CN102912302B - Method for preparing yttrium/silicon nitride compound coating material on surface of magnesium alloy - Google Patents
Method for preparing yttrium/silicon nitride compound coating material on surface of magnesium alloy Download PDFInfo
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- CN102912302B CN102912302B CN201210387689.9A CN201210387689A CN102912302B CN 102912302 B CN102912302 B CN 102912302B CN 201210387689 A CN201210387689 A CN 201210387689A CN 102912302 B CN102912302 B CN 102912302B
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Abstract
The invention discloses a method for preparing an yttrium/silicon nitride compound coating material on the surface of magnesium alloy, relates to the compound coating material on the surface of the magnesium alloy, and provides a method for preparing the yttrium/silicon nitride compound coating material with controllable film thickness and good corrosion resistance on the surface of the magnesium alloy. The method comprises the steps as follows: preprocessing a substrate; presputtering a target material; conducting direct current sputtering deposition on a metal Y film of a transition layer; and conducting radio-frequency reactive sputtering deposition on an outer-layer amorphous Si3N4 film. The metal Y is used as the transition layer, and the radio-frequency reactive sputtering deposition is conducted on the amorphous Si3N4 film on the basis of the transition layer. The Y/Si3N4 compound coating material with controllable film thickness and ultrastrong corrosion resistance is prepared by changing the sputtering time under the conditions of certain deposition pressure intensity, temperature, gas flow and the like. Through the electrochemical test of a potentiodynamic polarization curve and alternating-current impedance and the practical use test of a hydrogen evolution test and a salt fog test, the results show that the magnesium alloy covered with the Y/Si3N4 compound coating is good in corrosion resistance.
Description
Technical field
The present invention relates to a kind of Mg alloy surface composite coating material, especially relate at magnesium alloy substrate material surface and first deposit Y intermediate metal, then deposit outer amorphous Si
3n
4film, thickness is controlled, and a kind of Mg alloy surface with good corrosion energy is prepared the method for yttrium/silicon nitride composite coating material.
Background technology
Magnesium alloy, as the lightest engineering metal material, has many excellent characteristics, and for example specific tenacity, specific rigidity are high, heat conduction, conducts electricity very well, and has good electromagnetic shielding, damping and amortization, vibration damping and machinability.In recent years, magnesium alloy is widely used in the fields such as the vehicles such as automobile, motorcycle, bike, instrument, electronic apparatus, chemical industry metallurgical, aerospace, defence and military, bio-medical material.But the electropotential of magnesium is more negative, be easy to corrode, the second-phase in alloy or impurity phase also can accelerate the corrosion of magnesium alloy, have seriously hindered industrial applications and the popularization of magnesium-alloy material.So magnesium alloy workpiece must provide protection through certain protection against corrosion surface treatment before use, just can make magnesium alloy bring into play its good performance in industry.
Prevent that corrosion from effective means occurring is that base material is applied.Coat has stoped the contact between substrate and environment, has prevented the generation of corrosion.In order to reach sufficient protective value, coat must be even, fine and close, good with substrate associativity.The surface anticorrosive treatment process of magnesium alloy comprises (J.E.Gray, B.Luan.Journal of Alloys and Compounds.336 (2002) 88-113) such as electroless plating, plating, chemical conversion film, micro-arc anodic oxidation, cladding laser surfaces, surperficial infiltration layer processing, vapour deposition, organic coatings.Physical vapor deposition (PVD) is by gas phase material or makes to be deposited on solid material surface and to form film after material vaporization, thereby makes material obtain a kind of new technology of special surface properties.This kind of surface modifying method, technically facilitates controlledly, environment friendly and pollution-free, is particularly suitable for industrial green modification engineering.
As everyone knows, hard ceramic film plays very important effect in Surface Engineering, and they have higher hardness, good wear resistance, the solidity to corrosion of excellence and beautiful color and luster.TiN, TiC and CrN are current widely used film materials, extremely people pay close attention to.Process is to the great many of experiments of nitride ceramics rete and researching and analysing its mechanism such as CrN, TiN, AlN, NbN; we find that metal nitride film layers is of short duration to the protection of magnesium alloy; growth along with the test duration; between rete and matrix due to potential difference; the subchannel forming; can make very soon rete lose efficacy, thereby lose the protection to magnesium alloy substrate.Consider the factor of each side, we select silicon nitride film layer to test and obtain better result.Existing document is mentioned the preparation method about silicon nitride film layer: 1, Huang Jiamu, material Leader, 22 (2008) 384-386; 2, Mu Zongxin, vacuum science and technology journal, 32 (2012) 6-12.The present invention considers the life-time service of material, different from existing working method, uses innovatively metal Y as transition layer, then RF-reactively sputtered titanium deposited amorphous state Si on the basis of transition layer
3n
4embrane method, by modulation process parameter, finally prepares the thick controlled Y/Si with superpower corrosion resistance of each tunic
3n
4composite coating material.
Summary of the invention
The object of the present invention is to provide thickness controlled, a kind of Mg alloy surface with good corrosion energy is prepared the method for yttrium/silicon nitride composite coating material.
The present invention includes following steps:
1) substrate pretreatment;
2) target pre-sputtering;
3) d.c. sputtering deposition transition metal Y film;
4) RF-reactively sputtered titanium deposits outer amorphous Si
3n
4film.
In step 1), described substrate pretreatment, can carry out mechanical mill polished finish, ultrasonic cleaning processing, the processing of ion source Bombardment and cleaning successively.Described mechanical mill polished finish can first be ground to surfacing by magnesium alloy on 1000 order SiC silicon carbide papers, is placed in dehydrated alcohol ultrasonic cleaning 5min; Then on 2000 order SiC silicon carbide papers, be ground to cut in the same direction, be placed in ethanol ultrasonic cleaning 5min; Then on 5000 order SiC silicon carbide papers, along vertical 2000 order cut directions, grind 90 ~ 120s, be placed in ethanol ultrasonic cleaning 10min; With the diamond polishing cream that particle diameter is 1 μ m and 0.5 μ m, carry out polished finish on polishing disk successively again, polishing disk rotating speed is 600r/min, is polished to surface and is the nearly mirror status of light; Distilled water flushing is placed on ultrasonic cleaning 15min in acetone, is then placed in dehydrated alcohol ultrasonic cleaning 15min, moves to afterwards sample table, puts into cavity, vacuumizes and protects.Described ion source Bombardment and cleaning is processed, and can adopt Hall ion source to clean matrix, and substrate temperature is 250 ℃, regulates Ar flow to 10sccm, and environmental stress is 2.3 * 10
-2pa, regulating bias voltage is-80 ~-100V, and cathodic current is 28.5 ~ 29.5A, and cathode voltage is 16 ~ 18V, and anodic current is 6.8 ~ 7.2A, anode voltage is 56 ~ 58V, cleans 5 ~ 8min.
In step 2) in, described target pre-sputtering, cavity environment temperature can be heated to 120 ~ 150 ℃, magnesium alloy substrate temperature is heated to 250 ℃, pass into Ar gas (purity 99.999%), flow set, at 40sccm, regulates the interior operating pressure of cavity to 1.0Pa, by Y metal targets (purity 99.9%) power regulation to 180 ~ 200W, pre-sputtering 10min; Then direct supply is connected to pure Si target (purity 99.99%), power regulation to 180 ~ 200W, pre-sputtering 10min; To remove the contaminating impurities such as target material surface oxide compound, activation target material surface atom, carries the highly purified while and also improves the sputter rate of target.
In step 3), described d.c. sputtering deposition transition metal Y film, can confirm that cavity environment temperature is 120 ~ 150 ℃, and magnesium alloy substrate temperature is to proceed as follows after 250 ℃: regulate Ar flow to 60sccm, now chamber pressure is 1.50Pa, regulates chamber pressure to 0.30Pa; Rotate sample table, make sample table over against Y metal targets, both distances are 10cm; Target d.c. sputtering power is risen to 250W, opens target plate washer, start timing, sputtering sedimentation certain hour, to thickness be H
1(50 ~ 100nm), closes rapidly target plate washer afterwards, regulates direct supply power to 0W.
In step 4), described RF-reactively sputtered titanium deposits outer amorphous Si
3n
4film, can, after transition metal Y film deposition, proceed as follows: regulate Ar flow to 0sccm, keep 120 ~ 150 ℃ of cavity envrionment temperatures, magnesium alloy substrate temperature is 250 ℃, vacuumizes half an hour; Pass into afterwards high-purity N
2gas (purity 99.999%) and Ar gas, regulating nitrogen flow is 20 ~ 25%, total flux is 60sccm, regulates chamber pressure to 0.30Pa; Rotate sample table, make sample table over against pure Si target, both distances are 8cm; Access radio-frequency power supply, opens target plate washer, and target radio-frequency sputtering power is risen to 500W, starts timing, sputtering sedimentation for some time, to thickness be H
2, total film thickness meets H
1+ H
2=3.00 ± 0.05 μ m, closes rapidly target plate washer afterwards, regulates direct supply power to 0W.
The present invention creatively uses metal Y as transition layer, then RF-reactively sputtered titanium deposited amorphous state Si on the basis of transition layer
3n
4embrane method.Under the conditions such as certain deposition pressure, temperature, gas flow, by changing sputtering time, prepare the thick controlled Y/Si with superpower corrosion resistance of each tunic
3n
4composite coating material.By the electro-chemical test of electrokinetic potential polarization curve and alternating-current impedance and the actual use test of liberation of hydrogen test and salt-fog test, result shows surface coverage Y/Si
3n
4the magnesium alloy of compound coating has good corrosion resistance.
Accompanying drawing explanation
Fig. 1 is the GIXRD spectrogram of embodiment 1.In Fig. 1, X-coordinate be diffraction angle 2 θ/°, ordinate zou is intensity I ntensity(a.u.).
Fig. 2 is the XPS figure of embodiment 1 depth profiling.In Fig. 2, X-coordinate is that ordinate zou is intensity I ntensity(a.u. in conjunction with energy binding energy/eV); Magnification is 15000, and scale is 1 μ m.
Fig. 3 is the section SEM figure of embodiment 1.In Fig. 3, (a) magnification is 15000, and scale is 1 μ m(b) magnification is 60000, scale is 200nm.
Fig. 4 is the coating binding force test cross-reference figure of embodiment 1.In Fig. 4, (a) sample photo before test; (b) sample photo after test.
Fig. 5 is the electrokinetic potential polarization curve of the electro-chemical test of embodiment 1.In Fig. 5, X-coordinate is with respect to saturated calomel electrode current potential/V, and ordinate zou is current density/(A/cm
2).
Fig. 6 is the electro-chemical test alternating-current impedance figure of embodiment 1.In Fig. 6, real part/ohmcm that X-coordinate is resulting impedance
2, imaginary part/ohmcm that ordinate zou is resulting impedance
2.
Fig. 7 is the liberation of hydrogen tests in 7 days of embodiment 1.In Fig. 7, X-coordinate is soak time/h, and ordinate zou is hydrogen-separating quantity/(ml/cm
2).
Fig. 8 is 15 days salt-fog test cross-reference figure of embodiment 1.In Fig. 8, (a) sample photo before salt-fog test; (b) sample photo after 15 days salt-fog tests.
Fig. 9 is the section SEM figure of embodiment 4.In Fig. 9, (a) magnification is 15000, and scale is 1 μ m; (b) magnification is 60000, and scale is 200nm.
Figure 10 is the electrokinetic potential polarization curve of the electro-chemical test of embodiment 4.In Figure 10, X-coordinate is with respect to saturated calomel electrode current potential/V, and ordinate zou is current density/(A/cm
2).
Figure 11 is the alternating-current impedance figure of the electro-chemical test of embodiment 4.In Figure 11, real part/ohmcm that X-coordinate is resulting impedance
2, imaginary part/ohmcm that ordinate zou is resulting impedance
2.
Figure 12 is the liberation of hydrogen tests in 7 days of embodiment 4.In Figure 12, X-coordinate is soak time/h, and ordinate zou is hydrogen-separating quantity/(ml/cm
2).
Figure 13 is 15 days salt-fog test cross-reference figure of embodiment 4.In Figure 13, (a) sample photo before salt-fog test; (b) sample photo after 15 days salt-fog tests.
Embodiment
Embodiment 1
1, substrate pretreatment
(1) mechanical mill polished finish is first ground to surfacing by magnesium alloy on 1000 order SiC silicon carbide papers, is placed in dehydrated alcohol ultrasonic cleaning 5min; Then on 2000 order SiC silicon carbide papers, be ground to cut in the same direction, be placed in ethanol ultrasonic cleaning 5min; Then on 5000 order SiC silicon carbide papers, along vertical 2000 order cut directions, grind 90s, be placed in ethanol ultrasonic cleaning 10min; With the diamond polishing cream that particle diameter is 1 μ m and 0.5 μ m, carry out polished finish on polishing disk successively again, polishing disk rotating speed is 600r/min, is polished to surface and is the nearly mirror status of light, distilled water flushing.
(2) ultrasonic cleaning is processed, and is placed in acetone ultrasonic cleaning 15min, is then placed in dehydrated alcohol ultrasonic cleaning 15min, moves to afterwards sample table, puts into cavity, vacuumizes and protects.
(3) ion source Bombardment and cleaning is processed, and adopts Hall ion source to clean matrix, and substrate temperature is 250 ℃, regulates Ar flow to 10sccm, and environmental stress is 2.3 * 10
-2pa, regulates bias voltage to be-80V, and cathodic current is 29.5A, and cathode voltage is 18V, and anodic current is 7.2A, and anode voltage is 58V, cleans 5min.
2, metal Y, pure Si target pre-sputtering
Cavity environment temperature is heated to 120 ℃, and magnesium alloy substrate temperature is heated to 250 ℃, passes into Ar gas (purity 99.999%), flow set is at 40sccm, regulate in cavity operating pressure to 1.0Pa, by Y metal targets (purity 99.9%) power regulation to 180W, pre-sputtering 10min; Then direct supply is connected to pure Si target (purity 99.99%), power regulation is to 180W, pre-sputtering 10min; To remove the contaminating impurities such as target material surface oxide compound, activation target material surface atom, carries the highly purified while and also improves the sputter rate of target.
3, d.c. sputtering deposition transition metal Y film
Confirm that cavity environment temperature is 120 ℃, magnesium alloy substrate temperature is 250 ℃.Regulate Ar flow to 60sccm, now chamber pressure is 1.50Pa, regulates chamber pressure to 0.30Pa; Rotate sample table, make sample table over against Y metal targets, both distances are 10cm; Target d.c. sputtering power is risen to 250W, open target plate washer, start timing, sputtering sedimentation 15s, closes rapidly target plate washer afterwards, regulates direct supply power to 0W.
4, RF-reactively sputtered titanium deposits outer amorphous Si
3n
4film
After transition metal Y film deposition, regulate Ar flow to 0sccm, keep 120 ℃ of cavity envrionment temperatures, magnesium alloy substrate temperature is 250 ℃, normally vacuumizes half an hour; Pass into afterwards high-purity N
2gas (purity 99.999%) and Ar gas, regulating nitrogen flow is 20%, total flux is 60sccm, regulates chamber pressure to 0.30Pa; Rotate sample table, make sample table over against pure Si target, both distances are 8cm; Access radio-frequency power supply, opens target plate washer, and target radio-frequency sputtering power is risen to 500W, starts timing, and sputtering sedimentation 96min, closes rapidly target plate washer afterwards, regulates direct supply power to 0W.
5, Y/Si
3n
4the total film thickness of composite coating material characterizes and adopts Dektak3 Series film thickness measuring instrument, and total film thickness is 2.96 μ m.Fig. 1 is Y/Si
3n
4the GIXRD spectrogram of composite coating material, shows that the coating of preparation is the Y coating with close-packed hexagonal structure, does not occur the diffraction peak of silicon nitride, illustrates that silicon nitride is that non-crystalline state exists.Fig. 2 is the XPS figure of embodiment 1 depth profiling, and surface nitrogen SiClx is compound S i
3n
4.Fig. 3 is the section SEM figure of embodiment 1: (a) show that coating is fine and close, solid matter growth, non-columnar crystal structure; (b) thickness that roughly can find out Y transition layer is 50 ± 5nm.Fig. 4 is embodiment 1 coating binding force test cross-reference figure: (a) embodiment 1 sample before test; (b) sample after test.Experimental standard is with reference to ASTM D3359-02, and result shows, there is a small amount of disbonding at place, point of crossing, but area of infection is less than 5%, illustrates that coating binding force is good.Fig. 5 and Fig. 6 are that the Electrochemical results of embodiment 1: Fig. 5 is electrokinetic potential polarization curve; Fig. 6 is alternating-current impedance, and result shows, with respect to plated film magnesium alloy not, and surface coverage Y/Si
3n
4the magnesium alloy of compound coating has good corrosion resistance.Fig. 7 is the liberation of hydrogen tests in 7 days of embodiment 1, and result shows at duration of test, surface coverage Y/Si
3n
4the magnesium alloy of compound coating shows good corrosion resisting property (hydrogen-separating quantity levels off to zero).Fig. 8 is 15 days salt-fog test cross-reference figure of embodiment 1, and experimental standard is with reference to GBT6461-2002, and defect area is less than 0.5%, protection grading R
p>=8, consistent with test result before, surface coverage Y/Si is described
3n
4the magnesium alloy of compound coating has good corrosion resistance really.
Embodiment 2
1, substrate pretreatment
(1) mechanical mill polished finish is first ground to surfacing by magnesium alloy on 1000 order SiC silicon carbide papers, is placed in dehydrated alcohol ultrasonic cleaning 5min; Then on 2000 order SiC silicon carbide papers, be ground to cut in the same direction, be placed in ethanol ultrasonic cleaning 5min; Then on 5000 order SiC silicon carbide papers, along vertical 2000 order cut directions, grind 100s, be placed in ethanol ultrasonic cleaning 10min; With the diamond polishing cream that particle diameter is 1 μ m and 0.5 μ m, carry out polished finish on polishing disk successively again, polishing disk rotating speed is 600r/min, is polished to surface and is the nearly mirror status of light, distilled water flushing.
(2) ultrasonic cleaning is processed, with embodiment 1.
(3) ion source Bombardment and cleaning is processed, and adopts Hall ion source to clean matrix, and substrate temperature is 250 ℃, regulates Ar flow to 10sccm, and environmental stress is 2.3 * 10
-2pa, regulates bias voltage to be-90V, and cathodic current is 28.5A, and cathode voltage is 16V, and anodic current is 6.5A, and anode voltage is 56V, cleans 8min.
2, metal Y, pure Si target pre-sputtering
Cavity environment temperature is heated to 130 ℃, and magnesium alloy substrate temperature is heated to 250 ℃, passes into Ar gas (purity 99.999%), flow set is at 40sccm, regulate in cavity operating pressure to 1.0Pa, by Y metal targets (purity 99.9%) power regulation to 190W, pre-sputtering 10min; Then direct supply is connected to pure Si target (purity 99.99%), power regulation is to 190W, pre-sputtering 10min; To remove the contaminating impurities such as target material surface oxide compound, activation target material surface atom, carries the highly purified while and also improves the sputter rate of target.
3, d.c. sputtering deposition transition metal Y film
Confirm that cavity environment temperature is 130 ℃, magnesium alloy substrate temperature is 250 ℃.Regulate Ar flow to 60sccm, now chamber pressure is 1.50Pa, regulates chamber pressure to 0.30Pa; Rotate sample table, make sample table over against Y metal targets, both distances are 10cm; Target d.c. sputtering power is risen to 250W, open target plate washer, start timing, sputtering sedimentation 18s, closes rapidly target plate washer afterwards, regulates direct supply power to 0W.
4, RF-reactively sputtered titanium deposits outer amorphous Si
3n
4film
After transition metal Y film deposition, regulate Ar flow to 0sccm, keep 130 ℃ of cavity envrionment temperatures, magnesium alloy substrate temperature is 250 ℃, normally vacuumizes half an hour; Pass into afterwards high-purity N
2gas (purity 99.999%) and Ar gas, regulating nitrogen flow is 22%, total flux is 60sccm, regulates chamber pressure to 0.30Pa; Rotate sample table, make sample table over against pure Si target, both distances are 8cm; Access radio-frequency power supply, opens target plate washer, and target radio-frequency sputtering power is risen to 500W, starts timing, and sputtering sedimentation 95.5min, closes rapidly target plate washer afterwards, regulates direct supply power to 0W.
5, Y/Si
3n
4the total film thickness of composite coating material characterizes and adopts Dektak3 Series film thickness measuring instrument, and total film thickness is 3.01 μ m.The GIXRD spectrogram of embodiment 2 is with embodiment 1, and coating has the Y coating of close-packed hexagonal structure, does not occur the diffraction peak of silicon nitride, illustrates that silicon nitride is that non-crystalline state exists.The XPS figure of embodiment 2 depth profilings is with embodiment 1, and surface nitrogen SiClx is compound S i
3n
4.The section SEM figure similar embodiment 1 of embodiment 2, coating is fine and close, and the thickness of Y transition layer is 60 ± 5nm.The coating binding force test of embodiment 2 is with embodiment 1, and coating binding force is good.The Electrochemical results of embodiment 2 is with embodiment 1, with respect to plated film magnesium alloy not, and surface coverage Y/Si
3n
4the magnesium alloy of compound coating has good corrosion resistance.7 days liberations of hydrogen test of embodiment 2 is with embodiment 1, and result shows, at duration of test, and surface coverage Y/Si
3n
4the magnesium alloy of compound coating shows good corrosion resisting property (hydrogen-separating quantity levels off to zero).15 days salt-fog tests of embodiment 2 are with embodiment 1, and experimental standard is with reference to GBT6461-2002, and defect area is less than 0.5%, protection grading R
p>=8, consistent with test result before, surface coverage Y/Si is described
3n
4the magnesium alloy of compound coating has excellent corrosion resistance really.
Embodiment 3
1, substrate pretreatment
(1) mechanical mill polished finish is first ground to surfacing by magnesium alloy on 1000 order SiC silicon carbide papers, is placed in dehydrated alcohol ultrasonic cleaning 5min; Then on 2000 order SiC silicon carbide papers, be ground to cut in the same direction, be placed in ethanol ultrasonic cleaning 5min; Then on 5000 order SiC silicon carbide papers, along vertical 2000 order cut directions, grind 110s, be placed in ethanol ultrasonic cleaning 10min; With the diamond polishing cream that particle diameter is 1 μ m and 0.5 μ m, carry out polished finish on polishing disk successively again, polishing disk rotating speed is 600r/min, is polished to surface and is the nearly mirror status of light, distilled water flushing.
(2) ultrasonic cleaning is processed, with embodiment 1.
(3) ion source Bombardment and cleaning is processed, and adopts Hall ion source to clean matrix, and substrate temperature is 250 ℃, regulates Ar flow to 10sccm, and environmental stress is 2.3 * 10
-2pa, regulates bias voltage to be-100V, and cathodic current is 29A, and cathode voltage is 17V, and anodic current is 6.8A, and anode voltage is 57V, cleans 7min.
2, metal Y, pure Si target pre-sputtering
Cavity environment temperature is heated to 140 ℃, and magnesium alloy substrate temperature is heated to 250 ℃, passes into Ar gas (purity 99.999%), flow set is at 40sccm, regulate in cavity operating pressure to 1.0Pa, by Y metal targets (purity 99.9%) power regulation to 200W, pre-sputtering 10min; Then direct supply is connected to pure Si target (purity 99.99%), power regulation is to 200W, pre-sputtering 10min; To remove the contaminating impurities such as target material surface oxide compound, activation target material surface atom, carries the highly purified while and also improves the sputter rate of target.
3, d.c. sputtering deposition transition metal Y film
Confirm that cavity environment temperature is 140 ℃, magnesium alloy substrate temperature is 250 ℃.Regulate Ar flow to 60sccm, now chamber pressure is 1.50Pa, regulates chamber pressure to 0.30Pa; Rotate sample table, make sample table over against Y metal targets, both distances are 10cm; Target d.c. sputtering power is risen to 250W, open target plate washer, start timing, sputtering sedimentation 24s, closes rapidly target plate washer afterwards, regulates direct supply power to 0W.
4, RF-reactively sputtered titanium deposits outer amorphous Si
3n
4film
After transition metal Y film deposition, regulate Ar flow to 0sccm, keep 140 ℃ of cavity envrionment temperatures, magnesium alloy substrate temperature is 250 ℃, normally vacuumizes half an hour; Pass into afterwards high-purity N
2gas (purity 99.999%) and Ar gas, regulating nitrogen flow is 25%, total flux is 60sccm, regulates chamber pressure to 0.30Pa; Rotate sample table, make sample table over against pure Si target, both distances are 8cm; Access radio-frequency power supply, opens target plate washer, and target radio-frequency sputtering power is risen to 500W, starts timing, and sputtering sedimentation 95min, closes rapidly target plate washer afterwards, regulates direct supply power to 0W.
5, Y/Si
3n
4the total film thickness of composite coating material characterizes and adopts Dektak3 Series film thickness measuring instrument, and total film thickness is 2.97 μ m.The GIXRD spectrogram of embodiment 3 is with embodiment 1, and coating has the Y coating of close-packed hexagonal structure, does not occur the diffraction peak of silicon nitride, illustrates that silicon nitride is that non-crystalline state exists.The XPS figure of embodiment 3 depth profilings is with embodiment 1, and surface nitrogen SiClx is compound S i
3n
4.The section SEM figure similar embodiment 1 of embodiment 3, coating is fine and close, and the thickness of Y transition layer is 80 ± 5nm.The coating binding force test of embodiment 3 is with embodiment 1, and coating binding force is good.The Electrochemical results of embodiment 3 is with embodiment 1, with respect to plated film magnesium alloy not, and surface coverage Y/Si
3n
4the magnesium alloy of compound coating has good corrosion resistance.The liberation of hydrogen tests in 7 days of embodiment 3 are with embodiment 1, surface coverage Y/Si
3n
4the magnesium alloy of compound coating shows good corrosion resisting property (hydrogen-separating quantity convergence zero), and along with the prolongation of soak time, hydrogen-separating quantity increases to some extent, but still shows good corrosion resistance.7 days salt-fog tests of embodiment 3 are with embodiment 1, and experimental standard is with reference to GBT6461-2002, and defect area is less than 1%, protection grading R
p>=7, consistent with test result before, surface coverage Y/Si is described
3n
4the magnesium alloy of compound coating has good corrosion resistance really.
Embodiment 4
1, substrate pretreatment
(1) mechanical mill polished finish is first ground to surfacing by magnesium alloy on 1000 order SiC silicon carbide papers, is placed in dehydrated alcohol ultrasonic cleaning 5min; Then on 2000 order SiC silicon carbide papers, be ground to cut in the same direction, be placed in ethanol ultrasonic cleaning 5min; Then on 5000 order SiC silicon carbide papers, along vertical 2000 order cut directions, grind 120s, be placed in ethanol ultrasonic cleaning 10min; With the diamond polishing cream that particle diameter is 1 μ m and 0.5 μ m, carry out polished finish on polishing disk successively again, polishing disk rotating speed is 600r/min, is polished to surface and is the nearly mirror status of light, distilled water flushing.
(2) ultrasonic cleaning is processed, with embodiment 1.
(3) ion source Bombardment and cleaning is processed, and adopts Hall ion source to clean matrix, and substrate temperature is 250 ℃, regulates Ar flow to 10sccm, and environmental stress is 2.3 * 10
-2pa, regulates bias voltage to be-100V, and cathodic current is 29.2A, and cathode voltage is 17V, and anodic current is 7.2A, and anode voltage is 58V, cleans 6min.
2, metal Y, pure Si target pre-sputtering
Cavity environment temperature is heated to 150 ℃, and magnesium alloy substrate temperature is heated to 250 ℃, passes into Ar gas (purity 99.999%), flow set is at 40sccm, regulate in cavity operating pressure to 1.0Pa, by Y metal targets (purity 99.9%) power regulation to 200W, pre-sputtering 10min; Then direct supply is connected to pure Si target (purity 99.99%), power regulation is to 200W, pre-sputtering 10min; To remove the contaminating impurities such as target material surface oxide compound, activation target material surface atom, carries the highly purified while and also improves the sputter rate of target.
3, d.c. sputtering deposition transition metal Y film
Confirm that cavity environment temperature is 150 ℃, magnesium alloy substrate temperature is 250 ℃.Regulate Ar flow to 60sccm, now chamber pressure is 1.50Pa, regulates chamber pressure to 0.30Pa; Rotate sample table, make sample table over against Y metal targets, both distances are 10cm; Target d.c. sputtering power is risen to 250W, open target plate washer, start timing, sputtering sedimentation 30s, closes rapidly target plate washer afterwards, regulates direct supply power to 0W.
4, RF-reactively sputtered titanium deposits outer amorphous Si
3n
4film
After transition metal Y film deposition, regulate Ar flow to 0sccm, keep 150 ℃ of cavity envrionment temperatures, magnesium alloy substrate temperature is 250 ℃, normally vacuumizes half an hour; Pass into afterwards high-purity N
2gas (purity 99.999%) and Ar gas, regulating nitrogen flow is 25%, total flux is 60sccm, regulates chamber pressure to 0.30Pa; Rotate sample table, make sample table over against pure Si target, both distances are 8cm; Access radio-frequency power supply, opens target plate washer, and target radio-frequency sputtering power is risen to 500W, starts timing, and sputtering sedimentation 94min, closes rapidly target plate washer afterwards, regulates direct supply power to 0W.
5, Y/Si
3n
4the total film thickness of composite coating material characterizes and adopts Dektak3 Series film thickness measuring instrument, and total film thickness is 3.05 μ m.Y/Si in embodiment 4
3n
4with embodiment 1, there is Y diffraction peak in the GIXRD spectrogram of composite coating material, does not occur silicon nitride diffraction peak, and surface nitrogen SiClx exists with non-crystalline state.The XPS spectrum figure of embodiment 4 depth profilings is with embodiment 1, and result shows, silicon nitride is with compound S i
3n
4form exists.Fig. 9 is the section SEM figure of embodiment 4, (a) shows that Y is by Si
3n
4closely be connected with magnesium alloy substrate, coating is fine and close, and it is further amplified, and the thickness that can calculate Y transition layer from (b) is 100 ± 5nm.The coating binding force test of embodiment 4 is with embodiment 1, and coating binding force is good.Figure 10 and 11 is for the Electrochemical results of embodiment 4: Figure 10 is electrokinetic potential polarization curve, and Figure 11 is alternating-current impedance, and result shows, with respect to plated film magnesium alloy not, and surface coverage Y/Si
3n
4the magnesium alloy of compound coating has good corrosion resistance.Figure 12 is the liberation of hydrogen tests in 7 days of embodiment 4, and result shows, surface coverage Y/Si
3n
4the magnesium alloy of compound coating shows good corrosion resisting property (hydrogen-separating quantity is few), and along with the prolongation of soak time, hydrogen-separating quantity increases to some extent, but still shows good corrosion resistance.Figure 13 is 15 days salt-fog test cross-reference figure of embodiment 4, and experimental standard is with reference to GBT6461-2002, and defect area is less than 2.5%, protection grading R
p>=6, consistent with test result before, surface coverage Y/Si is described
3n
4the magnesium alloy of compound coating has good corrosion resistance.
Claims (6)
1. Mg alloy surface is prepared a method for yttrium/silicon nitride composite coating material, it is characterized in that comprising the following steps:
1) substrate pretreatment;
2) target pre-sputtering; Described target pre-sputtering, is that cavity environment temperature is heated to 120～150 ℃, and magnesium alloy substrate temperature is heated to 250 ℃, pass into Ar gas, flow set, at 40sccm, regulates the interior operating pressure of cavity to 1.0Pa, by Y metal targets power regulation to 180～200W, pre-sputtering 10min; Then direct supply is connected to Si target, power regulation to 180～200W, pre-sputtering 10min; To remove target material surface oxide impurity, pollute, activation target material surface atom, carries the highly purified while and also improves the sputter rate of target;
3) d.c. sputtering deposition transition metal Y film; Described d.c. sputtering deposition transition metal Y film, to confirm that cavity environment temperature is 120～150 ℃, magnesium alloy substrate temperature is to proceed as follows after 250 ℃: regulate Ar flow to 60sccm, now chamber pressure is 1.50Pa, regulates chamber pressure to 0.30Pa; Rotate sample table, make sample table over against Y metal targets, both distances are 10cm; Target d.c. sputtering power is risen to 250W, open target plate washer, start timing, sputtering sedimentation certain hour, to thickness H
1be 50～100nm, close rapidly afterwards target plate washer, regulate direct supply power to 0W;
4) RF-reactively sputtered titanium deposits outer amorphous Si
3n
4film; Described RF-reactively sputtered titanium deposits outer amorphous Si
3n
4film, is after transition metal Y film deposition, proceeds as follows: regulate Ar flow to 0sccm, keep 120～150 ℃ of cavity envrionment temperatures, magnesium alloy substrate temperature is 250 ℃, vacuumizes 30min; Pass into afterwards N
2gas and Ar gas, regulating nitrogen flow is 20～25%, total flux is 60sccm, regulates chamber pressure to 0.30Pa; Rotate sample table, make sample table over against pure Si target, both distances are 8cm; Access radio-frequency power supply, opens target plate washer, and target radio-frequency sputtering power is risen to 500W, starts timing, sputtering sedimentation for some time, to thickness be H
2, total film thickness meets H
1+ H
2=3.00 ± 0.05 μ m, closes rapidly target plate washer afterwards, regulates radio-frequency power supply power to 0W.
2. a kind of Mg alloy surface as claimed in claim 1 is prepared the method for yttrium/silicon nitride composite coating material, it is characterized in that in step 1) in, described substrate pretreatment is to carry out successively mechanical mill polished finish, ultrasonic cleaning processing, the processing of ion source Bombardment and cleaning.
3. a kind of Mg alloy surface as claimed in claim 2 is prepared the method for yttrium/silicon nitride composite coating material, it is characterized in that described mechanical mill polished finish, be first magnesium alloy to be ground to surfacing on 1000 order SiC silicon carbide papers, be placed in dehydrated alcohol ultrasonic cleaning 5min; Then on 2000 order SiC silicon carbide papers, be ground to cut in the same direction, be placed in ethanol ultrasonic cleaning 5min; Then on 5000 order SiC silicon carbide papers, along vertical 2000 order cut directions, grind 90～120s, be placed in ethanol ultrasonic cleaning 10min; With the diamond polishing cream that particle diameter is 1 μ m and 0.5 μ m, carry out polished finish on polishing disk successively again, polishing disk rotating speed is 600r/min, is polished to surface and is the nearly mirror status of light; Distilled water flushing is placed on ultrasonic cleaning 15min in acetone, is then placed in dehydrated alcohol ultrasonic cleaning 15min, moves to afterwards sample table, puts into cavity, vacuumizes and protects.
4. a kind of Mg alloy surface as claimed in claim 2 is prepared the method for yttrium/silicon nitride composite coating material, it is characterized in that described ion source Bombardment and cleaning processing, to adopt Hall ion source to clean matrix, substrate temperature is 250 ℃, regulate Ar flow to 10sccm, environmental stress is 2.3 * 10
-2pa, regulating bias voltage is-80～-100V, and cathodic current is 28.5～29.5A, and cathode voltage is 16～18V, and anodic current is 6.8～7.2A, anode voltage is 56～58V, cleans 5～8min.
5. a kind of Mg alloy surface as claimed in claim 1 is prepared the method for yttrium/silicon nitride composite coating material, and the purity that it is characterized in that described Ar gas is 99.999%; The purity of described Y metal targets is 99.9%; The purity of described Si target is 99.99%.
6. a kind of Mg alloy surface as claimed in claim 1 is prepared the method for yttrium/silicon nitride composite coating material, it is characterized in that described N
2the purity of gas is 99.999%.
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| CN109487214A (en) * | 2018-12-21 | 2019-03-19 | 昆山英利悦电子有限公司 | A kind of magnesium-alloy surface coating method and Corrosion-resistant magnesia alloy prepared therefrom |
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| US5268217A (en) * | 1990-09-27 | 1993-12-07 | Diamonex, Incorporated | Abrasion wear resistant coated substrate product |
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| Title |
|---|
| AZ31 镁合金表面磁控溅射SiN 薄膜及其性能研究;罗先盛;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20100115(第01期);B022-27 * |
| 罗先盛.AZ31 镁合金表面磁控溅射SiN 薄膜及其性能研究.《中国优秀硕士学位论文全文数据库 工程科技I辑》.2010,(第01期),B022-27. |
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