CN102912302A - 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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- CN102912302A CN102912302A CN2012103876899A CN201210387689A CN102912302A CN 102912302 A CN102912302 A CN 102912302A CN 2012103876899 A CN2012103876899 A CN 2012103876899A CN 201210387689 A CN201210387689 A CN 201210387689A CN 102912302 A CN102912302 A CN 102912302A
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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 the magnesium alloy substrate material surface and deposit first the Y intermediate metal, deposit again outer amorphous Si
3N
4Film, thickness is controlled, and a kind of Mg alloy surface with good corrosion energy prepares the method for yttrium/silicon nitride composite coating material.
Background technology
Magnesium alloy has many excellent characteristics as the lightest engineering metal material, 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, is easy to corrosion, and the second-phase in the alloy or impurity phase also can accelerate the corrosion of magnesium alloy, has 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 occuring is that base material is applied.Coat has stoped the contact between substrate and the environment, has prevented the generation of corrosion.In order to reach sufficient protective value, coat must be even, fine and close, good with the 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 to be deposited on solid material surface and to form film by gas phase material or after making the material vaporization, thereby makes material obtain a kind of new technology of special surface properties.This kind surface modifying method, technical convenience is controlled, and is environment friendly and pollution-free, is particularly suitable for industrial green modification engineering.
As everyone knows, the 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 present widely used film materials, and extremely people pay close attention to.Through analyzing to the great many of experiments of the nitride ceramics retes such as CrN, TiN, AlN, NbN and to its research on mechanism; 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 because potential difference; the subchannel that forms; 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, and is different from existing working method, uses innovatively metal Y as transition layer, then RF-reactively sputtered titanium deposited amorphous attitude Si on the basis of transition layer
3N
4Embrane method by the modulation process parameter, is finally prepared 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 prepares the method for yttrium/silicon nitride composite coating material.
The present invention includes following steps:
1) substrate pretreatment;
2) the pre-sputter of target;
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 be ground to surfacing with magnesium alloy at 1000 order SiC silicon carbide papers first, places dehydrated alcohol ultrasonic cleaning 5min; Then be ground to cut in the same direction at 2000 order SiC silicon carbide papers, place ethanol ultrasonic cleaning 5min; Then on 5000 order SiC silicon carbide papers, grind 90 ~ 120s along vertical 2000 order cut directions, place ethanol ultrasonic cleaning 10min; Be that the diamond polishing cream of 1 μ m and 0.5 μ m carries out polished finish at polishing disk with particle diameter successively again, the polishing disk rotating speed is 600r/min, is polished to the surface and is the nearly mirror status of light; Distilled water flushing is placed on ultrasonic cleaning 15min in the acetone, then places 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 the Hall ion source that matrix is cleaned, and substrate temperature is 250 ℃, regulates the Ar flow to 10sccm, and environmental stress is 2.3 * 10
-2Pa, regulate bias voltage and be-80 ~-100V, cathodic current is 28.5 ~ 29.5A, and cathode voltage is 16 ~ 18V, and anodic current is 6.8 ~ 7.2A, and anode voltage is 56 ~ 58V, cleaning 5 ~ 8min.
In step 2) in, the pre-sputter of described target, the cavity environment temperature can be heated to 120 ~ 150 ℃, the magnesium alloy substrate temperature is heated to 250 ℃, pass into Ar gas (purity 99.999%), flow set is regulated the interior operating pressure of cavity to 1.0Pa at 40sccm, with Y metal targets (purity 99.9%) power regulation to 180 ~ 200W, pre-sputter 10min; Then direct supply is connected to pure Si target (purity 99.99%), power regulation to 180 ~ 200W, pre-sputter 10min; Removing the contaminating impurity such as target material surface oxide compound, activation target material surface atom is carried the highly purified while and is also improved the sputter rate of target.
In step 3), described d.c. sputtering deposition transition metal Y film can confirm that the cavity environment temperature is 120 ~ 150 ℃, and the magnesium alloy substrate temperature is to proceed as follows after 250 ℃: regulate the Ar flow to 60sccm, this moment, chamber pressure was 1.50Pa, regulated chamber pressure to 0.30Pa; Rotate sample table, make sample table over against the Y metal targets, both distances are 10cm; Target d.c. sputtering power is risen to 250W, opens the target plate washer, the beginning timing, the sputtering sedimentation certain hour, to thickness be H
1(50 ~ 100nm), close rapidly afterwards the target plate washer, regulate 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 the Ar flow to 0sccm, keep 120 ~ 150 ℃ of cavity envrionment temperatures, the 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; The access radio-frequency power supply, open the target plate washer, target radio-frequency sputtering power is risen to 500W, the beginning timing, sputtering sedimentation for some time, to thickness be H
2, total film thickness satisfies H
1+ H
2=3.00 ± 0.05 μ m closes rapidly the 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 attitude 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, the result shows surface coverage Y/Si
3N
4The magnesium alloy of compound coating has good corrosion resistance.
Description of drawings
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 the test; (b) sample photo after the 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, X-coordinate is the real part/ohmcm of resulting impedance
2, ordinate zou is the imaginary part/ohmcm of 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 the 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, X-coordinate is the real part/ohmcm of resulting impedance
2, ordinate zou is the imaginary part/ohmcm of 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 the salt-fog test; (b) sample photo after 15 days salt-fog tests.
Embodiment
Embodiment 1
1, substrate pretreatment
(1) mechanical mill polished finish is ground to surfacing with magnesium alloy at 1000 order SiC silicon carbide papers first, places dehydrated alcohol ultrasonic cleaning 5min; Then be ground to cut in the same direction at 2000 order SiC silicon carbide papers, place ethanol ultrasonic cleaning 5min; Then on 5000 order SiC silicon carbide papers, grind 90s along vertical 2000 order cut directions, place ethanol ultrasonic cleaning 10min; Be that the diamond polishing cream of 1 μ m and 0.5 μ m carries out polished finish at polishing disk with particle diameter successively again, the polishing disk rotating speed is 600r/min, is polished to the surface and is the nearly mirror status of light, distilled water flushing.
(2) ultrasonic cleaning is processed, and places acetone ultrasonic cleaning 15min, then places dehydrated alcohol ultrasonic cleaning 15min, moves to afterwards sample table, puts into cavity, vacuumizes and protects.
(3) the ion source Bombardment and cleaning is processed, and adopts the Hall ion source that matrix is cleaned, and substrate temperature is 250 ℃, regulates the Ar flow to 10sccm, and environmental stress is 2.3 * 10
-2Pa regulates bias voltage and be-80V, and cathodic current is 29.5A, and cathode voltage is 18V, and anodic current is 7.2A, and anode voltage is 58V, cleaning 5min.
2, metal Y, the pre-sputter of pure Si target
The cavity environment temperature is heated to 120 ℃, and the magnesium alloy substrate temperature is heated to 250 ℃, passes into Ar gas (purity 99.999%), flow set is at 40sccm, regulate in the cavity operating pressure to 1.0Pa, with Y metal targets (purity 99.9%) power regulation to 180W, pre-sputter 10min; Then direct supply is connected to pure Si target (purity 99.99%), power regulation is to 180W, pre-sputter 10min; Removing the contaminating impurity such as target material surface oxide compound, activation target material surface atom is carried the highly purified while and is also improved the sputter rate of target.
3, d.c. sputtering deposition transition metal Y film
Confirm that the cavity environment temperature is 120 ℃, the magnesium alloy substrate temperature is 250 ℃.Regulate the Ar flow to 60sccm, this moment, chamber pressure was 1.50Pa, regulated chamber pressure to 0.30Pa; Rotate sample table, make sample table over against the Y metal targets, both distances are 10cm; Target d.c. sputtering power is risen to 250W, open the target plate washer, the beginning timing, sputtering sedimentation 15s closes rapidly the 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 the Ar flow to 0sccm, keep 120 ℃ of cavity envrionment temperatures, the 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; The access radio-frequency power supply is opened the target plate washer, and target radio-frequency sputtering power is risen to 500W, the beginning timing, and sputtering sedimentation 96min closes rapidly the 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, the coating that shows preparation are the Y coatings with close-packed hexagonal structure, the diffraction peak of silicon nitride do not occur, illustrate that silicon nitride is that non-crystalline state exists.Fig. 2 is the XPS figure of embodiment 1 depth profiling, and the surface nitrogen SiClx is compound S i
3N
4Fig. 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 the Y transition layer is 50 ± 5nm.Fig. 4 is embodiment 1 coating binding force test cross-reference figure: (a) embodiment 1 sample before the test; (b) sample after the test.Experimental standard is with reference to ASTM D3359-02, and the result shows that there is a small amount of disbonding at the place, point of crossing, but area of infection illustrates that less than 5% coating binding force is good.Fig. 5 and Fig. 6 are that the Electrochemical results of embodiment 1: Fig. 5 is the electrokinetic potential polarization curve; Fig. 6 is alternating-current impedance, and the 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 the 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 protected grading R less than 0.5%
p〉=8, consistent with before test result, surface coverage Y/Si is described
3N
4The magnesium alloy of compound coating has good corrosion resistance really.
1, substrate pretreatment
(1) mechanical mill polished finish is ground to surfacing with magnesium alloy at 1000 order SiC silicon carbide papers first, places dehydrated alcohol ultrasonic cleaning 5min; Then be ground to cut in the same direction at 2000 order SiC silicon carbide papers, place ethanol ultrasonic cleaning 5min; Then on 5000 order SiC silicon carbide papers, grind 100s along vertical 2000 order cut directions, place ethanol ultrasonic cleaning 10min; Be that the diamond polishing cream of 1 μ m and 0.5 μ m carries out polished finish at polishing disk with particle diameter successively again, the polishing disk rotating speed is 600r/min, is polished to the surface and is the nearly mirror status of light, distilled water flushing.
(2) ultrasonic cleaning is processed, with embodiment 1.
(3) the ion source Bombardment and cleaning is processed, and adopts the Hall ion source that matrix is cleaned, and substrate temperature is 250 ℃, regulates the Ar flow to 10sccm, and environmental stress is 2.3 * 10
-2Pa regulates bias voltage and be-90V, and cathodic current is 28.5A, and cathode voltage is 16V, and anodic current is 6.5A, and anode voltage is 56V, cleaning 8min.
2, metal Y, the pre-sputter of pure Si target
The cavity environment temperature is heated to 130 ℃, and the magnesium alloy substrate temperature is heated to 250 ℃, passes into Ar gas (purity 99.999%), flow set is at 40sccm, regulate in the cavity operating pressure to 1.0Pa, with Y metal targets (purity 99.9%) power regulation to 190W, pre-sputter 10min; Then direct supply is connected to pure Si target (purity 99.99%), power regulation is to 190W, pre-sputter 10min; Removing the contaminating impurity such as target material surface oxide compound, activation target material surface atom is carried the highly purified while and is also improved the sputter rate of target.
3, d.c. sputtering deposition transition metal Y film
Confirm that the cavity environment temperature is 130 ℃, the magnesium alloy substrate temperature is 250 ℃.Regulate the Ar flow to 60sccm, this moment, chamber pressure was 1.50Pa, regulated chamber pressure to 0.30Pa; Rotate sample table, make sample table over against the Y metal targets, both distances are 10cm; Target d.c. sputtering power is risen to 250W, open the target plate washer, the beginning timing, sputtering sedimentation 18s closes rapidly the 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 the Ar flow to 0sccm, keep 130 ℃ of cavity envrionment temperatures, the 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; The access radio-frequency power supply is opened the target plate washer, and target radio-frequency sputtering power is risen to 500W, the beginning timing, and sputtering sedimentation 95.5min closes rapidly the 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, the diffraction peak of silicon nitride do not occur, illustrates that silicon nitride is that non-crystalline state exists.The XPS figure of embodiment 2 depth profilings is with embodiment 1, and the surface nitrogen SiClx is compound S i
3N
4The 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 the 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 protected grading R less than 0.5%
p〉=8, consistent with before test result, 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 ground to surfacing with magnesium alloy at 1000 order SiC silicon carbide papers first, places dehydrated alcohol ultrasonic cleaning 5min; Then be ground to cut in the same direction at 2000 order SiC silicon carbide papers, place ethanol ultrasonic cleaning 5min; Then on 5000 order SiC silicon carbide papers, grind 110s along vertical 2000 order cut directions, place ethanol ultrasonic cleaning 10min; Be that the diamond polishing cream of 1 μ m and 0.5 μ m carries out polished finish at polishing disk with particle diameter successively again, the polishing disk rotating speed is 600r/min, is polished to the surface and is the nearly mirror status of light, distilled water flushing.
(2) ultrasonic cleaning is processed, with embodiment 1.
(3) the ion source Bombardment and cleaning is processed, and adopts the Hall ion source that matrix is cleaned, and substrate temperature is 250 ℃, regulates the Ar flow to 10sccm, and environmental stress is 2.3 * 10
-2Pa regulates bias voltage and be-100V, and cathodic current is 29A, and cathode voltage is 17V, and anodic current is 6.8A, and anode voltage is 57V, cleaning 7min.
2, metal Y, the pre-sputter of pure Si target
The cavity environment temperature is heated to 140 ℃, and the magnesium alloy substrate temperature is heated to 250 ℃, passes into Ar gas (purity 99.999%), flow set is at 40sccm, regulate in the cavity operating pressure to 1.0Pa, with Y metal targets (purity 99.9%) power regulation to 200W, pre-sputter 10min; Then direct supply is connected to pure Si target (purity 99.99%), power regulation is to 200W, pre-sputter 10min; Removing the contaminating impurity such as target material surface oxide compound, activation target material surface atom is carried the highly purified while and is also improved the sputter rate of target.
3, d.c. sputtering deposition transition metal Y film
Confirm that the cavity environment temperature is 140 ℃, the magnesium alloy substrate temperature is 250 ℃.Regulate the Ar flow to 60sccm, this moment, chamber pressure was 1.50Pa, regulated chamber pressure to 0.30Pa; Rotate sample table, make sample table over against the Y metal targets, both distances are 10cm; Target d.c. sputtering power is risen to 250W, open the target plate washer, the beginning timing, sputtering sedimentation 24s closes rapidly the 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 the Ar flow to 0sccm, keep 140 ℃ of cavity envrionment temperatures, the 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; The access radio-frequency power supply is opened the target plate washer, and target radio-frequency sputtering power is risen to 500W, the beginning timing, and sputtering sedimentation 95min closes rapidly the 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, the diffraction peak of silicon nitride do not occur, illustrates that silicon nitride is that non-crystalline state exists.The XPS figure of embodiment 3 depth profilings is with embodiment 1, and the surface nitrogen SiClx is compound S i
3N
4The 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 preferably 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 protected grading R less than 1%
p〉=7, consistent with before test result, surface coverage Y/Si is described
3N
4The magnesium alloy of compound coating has good corrosion resistance really.
1, substrate pretreatment
(1) mechanical mill polished finish is ground to surfacing with magnesium alloy at 1000 order SiC silicon carbide papers first, places dehydrated alcohol ultrasonic cleaning 5min; Then be ground to cut in the same direction at 2000 order SiC silicon carbide papers, place ethanol ultrasonic cleaning 5min; Then on 5000 order SiC silicon carbide papers, grind 120s along vertical 2000 order cut directions, place ethanol ultrasonic cleaning 10min; Be that the diamond polishing cream of 1 μ m and 0.5 μ m carries out polished finish at polishing disk with particle diameter successively again, the polishing disk rotating speed is 600r/min, is polished to the surface and is the nearly mirror status of light, distilled water flushing.
(2) ultrasonic cleaning is processed, with embodiment 1.
(3) the ion source Bombardment and cleaning is processed, and adopts the Hall ion source that matrix is cleaned, and substrate temperature is 250 ℃, regulates the Ar flow to 10sccm, and environmental stress is 2.3 * 10
-2Pa regulates bias voltage and be-100V, and cathodic current is 29.2A, and cathode voltage is 17V, and anodic current is 7.2A, and anode voltage is 58V, cleaning 6min.
2, metal Y, the pre-sputter of pure Si target
The cavity environment temperature is heated to 150 ℃, and the magnesium alloy substrate temperature is heated to 250 ℃, passes into Ar gas (purity 99.999%), flow set is at 40sccm, regulate in the cavity operating pressure to 1.0Pa, with Y metal targets (purity 99.9%) power regulation to 200W, pre-sputter 10min; Then direct supply is connected to pure Si target (purity 99.99%), power regulation is to 200W, pre-sputter 10min; Removing the contaminating impurity such as target material surface oxide compound, activation target material surface atom is carried the highly purified while and is also improved the sputter rate of target.
3, d.c. sputtering deposition transition metal Y film
Confirm that the cavity environment temperature is 150 ℃, the magnesium alloy substrate temperature is 250 ℃.Regulate the Ar flow to 60sccm, this moment, chamber pressure was 1.50Pa, regulated chamber pressure to 0.30Pa; Rotate sample table, make sample table over against the Y metal targets, both distances are 10cm; Target d.c. sputtering power is risen to 250W, open the target plate washer, the beginning timing, sputtering sedimentation 30s closes rapidly the 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 the Ar flow to 0sccm, keep 150 ℃ of cavity envrionment temperatures, the 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; The access radio-frequency power supply is opened the target plate washer, and target radio-frequency sputtering power is risen to 500W, the beginning timing, and sputtering sedimentation 94min closes rapidly the 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 among the embodiment 4
3N
4The GIXRD spectrogram of composite coating material the Y diffraction peak occurs with embodiment 1, the silicon nitride diffraction peak do not occur, and the surface nitrogen SiClx exists with non-crystalline state.The XPS spectrum figure of embodiment 4 depth profilings is with embodiment 1, and the result shows that 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 with Si
3N
4Closely be connected with magnesium alloy substrate, coating is fine and close, and to its further amplification, the thickness that can calculate the 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 the electrokinetic potential polarization curve, and Figure 11 is alternating-current impedance, and the 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 the result shows, surface coverage Y/Si
3N
4The magnesium alloy of compound coating shows preferably 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 preferably 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 protected grading R less than 2.5%
p〉=6, consistent with before test result, surface coverage Y/Si is described
3N
4The magnesium alloy of compound coating has good corrosion resistance.
Claims (9)
1. a Mg alloy surface prepares the method for yttrium/silicon nitride composite coating material, it is characterized in that may further comprise the steps:
1) substrate pretreatment;
2) the pre-sputter of target;
3) d.c. sputtering deposition transition metal Y film;
4) RF-reactively sputtered titanium deposits outer amorphous Si
3N
4Film.
2. a kind of Mg alloy surface as claimed in claim 1 prepares the method for yttrium/silicon nitride composite coating material, it is characterized in that in step 1), 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 prepares 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 at 1000 order SiC silicon carbide papers, place dehydrated alcohol ultrasonic cleaning 5min; Then be ground to cut in the same direction at 2000 order SiC silicon carbide papers, place ethanol ultrasonic cleaning 5min; Then on 5000 order SiC silicon carbide papers, grind 90 ~ 120s along vertical 2000 order cut directions, place ethanol ultrasonic cleaning 10min; Be that the diamond polishing cream of 1 μ m and 0.5 μ m carries out polished finish at polishing disk with particle diameter successively again, the polishing disk rotating speed is 600r/min, is polished to the surface and is the nearly mirror status of light; Distilled water flushing is placed on ultrasonic cleaning 15min in the acetone, then places 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 prepares the method for yttrium/silicon nitride composite coating material, it is characterized in that described ion source Bombardment and cleaning processing, to adopt the Hall ion source that matrix is cleaned, substrate temperature is 250 ℃, regulate the Ar flow to 10sccm, environmental stress is 2.3 * 10
-2Pa, regulate bias voltage and be-80 ~-100V, cathodic current is 28.5 ~ 29.5A, and cathode voltage is 16 ~ 18V, and anodic current is 6.8 ~ 7.2A, and anode voltage is 56 ~ 58V, cleaning 5 ~ 8min.
5. a kind of Mg alloy surface as claimed in claim 1 prepares the method for yttrium/silicon nitride composite coating material, it is characterized in that in step 2) in, the pre-sputter of described target, be that the cavity environment temperature is heated to 120 ~ 150 ℃, the magnesium alloy substrate temperature is heated to 250 ℃, passes into Ar gas, flow set is at 40sccm, regulate the interior operating pressure of cavity to 1.0Pa, with Y metal targets power regulation to 180 ~ 200W, pre-sputter 10min; Then direct supply is connected to the Si target, power regulation to 180 ~ 200W, pre-sputter 10min; Pollute to remove the target material surface oxide impurity, activation target material surface atom is carried the highly purified while and is also improved the sputter rate of target.
6. a kind of Mg alloy surface as claimed in claim 5 prepares 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%.
7. a kind of Mg alloy surface as claimed in claim 1 prepares the method for yttrium/silicon nitride composite coating material, it is characterized in that in step 3), described d.c. sputtering deposition transition metal Y film, to confirm that the cavity environment temperature is 120 ~ 150 ℃, the magnesium alloy substrate temperature is to proceed as follows after 250 ℃: regulate the Ar flow to 60sccm, this moment, chamber pressure was 1.50Pa, regulated chamber pressure to 0.30Pa; Rotate sample table, make sample table over against the Y metal targets, both distances are 10cm; Target d.c. sputtering power is risen to 250W, opens the target plate washer, the beginning timing, the sputtering sedimentation certain hour, to thickness be 50 ~ 100nm, close rapidly afterwards the target plate washer, regulate direct supply power to 0W.
8. a kind of Mg alloy surface as claimed in claim 1 prepares the method for yttrium/silicon nitride composite coating material, it is characterized in that in step 4), and described RF-reactively sputtered titanium deposits outer amorphous Si
3N
4Film is after transition metal Y film deposition, and proceed as follows: regulate the Ar flow to 0sccm, keep 120 ~ 150 ℃ of cavity envrionment temperatures, the magnesium alloy substrate temperature is 250 ℃, vacuumizes half an hour; 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; The access radio-frequency power supply, open the target plate washer, target radio-frequency sputtering power is risen to 500W, the beginning timing, sputtering sedimentation for some time, to thickness be H
2, total film thickness satisfies H
1+ H
2=3.00 ± 0.05 μ m closes rapidly the target plate washer afterwards, regulates direct supply power to 0W.
9. a kind of Mg alloy surface as claimed in claim 8 prepares 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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| CN114824229A (en) * | 2022-05-23 | 2022-07-29 | 厦门大学 | Preparation method of high-performance secondary zinc battery cathode silver-doped aluminum nitride coating |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103239761A (en) * | 2013-05-17 | 2013-08-14 | 天津理工大学 | Silicon-nitride-coated medical magnesium alloy material and preparation method thereof |
| WO2019014449A1 (en) * | 2017-07-13 | 2019-01-17 | Applied Materials, Inc. | Methods and apparatus for depositing yttrium-containing films |
| US20190017171A1 (en) * | 2017-07-13 | 2019-01-17 | Applied Materials, Inc. | Methods and Apparatus for Depositing Yttrium-Containing Films |
| KR20200019769A (en) * | 2017-07-13 | 2020-02-24 | 어플라이드 머티어리얼스, 인코포레이티드 | Methods and apparatus for depositing yttrium-containing films |
| CN110892507A (en) * | 2017-07-13 | 2020-03-17 | 应用材料公司 | Method and apparatus for depositing yttrium-containing films |
| US10760159B2 (en) * | 2017-07-13 | 2020-09-01 | Applied Materials, Inc. | Methods and apparatus for depositing yttrium-containing films |
| TWI770206B (en) * | 2017-07-13 | 2022-07-11 | 美商應用材料股份有限公司 | Methods and apparatus for depositing yttrium-containing films |
| CN110892507B (en) * | 2017-07-13 | 2023-07-18 | 应用材料公司 | Method and apparatus for depositing yttrium-containing films |
| TWI817555B (en) * | 2017-07-13 | 2023-10-01 | 美商應用材料股份有限公司 | Processing chambers |
| KR102633017B1 (en) * | 2017-07-13 | 2024-02-01 | 어플라이드 머티어리얼스, 인코포레이티드 | Methods and apparatus for depositing yttrium-containing films |
| 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 |
| CN114824229A (en) * | 2022-05-23 | 2022-07-29 | 厦门大学 | Preparation method of high-performance secondary zinc battery cathode silver-doped aluminum nitride coating |
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