CN108411279A - 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 PDF

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Publication number
CN108411279A
CN108411279A CN201810294227.XA CN201810294227A CN108411279A CN 108411279 A CN108411279 A CN 108411279A CN 201810294227 A CN201810294227 A CN 201810294227A CN 108411279 A CN108411279 A CN 108411279A
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presoma
film
speed steel
steel tool
preparation
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CN108411279B (en
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陈蓉
李云
单斌
曹坤
刘媛媛
杨惠之
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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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
    • C23C16/50—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

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  • Organic Chemistry (AREA)
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Abstract

The invention belongs to field of film preparation, and specifically disclose a kind of preparation method of high-speed steel tool protective coating, including：Tool surface is pre-processed, deposition micro inorganic film in plasma enhanced chemical vapor deposition equipment is placed it in；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, chemical reaction is completed to sequentially form saturation absorption in tool surface；Finally composite coating is made annealing treatment.The film that the present invention deposits the nanoscale to be formed by Plasma-Atomic layer can effectively reduce the defect on chemical vapour deposition film surface, and then realize the effective protection to cutter under processing, storage state.The preparation for utilizing chemical vapor deposition means to realize tool surface protective coating under cryogenic may be implemented in the present invention, and then realizes the effective protection to cutter.

Description

A kind of preparation method of high-speed steel tool protective coating
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 technology
High-speed steel is a kind of tool steel with high rigidity, high-wearing feature and high-fire resistance, is molded 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, when high-speed steel tool is not used, how effective protection is carried out to it, prevented 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 prepared in tool surface using the methods of magnetron sputtering, vapor deposition, ion plating 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, so that its performance is declined 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, cost is higher, and the protective coating chemical attachment power generated is not strong, and surface defect density is big, for complicated tool surface Coverage rate is also poor, it is difficult to reach expected design service life.
Invention content
For the disadvantages described above or Improvement requirement 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 realization is effectively protected tool surface, 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 present invention proposes a kind of preparation method 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 preserves 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；
Surface deposition is had the high-speed steel tool of micron order bottom film to be transferred to plasma enhanced atomic layer deposition by S3 Plasma enhanced atomic layer deposition is carried out in cavity, to prepare nano level top film on bottom film surface, to obtain Obtain the composite protection layer being made of bottom film and top film；
Deposition is had the high-speed steel tool of composite protection layer to be made annealing treatment under the conditions of 200 DEG C~500 DEG C by S4, 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 the carry out plasma enhanced chemical vapor deposition in step S2 is specially：It is 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 utilize remaining mixed gas and byproduct of reaction in vacuum pumped cavity.
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 SiNxOne in coating, AlN coatings, TiN coatings, TaN coatings 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 are with organic group The presoma of group, second of presoma are oxygen source presoma, for reacting nano level to prepare with the completion of the first presoma Top film, the third presoma are also oxygen source presoma, anti-for occurring with the first remaining presoma 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 Suddenly：
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 nano level 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 of film layer or combination；It is described The thickness of top film is 20nm~100nm.
As it is further preferred that during preparing top film, plasma enhanced atomic layer deposition cavity exists 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. the key of the present invention is to obtain intensity height, wearability first with plasma enhanced chemical vapor deposition means Good protective underlayer coating, then utilize plasma enhanced atomic technique prepare 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, the 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 carrying When gas is passed through, internal pressure remains less than 1Pa, ensures 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, cavity is easily caused 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. in the making technology and aftertreatment technology of composite film, reaction temperature is below the phase alternating temperature of cutter itself Degree, will not damage cutter；The composite film of micron level has many advantages, such as high rigidity, high intensity, good wearability, The 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 being coated without dead angle to cutter；Composite film can realize effective barrier to corrosive gas, especially empty Steam in gas and oxygen, 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 is 1500s~3000s can prepare height by above-mentioned technique The micron-sized bottom film that hardness, high intensity, wearability be good, good compactness thickness is 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 presomas 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, deposition is had to the high-speed steel tool of composite protection layer 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.
Description of the drawings
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 the front and back XRD characterization figure of composite coating annealing；
Fig. 3 is the SEM scanning figures of composite coating；
Fig. 4 is the burn-in test comparison diagram of different components, wherein a) be original state device shine observation chart；B) it is cladding Micron order silicon nitride aging 90h result figures；C) it is covered composite yarn aging of protective coating 500h result figures.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be 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 It does not constitute a conflict with each other and can be combined with each other.
The basic principle of the present invention is to carry out cleaning treatment to high-speed steel tool surface, after completing the aforementioned steps, will It 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, during it is equipped as plasma enhanced atomic layer deposition, 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.The film for the nanoscale to be formed is deposited by Plasma-Atomic layer can effectively reduce chemical gas 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 It utilizes chemical vapor deposition means to realize the preparation of tool surface protective coating 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 absolute ethyl alcohol, and is carried out using plasma cleaner Cleaning, then carries out wiping drying, and dried up using nitrogen air gun with non-dust cloth or dust-free paper.
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 preserves, the cleaning of holding 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 are mixed in certain proportion, and is passed into reaction cavity, utilize height The electric field transmitting plasma of frequency electric field such as 13.5MHz ionizes reaction gas, to be deposited on high-speed steel tool surface Bottom film (i.e. protective underlayer coating), it is secondary using remaining mixed gas in vacuum pumped cavity and reaction after deposition Product, vacuum pump are in and continuously vacuumize 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, pass 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 relatively low It is loose, and when power is excessively high, can cause the silicon nitride film generated to be destroyed by plasma bombardment, by studying plasma work( Rate is that 2000W~4000W is more suitable.
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 is micron order film, be can include but is not limited to：SiNx coatings, AlN coatings, It is one or more in TiN coatings, TaN coatings.Preferably, the thickness of protective underlayer coating is 5 μm~10 μm.
S3 prepares nano level top film on bottom film surface
There is the high-speed steel tool of micron order bottom film to be transferred to plasma enhanced atomic layer deposition surface deposition (PEALD) plasma enhanced atomic layer deposition is carried out in cavity, to prepare nano level 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 deposition there is into 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. nano level top layer Film) preparation.
Preferably, in the preparation of top layer protective coating, being passed through for each 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 passed through successively is three kinds of presomas, respectively the first presoma, second of presoma and the third Presoma, wherein the first presoma are the presoma with organic group, are passed through after cavity and form 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 that oxygen source presoma enables film more for further reacting away the first presoma remaining in top film It is fine and close.Three kinds of presomas include but 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, it is not thorough to easily cause cleaning 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 reaction temperature in cavity is set to 60 DEG C~150 DEG C, since ALD techniques are there are temperature window, Be 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, 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 thickness is 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, provide energy 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), with micron order bottom film chemisorption occurs for the first presoma being passed through, and the burst length is 0.1s~0.2s, is carried 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 Thoroughly CVD caused by possibility reacts, and the first presoma on micron order bottom film surface has formed saturation chemisorption, because This will not be removed by purging；
S33 cleanings are completed, and second plasma-activated of presoma are 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 cleanings are completed, and are 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 rise 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 nano level top film of required thickness, passes through control loop time Number control generates the thickness of top layer protective coating.
Preferably, after the nano level 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, is removed internal Extra reaction gas and by-product, especially plasma, avoid the harm brought to human body.
S4 makes annealing treatment
There is the high-speed steel tool of composite protection layer to make annealing treatment deposition, 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, it is not higher than the phase transition temperature (550 DEG C~600 DEG C) of high-speed steel, to remove the organic radicals inside film, is 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 Laminated film prepared by atomic layer deposition 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.
It is specific embodiment below：
Embodiment 1
The typical high-speed steel tool of the present embodiment pair one surface carries out the preparation of protective coating, and carries out comparison in fact using silicon chip It tests.
First, the silicon nitride film of one layer of 5 μ m thick, depositing temperature are deposited using plasma activated chemical vapour deposition method It it is 80 DEG C, two kinds of presomas being passed through are SiH4、NH3, the chemical equation for preparing silicon nitride film is：
And total reaction equation is：
Then, it is thin in silicon nitride using plasma enhanced atomic layer deposition method after silicon nitride film prepares completion 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。
The chemical equation for preparing aluminum oxide film is：
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 be：
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 fully reacted, the equation of reaction is：
2Al(CH3)3+3H2O→Al2O3+6CH4
Since the saturated vapor pressure of water at normal temperature (i.e. the third presoma) is relatively low, in the third presoma H2O is logical It is heated before entering to increase its saturated vapour pressure, it is 60 DEG C~100 to promote the abundant progress of reaction, heating temperature ℃。
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, it is made annealing treatment, high-speed steel tool is taken out, be put into progress vacuum in Muffle furnace and move back Fire processing, annealing temperature are 450 DEG C.
The top film of tool surface is tested using ellipsometer after annealing, 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 front and back film of annealing, the results are shown in Figure 2, according to fig. 2 it can be found that moving back Fiery front and back there is no the appearance of new characteristic peak, 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 in storing process by all kinds of gas picklings, and for example the steam in air, the present invention utilize compound Film layer protects the OLED device that area is 5cm × 5cm, can more intuitively 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.
It is 50nm that preparation method using the present invention prepares silicon nitride layer+thickness that thickness is 1 μm on OLED device surface 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 figure 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 occurred through 90 hours Effect, Fig. 4 c) be packaged with composite coating of the present invention OLED device illuminating state figure, do not fail yet after aging in 500 hours. There is high obstructing capacity for steam by the composite coating of the present invention known to experiment, 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 is also to only having the OLED device that primer coating is protected to carry out burn-in test, the service life is 92 hours, And the only device lifetime of 50nm aluminum oxide films is 128 hours, it is seen that composite film of the invention has good barrier energy Power, its service life was 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, all within the spirits and principles of the present invention made by all any modification, equivalent and improvement etc., should all include Within protection scope of the present invention.

Claims (10)

1. a kind of preparation method of high-speed steel tool protective coating, which is characterized in that include the following steps：
S1 pre-processes high-speed steel tool surface to be protected；
Above-mentioned pretreated high-speed steel tool is placed in glove box and preserves by S2, is then transferred to plasma enhancing It learns in vapor deposition chamber and carries out plasma enhanced chemical vapor deposition, micron order is obtained to be deposited on high-speed steel tool surface Bottom film；
Surface deposition is had the high-speed steel tool of micron order bottom film to be transferred to plasma enhanced atomic layer deposition cavity by S3 Middle carry out plasma enhanced atomic layer deposition, to prepare nano level top film on bottom film surface, to obtain by The composite protection layer that bottom film and top film are constituted；
Deposition is had the high-speed steel tool of composite protection layer to be made annealing treatment under the conditions of 200 DEG C~500 DEG C by S4, 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 progress in step S2 Plasma enhanced chemical vapor deposition is specially：Plasma enhancing chemical vapor deposition chamber body is preheated first, so The mixed gas of the different presomas mixed in proportion is passed through in cavity afterwards, high-frequency electric field is recycled to carry out electricity to mixed gas From to deposit bottom film on high-speed steel tool surface, remaining mixed gas in vacuum pumped cavity is utilized after deposition And byproduct of reaction.
3. the preparation method of high-speed steel tool protective coating as claimed in claim 2, which is characterized in that plasma enhancing The preheating temperature for learning vapor deposition chamber is 60 DEG C~400 DEG C；The plasma power used in deposition process for 2000W~ The pressure of 4000W, cavity are 150Pa~250Pa, and the flow of mixed gas is 3000sccm~5000sccm, and sedimentation time is 1500s~3000s, deposition thickness are 5 μm~10 μm.
4. the preparation method of high-speed steel tool protective coating as claimed in claim 2, which is characterized in that presoma is two kinds, Preferably SiH4/NH3、AlCl3/NH3、TiCl4/NH3Or TaCl4/NH3, the mixed proportion of two kinds of presomas is 1:5~1:10.
5. the preparation method of high-speed steel tool protective coating as described in claim 1, which is characterized in that the bottom film is SiNxIt is one or more in coating, AlN coatings, TiN coatings, TaN coatings.
6. the preparation method of high-speed steel tool protective coating as described in claim 1, which is characterized in that the progress in step S3 Three kinds of presomas, respectively the first presoma, second of presoma and third are passed through when plasma enhanced atomic layer deposition Kind presoma, wherein the first presoma are the presoma with organic group, and second of presoma is oxygen source presoma, is used for It is reacted with the completion of the first presoma to prepare nano level top film, the third presoma is also oxygen source presoma, is used for It reacts with the first remaining presoma in top film so that film is more fine and close.
7. the preparation method of high-speed steel tool protective coating as claimed in any one of claims 1 to 6, which is characterized in that step S3 In carry out plasma enhanced atomic layer deposition specifically comprise the following steps：
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 nano level top film of required thickness.
8. such as the preparation method of claim 6-7 any one of them high-speed steel tool protective coatings, which is characterized in that described the A kind of presoma, second of presoma and the third presoma are Al (CH3)3、O2And H2O, or be CH3Si[N(CH3)2]3、O2 And O3。
9. such as the preparation method of claim 1-8 any one of them high-speed steel tool protective coatings, which is characterized in that the top Layer film is Al2O3Film layer, SiO2One kind of film layer or combination；The thickness of the top film is 20nm~100nm.
10. such as the preparation method of claim 7-9 any one of them high-speed steel tool protective coatings, which is characterized in that making During standby top film, when no carrier gas is passed through, internal pressure is less than plasma enhanced atomic layer deposition cavity 1Pa。
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