CN108411279B - A kind of preparation method of high-speed steel tool protective coating - Google Patents
A kind of preparation method of high-speed steel tool protective coating Download PDFInfo
- Publication number
- CN108411279B CN108411279B CN201810294227.XA CN201810294227A CN108411279B CN 108411279 B CN108411279 B CN 108411279B CN 201810294227 A CN201810294227 A CN 201810294227A CN 108411279 B CN108411279 B CN 108411279B
- Authority
- CN
- China
- Prior art keywords
- presoma
- film
- speed steel
- cavity
- steel tool
- 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.)
- Active
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
- 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
- C23C16/50—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 using electric discharges
-
- 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
- C23C16/22—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 deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/301—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C23C16/303—Nitrides
-
- 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
- C23C16/22—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 deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
-
- 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
- C23C16/22—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 deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/345—Silicon nitride
-
- 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
- C23C16/22—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 deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
- C23C16/402—Silicon dioxide
-
- 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
- C23C16/22—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 deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/403—Oxides of aluminium, magnesium or beryllium
-
- 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
- C23C16/45536—Use of plasma, radiation or electromagnetic fields
- C23C16/4554—Plasma being used non-continuously in between ALD reactions
-
- 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]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
-
- 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]
- C23C16/45555—Atomic layer deposition [ALD] applied in non-semiconductor technology
-
- 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
- C23C16/56—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Electromagnetism (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The invention belongs to field of film preparation, and specifically disclose a kind of preparation method of high-speed steel tool protective coating, comprising: pre-process to tool surface, place it in deposition micro inorganic film in plasma enhanced chemical vapor deposition equipment；It places it in plasma enhanced atomic layer deposition equipment, under the conditions of temperature appropriate, pressure and suitable plasma power, different presomas is alternately passed through, complete chemical reaction to sequentially form saturation absorption in tool surface；Finally composite coating is made annealing treatment.The present invention can effectively reduce the defect on chemical vapour deposition film surface by the film that Plasma-Atomic layer deposits the nanoscale to be formed, and then realize the effective protection to cutter under processing, storage state.The preparation for realizing tool surface protective coating using chemical vapor deposition means under cryogenic may be implemented in the present invention, and then realizes the effective protection to cutter.
Description
Technical field
The invention belongs to field of film preparation, more particularly, to a kind of preparation method of high-speed steel tool protective coating.
Background technique
High-speed steel is a kind of tool steel with high rigidity, high-wearing feature and high-fire resistance, is formed in machine tooling, mold
Equal fields have a wide range of applications.But when it is in high-speed cutting state, steeply rising for cutting temperature easily leads to cutter material
Material is undergone phase transition, so that cutter is worn rapidly.In addition, how to carry out effective protection to it when high-speed steel tool is not used, prevent
Only it is corroded by all kinds of corrosive gas such as steam, oxygen in air and has great importance for the service life for extending cutter.
Traditional tool surface guard method is to be prepared using the methods of magnetron sputtering, vapor deposition, ion plating in tool surface
Tool high-wearing feature and good resistance superhard coating, this method can realize the system of protective coating under the conditions of 200~600 DEG C
It is standby, decline its performance without causing cutter itself to undergo phase transition.But this method be easy to cause the waste of raw material and the dirt of cavity
Dye, higher cost, and the protective coating chemical attachment power generated is not strong, surface defect density is big, for complicated tool surface
Coverage rate is also poor, it is difficult to reach expected design service life.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of high-speed steel tool protective coatings
Preparation method, its object is to combine nonthermal plasma chemistry vapor deposition and Plasma-Atomic layer deposition techniques, and it is right
Existing Plasma-Atomic deposition method is improved, tool surface preparation structure densification micron order thickness it is compound
Thus film solves the problems such as current cutter protection holiday density is big, and cost of manufacture is high, it can be achieved that in high-speed steel tool table
Face forms fine and close thinfilm protective coating, and tool surface is effectively protected in realization, can prevent cutter in use
It undergoes phase transition, and the erosion of the pernicious gases such as water oxygen can be prevented during storage.
To achieve the above object, the invention proposes a kind of preparation methods of high-speed steel tool protective coating comprising such as
Lower step:
S1 pre-processes high-speed steel tool surface to be protected；
Above-mentioned pretreated high-speed steel tool is placed in glove box and saves by S2, is then transferred to plasma increasing
Plasma enhanced chemical vapor deposition is carried out in extensive chemical vapor deposition chamber, it is micro- to be obtained in high-speed steel tool surface deposition
The bottom film of meter level；
The high-speed steel tool that surface is deposited with micron order bottom film is transferred to plasma enhanced atomic layer deposition by S3
Plasma enhanced atomic layer deposition is carried out in cavity, to prepare nanoscale top film on bottom film surface, to obtain
Obtain the composite protection layer being made of bottom film and top film；
S4 makes annealing treatment the high-speed steel tool for being deposited with composite protection layer under the conditions of 200 DEG C~500 DEG C, to subtract
Organic group inside few composite protection layer, and then the consistency of composite protection layer is promoted, enhance the anticorrosive of composite protection layer
Performance and obstructing capacity.
As it is further preferred that carry out plasma enhanced chemical vapor deposition in step S2 specifically: right first
Plasma enhanced chemical vapor deposition cavity is preheated, and then leads to the mixed gas of the different presomas mixed in proportion
Enter in cavity, high-frequency electric field is recycled to ionize to deposit bottom film, deposition on high-speed steel tool surface mixed gas
After using vacuum pump extraction cavity in remaining mixed gas and byproduct of reaction.
As it is further preferred that the preheating temperature of plasma enhanced chemical vapor deposition cavity is 60 DEG C~400 DEG C；
For the plasma power used in deposition process for 2000W~4000W, the pressure of cavity is 150Pa~250Pa, mixed gas
Flow be 3000sccm~5000sccm, sedimentation time be 1500s~3000s, deposition thickness be 5 μm~10 μm.
As it is further preferred that presoma be two kinds, preferably SiH4/NH3、AlCl3/NH3、TiCl4/NH3Or
TaCl4/NH3, the mixed proportion of two kinds of presomas is 1:5~1:10.
As it is further preferred that the bottom film is SiNxCoating, AlN coating, TiN coating, one in TaN coating
Kind is a variety of.
As it is further preferred that when carry out plasma enhanced atomic layer deposition in step S3 be passed through three kinds of forerunners
Body, respectively the first presoma, second of presoma and the third presoma, wherein the first presoma is with organic group
The presoma of group, second of presoma are oxygen source presoma, for reacting with the completion of the first presoma to prepare nanoscale
Top film, the third presoma are also oxygen source presoma, anti-for occurring with the first presoma remaining in top film
It answers, so that film is more fine and close.
As it is further preferred that the carry out plasma enhanced atomic layer deposition in step S3 specifically includes following step
It is rapid:
The temperature of plasma enhanced atomic layer deposition cavity is set as 60 DEG C~150 DEG C by S31, and to high-speed steel tool
Carry out the preheating of 10min~15min；
S32 is passed through the first presoma using carrier gas with impulse form, and the time of pulse is 0.1s~0.2s, carrier gas flux
Pressure for 50sccm~100sccm, inside cavity rises 30Pa~60Pa；The first presoma pulse to be done is passed through
Afterwards, the cleaning of 40s~60s is carried out to cavity using inert gas；
S33 is passed through second plasma-activated of presoma with impulse form using carrier gas, second of presoma with
The first precursor reacts, and the burst length is 0.1s~0.2s, and carrier gas flux is 50sccm~100sccm, inside cavity
Pressure rise 20Pa~40Pa；After reaction to be done, the cleaning of 40s~60s is carried out to cavity using inert gas；
S34 is passed through the third presoma using carrier gas with impulse form, the top film of the third presoma and generation
In the first remaining presoma react, the burst length be 0.1s~0.2s, carrier gas flux be 50sccm~100sccm,
The pressure of inside cavity rises 20Pa~40Pa；After reaction to be done, the clear of 40s~60s is carried out to cavity using inert gas
It washes；
S35 repeats step S32~S34, until obtaining the nanoscale top film of required thickness.
As it is further preferred that the first described presoma, second of presoma and the third presoma are Al
(CH3)3、O2And H2O, or be CH3Si[N(CH3)2]3、O2And O3。
As it is further preferred that the top film is Al2O3Film layer, SiO2One kind or combination of film layer；It is described
Top film with a thickness of 20nm~100nm.
As it is further preferred that plasma enhanced atomic layer deposition cavity exists during preparing top film
When not having carrier gas to be passed through, internal pressure is less than 1Pa.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, using laminated film pair
When high-speed steel tool is protected, following effect can be obtained:
1. key of the invention is to obtain intensity height, wearability first with plasma enhanced chemical vapor deposition means
Good protective underlayer coating, then prepared using plasma enhanced atomic technique the inorganic thin film of one layer of Nano grade with
The defect sites for reducing bottom film fill the comprehensive corrosion resistance for promoting cutter by coupling.
2. in the present invention, by the pretreatment cleaned, dried to high-speed steel tool, effectively reducing the oil of tool surface
Dirty and particle contamination, and realize by carrying out transfer inside glove box the preparation of dense protective coatings, to high-speed steel tool into
Row is effectively protected.
3. in the present invention, protection for high-speed steel tool, in the preparation process of bottom film, reaction temperature 60
~400 DEG C；And in the preparation of top film, reaction temperature is 60~150 DEG C；Subsequent anneal temperatures are 200~500 DEG C,
The strong composite coating of good compactness, corrosion resistance and good, obstructing capacity can not only be prepared, and will not be to cutter interior
Structure damage.
4. in the present invention, during preparing top layer protective coating, Plasma-Atomic layer deposition chamber is not being carried
When gas is passed through, internal pressure remains less than 1Pa, guarantees that presoma can realize uniformly diffusion in entire inside cavity, realizes
To the uniform cladding of tool surface.
5. the significantly promotion of the achievable raw material availability of the present invention, easily causes cavity compared to physical vapour deposition (PVD) means
Wall polluting is serious, and the low disadvantage of raw material availability can effectively improve the utilization rate of raw material using vapor deposition method.
6. reaction temperature is below the phase alternating temperature of cutter itself in the making technology and aftertreatment technology of composite film
Degree, will not damage cutter；The composite film of micron level has many advantages, such as high rigidity, high intensity, wearability are good,
The service performance of cutter will not be destroyed.
7. using vapor deposition method, effective protection, especially technique for atomic layer deposition can be carried out to complex surface
It introduces, it can be achieved that coating without dead angle to cutter；Composite film can be realized effective barrier to corrosive gas, especially empty
Steam and oxygen in gas, water oxygen rejection rate are up to 10-5g/m2Day greatly promotes the storage stability of high-speed steel tool itself
Energy.
8. the depositing operation that the present invention goes back plasma enhancing chemical vapor deposition is studied and designed, keep its pre-
Hot temperature is 60 DEG C~400 DEG C, and plasma power is 2000W~4000W, and the pressure of cavity is 150Pa~250Pa, mixing
The flow of gas is 3000sccm~5000sccm, and sedimentation time can prepare height by above-mentioned technique for 1500s~3000s
Hardness, high intensity, wearability be good, the good compactness micron-sized bottom film with a thickness of 5 μm~10 μm.
9. the depositing operation that the present invention goes back plasma enhancing atomic layer deposition is studied and designed, three kinds are utilized
The processing step and concrete technology of different presoma and combination S31-S35, can prepare fine and close nano-scale oxide film,
The covering to bottom defect sites is realized simultaneously.
10. the present invention also studies annealing process and designed, the high-speed steel tool of composite protection layer will be deposited with
It is made annealing treatment under 200 DEG C~500 DEG C annealing temperatures, the organic group inside composite protection layer can be effectively reduced, promoted
The consistency of composite protection layer, enhances the corrosion resistance and obstructing capacity of composite protection layer, and can avoid cutter and film by
Amorphous state changes to crystalline state.
Detailed description of the invention
Fig. 1 is a kind of flow chart of the preparation method of high-speed steel tool protective coating provided in an embodiment of the present invention；
Fig. 2 is composite coating annealing front and back XRD characterization figure；
Fig. 3 is the SEM scanning figure of composite coating；
Fig. 4 is the burn-in test comparison diagram of different components, wherein a) is the luminous observation chart of original state device；It b) is cladding
Micron order silicon nitride aging 90h result figure；It c) is covered composite yarn aging of protective coating 500h result figure.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
Basic principle of the invention is to carry out cleaning treatment to high-speed steel tool surface, after completing the aforementioned steps, will
It, which is placed in plasma enhanced chemical vapor deposition equipment, deposits the inorganic thin film of one layer of micro-meter scale on its surface；It completes
After the step, by it as in plasma enhanced atomic layer deposition equipment, under an appropriate temperature and pressure conditions, and select
Select suitable plasma power, by different types of presoma alternately be passed through, different precursors will tool surface successively
It forms saturation absorption and completes chemical reaction, control the film thickness of growth with this by control loop number；Finally to acquisition
Composite coating is made annealing treatment.Chemical gas can be effectively reduced by the film that Plasma-Atomic layer deposits the nanoscale to be formed
The defect on phase deposition film surface, and then realize the effective protection to cutter under processing, storage state.The present invention may be implemented
The preparation of tool surface protective coating is realized using chemical vapor deposition means under cryogenic, and then realizes have to cutter
Effect protection.
As shown in Figure 1, a kind of preparation method of high-speed steel tool protective coating provided in an embodiment of the present invention, in height
The laminated film of fast steel cutter surface deposition compact is to realize the protection to it, and this method comprises the following steps:
The pretreatment that S1 is cleaned, dried to high-speed steel tool surface to be protected
In above-mentioned cleaning, high-speed steel tool is soaked in dehydrated alcohol, and is carried out using plasma cleaner
Cleaning, then carries out wiping drying with non-dust cloth or dust-free paper, and dried up using nitrogen air gun.
S2 obtains micron-sized bottom film in high-speed steel tool surface deposition
By above-mentioned pre-treatment step, treated that high-speed steel tool is placed in glove box saves, and keeps the cleaning on surface
And drying, it is then shifted into plasma enhanced chemical vapor deposition (PECVD) cavity, to carry out plasma enhancing
Chemical vapor deposition；When deposition, cavity and substrate (i.e. high-speed steel tool) are preheated first, its temperature is made to be maintained at 60 DEG C
~400 DEG C, then two kinds of presomas is mixed, and be passed into reaction cavity in certain proportion, utilize height
The electric field transmitting plasma of frequency electric field such as 13.5MHz ionizes reaction gas, to deposit on high-speed steel tool surface
Bottom film (i.e. protective underlayer coating), it is secondary using remaining mixed gas in vacuum pump extraction cavity and reaction after deposition
Product, vacuum pump are in continuous evacuated state, and when airless is passed through, reference pressure should be pumped down to 1Pa or less.
Preferably, in deposition step, the mixed proportion of two kinds of presomas is 1:5~1:10, passes through above-mentioned mixed proportion
It may make the silicon nitride film deposition rate of acquisition moderate, and film more uniform compact.
Preferably, in deposition step, plasma power is 2000W~4000W, since film is more when power is lower
It is loose, and the silicon nitride film that when power is excessively high will lead to generation is destroyed by plasma bombardment, plasma function after study
Rate is that 2000W~4000W is more appropriate.
Preferably, in deposition step, the pressure of cavity is 150Pa~250Pa, under this pressure condition, so that thin
The deposition rate and refractive index of film tend towards stability, and are easily obtained the silicon nitride film that thickness is certain, has excellent performance.
Preferably, in deposition step, the flow of mixed gas is 3000sccm~5000sccm, by within the scope of this
The total flow of mixed gas is adjusted, and can obtain the primer coating having good uniformity
Preferably, in the preparation process of protective underlayer coating, sedimentation time is 1500s~3000s, by adjusting reaction
Time is to obtain the certain micron order primer coating of thickness.
Preferably, presoma is the two comprising but be not limited to: SiH4And NH3Or AlCl3And NH3Or TiCl4With
NH3Or TaCl4And NH3。
Preferably, protective underlayer coating be micron order film, can include but is not limited to: SiNx coating, AlN coating,
One of TiN coating, TaN coating are a variety of.Preferably, protective underlayer coating with a thickness of 5 μm~10 μm.
S3 prepares nanoscale top film on bottom film surface
The high-speed steel tool that surface is deposited with micron order bottom film is transferred to plasma enhanced atomic layer deposition
(PEALD) plasma enhanced atomic layer deposition is carried out in cavity, to prepare nanoscale top film on bottom film surface,
To obtain the composite protection layer being made of bottom film and top film.
Preferably, after the preparation for completing bottom film, surface is deposited with micron order bottom using glove box transitional storehouse
The high-speed steel tool of film, which is transferred in Plasma-Atomic layer deposition chamber, remains top layer protective coating (i.e. nanoscale top layer
Film) preparation.
Preferably, in the preparation of top layer protective coating, every kind of being passed through for presoma is carried by carrier gas with arteries and veins
The form of punching is squeezed into cavity, and forms saturation absorption in tool surface.
Preferably, the burst length of presoma is 0.1~0.2s.
Preferably, it after the input for completing certain presoma, is passed through inert gas and cavity is cleaned, scavenging period is
40s~60s.Preferably, purge gas is argon gas or helium, can not be nitrogen, it is avoided to be reacted by plasma-activated.
Preferably, what is be successively passed through is three kinds of presomas, respectively the first presoma, second of presoma and the third
Presoma, wherein the first presoma is the presoma with organic group, is passed through after cavity and forms saturation in bottom film
Absorption；Second of presoma is oxygen source presoma, for forming oxygen with the first forerunner's precursor reactant of bottom film adsorption
Compound film (i.e. top film), second of presoma needs are plasma-activated, and specific activating process is by applying
Added electric field, so that O2It is ionized as O-With electrically charged oxygen molecule, can directly react with the first presoma；The third
Presoma is also oxygen source presoma, for further reacting away the first presoma remaining in top film, enables film more
It is fine and close.Three kinds of presomas include but is not limited to: Al (CH3)3、O2And H2O or CH3Si[N(CH3)2]3、O2And O3。
Preferably, the carrier gas flux for carrying presoma is 50sccm~100sccm, and the throughput for carrying presoma is too small
When, reactant concentration is too low in cavity, and thin film growth process is unsaturated；And when carrier gas flux is excessive, easily cause cleaning not thorough
Bottom, growth course no longer have from restricted, and film thickness is uncontrollable, use above-mentioned carrier gas flux by research, can prepare and obtain
Obtain the controllable film of fine and close thickness.
Preferably, the intracorporal reaction temperature of chamber is set to 60 DEG C~150 DEG C, since ALD technique is there are temperature window,
It is not in that reaction precursor forms condensation on wall in the cavity, while can avoid generating in above-mentioned range of reaction temperature
Object thermally decomposes
Preferably, plasma power is 1000W~3000W, under above-mentioned power, so that film growth rate is suitable for,
And makes inside cavity plasma density moderate, film surface will not be destroyed
Preferably, top layer protective coating is nano-level thin-membrane, be can include but is not limited to: Al2O3Film, SiO2Film
One kind or combination.Preferably, top layer protective coating is with a thickness of 20nm~100nm.
Step S3 is further refined as following steps:
Carry out plasma enhanced atomic layer deposition in step S3 specifically comprises the following steps:
The temperature of plasma enhanced atomic layer deposition cavity is set as 60 DEG C~150 DEG C by S31, it is preferably controlled in 80~
100 DEG C, and the preheating of 10min~15min is carried out to high-speed steel tool, energy is provided for the absorption and reaction of presoma；
S32 using carrier gas by impulse form be passed through the first presoma (i.e. presoma by air-flow pulse in the form of lead to
Enter), chemisorption occurs for the first presoma and micron order bottom film being passed through, and the burst length is 0.1s~0.2s, carries
Throughput is 50sccm~100sccm, and inside cavity pressure rises 30Pa~60Pa, so that the first presoma and micron order
Bottom film realizes saturation chemisorption；After the saturation chemisorption of the first presoma to be done, inert gas (argon gas is utilized
Or helium) to cavity carry out 40s~60s cleaning to remove the first presoma extra in cavity, avoid due to clean not
The CVD reaction that thoroughly may cause, and the first presoma on micron order bottom film surface has formed saturation chemisorption, because
This will not be removed by purging；
S33 cleaning is completed, and second plasma-activated of presoma is passed through with impulse form using carrier gas, this is second
Presoma reacts with the first presoma for adsorbing bottom film surface in the micron-scale, prepares top film, pulse
Time be 0.1s~0.2s, carrier gas flux be 50sccm~100sccm, at this moment the pressure of inside cavity rise again 20Pa~
40Pa；After reaction to be done, the cleaning of 40s~60s is carried out to cavity using inert gas (argon gas or helium)；
S34 cleaning is completed, and is passed through the third presoma using carrier gas with impulse form, the third presoma and top layer are thin
The first remaining presoma continues to react in film, the burst length be 0.1s~0.2s, carrier gas flux be 50sccm~
100sccm, at this moment the pressure of inside cavity rises 20Pa~40Pa again；After reaction to be done, inert gas (argon gas or helium are utilized
Gas) to cavity carry out 40s~60s cleaning；
S35 repeats step S32~S34, until obtaining the nanoscale top film of required thickness, passes through control loop time
Number control generates the thickness of top layer protective coating.
Preferably, after the nanoscale top film for obtaining required thickness, using the inert gas of high carrier gas flux to chamber
Body and tool surface are cleaned, and flow set is 200~500sccm, and scavenging period is 10min~15min, are removed internal
Extra reaction gas and by-product, especially plasma avoid endangering to human body bring.
S4 annealing
The high-speed steel tool for being deposited with composite protection layer is made annealing treatment, to reduce-the CH inside composite protection layer3
Equal organic groups, and then the consistency of composite protection layer is promoted, enhance the corrosion resistance and obstructing capacity of composite protection layer.Tool
Body, after cleaning, pulling-out of cutter is placed in Muffle furnace and is made annealing treatment, annealing temperature is set as 200 DEG C~500
DEG C, not higher than the phase transition temperature (550 DEG C~600 DEG C) of high-speed steel, to remove the organic radicals inside film, protected with enhancing
Protect the corrosion resistance and obstructing capacity of coating.
It should be noted that used in the present invention utilize plasma enhanced chemical vapor deposition and plasma enhancing
The laminated film of atomic layer deposition preparation is not limited to existing double-layer structure.More generally, it can be applicable according to demand
The growth of multicomponent layered laminate film is realized in a variety of presoma combinations.
The following are specific embodiments:
Embodiment 1
The present embodiment carries out the preparation of protective coating to a typical high-speed steel tool surface, and compares reality using silicon wafer
It tests.
Firstly, depositing the silicon nitride film of one layer of 5 μ m thick, depositing temperature using plasma activated chemical vapour deposition method
It is 80 DEG C, two kinds of presomas being passed through are SiH4、NH3, prepare the chemical equation of silicon nitride film are as follows:
And total reaction equation are as follows:
Then, it is thin in silicon nitride using plasma enhanced atomic layer deposition method after silicon nitride film preparation is completed
The aluminum oxide film of one layer of 20nm thickness is deposited on film, depositing temperature is 80 DEG C, and three kinds of presomas being passed through are Al (CH3)3、O2
And H2O。
Prepare the chemical equation of aluminum oxide film are as follows:
AlOH*+Al(CH3)3→Al-O-(CH3)2+CH4
Al-CH3+4O→Al-OH+CO2+H2O
It is passed through the first and second presomas (Al (CH3)3And O2) total reaction equation are as follows:
2Al(CH3)3+12O2→Al2O3+6CO2+9H2O
It is passed through the third presoma H2After O, by the precursor A l (CH with substrate surface remnants3)3Or-CH3Equal organic groups
Group reacts, so that it is sufficiently reacted, the equation of reaction are as follows:
2Al(CH3)3+3H2O→Al2O3+6CH4
Since the saturated vapor pressure that room temperature is lauched (i.e. the third presoma) is lower, in the third presoma H2O is logical
It is heated before entering to increase its saturated vapour pressure, promote the abundant progress of reaction, heating temperature is 60 DEG C~100
℃。
The top layer protective coating that target thickness is obtained by the number of control loop, after being disposed, is blown using argon gas stream
Wash cavity 10min~15min；Finally, being made annealing treatment, high-speed steel tool is taken out, progress vacuum in Muffle furnace is put into and moves back
Fire processing, annealing temperature are 450 DEG C.
Tested after annealing using top film of the ellipsometer to tool surface, it is possible to find the thickness of film by
23.18nm decays to 15.71nm, it can therefore be concluded that internal organic group is largely eliminated after annealing, film is more
For densification.
At the same time, XRD characterization is carried out to the film of annealing front and back, as a result as shown in Fig. 2, according to fig. 2 it can be found that moving back
There is no new characteristic peaks to occur for fiery front and back, and film remains as amorphous state, has good barrier property.
In addition, being also observed analysis using scanning electron microscope to the cross section of deposition film, its section shape is obtained
Looks are as shown in Figure 3.From figure 3, it can be seen that after film deposition, so that tool surface securely covers one layer of dense uniform
Organic-inorganic Hybrid Protection Coating realizes the effective protection to cutter, while not interfering with the normal use of cutter.
Embodiment 2
Cutter is easy to by all kinds of gas picklings in storing process, and for example the steam in air, the present invention utilize compound
Film layer protects the OLED device that area is 5cm × 5cm, more intuitive can be seen using the illuminating state of OLED device
Survey barriering effect and the defect failure site of knife encapsulated layer, it can be verified that packaging film has good water vapor rejection ability.
Using preparation method of the invention OLED device surface prepare with a thickness of 1 μm silicon nitride layer+with a thickness of 50nm
Aluminum oxide film, reaction equation is same as Example 1.After completion of reaction, device is placed in 60 DEG C, 90% relative humidity
Burn-in test is carried out in environment, test comparison chart is as shown in Figure 4.Wherein, Fig. 4 a) be OLED device original state illuminating state
Figure, Fig. 4 b) be the silicon nitride that OLED device surface deposits micron level illuminating state figure, a wide range of lose is occurred within 90 hours
Effect, Fig. 4 c) it is the illuminating state figure for being packaged with the OLED device of composite coating of the present invention, it does not fail yet after aging in 500 hours.
There is high obstructing capacity for steam by composite coating of the invention known to test, utilize its water known to calcium film method of testing
Oxygen rejection rate is up to 10-5g/m2·day。
In addition, the present invention also carries out burn-in test to the OLED device of only primer coating protection, the service life is 92 hours,
And the device lifetime of only 50nm aluminum oxide film is 128 hours, it is seen that composite film of the invention has good barrier energy
Power, its service life is not less than 20000 hours when composite film of the invention is stored under atmospheric environment.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (4)
1. a kind of preparation method of high-speed steel tool protective coating, which comprises the steps of:
S1 pre-processes high-speed steel tool surface to be protected；
Above-mentioned pretreated high-speed steel tool is placed in glove box and saves by S2, is then transferred to plasma enhancing
It learns in vapor deposition chamber and carries out plasma enhanced chemical vapor deposition, obtain micron order to deposit on high-speed steel tool surface
Bottom film: first plasma enhancing chemical vapor deposition chamber body preheated, the difference that then will be mixed in proportion
The mixed gas of presoma is passed through in cavity, and high-frequency electric field is recycled to ionize on high-speed steel tool surface mixed gas
Bottom film is deposited, utilizes remaining mixed gas and byproduct of reaction in vacuum pump extraction cavity after deposition；Plasma
The preheating temperature that body enhances chemical vapor deposition chamber body is 60 DEG C~400 DEG C；The plasma power used in deposition process for
2000W~4000W, the pressure of cavity are 150Pa~250Pa, and the flow of mixed gas is 3000sccm~5000sccm, deposition
Time is 1500s~3000s, and deposition thickness is 5 μm~10 μm；Presoma is SiH4/NH3、AlCl3/NH3、TiCl4/NH3Or
TaCl4/NH3, the mixed proportion of two kinds of presomas is 1:5~1:10, bottom film SiNxCoating, AlN coating, TiN coating,
One of TaN coating is a variety of；
The high-speed steel tool that surface is deposited with micron order bottom film is transferred to plasma enhanced atomic layer deposition cavity by S3
Middle carry out plasma enhanced atomic layer deposition, with bottom film surface prepare nanoscale top film, thus obtain by
The composite protection layer that bottom film and top film are constituted:
The temperature of plasma enhanced atomic layer deposition cavity is set as 60 DEG C~150 DEG C by S31, and is carried out to high-speed steel tool
The preheating of 10min~15min；
S32 is passed through the first presoma using carrier gas with impulse form, and the time of pulse is 0.1s~0.2s, and carrier gas flux is
The pressure of 50sccm~100sccm, inside cavity rise 30Pa~60Pa；After being passed through of the first presoma pulse to be done,
The cleaning of 40s~60s is carried out to cavity using inert gas；
S33 is passed through second plasma-activated of presoma with impulse form using carrier gas, second of presoma and first
Kind precursor reacts, and the burst length is 0.1s~0.2s, and carrier gas flux is 50sccm~100sccm, the pressure of inside cavity
Power rises 20Pa~40Pa；After reaction to be done, the cleaning of 40s~60s is carried out to cavity using inert gas；
S34 is passed through the third presoma using carrier gas with impulse form, residual in the top film of the third presoma and generation
The first presoma stayed reacts, and the burst length is 0.1s~0.2s, and carrier gas flux is 50sccm~100sccm, cavity
Internal pressure rises 20Pa~40Pa；After reaction to be done, the cleaning of 40s~60s is carried out to cavity using inert gas；
S35 repeats step S32~S34, until obtaining the nanoscale top film of required thickness；Wherein, the first presoma
For the presoma with organic group, second of presoma is oxygen source presoma, for reacted with the completion of the first presoma with
Prepare nanoscale top film, the third presoma is also oxygen source presoma, for in top film it is remaining the first
Presoma reacts, so that film is more fine and close；
S4 makes annealing treatment the high-speed steel tool for being deposited with composite protection layer under the conditions of 200 DEG C~500 DEG C, multiple to reduce
The organic group inside protective layer is closed, and then promotes the consistency of composite protection layer, enhances the corrosion resistance of composite protection layer
And obstructing capacity.
2. the preparation method of high-speed steel tool protective coating as described in claim 1, which is characterized in that the first described forerunner
Body, second of presoma and the third presoma are Al (CH3)3、O2And H2O, or be CH3Si[N(CH3)2]3、O2And O3。
3. the preparation method of high-speed steel tool protective coating as described in claim 1, which is characterized in that the top film is
Al2O3Film layer, SiO2One kind or combination of film layer；The top film with a thickness of 20nm~100nm.
4. the preparation method of high-speed steel tool protective coating as described in any one of claims 1-3, which is characterized in that preparing
During top film, when no carrier gas is passed through, internal pressure is less than plasma enhanced atomic layer deposition cavity
1Pa。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810294227.XA CN108411279B (en) | 2018-03-30 | 2018-03-30 | A kind of preparation method of high-speed steel tool protective coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810294227.XA CN108411279B (en) | 2018-03-30 | 2018-03-30 | A kind of preparation method of high-speed steel tool protective coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108411279A CN108411279A (en) | 2018-08-17 |
| CN108411279B true CN108411279B (en) | 2019-07-09 |
Family
ID=63134183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810294227.XA Active CN108411279B (en) | 2018-03-30 | 2018-03-30 | A kind of preparation method of high-speed steel tool protective coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108411279B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108977767B (en) * | 2018-09-03 | 2020-06-02 | 湖南大学 | Wear-resistant delta-TaN film and preparation method and application thereof |
| EP3766888A1 (en) * | 2018-11-30 | 2021-01-20 | Hansol Chemical Co., Ltd | Silicon precursor and method of manufacturing silicon-containing thin film using the same |
| KR102157137B1 (en) | 2018-11-30 | 2020-09-17 | 주식회사 한솔케미칼 | Silicon precursor and fabrication method of silicon-containing thin film using the same |
| CN109518185B (en) * | 2019-01-11 | 2020-10-20 | 清华大学 | Surface protection method for device with movable structure |
| CN110212108B (en) * | 2019-05-17 | 2020-05-19 | 华中科技大学 | Packaging method and product of flexible display |
| CN113337808A (en) * | 2021-05-10 | 2021-09-03 | 西安交通大学 | Method for strengthening inner and outer surfaces of voltage reduction element with complex structure |
| CN115572400B (en) * | 2022-10-10 | 2023-11-07 | 兰州空间技术物理研究所 | Preparation method of high-density composite atomic oxygen protective film |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280632A (en) * | 1997-11-26 | 2001-01-17 | 桑德维克公司 | Method for depositing fine-grained alumina coatings on cutting tools |
| CN1939715A (en) * | 2005-09-27 | 2007-04-04 | 山高刀具公司 | Alumina layer with enhanced texture |
| CN101274493A (en) * | 2007-02-01 | 2008-10-01 | 山高刀具公司 | Texture-hardened alpha-alumina coated tool |
| CN102061454A (en) * | 2011-01-20 | 2011-05-18 | 厦门金鹭特种合金有限公司 | Method for preparing coating on cutter |
| JP2014124754A (en) * | 2012-12-27 | 2014-07-07 | Mitsubishi Materials Corp | Surface-coated cutting tool whose hard coating layer exerts excellent peeling and chipping resistances in high-speed intermittent cutting |
-
2018
- 2018-03-30 CN CN201810294227.XA patent/CN108411279B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280632A (en) * | 1997-11-26 | 2001-01-17 | 桑德维克公司 | Method for depositing fine-grained alumina coatings on cutting tools |
| CN1939715A (en) * | 2005-09-27 | 2007-04-04 | 山高刀具公司 | Alumina layer with enhanced texture |
| CN101274493A (en) * | 2007-02-01 | 2008-10-01 | 山高刀具公司 | Texture-hardened alpha-alumina coated tool |
| CN102061454A (en) * | 2011-01-20 | 2011-05-18 | 厦门金鹭特种合金有限公司 | Method for preparing coating on cutter |
| JP2014124754A (en) * | 2012-12-27 | 2014-07-07 | Mitsubishi Materials Corp | Surface-coated cutting tool whose hard coating layer exerts excellent peeling and chipping resistances in high-speed intermittent cutting |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108411279A (en) | 2018-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108411279B (en) | A kind of preparation method of high-speed steel tool protective coating | |
| Iatsunskyi et al. | Structural and XPS characterization of ALD Al2O3 coated porous silicon | |
| Karouta et al. | Structural, compositional and optical properties of PECVD silicon nitride layers | |
| Cholet et al. | Characterization of boron nitride films deposited from BCl 3-NH 3-H 2 mixtures in chemical vapour infiltration conditions | |
| Li et al. | Atomic layer deposition Al2O3 thin films in magnetized radio frequency plasma source | |
| Lee et al. | UV-enhanced atomic layer deposition of ZrO2 thin films at room temperature | |
| TWI811232B (en) | Atomic layer deposition coatings for high temperature heaters | |
| WO2010077728A3 (en) | Densification process for titanium nitride layer for submicron applications | |
| Kim et al. | Atomic layer deposition of TiO 2 from tetrakis-dimethylamido-titanium and ozone | |
| Han et al. | Preparation of a‐SiN x Thin Film with Low Hydrogen Content by Inductively Coupled Plasma Enhanced Chemical Vapor Deposition | |
| Haider et al. | Low‐Temperature Deposition of Hexagonal Boron Nitride via Sequential Injection of Triethylboron and N2/H2 Plasma | |
| CN109355641B (en) | Method for modifying surface of inorganic pigment | |
| Sampath et al. | Structural and morphological characterization of Al2O3 coated macro-porous silicon by atomic layer deposition | |
| Liu et al. | The role of plasma technology in barrier coating deposition | |
| RU2014146776A (en) | EL-COVERED SPRAY COVERED WITH AL-CR-O CONTAINING Si CONTAINING IMPROVED CAPABILITY | |
| CN104060239B (en) | Metal product surface protection method | |
| Andujar et al. | Plasma-enhanced chemical vapor deposition of boron nitride thin films from B 2 H 6–H 2–NH 3 and B 2 H 6–N 2 gas mixtures | |
| Ma et al. | Annealing effect on SiNx/SiO2 superlattice with ultrathin sublayer fabricated using plasma-enhanced atomic layer deposition | |
| Xu et al. | Growth characteristics and properties of yttrium oxide thin films by atomic layer deposition from novel Y (iPrCp) 3 precursor and O3 | |
| Zhu et al. | Residual stress study of thin films deposited by atomic layer deposition | |
| Shahidi et al. | Plasma-enhanced vapor deposition process for the modification of textile materials | |
| Park et al. | Thermal stability of MgO film on Si grown by atomic layer deposition using Mg (EtCp) 2 and H2O | |
| Lee et al. | Growth mechanism of Al2O3 film on an organic layer in plasma-enhanced atomic layer deposition | |
| Schilirò et al. | Effects of surface nature of different semiconductor substrates on the plasma enhanced atomic layer deposition growth of Al2O3 gate dielectric thin films | |
| Dill et al. | Atomic layer deposition of titanium phosphate onto reinforcing fibers using titanium tetrachloride, water, and tris (trimethylsilyl) phosphate as precursors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |