CN102560485B - Method for preparing hard protective film on magnesium alloy surface - Google Patents
Method for preparing hard protective film on magnesium alloy surface Download PDFInfo
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- CN102560485B CN102560485B CN201110379822.1A CN201110379822A CN102560485B CN 102560485 B CN102560485 B CN 102560485B CN 201110379822 A CN201110379822 A CN 201110379822A CN 102560485 B CN102560485 B CN 102560485B
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Abstract
The invention provides a method for preparing a hard protective film on a magnesium alloy surface. The method is characterized by comprising the following steps of: firstly, depositing a metal Cu layer by adopting arc ion plating, selecting a high-purity Cu target and using Ar gas as working gas; then, depositing a metal Ni layer by electroplating; and finally, depositing a CrN monofilm or Cr/Cr N multilayer films on the upper surface of the magnesium alloy through the arc ion plating by selecting a high-purity Cr target and using high-purity Ar gas and N2 gas as working gas. The invention provides a method for preparing the CrN monofilm or Cr/Cr N multilayer films on the surface of the magnesium alloy, wherein the method has good binding force, does not pollute the environment and is used for achieving a purpose of protecting and modifying the surface of a magnesium alloy construction member.
Description
Technical field
The present invention relates to Mg alloy surface processes and process for modifying surface, specifically at Mg alloy surface, deposit the method for CrN individual layer or Cr/CrN multilayer hard protective film, in order to improve solidity to corrosion, the wear resistance of magnesium alloy component, expand the use range of magnesium alloy component.
Background technology
Magnesium alloy is as a kind of lightweight engineered structured material, has that specific tenacity is high, Young's modulus is low, thermal conductivity is high, electromagnetic shielding, dimensional stability, machinability that damping capacity is good, high are good and be easy to reclaim etc. and a series of good performances such as environmental pollution is little.In fields such as the vehicles, communication product, aerospace, weaponrys, have a wide range of applications.These characteristics become magnesium alloy to have much the equivalent material of iron and steel and the aluminium of incentive, become one of 21st century engineering materials most with prospects.But current magnesium alloy application quantity is also very low, and year output approximately only has 1% of aluminium alloy.Cause the reason that the practical application of magnesium alloy is restricted to be that magnesium has some intrinsic performance deficiencies, as corrosion-resistant, alloying strengthening weak effect, the shortcoming such as toughness is not enough and wear no resistance.Especially inferior solidity to corrosion and wearability make the application of magnesium alloy can only be confined to static load part up to now.Corrosion and wearing and tearing are all the surface phenomena of material, thereby the approach that the most directly and effectively improves corrosion stability of magnesium alloy, wear resistance is to carry out surface treatment and surface modification.The surface treatment of common magnesium alloy and surface modifying method mainly contain plating, differential arc oxidation (comprising anodic oxidation), thermospray, Laser Surface Treatment, gas phase deposition technology etc.Yet because magnesium is an element that chemical property is extremely active, in electroplating technology process, surface is easy to occur burn into oxidation, therefore, the pretreatment process that Mg alloy surface is electroplated is complicated and very difficult, simultaneously some plating solution contaminate environment; Magnesium alloy surface micro-arc oxidation (comprising anodic oxidation), but at Mg alloy surface, form layer oxide film, but this film is loose porous, and the performance of rete is undesirable, though also there is the way of some sealing of holes, the processing of the differential arc oxidation of large part needs powerful power supply; The rete that thermospray produces is also because how empty pine performance can not get improving; Laser Surface Treatment is unfavorable for scale operation because processing area is limited; Gas phase deposition technology can generate fine and close magnesium-yttrium-transition metal nitride or carbide rete, is the comparatively desirable surface modifying treatment of magnesium alloy.
Arc ion plating (aip) ionization level is high, plated film speed is fast, can prepare certain thickness rete, is to prepare the comparatively desirable technology of hard protective film.Utilizing arc ions to be plated in Mg alloy surface deposition transition metal nitride rete is different from iron and steel and aluminum alloy surface, because magnesium alloy chemical is greatly active, very easily on surface, form thicker loose oxide film, under regular situation, in presedimentary icon bombardment cleaning, be also difficult to remove completely this layer of oxide film, this makes the bonding force of deposited film and magnesium alloy substrate very poor, and rete very easily comes off.General and right, the bombardment of energetic ion effects on surface causes the high density of defects of rim surface zona, as room, interstitial atom, dislocation etc.Atoms metal can pass through room, dislocation to internal divergence, and N atom also can be by gap and dislocation to internal divergence, thereby can form transition layer at substrate surface.The existence of transition layer has formed the interface of a depth, reduces the internal stress producing because of lattice misfit, thereby improves bonding force.In this sense, temperature is higher, and ion bombardment energy is larger, is more conducive to obtain high bonding force.But our experiment shows, for arc ions, be plated in and on magnesium alloy, deposit for transition metal nitride film, the too high acquisition that is also unfavorable for mortise power of bias voltage, its reason is mainly two aspects.First, the excess Temperature that high bias voltage causes has aggravated the composition phase β-Al of AZ series magnesium alloy
12mg
17softening, sheet specimens there will be the serious flexural deformation causing because of non-uniform temperature.In addition, magnesium and N
2at high temperature can also there is chemical reaction in gas, generate the Mg of powdery
3n
2, make Mg alloy surface be subject to serious etching and evaporation.Secondly, because the thermal expansivity of Mg and transition metal nitride differs greatly, depositing temperature is too high will cause the larger tensile stress of generation between cooling rear rete and substrate, thereby reduce the bonding force of film.Therefore, from reducing thermal stresses and the magnesium alloy substrate factor at interface, consider, temperature is unsuitable too high.Like this, on magnesium alloy, the depositing temperature of Direct precipitation transition metal nitride rete is difficult for controlling.The film of preparing due to arc ion plating there will be macrobead and the growth defect (micropore, column crystal boundary etc.) of some amount, add that magnesium alloy electropotential is very negative, very easily corrosion, when there is corrosive medium, easily forms the galvanic corrosion process at micropore and macrobead place.Like this, simple transition metal nitride film can not have good protective effect, can select plated metal Ni layer, plays and prevents medium and Mg alloy surface crevice corrosion.Adopting multilayer film is in order to improve the toughness of rete, is difficult for forming crackle; Meanwhile, the stratum boundary of multilayer film can also reduce the micropore quantity running through in nitride film, improves the erosion resistance of rete.
At present, also on magnesium alloy, do not obtain the technology of metal nitride layer and metal Ni layer CrN series combination and that bonding force is good rete.
Summary of the invention
Goal of the invention: the invention provides a kind of method of preparing hard protective film on magnesium alloy surface, its objective is the undesirable problem of rete effect on solution magnesium alloy in the past.
Technical scheme: the present invention is achieved through the following technical solutions:
A method for preparing hard protective film on magnesium alloy surface, is characterized in that: first adopt arc ion plating, select high-purity Cu target and use Ar gas as working gas, metal refining Cu layer; Then by plating, metal refining Ni layer; Finally, by arc ion plating, select high-purity Cr target, use high-purity Ar gas and N
2gas, as working gas, at magnesium alloy upper surface deposition CrN unitary film or Cr/CrN multilayer film, specifically comprises the following steps:
(1), before magnesium alloy member puts into deposition apparatus, through mechanical mill, polishing, then with an organic solvent oil removing and chemical degreasing pre-treatment;
(2), the magnesium alloy print of pre-treatment is fixed on the substrate support in arc ion plating apparatus, and arc ion plating apparatus canyon is vacuumized;
(3), use high-purity Cu target, Ar gas is passed into vacuum chamber, the electric arc that ignites, metal refining Cu layer on magnesium alloy under subatmospheric; Original position is carried out vacuum heat treatment subsequently;
(4), on magnesium alloy, after the Cu film of pre-deposition, to carry out vacuum aging processing; 200 ℃-400 ℃ for the treatment of temps, aging time is 0.5-2.0 hour.
(5), in vacuum chamber, take out the magnesium alloy sample of the deposition Cu layer thermal treatment, carry out plated metal Ni layer, carry out subsequently surface cleaning, dry;
(6), the sample of the plated metal Ni layer drying is put on arc ion plating vacuum chamber substrate support, and canyon is vacuumized; Pass into Ar gas, select high-purity Cr target, open arc, utilize the pulsed bias of 600V-800V dutycycle 20%-40% to carry out conventional clean;
(7), after magnesium alloy plating metal Ni layer, adopt electric arc ion-plating deposition CrN hard films; During deposition, add reactant gases N
2gas, keeping vacuum indoor gas total pressure is 0.03-2.0Pa; When deposition Cr/CrN multilayer proofing film, also can periodically alternately add environmental gas Ar gas and N
2gas, keeping vacuum indoor gas total pressure is 0.03-2.0Pa, by controlling Ar gas or N
2gas passes into the time, controls Cr phase and CrN phase thickness in multilayer film, prepares the multilayer film in different modulating cycle;
(8), after deposition finishes, close pulsed bias and arc power, close gas, treat print cool to room temperature in vacuum chamber, open vacuum chamber and take out.
(5), in step, Ni layer thickness is at 10-30 μ m; Electroplating bath components and technique that plated metal Ni layer is used are as follows: single nickel salt 200～350g/L, and nickelous chloride 20～40g/L, boric acid 20～40g/L, coumarin 1～2 g/L, plating Ni additive 1～2 g/L, surplus is deionized water, pre-plating solution PH4～6; Electroplating temperature is at 10 ℃-25 ℃, current density 1～10A/dm
2, at room temperature preplating 0.5h～2.0h, rinses and dries with flowing water after taking-up.
(3) the metal Cu layer thickness in step is 0.1-1.0 μ m.
(1) mechanical mill in step is polished with the silicon carbide paper of 400#, 800#, 1200# and 1500# successively; Mechanical polishing, for selecting the cloth wheel of 18-25m/s, is used chrome oxide particle rubbing paste; Solvent degreasing and chemical degreasing step are that the magnesium alloy after grinding and polishing is put into alcohol or acetone ultrasonic cleaning 5-10min, temperature room temperature, and ultrasonic frequency is 22KHz; Cold wind dries up.
(2) vacuum tightness of step is less than 6.7 * 10
-3pa.
(3) in step, high-purity Cu target and magnesium alloy print distance are 100-400mm; In this step, Ar gas is passed into vacuum chamber, the electric arc that ignites under subatmospheric, deposition Cu film under 0.1-2.5Pa; Arc current is that 40-80A, arc voltage are 20-30V; On magnesium alloy print, apply pulsed bias 200-600V bombardment, dutycycle 15-45%, frequency 51KHz;
(5) electroplating bath components and the technique of plated metal Ni layer in step: single nickel salt 200～350g/L, nickelous chloride 20～40g/L, boric acid 20～40g/L, coumarin 1～2 g/L, plating Ni additive 1～2 g/L, surplus is deionized water, pre-plating solution PH4～6; Electroplating temperature is room temperature, current density 1～10A/dm
2, preplating 0.5h～2.0h, rinses and dries with flowing water after taking-up.
(6) vacuumizing in step, vacuum tightness is less than 6.7 * 10
-3after Pa, in this step, Ar gas is passed into vacuum chamber, the electric arc that ignites under subatmospheric under 0.1-2.5Pa, arc current is that 40-80A, arc voltage are 20-30V; On magnesium alloy print, apply pulsed bias 400-800V bombardment, dutycycle 15-45%, frequency 51KHz; Bombardment time 1-5min.
(7) environmental gas in step is Ar or N
2gas, two kinds of gases can pass into separately or alternately pass into, and each gas passes into the time and can adjust, when alternately passing into Ar and N
2during gas, Ar and N
2the time of gas is than being 1:1～3; ; Cavity pressure is controlled at 0.1-2.5Pa; On magnesium alloy print, apply pulsed bias 0-400V, dutycycle 10-40%, frequency 51KHz; Magnesium alloy substrate temperature 25-200 ℃; Arc current 40-80A, arc voltage 20-30V.
Advantage and effect: the invention provides a kind of method of preparing hard protective film on magnesium alloy surface, it first adopts arc ion plating, select high-purity Cu target and use Ar gas as working gas, metal refining Cu layer; Then by plating, metal refining Ni layer; Finally, by arc ion plating, select high-purity Cr target, use high-purity Ar gas and N
2gas is as working gas, at magnesium alloy upper surface deposition CrN unitary film or Cr/CrN multilayer film.
Concrete grammar is as follows:
1. pair Mg alloy surface carries out pre-treatment; Mechanical mill, polishing and alcohol liquid ultrasonic cleaning etc.
2. the magnesium alloy print of pre-treatment is fixed on the substrate support in arc ion plating apparatus, and canyon is vacuumized;
3. Ar gas is passed into vacuum chamber, the electric arc that ignites, metal refining Cu layer on magnesium alloy under subatmospheric; Original position is carried out vacuum heat treatment subsequently.
4. in vacuum chamber, take out the magnesium alloy sample of the deposition Cu layer thermal treatment, carry out plated metal Ni layer.Carry out subsequently surface cleaning, dry.
5. the sample of the plated metal Ni layer drying is put on arc ion plating vacuum chamber substrate support, and canyon is vacuumized.
6. pass into Ar gas, select high-purity Cr target, open arc, utilize high pulsed bias to carry out conventional clean; Then pass into growth gasses, reduce the pulsed bias applying, adjust print temperature, control arc current and the arc voltage of Metal Cr target arc power, on magnesium alloy print, grow CrN unitary film or Cr/CrN multilayer film.
5. after deposition finishes, close pulsed bias and arc power, close gas, treat print cool to room temperature in vacuum chamber, open vacuum chamber and take out print.
The present invention compared with prior art, has remarkable advantage: (1) first uses electric arc ion-plating deposition metal Cu layer on magnesium alloy, and by timeliness thermal treatment, improves the bonding strength of Cu layer and magnesium alloy; Owing to there being Cu layer, save activation in common Mg alloy surface plated metal Ni layer process and the process of preplating Zn or Zn-Al alloy layer, make plated metal Ni layer become easy.(2) adopt arc ion plating (aip) on the Ni of Mg alloy surface layer, grow CrN unitary film or Cr/CrN multilayer film, free from environmental pollution, meet environmental requirement; (3) plated metal Ni layer plating solution used is cheap and not contain the layer of nitride film of growing on composition (4) the Mg alloy surface metal Ni layer of serious environment pollution high in conjunction with bonding strength, and thickness can reach 10-20 μ m, and hardness is high, wear-resistant.(5) owing to containing plated metal Ni layer, the corrosion resistant natural disposition of rete obtains significant improvement; (6) coating growth speed of the present invention is fast, and growth area is large, is applicable to large-scale industrial production.
accompanying drawing explanation:
Fig. 1 is for passing into Ar gas and N
2when the gas time, ratio was for 2min:2min, the surface topography of Cr/CrN multilayer film and the elemental line scan figure of cross section, wherein Fig. 1-1 is surface topography map, Fig. 1-2 is cross-sectional morphology and elemental line scan figure;
Fig. 2 is for passing into Ar gas and N
2when the gas time, ratio was for 2min:6min, the surface topography of Cr/CrN multilayer film and the elemental line scan figure of cross section, wherein Fig. 2-1 is surface topography,, Fig. 2-2 are cross-sectional morphology and elemental line scan.
embodiment:below in conjunction with accompanying drawing, the present invention is described further:
As shown in Figure 1, the invention provides a kind of method of preparing hard protective film on magnesium alloy surface, first adopt arc ion plating, select high-purity Cu target and use Ar gas as working gas, metal refining Cu layer; Then by plating, metal refining Ni layer; Finally, by arc ion plating, select high-purity Cr target, use high-purity Ar gas and N
2gas is as working gas, and at magnesium alloy upper surface deposition CrN unitary film or Cr/CrN multilayer film, arc ion plating apparatus is a kind of common equipment of growing metal film and hard films, high pure metal Cu and Cr and high-purity Ar gas, N
2gas is also industrial conventional starting material.
Of the present inventionly specifically comprise the following steps:
(1), before magnesium alloy member puts into deposition apparatus, through mechanical mill, polishing, then with an organic solvent oil removing and chemical degreasing pre-treatment;
(2), the magnesium alloy print of pre-treatment is fixed on the substrate support in arc ion plating apparatus, and arc ion plating apparatus canyon is vacuumized;
(3), use high-purity Cu target, Ar gas is passed into vacuum chamber, the electric arc that ignites, metal refining Cu layer on magnesium alloy under subatmospheric; Original position is carried out vacuum heat treatment subsequently;
(4), on magnesium alloy, after the Cu film of pre-deposition, to carry out vacuum aging processing; 200 ℃-400 ℃ for the treatment of temps, aging time is 0.5-2.0 hour.
(5), in vacuum chamber, take out the magnesium alloy sample of the deposition Cu layer thermal treatment, carry out plated metal Ni layer, carry out subsequently surface cleaning, dry;
(6), the sample of the plated metal Ni layer drying is put on arc ion plating vacuum chamber substrate support, and canyon is vacuumized; Pass into Ar gas, select high-purity Cr target, open arc, utilize the pulsed bias of 600V-800V dutycycle 20%-40% to carry out conventional clean;
(7), after magnesium alloy plating metal Ni layer, adopt electric arc ion-plating deposition CrN hard films; During deposition, add reactant gases N
2gas, keeping vacuum indoor gas total pressure is 0.03-2.0Pa; When deposition Cr/CrN multilayer proofing film, also can periodically alternately add environmental gas Ar gas and N
2gas, keeping vacuum indoor gas total pressure is 0.03-2.0Pa, by controlling Ar gas or N
2gas passes into the time, controls Cr phase and CrN phase thickness in multilayer film, prepares the multilayer film in different modulating cycle;
(8), after deposition finishes, close pulsed bias and arc power, close gas, treat print cool to room temperature in vacuum chamber, open vacuum chamber and take out.
Be exactly specifically that, in " (5) " step, Ni layer thickness is at 10-30 μ m; Electroplating bath components and technique that plated metal Ni layer is used are as follows: single nickel salt 200～350g/L, and nickelous chloride 20～40g/L, boric acid 20～40g/L, coumarin 1～2 g/L, plating Ni additive 1～2 g/L, surplus is deionized water, pre-plating solution PH4～6; 10 ℃-25 ℃ of electroplating temperatures, current density 1～10A/dm
2, at room temperature preplating 0.5h～2.0h, rinses and dries with flowing water after taking-up.
(3) the metal Cu layer thickness in step is 0.1-1.0 μ m.
(1) mechanical mill in step is polished with the silicon carbide paper of 400#, 800#, 1200# and 1500# successively; Mechanical polishing, for selecting the cloth wheel of 18-25m/s, is used chrome oxide particle rubbing paste; Solvent degreasing and chemical degreasing step are that the magnesium alloy after grinding and polishing is put into alcohol or acetone ultrasonic cleaning 5-10min, temperature room temperature, and ultrasonic frequency is 22KHz; Cold wind dries up.
(2) vacuum tightness of step is less than 6.7 * 10
-3pa.
(3) in step, high-purity Cu target and magnesium alloy print distance are 100-400mm; In this step, Ar gas is passed into vacuum chamber, the electric arc that ignites under subatmospheric, deposition Cu film under 0.1-2.5Pa; Arc current is that 40-80A, arc voltage are 20-30V; On magnesium alloy print, apply pulsed bias 200-600V bombardment, dutycycle 15-45%, frequency 51KHz;
(5) electroplating bath components and the technique of plated metal Ni layer in step: single nickel salt 200～350g/L, nickelous chloride 20～40g/L, boric acid 20～40g/L, coumarin 1～2 g/L, plating Ni additive 1～2 g/L, surplus is deionized water, pre-plating solution PH4～6; Electroplating temperature is room temperature, current density 1～10A/dm
2, preplating 0.5h～2.0h, rinses and dries with flowing water after taking-up.
(6) vacuumizing in step, vacuum tightness is less than 6.7 * 10
-3after Pa, in this step, Ar gas is passed into vacuum chamber, the electric arc that ignites under subatmospheric under 0.1-2.5Pa, arc current is that 40-80A, arc voltage are 20-30V; On magnesium alloy print, apply pulsed bias 400-800V bombardment, dutycycle 15-45%, frequency 51KHz; Bombardment time 1-5min.
(7) in step, in vacuum chamber, pass into environmental gas, control chamber internal pressure, reduces the pulsed bias applying, and deposits transition metal hard film layer on magnesium alloy, and the environmental gas of this step is Ar or N
2gas, two kinds of gases can pass into separately or alternately pass into, and each gas passes into the time and can adjust, when alternately passing into Ar and N
2during gas, Ar and N
2the time of gas is than being 1:1～3; Cavity pressure is controlled at 0.1-2.5Pa; On magnesium alloy print, apply pulsed bias 0-400V, dutycycle 10-40%, frequency 51KHz; Magnesium alloy substrate temperature 25-200 ℃; Arc current 40-80A, arc voltage 20-30V.
In the embodiment of the present invention, select AZ31B magnesium alloy.It is below the preferred embodiment of the present invention.
Embodiment 1
Selecting AZ31B magnesium alloy to be processed into the length of side is 20 * 15mm, the print that thickness is 3mm, and target is selected high-purity Cu or Cr target.
Concrete operation step is:
(1) pre-treatment of magnesium alloy: the magnesium alloy print after adopting common washing composition to processing carries out oil removing and decontamination is processed, and then uses successively 400-1500# sand papering sample, last mechanical polishing.Magnesium alloy print after polishing is put into alcohol or acetone liquid ultrasonic cleaning 5min, and cold wind dries up, stand-by.
(2) above-mentioned pretreated magnesium alloy print is fixed on the indoor substrate holder of equipment vacuum, between print and Cu target, distance is 100mm.Then close vacuum chamber, utilize mechanical pump and diffusion pump to be evacuated to base vacuum 6.7 * 10
-3pa.In chamber pressure, arrive after base vacuum, pass into Ar gas, when vacuum is stabilized in 0.3Pa, open target power supply, arc current is 70A, and arc voltage is 20V, and pulsed bias is 400V, dutycycle 40%, and frequency 51KHz, to magnesium alloy print deposition Cu film, time 10min.
(3) after Cu film deposition finishes, 500 ℃ of sample In Situ Heatings, and be incubated 1.0 hours.
(4) from vacuum chamber, take out the sample of deposition Cu timeliness, be put in distilled water and clean a moment, be put in electroplate liquid and electroplate.Solution composition and technique: single nickel salt 300g/L, nickelous chloride 20g/L, boric acid 40g/L, tonka bean camphor 2 g/L, plating Ni additive 1 g/L, surplus is deionized water, pre-plating solution pH value is 6; Electroplating temperature room temperature, current density 5A/dm
2, at room temperature preplating 1h, rinses and dries with flowing water after taking-up.
(5) electroplated Ni layer the sample that dries, be put on the substrate holder in arc ion plating chamber, and high-purity Cr range, from sample 200mm, is evacuated to 6.7 * 10
-3pa.
(6) pass into Ar gas, when vacuum is stabilized in 0.6Pa, open target power supply, arc current is 70A, and arc voltage is 20V, and pulsed bias is 600V, dutycycle 40%, and frequency 51KHz, bombards, time 2min.
(3) after print bombardment, periodically pass into Ar gas and N
2gas, the time, keeping gas pressure intensity was that 0.6Pa reduction pulsed bias is 200V than being 2min:6min, dutycycle 20%, frequency keeps 51KHz, carries out the growth of Cr/CrN multilayer film.Growth time is 60min.
(4) after deposition finishes, close pulsed bias and arc power, close gas, treat print cool to room temperature in vacuum chamber, open vacuum chamber and take out print.
Fig. 2 is the Cr/CrN multilayer film of Mg alloy surface growth under this condition.
Embodiment 2
Selecting AZ31B magnesium alloy to be processed into the length of side is 20 * 15mm, the print that thickness is 3mm, and target is selected high-purity Cu or Cr target.
Concrete operation step is:
(pre-treatment of (1) magnesium alloy: the magnesium alloy print after adopting common washing composition to processing carries out oil removing and decontamination is processed, and then uses successively 400-1500# sand papering sample, last mechanical polishing.Magnesium alloy print after polishing is put into alcohol or acetone liquid ultrasonic cleaning 5min, and cold wind dries up, stand-by.
(2) above-mentioned pretreated magnesium alloy print is fixed on the indoor substrate holder of equipment vacuum, between print and Cu target, distance is 150mm.Then close vacuum chamber, utilize mechanical pump and diffusion pump to be evacuated to base vacuum 6.7 * 10
-3pa.In chamber pressure, arrive after base vacuum, pass into Ar gas, when vacuum is stabilized in 0.5Pa, open target power supply, arc current is 60A, and arc voltage is 20V, and pulsed bias is 500V, dutycycle 40%, and frequency 51KHz, to magnesium alloy print deposition Cu film, time 10min.
(3) after Cu film deposition finishes, 450 ℃ of sample In Situ Heatings, and be incubated 1.0 hours.
(4) from vacuum chamber, take out the sample of deposition Cu timeliness, be put in distilled water and clean a moment, be put in electroplate liquid and electroplate.Solution composition and technique: single nickel salt 350g/L, nickelous chloride 25g/L, boric acid 33g/L, coumarin 1 g/L, plating Ni additive 2 g/L, surplus is deionized water, pre-plating solution pH value is 6; Electroplating temperature room temperature, current density 8A/dm
2, at room temperature preplating 1h, rinses and dries with flowing water after taking-up.
(5) electroplated Ni layer the sample that dries, be put on the substrate holder in arc ion plating chamber, and high-purity Cr range, from sample 200mm, is evacuated to 6.7 * 10
-3pa.
(6) pass into Ar gas, when vacuum is stabilized in 0.6Pa, open target power supply, arc current is 60A, and arc voltage is 20V, and pulsed bias is 600V, dutycycle 40%, and frequency 51KHz, bombards, time 2min.
(3) after print bombardment, periodically pass into Ar gas and N
2gas, the time, keeping gas pressure intensity was that 0.6Pa reduction pulsed bias is 150V than being 2min:4min, dutycycle 20%, frequency keeps 51KHz, carries out the growth of Cr/CrN multilayer film.Growth time is 60min.
(4) after deposition finishes, close pulsed bias and arc power, close gas, treat print cool to room temperature in vacuum chamber, open vacuum chamber and take out print.
Embodiment 3
Selecting AZ31B magnesium alloy to be processed into the length of side is 20 * 15mm, the print that thickness is 3mm, and target is selected high-purity Cu or Cr target.
Concrete operation step is:
(1) pre-treatment of magnesium alloy: the magnesium alloy print after adopting common washing composition to processing carries out oil removing and decontamination is processed, and then uses successively 400-1500# sand papering sample, last mechanical polishing.Magnesium alloy print after polishing is put into alcohol or acetone liquid ultrasonic cleaning 5min, and cold wind dries up, stand-by.
(2) above-mentioned pretreated magnesium alloy print is fixed on the indoor substrate holder of equipment vacuum, between print and Cu target, distance is 220mm.Then close vacuum chamber, utilize mechanical pump and diffusion pump to be evacuated to base vacuum 6.7 * 10
-3pa.In chamber pressure, arrive after base vacuum, pass into Ar gas, when vacuum is stabilized in 0.6Pa, open target power supply, arc current is 60A, and arc voltage is 20V, and pulsed bias is 400V, dutycycle 40%, and frequency 51KHz, to magnesium alloy print deposition Cu film, time 10min.
(3) after Cu film deposition finishes, 550 ℃ of sample In Situ Heatings, and be incubated 0.5 hour.
(4) from vacuum chamber, take out the sample of deposition Cu timeliness, be put in distilled water and clean a moment, be put in electroplate liquid and electroplate.Solution composition and technique: single nickel salt 290g/L, nickelous chloride 36g/L, boric acid 30g/L, tonka bean camphor 2 g/L, plating Ni additive 2 g/L, surplus is deionized water, pre-plating solution pH value is 6; Electroplating temperature room temperature, current density 3A/dm
2, at room temperature preplating 1h, rinses and dries with flowing water after taking-up.
(5) electroplated Ni layer the sample that dries, be put on the substrate holder in arc ion plating chamber, and high-purity Cr range, from sample 220mm, is evacuated to 6.7 * 10
-3pa.
(6) pass into Ar gas, when vacuum is stabilized in 0.6Pa, open target power supply, arc current is 70A, and arc voltage is 20V, and pulsed bias is 550V, and dutycycle 40%, frequency 51KHz, bombards, time 2min.(3) after print bombardment, pass into N
2gas, keeping gas pressure intensity is that 0.6Pa reduction pulsed bias is 150V, dutycycle 20%, frequency keeps 51KHz, carries out the growth of CrN unitary film.Growth time is 50min.
(4) after deposition finishes, close pulsed bias and arc power, close gas, treat print cool to room temperature in vacuum chamber, open vacuum chamber and take out print.
Embodiment 4
Selecting AZ31B magnesium alloy to be processed into the length of side is 20 * 15mm, the print that thickness is 3mm, and target is selected high-purity Cu or Cr target.
Concrete operation step is:
(1) pre-treatment of magnesium alloy: the magnesium alloy print after adopting common washing composition to processing carries out oil removing and decontamination is processed, and then uses successively 400-1500# sand papering sample, last mechanical polishing.Magnesium alloy print after polishing is put into alcohol or acetone liquid ultrasonic cleaning 5min, and cold wind dries up, stand-by.
(2) above-mentioned pretreated magnesium alloy print is fixed on the indoor substrate holder of equipment vacuum, between print and Cu target, distance is 200mm.Then close vacuum chamber, utilize mechanical pump and diffusion pump to be evacuated to base vacuum 5.2 * 10
-3pa.In chamber pressure, arrive after base vacuum, pass into Ar gas, when vacuum is stabilized in 0.3Pa, open target power supply, arc current is 80A, and arc voltage is 20V, and pulsed bias is 300V, dutycycle 40%, and frequency 51KHz, to magnesium alloy print deposition Cu film, time 10min.
(3) after Cu film deposition finishes, 450 ℃ of sample In Situ Heatings, and be incubated 1.5 hours.
(4) from vacuum chamber, take out the sample of deposition Cu timeliness, be put in distilled water and clean a moment, be put in electroplate liquid and electroplate.Solution composition and technique: electroplating bath components and technique: single nickel salt 250g/L, nickelous chloride 35g/L, boric acid 20g/L, tonka bean camphor 2 g/L, plating Ni additive 1 g/L, surplus is deionized water, pre-plating solution pH value is 5; Electroplating temperature room temperature, current density 5A/dm
2, at room temperature preplating 1h, rinses and dries with flowing water after taking-up.
(5) electroplated Ni layer the sample that dries, be put on the substrate holder in arc ion plating chamber, and high-purity Cr range, from sample 200mm, is evacuated to 6.7 * 10
-3pa.
(6) pass into Ar gas, when vacuum is stabilized in 0.6Pa, open target power supply, arc current is 65A, and arc voltage is 20V, and pulsed bias is 600V, dutycycle 40%, and frequency 51KHz, bombards, time 2min.
(7) after print bombardment, pass into N
2gas, keeping gas pressure intensity is that 0.6Pa reduction pulsed bias is 200V, dutycycle 20%, frequency keeps 51KHz, carries out the growth of CrN unitary film.Growth time is 50min.
(4) after deposition finishes, close pulsed bias and arc power, close gas, treat print cool to room temperature in vacuum chamber, open vacuum chamber and take out print.
Embodiment 5
Selecting AZ31B magnesium alloy to be processed into the length of side is 20 * 15mm, the print that thickness is 3mm, and target is selected high-purity Cu or Cr target.
Concrete operation step is:
(1) pre-treatment of magnesium alloy: the magnesium alloy print after adopting common washing composition to processing carries out oil removing and decontamination is processed, and then uses successively 400-1500# sand papering sample, last mechanical polishing.Magnesium alloy print after polishing is put into alcohol or acetone liquid ultrasonic cleaning 5min, and cold wind dries up, stand-by.
(2) above-mentioned pretreated magnesium alloy print is fixed on the indoor substrate holder of equipment vacuum, between print and Cu target, distance is 100mm.Then close vacuum chamber, utilize mechanical pump and diffusion pump to be evacuated to base vacuum 6.7 * 10
-3pa.In chamber pressure, arrive after base vacuum, pass into Ar gas, when vacuum is stabilized in 0.3Pa, open target power supply, arc current is 70A, and arc voltage is 20V, and pulsed bias is 400V, dutycycle 40%, and frequency 51KHz, to magnesium alloy print deposition Cu film, time 10min.
(3) after Cu film deposition finishes, 500 ℃ of sample In Situ Heatings, and be incubated 1.0 hours.
(4) from vacuum chamber, take out the sample of deposition Cu timeliness, be put in distilled water and clean a moment, be put in electroplate liquid and electroplate.Solution composition and technique: single nickel salt 300g/L, nickelous chloride 20g/L, boric acid 40g/L, tonka bean camphor 2 g/L, plating Ni additive 1 g/L, surplus is deionized water, pre-plating solution pH value is 6; Electroplating temperature room temperature, current density 5A/dm
2, at room temperature preplating 1h, rinses and dries with flowing water after taking-up.
(5) electroplated Ni layer the sample that dries, be put on the substrate holder in arc ion plating chamber, and high-purity Cr range, from sample 200mm, is evacuated to 6.7 * 10
-3pa.
(6) pass into Ar gas, when vacuum is stabilized in 0.6Pa, open target power supply, arc current is 70A, and arc voltage is 20V, and pulsed bias is 600V, dutycycle 40%, and frequency 51KHz, bombards, time 2min.
(3) after print bombardment, periodically pass into Ar gas and N
2gas, the time, keeping gas pressure intensity was that 0.6Pa reduction pulsed bias is 200V than being 2min:2min, dutycycle 20%, frequency keeps 51KHz, carries out the growth of Cr/CrN multilayer film.Growth time is 60min.
(4) after deposition finishes, close pulsed bias and arc power, close gas, treat print cool to room temperature in vacuum chamber, open vacuum chamber and take out print.
Fig. 1 is the Cr/CrN multilayer film of Mg alloy surface growth under this condition.
The present invention proposes the method that a kind of bonding force Mg alloy surface good, free from environmental pollution is prepared CrN unitary film or Cr/CrN multilayer film, in order to realize the object of magnesium alloy component surfacecti proteon and modification.
Claims (6)
1. a method for preparing hard protective film on magnesium alloy surface, is characterized in that: first adopt arc ion plating, select high-purity Cu target and use Ar gas as working gas, metal refining Cu layer; Then by plating, metal refining Ni layer; Finally, by arc ion plating, select high-purity Cr target, use high-purity Ar gas and N
2gas, as working gas, at magnesium alloy upper surface deposition CrN unitary film or Cr/CrN multilayer film, specifically comprises the following steps:
(1), before magnesium alloy member puts into deposition apparatus, through mechanical mill, polishing, then with an organic solvent oil removing and chemical degreasing pre-treatment;
(2), the magnesium alloy print of pre-treatment is fixed on the substrate support in arc ion plating apparatus, and arc ion plating apparatus canyon is vacuumized;
(3), use high-purity Cu target, Ar gas is passed into vacuum chamber, the electric arc that ignites, metal refining Cu layer on magnesium alloy under subatmospheric; Original position is carried out vacuum heat treatment subsequently;
(4), on magnesium alloy, after the Cu film of pre-deposition, to carry out vacuum aging processing; 200 ℃-400 ℃ for the treatment of temps, aging time is 0.5-2.0 hour;
(5), in vacuum chamber, take out the magnesium alloy sample of the deposition Cu layer thermal treatment, carry out plated metal Ni layer, carry out subsequently surface cleaning, dry;
(6), the sample of the plated metal Ni layer drying is put on arc ion plating vacuum chamber substrate support, and canyon is vacuumized; Pass into Ar gas, select high-purity Cr target, open arc, utilize the pulsed bias of 400V-800V dutycycle 15%-40% to carry out conventional clean;
(7), after magnesium alloy plating metal Ni layer, adopt electric arc ion-plating deposition CrN hard films,, during deposition, add reactant gases N
2gas, keeping vacuum indoor gas total pressure is 0.03-2.0Pa; When deposition Cr/CrN multilayer proofing film, also can periodically alternately add environmental gas Ar gas and N
2gas, keeping vacuum indoor gas total pressure is 0.03-2.0Pa, by controlling Ar gas or N
2gas passes into the time, controls Cr phase and CrN phase thickness in multilayer film, prepares the multilayer film in different modulating cycle;
(8), after deposition finishes, close pulsed bias and arc power, close gas, treat print cool to room temperature in vacuum chamber, open vacuum chamber and take out;
In step (5), Ni layer thickness is at 10-30 μ m; Electroplating bath components and technique that plated metal Ni layer is used are as follows: single nickel salt 200～350g/L, and nickelous chloride 20～40g/L, boric acid 20～40g/L, coumarin 1～2g/L, plating Ni additive 1～2g/L, surplus is deionized water, pre-plating solution pH4～6; Electroplating temperature is at 10 ℃-25 ℃, current density 1～10A/dm
2, at room temperature preplating 0.5h～2.0h, rinses and dries with flowing water after taking-up;
Metal Cu layer thickness in step (3) is 0.1-1.0 μ m.
2. the method for preparing hard protective film on magnesium alloy surface according to claim 1, is characterized in that: the mechanical mill in step (1) is polished with the silicon carbide paper of 400#, 800#, 1200# and 1500# successively; Mechanical polishing is to select the cloth of 18-25m/s wheel, uses chrome oxide particle rubbing paste; Solvent degreasing and chemical degreasing step are that the magnesium alloy after grinding and polishing is put into alcohol or acetone ultrasonic cleaning 5-10min, temperature room temperature, and ultrasonic frequency is 22KHz; Cold wind dries up.
3. the method for preparing hard protective film on magnesium alloy surface according to claim 1, is characterized in that: the vacuum tightness of step (2) is less than 6.7 * 10
-3pa.
4. the method for preparing hard protective film on magnesium alloy surface according to claim 1, is characterized in that: in step (3), high-purity Cu target and magnesium alloy print distance are 100-400mm; In this step, Ar gas is passed into vacuum chamber, the electric arc that ignites under subatmospheric, deposition Cu film under 0.1-2.5Pa; Arc current is that 40-80A, arc voltage are 20-30V; On magnesium alloy print, apply pulsed bias 200-600V bombardment, dutycycle 15-45%, frequency 51KHz.
5. the method for preparing hard protective film on magnesium alloy surface according to claim 1, is characterized in that: vacuumizing in step (6), vacuum tightness is less than 6.7 * 10
-3after Pa, in this step, Ar gas is passed into vacuum chamber, the electric arc that ignites under 0.1-2.5Pa subatmospheric, arc current is that 40-80A, arc voltage are 20-30V; On magnesium alloy print, apply pulsed bias 400-800V bombardment, dutycycle 15-40%, frequency 51KHz; Bombardment time 1-5min.
6. the method for preparing hard protective film on magnesium alloy surface according to claim 1, is characterized in that: the environmental gas in step (7) is Ar or N
2gas, two kinds of gases can pass into separately or alternately pass into, and each gas passes into the time and can adjust, when alternately passing into Ar and N
2during gas, Ar and N
2the time of gas, cavity pressure was controlled at 0.1-2.0Pa than being 1:1～3; On magnesium alloy print, apply pulsed bias 0-400V, dutycycle 10-40%, frequency 51KHz; Magnesium alloy substrate temperature 25-200 ℃; Arc current 40-80A, arc voltage 20-30V.
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