipments：Ke You vacuum techniques research institute of Shenyang City；
X x ray diffractometer xs：（Place of production Japan, model Rigaku D/MAX 2500）.Detect the composition of film layer phase；
CETR UMT-3 frictiographs：Using the fast formula friction test of ball-film, sample wearability is detected；
Optical profilometer（Wyko NT 9100, VEECO Instruments Inc.）：Detect Wear track depth；
CHI660 electrochemical workstations（Shanghai Chen Hua instrument company）：Detect the corrosion resistance of film.
Comparative example 1：Under the same conditions, with brass base（I.e. without the brass of processing）Surveyed as a comparison
Examination.As depicted in figs. 1 and 2, the Brass sample that the embodiment 1 that Fig. 1 is represented obtains rubs obtained by 30min experimental result under 50N
The polishing scratch figure comparison diagram that the polishing scratch figure and the brass base of comparative example 1 arrived is rubbed under 10N obtained by 30min.
It can be seen that under this kind of parameter setting, Wear track depth of the embodiment 1 under 50N is 15.6 microns, and
Only using the Wear track depth of the comparative example 1 for the 30min that rubbed under 10N as 34.5 microns, think that its wearability carries through simple conversion
It is high 11 times.
The Brass sample and the brass base of comparative example 1 that Fig. 2 expressions embodiment 1 obtains are in 3.5% NaCl electrolyte
Polarization curve comparison diagram.The corrosion resistance electric current of embodiment 1 is reduced compared with the corrosion resistance electric current of the brass base of comparative example 1
2 orders of magnitude, curve is more past moves to left, and represents that corrosion resistance is better, current density is also just smaller.
Embodiment 2：The differential arc oxidation for carrying out the present invention to copper by the condition of embodiment 1 is handled, wherein first through magnetron sputtering
The aluminium film thickness of preparation is 60 microns.17 times are about improved with corresponding undressed copper contrast wearability, corrosion resistance electric current phase
Than reducing about 3 orders of magnitude.
Embodiment 3：The differential arc oxidation for carrying out the present invention to zinc by the condition of embodiment 1 is handled, wherein first through magnetron sputtering
The aluminium film thickness of preparation is 45 microns.12 times are about improved with corresponding undressed zinc contrast wearability, corrosion resistance electric current phase
Than reducing about 2 orders of magnitude.
Embodiment 4：The differential arc oxidation for carrying out the present invention to kirsite by the condition of embodiment 1 is handled, wherein first through magnetic control
Aluminium film thickness prepared by sputtering is 50 microns.15 times are about improved with corresponding undressed kirsite contrast wearability, it is corrosion-resistant
Property electric current compared to reducing about 2.5 orders of magnitude.
Although aluminium film prepared by magnetron sputtering, which reaches 6 microns, can carry out differential arc oxidation, present invention discover that aluminium film reaches
During 40-60 microns, wear-resisting and decay resistance both can reach preferable level, though can continue to increase the thickness of aluminium film, can increase
Process costs.
Claims (4)
1. one kind is in copper, copper alloy, zinc, zinc alloy surface differential arc oxidation method, it is characterised in that is first existed with magnetron sputtering method
Copper, copper alloy, zinc or zinc alloy surface prepare aluminium film, then the aluminium film is handled with micro-arc oxidation, obtain aluminum oxide
Ceramic membrane；The design parameter of the micro-arc oxidation is：There are copper, copper alloy, zinc or kirsite after aluminium film to make anode to prepare,
Steel plate makees negative electrode；20-30 DEG C of temperature；Power parameter is arranged to：Positive current is 2-10A/dm2, negative current 1-9A/dm2, it is positive and negative
Dutycycle is 10%-30%, frequency 1000-3000Hz；Electrolyte is 32-60g/L aluminate and 1-5g/L potassium hydroxide
Composition.
2. the method as described in claim 1, it is characterised in that the thickness of the aluminium film is 6-200 microns.
3. the method as described in claim 1, it is characterised in that the thickness of the aluminium film is 40-60 microns.
4. the method as described in claim 1, it is characterised in that the aluminate is sodium salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510647800.7A CN105331941B (en) | 2015-10-09 | 2015-10-09 | One kind is in copper, copper alloy, zinc and zinc alloy surface differential arc oxidation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510647800.7A CN105331941B (en) | 2015-10-09 | 2015-10-09 | One kind is in copper, copper alloy, zinc and zinc alloy surface differential arc oxidation method |
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| CN105331941A CN105331941A (en) | 2016-02-17 |
| CN105331941B true CN105331941B (en) | 2017-12-08 |
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| CN201510647800.7A Expired - Fee Related CN105331941B (en) | 2015-10-09 | 2015-10-09 | One kind is in copper, copper alloy, zinc and zinc alloy surface differential arc oxidation method |
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|---|---|---|---|---|
| CN110016708B (en) * | 2019-04-16 | 2021-02-23 | 湖南大学 | Micro-arc oxidation surface treatment method suitable for copper and copper alloy and product |
| CN110453228A (en) * | 2019-08-19 | 2019-11-15 | 西南交通大学 | A kind of preparation method of depth narrow-gap gas metal arc welding ignition tip |
| CN111394771B (en) * | 2020-04-22 | 2021-05-04 | 哈尔滨工业大学 | Method for preparing coating on surface of copper and copper alloy and copper product |
| CN111763898B (en) * | 2020-06-01 | 2021-10-01 | 武汉大学 | Metal surface treatment for electrical insulation equipment for preventing C5F10O gas etching method |
| CN111705287B (en) * | 2020-07-10 | 2021-07-30 | 武汉大学 | Metal surface treatment for electrical insulation equipment for preventing C4F7N etching method |
| CN112226768B (en) * | 2020-10-13 | 2022-09-23 | 辽宁科技大学 | Composite preparation method of micro-arc oxidation CrAlN coating |
| CN112813392A (en) * | 2020-12-31 | 2021-05-18 | 中国科学院宁波材料技术与工程研究所 | Solid-liquid compound wear-resistant antibacterial material based on capillary action, preparation method and application |
| CN115233157A (en) * | 2022-06-14 | 2022-10-25 | 沈阳大学 | Method for preparing copper film on surface of zinc and zinc alloy through magnetron sputtering |
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| CN103628016A (en) * | 2013-12-18 | 2014-03-12 | 江苏科技大学 | Protection method for high-temperature corrosion resistance of ultrasonic amplitude transformer |
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2015
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| CN101265603A (en) * | 2008-01-29 | 2008-09-17 | 四川大学 | Multiple layer hydrogen infiltration -resistant compound film preparation method |
| CN103628016A (en) * | 2013-12-18 | 2014-03-12 | 江苏科技大学 | Protection method for high-temperature corrosion resistance of ultrasonic amplitude transformer |
| CN103981498A (en) * | 2014-04-30 | 2014-08-13 | 南昌航空大学 | Method for improving wear resistant property of metal material |
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