CN100588756C - A kind of surface treating method for magnesium lithium alloy - Google Patents

A kind of surface treating method for magnesium lithium alloy Download PDF

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Publication number
CN100588756C
CN100588756C CN200810064145A CN200810064145A CN100588756C CN 100588756 C CN100588756 C CN 100588756C CN 200810064145 A CN200810064145 A CN 200810064145A CN 200810064145 A CN200810064145 A CN 200810064145A CN 100588756 C CN100588756 C CN 100588756C
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arc oxidation
differential arc
lithium alloy
magnesium lithium
treating method
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CN101245485A (en
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袁艺
于方
朱果逸
宋来文
景晓燕
张密林
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Harbin Engineering University
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Harbin Engineering University
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Abstract

The present invention is to provide a kind of surface treating method for magnesium lithium alloy.Differential arc oxidization technique is successfully applied to the magnesium lithium alloy surface treatment.Utilize the multiplexing power supply of DC-DC pulse/alternating-current pulse, in sodium polyphosphate, water glass, Sodium hexametaphosphate 99, sodium hydroxide combined electrolysis liquid system, the magnesium lithium alloy of different lithium content is carried out the differential arc oxidation of 2-120min, generate the ceramic coating of 10-100 μ m at the magnesium lithium alloy surface in situ, hardness can reach more than the 200Hv, corrosion resisting property significantly improves than alloy substrate, solved a magnesium lithium alloy surface treatment difficult problem of generally acknowledging both at home and abroad, widened the application of magnesium lithium alloy in fields such as Aeronautics and Astronautics, automobile, electronics.

Description

A kind of surface treating method for magnesium lithium alloy
(1) technical field
What the present invention relates to is a kind of surface treatment method of alloy, specifically a kind of surface treatment method of magnesium lithium alloy.
(2) background technology
Magnesium lithium alloy is the lightest structural metallic materials, and its density only is 2/3~3/4 of ordinary magnesium alloy, 1/2~2/3 of aluminium alloy.In the light-weighted while of alloy, magnesium lithium alloy has higher specific tenacity, specific rigidity concurrently, and plastic degeneration's ability and electromagnetic shielding ability have broad application prospects at aspects such as Aeronautics and Astronautics, automobile and electronics preferably.But since the standard potential of lithium than magnesium more negative ( E Li + / Li O = - 3.05 Vvs . NHE , E Mg 2 + / Mg O = - 2.36 Vvs . NHE ), the magnesium lithium alloy solidity to corrosion is poorer than ordinary magnesium alloy.The solidity to corrosion difference is the bottleneck of restriction magnesium lithium alloy widespread use.
Surface treatment is to improve one of effective ways of metal and alloy corrosion resistance always.But rarely has report both at home and abroad so far about the magnesium lithium alloy surface treatment.Its reason is that lithium is too active, and magnesium lithium alloy is very easily corrosion in traditional high temperature or liquid phase surface treatment environment, causes surface treatment and surface corrosion to carry out simultaneously, and surface treatment effect is not good.In only several pieces of documents, Sharma etc. adopt K 2Cr 2O 7+ H 2SO 1Electrolytic solution, realize the constant current anodic oxidation of Mg-10~13Li-1.25~1.75Al alloy, obtain oxide film (the Galvanic Black Anodizing on Mg-Li Alloys that one deck contains Cr at alloy surface, Journal of AppliedElectrochemistry, 1,993 23 (5), 500-507.) .J.F.Li etc. is on achievement in research bases such as Sharma, use surface treatment (the Preparation and galvanic anodizing of a Mg-Li alloy that the constant current anodic oxidation realizes the Mg-10.02Li-3.86Zn-2.54Al-1.76Cu alloy, MaterialsScience and Engineering:A, 2006,433 (1-2), 233-240.).It is coarse that magnesium lithium alloy contains Cr constant current anode oxide film surface porosity, and be full of cracks is serious, corrosion resisting property and all very poor with the matrix bond ability.N.Yamauchi etc. utilize plasma vapor deposition processes to plate one deck diamond-like carbon film at the Mg-14Li alloy surface, significantly improve that alloy is anti-corrosion, wear resistance (DLC coating on Mg-Li alloy, Surface ﹠amp; Coatings Technology, 2007,201,4913-4918.); K.Schemme etc. utilize the laser particle injection method that the SiC particle is injected the Mg-Li alloy surface, strengthened wear resisting property (the Surfacemodifications of Mg-Li alloys by laser alloying and by laser particlesimpregnation of alloy, Metall, 1993,47 (6), 541-546).These two kinds of method costs are too high, and disposable processing workpiece area is limited simultaneously, is not suitable for the surface treatment of high surface area magnesium lithium alloy workpiece.Differential arc oxidization technique is one of the most potential process for treating surface.It is on anodised basis, make operating voltage break through the faraday interval, by microplasma discharge between anode test specimen under the high-voltage (200-1000V) and the electrolytic solution contact surface, directly at metal and alloy surface growth in situ ceramic coatings thereof such as Al, Mg, Ti, realize surface modification, strengthened anticorrosion, the insulation of material, performance such as heat-resisting, shock-resistant, wear-resistant.The application of differential arc oxidization technique in the magnesium lithium alloy surface treatment do not appear in the newspapers so far.
(3) summary of the invention
The object of the present invention is to provide a kind of efficient height with low cost, can improve the corrosion resisting property of magnesium lithium alloy, widen the surface treating method for magnesium lithium alloy of the practical ranges of magnesium lithium alloy.
The object of the present invention is achieved like this:
(1) pre-treatment
Utilize abrasive paper for metallograph jettisoning magnesium lithium alloy surface black loose membrane, cleaning also then, cold wind dries up;
(2) differential arc oxidation
To place electrolytic solution through the magnesium lithium alloy of pre-treatment; Electrolytic solution is main membrane-forming agent with sodium polyphosphate 5-60g/L or Sodium hexametaphosphate 99 1-20g/L, and a kind of among glycerol 5-20mL/L, trolamine 10-30mL/L or the quadrol 5-30mL/L or its are composite to be additive; Adjust pH is (11-13); The differential arc oxidation that adopts direct current, DC pulse or the alternating-current pulse electricity way of output to carry out alloy is handled;
(3) aftertreatment
The washing of magnesium lithium alloy behind the differential arc oxidation, cold wind are dried up, adopt the water glass solution of water glass content 30-100g/L, in 90 ℃ of processing 5-20min, after cooling in the acetone solution, washing were placed in taking-up, cold wind dried up.
The present invention can also comprise:
1, also can contain silicon-dioxide nano/micron powder 5-30g/L, titanium dioxide nano/micron powder 5-30g/L in the described electrolytic solution, zirconium dioxide nano/micron powder 5-30g/L or aluminium sesquioxide nano/micron powder 10-20g/L receive a kind of in the micro-powder or selectivity is composite as activator.
2, to handle be to adopt direct current, DC-pulse output mode for described differential arc oxidation, adopts a kind of in such three kinds of patterns: (a) constant current mode: outward current density constant 1A/dm 2-15A/dm 2, output voltage constantly changes in the oxidising process, and the differential arc oxidation time generally is no more than 40min, reaches differential arc oxidation stage output voltage at 350V-500V; (b) constant voltage mode: the constant 350V-550V of output voltage, the outward current experience rises sharply-gradually falls-stable process in the oxidising process, and the differential arc oxidation time is 2min-2h; (c) stage boost mode: the stage of output voltage raises, and the differential arc oxidation time is generally 10min-4h, reaches differential arc oxidation stage output voltage at 350V-600V.
3, described differential arc oxidation processing is to adopt the output of alternating-current pulse electricity, the constant 50V-250V of negative pulse voltage in the differential arc oxidation process, and positive pulse voltage is 2min-4h in 400V-600V, differential arc oxidation time.
4, the cleaning in the described pre-treatment process is for using acetone, alcohol flushing successively.
5, the cleaning in the described pre-treatment process is put into the acetone soln ultrasonic cleaning, alcohol flushing after polishing.
6, before the sand paper polishing, put it into degreasing in the 80g/L strong caustic in the described pre-treatment process, skimming temp 80-95 ℃, degreasing time 10-20min.
7, electrolyte temperature is lower than 60 ℃ in the differential arc oxidation process.
Treatment process of the present invention is being undertaken by comprising in the treatment unit that the multiplexing power supply 1 of DC-DC pulse/alternating-current pulse, controller 2, outer circulation water coolant 3, aeration tube 4, anode workpiece 5 and stainless steel cathode 6 are formed.Concrete structure is seen accompanying drawing 1.
Consisting of as shown in Figure 2 of the multiplexing power supply of described DC-DC pulse/alternating-current pulse, input electrical signal is through constant pressure source V1, during V2, realize that by irreversible rectification, full-bridge inverting, the rectification of filtering secondary and filtering output alternating-current is to galvanic conversion, the PWM width modulation of this one-level has been guaranteed to supply with the stable constant pressure source of output, realizes complete machine constant voltage function.The power output unit is pulse formation, and shaping is amplified, and power fail the unit, and its PWM width modulation realizes that constant current regulates and control, so that one constant current is provided and is not subjected to the influence of load or power source change to load.Simultaneously power stage also has frequency, the duty cycle adjustment characteristic of wide region, and its advantage is a working stability, disturbs very for a short time, and waveform is clean.The complete machine output form is: the output of 1 alternating-current pulse.Its just, the negative pulse amplitude is respectively adjustable, at the micro-arc oxidation process characteristics, adopts not constant amplitude output of generating positive and negative voltage, positive pulse voltage (400-600V) is far above negative pulse voltage (50-250V).The output of 2 DC pulse: this moment, V2 withdrawed from power supply, was powered separately by V1, realized the output of direct current constant amplitude pulse.3 direct currents output: it is directly with V1, and V2 draws use, provide the direct current of 0-750V and two kinds of voltage ranges of 0-250V export above function conversion by one or electronics or mechanical switch finish.They realize interlocking, interlocking, interlock.To guarantee safety, reliability service.Certainly, method of the present invention also can be selected existing supply unit for use.
Beneficial effect of the present invention is as follows:
(1) realized the Microarc Oxidation Surface Treatment of magnesium lithium alloy the first time, prepare the good micro-arc oxidation films of corrosion resisting property, the magnesium reason alloy surface that a kind of cost is low, efficient is high, effect is excellent treatment process is provided, has solved a domestic and international magnesium lithium alloy surface-treated difficult problem;
(2) adopt the multiplexing mao power source of DC-DC pulse/alternating-current pulse, provide more and can reconcile the power supply way of output,, can select the suitable power supply way of output, guarantee differential arc oxidation effect optimization at different-alloy and electrolytic solution;
(3) introduce the composite electrolytic solution notion, for the first time suspension liquid is applied to differential arc oxidation.When growing micro-arc oxidation films in position, cover the composition that changes micro-arc oxidation films, improve its mechanical property and corrosion resisting property by receiving melting of micron particle.
(4) description of drawings
Fig. 1 is the synoptic diagram of micro arc oxidation treatment device of the present invention.
Fig. 2 is DC-DC pulse/alternating-current pulse differential arc oxidation composite power source functional block diagram.
(5) embodiment
For example the present invention is done description in more detail below in conjunction with accompanying drawing:
1 pre-treatment
Because magnesium lithium alloy places air to be easy to corrosion, generate the loose black thin film of one deck on the surface, at first utilize 500# abrasive paper for metallograph jettisoning magnesium lithium alloy surface black loose membrane, use acetone, alcohol flushing afterwards successively, cold wind dries up.For the smallclothes magnesium lithium alloy, put it into the acetone soln ultrasonic cleaning after also can polishing, alcohol flushing, cold wind dry up.If the magnesium alloy matrix surface grease is more, can before the sand paper polishing, put it into degreasing in the 80g/L strong caustic, skimming temp 80-95 ℃, degreasing time 10-20min.
2 differential arc oxidations
To place the electrolytic solution of differential arc oxidation shown in Figure 1 system through the magnesium lithium alloy of pre-treatment, be threaded between suspension member and the magnesium lithium alloy.For DC pulse and alternating-current pulse output mode, preestablish output frequency (5-26000Hz is adjustable), dutycycle (3%-85% is adjustable).For the direct current or the DC-pulse way of output, can adopt three kinds of patterns: (a) constant current mode: outward current density constant 1A/dm 2-15A/dm 2, output voltage constantly changes in the oxidising process, and this pattern differential of the arc oxidization time generally is no more than 40min, reaches differential arc oxidation stage output voltage at 350V-500V; (b) constant voltage mode: the constant 350V-550V of output voltage, the outward current experience rises sharply-gradually falls-stable process in the oxidising process, and this pattern differential of the arc oxidization time scope is wider, is generally 2min-2h; (c) stage boost mode: this output mode is between constant voltage and constant current output mode, stage by output voltage raises and guarantees oxidation current density when being implemented in control differential arc oxidation voltage, characteristics with control handiness, the differential arc oxidation time is generally 10min-4h, reaches differential arc oxidation stage output voltage at 350V-600V.For alternating-current pulse electricity output, the constant 50V-250V of negative pulse voltage in the differential arc oxidation process, for continuity and the stability of keeping micro-arc discharge, positive pulse voltage-as at 400V-600V.
3 aftertreatments
The washing of magnesium lithium alloy sample behind the differential arc oxidation, cold wind are dried up.Utilize prior art, adopt the water glass solution of water glass content 30-100g/L, in 90 ℃ of processing 5-20min, after cooling in the acetone solution, washing were placed in taking-up, cold wind dried up.
Beneficial effect of the present invention is as follows:
(1) realized the Microarc Oxidation Surface Treatment of magnesium lithium alloy the first time, prepare the good micro-arc oxidation films of corrosion resisting property, the magnesium reason alloy surface that a kind of cost is low, efficient is high, effect is excellent treatment process is provided, has solved a domestic and international magnesium lithium alloy surface-treated difficult problem;
(2) adopt the multiplexing mao power source of DC-DC pulse/alternating-current pulse, provide more and can reconcile the power supply way of output,, can select the suitable power supply way of output, guarantee differential arc oxidation effect optimization at different-alloy and electrolytic solution;
(3) introduce the composite electrolytic solution notion, for the first time suspension liquid is applied to differential arc oxidation.When growing micro-arc oxidation films in position, cover the composition that changes micro-arc oxidation films, improve its mechanical property and corrosion resisting property by receiving melting of micron particle.
Embodiment 1
Using alloy is the Mg-5.6%Li-3.5%Al-1%Zn-1.2%Ce-1.5%Mn alloy, and sample is cylindrical, bottom surface diameter 16cm, and high 15cm, screw thread is revolved in the center of circle, bottom surface.
The composition of differential arc oxidation electrolytic solution in table 1 different instances
Example 1 Example 2 Example 3
Sodium polyphosphate g/L 4 8 10
Sodium hexametaphosphate 99 g/L 0.5 2 5
Sodium hydroxide g/L 3 4 3
Trolamine mL/L 10 10 0
Quadrol mL/L 0 0 10
Glycerol mL/L 0 5 10
Silica nanometer powder g/L 0 0 5
Titanic oxide nano g/L 0 5 0
Aluminium sesquioxide nano powder g/L 0 0 5
(a) pre-treatment
Sample in 80 ℃, 60g/L sodium hydroxide solution degreasing 7min post-flush, dry up, at ultrasonic, the alcohol flushing of 500# abrasive paper for metallograph polishing back acetone, cold wind dries up.
(b) differential arc oxidation
Sample immerses differential arc oxidation electrolytic solution fully, and power supply is transferred to the DC pulse shelves, adopts constant current differential arc oxidation pattern, pulse-repetition 1000Hz, dutycycle 15%, outward current density 5A/dm 2, differential arc oxidation time: 5-40min, differential arc oxidation electrolytic solution is as shown in table 1.
(c) aftertreatment
Directly the washing of the magnesium lithium alloy sample behind the differential arc oxidation, cold wind are dried up, obtain solidity to corrosion magnesium lithium alloy micro-arc oxidation films.
This method obtains the oyster white micro-arc oxidation films, and thickness 10-60 μ m is 30min when the differential arc oxidation time, and oxide thickness is 52.7 μ m, and hardness reaches 170Hv.Sample electrokinetic potential polarization corrosion current potential, corrosion current such as table 2, the salt air corrosion time surpasses 48h in 5% sodium-chlor.
Corrosion voltage before and after the magnesium lithium alloy differential arc oxidation is handled in table 2 example 1 and corrosion current contrast
Corrosion voltage (V) Corrosion electric current density (A/cm 2)
Before the differential arc oxidation -1.528 2.02×10 -4
Behind the differential arc oxidation -1.388 1.17×10 -6
Embodiment 2
Using alloy is the Mg-11.2%Li-3%Al-1.4%Zn-1.5%Ce-1.8%Mn alloy, and sample is cylindrical, bottom surface diameter 16cm, and high 15cm, screw thread is revolved in the center of circle, bottom surface.
Corrosion voltage before and after the magnesium lithium alloy differential arc oxidation is handled in table 3 example 2 and corrosion current contrast
Corrosion voltage (V) Corrosion electric current density (A/cm 2)
Before the differential arc oxidation -1.536 1.59×10 -3
Behind the differential arc oxidation -1.360 2.42×10 -6
(a) pre-treatment
Sample in 90 ℃, 80g/L sodium hydroxide solution degreasing 10min post-flush, dry up, at 500# abrasive paper for metallograph polishing back acetone rinsing, alcohol flushing, cold wind dries up.
(b) differential arc oxidation
Sample immerses differential arc oxidation electrolytic solution fully, and power supply is transferred to the alternating-current pulse shelves, adopts constant voltage differential arc oxidation pattern, pulse-repetition 3000Hz, dutycycle 50%, positive pulse voltage 500V, negative pulse voltage 170V, differential arc oxidation time: 5min-1h, differential arc oxidation electrolytic solution is as shown in table 1.
(c) aftertreatment
Directly the washing of the magnesium lithium alloy sample behind the differential arc oxidation, cold wind are dried up.Put into and contain water glass 80g/L, 80 ℃ of water glass solution 10min sealing of holes, take out after washing, cold wind dries up, and obtains the solidity to corrosion magnesium lithium alloy micro-arc oxidation films of high rigidity.
This method obtains silvery white micro-arc oxidation films, thickness 30-80 μ m, and the differential arc oxidation time, oxide thickness was 66.5 μ m when being 40min, hardness reaches 185Hv.Sample electrokinetic potential polarization corrosion current potential, corrosion current such as table 2, the salt air corrosion time surpasses 60h in 5% sodium-chlor.
Embodiment 3
Using alloy is the Mg-14.2%Li-3.1%Al-1.1%Zn-1.5%Ce alloy, and sample is cylindrical, bottom surface diameter 16cm, and high 15cm, screw thread is revolved in the center of circle, bottom surface.
Corrosion voltage before and after the magnesium lithium alloy differential arc oxidation is handled in table 4 example 3 and corrosion current contrast
Corrosion voltage (V) Corrosion electric current density (A/cm 2)
Before the differential arc oxidation -1.540 2.28×10 -3
Behind the differential arc oxidation -1.340 4.12×10 -6
(a) pre-treatment
Sample in 90 ℃, 80g/L sodium hydroxide solution degreasing 10min post-flush, dry up, at 500# abrasive paper for metallograph polishing back acetone rinsing, alcohol flushing, cold wind dries up.
(b) differential arc oxidation
Sample immerses differential arc oxidation electrolytic solution fully, power supply is transferred to the alternating-current pulse shelves, the employing stage differential arc oxidation pattern of boosting, pulse-repetition 3000Hz, dutycycle 50%, positive pulse initial voltage 200V, negative pulse voltage 50V, every 5min voltage rising 50V, voltage keeps the constant voltage differential arc oxidation after rising to 520V.Differential arc oxidation time: 30min-1h, differential arc oxidation electrolytic solution is as shown in table 1.
(c) aftertreatment
Directly the washing of the magnesium lithium alloy sample behind the differential arc oxidation, cold wind are dried up.Put into and contain water glass 100g/L, 90 ℃ of water glass solution 20min sealing of holes, take out after washing, cold wind dries up, and obtains strong solidity to corrosion magnesium lithium alloy micro-arc oxidation films.
This method obtains the mazarine micro-arc oxidation films, thickness 10-50 μ m, and the differential arc oxidation time, oxide thickness was 45.5 μ m when being 30min, hardness reaches 220Hv.Sample electrokinetic potential polarization corrosion current potential, corrosion current such as table 4, the salt air corrosion time surpasses 60h in 5% sodium-chlor.

Claims (10)

1, a kind of surface treating method for magnesium lithium alloy is characterized in that:
(1) pre-treatment
Utilize abrasive paper for metallograph jettisoning magnesium lithium alloy surface black loose membrane, cleaning also then, cold wind dries up;
(2) differential arc oxidation
To place electrolytic solution through the magnesium lithium alloy of pre-treatment; Electrolytic solution is main membrane-forming agent with sodium polyphosphate 5-60g/L or Sodium hexametaphosphate 99 1-20g/L, and a kind of among glycerol 5-20mL/L, trolamine 10-30mL/L or the quadrol 5-30mL/L or its are composite to be additive; Adjust pH is 11-13; The differential arc oxidation that adopts direct current, DC pulse or the alternating-current pulse electricity way of output to carry out alloy is handled;
(3) aftertreatment
The washing of magnesium lithium alloy behind the differential arc oxidation, cold wind are dried up, adopt the water glass solution of water glass content 30-100g/L, in 90 ℃ of processing 5-20min, after cooling in the acetone solution, washing were placed in taking-up, cold wind dried up.
2, surface treating method for magnesium lithium alloy according to claim 1, it is characterized in that: also contain silicon-dioxide nano/micron powder 5-30g/L, titanium dioxide nano/micron powder 5-30g/L in the described electrolytic solution, zirconium dioxide nano/micron powder 5-30g/L or aluminium sesquioxide nano/micron powder 10-20g/L receive a kind of in the micro-powder or selectivity is composite as activator.
3, surface treating method for magnesium lithium alloy according to claim 2 is characterized in that: before the sand paper polishing, put it into degreasing in the 80g/L strong caustic in the described pre-treatment process, and skimming temp 80-95 ℃, degreasing time 10-20min.
4, surface treating method for magnesium lithium alloy according to claim 3 is characterized in that: electrolyte temperature is lower than 60 ℃ in the differential arc oxidation process.
5, according to any one described surface treating method for magnesium lithium alloy of claim 1-4, it is characterized in that: the cleaning in the described pre-treatment process is for using acetone, alcohol flushing successively.
6, according to any one described surface treating method for magnesium lithium alloy of claim 1-4, it is characterized in that: the cleaning in the described pre-treatment process is put into the acetone soln ultrasonic cleaning, alcohol flushing after polishing.
7, surface treating method for magnesium lithium alloy according to claim 5, it is characterized in that: it is to adopt direct current, DC-pulse output mode that described differential arc oxidation is handled, and adopts a kind of in such three kinds of patterns: (a) constant current mode: outward current density constant 1A/dm 2-15A/dm 2, output voltage constantly changes in the oxidising process, and the differential arc oxidation time is no more than 40min, reaches differential arc oxidation stage output voltage at 350V-500V; (b) constant voltage mode: the constant 350V-550V of output voltage, the outward current experience rises sharply-gradually falls-stable process in the oxidising process, and the differential arc oxidation time is 2min-2h; (c) stage boost mode: the stage of output voltage raises, and the differential arc oxidation time is 10min-4h, reaches differential arc oxidation stage output voltage at 350V-600V.
8, surface treating method for magnesium lithium alloy according to claim 6, it is characterized in that: it is to adopt direct current, DC-pulse output mode that described differential arc oxidation is handled, and adopts a kind of in such three kinds of patterns: (a) constant current mode: outward current density constant 1A/dm 2-15A/dm 2, output voltage constantly changes in the oxidising process, and the differential arc oxidation time is no more than 40min, reaches differential arc oxidation stage output voltage at 350V-500V; (b) constant voltage mode: the constant 350V-550V of output voltage, the outward current experience rises sharply-gradually falls-stable process in the oxidising process, and the differential arc oxidation time is 2min-2h; (c) stage boost mode: the stage of output voltage raises, and the differential arc oxidation time is 10min-4h, reaches differential arc oxidation stage output voltage at 350V-600V.
9, surface treating method for magnesium lithium alloy according to claim 5, it is characterized in that: it is to adopt the output of alternating-current pulse electricity that described differential arc oxidation is handled, the constant 50V-250V of negative pulse voltage in the differential arc oxidation process, positive pulse voltage is 2min-4h in 400V-600V, differential arc oxidation time.
10, surface treating method for magnesium lithium alloy according to claim 6, it is characterized in that: it is to adopt the output of alternating-current pulse electricity that described differential arc oxidation is handled, the constant 50V-250V of negative pulse voltage in the differential arc oxidation process, positive pulse voltage is 2min-4h in 400V-600V, differential arc oxidation time.
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