CN104805345A - Magnesium alloy surface treatment method - Google Patents

Magnesium alloy surface treatment method Download PDF

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Publication number
CN104805345A
CN104805345A CN201510213136.5A CN201510213136A CN104805345A CN 104805345 A CN104805345 A CN 104805345A CN 201510213136 A CN201510213136 A CN 201510213136A CN 104805345 A CN104805345 A CN 104805345A
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magnesium alloy
alloy plate
spraying
coating
spray
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吴明
黄世宇
刘芳
黄莉
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Suzhou Tong Ming Machinery Co Ltd
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Suzhou Tong Ming Machinery Co Ltd
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Priority to CN201510213136.5A priority Critical patent/CN104805345A/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C23/00Alloys based on magnesium
    • C22C23/02Alloys based on magnesium with aluminium as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18After-treatment

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coating By Spraying Or Casting (AREA)

Abstract

The invention discloses a magnesium alloy surface treatment method which comprises three stages including a pretreatment stage, a spraying stage and an after-spraying treatment stage. By adoption of a compound spraying method, an anti-corrosion and anti-abrasion coating layer which is high in bonding strength, high in compactness and small in environment pollution is formed on the magnesium alloy surface; the surface treatment method is simple and feasible and is low in cost.

Description

A kind of surface treatment method of Mg alloy
Technical field
The invention belongs to the field of thermal spray of Materials Processing Engineering, relate to a kind of hot spray process that utilizes and form the surface treatment method of Mg alloy of corrosion resistant anti-corrosion coating at Mg alloy surface.
Background technology
China is the country that magnesium resource is the abundantest in the world, and magnesite proven reserve account for 1/4 of the world, has the congenital basic condition of development magnesium industry; In addition, China not still motorcycle produce, consumption and big export country, be also an automobile production and consumption big country, the market application foreground of Mg-based hydrogen storage product is wide; Ordinary magnesium alloy disadvantage is oxidizable burning in fusing and moulding process, this makes the melting of magnesium alloy always very thorny, there iing melting under flux or gas shield, although the burning of magnesium alloy can be stoped, but still there is a lot of problem, inherently do not solve the problem of its oxidizable burning, to such an extent as to cause the environmental pollution in production, equipment complexity and alloy property to reduce; So people reach fire-retardant object by the method for alloying, to eliminate the disadvantageous effect that first two method is brought, and be referred to as alloying ignition-proof method, its mechanism in magnesium alloy smelting process, adds specific alloying element to affect thermodynamical reaction and the dynamic process of alloy oxidation, form the dense oxidation film with provide protection, reach the object stoping alloy vigorous oxidation, and the tendency of the oxidizing fire of magnesium alloy in following process process is reduced greatly, thus improves the processing safety of magnesium alloy; Normally in magnesium alloy, add the alloy such as basic metal, rare earth ignition-proof element, thus improve the burning-point of magnesium alloy, make not produce burning when melting and casting, improve the processing safety of magnesium alloy; Perishable for magnesium alloy, not wear-resisting shortcoming, except exploitation high purity magnesium and novel magnesium alloy, carrying out suitable surface treatment is also a kind of effective way.
At present, although the surface treatment method such as application, anodic oxidation treatment, differential arc oxidation process, the chemical transformation process etc. that adopt can improve its anti-oxidant and corrosion resistance nature, but also there is very important limitation, although differential arc oxidation process, chemical transformation process etc. can improve its anti-oxidant and corrosion resistance nature, also there is very important limitation; Show that chemical conversion film slowing down corrosion speed can only effectively can not prevent corrosion to the solidity to corrosion research of chemical conversion film, and anode oxide film has the feature of porous, therefore coating must carry out sealing treatment, complex process; Differential arc oxidation also exists again the major defect producing harmful ion, does not meet the requirement of present environmental protection development; And be very difficult in Mg alloy surface plating or chemical plating metal usually, reason is that magnesium alloy is very active, and surface forms rapidly oxide film and stops between coated metal and matrix and form Metal-Metal bond; Magnesium is alkaline-earth metal, very violent with the replacement(metathesis)reaction of other metal ion in the solution.Again due to the low easy burning of magnesium alloy burning-point, so generally do not adopt thermospraying and hot dip process to sum up, the surface treatment method of Mg alloy adopted now all also exists some shortcomings such as such as complex process, cost are higher, contaminate environment, thus considerably increases the use cost of magnesium alloy; Therefore, research and develop a kind of can overcome above defect surface treatment method of Mg alloy become those skilled in the art's technical problem urgently to be resolved hurrily.
Summary of the invention
Technical problem to be solved by this invention is, for the shortcoming that above prior art exists, a kind of surface treatment method of Mg alloy is proposed, this surface treatment method adopts the method for compound composite spraying to form high and anti-corrosion, the wear-resisting coating that compactness good, environmental pollution is little of bonding strength at Mg alloy surface, this surface treatment method is simple, with low cost.
The technical scheme that the present invention solves above technical problem is:
A kind of surface treatment method of Mg alloy, this surface treatment method comprises three phases, i.e. pretreatment stage, spraying stage and spray post-processing stages, wherein:
(1) pretreatment stage:
The magnesium alloy plate sand paper selected is polished, then with acetone, the surface after polishing is cleaned, then naturally dry, dry the rear surface to magnesium alloy plate and carry out sandblasting roughening treatment, with pressurized air, winding-up process is carried out to magnesium alloy plate after sandblasting, and then with the surface of acetone cleaning magnesium alloy plate, naturally dry and rear 80-95 DEG C is heated to magnesium alloy plate, be incubated 5-10min stand-by;
Magnesium alloy plate block of material is made up of Mg, Al, Mn, Zn, Cu, Ni, Sc, P, Zr, Y, Ca, Sr, B, Co, rare earth element, and the percentage composition of its each component is:
Al:18-20%, Mn:3-6%, Zn:10-13%, Ni:1-3%, Cu:1-3%, Sc:2-3%, P:0.5-0.8%, Zr:3-6%, Ca:10-13%, B:2-4%, Sr:2-5%, Co:2-4%, rare earth element 0.5-0.8%, all the other are Mg;
Rare earth element comprises following component by weight percentage: Ce:8-10%, Nd:15-18%, Gd:10-15%, Pr:11-13%, Yb:3-5%, La:12-15%, Sm:10-15%, and all the other are lanthanon;
(2) spraying stage:
A. first on magnesium alloy plate on the surface flame plating, spray the bottoming of NiCrAlY bond coating, the distance controlling spraying is 90-100mm, and the angle of spraying is 60-85 °, and powder feeding gas flow is 0.5-0.7m 3/ h, after spraying, the thickness of bond coating is 85-95 μm;
B. on bond coating with plasma flame flow preheating 5-8min, plasma flame flow axis be 45-60 ° by the angle spraying magnesium alloy panel surface, then plasma spraying working lining ZrO 2/ TiO 2/ Y 2o 3coating, spray distance is 100-120mm, and spray angle is 50-60 °, and powder feeding gas flow is 0.6-0.8 m 3/ h, the coat-thickness of spraying is 200-300 μm;
C. at working lining ZrO 2/ TiO 2/ Y 2o 3ceramic coating adopt electric arc spraying process obtain NiCrAl metal corrosion resistant anti-corrosion coating, use the fine aluminium silk material that diameter is 3-5mm, the coating of spraying is 250-320 μm, the processing parameter of electric arc spraying is: voltage 28-30V, air pressure 0.5-0.6MPa, spray distance is 110-150mm, and spray angle is 80-90 °;
(3) post-processing stages is sprayed:
Carry out sealing pores to magnesium alloy plate, sealing pores is specially:
A. the preparation of colloidal sol:
In reaction flask pipe add dehydrated alcohol and too acid butyl ester mix, then under the effect at catalyzer TiO2, stir 15-20min, obtain flaxen TiO2 colloidal sol;
By tetraethoxy and dehydrated alcohol mix and blend 5-10min, then add SiO2, at room temperature stir 5-8min sealing and standing, after ageing 1-3h, obtain SiO2 colloidal sol;
By the TiO2 colloidal sol for preparing and SiO2 colloidal sol by the volume ratio mix and blend 20-25min of 1:2, by the mixed sols of gained at room temperature sealing and standing, after natural ageing 2-3h, sealing of hole is carried out to the coating on magnesium alloy plate;
B. the magnesium alloy plate after step (2) being sprayed at room temperature is put into mixed sols and is flooded 5-8min, then the magnesium alloy plate after dipping is lifted out the liquid level of mixed sols, vertically places 5-6min aloft;
C. 30-50min is at room temperature placed to after becoming stable gel film by being impregnated with the magnesium alloy plate after mixed sols, put into resistance furnace to heat, heat-up rate is 1-3 DEG C/min, 1-3h is incubated when being warming up to 420-430 DEG C, last air cooling is to room temperature, and the surface of magnesium alloy plate obtains fine and close smooth corrosion resistant anti-corrosion coating.
The technical scheme that the present invention limits further is:
In aforementioned surface treatment method of Mg alloy, in step (1), sandblasting roughening treatment is specially: with sandblast machine by the surface of corundum sand even application at magnesium alloy plate, wherein:
The pressure of sandblast machine is 1.2-1.6MPa, compressed air drying, nothing oil; Corundum sand granularity is No. 10, and corundum sand cleans dry oil free dirt.
In aforementioned surface treatment method of Mg alloy, in step (2), carrying out plasma spraying working lining ZrO 2/ TiO 2/ Y 2o 3during coating, in working lining, the percentage composition of each component is, ZrO 2: 80-85%, TiO 2: 10-15%, Y 2o 3: 6-8%, above each component sum is 100%.
The invention has the beneficial effects as follows:
Containing a small amount of Ni, Sc in the raw material of the magnesium alloy plate in the present invention, Cu cost is low, can reduce the heat sensitivity of magnesium alloy, puies forward heavy alloyed weldability, extends work-ing life, rare earth element is with the addition of in raw material magnesium alloy, rare earth element is because having unique configuration of extra-nuclear electron, in metallurgical process, it can improve tissue, put forward heavy alloyed room temperature and high-temperature behavior, strengthen the resistance to candle of alloy, add rare earth element ce in magnesium alloy and can improve alloy initial stage melting temperature, Nd realizes Dynamic Precipitation and stops grain growth, thus the mechanical property improved after extruding, Gd, Ce improves alloy incipient melting temperature, improve unit elongation and the extrusion speed of magnesium alloy, the high quality of magnesium alloy ensure that the stability in surface treatment process, and the erosion resistance of the coating obtained after process, ensure that the coating high quality of final preparation.
The present invention uses acetone to clean the surface of magnesium alloy plate at the beginning, because magnesium alloy is very easily oxidized, surface easily forms magnesium oxide, this layer of magnesium oxide loosens, as the surface treatment do not carried out, the bonding force of middle layer and matrix can be caused poor, do not have etch-proof effect, so the present invention first uses acetone clean surface, object is all dirts of removing specimen surface, as oxide skin, oil stain, paint and other dirt, key is the specimen surface that removing can have a strong impact on bonding strength between coating and matrix and the grease infiltrated wherein; Secondly coating is relevant with the degree of cleaning of matrix surface with the bonding strength of matrix, therefore before spraying, workpiece surface should be dry, free from dust.
Adopt sandblasting roughening treatment, increase the contact surface between coating and matrix, increase the mechanical snap power of coating and matrix, the surface that purifying treatment is crossed activates more, to improve the bonding strength of coating and matrix, simultaneously, the alligatoring of substrate surface also changes the residual stress distribution in coating, also be favourable to improving the bonding strength of coating, because magnesium alloy plate is soft matrix, shot blasting particles may be embedded in matrix surface, also need after sandblasting to adopt pressurized air to carry out winding-up process, with remove any may by the particle inlayed, then by acetone clean surface again, guarantee the absolute cleaning of spray-coating surface.
Finally magnesium alloy plate is heated at pretreatment stage, moisture and the moisture of specimen surface can be eliminated, improve interface temperature when spraying particle and magnesium alloy plate surface contact, reduce the coating cracking that stress that the thermal dilation difference because of magnesium alloy plate and coated material causes causes, thus the bonding strength of raising coating and magnesium alloy plate matrix.
ZrO2 has excellent heat insulation and resistance toheat, and ZrO2 to have fusing point high, the feature that thermal conductivity is low, it is a kind of desirable thermal insulation material, but pure ZrO2 has different phase structures, phase structure will be there is at different temperatures change, in the process that phase structure changes, the volume being attended by 4-6% increases, this volume increase causes high pressure stress, easily cause the formation of crackle and the damage of material, therefore, use hot spray coating poor-performing prepared by pure zirconium white, add the ionic radius cerium oxide close with zirconium white as stablizer, the constancy of volume and enhance thermal fatigue resistance at temperature of controlled oxidization zirconium, the TiO2 added has lower Young's modulus and shearing resistance, join in ZrO2 coating and can improve its wear resisting property.
The present invention prepares NiCrAlY bond coating and carries out bottoming, due to all larger thermal stresses can be produced in preparation coating and coating use procedure, thus cause coating performance to reduce, affect work-ing life, between the coating and magnesium alloy panel surface of preparation, increase one deck bond coating carry out bottoming, alleviate the difference of thermal expansivity between preparation coating and magnesium alloy panel surface, improve resistance to high temperature corrosion and the oxidation susceptibility of magnesium alloy plate, Al in alloy is that generation oxide film protection layer is necessary, Cr can facilitate generation Al2O3 and improve resistance to corrosion, and Y can improve the bonding strength between Al2O3 and NiCrAlY.
Adopt electric-arc thermal spray coating; the aluminium lamination of one deck densification is formed on the surface of magnesium alloy; again at isothermal holding 1-3h; obtain the diffusion layer that the magnesium in magnesium alloy plate matrix spreads to coating; complete protective layer can be obtained after carrying out sealing pores; the combination of coating and magnesium alloy plate matrix is firm, and substantially increases the corrosion resistance nature of alloy.
Embodiment
embodiment 1
The present embodiment provides a kind of surface treatment method of Mg alloy, and this surface treatment method comprises three phases, i.e. pretreatment stage, spraying stage and spray post-processing stages, wherein:
(1) pretreatment stage:
The magnesium alloy plate sand paper selected is polished, then with acetone, the surface after polishing is cleaned, then naturally dry, dry the rear surface to magnesium alloy plate and carry out sandblasting roughening treatment, sandblasting roughening treatment is specially: with sandblast machine by the surface of corundum sand even application at magnesium alloy plate, wherein: the pressure of sandblast machine is 1.4MPa, compressed air drying, nothing oil; Corundum sand granularity is No. 10, and corundum sand cleans dry oil free dirt, with pressurized air, winding-up process is carried out to magnesium alloy plate after sandblasting, and then clean the surface of magnesium alloy plate with acetone, naturally dry and be heated to 80 DEG C to magnesium alloy plate afterwards, 8min is stand-by in insulation;
Magnesium alloy plate block of material is made up of Mg, Al, Mn, Zn, Cu, Ni, Sc, P, Zr, Y, Ca, Sr, B, Co, rare earth element, and the percentage composition of its each component is:
Al:18%, Mn:5%, Zn:13%, Ni:2%, Cu:1%, Sc:2%, P:0.6%, Zr:3%, Ca:10%, B:4%, Sr:2%, Co:2%, rare earth element 0.5%, all the other are Mg;
Rare earth element comprises following component by weight percentage: Ce:8%, Nd:18%, Gd:10%, Pr:12%, Yb:5%, La:12%, Sm:13%, and all the other are lanthanon;
(2) spraying stage:
A. first on magnesium alloy plate on the surface flame plating, spray the bottoming of NiCrAlY bond coating, the distance controlling spraying is 100mm, and the angle of spraying is 60 °, and powder feeding gas flow is 0.7m 3/ h, after spraying, the thickness of bond coating is 85 μm;
B. on bond coating with plasma flame flow preheating 8min, plasma flame flow axis be 50 ° by the angle spraying magnesium alloy panel surface, then plasma spraying working lining ZrO 2/ TiO 2/ Y 2o 3coating, spray distance is 110mm, and spray angle is 60 °, and powder feeding gas flow is 0.6m 3/ h, the coat-thickness of spraying is 200 μm;
Working lining ZrO 2/ TiO 2/ Y 2o 3in coating, the percentage composition of each component is, ZrO 2: 80%, TiO 2: 12%, Y 2o 3: 8%;
C. at working lining ZrO 2/ TiO 2/ Y 2o 3ceramic coating adopts electric arc spraying process obtain NiCrAl metal corrosion resistant anti-corrosion coating, use the fine aluminium silk material that diameter is 3mm, the coating of spraying is 320 μm, the processing parameter of electric arc spraying is: voltage 29V, air pressure 0.6MPa, spray distance is 130mm, and spray angle is 85 °;
(3) post-processing stages is sprayed:
Carry out sealing pores to magnesium alloy plate, sealing pores is specially:
A. the preparation of colloidal sol:
In reaction flask pipe add dehydrated alcohol and too acid butyl ester mix, then under the effect at catalyzer TiO2, stir 18min, obtain flaxen TiO2 colloidal sol;
By tetraethoxy and dehydrated alcohol mix and blend 5min, then add SiO2, at room temperature stir 8min sealing and standing, after ageing 2h, obtain SiO2 colloidal sol;
By the TiO2 colloidal sol for preparing and SiO2 colloidal sol by the volume ratio mix and blend 20min of 1:2, by the mixed sols of gained at room temperature sealing and standing, after natural ageing 3h, sealing of hole is carried out to the coating on magnesium alloy plate;
B. the magnesium alloy plate after step (2) being sprayed at room temperature is put into mixed sols and is flooded 5min, then the magnesium alloy plate after dipping is lifted out the liquid level of mixed sols, vertically places 6min aloft;
C. 40min is at room temperature placed to after becoming stable gel film by being impregnated with the magnesium alloy plate after mixed sols, put into resistance furnace to heat, heat-up rate is 2 DEG C/min, 2h is incubated when being warming up to 425 DEG C, last air cooling is to room temperature, and the surface of magnesium alloy plate obtains fine and close smooth corrosion resistant anti-corrosion coating.
embodiment 2
The present embodiment provides a kind of surface treatment method of Mg alloy, and this surface treatment method comprises three phases, i.e. pretreatment stage, spraying stage and spray post-processing stages, wherein:
(1) pretreatment stage:
The magnesium alloy plate sand paper selected is polished, then with acetone, the surface after polishing is cleaned, then naturally dry, dry the rear surface to magnesium alloy plate and carry out sandblasting roughening treatment, sandblasting roughening treatment is specially: with sandblast machine by the surface of corundum sand even application at magnesium alloy plate, wherein: the pressure of sandblast machine is 1.2MPa, compressed air drying, nothing oil; Corundum sand granularity is No. 10, and corundum sand cleans dry oil free dirt, with pressurized air, winding-up process is carried out to magnesium alloy plate after sandblasting, and then clean the surface of magnesium alloy plate with acetone, naturally dry and be heated to 95 DEG C to magnesium alloy plate afterwards, 5min is stand-by in insulation;
Magnesium alloy plate block of material is made up of Mg, Al, Mn, Zn, Cu, Ni, Sc, P, Zr, Y, Ca, Sr, B, Co, rare earth element, and the percentage composition of its each component is:
Al:20%, Mn:3%, Zn:10%, Ni:1%, Cu:2%, Sc:3%, P:0.5%, Zr:5%, Ca:12%, B:2%, Sr:5%, Co:3%, rare earth element 0.8%, all the other are Mg;
Rare earth element comprises following component by weight percentage: Ce:10%, Nd:17%, Gd:15%, Pr:11%, Yb:4%, La:15%, Sm:10%, and all the other are lanthanon;
(2) spraying stage:
A. first on magnesium alloy plate on the surface flame plating, spray the bottoming of NiCrAlY bond coating, the distance controlling spraying is 90mm, and the angle of spraying is 70 °, and powder feeding gas flow is 0.5m 3/ h, after spraying, the thickness of bond coating is 95 μm;
B. on bond coating with plasma flame flow preheating 5min, plasma flame flow axis be 45 ° by the angle spraying magnesium alloy panel surface, then plasma spraying working lining ZrO 2/ TiO 2/ Y 2o 3coating, spray distance is 100mm, and spray angle is 55 °, and powder feeding gas flow is 0.7 m 3/ h, the coat-thickness of spraying is 300 μm;
Working lining ZrO 2/ TiO 2/ Y 2o 3in coating, the percentage composition of each component is, ZrO 2: 80%, TiO 2: 13%, Y 2o 3: 7%;
C. at working lining ZrO 2/ TiO 2/ Y 2o 3ceramic coating adopts electric arc spraying process obtain NiCrAl metal corrosion resistant anti-corrosion coating, use the fine aluminium silk material that diameter is 4mm, the coating of spraying is 250 μm, the processing parameter of electric arc spraying is: voltage 28V, air pressure 0.5MPa, spray distance is 110mm, and spray angle is 80 °;
(3) post-processing stages is sprayed:
Carry out sealing pores to magnesium alloy plate, sealing pores is specially:
A. the preparation of colloidal sol:
In reaction flask pipe add dehydrated alcohol and too acid butyl ester mix, then under the effect at catalyzer TiO2, stir 15min, obtain flaxen TiO2 colloidal sol;
By tetraethoxy and dehydrated alcohol mix and blend 10min, then add SiO2, at room temperature stir 6min sealing and standing, after ageing 1h, obtain SiO2 colloidal sol;
By the TiO2 colloidal sol for preparing and SiO2 colloidal sol by the volume ratio mix and blend 22min of 1:2, by the mixed sols of gained at room temperature sealing and standing, after natural ageing 2h, sealing of hole is carried out to the coating on magnesium alloy plate;
B. the magnesium alloy plate after step (2) being sprayed at room temperature is put into mixed sols and is flooded 8min, then the magnesium alloy plate after dipping is lifted out the liquid level of mixed sols, vertically places 5min aloft;
C. 30min is at room temperature placed to after becoming stable gel film by being impregnated with the magnesium alloy plate after mixed sols, put into resistance furnace to heat, heat-up rate is 1 DEG C/min, 1h is incubated when being warming up to 420 DEG C, last air cooling is to room temperature, and the surface of magnesium alloy plate obtains fine and close smooth corrosion resistant anti-corrosion coating.
embodiment 3
The present embodiment provides a kind of surface treatment method of Mg alloy, and this surface treatment method comprises three phases, i.e. pretreatment stage, spraying stage and spray post-processing stages, wherein:
(1) pretreatment stage:
The magnesium alloy plate sand paper selected is polished, then with acetone, the surface after polishing is cleaned, then naturally dry, dry the rear surface to magnesium alloy plate and carry out sandblasting roughening treatment, sandblasting roughening treatment is specially: with sandblast machine by the surface of corundum sand even application at magnesium alloy plate, wherein: the pressure of sandblast machine is 1.6MPa, compressed air drying, nothing oil; Corundum sand granularity is No. 10, and corundum sand cleans dry oil free dirt, with pressurized air, winding-up process is carried out to magnesium alloy plate after sandblasting, and then clean the surface of magnesium alloy plate with acetone, naturally dry and be heated to 90 DEG C to magnesium alloy plate afterwards, 10min is stand-by in insulation;
Magnesium alloy plate block of material is made up of Mg, Al, Mn, Zn, Cu, Ni, Sc, P, Zr, Y, Ca, Sr, B, Co, rare earth element, and the percentage composition of its each component is:
Al:19%, Mn:6%, Zn:11%, Ni:3%, Cu:3%, Sc:2%, P:0.8%, Zr:6%, Ca:13%, B:3%, Sr:4%, Co:4%, rare earth element 0.6%, all the other are Mg;
Rare earth element comprises following component by weight percentage: Ce:9%, Nd:15%, Gd:12%, Pr:13%, Yb:3%, La:13%, Sm:15%, and all the other are lanthanon;
(2) spraying stage:
A. first on magnesium alloy plate on the surface flame plating, spray the bottoming of NiCrAlY bond coating, the distance controlling spraying is 95mm, and the angle of spraying is 85 °, and powder feeding gas flow is 0.6m 3/ h, after spraying, the thickness of bond coating is 90 μm;
B. on bond coating with plasma flame flow preheating 7min, plasma flame flow axis be 60 ° by the angle spraying magnesium alloy panel surface, then plasma spraying working lining ZrO 2/ TiO 2/ Y 2o 3coating, spray distance is 120mm, and spray angle is 50 °, and powder feeding gas flow is 0.8 m 3/ h, the coat-thickness of spraying is 250 μm;
Working lining ZrO 2/ TiO 2/ Y 2o 3in coating, the percentage composition of each component is, ZrO 2: 84%, TiO 2: 10%, Y 2o 3: 6%;
C. at working lining ZrO 2/ TiO 2/ Y 2o 3ceramic coating adopts electric arc spraying process obtain NiCrAl metal corrosion resistant anti-corrosion coating, use the fine aluminium silk material that diameter is 5mm, the coating of spraying is 300 μm, the processing parameter of electric arc spraying is: voltage 30V, air pressure 0.5MPa, spray distance is 150mm, and spray angle is 90 °;
(3) post-processing stages is sprayed:
Carry out sealing pores to magnesium alloy plate, sealing pores is specially:
A. the preparation of colloidal sol:
In reaction flask pipe add dehydrated alcohol and too acid butyl ester mix, then under the effect at catalyzer TiO2, stir 20min, obtain flaxen TiO2 colloidal sol;
By tetraethoxy and dehydrated alcohol mix and blend 8min, then add SiO2, at room temperature stir 5min sealing and standing, after ageing 3h, obtain SiO2 colloidal sol;
By the TiO2 colloidal sol for preparing and SiO2 colloidal sol by the volume ratio mix and blend 25min of 1:2, by the mixed sols of gained at room temperature sealing and standing, after natural ageing 2h, sealing of hole is carried out to the coating on magnesium alloy plate;
B. the magnesium alloy plate after step (2) being sprayed at room temperature is put into mixed sols and is flooded 7min, then the magnesium alloy plate after dipping is lifted out the liquid level of mixed sols, vertically places 5min aloft;
C. 50min is at room temperature placed to after becoming stable gel film by being impregnated with the magnesium alloy plate after mixed sols, put into resistance furnace to heat, heat-up rate is 3 DEG C/min, 3h is incubated when being warming up to 430 DEG C, last air cooling is to room temperature, and the surface of magnesium alloy plate obtains fine and close smooth corrosion resistant anti-corrosion coating.
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of application claims.

Claims (3)

1. a surface treatment method of Mg alloy, is characterized in that, this surface treatment method comprises three phases, i.e. pretreatment stage, spraying stage and spray post-processing stages, wherein:
(1) pretreatment stage:
The magnesium alloy plate sand paper selected is polished, then with acetone, the surface after polishing is cleaned, then naturally dry, dry the rear surface to magnesium alloy plate and carry out sandblasting roughening treatment, with pressurized air, winding-up process is carried out to magnesium alloy plate after sandblasting, and then with the surface of acetone cleaning magnesium alloy plate, naturally dry and rear 80-95 DEG C is heated to magnesium alloy plate, be incubated 5-10min stand-by;
Described magnesium alloy plate block of material is made up of Mg, Al, Mn, Zn, Cu, Ni, Sc, P, Zr, Y, Ca, Sr, B, Co, rare earth element, and the percentage composition of its each component is:
Al:18-20%, Mn:3-6%, Zn:10-13%, Ni:1-3%, Cu:1-3%, Sc:2-3%, P:0.5-0.8%, Zr:3-6%, Ca:10-13%, B:2-4%, Sr:2-5%, Co:2-4%, rare earth element 0.5-0.8%, all the other are Mg;
Described rare earth element comprises following component by weight percentage: Ce:8-10%, Nd:15-18%, Gd:10-15%, Pr:11-13%, Yb:3-5%, La:12-15%, Sm:10-15%, and all the other are lanthanon;
(2) spraying stage:
A. first on magnesium alloy plate on the surface flame plating, spray the bottoming of NiCrAlY bond coating, the distance controlling spraying is 90-100mm, and the angle of spraying is 60-85 °, and powder feeding gas flow is 0.5-0.7m 3/ h, after spraying, the thickness of bond coating is 85-95 μm;
B. on bond coating with plasma flame flow preheating 5-8min, plasma flame flow axis be 45-60 ° by the angle spraying magnesium alloy panel surface, then plasma spraying working lining ZrO 2/ TiO 2/ Y 2o 3coating, spray distance is 100-120mm, and spray angle is 50-60 °, and powder feeding gas flow is 0.6-0.8 m 3/ h, the coat-thickness of spraying is 200-300 μm;
C. at working lining ZrO 2/ TiO 2/ Y 2o 3ceramic coating adopt electric arc spraying process obtain NiCrAl metal corrosion resistant anti-corrosion coating, use the fine aluminium silk material that diameter is 3-5mm, the coating of spraying is 250-320 μm, the processing parameter of electric arc spraying is: voltage 28-30V, air pressure 0.5-0.6MPa, spray distance is 110-150mm, and spray angle is 80-90 °;
(3) post-processing stages is sprayed:
Carry out sealing pores to magnesium alloy plate, described sealing pores is specially:
A. the preparation of colloidal sol:
In reaction flask pipe add dehydrated alcohol and too acid butyl ester mix, then under the effect at catalyzer TiO2, stir 15-20min, obtain flaxen TiO2 colloidal sol;
By tetraethoxy and dehydrated alcohol mix and blend 5-10min, then add SiO2, at room temperature stir 5-8min sealing and standing, after ageing 1-3h, obtain SiO2 colloidal sol;
By the TiO2 colloidal sol for preparing and SiO2 colloidal sol by the volume ratio mix and blend 20-25min of 1:2, by the mixed sols of gained at room temperature sealing and standing, after natural ageing 2-3h, sealing of hole is carried out to the coating on magnesium alloy plate;
B. the magnesium alloy plate after step (2) being sprayed at room temperature is put into mixed sols and is flooded 5-8min, then the magnesium alloy plate after dipping is lifted out the liquid level of mixed sols, vertically places 5-6min aloft;
C. 30-50min is at room temperature placed to after becoming stable gel film by being impregnated with the magnesium alloy plate after mixed sols, put into resistance furnace to heat, heat-up rate is 1-3 DEG C/min, 1-3h is incubated when being warming up to 420-430 DEG C, last air cooling is to room temperature, and the surface of magnesium alloy plate obtains fine and close smooth corrosion resistant anti-corrosion coating.
2. surface treatment method of Mg alloy according to claim 1, is characterized in that: the sandblasting roughening treatment described in step (1) is specially: with sandblast machine by the surface of corundum sand even application at magnesium alloy plate, wherein:
The pressure of described sandblast machine is 1.2-1.6MPa, described compressed air drying, nothing oil; Described corundum sand granularity is No. 10, and corundum sand cleans dry oil free dirt.
3. surface treatment method of Mg alloy according to claim 1, is characterized in that: carrying out plasma spraying working lining ZrO in step (2) 2/ TiO 2/ Y 2o 3during coating, in working lining, the percentage composition of each component is, ZrO 2: 80-85%, TiO 2: 10-15%, Y 2o 3: 6-8%, above each component sum is 100%.
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