CN101457384B - Magnesium alloy ultrasound wet shot blasting method - Google Patents

Magnesium alloy ultrasound wet shot blasting method Download PDF

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Publication number
CN101457384B
CN101457384B CN2009100450286A CN200910045028A CN101457384B CN 101457384 B CN101457384 B CN 101457384B CN 2009100450286 A CN2009100450286 A CN 2009100450286A CN 200910045028 A CN200910045028 A CN 200910045028A CN 101457384 B CN101457384 B CN 101457384B
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magnesium alloy
shot blasting
blasting method
wet shot
ultrasonic field
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CN101457384A (en
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刘文才
张平
董杰
郭兴伍
赵鑫
张新平
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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Abstract

The invention relates to an ultrasonic wet shot blasting method of a magnesium alloy, and belongs to the technical field of magnesium alloy surface treatment. The method comprises the following steps: step 1: washing a magnesium alloy workpiece to be treated with and then washing with water; step 2: washing the magnesium alloy workpiece treated in the step 1 with acid and then washing with water; step 3: putting the magnesium alloy workpiece treated in the step 2 into an electrolytic tank, adding a diluent of 20-40g/l and shot blast granules of 50-90g/l to electrolyte to form a suspension, and then applying an ultrasonic field to the suspension and shot blasting the magnesium alloy workpiece. In the method, when an anode oxide coating is formed on the surface of the magnesium alloy during anode oxidation, the ultrasonic wet shot blasting is carried out to introduce a residual compressive stress into the anode oxide coating so as to counteract the residual compressive stress introduced by the anode oxidation, thus improving the anti-corrosion property of the magnesium alloy while lowering the damage to the fatigue property caused by the anode oxidation.

Description

Magnesium alloy ultrasound wet shot blasting method
Technical field
The present invention relates to a kind of method of technical field of magnesium alloy surface treatment, specifically, what relate to is a kind of magnesium alloy ultrasound wet shot blasting method.
Background technology
The electrochemical activity of magnesium is very high, and there is serious etching problem in conventional magnesium alloy, and therefore, its product generally all needs to carry out chemistry or electrochemical surface to be handled and improve corrosion resistance.In numerous surface treatment method of Mg alloy, anode oxidation method be performance and effect better and have one of important method of the market competitiveness.Anodic oxidation commonly used is a kind of electrochemistry oxygen metallization processes.Needs are carried out the anode of anodised workpiece connection direct supply and make anode, another kind of nullvalent metal (for example, stainless steel) negative terminal that connects direct current (D.C.) power supply is done in the suitable electrolytic solution of negative electrode immersion, when electric current passes through electrolyte solution, the negatively charged ions anode moves and at anode discharge, this process is followed the generation of atomic oxygen and formed oxide coating.Anode oxidation process can adopt direct current (D.C.) now, exchange the stack (A.C+D.C) and the pulsed current (P.C.) of (A.C.) or AC and DC.When the curtage that is applied during greater than certain value, on anodized workpiece, will produce spark or little electric arc, therefore, people are called anodic oxidation differential arc oxidation or micro-plasma oxidation again.Only important reaction is to produce hydrogen on negative electrode, metal anode is consumed and changes into a kind of oxide coating of self, this coating begins to form attached on the metal from metal one side near solution, metal ion in the oxide ceramic layer results from metal, and oxygen results from the anodic reaction in the water electrolysis liquor.The plasma temperature that measuring produced is about 7000 ℃, under this plasma body temperature, oxide ceramics is liquid, on one side near metal, the time that produces plasma body is enough to allow the fused oxide ceramics produce suitably contraction, thereby forms a kind of sintered ceramic oxide layer with hole.Near one side of electrolyte solution, the fused oxide ceramics is cooled off rapidly by electrolyte solution, just at escaping gas, especially oxygen and water vapour, make the oxide ceramic layer of formation have by kapillary link to each other mesh-structured.For example, the pore diameter of aluminium alloy anode oxide coating adopts scanning electron microscope to be measured as 0.1 μ m～30 μ m.
Find through literature search prior art, the Chinese invention patent application number is 200510085466.7, notification number be CN1724719A patent disclosure the magnesium alloy matrix surface anode oxidative treatment method under a kind of colloidal sol effect, employing is used to prepare powder with this routine of sol-gel, the technology of film coating material is incorporated on the surperficial anodic oxidation treatment of magnesium alloy, selected a kind of anodic oxidation of magnetism alloy base soln that has the performance that well mixes with silicon sol, utilize the adsorption of sol particle at magnesium alloy matrix surface, and a large amount of heats that distinctive spark phenomenon produces in the anodic oxidation of magnetism alloy process solidify sol particle, final and the product one of the anodic oxidation Mg alloy surface that coexists own has formed one deck anodic oxidation composite film, the hardness height of this anodic oxidation composite film, good insulation preformance, has corrosion resistance nature preferably, its weak point is: anodic oxidation is when improving the corrosion stability of magnesium alloy energy, also introduce residual tension, the fatigue property of damage magnesium alloy on its surface.In addition, the Influence of anodization on the fatigue life ofWE43A-T6magnesium (anodic oxidation is to magnesium alloy WE43A-T6 Fatigue Life) that A.J.Eifert etc. delivered on the phase 929-935 page or leaf at " Scripta Materialia " (material wall bulletin) in 1999 the 8th has studied anodic oxidation to magnesium alloy WE43A-T6 Fatigue Life, the result shows that anodic oxidation makes the high-cycle fatigue strength of WE43A magnesium alloy reduce by 10%.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of magnesium alloy ultrasound wet shot blasting method is provided, promptly in anodic oxidation of magnetism alloy, carried out ultrasound wet shot blasting, wherein anodic oxidation forms coating to improve the corrosion resisting property of magnesium alloy at Mg alloy surface, the stress of ultrasound wet shot blasting introducing simultaneously can be offset the tensile stress that anodic oxidation produces, thereby has reduced the damage of anodic oxidation to fatigue behavior.
The present invention is achieved by the following technical solutions, and the present invention adds thinner and shot blast particles in the electrolytic solution that existing anodic oxidation of magnetism alloy method adopts, form suspension, apply ultrasonic field, in the oxidation that begins to switch on, start the ultrasonic field that is applied, carry out ultrasound wet shot blasting.
Method of the present invention comprises following concrete steps:
Step 1: pending magnesium alloy workpiece is carried out washing again after the alkali cleaning earlier.
Step 2: the magnesium alloy workpiece after will handling through step 1 carries out washing after the pickling again.
Step 3: the magnesium alloy workpiece after will handling through step 2 is put into electrolyzer, adds thinner and shot blast particles in electrolytic solution, forms suspension, then this suspension is applied ultrasonic field and magnesium alloy workpiece is carried out shot-peening.
The related process parameter of the effective anodic oxidation of magnetism alloy method of practical application is adopted in anodic oxidation in the magnesium alloy ultrasound wet shot blasting process, for example, and solution formula, solution pH value, electrical parameter etc.Electrolytic solution of the present invention can be any electrolytic solution that is applicable to magnesium alloy, and adding the thinner of 20～40g/l and the diameter of 50～90g/l in electrolytic solution is the shot blast particles composition suspension of 20～50 μ m.In used suspension, apply the ultrasonic field that the ultrasonic frequency scope is 25～600KHz, preferential range of choice is 100～350KHz.In the oxidation that begins to switch on, start the ultrasonic field that is applied.
Described thinner can be the conventional thinner of using in the prior art, preferred polyoxyethylene glycol PEG-400 and PEG-800.
Described shot blast particles is that density is 2～4g/cm 3, mohs hardness greater than 5, diameter is the spherical non-metallic particle of 20～50 μ m, preferred silicon-dioxide.
The present invention carries out having applied ultrasonic field in the anode oxidation process in suspension, in the magnesium alloy ultrasound wet shot blasting process, ultrasonic field can play the effect of stirred suspension, reduce the concentration gradient at metal/gas/electrolyte solution phase interface place on the one hand, increase ion diffusion speed, improve speed of response, and ultrasonic field can play generation OH -1Ion and oxydol H 2O 2Effect, for anodic oxidation reactions provides required atomic oxygen; On the other hand, the silica dioxide granule that ultrasonic field can shake in the suspension carries out shot-peening to magnesium alloy workpiece, on anodised magnesium alloy work-piece surface, introducing residual compressive stress, offsetting the residual tension that anodic oxidation produces at magnesium alloy work-piece surface, and then when improving the magnesium alloy workpiece corrosion resisting property, do not damage even increase its fatigue property.
The present invention is suitable for realizing anodised all magnesium and magnesium alloy, as: AS41, AM60, AZ61, AZ81, AZ91, AZ92, HK31, QE22, ZE41, ZK61, EZ33, the wrought magnesium alloy of the HZ32 and the following trade mark: AZ31, AZ61, AZ80, M1, ZK60, ZK40, GW102, GW103, GW123 etc.
Description of drawings
The wiring layout that Fig. 1 adopts for the embodiment of the invention.
Among the figure, 1-electrolyzer, 2-suspension, 3-ultrasonic wave, 4-electrode, 5-power supply.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
As shown in Figure 1, the wiring layout that adopts for the embodiment of the invention.By the suspension of being made up of electrolytic solution, thinner and silicon-dioxide 2, be placed on the positive and negative electrode that two electrodes 4 in the suspension 2 connect power supply 5 respectively in electrolyzer 1, the ultrasonic wave 3 that ultrasonic generator sends is applied in the suspension 2.To put into electrolyzer 1 through the pending magnesium alloy workpiece of alkali cleaning and pickling, and then the suspension in the electrolyzer 12 be applied ultrasonic field and magnesium alloy workpiece is carried out shot-peening.
Described alkali cleaning and pickling are operation commonly used in the prior art, and soon magnesium alloy workpiece is washed after being placed on and cleaning in basic solution or the acidic solution again.Such as by sodium hydroxide 40～60g/l, sodium phosphate 5～15g/l, the basic solution that artificial soap lye wetting agent 20ml/l and water are formed; By phosphoric acid (volumetric concentration is 85%) 250～450ml/l, sulfuric acid (volumetric concentration is 98%) 12～20ml/l, the acidic solution that water 550～650ml/l forms.
Described electrolytic solution can be any electrolytic solution that is applicable to magnesium alloy, and the application of three kinds of electrolytic solution is provided in following examples: 1. hydrofluoric acid (HF) 30g/l, phosphoric acid (H 3PO 4) 60g/l, boric acid (H 3BO 3) 70g/l, surplus is a water; 2. Potassium monofluoride (KF) 28g/l, potassiumphosphate (K 3PO 4) 58g/l, potassium borate (K 3BO 3) 35g/l, hexamethylenetetramine 360g/l, surplus be water; 3. vitriolate of tartar (K 3SiO 3) 75ml/l, sodium hydroxide (NaOH) 25g/l, HF.H 2O (volumetric concentration is 10%) 10ml/l, surplus are water.But this also is not used in the scope of the present invention that limits.
Described thinner can be the conventional thinner of using in the prior art, preferred polyoxyethylene glycol PEG-400 and PEG-800.
Described power supply 5 can adopt direct current (D.C.), exchange the stack (D.C+P.C) of stack (A.C+D.C), pulsed current (P.C.) or the direct current and the pulse of (A.C.), AC and DC.
Embodiment 1:
To push attitude magnesium alloy ZK60 fatiguespecimen earlier and in the basic solution of following composition, carry out alkali cleaning:
Figure G2009100450286D00051
In the present embodiment, it is 1.6A/dm that current density is adopted in anodic oxidation 2Direct current to be superimposed with watt current density be 0.5A/dm 2, frequency is the alternating-current of 50Hz; The setting end voltage is 250V; In suspension, apply the ultrasonic field that frequency is 80Hz; Anodic oxidation and ultrasound wet shot blasting continue 20min, and the pore diameter of resulting anodized coating does not have the variation of shot-peening little relatively, and corresponding to fatigue lifetime of 160MPa 6 * 10 during by shot-peening not 4Bring up to 1.5 * 10 5
Embodiment 2:
Adopt the solution of embodiment 1 to carry out alkali cleaning and pickling extruding attitude magnesium alloy ZK60 fatiguespecimen, in following suspension, carry out anodic oxidation and ultrasound wet shot blasting then.
Figure G2009100450286D00052
Use NH 4OH (25%) regulates pH value to 7.5, and the employing current density is 1.4A/dm 2Direct current: final voltage is 325V; Solution temperature is 16 ℃, and added ultrasonic frequency is 25KHz, and the treatment time is 20min, and the pore diameter of resulting anodized coating does not have the variation of shot-peening little relatively, and corresponding to fatigue lifetime of 160MPa 6 * 10 during by shot-peening not 4Bring up to 1.1 * 10 5
Embodiment 3:
Adopt the solution of embodiment 1 to carry out alkali cleaning and pickling extruding attitude magnesium alloy ZK60 fatiguespecimen, in following suspension, carry out anodic oxidation and ultrasound wet shot blasting then.
Figure G2009100450286D00053
Figure G2009100450286D00061
Use NH 4OH (25%) regulates pH value to 7.3, and the employing current density is 1.4A/dm 2Direct current: final voltage is 325V; Solution temperature is 15 ℃, and added ultrasonic frequency is 250KHz, and the treatment time is 20min, and the pore diameter of resulting anodized coating does not have the variation of shot-peening little relatively, and corresponding to fatigue lifetime of 160MPa 6 * 10 during by shot-peening not 4Bring up to 1.9 * 10 5
Embodiment 4:
Adopt the solution of embodiment 1 to carry out alkali cleaning and pickling extruding attitude magnesium alloy ZK60 fatiguespecimen, in following suspension, carry out anodic oxidation and ultrasound wet shot blasting then.
Figure G2009100450286D00062
Use NH 4OH (25%) regulates pH value to 7.5, and the employing current density is 1.4A/dm 2Direct current: final voltage is 325V; Solution temperature is 18 ℃, and added ultrasonic frequency is 550KHz, and the treatment time is 15min, and the pore diameter of resulting anodized coating does not have the variation of shot-peening little relatively, and corresponding to fatigue lifetime of 160MPa 6 * 10 during by shot-peening not 4Bring up to 1.18 * 10 5
Embodiment 5:
Adopt the solution of embodiment 1 to carry out alkali cleaning and pickling extruding attitude magnesium alloy ZK60 fatiguespecimen, in following suspension, carry out anodic oxidation and ultrasound wet shot blasting then.
Figure G2009100450286D00063
In the present embodiment, it is 1.4A/dm that current density is adopted in anodic oxidation 2Direct current to be superimposed with watt current density be 0.6A/dm 2, frequency is the alternating-current of 50Hz; The setting end voltage is 250V; In suspension, apply the ultrasonic field that frequency is 80Hz; Anodic oxidation and ultrasound wet shot blasting continue 20min, and the pore diameter of resulting anodized coating does not have the variation of shot-peening little relatively, and corresponding to fatigue lifetime of 160MPa 6 * 10 during by shot-peening not 4Bring up to 9.8 * 10 4

Claims (7)

1. a magnesium alloy ultrasound wet shot blasting method is characterized in that comprising the steps:
Step 1: pending magnesium alloy workpiece is carried out washing again after the alkali cleaning earlier;
Step 2: the magnesium alloy workpiece after will handling through step 1 carries out washing after the pickling again;
Step 3: the magnesium alloy workpiece after will handling through step 2 is put into electrolyzer, in electrolytic solution, add the thinner of 20～40g/l and the shot blast particles of 50～90g/l and form suspension, then this suspension is applied ultrasonic field, in the oxidation that begins to switch on, start the ultrasonic field that is applied magnesium alloy workpiece is carried out shot-peening.
2. magnesium alloy ultrasound wet shot blasting method according to claim 1 is characterized in that, described thinner is polyoxyethylene glycol PEG-400 or PEG-800.
3. magnesium alloy ultrasound wet shot blasting method according to claim 1 is characterized in that, described shot blast particles is that density is 2～4g/cm 3, mohs hardness greater than 5, diameter is the spherical non-metallic particle of 20～50 μ m.
4. magnesium alloy ultrasound wet shot blasting method according to claim 3 is characterized in that described shot blast particles is a silicon-dioxide.
5. magnesium alloy ultrasound wet shot blasting method according to claim 1 is characterized in that, described ultrasonic field is that the ultrasonic frequency scope is the ultrasonic field of 25～600KHz, in the oxidation that begins to switch on, starts ultrasonic field.
6. magnesium alloy ultrasound wet shot blasting method according to claim 5 is characterized in that, described ultrasonic field is that the ultrasonic frequency scope is the ultrasonic field of 100～350KHz.
7. magnesium alloy ultrasound wet shot blasting method according to claim 1 is characterized in that, described electrolyzer, its power supply are stack, pulse or the direct current of direct current, interchange, AC and DC and the stack power supply of pulse.
CN2009100450286A 2009-01-08 2009-01-08 Magnesium alloy ultrasound wet shot blasting method Expired - Fee Related CN101457384B (en)

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CN104109894B (en) * 2014-07-18 2016-06-01 郑州轻工业学院 Magnesium alloy compound surface protective treatment equipment and method
CN109487183B (en) * 2018-12-10 2020-11-27 同济大学 Wet shot blasting surface modification method suitable for aluminum-lithium alloy

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