CN109082641A - A kind of trilamellar membrane structure coating and preparation method thereof - Google Patents
A kind of trilamellar membrane structure coating and preparation method thereof Download PDFInfo
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- CN109082641A CN109082641A CN201810986292.9A CN201810986292A CN109082641A CN 109082641 A CN109082641 A CN 109082641A CN 201810986292 A CN201810986292 A CN 201810986292A CN 109082641 A CN109082641 A CN 109082641A
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- 238000000576 coating method Methods 0.000 title claims abstract description 53
- 239000011248 coating agent Substances 0.000 title claims abstract description 52
- 239000012528 membrane Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 48
- 239000011159 matrix material Substances 0.000 claims abstract description 47
- 239000010410 layer Substances 0.000 claims abstract description 37
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 36
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 21
- 239000000956 alloy Substances 0.000 claims abstract description 21
- 238000004544 sputter deposition Methods 0.000 claims abstract description 18
- 229910000997 High-speed steel Inorganic materials 0.000 claims abstract description 13
- 239000010959 steel Substances 0.000 claims abstract description 13
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 11
- 239000002344 surface layer Substances 0.000 claims abstract description 10
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000008246 gaseous mixture Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 abstract description 13
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005477 sputtering target Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006557 surface reaction Methods 0.000 description 3
- 238000005496 tempering Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0688—Cermets, e.g. mixtures of metal and one or more of carbides, nitrides, oxides or borides
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/081—Oxides of aluminium, magnesium or beryllium
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention belongs to metal coating preparation technical field, a kind of trilamellar membrane structure coating and preparation method thereof is disclosed.The trilamellar membrane structure coating is by two-phase Cr+ α-(Al, Cr)2O3Bond matrix layer, single-phase α-(Al, Cr)2O3Supporting layer and single phase nano α-Al2O3Surface layer is constituted.With CrAl alloys target, Cr+ α-(Al, Cr) is sequentially depositing by magnetically controlled DC sputtering2O3Bond matrix layer and α-(Al, Cr)2O3Supporting layer；With Al+ α-Al2O3Composition target obtains single phase nano α-Al by rf magnetron sputtering2O3Surface layer.The work layer on surface of gained coating of the invention is single phase nano α-Al2O3Structure, hardness is high, good toughness, and high high-temp stability is high, and coefficient of friction is small when rubbing with metallic matrix, and with high-speed steel, the matrixes such as hot die steel and high temperature alloy are firmly combined.
Description
Technical field
The invention belongs to metal coating preparation technical fields, and in particular to a kind of trilamellar membrane structure coating and its preparation side
Method.
Background technique
Modern times processing increasingly tends to high speed, precise treatment and automation, proposes to the lathe tool, drill bit and milling cutter etc. of processing
Higher performance requirement.High-speed machining cutting edge roundness temperature may be up to 700~1000 DEG C, traditional cutter with carbide (such as
High-speed steel, hard alloy etc.) and nitride (titanium nitride, titanium carbonitride) coating improve the hardness of cutter, even sintering oxygen
Change aluminium cutter, still improves stage property toughness mixed with 30% TiC, carbon content is also very high.Carbon when high temperature, nitrogen diffusion activity very
Height, the high temperature that when High-speed machining generates spread carbon, nitrogen quickly to workpiece and form the carbide and nitride of high rigidity,
Violent abrasive wear and adhesive wear are formed with cutter, when high-carbon, nitrogen cutter at high speeds are processed and the coefficient of friction of workpiece is high, rubs
It is big to wipe resistance, processing heat is high, further promotes point of a knife temperature, forms vicious circle, cutter is worn quickly, and causes to process
Low precision, at high cost, a series of problems, such as processing efficiency is low.α-Al2O3Coating has high temperature hardness high, in oxidizing atmosphere
Thermal stability is good, and can effectively prevent the diffusion of the elements such as carbon under high temperature, nitrogen, is the ideal chose of cutter coat.With traditional
Chemical vapor deposition (CVD method) method deposits α-Al2O3, depositing temperature is up to 1000 DEG C, hard alloy can only be selected to make matrix, and apply
Layer internal stress is big, and coarse grains, brittleness is big, and film/base junction resultant force is poor etc., while there is also exhaust emissions environmental pollutions etc. to ask
Topic.Have many advantages, such as that temperature is low with physical vapour deposition (PVD) (PVD) method deposition of aluminium oxide coatings, it is friendly to environment, but deposited
Coating contains a large amount of amorphous and γ-Al2O3Etc. metastable phases, it is difficult to practical engineering application, be difficult at present in high-speed steel with PVD method and
The matrix surfaces reactive deposition such as hard alloy goes out single-phase α-Al2O3Coating；In addition, high-speed steel and oxide coating poor compatibility, apply
Layer is poor with basal body binding force, cooling often due to thermal stress directly from matrix avalanche；High-speed steel tempering temperature at 600 DEG C hereinafter,
Higher temperature deposition α-Al2O3Matrix will be softened, matrix is made to be difficult to support the α-Al of high rigidity2O3Coating.Directly in high-speed steel
Upper low temperature depositing α-Al2O3No matter coating is all difficult to realize from the purity of coating or on basal body binding force, causes not having also at present
There is surface of high speed steel to deposit α-Al2O3The report of coating.
Summary of the invention
In place of the above shortcoming and defect of the existing technology, the primary purpose of the present invention is that providing three layers a kind of
Membrane structure coating.Trilamellar membrane structure coating of the present invention is by two-phase Cr+ α-(Al, Cr)2O3Bond matrix layer, single-phase α-(Al, Cr)2O3Supporting layer and single phase nano α-Al2O3Surface layer is constituted.
Another object of the present invention is to provide the preparation methods of above-mentioned trilamellar membrane structure coating.
The object of the invention is achieved through the following technical solutions:
A kind of trilamellar membrane structure coating, by two-phase Cr+ α-(Al, Cr)2O3Bond matrix layer, single-phase α-(Al, Cr)2O3Branch
Support layer and single phase nano α-Al2O3Surface layer is constituted.Wherein Cr+ α-(Al, Cr)2O3Bond matrix layer is for improving oxide coating
With the binding force of matrix, α-(Al, Cr)2O3Supporting layer is for promoting low temperature depositing α-Al2O3Surface layer, and to α-Al2O3It is formed with
The hardness of effect supports, while restraining amorphous or other metastable phase aluminas generations.
Further, two-phase Cr+ α-(Al, the Cr)2O3Bond matrix layer with a thickness of 0.2~0.3 μm, single-phase α-
(Al,Cr)2O3Supporting layer with a thickness of 0.3~0.5 μm, single phase nano α-Al2O3Surface layer with a thickness of 1.0~1.5 μm.
The preparation method of above-mentioned trilamellar membrane structure coating, including following preparation step:
(1) substrate temperature is at 550 DEG C~650 DEG C, and CrAl alloys target Sputtering power density is in 8~10W/cm2Range, Ar+O2
O in gaseous mixture2Partial pressure deposits to obtain Cr+ α-in matrix surface by magnetically controlled DC sputtering under 6%~9% range of condition
(Al,Cr)2O3Bond matrix layer；
(2) substrate temperature is at 550 DEG C~650 DEG C, and CrAl alloys target Sputtering power density is in 7~10W/cm2Range, Ar+O2
O in gaseous mixture2Partial pressure is under 10%~15% range of condition, by magnetically controlled DC sputtering at Cr+ α-(Al, Cr)2O3Matrix is viscous
Knot layer surface deposits to obtain α-(Al, Cr)2O3Supporting layer；
(3) substrate temperature is at 550 DEG C~650 DEG C, Al+ α-Al2O3Film by Sputtering of Composite Target power density is in 6~8W/cm2Range,
Ar+O2O in gaseous mixture2Partial pressure is under 12%~15% range of condition, by rf magnetron sputtering at α-(Al, Cr)2O3Support
Layer surface deposits to obtain compact single-phase nanometer α-Al2O3Surface layer.
Further, the matrix refers to high-speed steel, hot die steel or high temperature alloy matrix.
Further, Al content range is 35~50wt.% in CrAl alloys target described in step (1) and step (2)；Step
Suddenly (1) Ar+O2O in gaseous mixture2Divide obtaining value method are as follows: when Al content is in 50wt.% in CrAl alloys target, O2Point
Pressure takes 9%, when Al content is 35.%, O2Partial pressure takes 6%；Step (2) described Ar+O2O in gaseous mixture2Divide obtaining value method
For, when Al content is in 50wt.% in CrAl alloys target, O2Partial pressure takes 15%, when Al content is 35wt.%, O2Partial pressure takes
10%.
Further, Al+ α-Al described in step (3)2O3α-Al in composition target2O3Content be 10~15wt.%；Step
Suddenly Ar+O described in (3)2O in gaseous mixture2Divide obtaining value method are as follows: as Al+ α-Al2O3α-Al in composition target2O3Content be
When 10wt.%, O2Partial pressure takes 15%, as α-Al2O3Content be 15% when, O2Partial pressure takes 12%.
Further, radio frequency magnetron described in magnetically controlled DC sputtering described in step (1) and step (2) and step (3)
The matrix of sputtering is 50~100mm range at a distance from target.
Further, radio frequency magnetron described in magnetically controlled DC sputtering described in step (1) and step (2) and step (3)
The operating air pressure of sputtering is 0.4~1.0Pa.
Trilamellar membrane structure coating of the invention have the following advantages that and the utility model has the advantages that
Cr+ α-(Al, Cr) of the invention2O3/α-(Al,Cr)2O3/α-Al2O3Trilamellar membrane structure coating, Cr+ α-(Al,
Cr)2O3As improve with the bonding transition zone of high-speed steel, hot die steel or high temperature alloy matrix, while also improve to α-(Al,
Cr)2O3The hardness of film supports transition；α-(Al,Cr)2O3To promote low temperature depositing α-Al2O3, eliminate interface amorphous and other be metastable
Phase alumina transition zone, and be α-Al2O3Enough hardness supports are provided, coating internal stress is reduced；Nanometer α-Al2O3For surface
Working lining has high temperature hardness height, the good advantage of high temperature oxidation resistance, while also having high temperature when preventing cutter at high speeds from processing
The diffusion adhesive wear of blade reduces the summations performances such as coefficient of friction.Without amorphous and other aluminium oxide in entire coating system
Metastable phase, high high-temp stability is good, and coating depositing temperature is less than 650 DEG C, to high-speed steel, hot die steel and high temperature alloy matrix
Hardness influences small.
Detailed description of the invention
Fig. 1 is the resulting Cr+ α-(Al, Cr) of the embodiment of the present invention 12O3/α-(Al,Cr)2O3/α-Al2O3Trilamellar membrane structure
The XRD spectra of work layer on surface in coating.
Fig. 2 is the resulting Cr+ α-(Al, Cr) of the embodiment of the present invention 12O3/α-(Al,Cr)2O3/α-Al2O3Trilamellar membrane structure
The SEM shape appearance figure of coating surface.
Fig. 3 is the resulting Cr+ α-(Al, Cr) of the embodiment of the present invention 12O3/α-(Al,Cr)2O3/α-Al2O3Trilamellar membrane structure
The nano hardness indentation curves figure of coating.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
The present embodiment deposits trilamellar membrane structure coating in surface of high speed steel:
(1) W6Mo5Cr4V2 high-speed steel is selected to make matrix, after being cut into Φ 10 × 5mm specification, through conventional quenching+
Matrix hardness is HRC60 after 560 DEG C of (3 times) tempering, grinds and polishes coated surface, be placed in absolute alcohol solution and be cleaned by ultrasonic
15min oil removing, drying are placed on sample stage, adjust sample and range from for 80mm；
(2) CrAl (50wt.%) and Al+ α-Al are selected2O3(15wt.%) makees sputtering target, is separately mounted to direct current and radio frequency
Magnetron sputtering respective target station；
(3) heating in vacuum baking system is opened after taking out base vacuum to 10~20Pa in advance, baking temperature is arranged at 150 DEG C,
Then it is evacuated to base vacuum 6 × 10-4Pa, Ar gas is filled into vacuum chamber and adjusts throttle valve to vacuum degree returns to 20Pa, stablizes
Throttle valve is opened after 10min, then is evacuated to 6 × 10-4The base vacuum of Pa；
(4) baking is closed, matrix is heated to 560 DEG C, fills Ar gas to 0.5Pa, matrix application -700V back bias voltage, starting
CrAl target power supply is to matrix surface sputter clean 15min；
(5) substrate bias is closed, is passed through Ar+O to system mixing chamber2Gas adjusts O2Partial pressure is to 9%, and control throttle valve is extremely
Vacuum degree opens CrAl sputtering target in 0.6~0.7Pa range, when target power density is 9W/cm2When deposit 20min, obtain about
0.3 μm of Cr+ α-(Al, Cr)2O3Bond matrix layer；
(6) adjustment O is improved2For partial pressure to 15%, the power density of target is 9W/cm2When deposit 60min, obtain 0.5 μm of α-
(Al,Cr)2O3Supporting layer；
(7) CrAl target power supply is closed, sample is gone into Al+ α-Al2O3Target station adjusts Ar+O2O in gaseous mixture2Partial pressure
To 12%, radio-frequency power supply is opened, when target power density is 8W/cm2When deposit 180min, at α-(Al, Cr)2O3Surface reaction is splashed
It penetrates and deposits fine and close α-Al2O3Film, α-Al2O3Thin crystallite dimension is 30~40nm, with a thickness of 1.5 μm.
(8) radio frequency target power supply is closed after depositing, and closes Ar+O2Gas, vacuum chamber close base after taking out background vacuum
Body heating power supply takes out sample after cooling to the furnace lower than 150 DEG C, obtain and deposit Cr+ α-(Al, Cr) in surface of high speed steel2O3/
α-(Al,Cr)2O3/α-Al2O3The sample of trilamellar membrane structure coating.The nano hardness of coating is 27GPa.
XRD spectrum, surface SEM pattern and the nano hardness indentation curves of composite coating obtained by the present embodiment respectively as Fig. 1,
Shown in Fig. 2 and Fig. 3, the work layer on surface of composite coating is single-phase α-Al as the result is shown2O3, crystallite dimension 30nm, nano hardness
For 27GPa (supporting layer α-(Al, Cr)2O3With working lining α-Al2O3The difference very little on SEM and mechanical property, but and steel
The coefficient of friction difference of equal matrixes is larger, α-Al2O3Coefficient of friction is small when cutting steel, α-(Al, Cr)2O3With the friction of steel
Coefficient is big, α-(Al, Cr)2O3Effect be to ensure that low temperature preparation α-Al2O3When do not form metastable phase, while giving α-Al2O3It is formed
Enough hardness supports).
Embodiment 2
The present embodiment deposits trilamellar membrane structure coating on 3Cr2W8V hot die steel:
(1) 3Cr2W8V hot die steel is selected to make matrix, after being cut into Φ 10 × 5mm specification, through conventional quenching+
600 DEG C of (3 times) tempering, matrix hardness HRC52 grind and polish coated surface, be placed in absolute alcohol solution and be cleaned by ultrasonic
15min oil removing, drying are placed on sample stage, adjust sample and range from for 80mm；
(2) CrAl (40wt.%) and Al+ α-Al are selected2O3(12wt.%) makees sputtering target, is separately mounted to direct current and radio frequency
Magnetron sputtering respective target station；
(3) heating in vacuum baking system is opened after taking out base vacuum to 10~20Pa in advance, baking temperature is arranged at 150 DEG C,
Then it is evacuated to base vacuum 6 × 10-4Pa, Ar gas is filled into vacuum chamber and adjusts throttle valve to vacuum degree returns to 20Pa, stablizes
Throttle valve is opened after 10min, then is evacuated to 6 × 10-4The base vacuum of Pa；
(4) baking is closed, matrix is heated to 600 DEG C, fills Ar gas to 0.5Pa, matrix application -700V back bias voltage, starting
CrAl target power supply is to matrix surface sputter clean 15min；
(5) substrate bias is closed, is passed through Ar+O to system mixing chamber2Gas adjusts O2Partial pressure is to 7%, and control throttle valve is extremely
Vacuum degree opens CrAl sputtering target in 0.6~0.7Pa range, when target power density is 8W/cm2When deposit 20min, obtain about
0.2 μm of Cr+ α-(Al, Cr)2O3Bond matrix layer；
(6) adjustment O is improved2For partial pressure to 12%, the power density of target is 8W/cm2When deposit 60min, obtain 0.5 μm of α-
(Al,Cr)2O3Supporting layer；
(7) CrAl target power supply is closed, sample is gone into Al+ α-Al2O3Target station adjusts Ar+O2O in gaseous mixture2Partial pressure
To 13.5%, radio-frequency power supply is opened, when target power density is 8W/cm2When deposit 150min, at α-(Al, Cr)2O3Surface reaction
Sputtering sedimentation goes out densification α-Al2O3Film, α-Al2O3Thin crystallite dimension is 30~40nm, with a thickness of 1.2 μm.
(8) radio frequency target power supply is closed after depositing, and closes Ar+O2Gas, vacuum chamber close base after taking out background vacuum
Body heating power supply, takes out sample after cooling to the furnace lower than 150 DEG C, obtain surface of hot die steel deposit Cr+ α-(Al,
Cr)2O3/α-(Al,Cr)2O3/α-Al2O3The sample of trilamellar membrane structure coating.The nano hardness of coating is 25GPa.
Embodiment 3
The present embodiment is depositing trilamellar membrane structure coating in GH2036 high-temperature alloy surface:
(1) GH2036 high temperature alloy is selected to make matrix, after being cut into Φ 10 × 5mm specification, when through+670 DEG C of solid solution
After effect, matrix hardness HRC40 grinds and polishes coated surface, is placed in ultrasonic cleaning 15min oil removing in absolute alcohol solution,
Drying is placed on sample stage, adjusts sample and range from for 60mm；
(2) CrAl (35wt.%) and Al+ α-Al are selected2O3(10wt.%) makees sputtering target, is separately mounted to direct current and radio frequency
Magnetron sputtering respective target station；
(3) heating in vacuum baking system is opened after taking out base vacuum to 10~20Pa in advance, baking temperature is arranged at 150 DEG C,
Then it is evacuated to base vacuum 6 × 10-4Pa, Ar gas is filled into vacuum chamber and adjusts throttle valve to vacuum degree returns to 20Pa, stablizes
Throttle valve is opened after 10min, then is evacuated to 6 × 10-4The base vacuum of Pa；
(4) baking is closed, matrix is heated to 660 DEG C, fills Ar gas to 0.5Pa, matrix application -700V back bias voltage, starting
CrAl target power supply is to matrix surface sputter clean 15min；
(5) substrate bias is closed, is passed through Ar+O to system mixing chamber2Gas adjusts O2Partial pressure is to 6%, and control throttle valve is extremely
Vacuum degree opens CrAl sputtering target in 0.6~0.7Pa range, when target power density is 8W/cm2When deposit 20min, obtain about
0.3 μm of Cr+ α-(Al, Cr)2O3Bond matrix layer；
(6) adjustment O is improved2For partial pressure to 10%, the power density of target is 8W/cm2When deposit 60min, obtain 0.5 μm of α-
(Al,Cr)2O3Supporting layer；
(7) CrAl target power supply is closed, sample is gone into Al+ α-Al2O3Target station adjusts Ar+O2O in gaseous mixture2Partial pressure
To 15%, radio-frequency power supply is opened, when target power density is 9W/cm2When deposit 180min, at α-(Al, Cr)2O3Surface reaction is splashed
It penetrates and deposits fine and close α-Al2O3Film, α-Al2O3Thin crystallite dimension is 40nm, with a thickness of 1.5 μm.
(8) radio frequency target power supply is closed after depositing, and closes Ar+O2Gas, vacuum chamber close base after taking out background vacuum
Body heating power supply takes out sample after cooling to the furnace lower than 150 DEG C, obtain and deposit Cr+ α-(Al, Cr) in surface of high speed steel2O3/
α-(Al,Cr)2O3/α-Al2O3The sample of trilamellar membrane structure coating.The nano hardness of coating is 25GPa.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of trilamellar membrane structure coating, it is characterised in that: by two-phase Cr+ α-(Al, Cr)2O3Bond matrix layer, single-phase α-(Al,
Cr)2O3Supporting layer and single phase nano α-Al2O3Surface layer is constituted.
2. a kind of trilamellar membrane structure coating according to claim 1, it is characterised in that: two-phase Cr+ α-(Al, the Cr)2O3
Bond matrix layer with a thickness of 0.2~0.3 μm, single-phase α-(Al, Cr)2O3Supporting layer with a thickness of 0.3~0.5 μm, single phase nano
α-Al2O3Surface layer with a thickness of 1.0~1.5 μm.
3. a kind of preparation method of trilamellar membrane structure coating of any of claims 1 or 2, it is characterised in that including preparing step as follows
It is rapid:
(1) substrate temperature is at 550 DEG C~650 DEG C, and CrAl alloys target Sputtering power density is in 8~10W/cm2Range, Ar+O2Mixing
O in gas2Partial pressure under 6%~9% range of condition, by magnetically controlled DC sputtering matrix surface deposit to obtain Cr+ α-(Al,
Cr)2O3Bond matrix layer；
(2) substrate temperature is at 550 DEG C~650 DEG C, and CrAl alloys target Sputtering power density is in 7~10W/cm2Range, Ar+O2Mixing
O in gas2Partial pressure is under 10%~15% range of condition, by magnetically controlled DC sputtering at Cr+ α-(Al, Cr)2O3Bond matrix layer
Surface deposits to obtain α-(Al, Cr)2O3Supporting layer；
(3) substrate temperature is at 550 DEG C~650 DEG C, Al+ α-Al2O3Film by Sputtering of Composite Target power density is in 6~8W/cm2Range, Ar+O2
O in gaseous mixture2Partial pressure is under 12%~15% range of condition, by rf magnetron sputtering at α-(Al, Cr)2O3Supporting layer table
Face deposits to obtain compact single-phase nanometer α-Al2O3Surface layer.
4. a kind of preparation method of trilamellar membrane structure coating according to claim 3, it is characterised in that: the matrix is
Refer to high-speed steel, hot die steel or high temperature alloy matrix.
5. a kind of preparation method of trilamellar membrane structure coating according to claim 3, it is characterised in that: step (1) and step
Suddenly Al content range is 35~50wt.% in CrAl alloys target described in (2).
6. a kind of preparation method of trilamellar membrane structure coating according to claim 5, it is characterised in that: step (1) is described
Ar+O2O in gaseous mixture2Divide obtaining value method are as follows: when Al content is in 50wt.% in CrAl alloys target, O2Partial pressure takes 9%, when
When Al content is 35.%, O2Partial pressure takes 6%；Step (2) described Ar+O2O in gaseous mixture2Dividing obtaining value method is to work as CrAl
Al content is in 50wt.% in alloys target, O2Partial pressure takes 15%, when Al content is 35wt.%, O2Partial pressure takes 10%.
7. a kind of preparation method of trilamellar membrane structure coating according to claim 3, it is characterised in that: institute in step (3)
State Al+ α-Al2O3α-Al in composition target2O3Content be 10~15wt.%.
8. a kind of preparation method of trilamellar membrane structure coating according to claim 7, it is characterised in that: institute in step (3)
State Ar+O2O in gaseous mixture2Divide obtaining value method are as follows: as Al+ α-Al2O3α-Al in composition target2O3Content be 10wt.% when,
O2Partial pressure takes 15%, as α-Al2O3Content be 15% when, O2Partial pressure takes 12%.
9. a kind of preparation method of trilamellar membrane structure coating according to claim 3, it is characterised in that: step (1) and step
Suddenly the matrix of rf magnetron sputtering described in magnetically controlled DC sputtering described in (2) and step (3) at a distance from target for 50~
100mm range.
10. a kind of preparation method of trilamellar membrane structure coating according to claim 3, it is characterised in that: step (1) and step
Suddenly the operating air pressure of rf magnetron sputtering described in magnetically controlled DC sputtering described in (2) and step (3) is 0.4~1.0Pa.
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