CN107164744A - A kind of Mg alloy surface anti-corrosion coating preparation method - Google Patents
A kind of Mg alloy surface anti-corrosion coating preparation method Download PDFInfo
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- CN107164744A CN107164744A CN201710164755.9A CN201710164755A CN107164744A CN 107164744 A CN107164744 A CN 107164744A CN 201710164755 A CN201710164755 A CN 201710164755A CN 107164744 A CN107164744 A CN 107164744A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
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Abstract
A kind of Mg alloy surface anti-corrosion coating preparation method, comprises the following steps：（1）Magnesium alloy dehydrogenation；（2）ALD working chambers prepare；（3）ALD prepares anti-corrosion coating；（4）ALD working chambers are reduced.Using atomic layer epitaxy technology, the self limiting of preparation process is utilized（Adsorb self limiting and reaction self limiting）, prepare that thickness evenness is good, component control is accurate, compactness is good, each type oxide strong with the associativity of magnesium alloy substrate, nitride, composite corrosion proof coating in Mg alloy surface., can be in Arbitrary surfaces prepares coating in preparation, and temperature is unique technological parameter, easy to control and technology stability is good.
Description
Technical field
The invention belongs to Magnesiumalloy surface modifying treatment technology, prepared by the more particularly to anticorrosive coating on surface of magnesium alloy.
Background technology
Magnesium alloy is structural metallic materials most light in practical application, has the advantages that height than mould and is easily reclaimed than strong, high,
It is described as " 21st century green engineering material ".With the increasingly depleted of many metallic mineral resources, magnesium day with its aboundresources
Benefit is taken seriously, and particularly China requires higher big aircraft, around the moon, high-speed rail transportation, electronic to structure lightened at present
The startup of the Larger Engineering Projects such as automobile, there is bigger demand to magnesium alloy.With deepening continuously for China magnesium alloy research,
Significant progress is achieved in terms of the technical research such as magnesium alloyization design, plastic deformation.But magnesium is in structural metallic materials
With minimum standard electrode potential, and its oxide-film is loose porous, and the PBR ratios of oxide-film are 0.81, it is impossible to form effective
Stable diaphragm, easily there are the etching problems such as galvanic corrosion, environmental corrosion under most of corrosive atmospheres, it is impossible to continue
Use.Improve the corrosion resistance of magnesium alloy has turned into magnesium alloy extensively using the key issue that must be solved.
Magnesium alloy and corrosive medium are completely cut off, surface coating is fine and close, chemical inertness and with good resistance to of magnesium alloy associativity
Erosion resisting coating is to improve one of most effective approach of corrosion stability of magnesium alloy energy.Current anti-corrosion coating mainly has organic coating, anti-corrosion gold
Belong to coating and compound coat etc..Organic coating use main technique have japanning, electrostatic spraying, electrophoresis etc. Hu R G,
Zhang S, Bu J F, et al. Progress in Organic Coatings, 2012,73:129-141 ］, metal and
The major technique that compound coat is used is electricity/chemical plating ［ Liu J J, Wang X D, et al. Applied surface
science, 2015, 356:289-293 ］, cold spraying ［ Xiong Y M, Zhang M X. Surface ＆Coatings
Technology, 2014, 253:89-95 ］, sputtering [Li Zhonghou, Guo Tengteng, Gong Xuebo, wait sufacings, 2014,
43( 6) :121-124], technology [Zhu R D, Li Z Y, the et al. Applied such as high energy beam current surface cladding
Surface Science, 2015, 353: 405-413].Above-mentioned coating technique can only typically adapt to one or more of anti-corrosion paintings
The preparation of layer, adapts to anti-corrosion coating material category limited；And generally existing coating thickness evenness, component control accuracy,
Compactness, associativity, industrial Applicability problem with magnesium alloy substrate；And be difficult to generate three-dimensionality anticorrosion layer or Step Coverage.
The content of the invention
The purpose of the present invention is to propose to a kind of Mg alloy surface anti-corrosion coating preparation method.Using atomic layer epitaxy technology
（atomic layer deposition, ALD）, utilize the self limiting of preparation process（Adsorb self limiting and reaction self limiting）,
Prepare that thickness evenness is good, component control is accurate, compactness is good in Mg alloy surface, with the associativity of magnesium alloy substrate by force each
Type oxide, nitride, composite corrosion proof coating., can be in Arbitrary surfaces prepares coating in preparation, and temperature is unique work
Skill parameter, easy to control and technology stability is good.
The present invention is to be achieved through the following technical solutions.
A kind of Mg alloy surface anti-corrosion coating preparation method of the present invention, comprises the following steps.
（1）Magnesium alloy dehydrogenation：160 ~ 200 DEG C of controlled atmosphere furnace furnace temperature, is incubated 1 ~ 2 hour.
（2）ALD working chambers prepare：Confirm supply gas pressure, dry air storage pressure is 0.45 ~ 0.55MPa, reactant gas source
Storage pressure is 0.2MPa；It is respectively 100 DEG C, 100 DEG C, 100 DEG C, 300 DEG C to set heater, cavity, purging, hot trap temperature,
Open vavuum pump, flowmeter；Temperature stabilization is treated, heater, vavuum pump, mass air flow sensor is closed, being inflated to pressure is
760torr；Working cavity is opened, magnesium alloy sample is put into, chamber door is closed, vavuum pump is opened.
（3）ALD prepares anti-corrosion coating：Anticorrosion layer can be any oxide, any nitride film.Membrane-film preparation process
Relate generally to two kinds of reactant gas sources, its process is：According to film species, set heter temperature, purging temperature, hot trap temperature,
Pump tube temperature, operation pressure；Into the formula page, each source of the gas gas injection/purge time, the order and global cycle of source of the gas gas injection are set
Number of times.The first reactant gas source gas injection, in Mg alloy surface physical absorption, purges the first gas not to be adsorbed；Second anti-
Answer source of the gas gas injection in Mg alloy surface, chemically reacted with the first reactant gas source, purge second of gas not to be adsorbed；It is inhaled
Attached process and course of reaction are respectively provided with self limiting, with the accuracy for the molecular scale for ensureing film chemical component.The thickness of film
It is single cycle film thickness typically 0.05 ~ 0.1nm of increase, to ensure receiving for film integral thickness by cycle-index control
Meter level accuracy.
Described oxide is Al2O3、TiO2、HfO2Deng.
Described nitride is InN, AlN, GaN etc..
Gradually plural layers can also be prepared on single thin film of the present invention by stack, form composite bed.
（4）ALD working chambers are reduced：Reactant gas source is closed, it is respectively 100 to set heater, cavity, purging, hot trap temperature
℃、100℃、100℃、300℃；Temperature stabilization is treated, vavuum pump, flowmeter, heater is closed, pressure is inflated to for 760torr；
Working cavity is opened, magnesium alloy sample is taken out, chamber door is closed.
The present invention is completed in PE-ALD equipment.
The present invention proposes prepared by a kind of Mg alloy surface anticorrosion layer, available for oxide mono, nitride individual layer or compound
It is prepared by layer anticorrosion layer.Prepared coating has high fine and close, uniform, precise stoichiometry than feature, can be in Arbitrary surfaces
Prepares coating, and temperature is unique technological parameter, easy to control and technology stability is good.
Embodiment
The present invention will be further described with the following Examples.
Embodiments of the invention are completed in PE-ALD-100A equipment.
Embodiment 1.
Magnesium alloy sample is the AZ31 of 90mm × 90mm × 0.5mm sizes, surface mirror finish（Below Ra0.2）, plating
20nm thickness Al2O3Anticorrosion layer, with trimethyl aluminium（Abbreviation TMA）, water（H2O）For reactant gas source.Sample dehydrogenation.ALD working chambers
Prepare.It is respectively 150 DEG C, 120 DEG C/80 DEG C, 400 DEG C, 100 DEG C to set heater, purging, hot trap, pump tube temperature；Operation pressure
For 0.15torr；TMA gas injections, purge time are 0.02s and 60s, H2O gas injections, purge time are 0.02s and 60s, through 400 times
Circulation completes coating and prepared.ALD working chambers are reduced, sampling.Characterized by atom-probe（AFM）Detection, obtaining coating layer thickness is
20nm；Plate the forward and backward droplet test of anticorrosion layer（0.05 g potassium permanganate and 5 ml nitric acid are dissolved in the purple in 95 ml distilled water
Solution drops in specimen surface, sees the time that solution is become colorless by purple）It is respectively 3.4s and 39.6s for the time；Microhardness
80.38 HV are increased to by 63.42 HV；Corrosion potential in 3.5% NaCl solution is changed into -1.445V from -1.621V；
Corrosion current density is by 5.517 × 10-8A/cm2Change turns to 3.462 × 10-8A/cm2。
Embodiment 2.
Magnesium alloy sample is the AZ31 of 90mm × 90mm × 0.5mm sizes, surface mirror finish（Below Ra0.2）Plate 25nm
Thick Al2O3Anticorrosion layer, with trimethyl aluminium（Abbreviation TMA）, water（H2O）For reactant gas source.Sample dehydrogenation.ALD working chambers are accurate
It is standby.It is respectively 150 DEG C, 120 DEG C/80 DEG C, 400 DEG C, 100 DEG C to set heater, purging, hot trap, pump tube temperature；Operation pressure is
0.15torr；TMA gas injections, purge time are 0.02s and 60s, H2O gas injections, purge time are 0.02s and 60s, are followed through 500 times
Ring completes coating and prepared.ALD working chambers are reduced, sampling.Characterized by atom-probe（AFM）Detection, obtains coating layer thickness for 25nm；
Plate the forward and backward droplet test of anticorrosion layer（0.05 g potassium permanganate and 5 ml nitric acid are dissolved in the purple solution drop in 95 ml distilled water
In specimen surface, the time that solution is become colorless by purple is seen）It is respectively 3.4s and 52.5s for the time；Microhardness is by 63.42
HV increases to 97.5 HV；Corrosion potential in 3.5% NaCl solution is changed into -1.358V from -1.621V；Corrosion current
Density is by 5.517 × 10-8A/cm2Change turns to 2.455 × 10-8A/cm2。
Embodiment 3.
Magnesium alloy sample is the AZ31 of 90mm × 90mm × 0.5mm sizes, surface mechanical attrition treatment（SMAT processing
3min, Ra10）Plate 20nm thickness Al2O3Anticorrosion layer, with trimethyl aluminium（Abbreviation TMA）, water（H2O）For reactant gas source.Sample dehydrogenation
Processing.ALD working chambers prepare.To set heater, purging, hot trap, pump tube temperature be respectively 150 DEG C, 120 DEG C/80 DEG C, 400 DEG C,
100℃；Operation pressure is 0.15torr；TMA gas injections, purge time are 0.02s and 60s, H2O gas injections, purge time are 0.02s
And 60s, complete coating through 400 circulations and prepare.ALD working chambers are reduced, sampling.Coating layer thickness is 20nm；Plate anticorrosion layer forward and backward
Droplet test（The purple solution that 0.05 g potassium permanganate and 5 ml nitric acid are dissolved in 95 ml distilled water is dropped in into specimen surface, seen
The time that solution is become colorless by purple）It is respectively 3.2s and 66s for the time；Microhardness increases to 90.4 HV by 76 HV；
Corrosion potential in 3.5% NaCl solution is changed into -1.375V from -1.701V；Corrosion current density by 6.5017 ×
10-8A/cm2Change turns to 2.062 × 10-8A/cm2。
Embodiment 4.
Magnesium alloy sample is the AZ31 of 90mm × 90mm × 0.5mm sizes, surface mechanical attrition treatment（SMAT processing
6min, Ra20）Plate 20nm thickness Al2O3Anticorrosion layer, with trimethyl aluminium（Abbreviation TMA）, water（H2O）For reactant gas source.Sample dehydrogenation
Processing.ALD working chambers prepare.To set heater, purging, hot trap, pump tube temperature be respectively 150 DEG C, 120 DEG C/80 DEG C, 400 DEG C,
100℃；Operation pressure is 0.15torr；TMA gas injections, purge time are 0.02s and 60s, H2O gas injections, purge time are 0.02s
And 60s, complete coating through 400 circulations and prepare.ALD working chambers are reduced, sampling.Coating layer thickness is 20nm；Plate anticorrosion layer forward and backward
Droplet test（The purple solution that 0.05 g potassium permanganate and 5 ml nitric acid are dissolved in 95 ml distilled water is dropped in into specimen surface, seen
The time that solution is become colorless by purple）It is respectively 7.9s and 192.1s for the time；Microhardness is increased to by 96.2 HV
100.2HV；Corrosion potential in 3.5% NaCl solution is changed into -1.400V from -1.710V；Corrosion current density by
7.332×10-8A/cm2Change turns to 3.642 × 10-8A/cm2。
Embodiment 5.
Magnesium alloy sample is the AZ31 of 90mm × 90mm × 0.5mm sizes, surface mirror finish（Below Ra0.2）, plating
20nm thickness TiO2Anticorrosion layer, with different oxygen titanium propanolate, water（H2O）For reactant gas source.Sample dehydrogenation.ALD working chambers prepare.If
It is respectively 250 DEG C, 120 DEG C/80 DEG C, 400 DEG C, 100 DEG C to put heater, purging, hot trap, pump tube temperature；Operation pressure is
0.15torr, different oxygen titanium propanolate gas injection, purge time are 0.2s and 80s, and water gas injection, purge time are 0.015s and 80s, warp
400 circulations complete coating and prepared.ALD working chambers are reduced, sampling.Characterized by atom-probe（AFM）Detection, obtains coating layer thickness
For 20nm；Plate the forward and backward droplet test of anticorrosion layer（0.05 g potassium permanganate and 5 ml nitric acid are dissolved in the purple in 95 ml distilled water
Color solution drops in specimen surface, sees the time that solution is become colorless by purple）It is respectively 3.4s and 50s for the time；Microhardness
90.02 HV are increased to by 63.42 HV；Corrosion potential in 3.5% NaCl solution is changed into -1.345V from -1.621V；
Corrosion current density is by 5.517 × 10-8A/cm2Change turns to 3.062 × 10-8A/cm2。
Embodiment 6.
Magnesium alloy sample is the AZ31 of 90mm × 90mm × 0.5mm sizes, surface mirror finish（Below Ra0.2）, plating
20nm thickness InN anticorrosion layers, with trimethyl indium（Abbreviation TMIn）, nitrogen（N2）For reactant gas source.Sample dehydrogenation.ALD works
Chamber prepares.It is respectively 250 DEG C, 120 DEG C/80 DEG C, 400 DEG C, 100 DEG C to set heater, purging, hot trap, pump tube temperature；Technique pressure
Power is 0.15torr；TMIn gas injections, purge time are 0.3s and 80s, N2Gas injection, purge time are 0.02s and 60s, through 400 times
Circulation completes coating and prepared.ALD working chambers are reduced, sampling.Characterized by atom-probe（AFM）Detection, obtaining coating layer thickness is
20nm；Plate the forward and backward droplet test of anticorrosion layer（0.05 g potassium permanganate and 5 ml nitric acid are dissolved in the purple in 95 ml distilled water
Solution drops in specimen surface, sees the time that solution is become colorless by purple）It is respectively 3.3s and 35s for the time；Microhardness by
63.42 HV increase to 79.0 HV；Corrosion potential in 3.5% NaCl solution is changed into -1.545V from -1.621V；From corruption
Current density is lost by 5.517 × 10-8A/cm2Change turns to 3.862 × 10-8A/cm2。
Embodiment 7.
Magnesium alloy sample is the AZ31 of 90mm × 90mm × 0.5mm sizes, surface mirror finish（Below Ra0.2）, plating
20nm thickness Al2O3/TiO2Anticorrosion layer.With trimethyl aluminium（Abbreviation TMA）, different oxygen titanium propanolate, water（H2O）For reactant gas source.Sample is removed
Hydrogen processing.ALD working chambers prepare.With different oxygen titanium propanolate, water（H2O）For reactant gas source.Heater, purging, hot trap, pump line are set
Temperature is respectively 250 DEG C, 120 DEG C/80 DEG C, 400 DEG C, 100 DEG C；Operation pressure is 0.15torr；Different oxygen titanium propanolate gas injection, purging
Time is 0.2s and 80s, and water gas injection, purge time are 0.015s and 80s, and TiO is completed through 200 circulations2Coating；With front three
Base aluminium（Abbreviation TMA）, water（H2O）For reactant gas source, to set heater, purging, hot trap, pump tube temperature be respectively 150 DEG C, 120
℃/80℃、400℃、100℃；Operation pressure is 0.15torr；TMA gas injections, purge time are 0.02s and 60s, H2O gas injections,
Purge time is 0.02s and 60s, and Al is completed through 200 circulations2O3It is prepared by coating.ALD working chambers are reduced, sampling.Visited by atom
Pin is characterized（AFM）Detection, obtains coating layer thickness for 20nm；Plate the forward and backward droplet test of anticorrosion layer（By 0.05 g potassium permanganate and 5
The purple solution that ml nitric acid is dissolved in 95 ml distilled water drops in specimen surface, sees the time that solution is become colorless by purple）For when
Between be respectively 3.4s and 70s；Microhardness increases to 112.6HV by 63.42 HV；Self-corrosion in 3.5% NaCl solution
Current potential is changed into -1.245V from -1.621V；Corrosion current density is by 5.517 × 10-8A/cm2Change turns to 2.862 × 10-8A/
cm2。
Embodiment 8.
Magnesium alloy sample is the AZ91 of 90mm × 90mm × 0.5mm sizes, surface mirror finish（Below Ra0.2）, plating
20nm thickness Al2O3/ GaN anticorrosion layers, with trimethyl aluminium（Abbreviation TMA）, water（H2O）, trimethyl gallium（Abbreviation TMGa）, ammonia（NH3）
For reactant gas source.Sample dehydrogenation.ALD working chambers prepare.With trimethyl gallium（Abbreviation TMGa）, ammonia（NH3）For reaction gas
Source, it is respectively 250 DEG C, 120 DEG C/80 DEG C, 400 DEG C, 100 DEG C to set heater, purging, hot trap, pump tube temperature；Operation pressure is
0.15torr；TMGa gas injections, purge time are 0.3s and 80s, NH3Gas injection, purge time are 0.02s and 60s, are followed through 200 times
Ring completes GaN coatings and prepared.To set heater, purging, hot trap, pump tube temperature be respectively 150 DEG C, 120 DEG C/80 DEG C, 400 DEG C,
100℃；Operation pressure is 0.15torr, and TMA gas injections, purge time are 0.02s and 60s, H2O gas injections, purge time are 0.02s
And 60s, complete Al through 200 circulations2O3It is prepared by coating.ALD working chambers are reduced, sampling.Characterized by atom-probe（AFM）Detection,
Coating layer thickness is obtained for 20nm；Plate the forward and backward droplet test of anticorrosion layer（0.05 g potassium permanganate and 5 ml nitric acid are dissolved in 95 ml
Purple solution in distilled water drops in specimen surface, sees the time that solution is become colorless by purple）For the time be respectively 3.9s and
40.5s；Microhardness increases to 70.38 HV by 55 HV；Corrosion potential in 3.5% NaCl solution is become by -1.621V
For -1.321V；Corrosion current density is by 5.517 × 10-8A/cm2Change turns to 0.423 × 10-8A/cm2。
Claims (4)
1. a kind of Mg alloy surface anti-corrosion coating preparation method, it is characterized in that comprising the following steps：
（1）Magnesium alloy dehydrogenation：160 ~ 200 DEG C of controlled atmosphere furnace furnace temperature, is incubated 1 ~ 2 hour；
（2）ALD working chambers prepare：Confirm supply gas pressure, dry air storage pressure is 0.45 ~ 0.55MPa, reactant gas source gas cylinder
Pressure is 0.2MPa；It is respectively 100 DEG C, 100 DEG C, 100 DEG C, 300 DEG C to set heater, cavity, purging, hot trap temperature, is opened
Vavuum pump, flowmeter；Temperature stabilization is treated, heater, vavuum pump, mass air flow sensor is closed, pressure is inflated to for 760torr；Beat
Working cavity is opened, magnesium alloy sample is put into, chamber door is closed, vavuum pump is opened；
（3）ALD prepares anti-corrosion coating：Anticorrosion layer is any oxide, any nitride film；Membrane-film preparation process is related to two kinds
Reactant gas source, its process is：According to film species, heter temperature, purging temperature, hot trap temperature, pump tube temperature, technique are set
Pressure；Into the formula page, each source of the gas gas injection/purge time, the order and global cycle number of times of source of the gas gas injection are set；The first is anti-
Source of the gas gas injection is answered, in Mg alloy surface physical absorption, the first gas not to be adsorbed is purged；Second of reactant gas source gas injection is in magnesium
Alloy surface, is chemically reacted with the first reactant gas source, purges second of gas not to be adsorbed；Its adsorption process and reacted
Journey is respectively provided with self limiting, with the accuracy for the molecular scale for ensureing film chemical component；The thickness of film is by cycle-index
Control, single cycle film thickness typically 0.05 ~ 0.1nm of increase, to ensure the nanoscale accuracy of film integral thickness；
（4）ALD working chambers are reduced：Reactant gas source is closed, to set heater, cavity, purging, hot trap temperature be respectively 100 DEG C,
100℃、100℃、300℃；Temperature stabilization is treated, vavuum pump, flowmeter, heater is closed, pressure is inflated to for 760torr；Beat
Working cavity is opened, magnesium alloy sample is taken out, chamber door is closed.
2. a kind of Mg alloy surface anti-corrosion coating preparation method according to claim 1, it is characterized in that step（3）Described in
Oxide be Al2O3、TiO2Or HfO2。
3. a kind of Mg alloy surface anti-corrosion coating preparation method according to claim 1, it is characterized in that step（3）Described in
Nitride be InN, AlN or GaN.
4. a kind of Mg alloy surface anti-corrosion coating preparation method according to claim 1, it is characterized in that step（3）Middle individual layer
Gradually plural layers can be prepared on film by stack, form composite bed.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108893727A (en) * | 2018-06-19 | 2018-11-27 | 南昌大学 | A kind of preparation method of gallium nitride/aluminium oxide nano composite corrosion proof coating |
| WO2021081219A1 (en) * | 2019-10-23 | 2021-04-29 | Applied Materials, Inc. | Hafnium aluminum oxide coatings deposited by atomic layer deposition |
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| CN101418435A (en) * | 2007-10-26 | 2009-04-29 | 林新智 | Method for forming protective layer on contour of work piece |
| CN101974734A (en) * | 2010-11-30 | 2011-02-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing substrate material with multilayer composite protective film |
| CN106086812A (en) * | 2016-07-20 | 2016-11-09 | 南京航空航天大学 | A kind of anti abrasive composite coating of metal surface anticorrosive and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418435A (en) * | 2007-10-26 | 2009-04-29 | 林新智 | Method for forming protective layer on contour of work piece |
| CN101974734A (en) * | 2010-11-30 | 2011-02-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing substrate material with multilayer composite protective film |
| CN106086812A (en) * | 2016-07-20 | 2016-11-09 | 南京航空航天大学 | A kind of anti abrasive composite coating of metal surface anticorrosive and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108893727A (en) * | 2018-06-19 | 2018-11-27 | 南昌大学 | A kind of preparation method of gallium nitride/aluminium oxide nano composite corrosion proof coating |
| WO2021081219A1 (en) * | 2019-10-23 | 2021-04-29 | Applied Materials, Inc. | Hafnium aluminum oxide coatings deposited by atomic layer deposition |
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Application publication date: 20170915 |