CN102345151A - Method for preparing ZrO2 compound ceramic film on surfaces of magnesium and magnesium alloy through microarc oxidization - Google Patents
Method for preparing ZrO2 compound ceramic film on surfaces of magnesium and magnesium alloy through microarc oxidization Download PDFInfo
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Abstract
The invention discloses a method for preparing a ZrO2 compound ceramic film on surfaces of magnesium and magnesium alloy through microarc oxidization. The method comprises the steps of: based on a zirconium salt system solution as an electrolyte, placing the magnesium or magnesium alloy in the electrolyte to be used as an anode, taking a stainless steel plate as a cathode, controlling the temperature of the electrolyte to be 10-35 DEG C, regulating the pulse frequency to be 300-1000Hz and the duty cycle to be 5-45%, carrying out constant-voltage treatment for 10-30 minutes under the condition that the voltage is 250-300V, then raising the voltage to 400-450V, and carrying out constant-voltage treatment for 20-60 minutes, thereby growing a uniform and compact ZrO2 compound ceramic film in situ on the surface of the magnesium or magnesium alloy. By adopting the method disclosed by the invention, the compact ZrO2 compound ceramic film can be rapidly obtained on the surface of the magnesium alloy. The method has no special requirements for materials, shapes, sizes and the like of the magnesium or magnesium alloy, and has better generality.
Description
Technical field
The invention belongs to the differential arc oxidation processing technology field, be specifically related to a kind of magnesium and magnesium alloy surface micro-arc oxidation and prepare ZrO
2The method of composite ceramic film.
Background technology
Magnesium alloy is to be applied in the lightest a kind of alloy of proportion in the modern industry alloy, and it has higher strength-weight ratio and good shockproof properties, is mainly used in the missile-operation control system, and component such as wheel hub, engine casing rise and fall.Magnesium and alloy thereof become the important substitute products of lightweight structural material in recent years.Magnesium alloy also is applied in high strength, high damping, electromagnetic wave shielding and requires the automobile and the electronics industry of good mechanical performance.Because these good characteristics of magnesium, the consumption to magnesium increases day by day in the world, and is also actively carrying out the development research of magnesium and alloy thereof countries in the world.The magnesium of China is contained abundant, and in recent years, China begins one's study and develops the moulding and the process of surface treatment of magnesium products.
Micro-arc oxidation process is a kind of non-ferrous metal (like aluminium, magnesium, titanium etc.) process of surface treatment that development in recent years is got up, and especially since nineteen nineties, this technology has become the research focus of domestic academia, and obtains the approval of industrial community gradually.Especially magnesium alloy surface micro-arc oxidation is handled, because higher hardness, anti scuffing and the resistance to corrosion of arc differential oxide ceramic layer make this technology be widely used in the surface treatment of magnesium-alloy material.Particularly the ceramic layer surface is uniform-distribution with the characteristic of a large amount of blind property micropores, can increase the follow-up decorative coveringn of magnesium-alloy material and the bonding strength of ceramic layer.
During at present to magnesium alloy differential arc oxidation, adopt silicate, phosphoric acid salt and meta-aluminate solution system, the ceramic membrane of preparation is improved at aspects such as solidity to corrosion, hardness, wear resistancies significantly more.Yet,, the requirement of magnesium alloy differential arc oxidation ceramic membrane is also improved constantly along with the continuous popularization of magnesium alloy range of application.Especially magnesium alloy is had higher requirement to solidity to corrosion, the pyro-oxidation resistance of ceramic membrane in the application of space flight, aviation field, and the ceramic membrane of therefore existing technology preparation can't satisfy the requirement of space flight, aviation field.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of magnesium and magnesium alloy surface micro-arc oxidation to prepare ZrO to above-mentioned deficiency of the prior art
2The method of composite ceramic film.Adopt processing parameter of the present invention, can obtain fine and close ZrO at magnesium or Mg alloy surface fast
2Composite ceramic film, the speed of growth of this ceramic film are up to more than the 4 μ m/min, and the ceramic membrane of preparation is not when carrying out the sealing of hole aftertreatment, and anti-neutral NaCl salt air corrosion reaches more than the 400h, and microhardness can reach more than the 1000HV.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: a kind of magnesium and magnesium alloy surface micro-arc oxidation prepare ZrO
2The method of composite ceramic film is characterized in that, this method may further comprise the steps:
Step 1, with water solvent preparation zirconates system solution; Contain zirconates 5g～30g in every liter of zirconates system solution; Sodium hexametaphosphate 99 5g～30g; Water glass 2g～10g; Sodium Fluoride 1g～30g, glycerine 5mL～30mL, ammoniacal liquor 2mL～10mL; The pH value of regulating the zirconates system solution is 4～12, then the zirconates system solution is placed electrolyzer to leave standstill the back as electrolytic solution;
Step 2, place the said electrolytic solution of step 1 as anode in pending magnesium or magnesium alloy; Stainless steel plate is as negative electrode; The temperature of control electrolytic solution is 10 ℃～35 ℃; Setting mao power source is the constant voltage mode of operation; The regulating impulse frequency is 300Hz～1000Hz; Dutycycle is 5%～45%; Be that constant voltage is handled 10min～30min under the condition of 250V～300V at voltage; Then voltage is increased to 400V～450V; Constant voltage is handled 20min～60min, promptly at the ZrO of magnesium or Mg alloy surface growth in situ one deck even compact
2Composite ceramic film.
Zirconates described in the above-mentioned steps one is acetic acid zirconium, zirconium hydroxide, zirconium carbonate, zirconium ammonium fluoride or zirconium silicate.
Mao power source described in the above-mentioned steps two is a direct current pulse power source.
Pulse-repetition described in the above-mentioned steps two is 500Hz～700Hz.
Dutycycle described in the above-mentioned steps two is 10%～30%.
The present invention compared with prior art has the following advantages:
1, the present invention contains ZrO through in electrolytic solution, adding the Zr element, make in the magnesium prepared or the magnesium alloy differential arc oxidation ceramic membrane
2Composite ceramics is to improve the solidity to corrosion of ceramic membrane.The ceramic membrane of preparation is not when carrying out the sealing of hole aftertreatment, and anti-neutral NaCl salt air corrosion reaches more than the 400h, and microhardness can reach more than the 1000HV.
2, adopt processing parameter of the present invention, can obtain fine and close ZrO at magnesium or Mg alloy surface fast
2Composite ceramic film, the speed of growth of this ceramic film are up to more than the 4 μ m/min, and this method has efficiently, energy-saving advantages.
3, zirconates system electrolytic solution used in the present invention, work-ing life is up to more than 6 months.Owing to do not contain high valence chrome etc. in the electrolytic solution environment is not produced the metal ion of severe contamination, advantage long-acting, environmental protection that electrolytic solution long service life, so electrolytic solution in addition has.
4, treatment process of the present invention is to no particular requirements such as the material of magnesium or magnesium alloy, shape, sizes; Every magnesium or magnesium alloy that is immersed in the electrolytic solution; Differential arc oxidation all can obtain even, fine and close ceramic membrane on the surface after handling, so this technology has good versatility.
Below in conjunction with accompanying drawing and embodiment, technical scheme of the present invention is done further detailed description.
Description of drawings
Fig. 1 is the outside drawing of ordinary magnesium alloy.
Fig. 2 is the outside drawing of the magnesium alloy after the embodiment of the invention 1 differential arc oxidation is handled.
Fig. 3 is the outside drawing of ordinary magnesium alloy behind neutral NaCl salt air corrosion 480h.
Fig. 4 is the outside drawing of magnesium alloy behind neutral NaCl salt air corrosion 480h after the embodiment of the invention 1 differential arc oxidation is handled.
Fig. 5 carries out Scanning Probe Microscopy (AFM) photo of the ceramic membrane surface pattern of the magnesium alloy that differential arc oxidation handles for adopting the traditional silicon acid salt solution.
Fig. 6 carries out Scanning Probe Microscopy (AFM) photo of the ceramic membrane surface pattern of the magnesium alloy that differential arc oxidation handles for adopting the conventional aluminum acid salt solution.
Fig. 7 is Scanning Probe Microscopy (AFM) photo of the ceramic membrane surface pattern of the magnesium alloy after the embodiment of the invention 1 differential arc oxidation is handled.
Fig. 8 is the X-ray diffracting spectrum of the magnesium alloy ceramic membrane after the embodiment of the invention 1 differential arc oxidation is handled.
Embodiment
Embodiment 1
Step 1, with water solvent preparation zirconates system solution; Contain zirconates 15g in every liter of zirconates system solution; Sodium hexametaphosphate 99 10g; Water glass 3g; Sodium Fluoride 4g, glycerine 12mL, ammoniacal liquor 8mL; The pH value of regulating the zirconates system solution is 7～8, then the zirconates system solution is placed electrolyzer to leave standstill behind the 24h as electrolytic solution; Said zirconates is the acetic acid zirconium;
Step 2, place the said electrolytic solution of step 1 as anode in pending magnesium alloy; Stainless steel plate is as negative electrode; The temperature of control electrolytic solution is 10 ℃; Setting mao power source (direct current pulse power source) is the constant voltage mode of operation, and the regulating impulse frequency is 600Hz, and dutycycle is 20%; Be that constant voltage is handled 10min under the condition of 280V at voltage; Then voltage is increased to 400V, constant voltage is handled 30min, promptly at even, the fine and close ZrO of Mg alloy surface growth in situ one deck
2Composite ceramic film.
Fig. 1 is the outside drawing of ordinary magnesium alloy, and as can be seen from the figure, the ordinary magnesium alloy surface has metalluster; Fig. 2 is the outside drawing of the magnesium alloy after the present embodiment differential arc oxidation is handled, and the Mg alloy surface metalluster after as can be seen from the figure the present embodiment differential arc oxidation is handled disappears, and the ceramic membrane color and luster is even; Fig. 3 is the outside drawing of ordinary magnesium alloy behind neutral NaCl salt air corrosion 480h, from figure, can find out that ordinary magnesium alloy (Fig. 3) behind neutral NaCl salt air corrosion 480h, serious corrosion takes place, and the surface exists a large amount of corrosion dells and linen corrosion product; Fig. 4 is the outside drawing of magnesium alloy behind neutral NaCl salt air corrosion 480h after the present embodiment differential arc oxidation is handled; Can find out that from figure magnesium alloy after the present embodiment differential arc oxidation is handled is behind neutral NaCl salt air corrosion 480h; The ceramic coating formed by micro-arc oxidation of sample surfaces with the corrosion before compare; No considerable change; Do not find signs of corrosion, this shows that the corrosion resistance of magnesium alloy behind the present embodiment differential arc oxidation increases substantially.
Fig. 6 adopts the conventional aluminum acid salt solution to carry out Scanning Probe Microscopy (AFM) photo of the ceramic membrane surface pattern of the magnesium alloy that differential arc oxidation handles; As can be seen from the figure; The ceramic membrane growth of magnesium alloy thickens prolongs the vertical surface direction; Similar " mountain peak shape " pattern is arranged; Because the such growth pattern of ceramic membrane can not produce retardation effectively to corrosive medium; Corrosive medium solution arrives the interface of ceramic membrane and magnesium alloy substrate through the gap between " mountain peak "; And then to magnesium alloy substrate generation corrosion, therefore unfavorable to solidity to corrosion; Fig. 7 is Scanning Probe Microscopy (AFM) photo of the ceramic membrane surface pattern of the magnesium alloy after the present embodiment differential arc oxidation is handled; As can be seen from the figure; Ceramic membrane does not have tangible mountain peak shape pattern; On the contrary; Texture with lateral extension; In growth, can react the duct to other and produce the covering sealing process, this growth pattern helps corrosive medium is produced effectively laterally retardance, and matrix is had the better protection effect; Fig. 5 adopts the traditional silicon acid salt solution to carry out Scanning Probe Microscopy (AFM) photo of the ceramic membrane surface pattern of the magnesium alloy that differential arc oxidation handles; As can be seen from the figure; The ceramic membrane pattern is between the two above-mentioned; Existing horizontal texture; The pattern that part mountain peak shape is arranged again, thus aspect the solidity to corrosion of ceramic membrane also the boundary between above-mentioned two kinds of ceramic membranes.
Fig. 8 is the X-ray diffracting spectrum of the magnesium alloy ceramic membrane after the present embodiment differential arc oxidation is handled, as can be seen from the figure, and the Mg alloy surface ZrO of present embodiment preparation
2There is ZrO in composite ceramic film in the XRD diffraction peak
2, MgF
2, and (Mg
2Zr
5O
12) zirconium white magnesium phase, ceramic membrane is mainly by ZrO
2Phase composite, (Mg
2Zr
5O
12) molecular formula i.e. (MgO) of zirconium white magnesium phase
2(ZrO
2)
5, this this material of explanation is by MgO and ZrO
2According to the compound that 2: 5 ratios are formed, this is illustrated in the Zr element that adds in the solution complex reaction through differential arc oxidation and has got in the rete, and the excellent properties of further having verified ceramic membrane is to come from ZrO
2Characteristic.
Present embodiment makes in the magnesium alloy differential arc oxidation ceramic membrane of preparing and contains ZrO through in electrolytic solution, adding the Zr element
2Composite ceramics, to improve the solidity to corrosion of ceramic membrane, the ceramic membrane of preparation is not when carrying out the sealing of hole aftertreatment, and anti-neutral NaCl salt air corrosion reaches more than the 400h, and microhardness can reach more than the 1000HV.
Embodiment 2
The preparation method of present embodiment is identical with embodiment 1, and wherein difference is: said zirconates is zirconium hydroxide, zirconium carbonate, zirconium ammonium fluoride or zirconium silicate.
Present embodiment makes in the magnesium alloy differential arc oxidation ceramic membrane of preparing and contains ZrO through in electrolytic solution, adding the Zr element
2Composite ceramics, to improve the solidity to corrosion of ceramic membrane, the ceramic membrane of preparation is not when carrying out the sealing of hole aftertreatment, and anti-neutral NaCl salt air corrosion reaches more than the 400h, and microhardness can reach more than the 1000HV.
Embodiment 3
Step 1, with water solvent preparation zirconates system solution; Contain zirconates 12g in every liter of zirconates system solution; Sodium hexametaphosphate 99 12g; Water glass 5g; Sodium Fluoride 2g, glycerine 10mL, ammoniacal liquor 8mL; The pH value of regulating the zirconates system solution is 9～10, then the zirconates system solution is placed electrolyzer to leave standstill behind the 20h as electrolytic solution; Said zirconates is a zirconium hydroxide;
Step 2, place the said electrolytic solution of step 1 as anode in pending magnesium; Stainless steel plate is as negative electrode; The temperature of control electrolytic solution is 35 ℃; Setting mao power source (direct current pulse power source) is the constant voltage mode of operation, and the regulating impulse frequency is 500Hz, and dutycycle is 10%; Be that constant voltage is handled 20min under the condition of 250V at voltage; Then voltage is increased to 400V, constant voltage is handled 20min, promptly at even, the fine and close ZrO of magnesium surface growth in situ one deck
2Composite ceramic film.
Present embodiment makes in the magnesium ceramic coating formed by micro-arc oxidation of preparing and contains ZrO through in electrolytic solution, adding the Zr element
2Composite ceramics, to improve the solidity to corrosion of ceramic membrane, the ceramic membrane of preparation is not when carrying out the sealing of hole aftertreatment, and anti-neutral NaCl salt air corrosion reaches more than the 400h, and microhardness can reach more than the 1000HV.
Embodiment 4
The preparation method of present embodiment is identical with embodiment 3, and wherein difference is: said zirconates is acetic acid zirconium, zirconium carbonate, zirconium ammonium fluoride or zirconium silicate.
Present embodiment makes in the magnesium alloy differential arc oxidation ceramic membrane of preparing and contains ZrO through in electrolytic solution, adding the Zr element
2Composite ceramics, to improve the solidity to corrosion of ceramic membrane, the ceramic membrane of preparation is not when carrying out the sealing of hole aftertreatment, and anti-neutral NaCl salt air corrosion reaches more than the 400h, and microhardness can reach more than the 1000HV.
Embodiment 5
Step 1, with water solvent preparation zirconates system solution; Contain zirconates 20g in every liter of zirconates system solution; Sodium hexametaphosphate 99 12g; Water glass 2g; Sodium Fluoride 5g, glycerine 10mL, ammoniacal liquor 8mL; The pH value of regulating the zirconates system solution is 5～6, then the zirconates system solution is placed electrolyzer to leave standstill behind the 24h as electrolytic solution; Said zirconates is a zirconium carbonate;
Step 2, place the said electrolytic solution of step 1 as anode in pending magnesium; Stainless steel plate is as negative electrode; The temperature of control electrolytic solution is 25 ℃; Setting mao power source (direct current pulse power source) is the constant voltage mode of operation, and the regulating impulse frequency is 700Hz, and dutycycle is 30%; Be that constant voltage is handled 30min under the condition of 300V at voltage; Then voltage is increased to 450V, constant voltage is handled 20min, promptly at even, the fine and close ZrO of magnesium surface growth in situ one deck
2Composite ceramic film.
Present embodiment makes in the magnesium ceramic coating formed by micro-arc oxidation of preparing and contains ZrO through in electrolytic solution, adding the Zr element
2Composite ceramics, to improve the solidity to corrosion of ceramic membrane, the ceramic membrane of preparation is not when carrying out the sealing of hole aftertreatment, and anti-neutral NaCl salt air corrosion reaches more than the 400h, and microhardness can reach more than the 1000HV.
Embodiment 6
The preparation method of present embodiment is identical with embodiment 5, and wherein difference is: said zirconates is acetic acid zirconium, zirconium hydroxide, zirconium ammonium fluoride or zirconium silicate.
Present embodiment makes in the magnesium alloy differential arc oxidation ceramic membrane of preparing and contains ZrO through in electrolytic solution, adding the Zr element
2Composite ceramics, to improve the solidity to corrosion of ceramic membrane, the ceramic membrane of preparation is not when carrying out the sealing of hole aftertreatment, and anti-neutral NaCl salt air corrosion reaches more than the 400h, and microhardness can reach more than the 1000HV.
Embodiment 7
Step 1, with water solvent preparation zirconates system solution; Contain zirconates 5g in every liter of zirconates system solution; Sodium hexametaphosphate 99 5g; Water glass 2g; Sodium Fluoride 1g, glycerine 5mL, ammoniacal liquor 2mL; The pH value of regulating the zirconates system solution is 9～10, then the zirconates system solution is placed electrolyzer to leave standstill behind the 10h as electrolytic solution; Said zirconates is a zirconium silicate;
Step 2, place the said electrolytic solution of step 1 as anode in pending magnesium; Stainless steel plate is as negative electrode; The temperature of control electrolytic solution is 20 ℃; Setting mao power source (direct current pulse power source) is the constant voltage mode of operation, and the regulating impulse frequency is 1000Hz, and dutycycle is 45%; Be that constant voltage is handled 20min under the condition of 280V at voltage; Then voltage is increased to 420V, constant voltage is handled 40min, promptly at even, the fine and close ZrO of magnesium surface growth in situ one deck
2Composite ceramic film.
Present embodiment makes in the magnesium ceramic coating formed by micro-arc oxidation of preparing and contains ZrO through in electrolytic solution, adding the Zr element
2Composite ceramics, to improve the solidity to corrosion of ceramic membrane, the ceramic membrane of preparation is not when carrying out the sealing of hole aftertreatment, and anti-neutral NaCl salt air corrosion reaches more than the 400h, and microhardness can reach more than the 1000HV.
Embodiment 8
The preparation method of present embodiment is identical with embodiment 7, and wherein difference is: said zirconates is acetic acid zirconium, zirconium hydroxide, zirconium carbonate or zirconium ammonium fluoride.
Present embodiment makes in the magnesium alloy differential arc oxidation ceramic membrane of preparing and contains ZrO through in electrolytic solution, adding the Zr element
2Composite ceramics, to improve the solidity to corrosion of ceramic membrane, the ceramic membrane of preparation is not when carrying out the sealing of hole aftertreatment, and anti-neutral NaCl salt air corrosion reaches more than the 400h, and microhardness can reach more than the 1000HV.
Embodiment 9
Step 1, with water solvent preparation zirconates system solution; Contain zirconates 30g in every liter of zirconates system solution; Sodium hexametaphosphate 99 20g; Water glass 10g; Sodium Fluoride 15g, glycerine 30mL, ammoniacal liquor 10mL; The pH value of regulating the zirconates system solution is 4～5, then the zirconates system solution is placed electrolyzer to leave standstill behind the 30h as electrolytic solution; Said zirconates is a zirconium ammonium fluoride;
Step 2, place the said electrolytic solution of step 1 as anode in pending magnesium alloy; Stainless steel plate is as negative electrode; The temperature of control electrolytic solution is 10 ℃; Setting mao power source (direct current pulse power source) is the constant voltage mode of operation, and the regulating impulse frequency is 300Hz, and dutycycle is 5%; Be that constant voltage is handled 30min under the condition of 300V at voltage; The 450V that then voltage raise, constant voltage is handled 30min, promptly at even, the fine and close ZrO of Mg alloy surface growth in situ one deck
2Composite ceramic film.
Present embodiment makes in the magnesium alloy differential arc oxidation ceramic membrane of preparing and contains ZrO through in electrolytic solution, adding the Zr element
2Composite ceramics, to improve the solidity to corrosion of ceramic membrane, the ceramic membrane of preparation is not when carrying out the sealing of hole aftertreatment, and anti-neutral NaCl salt air corrosion reaches more than the 400h, and microhardness can reach more than the 1000HV.
Embodiment 10
The preparation method of present embodiment is identical with embodiment 9, and wherein difference is: said zirconates is acetic acid zirconium, zirconium hydroxide, zirconium carbonate or zirconium silicate.
Present embodiment makes in the magnesium alloy differential arc oxidation ceramic membrane of preparing and contains ZrO through in electrolytic solution, adding the Zr element
2Composite ceramics, to improve the solidity to corrosion of ceramic membrane, the ceramic membrane of preparation is not when carrying out the sealing of hole aftertreatment, and anti-neutral NaCl salt air corrosion reaches more than the 400h, and microhardness can reach more than the 1000HV.
Embodiment 11
Step 1, with water solvent preparation zirconates system solution; Contain zirconates 15g in every liter of zirconates system solution; Sodium hexametaphosphate 99 30g; Water glass 6g; Sodium Fluoride 30g, glycerine 20mL, ammoniacal liquor 6mL; The pH value of regulating the zirconates system solution is 11～12, then the zirconates system solution is placed electrolyzer to leave standstill behind the 5h as electrolytic solution; Said zirconates is a zirconium carbonate;
Step 2, place the said electrolytic solution of step 1 as anode in pending magnesium alloy; Stainless steel plate is as negative electrode; The temperature of control electrolytic solution is 30 ℃; Setting mao power source (direct current pulse power source) is the constant voltage mode of operation, and the regulating impulse frequency is 600Hz, and dutycycle is 25%; Be that constant voltage is handled 10min under the condition of 300V at voltage; Then voltage is increased to 400V, constant voltage is handled 60min, promptly at even, the fine and close ZrO of Mg alloy surface growth in situ one deck
2Composite ceramic film.
Present embodiment makes in the magnesium alloy differential arc oxidation ceramic membrane of preparing and contains ZrO through in electrolytic solution, adding the Zr element
2Composite ceramics, to improve the solidity to corrosion of ceramic membrane, the ceramic membrane of preparation is not when carrying out the sealing of hole aftertreatment, and anti-neutral NaCl salt air corrosion reaches more than the 400h, and microhardness can reach more than the 1000HV.
The preparation method of present embodiment is identical with embodiment 11, and wherein difference is: said zirconates is acetic acid zirconium, zirconium hydroxide, zirconium ammonium fluoride or zirconium silicate.
Present embodiment makes in the magnesium alloy differential arc oxidation ceramic membrane of preparing and contains ZrO through in electrolytic solution, adding the Zr element
2Composite ceramics, to improve the solidity to corrosion of ceramic membrane, the ceramic membrane of preparation is not when carrying out the sealing of hole aftertreatment, and anti-neutral NaCl salt air corrosion reaches more than the 400h, and microhardness can reach more than the 1000HV.
The above; It only is preferred embodiment of the present invention; Be not that the present invention is done any restriction, every according to inventing technical spirit to any simple modification, change and equivalent structure variation that above embodiment did, all still belong in the protection domain of technical scheme of the present invention.
Claims (5)
1. magnesium and magnesium alloy surface micro-arc oxidation prepare ZrO
2The method of composite ceramic film is characterized in that, this method may further comprise the steps:
Step 1, with water solvent preparation zirconates system solution; Contain zirconates 5g～30g in every liter of zirconates system solution; Sodium hexametaphosphate 99 5g～30g; Water glass 2g～10g; Sodium Fluoride 1g～30g, glycerine 5mL～30mL, ammoniacal liquor 2mL～10mL; The pH value of regulating the zirconates system solution is 4～12, then the zirconates system solution is placed electrolyzer to leave standstill the back as electrolytic solution;
Step 2, place the said electrolytic solution of step 1 as anode in pending magnesium or magnesium alloy; Stainless steel plate is as negative electrode; The temperature of control electrolytic solution is 10 ℃～35 ℃; Setting mao power source is the constant voltage mode of operation; The regulating impulse frequency is 300Hz～1000Hz; Dutycycle is 5%～45%; Be that constant voltage is handled 10min～30min under the condition of 250V～300V at voltage; Then voltage is increased to 400V～450V constant voltage and handles 20min～60min, promptly at the ZrO of magnesium or Mg alloy surface growth in situ one deck even compact
2Composite ceramic film.
2. magnesium according to claim 1 and magnesium alloy surface micro-arc oxidation prepare ZrO
2The method of composite ceramic film is characterized in that, zirconates described in the step 1 is acetic acid zirconium, zirconium hydroxide, zirconium carbonate, zirconium ammonium fluoride or zirconium silicate.
3. magnesium according to claim 1 and magnesium alloy surface micro-arc oxidation prepare ZrO
2The method of composite ceramic film is characterized in that, mao power source described in the step 2 is a direct current pulse power source.
4. magnesium according to claim 1 and magnesium alloy surface micro-arc oxidation prepare ZrO
2The method of composite ceramic film is characterized in that, pulse-repetition described in the step 2 is 500Hz～700Hz.
5. magnesium according to claim 1 and magnesium alloy surface micro-arc oxidation prepare ZrO
2The method of composite ceramic film is characterized in that, dutycycle described in the step 2 is 10%～30%.
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| CN112899664B (en) * | 2021-01-27 | 2022-08-02 | 太原科技大学 | Magnesium alloy surface zirconia-based film and preparation method thereof |
| CN113089053A (en) * | 2021-03-29 | 2021-07-09 | 长安大学 | ZrO on magnesium alloy2MgO wear-resistant film layer and preparation method thereof |
| CN113089053B (en) * | 2021-03-29 | 2022-05-31 | 长安大学 | ZrO on magnesium alloy2MgO wear-resistant film layer and preparation method thereof |
| CN115418697A (en) * | 2022-09-23 | 2022-12-02 | 西北有色金属研究院 | Environment-friendly electrolyte for preparing corrosion-resistant coating with high compact structure on surface of magnesium alloy and application of environment-friendly electrolyte |
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