CN105908176A - Method for generating aluminum nitride thin film on aluminum plate through discharging in liquid - Google Patents
Method for generating aluminum nitride thin film on aluminum plate through discharging in liquid Download PDFInfo
- Publication number
- CN105908176A CN105908176A CN201610303934.1A CN201610303934A CN105908176A CN 105908176 A CN105908176 A CN 105908176A CN 201610303934 A CN201610303934 A CN 201610303934A CN 105908176 A CN105908176 A CN 105908176A
- Authority
- CN
- China
- Prior art keywords
- liquid
- ammonium
- aluminium
- aluminum plate
- discharge
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
- C23C22/66—Treatment of aluminium or alloys based thereon
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
Abstract
The invention discloses a method for generating an aluminum nitride thin film on an aluminum plate through discharging in liquid. The method is characterized in that the aluminum plate is soaked in the nitrogen-containing liquid, nitrogen in the nitrogen-containing liquid and aluminum on the surface of the aluminum plate react through discharging in the liquid, and then the aluminum nitride thin film is generated on the surface of the aluminum plate. According to the method, the aluminum plate is soaked in the nitrogen-containing liquid, the aluminum nitride thin film is generated on the surface of the aluminum plate through discharging in the liquid, the processing efficiency is high, and the uniformity of the obtained aluminum nitride thin film is good. In addition, the requirement for the discharging interval in a spark discharging method is overcome, and the method is not limited by the discharging distance and the shape of the surface of a workpiece, and is particularly suitable for rapid generation of aluminum nitride on the surface of the aluminum plate with a large area.
Description
Technical field
The present invention relates to high thermal conductive substrate preparing technical field, particularly relate to a kind of discharge in liquid that passes through and exist
The method generating aluminium nitride film on aluminium sheet.
Background technology
LED has obtained increasingly being widely applied as a new generation's lighting engineering.Along with LED power
Continuing to increase, heat dissipation problem is focused on the most day by day.At present, in the selection of LED heat radiation substrate, common
Mainly have: ceramic substrate and metal substrate.Comparatively speaking, metal substrate has more preferable thermal conductivity, but
The thermal coefficient of expansion of metal substrate is much larger than LED chip substrate, during work, is affected by cold cycling, LED
Chip, by bearing the biggest thermal stress and stress impact, easily causes and snaps.
To this end, someone designs a kind of composite base plate in the industry, i.e. arrange on aluminium, copper or ceramic bottom board
One layer of aln layer.Because aluminium nitride has thermal conductivity (275W/ (m K)) height, good insulating, thermal expansion system
The feature that number is close with LED chip substrate, applies the problem that can solve in LED-baseplate.
Traditional aluminium nitride composite base plate manufacture method mainly has two kinds: one is directly to be coated with on base plate
Cover one layer of aln layer, such as the Chinese patent application of Publication No. CN103555195A, open a kind of nitrogen
Change aluminium heat radiation coating, by organic siliconresin, Polyamide-Polyamsne-Epichlorohydrin resin, tri-methyl hexamethylene
Diamines, aluminium nitride, boron nitride, nano-hollow microballon, Ludox etc. form.By adding aluminum nitride powder,
Heat conduction rate is high, good heat dissipation effect；By adding Ludox, enhance cohesive force, make coating firm.So
And, owing to being simple physical adhesion between Aluminum nitride heat radiation paint and base plate, during LED operation, catch a cold
, there is heat radiation coating and peel off hidden danger in heat alternately impact.Another kind is that the mode using vacuum sputtering is on base plate
Form aln layer, such as a Publication No. CN102969437A Chinese patent application, disclose a kind of LED and send out
Optic component, including LED chip, glass substrate, fixes LED chip and metal conductive wire above glass substrate
Road, glass substrate and LED chip joint face scribble aluminium nitride coating, and described aluminium nitride coating passes through magnetic control
The thin film-forming method of sputtering grows on the glass substrate.But, when using the mode of magnetron sputtering to generate aluminium nitride
Speed is very slow, and manufacturing cost is high, is at the most greatly the experimental stage, it is difficult to carry out industrialization.
The present inventor designs a kind of method generating aluminium nitride film on aluminium sheet, sees Publication No.
The Chinese invention patent application of CN104617213A.The open one of this application utilizes electric spark in a nitrogen environment
The high temperature produced makes the aluminium of surface of aluminum plate react with nitrogen, and then generates aluminium nitride film layer in surface of aluminum plate
Method.Specifically include following steps: 1) clean, first aluminium sheet is placed in equipped with in the supersonic wave cleaning machine of acetone
Clean and remove surface of aluminum plate greasy dirt, then aluminium sheet is placed in alkali lye and soaks the oxide layer removing surface of aluminum plate；
2) prepared by aluminium nitride film layer, in a nitrogen environment, is connected with aluminium sheet a pole of the pulse power, by pulse electricity
Another pole in source is connected with tool-electrode, utilizes the TRANSIENT HIGH TEMPERATURE produced of discharging between tool-electrode and aluminium sheet by aluminium
The aluminium on plate surface is nitrided into aluminium nitride.Compared with traditional aluminium nitride composite base plate manufacture method, this invention is special
It is simple that profit application has preparation technology, and working (machining) efficiency is high, and production cost is low, and aluminium nitride film layer is difficult to peel off
Feature.But the gap between this technological requirement tool-electrode and aluminium sheet is between 0.01mm-0.2mm, gap
Little, it is the most difficult, especially in the case of surface of aluminum plate is nonplanar that large area generates uniform aluminium nitride
Implement this technique to be limited to.
Summary of the invention
For problems of the prior art, it is an object of the invention to provide one by electric discharge away from
Generate and aluminium nitride film in uniform thickness generation method from limiting, be applicable to large area with surface of the work shape.
For reaching object above, the present invention adopts the following technical scheme that.
A kind of method being generated aluminium nitride film by discharge in liquid on aluminium sheet, it is characterised in that will
Aluminium sheet is immersed in nitrogenous liquid, utilizes discharge in liquid to make the aluminium generation of the nitrogen in nitrogenous liquid and surface of aluminum plate
React and then generate aluminium nitride film in surface of aluminum plate.
As with improvement, described discharge in liquid is in the boundary of the aluminium sheet being immersed in nitrogenous liquid Yu working solution
Producing on face, a pole of the pulse power is connected with aluminium sheet, and another pole of the pulse power is with aid electrode even
Connect.
As with improvement, described nitrogenous liquid is the conducting liquid containing ammonium radical ion.
As with improvement, the monophasic pulses if voltage of the described pulse power is 100-800V, and pulsewidth is 200 μ
S, is 1000 μ s between arteries and veins.
As with improvement, described nitrogenous liquid is urea liquid or ammonium salt solution, adds in nitrogenous liquid
Added with disodium ethylene diamine tetraacetate and calgon.
As with improvement, described ammonium salt be ammonium carbonate, ammonium hydrogen carbonate, diammonium hydrogen phosphate, ammonium chloride or
Ammonium sulfate.
As with improvement, every liter includes containing in nitrogen solution: 10-50g urea, 1-5g ethylenediamine tetra-acetic acid
Disodium, 0.1-1g calgon.
As with improvement, every liter includes containing in nitrogen solution: 30g urea, 3g disodium ethylene diamine tetraacetate,
0.5g calgon；Discharge in liquid uses monophasic pulses if, and operating voltage is 470V, and pulsewidth is 200 μ s, arteries and veins
Between be 1000 μ s, process time is 30min.
As with improvement, every liter includes containing in nitrogen solution: 150-250g ammonium carbonate, 15-25g ethylenediamine
Tetraacethyl disodium, 1-5g calgon.
As with improvement, every liter includes containing in nitrogen solution: 167g ammonium carbonate, 15g ethylenediamine tetra-acetic acid
Disodium, 2.5g calgon；Discharge in liquid uses monophasic pulses if, and operating voltage is 200V, and pulsewidth is 200
μ s, is 1000 μ s between arteries and veins, and process time is 30min.
Compared with prior art, the invention has the beneficial effects as follows:
One, aluminium sheet is immersed in nitrogenous liquid, uses the mode of discharge in liquid to generate nitrogen in surface of aluminum plate
Changing aluminium film, not only working (machining) efficiency aluminum nitride thin film uniformity high, that prepare is good, and overcomes electric spark
The electric discharge requirement to discharging gap, is not limited by arcing distance and workpiece (aluminium sheet) surface configuration, the suitableeest
For quickly generating of large area surface of aluminum plate aluminium nitride.
Two, by the composition of nitrogenous liquid, the restriction of pulse power running parameter, being prevented effectively from liquid
The generation of aluminum oxide during middle electric discharge, the aluminium nitride film purity that surface of aluminum plate generates is high, perfect heat-dissipating.
Detailed description of the invention
The essence of the present invention, the tool to the present invention below it is more fully understood that for convenience of those skilled in the art
Body embodiment is described in detail.
Embodiment one
A kind of method being generated aluminium nitride film by discharge in liquid on aluminium sheet, it is characterised in that will
Aluminium sheet is immersed in nitrogenous liquid, utilizes discharge in liquid to make the aluminium generation of the nitrogen in nitrogenous liquid and surface of aluminum plate
React and then generate aluminium nitride film in surface of aluminum plate.
Wherein, described discharge in liquid is on the interface of the aluminium sheet being immersed in nitrogenous liquid and working solution
Producing, a pole of the pulse power is connected with aluminium sheet, and another pole of the pulse power is connected with aid electrode.
In the present embodiment, the most nitrogenous liquid is urea liquid, contains in every liter of urea liquid: 30g urinates
Element, 3g disodium ethylene diamine tetraacetate, 0.5g calgon.
In other embodiments, in urea liquid, the content of each composition can be carried out suitably by following scope
Adjusting, every liter includes containing in nitrogen solution: 10-50g urea, 1-5g disodium ethylene diamine tetraacetate, 0.1-1g six
Sodium metaphosphate；It is not limited to the present embodiment.
When specifically discharging, using monophasic pulses if, operating voltage is 470V, and pulsewidth is 200 μ s, between arteries and veins
Being 1000 μ s, process time is 30min.In discharge process, the ammonium radical ion in urea liquid high temperature,
Under hyperbaric environment, aluminium with surface of aluminum plate reacts generation aluminium nitride.Test through reality, finally on aluminium sheet
The aluminum nitride thin film thickness produced is 1 μm.
Aluminium sheet is immersed in nitrogenous liquid by the present embodiment, and the mode using discharge in liquid is raw in surface of aluminum plate
Becoming aluminium nitride film, not only working (machining) efficiency aluminum nitride thin film uniformity high, that prepare is good, and overcomes electricity
The spark discharge requirement to discharging gap, is not limited and workpiece (aluminium sheet) surface configuration, spy by arcing distance
It is not applicable to quickly generating of large area surface of aluminum plate aluminium nitride.Meanwhile, by the composition of nitrogenous liquid,
Pulse power running parameter, reaction condition strictly control, the product of aluminum oxide when being prevented effectively from discharge in liquid
Raw, the aluminium nitride film purity that surface of aluminum plate generates is high, perfect heat-dissipating.
Embodiment two
The present embodiment provides a kind of method being generated aluminium nitride film by discharge in liquid on aluminium sheet, its
Principle is basically identical with embodiment one, and difference is:
Described nitrogenous liquid is sal volatile, and every liter includes containing in nitrogen solution: 200g ammonium carbonate,
18g disodium ethylene diamine tetraacetate, 3g calgon.When specifically discharging, use monophasic pulses if, operating voltage
For 200V, pulsewidth is 200 μ s, is 1000 μ s between arteries and veins, and process time is 30min.Test through reality,
The aluminum nitride thin film thickness produced on aluminium sheet eventually is 4.7 μm.
In other embodiments, in sal volatile, the content of each composition can be fitted by following scope
Working as adjustment, every liter includes containing in nitrogen solution: 150-250g ammonium carbonate, 15-25g disodium ethylene diamine tetraacetate,
1-5g calgon；It is not limited to the present embodiment.
Embodiment three
The present embodiment provides a kind of method being generated aluminium nitride film by discharge in liquid on aluminium sheet, its
Principle is basically identical with embodiment one, and difference is:
Described nitrogenous liquid is ammonium chloride solution, and every liter includes containing in nitrogen solution: 20g ammonium chloride, 2g
Disodium ethylene diamine tetraacetate, 0.3g calgon.When specifically discharging, using monophasic pulses if, operating voltage is
800V, pulsewidth is 200 μ s, is 1000 μ s between arteries and veins, and process time is 30min.Test through reality, finally
The aluminum nitride thin film thickness produced on aluminium sheet is 1.5 μm.
Embodiment four
The present embodiment provides a kind of method being generated aluminium nitride film by discharge in liquid on aluminium sheet, its
Principle is basically identical with embodiment one, and difference is:
Described nitrogenous liquid is ammonium chloride solution, and every liter includes containing in nitrogen solution: 200g ammonium hydrogen carbonate,
20g disodium ethylene diamine tetraacetate, 5g calgon.When specifically discharging, use monophasic pulses if, operating voltage
For 100V, pulsewidth is 200 μ s, is 1000 μ s between arteries and veins, and process time is 30min.Test through reality,
The aluminum nitride thin film thickness produced on aluminium sheet eventually is 4 μm.
The essence of the present invention has been described in detail by above detailed description of the invention, but can not come with this
Protection scope of the present invention is limited.It should be evident that under the enlightenment of essence of the present invention, this technology
Field those of ordinary skill also can carry out many improvement and modification, such as ammonium salt employing ammonium sulfide or multiple ammonium salt
Mixture etc..It should be noted that these improve and modify all to fall at the claims of the present invention
Within.
Claims (10)
1. the method generating aluminium nitride film on aluminium sheet by discharge in liquid, it is characterised in that aluminium sheet is soaked
Enter in nitrogenous liquid, utilize discharge in liquid make the aluminium of nitrogen in nitrogenous liquid and surface of aluminum plate react into
And generate aluminium nitride film in surface of aluminum plate.
Method the most according to claim 1, it is characterised in that described discharge in liquid is in being immersed in nitrogenous liquid
Aluminium sheet and working solution interface on produce, a pole of the pulse power is connected with aluminium sheet, the pulse power another
One pole is connected with aid electrode.
Method the most according to claim 2, it is characterised in that described nitrogenous liquid is containing ammonium radical ion
Conducting liquid.
Method the most according to claim 2, it is characterised in that the monophasic pulses if voltage of the described pulse power is
100-800V, pulsewidth is 200 μ s, is 1000 μ s between arteries and veins.
Method the most according to claim 1, it is characterised in that described nitrogenous liquid is urea liquid or ammonium salt
Solution, is added with disodium ethylene diamine tetraacetate and calgon in nitrogenous liquid.
Method the most according to claim 5, it is characterised in that described ammonium salt be ammonium carbonate, ammonium hydrogen carbonate,
Diammonium hydrogen phosphate, ammonium chloride or ammonium sulfate.
Method the most according to claim 1, it is characterised in that every liter includes containing in nitrogen solution: 10-50g
Urea, 1-5g disodium ethylene diamine tetraacetate, 0.1-1g calgon.
Method the most according to claim 7, it is characterised in that every liter includes containing in nitrogen solution: 30g urinates
Element, 3g disodium ethylene diamine tetraacetate, 0.5g calgon；Discharge in liquid uses monophasic pulses if, work electricity
Pressure is 470V, and pulsewidth is 200 μ s, is 1000 μ s between arteries and veins, and process time is 30min.
Method the most according to claim 1, it is characterised in that every liter includes containing in nitrogen solution: 150-250g
Ammonium carbonate, 15-25g disodium ethylene diamine tetraacetate, 1-5g calgon.
Method the most according to claim 9, it is characterised in that every liter includes containing in nitrogen solution: 167g
Ammonium carbonate, 15g disodium ethylene diamine tetraacetate, 2.5g calgon；Discharge in liquid uses monophasic pulses if, work
Being 200V as voltage, pulsewidth is 200 μ s, is 1000 μ s between arteries and veins, and process time is 30min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610303934.1A CN105908176A (en) | 2016-05-09 | 2016-05-09 | Method for generating aluminum nitride thin film on aluminum plate through discharging in liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610303934.1A CN105908176A (en) | 2016-05-09 | 2016-05-09 | Method for generating aluminum nitride thin film on aluminum plate through discharging in liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105908176A true CN105908176A (en) | 2016-08-31 |
Family
ID=56748779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610303934.1A Pending CN105908176A (en) | 2016-05-09 | 2016-05-09 | Method for generating aluminum nitride thin film on aluminum plate through discharging in liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105908176A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62148310A (en) * | 1985-12-20 | 1987-07-02 | Yoshio Yamazaki | Preparation of aluminum nitride |
| CN102732822A (en) * | 2012-07-17 | 2012-10-17 | 南昌航空大学 | Liquid-phase plasma electrolysis osmosis treatment device |
| CN103060742A (en) * | 2013-01-11 | 2013-04-24 | 南昌航空大学 | Liquid phase plasma electrolytically nitriding electrolyte |
-
2016
- 2016-05-09 CN CN201610303934.1A patent/CN105908176A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62148310A (en) * | 1985-12-20 | 1987-07-02 | Yoshio Yamazaki | Preparation of aluminum nitride |
| CN102732822A (en) * | 2012-07-17 | 2012-10-17 | 南昌航空大学 | Liquid-phase plasma electrolysis osmosis treatment device |
| CN103060742A (en) * | 2013-01-11 | 2013-04-24 | 南昌航空大学 | Liquid phase plasma electrolytically nitriding electrolyte |
Non-Patent Citations (3)
| Title |
|---|
| 何翔 等: "电解液微弧放电制备氮化铝陶瓷膜研究", 《兵器材料科学与工程》 * |
| 孙奉娄 等: "纯铝材电解液微弧氮化工艺探讨", 《材料保护》 * |
| 柳永康 等: "时间和电压对TCA合金表面等离子碳氮共渗层的影响", 《中国表面工程》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103695858B (en) | A kind of multi-functional full-automatic ion film coating machine for cutter coat deposition and using method thereof | |
| CN102409339B (en) | Method and device for preparing diamond-like carbon coating by cladding fiber laser | |
| CN100420775C (en) | Microarc oxidation process method for surface of steel and ion | |
| CN104087996A (en) | Aluminum alloy surface easy-cleaning micro-arc oxidation ceramic membrane layer and preparation method thereof | |
| CN109112602B (en) | Laser method for improving binding force between ceramic coating and metal substrate | |
| CN106958009A (en) | A kind of aluminium nitride ceramics copper-clad plate and preparation method thereof | |
| CN104746072B (en) | A kind of magnesium alloy differential arc ion plating surface treatment method | |
| CN102179970B (en) | Heat conducting material, preparation process thereof and LED (light-emitting diode) circuit board using heat conducting material | |
| CN104617213A (en) | Method for generating aluminum nitride thin film on aluminum plate | |
| CN206494965U (en) | Multifunctional vacuum ion plating equipment | |
| CN103342913B (en) | Conductive coating material for insulating-ceramic electrosparking technology and method for preparing auxiliary electrode by the conductive coating material | |
| CN103031524B (en) | Method for realizing metallization of back of indium tin oxide (ITO) target material by ion deposition | |
| CN102899622A (en) | Film-coated component and preparation method thereof | |
| CN104193419A (en) | Preparation method of metallic coating on ceramic surface | |
| CN105908176A (en) | Method for generating aluminum nitride thin film on aluminum plate through discharging in liquid | |
| CN108505089A (en) | A kind of aluminum alloy surface Al based on sodium tetraborate2O3-AlB12The preparation method of composite ceramics film layer | |
| CN102740591A (en) | Double-sided aluminum base circuit board with super-high thermal conductivity and preparation method thereof | |
| CN104498861A (en) | Preparation method of sealing coating with high peeling failure resistance | |
| CN110205628A (en) | A kind of process for electric spark deposition preparation of the self-lubricating coat in use based on non-conductive ceramic | |
| CN105385992A (en) | Method for preparing nitrogen-aluminum-titanium coating on surface of tool | |
| CN108754563A (en) | The 6063 aluminum alloy surface Al based on dipotassium tetraborate2O3-AlB12The preparation method of composite ceramics film layer | |
| CN102162087B (en) | Processing method of thermal compensation molybdenum wafer surface coating | |
| CN103354220B (en) | For the pattern structure substrate of optics and electronic device | |
| CN209923428U (en) | Device for preparing porous thermal barrier coating by adopting low-temperature plasma | |
| CN102242346A (en) | Device and process for growing TiAlN film on surface of aluminum alloy in situ |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160831 |