CN103726059A - Preparation method of magnesium alloy surface composite film - Google Patents
Preparation method of magnesium alloy surface composite film Download PDFInfo
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- CN103726059A CN103726059A CN201310747008.XA CN201310747008A CN103726059A CN 103726059 A CN103726059 A CN 103726059A CN 201310747008 A CN201310747008 A CN 201310747008A CN 103726059 A CN103726059 A CN 103726059A
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- phosphate
- conversion
- magnesium alloy
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- phosphate conversion
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 86
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 63
- 239000010452 phosphate Substances 0.000 claims abstract description 63
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 62
- 238000000151 deposition Methods 0.000 claims abstract description 43
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 40
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 23
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000011282 treatment Methods 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 24
- 238000012545 processing Methods 0.000 claims description 24
- 239000012528 membrane Substances 0.000 claims description 21
- 238000005229 chemical vapour deposition Methods 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 150000002696 manganese Chemical class 0.000 claims description 16
- 238000005498 polishing Methods 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 13
- 150000003016 phosphoric acids Chemical class 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 12
- 239000013049 sediment Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical group [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 claims description 6
- 238000005282 brightening Methods 0.000 claims description 6
- 239000001506 calcium phosphate Substances 0.000 claims description 6
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 6
- 235000011010 calcium phosphates Nutrition 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910003460 diamond Inorganic materials 0.000 claims description 6
- 239000010432 diamond Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 238000005488 sandblasting Methods 0.000 claims description 6
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 239000007792 gaseous phase Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 abstract description 6
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 description 17
- 230000007797 corrosion Effects 0.000 description 17
- 238000005516 engineering process Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000013532 laser treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Abstract
The invention provides a preparation method of a magnesium alloy surface composite film, which comprises the following steps in sequence: step [1] carrying out phosphate conversion treatment on the surface of the magnesium alloy to form a layer of phosphate conversion film on the surface of the magnesium alloy; step [2] depositing a silicon dioxide layer on the surface of the phosphate conversion film of the magnesium alloy treated in the step [1] by adopting a plasma enhanced chemical vapor deposition method; and (3) depositing a silicon nitride layer on the surface of the silicon dioxide layer of the magnesium alloy treated in the step (2) by adopting a plasma enhanced chemical vapor deposition method. The silicon dioxide layer deposited on the phosphate conversion film base layer can be planted in micropores uniformly distributed on the phosphate conversion film base layer to grow, so that the effective combination of the phosphate conversion film base layer and the silicon dioxide layer is promoted, the silicon dioxide layer is favorable for the growth of a plasma enhanced chemical vapor deposition silicon nitride layer, and the silicon nitride layer has good oxidation resistance and insulating property.
Description
Technical field
The present invention relates to alloy surface processing technology field, particularly a kind of preparation method of magnesium alloy phosphate basic unit/silicon dioxide/silicon nitride composite membrane.
Background technology
The density of magnesium alloy is approximately 2/3rds of aluminium alloy density, is 1/4th of iron and steel density, however its intensity but apparently higher than aluminium alloy and steel, rigidity is also suitable with aluminium alloy and steel higher than engineering plastics far away.Current, resource and environment has become the matter of utmost importance of human kind sustainable development, and magnesium alloy is as the lightest structural metallic materials, has unique advantage aspect energy-saving and emission-reduction; And there are excellent properties such as good heat conduction, damping, electromagnetic shielding, in fields such as traffic, telecommunications, aerospace, defence and militaries, there is extremely wide application prospect, and can also recycling, be therefore described as " 21 century green engineering material ".Yet, because the chemical property of magnesium is active, electropotential very low (2.73V), and the oxide film forming is thinner, especially under moist environment, cause magnesium alloy very easily to suffer corrosion failure when application, etching problem is seriously restricting the exploitation of magnesium alloy and is applying.
The corrosion of magnesium alloy in most cases belongs to local corrosion, experiment showed, generally, and pure magnesium belongs to transgranular corrosion, and magnesium alloy is uniform corrosion.Its form of corrosion mainly contains: spot corrosion, galvanic corrosion, stress corrosion crack and high temperature corrosion.
Magnesium alloy surface in air can generate oxide film, but this oxide film can not effectively protect matrix, avoids corrosion, need to form by effects on surface conversion processing protective membrane or the coating of one deck densification, to reach the object that improves erosion resistance.At present, magnesium alloy corrosion-resistant treatments is mainly divided into surface modification and surface conversion treatment.Surface modification treatment is between metallic surface and external environment, to prepare Corrosion Resistant Film to strengthen erosion resistance, and more general surface modification has at present: ion implantation technique, laser treatment technique, physical gas phase deposition technology and chemical vapour deposition technique.Conversion Coating Technology is the effective ways that improve corrosion stability of magnesium alloy energy; Yet this technology is not used widely so far, mainly contains reason and be: 1, the erosion resistance of single conversion rete cannot reach engineering service requirements.2, transform film surface and have more tiny crack with inner, for corrosive medium provides passage, resistance to corrosion declines.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of preparation method of Mg alloy surface composite membrane, it makes up the deficiency of single treatment process by compound treatment process, strengthens use properties, the especially resistance to corrosion of magnesium alloy.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method of Mg alloy surface composite membrane, comprises the following steps of carrying out in order:
Step [1] is carried out phosphate conversion processing by Mg alloy surface, at Mg alloy surface, forms one deck phosphate conversion film;
Step [2] using plasma strengthens chemical gaseous phase depositing process at the phosphate conversion film surface deposition layer of silicon dioxide layer of magnesium alloy after step [1] is processed;
Step [3] using plasma strengthens chemical gaseous phase depositing process at silicon dioxide layer surface deposition one deck silicon nitride layer of magnesium alloy after step [2] is processed.
Further, the described phosphate conversion treatment step of step [1] is: first magnesium alloy sample is roughly ground to 1000 object waterproof abrasive papers with 600 orders, then use 1500 orders to 2000 object waterproof abrasive paper fine grindings, with the diamond paste of w1.0, add assisting of dehydrated alcohol and on polishing flannelet, be polished to surface-brightening no marking, then use successively acetone, dehydrated alcohol, deionized water ultrasonic cleaning 10～20 minutes, use afterwards hot blast drying, carry out again sandblasting 3 minutes to remove surface film oxide, increase surfaceness, finally by phosphoric acid salt, manganese salt, in the aqueous solution that phosphoric acid forms, carry out described phosphate conversion processing.
Further, the mixture that the potassium primary phosphate that described phosphoric acid salt is 1:1:1 by mass ratio, calcium phosphate and barium phosphate form, the mixture that the manganous carbonate that described manganese salt is 1:1 by mass ratio and potassium permanganate form.
Further, it is 80～200g/L that described phosphate conversion is processed phosphate concn described in conversion treating solution used, and the concentration of described manganese salt is 30～50g/L, and the pH of conversion treating solution is 3～5.
Further, in described phosphate conversion treating processes, conversion processing temperature is 40～50 ℃, and the conversion processing time is 15～40 minutes, and conversion processing process adopts constant temperature blender with magnetic force to carry out auxiliary treatment.
Further, the concrete operation step of described step [2] is: the magnesium alloy sample after phosphate conversion is processed is put into the sediment chamber of plasma reinforced chemical vapour deposition equipment, system is evacuated to 5 * 10
-4～1 * 10
-5pa, with SiH
4, CO
2and N
2the gas mixture of O is reactant gas source, SiH
4flow be 30～60sccm, CO
2flow be 20～30sccm, N
2the flow of O is 20～30sccm, and depositing temperature is 150～300 ℃, and radio frequency power is 80～120W, and depositing time is 20～40 minutes, on the surface of phosphate conversion film, makes described silicon dioxide layer after cooling.
Further, the concrete operation step of described step [3] is: the magnesium alloy sample after deposition of silica layer is put into the sediment chamber of plasma reinforced chemical vapour deposition equipment, system is evacuated to 5 * 10
-4～1 * 10
-5pa, with SiH
4, N
2and NH
3gas mixture be reactant gas source, SiH
4flow be 90～120sccm, N
2flow be 1～20sccm, NH
3flow be 100～200sccm, depositing temperature is 200～300 ℃, radio frequency power is 70～110W, depositing time is 50～75 minutes, just on the surface of silica coating, makes silicon nitride layer after cooling.
Positively effect of the present invention: in the present invention, phosphate conversion is processed and has been used the auxiliary of magnetic field, utilized MHD effect herein, the bubble hydrogen forming process that can regulate reaction interface ion transport and reaction to generate, has to form the phosphate conversion film basic unit that is uniformly distributed microporosity.Plasma enhanced chemical vapor deposition technology utilizes high-frequency electric field make low temperature, low pressure reaction ionization of gas form plasma body and carry out chemical vapour deposition, even so the very low substrate that makes of temperature of reaction under room temperature, also can deposit.The major advantage of plasma enhanced chemical vapor deposition technology has: substrate heating temperature is low, good process repeatability, and the film of deposition is even, and the defect concentration of film is little, can in same equipment reactor, complete the deposition of different thickness film.In phosphate conversion film basic unit, utilizing the silicon dioxide layer of plasma enhanced chemical vapor deposition can be planted in the equally distributed microporosity of phosphate conversion film basic unit grows, promoted effective combination of phosphate conversion film basic unit and silicon dioxide layer, silicon dioxide layer is conducive to the growth of pecvd silicon nitride layer, and silicon nitride layer has good oxidation-resistance and insulating property, there is the good sodium ion that stops simultaneously, the ability of barrier metal ion and chlorion diffusion, can realize the preparation of magnesium alloy phosphate basic unit/silicon dioxide/silicon nitride composite membrane of excellent combination property.
Accompanying drawing explanation
Fig. 1 is the surperficial SEM experimental result of AZ91D magnesium alloy phosphate conversion film.
Fig. 2 is the section S EM experimental result that AZ91D magnesium alloy phosphate transforms rete.
Fig. 3 is the surperficial SEM experimental result of AZ91D magnesium alloy phosphate basic unit/silicon dioxide/silicon nitride composite membrane.
Fig. 4 is the section S EM experimental result of AZ91D magnesium alloy phosphate basic unit/silicon dioxide/silicon nitride composite membrane.
Fig. 5 is the schematic diagram of AZ91D magnesium alloy phosphate basic unit/silicon dioxide/silicon nitride composite membrane.
Embodiment
Below in conjunction with accompanying drawing to a preferred embodiment of the present invention will be described in detail.
Concrete enforcement selected AZ91D magnesium alloy, represents that this magnesium alloy contains 9% aluminium element and closes 1% zinc element.
Embodiment 1
1) polishing of AZ91D magnesium alloy sample to first be roughly ground to 1000 object waterproof abrasive papers with 600 orders, then use 1500 orders to 2000 order waterproof abrasive paper fine grindings.Polishing will add with the diamond paste of w1.0 assisting of dehydrated alcohol and on polishing flannelet, proceed to surface-brightening no marking.Then use successively acetone, dehydrated alcohol, deionized water ultrasonic cleaning 10～20 minutes.After use hot blast drying, then carry out sandblasting 3 minutes.
2) then carry out conversion processing, conversion treating solution comprises that concentration is the phosphoric acid salt of 90g/L and the manganese salt that concentration is 30g/L, the mixture of the potassium primary phosphate of described phosphoric acid salt 1:1:1, calcium phosphate and barium phosphate, described manganese salt is that mass ratio is the potassium permanganate of 1:1 and the mixture of manganous carbonate, conversion processing process adopts constant temperature blender with magnetic force to carry out auxiliary treatment, the pH value of conversion treating solution is 4, and temperature is 45 ℃, and the conversion processing time is 25 minutes.
The surface of the AZ91D magnesium alloy phosphate conversion film of process phosphatizing treatment and section S EM experimental result are respectively as depicted in figs. 1 and 2, wherein in Fig. 2, there is AZ91D magnesium alloy substrate layer 201, phosphate conversion layer 202, for the fixing conduction heat of sample, inlay resin 203, can find out that simple phosphate conversion film thicknesses of layers is inhomogeneous, and longitudinal crack is more, even there is the discontinuous of rete.
3) magnesium alloy sample after phosphate conversion is processed is put into the sediment chamber of plasma reinforced chemical vapour deposition equipment, system is evacuated to 5 * 10
-4～1 * 10
-5pa, with SiH
4, CO
2and N
2the gas mixture of O is reactant gas source, SiH
4flow be 50sccm, CO
2flow be 30sccm, N
2the flow of O is 30sccm, and depositing temperature is 180 ℃, and radio frequency power is 90W, and depositing time is 30 minutes, on the surface of phosphate conversion film, makes described silicon dioxide layer after cooling.
4) magnesium alloy sample after deposition of silica layer is put into the sediment chamber of plasma reinforced chemical vapour deposition equipment, system is evacuated to 5 * 10
-4～1 * 10
-5pa, with SiH
4, N
2and NH
3gas mixture be reactant gas source, SiH
4flow be 100sccm, N
2flow be 20sccm, NH
3flow be 150sccm, depositing temperature is 250 ℃, radio frequency power is 80W, depositing time is 60 minutes, just on the surface of silica coating, makes silicon nitride layer after cooling.
The surface of the AZ91D magnesium alloy phosphate basic unit/silicon dioxide/silicon nitride composite membrane so far making and section S EM experimental result are respectively as shown in Figure 3 and Figure 4, wherein in Fig. 4, obviously there is phosphate conversion basic unit 401, plasma reinforced chemical vapour deposition silicon dioxide layer 402, plasma reinforced chemical vapour deposition silicon nitride layer 403, the hole that when although there is plasma reinforced chemical vapour deposition on its surface as seen from the figure, air-flow is advertised out, but the crackle of film surface obviously reduces, and crack size reduce also very remarkable.Phosphoric acid salt basic unit/silicon dioxide/silicon nitride composite membrane of having prepared to combine closely with magnesium alloy substrate through twice plasma reinforced chemical vapour deposition, can strengthen the resistance to corrosion of magnesium alloy substrate effectively.
Fig. 5 is the structural representation of AZ91D magnesium alloy phosphate basic unit/silicon dioxide/silicon nitride composite membrane of preparation, and the sample product of preparing through the method for the invention as seen from the figure comprises AZ91D magnesium alloy substrate 501, phosphate conversion basic unit 502, plasma reinforced chemical vapour deposition silicon dioxide layer 503, plasma reinforced chemical vapour deposition silicon nitride layer 504.
Embodiment 2
1) polishing of AZ91D magnesium alloy sample to first be roughly ground to 1000 object waterproof abrasive papers with 600 orders, then use 1500 orders to 2000 order waterproof abrasive paper fine grindings.Polishing will add with the diamond paste of w1.0 assisting of dehydrated alcohol and on polishing flannelet, proceed to surface-brightening no marking.Then use successively acetone, dehydrated alcohol, deionized water ultrasonic cleaning 10～20 minutes.After use hot blast drying, then carry out sandblasting 3 minutes.
2) then carry out conversion processing, conversion treating solution comprises that concentration is the phosphoric acid salt of 120g/L and the manganese salt that concentration is 40g/L, the mixture of the potassium primary phosphate of described phosphoric acid salt 1:1:1, calcium phosphate and barium phosphate, described manganese salt is that mass ratio is the potassium permanganate of 1:1 and the mixture of manganous carbonate, conversion processing process adopts constant temperature blender with magnetic force to carry out auxiliary treatment, the pH value of conversion treating solution is 4, and temperature is 45 ℃, and the conversion processing time is 25 minutes.
3) magnesium alloy sample after phosphate conversion is processed is put into the sediment chamber of plasma reinforced chemical vapour deposition equipment, system is evacuated to 5 * 10
-4～1 * 10
-5pa, with SiH
4, CO
2and N
2the gas mixture of O is reactant gas source, SiH
4flow be 50sccm, CO
2flow be 30sccm, N
2the flow of O is 30sccm, and depositing temperature is 180 ℃, and radio frequency power is 90W, and depositing time is 30 minutes, on the surface of phosphate conversion film, makes described silicon dioxide layer after cooling.
4) magnesium alloy sample after deposition of silica layer is put into the sediment chamber of plasma reinforced chemical vapour deposition equipment, system is evacuated to 5 * 10
-4～1 * 10
-5pa, with SiH
4, N
2and NH
3gas mixture be reactant gas source, SiH
4flow be 100sccm, N
2flow be 20sccm, NH
3flow be 150sccm, depositing temperature is 250 ℃, radio frequency power is 80W, depositing time is 60 minutes, just on the surface of silica coating, makes silicon nitride layer after cooling.
Embodiment 3
1) polishing of AZ91D magnesium alloy sample to first be roughly ground to 1000 object waterproof abrasive papers with 600 orders, then use 1500 orders to 2000 order waterproof abrasive paper fine grindings.Polishing will add with the diamond paste of w1.0 assisting of dehydrated alcohol and on polishing flannelet, proceed to surface-brightening no marking.Then use successively acetone, dehydrated alcohol, deionized water ultrasonic cleaning 10～20 minutes.After use hot blast drying, then carry out sandblasting 3 minutes.
2) then carry out conversion processing, conversion treating solution comprises that concentration is the phosphoric acid salt of 150g/L and the manganese salt that concentration is 50g/L, the mixture of the potassium primary phosphate of described phosphoric acid salt 1:1:1, calcium phosphate and barium phosphate, described manganese salt is that mass ratio is the potassium permanganate of 1:1 and the mixture of manganous carbonate, conversion processing process adopts constant temperature blender with magnetic force to carry out auxiliary treatment, the pH value of conversion treating solution is 4, and temperature is 45 ℃, and the conversion processing time is 25 minutes.
3) magnesium alloy sample after phosphate conversion is processed is put into the sediment chamber of plasma reinforced chemical vapour deposition equipment, system is evacuated to 5 * 10
-4～1 * 10
-5pa, with SiH
4, CO
2and N
2the gas mixture of O is reactant gas source, SiH
4flow be 50sccm, CO
2flow be 30sccm, N
2the flow of O is 30sccm, and depositing temperature is 200 ℃, and radio frequency power is 90W, and depositing time is 40 minutes, on the surface of phosphate conversion film, makes described silicon dioxide layer after cooling.
4) magnesium alloy sample after deposition of silica layer is put into the sediment chamber of plasma reinforced chemical vapour deposition equipment, system is evacuated to 5 * 10
-4～1 * 10
-5pa, with SiH
4, N
2and NH
3gas mixture be reactant gas source, SiH
4flow be 100sccm, N
2flow be 20sccm, NH
3flow be 150sccm, depositing temperature is 300 ℃, radio frequency power is 80W, depositing time is 75 minutes, just on the surface of silica coating, makes silicon nitride layer after cooling.
Embodiment 4
1) polishing of AZ91D magnesium alloy sample to first be roughly ground to 1000 object waterproof abrasive papers with 600 orders, then use 1500 orders to 2000 order waterproof abrasive paper fine grindings.Polishing will add with the diamond paste of w1.0 assisting of dehydrated alcohol and on polishing flannelet, proceed to surface-brightening no marking.Then use successively acetone, dehydrated alcohol, deionized water ultrasonic cleaning 10～20 minutes.After use hot blast drying, then carry out sandblasting 3 minutes.
2) then carry out conversion processing, conversion treating solution comprises that concentration is the phosphoric acid salt of 150g/L and the manganese salt that concentration is 40g/L, the mixture of the potassium primary phosphate of described phosphoric acid salt 1:1:1, calcium phosphate and barium phosphate, described manganese salt is that mass ratio is the potassium permanganate of 1:1 and the mixture of manganous carbonate, conversion processing process adopts constant temperature blender with magnetic force to carry out auxiliary treatment, the pH value of conversion treating solution is 4, and temperature is 45 ℃, and the conversion processing time is 25 minutes.
3) magnesium alloy sample after phosphate conversion is processed is put into the sediment chamber of plasma reinforced chemical vapour deposition equipment, system is evacuated to 5 * 10
-4～1 * 10
-5pa, with SiH
4, CO
2and N
2the gas mixture of O is reactant gas source, SiH
4flow be 50sccm, CO
2flow be 30sccm, N
2the flow of O is 30sccm, and depositing temperature is 150 ℃, and radio frequency power is 90W, and depositing time is 40 minutes, on the surface of phosphate conversion film, makes described silicon dioxide layer after cooling.
4) magnesium alloy sample after deposition of silica layer is put into the sediment chamber of plasma reinforced chemical vapour deposition equipment, system is evacuated to 5 * 10
-4～1 * 10
-5pa, with SiH
4, N
2and NH
3gas mixture be reactant gas source, SiH
4flow be 100sccm, N
2flow be 20sccm, NH
3flow be 150sccm, depositing temperature is 250 ℃, radio frequency power is 80W, depositing time is 75 minutes, just on the surface of silica coating, makes silicon nitride layer after cooling.
Above-described is only the preferred embodiments of the present invention; institute is understood that; the explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof; the protection domain being not intended to limit the present invention; all any modifications of making, be equal to replacement etc., within protection scope of the present invention all should be included within thought of the present invention and principle.
Claims (9)
1. a preparation method for Mg alloy surface composite membrane, is characterized in that: comprise the following steps of carrying out in order:
Step [1] is carried out phosphate conversion processing by Mg alloy surface, at Mg alloy surface, forms one deck phosphate conversion film;
Step [2] using plasma strengthens chemical gaseous phase depositing process at the phosphate conversion film surface deposition layer of silicon dioxide layer of magnesium alloy after step [1] is processed;
Step [3] using plasma strengthens chemical gaseous phase depositing process at silicon dioxide layer surface deposition one deck silicon nitride layer of magnesium alloy after step [2] is processed.
2. the preparation method of a kind of Mg alloy surface composite membrane according to claim 1, it is characterized in that: the described phosphate conversion treatment step of step [1] is: first magnesium alloy sample is roughly ground to 1000 object waterproof abrasive papers with 600 orders, then use 1500 orders to 2000 object waterproof abrasive paper fine grindings, with the diamond paste of w1.0, add assisting of dehydrated alcohol and on polishing flannelet, be polished to surface-brightening no marking, then use successively acetone, dehydrated alcohol, deionized water ultrasonic cleaning 10～20 minutes, use afterwards hot blast drying, carry out again sandblasting 3 minutes to remove surface film oxide, increase surfaceness, finally by phosphoric acid salt, manganese salt, in the aqueous solution that phosphoric acid forms, carry out described phosphate conversion processing.
3. the preparation method of a kind of Mg alloy surface composite membrane according to claim 2, it is characterized in that: the mixture that the potassium primary phosphate that described phosphoric acid salt is 1:1:1 by mass ratio, calcium phosphate and barium phosphate form, the mixture that the manganous carbonate that described manganese salt is 1:1 by mass ratio and potassium permanganate form.
4. the preparation method of a kind of Mg alloy surface composite membrane according to claim 3, it is characterized in that: it is 80～200g/L that described phosphate conversion is processed phosphate concn described in conversion treating solution used, the concentration of described manganese salt is 30～50g/L, and the pH of conversion treating solution is 3～5.
5. the preparation method of a kind of Mg alloy surface composite membrane according to claim 4, it is characterized in that: it is 90g/L that described phosphate conversion is processed phosphate concn described in conversion treating solution used, the concentration of described manganese salt is 30g/L, and the pH of conversion treating solution is 4.
6. the preparation method of a kind of Mg alloy surface composite membrane according to claim 4, it is characterized in that: it is 120g/L that described phosphate conversion is processed phosphate concn described in conversion treating solution used, the concentration of described manganese salt is 40g/L, and the pH of conversion treating solution is 4.
7. the preparation method of a kind of Mg alloy surface composite membrane according to claim 4, it is characterized in that: in described phosphate conversion treating processes, conversion processing temperature is 40～50 ℃, the conversion processing time is 15～40 minutes, and conversion processing process adopts constant temperature blender with magnetic force to carry out auxiliary treatment.
8. the preparation method of a kind of Mg alloy surface composite membrane according to claim 1, it is characterized in that: the concrete operation step of described step [2] is: the magnesium alloy sample after phosphate conversion is processed is put into the sediment chamber of plasma reinforced chemical vapour deposition equipment, system is evacuated to 5 * 10
-4～1 * 10
-5pa, with SiH
4, CO
2and N
2the gas mixture of O is reactant gas source, SiH
4flow be 30～60sccm, CO
2flow be 20～30sccm, N
2the flow of O is 20～30sccm, and depositing temperature is 150～300 ℃, and radio frequency power is 80～120W, and depositing time is 20～40 minutes, on the surface of phosphate conversion film, makes described silicon dioxide layer after cooling.
9. the preparation method of a kind of Mg alloy surface composite membrane according to claim 1, it is characterized in that: the concrete operation step of described step [3] is: the magnesium alloy sample after deposition of silica layer is put into the sediment chamber of plasma reinforced chemical vapour deposition equipment, system is evacuated to 5 * 10
-4～1 * 10
-5pa, with SiH
4, N
2and NH
3gas mixture be reactant gas source, SiH
4flow be 90～120sccm, N
2flow be 1～20sccm, NH
3flow be 100～200sccm, depositing temperature is 200～300 ℃, radio frequency power is 70～110W, depositing time is 50～75 minutes, just on the surface of silica coating, makes silicon nitride layer after cooling.
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| CN106756876B (en) * | 2016-12-20 | 2019-06-25 | 北方工业大学 | Magnesium alloy parent/super-hydrophobic controllable composite membrane in region preparation method |
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| CN109468615A (en) * | 2018-12-18 | 2019-03-15 | 湖北大学 | Nano coating and preparation method thereof |
| CN109650738A (en) * | 2018-12-18 | 2019-04-19 | 湖北大学 | Super-hydrophobic coat with high adhesion force and preparation method thereof and electronic product |
| CN109609955A (en) * | 2019-01-21 | 2019-04-12 | 深圳市纳明特科技发展有限公司 | Magnesium alloy matrix surface T processing method |
| CN112795909A (en) * | 2020-12-17 | 2021-05-14 | 广东剑鑫科技股份有限公司 | High-salt-spray-resistant magnesium alloy coating agent and preparation method thereof |
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