CN108505089A - A kind of aluminum alloy surface Al based on sodium tetraborate2O3-AlB12The preparation method of composite ceramics film layer - Google Patents

A kind of aluminum alloy surface Al based on sodium tetraborate2O3-AlB12The preparation method of composite ceramics film layer Download PDF

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CN108505089A
CN108505089A CN201810615062.1A CN201810615062A CN108505089A CN 108505089 A CN108505089 A CN 108505089A CN 201810615062 A CN201810615062 A CN 201810615062A CN 108505089 A CN108505089 A CN 108505089A
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working solution
sodium tetraborate
aluminum alloy
film layer
water
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吕鹏翔
吴蒙华
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Dalian University
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/026Anodisation with spark discharge
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/06Alloys based on aluminium with magnesium as the next major constituent
    • C22C21/08Alloys based on aluminium with magnesium as the next major constituent with silicon
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/024Anodisation under pulsed or modulated current or potential
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/04Anodisation of aluminium or alloys based thereon
    • C25D11/06Anodisation of aluminium or alloys based thereon characterised by the electrolytes used

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  • Metallurgy (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

A kind of aluminum alloy surface Al based on sodium tetraborate2O3‑AlB12The preparation method of composite ceramics film layer, using 6061 Al alloy parts as anode, using the stainless steel plate of electrolytic cell as cathode, workpiece anode is immersed in working solution, then apply bipolar pulse electricity between a cathode and an anode, differential arc oxidation processing is carried out, makes the aluminium in the sodium tetraborate and 6061 alloy matrix aluminums in working solution that plasma chemical reaction occur, to obtain 6061 aluminum alloy surface Al2O3‑AlB12Composite ceramics film layer.The present invention solves existing Al2O3‑AlB12The problem of preparation process of composite ceramics film layer is complicated, the time is long, high energy consumption.Improve 6061 micro-arc oxidation of aluminum alloy surface ceramic film bending strengths and fracture toughness simultaneously.

Description

A kind of aluminum alloy surface Al based on sodium tetraborate2O3-AlB12Composite ceramics film layer Preparation method
Technical field
The present invention relates to metal surface modification fields, more particularly to aluminum alloy surface ceramic film layer and preparation method thereof.
Background technology
6061 alloys make it have processing performance is splendid, excellent extrusion molding, excellent since it is containing magnesium, element silicon Weld characteristics and indeformable, the fine and close zero defect of material and be easy to throw after plating resistance, good corrosion resistance, toughness is high and processing Light, the good characteristics such as colouring film is easy, oxidation effectiveness is splendid.Be widely used in decoration, packaging, building, transport, electronics, aviation, The all trades and professions such as space flight, weapons are commonly used to do automated machine part, Precision Machining, mold manufacturing etc. in machinery industry, these Purposes needs him to have the anti-destructive robbed in surface, this just needs to be modified reinforcing to 6061 aluminum alloy surfaces, improves its table The wearability and fracture toughness in face.
Differential arc oxidization technique is usually utilized to improve the performance of aluminum alloy surface.Micro-arc oxidation of aluminum alloy surface ceramic film Main component be Al2O3, have with basal body binding force is good, hardness is high, corrosion-resistant, rub resistance, insulation resistance height, heat shock resistance, Thermal stability well equal excellent performances, this effectively expands the application range of aluminium alloy, make its aerospace, equipment manufacturing, The fields such as textile machine and electronic communication are with a wide range of applications.However, Al2O3The ceramic brittleness of itself limits its Further apply.Currently, toughening is to solve the problems, such as the more effective method, increase including dis-persion toughening, fiber and whisker Tough, zirconium oxide transformation toughening, composite toughening etc..
AlB12Microhardness, wearability, breaking load and be far longer than white fused alumina than breaking load and (contain Al2O399% or more), often studied personnel are used for Al2O3Ceramics carry out composite toughening.Its technical process is:Al powder with B2O3Powder mixes, compression moulding, leads to protection gas, high-temperature heating, self-propagating reaction, Slow cooling, mechanical crushing, sieving.It is utilizing AlB12To Al2O3Toughening forms Al2O3-AlB12During composite ceramics film layer, to realize that self- propagating process, high-temperature heating need More than 1800K;And Slow cooling is then conducive to AlB12The formation of crystal.This method obtains Al2O3-AlB12Composite ceramic End.Then using process for treating surface such as sprayings, Al is formed in metal surface2O3-AlB12It is protected with the composite ceramics of matrix Layer.Although it efficiently solves Al2O3Toughening problem, but the processing procedure, complex process, high energy consumption is of long duration, and Film layer is poor with basal body binding force.
Invention content
The present invention is to improve 6061 micro-arc oxidation of aluminum alloy surface ceramic film bending strengths and fracture toughness, is solved simultaneously Existing Al2O3-AlB12Preparation process complexity, time length, high energy consumption, the problem with basal body binding force difference of composite ceramics film layer, And provide a kind of 6061 aluminum alloy surface Al based on sodium tetraborate2O3-AlB12The preparation method of composite ceramics film layer.
The present invention inventive concept be:It can be worked in aluminum alloy surface growth in situ ceramic film by interpolar discharge When Al alloy parts connect the anode of mao power source, cathode connects stainless steel electrolytic slot, is full of working solution, working solution therebetween It inside stainless steel electrolytic slot, and is only connected, cannot be contacted with each other by working solution between Al alloy parts and electrolytic cell Or it is connected with other conductors.When processing starts, with the raising of voltage across poles, the reactant in working solution is under the action of electric field It is collected around to anode movement, and in discharge channel, it, will be in gold when the voltage of two interpolar of negative and positive is more than faraday's region of discharge Metal surface generate micro arc plasma body electric discharge, differential arc oxidation electric discharge be plasma arc light electric discharge, process be divided into superficial electric discharge, Depth is discharged and submerged arc electric discharge three phases, and the high temperature and pressure that plasma discharge is generated in discharge channel, DIE Temperature can Up to 6800K~9500K, channel edge temperature also may be up to 2000K, and such high temperature and pressure makes the metal of workpiece surface, work Plasma chemical reaction occurs for ion or suspension particles in liquid, and reactant can be pushed to discharge channel bottom by submerged arc discharge regime Portion, and micro- molten bath is formed in discharge channel bottom and base contact portion, so that reactant, base aluminum is sufficiently mixed in micro- molten bath, And reaction forms new product rapidly.The discharge channel of long and narrow complications has delayed the reduction of micro- bath temperature.Ceramic coating formed by micro-arc oxidation With that the high bond strength between matrix of corrosion-resistant, wear-resisting, insulation resistance is high, thicknesses of layers and roughness are controllable etc. is many Advantage.Differential arc oxidation discharge energy can be controlled by electrical parameter;Boron element can be drawn by the form of solvent or suspended things Enter into working solution, and then participates in differential arc oxidation reaction;It is long and narrow curved due to putting a channel in the submerged arc discharge regime of differential arc oxidation The cooling effect of song, working solution weakens so that the temperature reduction in micro- molten bath is slower, this is all conducive to AlB12The formation of crystal, into And in one layer of Al of workpiece surface in-situ preparation2O3-AlB12Composite ceramics film layer.
A kind of 6061 aluminum alloy surface Al based on sodium tetraborate2O3-AlB12The preparation method of composite ceramics film layer be by It is carried out according to following steps:
Using 6061 Al alloy parts as anode, using the stainless steel plate of electrolytic cell as cathode, equipped with preparation in advance in electrolytic cell Good working solution, anode is immersed in working solution, then applies bipolar pulse electricity between a cathode and an anode, and make forward direction Voltage is 50V~620V, backward voltage is 20V~95V, current density 10A/dm2~20A/dm2, frequency be 500Hz~ 2000Hz, under conditions of working solution temperature is 20 DEG C~80 DEG C, processing 30min~60min is to get to 6061 aluminum alloy surfaces Al2O3-AlB12Composite ceramics film layer, wherein the working solution includes the nothing of sodium tetraborate, water and at least one or two or more Machine salt, alkali or Organic Alcohol.Keep a concentration of 5-20g/L of the sodium tetraborate in working solution.
Sodium tetraborate determines whether plasma chemical reaction can be normally carried out in the concentration of working solution.Sodium tetraborate concentration It, then can not regular picture more than 30g/L.
6061 aluminium alloy elements form, copper:0.15wt%~0.4wt%;Manganese:0.15;Magnesium:0.8wt%~1.2wt%; Zinc:0.25wt%;Chromium:0.04wt%~0.35wt%;Titanium:0.15wt%;Silicon:0.4wt%~0.8wt%;Iron:0.7wt%; Aluminium:Surplus.
The working solution is made of sodium tetraborate, water and inorganic salts;Or the working solution is by sodium tetraborate, water and alkali Composition;Or the working solution is made of sodium tetraborate, water and Organic Alcohol;Or the working solution is by sodium tetraborate, water, organic Alcohol and inorganic salts composition;Or the working solution is made of sodium tetraborate, water, Organic Alcohol and alkali;Or the working solution is by four Boratex, water, alkali and inorganic salts composition;Or the working solution is made of sodium tetraborate, water, Organic Alcohol, alkali and inorganic salts.
The water is deionized water;The inorganic salts are silicate, phosphate, tungstates, molybdate or aluminate One or more of;The Organic Alcohol is one kind or two in methanol, ethyl alcohol, ethylene glycol, glycerine or isopropanol Kind or more;The alkali is one or more of potassium hydroxide, sodium hydroxide, lithium hydroxide or barium hydroxide.
The beneficial effects of the invention are as follows:
1, a kind of 6061 aluminum alloy surface Al based on sodium tetraborate prepared by the present invention2O3-AlB12Composite ceramics film layer, With sodium tetraborate and other boron-containing compounds are free of in working solution, and under other technological parameter the same terms, obtain identical film layer The common 6061 aluminum alloy differential arc oxidation film layer of thickness is compared, and bending strength improves 20%~34%, and fracture toughness improves 20%~33%.It is effectively improved the mechanical performance of 6061 micro-arc oxidation of aluminum alloy surface ceramic films.
2, the differential arc oxidation treatment method that the present invention uses, technical process is simple, only needs differential arc oxidation electric discharge, cleaning and does Dry 3 procedure.Micro-arc discharge processing time is generally in 30min~60min, more existing Al2O3-AlB12The processing of composite ceramics film layer Time greatly shortens, and processing efficiency significantly improves.React the Al generated2O3And AlB12It is sufficiently mixed in micro- molten bath, after cooling Directly Al is formed in workpiece surface2O3-AlB12The temperature of composite ceramics film layer, workpiece substrate changes before and after the processing in differential arc oxidation Less, discharge energy is mainly used for the generation of film layer, therefore the more existing Al of energy utilization rate of differential arc oxidation2O3-AlB12It is multiple It is high to close ceramic film manufacturing process.
Specific implementation mode
The present invention is described in detail below by specific embodiment, but is not limited the scope of the invention.Unless otherwise specified, originally Experimental method is conventional method used by invention, and experiment equipment used, material, reagent etc. commercially obtain.
Embodiment 1
A kind of 6061 aluminum alloy surface Al based on sodium tetraborate2O3-AlB12The preparation method of composite ceramics film layer be by It is carried out according to following steps:
Using 6061 Al alloy parts as anode, using the stainless steel plate of electrolytic cell as cathode, anode is immersed in working solution, Then apply Bipolar pulse power between a cathode and an anode, and be 50V, forward voltage end value in forward voltage initial value For 540V, backward voltage initial value is 20V, backward voltage end value is 80V, current density 10A/dm2, frequency is 2000Hz, under conditions of working solution temperature is 30 DEG C~65 DEG C, processing time 30min is to get to 6061 aluminum alloy surfaces Al2O3-AlB12Composite ceramics film layer.
The 6061 Al alloy parts sizes are 50mm × 100mm × 2mm.
The working solution is mixed by deionized water, sodium hydroxide, sodium metasilicate, sodium tetraborate;The working solution A concentration of 2.5g/L of middle sodium hydroxide;A concentration of 3.5g/L of sodium metasilicate in the working solution;Four in the working solution A concentration of 8g/L of Boratex.
The present embodiment working solution initial temperature is 30 DEG C, 65 DEG C of maximum temperature in the course of work.
6061 aluminum alloy surface Al manufactured in the present embodiment2O3-AlB12Composite ceramics thicknesses of layers is 35 μm~38 μm, Bending strength is 219.77MPa, fracture toughness 1.75MPam1/2;Sodium tetraborate and other boracic chemical combination are free of in working solution Object under other technological parameter the same terms, obtains the bending resistance of the common 6061 aluminum alloy differential arc oxidation film layer of identical thicknesses of layers Intensity is 183.14MPa, fracture toughness 1.46MPam1/2.As it can be seen that compared with common 6061 aluminum alloy differential arc oxidation film layer, 6061 aluminum alloy surface Al2O3-AlB12The bending strength of composite ceramics film layer improves 20%, and fracture toughness improves 20%.
Embodiment 2
A kind of 6061 aluminum alloy surface Al based on sodium tetraborate2O3-AlB12The preparation method of composite ceramics film layer be by It is carried out according to following steps:
Using 6061 Al alloy parts as anode, using the stainless steel plate of electrolytic cell as cathode, anode is immersed in working solution, Then apply Bipolar pulse power between a cathode and an anode, and be 50V, forward voltage end value in forward voltage initial value For 580V, backward voltage initial value is 20V, backward voltage end value is 85V, current density 15A/dm2, frequency is 1200Hz, under conditions of working solution temperature is 20 DEG C~65 DEG C, processing time 40min is to get to 6061 aluminum alloy surfaces Al2O3-AlB12Composite ceramics film layer.
The 6061 Al alloy parts sizes are 35mm × 70mm × 1mm.
The working solution is mixed by deionized water, sodium hydroxide, sodium metasilicate, glycerine and sodium tetraborate;It is described Working solution in sodium hydroxide a concentration of 1.5g/L;A concentration of 3.5g/L of sodium metasilicate in the working solution;The work Make a concentration of 32mL/L of glycerine in liquid;A concentration of 5g/L of sodium tetraborate in the working solution;
The present embodiment working solution initial temperature is 20 DEG C, 65 DEG C of maximum temperature in the course of work.
6061 aluminum alloy surface Al manufactured in the present embodiment2O3-AlB12Composite ceramics thicknesses of layers is 54 μm~56 μm, Bending strength is 305.34MPa, fracture toughness 2.52MPam1/2;Sodium tetraborate and other boracics are free of in working solution Object is closed, under other technological parameter the same terms, obtains the anti-of the common 6061 aluminum alloy differential arc oxidation film layer of identical thicknesses of layers Curved intensity is 244.27MPa, fracture toughness 2.03MPam1/2.As it can be seen that with common 6061 aluminum alloy differential arc oxidation film layer phase Than 6061 aluminum alloy surface Al2O3-AlB12The bending strength of composite ceramics film layer improves 25%, and fracture toughness improves 24%.
Embodiment 3
A kind of 6061 aluminum alloy surface Al based on sodium tetraborate2O3-AlB12The preparation method of composite ceramics film layer be by It is carried out according to following steps:
Using 6061 Al alloy parts as anode, using the stainless steel plate of electrolytic cell as cathode, anode is immersed in working solution, Then apply Bipolar pulse power between a cathode and an anode, and be 50V, forward voltage end value in forward voltage initial value For 600V, backward voltage initial value is 20V, backward voltage end value is 86V, current density 16A/dm2, frequency 800Hz, Under conditions of working solution temperature is 35 DEG C~80 DEG C, processing time 50min is to get to 6061 aluminum alloy surface Al2O3-AlB12 Composite ceramics film layer.
The 6061 Al alloy parts sizes are 40mm × 60mm × 1mm.
The working solution is mixed by deionized water, potassium hydroxide, sodium metasilicate, sodium tetraborate;The working solution A concentration of 1.5g/L of middle potassium hydroxide;A concentration of 5.5g/L of sodium metasilicate in the working solution;Four in the working solution A concentration of 12.5g/L of Boratex.
The present embodiment working solution initial temperature is 35 DEG C, 80 DEG C of maximum temperature in the course of work.
6061 aluminum alloy surface Al manufactured in the present embodiment2O3-AlB12Composite ceramics thicknesses of layers is 67 μm~69 μm, Bending strength is 393.59MPa, fracture toughness 3.09MPam1/2;Sodium tetraborate and other boracic chemical combination are free of in working solution Object under other technological parameter the same terms, obtains the bending resistance of the common 6061 aluminum alloy differential arc oxidation film layer of identical thicknesses of layers Intensity is 305.11MPa, fracture toughness 2.38MPam1/2.As it can be seen that compared with common 6061 aluminum alloy differential arc oxidation film layer, 6061 aluminum alloy surface Al2O3-AlB12The bending strength of composite ceramics film layer improves 29%, and fracture toughness improves 30%.
Embodiment 4
A kind of 6061 aluminum alloy surface Al based on sodium tetraborate2O3-AlB12The preparation method of composite ceramics film layer be by It is carried out according to following steps:
Using 6061 Al alloy parts as anode, using the stainless steel plate of electrolytic cell as cathode, anode is immersed in working solution, Then apply Bipolar pulse power between a cathode and an anode, and be 50V, forward voltage end value in forward voltage initial value For 620V, backward voltage initial value is 20V, backward voltage end value is 95V, current density 20A/dm2, frequency 500Hz, Under conditions of working solution temperature is 20 DEG C~80 DEG C, processing time 60min is to get to 6061 aluminum alloy surface Al2O3-AlB12 Composite ceramics film layer.
The 6061 Al alloy parts sizes are 50mm × 100mm × 2mm.
The working solution is mixed by deionized water, potassium hydroxide, sodium metasilicate, sodium tetraborate, sodium metaaluminate;It is described Working solution in potassium hydroxide a concentration of 3.5g/L;A concentration of 7g/L of sodium metasilicate in the working solution;The work A concentration of 20g/L of sodium tetraborate in liquid;A concentration of 4.5g/L of sodium metaaluminate.
The present embodiment working solution initial temperature is 20 DEG C, 80 DEG C of maximum temperature in the course of work.
6061 aluminum alloy surface Al manufactured in the present embodiment2O3-AlB12Composite ceramics thicknesses of layers is 77 μm~80 μm, Bending strength is 402.87MPa, fracture toughness 3.74MPam1/2;Working solution is free of sodium tetraborate and other boracic chemical combination Object under other technological parameter the same terms, obtains the bending resistance of the common 6061 aluminum alloy differential arc oxidation film layer of identical thicknesses of layers Intensity is 302.91MPa, fracture toughness 2.79MPam1/2.As it can be seen that compared with common 6061 aluminum alloy differential arc oxidation film layer 6061 aluminum alloy surface Al2O3-AlB12The bending strength of composite ceramics film layer improves 33%, and fracture toughness improves 34%.

Claims (3)

1. a kind of 6061 aluminum alloy surface Al based on sodium tetraborate2O3-AlB12The preparation method of composite ceramics film layer, feature It is, follows the steps below:
Using 6061 Al alloy parts as anode, using the stainless steel plate of electrolytic cell as cathode, equipped with prepared in advance in electrolytic cell Anode is immersed in working solution by working solution, then applies bipolar pulse electricity between a cathode and an anode, and in forward voltage It is 20V~95V, current density 10A/dm for 50V~620V, backward voltage2~20A/dm2, frequency is 500Hz~2000Hz, Under conditions of working solution temperature is 20 DEG C~80 DEG C, processing 30min~60min is to get to 6061 aluminum alloy surface Al2O3- AlB12Composite ceramics film layer;The wherein described working solution includes the inorganic salts of sodium tetraborate, water and at least one or two or more, alkali Or Organic Alcohol, keep a concentration of 5-20g/L of the sodium tetraborate in working solution.
2. according to the method described in claim 1, it is characterized in that, the working solution is by sodium tetraborate, water and inorganic salts group At;Or the working solution is made of sodium tetraborate, water and alkali;Or the working solution is by sodium tetraborate, water and Organic Alcohol group At;Or the working solution is made of sodium tetraborate, water, Organic Alcohol and inorganic salts;Or the working solution by sodium tetraborate, Water, Organic Alcohol and alkali composition;Or the working solution is made of sodium tetraborate, water, alkali and inorganic salts;Or the working solution by Sodium tetraborate, water, Organic Alcohol, alkali and inorganic salts composition.
3. according to the method described in claim 1, it is characterized in that, the water is deionized water;The inorganic salts are silicon One or more of hydrochlorate, phosphate, tungstates, molybdate or aluminate;The Organic Alcohol be methanol, ethyl alcohol, One or more of ethylene glycol, glycerine or isopropanol;The alkali is potassium hydroxide, sodium hydroxide, lithium hydroxide Or one or more of barium hydroxide.
CN201810615062.1A 2018-06-14 2018-06-14 A kind of aluminum alloy surface Al based on sodium tetraborate2O3-AlB12The preparation method of composite ceramics film layer Pending CN108505089A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109023470A (en) * 2018-09-25 2018-12-18 巩义市宏盛稀有金属有限公司 The modified aluminium alloy extrusions of a kind of aluminium alloy section surface differential arc oxidation method of modifying and surface
WO2021031548A1 (en) * 2019-08-21 2021-02-25 大连理工大学 Electrolyte for preparing hierarchical structure porous coating on titanium alloy surface by micro-arc oxidation
CN113899071A (en) * 2021-10-25 2022-01-07 西安建筑科技大学 Electric heating water boiler and water treatment and purification method

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104087996A (en) * 2014-07-28 2014-10-08 吕鹏翔 Aluminum alloy surface easy-cleaning micro-arc oxidation ceramic membrane layer and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104087996A (en) * 2014-07-28 2014-10-08 吕鹏翔 Aluminum alloy surface easy-cleaning micro-arc oxidation ceramic membrane layer and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109023470A (en) * 2018-09-25 2018-12-18 巩义市宏盛稀有金属有限公司 The modified aluminium alloy extrusions of a kind of aluminium alloy section surface differential arc oxidation method of modifying and surface
WO2021031548A1 (en) * 2019-08-21 2021-02-25 大连理工大学 Electrolyte for preparing hierarchical structure porous coating on titanium alloy surface by micro-arc oxidation
CN113899071A (en) * 2021-10-25 2022-01-07 西安建筑科技大学 Electric heating water boiler and water treatment and purification method

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