CN106086988B - A kind of method of laser melting coating closing aluminium alloy anode oxide film - Google Patents

A kind of method of laser melting coating closing aluminium alloy anode oxide film Download PDF

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Publication number
CN106086988B
CN106086988B CN201610645683.5A CN201610645683A CN106086988B CN 106086988 B CN106086988 B CN 106086988B CN 201610645683 A CN201610645683 A CN 201610645683A CN 106086988 B CN106086988 B CN 106086988B
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aluminium alloy
oxide film
anode oxide
powder
alloy anode
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CN106086988A (en
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周圣丰
戴晓琴
王梅丰
雷剑波
郭津博
顾振杰
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Tianjin Polytechnic University
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Tianjin Polytechnic University
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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
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • C25D11/246—Chemical after-treatment for sealing layers
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/003—Alloys based on aluminium containing at least 2.6% of one or more of the elements: tin, lead, antimony, bismuth, cadmium, and titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/04—Alloys containing less than 50% by weight of each constituent containing tin or lead
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0036—Matrix based on Al, Mg, Be or alloys thereof
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides

Abstract

A kind of method of laser melting coating closing aluminium alloy anode oxide film, it is the characteristics of this method：（1）Aluminium alloy anode oxide film is cleaned in spirituous ultrasonic cleaner is filled；（2）By dedicated aluminium alloy powder ball milling into the cladding powder that particle diameter is 2 ~ 10 microns, Laser Cladding Treatment is then carried out in the closed chamber filled with argon gas, realizes the closing of aluminium alloy anode oxide film.The present invention uses special Al alloy powder, is melted using laser melting and coating technique, and after the metallurgical chemistry reaction that complexity occurs, the cladding layer that quick solidification is formed can be effectively sealing off aluminium alloy anode oxide film.Therefore, method efficiency high of the invention, cost are low, and the compactness that can enable aluminum alloy to anode oxide film brings up to more than 98%, so as to be greatly enhanced the dicoration of aluminium alloy anode oxide film, corrosion resistance and service life.

Description

A kind of method of laser melting coating closing aluminium alloy anode oxide film
Technical field
The invention belongs to material science and field of surface engineering technique, more particularly to a kind of laser melting coating closing aluminium alloy sun The method of pole oxide-film.
Background technology
Aluminium alloy has the advantages that density is small, intensity is high, easy processing, cheap, has in industrial circle quite varied Application.But aluminium alloy corrodes in acid-base solution or easily when being contacted with the metal of other high potentials, significantly limit Its application.Therefore, aluminium alloy is surface-treated, improves its corrosion resisting property tool and be of great significance.
In general, carrying out anodic oxidation and Seal treatment to aluminum alloy surface, the decoration of aluminium alloy can be not only improved Property, pollution resistance and corrosion resistance, and the feature that the anode oxide film that can assign aluminum alloy surface is certain.At present, aluminium is closed The method that gold anode oxide-film carries out Seal treatment mainly has：High-temperature vapor is closed, with NiF2Based on normal temperature closing, with chromium Inorganic salts closing based on hydrochlorate, silicate etc., is closed using the organic acid based on stearic acid etc..Although these methods are certain In degree Seal treatment can be carried out to positive pole oxidation film on aluminum alloy surface, but the processing efficiency of these methods is relatively low, it is different Environmental pollution in degree be present, and obtained close membrane flexibility is poor, sealing of hole rate is not high causes aluminium alloy corrosion resistance poor The problems such as.
Laser melting coating is a kind of new process for modifying surface, and it utilizes height by adding cladding material in substrate surface The laser beam of energy density is allowed to rapid melting, and when laser beam flying later quick solidification forms cladding layer, this method has green The advantages that environmentally friendly, automaticity height, tiny and fine and close material structure prepared.But cover dedicated aluminium alloy powder using laser The method of end closing aluminium alloy anode oxide film yet there are no document report.
The content of the invention
It is an object of the invention to provide a kind of method of laser melting coating closing aluminium alloy anode oxide film.The present invention is this Come what is realized, its method is sample with step：
（1）Aluminium alloy anode oxide film is cleaned in spirituous ultrasonic cleaner is filled；
（2）The preparation of cladding powder：Dedicated aluminium alloy powder is positioned in high energy ball mill and carried out at mechanical alloying Reason, acquisition particle diameter is 2 ~ 10 microns and thing is mutually mainly by α-Al, Al2The cladding powder of Cu and rich Sn compositions；
（3）Cladding powder is preset in aluminium alloy anode oxide film surface, laser is carried out in the closed chamber filled with argon gas Cladding is handled, and realizes the closing of aluminium alloy anode oxide film.
The present invention is carrying out described step（2）When, the chemical composition of dedicated aluminium alloy powder is：Si 3.0~15.0 Wt.%, B 2.0 ~ 5.0 wt.%, CeO20.2 ~ 1.0 wt.%, Ni 0.5 ~ 1.8 wt.%, Cu 5.0 ~ 10.0 wt.%, Sn 15.0 ~ 30.0 wt.%, surplus Al；Milling parameters are：400 ~ 450 revs/min of rotating speed, time are 10 ~ 15 hours, ball milling During use a diameter of 2 ~ 10mm stainless steel ball, the mass ratio of stainless steel ball and dedicated aluminium alloy powder is 8:1, use liquid Nitrogen is protected, and prevents dedicated aluminium alloy Powder Oxidation；
The present invention is carrying out described step（3）When, the pre-set thickness of cladding powder is 0.5 ~ 1.0mm；Filled with argon gas Closed chamber in carry out laser melting coating technological parameter be：Semiconductor laser 0.5 ~ 0.8kW of power, spot diameter 15mm × 5mm, 300 ~ 480mm/min of sweep speed.
Compared with prior art, it is an advantage of the invention that：Closed using the laser melting coating based on dedicated aluminium alloy powder The method of aluminium alloy anode oxide film belongs to green manufacture technology pollution-free, that automaticity is high, and efficiency high, cost are low, can So that the compactness of aluminium alloy anode oxide film brings up to more than 98%, so as to be greatly enhanced the dress of aluminium alloy anode oxide film Decorations property, corrosion resistance and service life.
Embodiment
Embodiment 1
Using laser melting and coating technique to LY6 aluminium alloy anode oxide films carry out Seal treatment, specimen size be 150mm × 80mm×5 mm（Length × width × height）, after testing：By the hole of the LY6 aluminium alloy anode oxide films of laser melting coating Seal treatment Rate is less than 5%, and specific implementation process is as follows：
（1）Aluminium alloy anode oxide film is cleaned in spirituous ultrasonic cleaner is filled；
（2）The preparation of cladding powder：Dedicated aluminium alloy powder is positioned in high energy ball mill and carried out at mechanical alloying Reason, acquisition average grain diameter is about 2 microns and thing is mutually mainly by α-Al, Al2The cladding powder of Cu and rich Sn compositions；Special aluminium closes Bronze end chemical composition be：Si 3.0 ~ 15.0 wt.%, B 2.0 ~ 5.0 wt.%, CeO20.2 ~ 1.0 wt.%, Ni 0.5 ~ 1.8 wt.%, Cu 5.0 ~ 10.0 wt.%, Sn 15.0 ~ 30.0 wt.%, surplus Al；Milling parameters are：Rotating speed 400 Rev/min, the time is 15 hours, and a diameter of 2 ~ 10mm stainless steel ball, stainless steel ball and dedicated aluminium alloy are used in mechanical milling process The mass ratio of powder is 8:1, using protection of liquid nitrogen, prevent dedicated aluminium alloy Powder Oxidation；
（3）Cladding powder is preset in aluminium alloy anode oxide film surface, laser is carried out in the closed chamber filled with argon gas Cladding is handled, and realizes the closing of aluminium alloy anode oxide film；The pre-set thickness of cladding powder is 0.5mm；Filled with the close of argon gas The technological parameter for sealing indoor carry out laser melting coating is：Semiconductor laser power 0.5kW, spot diameter 15mm × 5mm, scanning speed Spend 300mm/min.
Embodiment 2
Using laser melting and coating technique to 2A12 aluminium alloy anode oxide films carry out Seal treatment, specimen size be 120mm × 60mm×4mm（Length × width × height）, after testing：By the hole of the 2A12 aluminium alloy anode oxide films of laser melting coating Seal treatment Rate is less than 3%, and specific implementation process is as follows：
（1）Aluminium alloy anode oxide film is cleaned in spirituous ultrasonic cleaner is filled；
（2）The preparation of cladding powder：Dedicated aluminium alloy powder is positioned in high energy ball mill and carried out at mechanical alloying Reason, acquisition average grain diameter is about 5 microns and thing is mutually mainly by α-Al, Al2The cladding powder of Cu and rich Sn compositions；Special aluminium closes Bronze end chemical composition be：Si 3.0 ~ 15.0 wt.%, B 2.0 ~ 5.0 wt.%, CeO20.2 ~ 1.0 wt.%, Ni 0.5 ~ 1.8 wt.%, Cu 5.0 ~ 10.0 wt.%, Sn 15.0 ~ 30.0 wt.%, surplus Al；Milling parameters are：Rotating speed 420 Rev/min, the time is 12 hours, and a diameter of 2 ~ 10mm stainless steel ball, stainless steel ball and dedicated aluminium alloy are used in mechanical milling process The mass ratio of powder is 8:1, using protection of liquid nitrogen, prevent dedicated aluminium alloy Powder Oxidation；
（3）Cladding powder is preset in aluminium alloy anode oxide film surface, laser is carried out in the closed chamber filled with argon gas Cladding is handled, and realizes the closing of aluminium alloy anode oxide film；The pre-set thickness of cladding powder is 0.8mm；Filled with the close of argon gas The technological parameter for sealing indoor carry out laser melting coating is：Semiconductor laser power 0.65kW, spot diameter 15mm × 5mm, scanning Speed 400mm/min.
Embodiment 3
Seal treatment is carried out to ZAlCu5Mn aluminium alloy anode oxide films using laser melting and coating technique, specimen size is 100mm×50mm×3mm（Length × width × height）, after testing：By the ZAlCu5Mn aluminum alloy anodes of laser melting coating Seal treatment The porosity of oxide-film is less than 2%, and specific implementation process is as follows：
（1）Aluminium alloy anode oxide film is cleaned in spirituous ultrasonic cleaner is filled；
（2）The preparation of cladding powder：Dedicated aluminium alloy powder is positioned in high energy ball mill and carried out at mechanical alloying Reason, acquisition average grain diameter is about 10 microns and thing is mutually mainly by α-Al, Al2The cladding powder of Cu and rich Sn compositions；Special aluminium The chemical composition of alloy powder is：Si 3.0 ~ 15.0 wt.%, B 2.0 ~ 5.0 wt.%, CeO20.2 ~ 1.0 wt.%, Ni 0.5 ~ 1.8 wt.%, Cu 5.0 ~ 10.0 wt.%, Sn 15.0 ~ 30.0 wt.%, surplus Al；Milling parameters are：Rotating speed 450 Rev/min, the time is 10 hours, and a diameter of 2 ~ 10mm stainless steel ball, stainless steel ball and dedicated aluminium alloy are used in mechanical milling process The mass ratio of powder is 8:1, using protection of liquid nitrogen, prevent dedicated aluminium alloy Powder Oxidation；
（3）Cladding powder is preset in aluminium alloy anode oxide film surface, laser is carried out in the closed chamber filled with argon gas Cladding is handled, and realizes the closing of aluminium alloy anode oxide film；The pre-set thickness of cladding powder is 1.0mm；Filled with the close of argon gas The technological parameter for sealing indoor carry out laser melting coating is：The mm of semiconductor laser power 0.8kW, spot diameter 15mm × 5, scanning Speed 480mm/min.

Claims (1)

1. a kind of method of laser melting coating closing aluminium alloy anode oxide film, its method are with step：
（1）Aluminium alloy anode oxide film is cleaned in spirituous ultrasonic cleaner is filled；
（2）The preparation of cladding powder：Dedicated aluminium alloy powder is positioned over progress mechanical alloying processing in high energy ball mill, obtained Particle diameter is 2 ~ 10 microns and thing mutually mainly by α-Al, Al2The cladding powder of Cu and rich Sn compositions；Dedicated aluminium alloy powder Chemical composition is：Si 3.0 ~ 15.0 wt.%, B 2.0 ~ 5.0 wt.%, CeO2The wt.% of 0.2 ~ 1.0 wt.%, Ni 0.5 ~ 1.8, Cu 5.0 ~ 10.0 wt.%, Sn 15.0 ~ 30.0 wt.%, surplus Al；Milling parameters are：400 ~ 450 revs/min of rotating speed, Time is 10 ~ 15 hours, and a diameter of 2 ~ 10mm stainless steel ball, stainless steel ball and dedicated aluminium alloy powder are used in mechanical milling process Mass ratio be 8:1, using protection of liquid nitrogen, prevent dedicated aluminium alloy from being aoxidized in mechanical milling process；
（3）Cladding powder is preset in aluminium alloy anode oxide film surface, laser is then carried out in the closed chamber filled with argon gas Cladding is handled, and realizes the closing of aluminium alloy anode oxide film；The pre-set thickness of cladding powder is 0.5 ~ 1.0mm；Laser melting coating Technological parameter is：Semiconductor laser 0.5 ~ 0.8kW of power, spot diameter 15mm × 5mm, 300 ~ 480mm/min of sweep speed.
CN201610645683.5A 2016-08-09 2016-08-09 A kind of method of laser melting coating closing aluminium alloy anode oxide film Expired - Fee Related CN106086988B (en)

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CN110524133A (en) * 2017-07-28 2019-12-03 成都盘涅科技有限公司 The method for improving aluminium alloy electronic device packaging air tightness
CN107675176B (en) * 2017-08-21 2019-05-17 陕西天元智能再制造股份有限公司 A kind of workpiece surface enhanced processing method that differential arc oxidation is combined with vacuum cladding
CN109161890B (en) * 2018-09-26 2020-05-05 广西大学 SiO (silicon dioxide)2Micro-arc oxidation composite coating and preparation method thereof
CN112458519A (en) * 2020-11-06 2021-03-09 安徽鑫发铝业有限公司 Preparation method of anti-corrosion electrophoresis extinction aluminum profile

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