CN109082641B - A kind of three-layer film structure coating and preparation method thereof - Google Patents
A kind of three-layer film structure coating and preparation method thereof Download PDFInfo
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 34
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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
- 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
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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
- 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
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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
- 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
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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
- 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
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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
- 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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Abstract
本发明属于金属涂层制备技术领域，公开了一种三层膜结构涂层及其制备方法。所述三层膜结构涂层由双相Cr+α‑(Al,Cr)2O3基体粘结层、单相α‑(Al,Cr)2O3支撑层和单相纳米α‑Al2O3表层构成。以CrAl合金靶，通过直流磁控溅射依次沉积Cr+α‑(Al,Cr)2O3基体粘结层和α‑(Al,Cr)2O3支撑层；以Al+α‑Al2O3复合靶，通过射频磁控溅射得到单相纳米α‑Al2O3表层。本发明所得涂层的表面工作层为单相纳米α‑Al2O3结构，硬度高，韧性好，高温热稳定性高，与金属基体摩擦时摩擦系数小，与高速钢，热作模具钢和高温合金等基体结合牢固。
The invention belongs to the technical field of metal coating preparation, and discloses a three-layer film structure coating and a preparation method thereof. The three-layer film structure coating is composed of a dual-phase Cr+α-(Al,Cr) 2 O 3 matrix bonding layer, a single-phase α-(Al, Cr) 2 O 3 support layer and a single-phase nano-α-Al 2 O 3 surface composition. A CrAl alloy target was used to deposit Cr+α‑(Al,Cr) 2 O 3 matrix bonding layer and α‑(Al,Cr) 2 O 3 support layer in turn by DC magnetron sputtering; Al+α‑Al 2 O 3 composite target, single-phase nano-α-Al 2 O 3 surface layer is obtained by radio frequency magnetron sputtering. The surface working layer of the coating obtained by the invention has a single-phase nano-α-Al 2 O 3 structure, which has high hardness, good toughness, high thermal stability at high temperature, and a small friction coefficient when rubbing against a metal matrix. It is firmly bonded to the matrix such as superalloy.
Description
Technical Field
The invention belongs to the technical field of metal coating preparation, and particularly relates to a three-layer film structure coating and a preparation method thereof.
Background
Modern machining tends to be high-speed, precise and automatic increasingly, and higher performance requirements are put forward on turning tools, drill bits, milling cutters and the like for machining. The temperature of the cutting edge of the high-speed machining cutter can reach 700-1000 ℃, and the traditional cutters are all made of carbide (such as high-speed steel and hard materials)Alloy, etc.) and nitride (titanium nitride, titanium carbonitride) coating to improve the hardness of the tool, even sintered alumina tool, still mix 30% TiC to improve the toughness of the tool, the carbon content is also very high, the diffusion activity of carbon, nitrogen is very high at high temperature, the high temperature produced when high speed processing makes carbon, nitrogen element diffuse to the work piece fast and form carbide and nitride of high hardness, form violent abrasive wear and adhesive wear with the tool, the high carbon, nitrogen tool high speed processing and friction coefficient of the work piece high, the frictional resistance is large, the processing heat quantity is high, further raise the temperature of the tool tip, form vicious circle, the tool is worn out very fast, and cause a series of problems such as poor processing precision, high cost, low processing efficiency, α -Al2O3The coating has high-temperature hardness and good thermal stability in an oxidizing atmosphere, can effectively prevent elements such as carbon, nitrogen and the like from diffusing at high temperature, is an ideal choice for the cutter coating, and is α -Al deposited by using a traditional Chemical Vapor Deposition (CVD) method2O3The deposition temperature is as high as 1000 ℃, only hard alloy can be selected as a substrate, the coating has large internal stress, large crystal grains, large brittleness, poor membrane/substrate binding force and the like, and the problems of environmental pollution caused by tail gas emission and the like exist. The Physical Vapor Deposition (PVD) method for depositing the alumina coating has the advantages of low temperature, environmental friendliness, etc., but the deposited coating contains a large amount of amorphous and gamma-Al2O3Equal metastable phase, difficult practical engineering application, and difficult reaction deposition of single phase α -Al on the surface of high-speed steel, hard alloy and other substrates by PVD method at present2O3In addition, the compatibility of the high-speed steel and the oxide coating is poor, the bonding force between the coating and the substrate is poor, the high-speed steel is directly disintegrated from the substrate due to thermal stress when cooled, the tempering temperature of the high-speed steel is below 600 ℃, α -Al is deposited at a higher temperature2O3The α -Al which softens the matrix and makes the matrix difficult to support with high hardness2O3Direct low temperature deposition of α -Al on high speed steel2O3The coating is difficult to realize from the purity of the coating and the bonding force with a substrate, so that α -Al is not deposited on the surface of high-speed steel at present2O3And (3) reporting the coating.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention provides a three-layer film structure coating which is formed by two phases of Cr + α - (Al, Cr)2O3Substrate bonding layer, Single phase α - (Al, Cr)2O3Support layer and single-phase nano α -Al2O3A surface layer.
The invention also aims to provide a preparation method of the three-layer film structure coating.
The purpose of the invention is realized by the following technical scheme:
a three-layer film structure coating is prepared from biphase Cr + α - (Al, Cr)2O3Substrate bonding layer, Single phase α - (Al, Cr)2O3Support layer and single-phase nano α -Al2O3Surface layer, wherein Cr + α - (Al, Cr)2O3The substrate bonding layer is used for improving the bonding force between the oxide coating and the substrate, α - (Al, Cr)2O3The support layer is used for promoting low-temperature deposition α -Al2O3Surface layer, and pairs α -Al2O3Forming an effective hardness support while suppressing amorphous or other metastable phase alumina production.
Further, the biphase Cr + α - (Al, Cr)2O3The thickness of the substrate bonding layer is 0.2-0.3 μm, and the substrate bonding layer is single-phase α - (Al, Cr)2O3The thickness of the supporting layer is 0.3-0.5 mu m, and the single-phase nano α -Al2O3The thickness of the surface layer is 1.0 to 1.5 μm.
The preparation method of the three-layer film structure coating comprises the following preparation steps:
(1) the temperature of the substrate is 550-650 ℃, the sputtering power density of the CrAl alloy target is 8-10W/cm2Range, Ar + O2O in the gas mixture2Under the condition of partial pressure of 6-9%, depositing Cr + α - (Al, Cr) on the surface of the substrate by direct current magnetron sputtering2O3A substrate bonding layer;
(2) the temperature of the substrate is 550-650 ℃, the sputtering power density of the CrAl alloy target is 7-10W/cm2Range, Ar + O2O in the gas mixture2Partial pressure is in the range of 10-15%Under the surrounding conditions, the alloy is sputtered on Cr + α - (Al, Cr)2O3α - (Al, Cr) is obtained by deposition on the surface of the substrate bonding layer2O3A support layer;
(3) the temperature of the substrate is 550-650 ℃, and Al + α -Al2O3The sputtering power density of the composite target is 6-8W/cm2Range, Ar + O2O in the gas mixture2Under the condition of 12-15% partial pressure, α - (Al, Cr) is sputtered by radio frequency magnetron sputtering2O3The surface of the supporting layer is deposited to obtain compact single-phase nano α -Al2O3A surface layer.
Furthermore, the matrix is high-speed steel, hot-work die steel or a high-temperature alloy matrix.
Further, the content of Al in the CrAl alloy target in the step (1) and the step (2) ranges from 35 wt.% to 50 wt.%; ar + O in the step (1)2O in the gas mixture2The partial pressure value taking method comprises the following steps: o when the Al content of the CrAl alloy target is 50 wt%2The partial pressure is taken to be 9%, and when the Al content is 35 wt.%, O is present2The partial pressure is 6 percent; ar + O in the step (2)2O in the gas mixture2The partial pressure value taking method is that when the Al content in the CrAl alloy target is 50 wt.%, O2The partial pressure is taken to be 15%, and when the Al content is 35 wt.%, O is present2The partial pressure was 10%.
Further, Al + α -Al in the step (3)2O3α -Al in composite target2O3The content of (a) is 10-15 wt.%; ar + O in the step (3)2O in the gas mixture2The partial pressure value is obtained when Al + α -Al2O3α -Al in composite target2O3When the content of (B) is 10 wt.%, O2The partial pressure is 15 percent when α -Al2O3When the content of (B) is 15 wt.%, O2The partial pressure was 12%.
Further, the distance between the substrate and the target in the direct current magnetron sputtering in the step (1) and the step (2) and the distance between the substrate and the target in the radio frequency magnetron sputtering in the step (3) are within the range of 50-100 mm.
Further, the working air pressure of the direct current magnetron sputtering in the step (1) and the step (2) and the working air pressure of the radio frequency magnetron sputtering in the step (3) are 0.4-1.0 Pa.
The three-layer film structure coating has the following advantages and beneficial effects:
cr + α - (Al, Cr) of the present invention2O3/α-(Al,Cr)2O3/α-Al2O3Three-layer film structure coating, Cr + α - (Al, Cr)2O3Used as a transition layer for improving the adhesion with a high-speed steel, hot-work die steel or high-temperature alloy matrix and improving the pair α - (Al, Cr)2O3Hardness supporting transition of the film α - (Al, Cr)2O3To promote low temperature deposition of α -Al2O3Eliminating interface amorphous and other metastable phase alumina transition layer and is α -Al2O3Providing enough hardness support and reducing internal stress of coating, nano α -Al2O3The surface working layer has the advantages of high-temperature hardness and good high-temperature oxidation resistance, and simultaneously has the total performances of preventing diffusion, adhesion and abrasion of a high-temperature cutting edge during high-speed processing of the cutter, reducing the friction coefficient and the like. The whole coating system does not contain amorphous and other metastable phases of alumina, has good high-temperature thermal stability, has the deposition temperature of less than 650 ℃, and has little influence on the hardness of high-speed steel, hot-work die steel and high-temperature alloy matrixes.
Drawings
FIG. 1 shows Cr + α - (Al, Cr) obtained in example 1 of the present invention2O3/α-(Al,Cr)2O3/α-Al2O3XRD spectrogram of a surface working layer in the three-layer film structure coating.
FIG. 2 shows Cr + α - (Al, Cr) obtained in example 1 of the present invention2O3/α-(Al,Cr)2O3/α-Al2O3SEM topography of the surface of the three-layer film structure coating.
FIG. 3 shows Cr + α - (Al, Cr) obtained in example 1 of the present invention2O3/α-(Al,Cr)2O3/α-Al2O3And (3) a nano-hardness indentation curve diagram of the three-layer film structure coating.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
This example deposits a three-layer film structure coating on the surface of high speed steel:
(1) selecting W6Mo5Cr4V2 high-speed steel as a substrate, cutting into phi 10 multiplied by 5mm specification and size, tempering through conventional quenching and 560 ℃ (3 times), wherein the hardness of the substrate is HRC60, grinding and polishing the coated surface, placing in an absolute alcohol solution for ultrasonic cleaning for 15min to remove oil, placing on a sample table after drying, and adjusting the distance between the sample and a target to be 80 mm;
(2) CrAl (50 wt.%) and Al + α -Al were chosen2O3(15 wt.%) as sputtering target, respectively installed at the stations corresponding to DC and RF magnetron sputtering targets;
(3) pre-pumping background vacuum to 10-20 Pa, starting a vacuum heating baking system, setting the baking temperature at 150 ℃, and pumping to the background vacuum of 6 multiplied by 10-4Pa, filling Ar gas into the vacuum chamber, adjusting the throttle valve to vacuum degree and returning to 20Pa, opening the throttle valve after stabilizing for 10min, and pumping to 6 × 10-4Background vacuum of Pa;
(4) closing the baking, heating the substrate to 560 ℃, charging Ar gas to 0.5Pa, applying negative bias of-700V to the substrate, and starting a CrAl target power supply to sputter and clean the surface of the substrate for 15 min;
(5) closing the bias voltage of the substrate, and introducing Ar + O into the gas mixing chamber of the system2Gas, adjusting O2Partial pressure is 9%, a throttle valve is controlled to the vacuum degree within the range of 0.6-0.7 Pa, a CrAl sputtering target is opened, and when the target power density is 9W/cm2Then depositing for 20min to obtain Cr + α - (Al, Cr) of about 0.3 μm2O3A substrate bonding layer;
(6) increase the adjustment of O2Partial pressure is up to 15%, and power density of the target is 9W/cm2Then depositing for 60min to obtain α - (Al, Cr) with the particle size of 0.5 mu m2O3A support layer;
(7) the CrAl target power supply is turned off, and the sample is switched to Al + α -Al2O3Target station, adjusting Ar + O2O in the gas mixture2Dividing the voltage to 12%, starting the radio frequency power supply, and when the target power density is 8W/cm2Then depositing for 180min at α - (Al, Cr)2O3Depositing compact α -Al on the surface by reactive sputtering2O3Film, α -Al2O3The thin crystal grain size is 30-40 nm and the thickness is 1.5 μm.
(8) After deposition, the power supply of the radio frequency target is turned off, and Ar + O is turned off2Gas, after the vacuum chamber is pumped to the background vacuum degree, the substrate heating power supply is closed, the substrate is cooled to be lower than 150 ℃ along with the furnace, and then the sample is taken out, thereby obtaining the Cr + α - (Al, Cr) deposited on the surface of the high-speed steel2O3/α-(Al,Cr)2O3/α-Al2O3Three-layer film structure coated samples. The nano-hardness of the coating was 27 GPa.
The XRD pattern, surface SEM morphology and nano-hardness indentation curve of the composite coating obtained in the embodiment are respectively shown in fig. 1, fig. 2 and fig. 3, and the result shows that the surface working layer of the composite coating is single-phase α -Al2O3With a grain size of 30nm and a nano-hardness of 27GPa (supporting layer α - (Al, Cr)2O3And a working layer α -Al2O3Has little difference in SEM and mechanical properties, but has great difference in friction coefficient with steel and other matrixes, α -Al2O3Small friction coefficient when cutting steel, α - (Al, Cr)2O3High friction coefficient with steel α - (Al, Cr)2O3The function of (a) is to ensure low-temperature preparation of α -Al2O3Without formation of metastable phase, while α -Al is supplied2O3Forming a sufficiently stiff support).
Example 2
This example deposited a three layer film structural coating on 3Cr2W8V hot work die steel:
(1) selecting 3Cr2W8V hot-working die steel as a matrix, cutting into phi 10 multiplied by 5mm specification and size, tempering through conventional quenching and 600 ℃ (3 times), wherein the matrix hardness is HRC52, grinding and polishing the coated surface, placing in an absolute alcohol solution for ultrasonic cleaning for 15min to remove oil, placing on a sample table after drying, and adjusting the distance between the sample and a target to be 80 mm;
(2) CrAl (40 wt.%) and Al + α -Al were chosen2O3(12 wt.%) as sputtering target, respectively installed at the stations corresponding to DC and RF magnetron sputtering targets;
(3) pre-pumping notebookStarting a vacuum heating baking system after the bottom vacuum reaches 10-20 Pa, setting the baking temperature at 150 ℃, and then pumping to the bottom vacuum of 6 multiplied by 10-4Pa, filling Ar gas into the vacuum chamber, adjusting the throttle valve to vacuum degree and returning to 20Pa, opening the throttle valve after stabilizing for 10min, and pumping to 6 × 10-4Background vacuum of Pa;
(4) closing the baking, heating the substrate to 600 ℃, filling Ar gas to 0.5Pa, applying negative bias of-700V to the substrate, and starting a CrAl target power supply to sputter and clean the surface of the substrate for 15 min;
(5) closing the bias voltage of the substrate, and introducing Ar + O into the gas mixing chamber of the system2Gas, adjusting O2Partial pressure is controlled to be 7%, a throttle valve is controlled to be in a range of 0.6-0.7 Pa, a CrAl sputtering target is opened, and when the target power density is 8W/cm2Then depositing for 20min to obtain Cr + α - (Al, Cr) of about 0.2 μm2O3A substrate bonding layer;
(6) increase the adjustment of O2The partial pressure is 12 percent, and the power density of the target is 8W/cm2Then depositing for 60min to obtain α - (Al, Cr) with the particle size of 0.5 mu m2O3A support layer;
(7) the CrAl target power supply is turned off, and the sample is switched to Al + α -Al2O3Target station, adjusting Ar + O2O in the gas mixture2The partial pressure reaches 13.5 percent, the radio frequency power supply is started, and when the target power density is 8W/cm2Is deposited for 150min at α - (Al, Cr)2O3Depositing compact α -Al on the surface by reactive sputtering2O3Film, α -Al2O3The thin crystal grain size is 30-40 nm and the thickness is 1.2 μm.
(8) After deposition, the power supply of the radio frequency target is turned off, and Ar + O is turned off2After the vacuum degree of the vacuum chamber is pumped, the heating power supply of the matrix is closed, the matrix is cooled to be lower than 150 ℃ along with the furnace, and the sample is taken out to obtain the Cr + α - (Al, Cr) deposited on the surface of the hot-work die steel2O3/α-(Al,Cr)2O3/α-Al2O3Three-layer film structure coated samples. The nano-hardness of the coating was 25 GPa.
Example 3
In this embodiment, a three-layer film structure coating is deposited on the surface of the GH2036 superalloy:
(1) selecting GH2036 high-temperature alloy as a substrate, cutting into specification sizes of phi 10 multiplied by 5mm, performing solid solution at +670 ℃ for aging, wherein the hardness of the substrate is HRC40, grinding and polishing the coated surface, placing the coated surface in an absolute alcohol solution for ultrasonic cleaning for 15min to remove oil, placing the dried coated surface on a sample table, and adjusting the distance between the sample and a target to be 60 mm;
(2) CrAl (35 wt.%) and Al + α -Al were chosen2O3(10 wt.%) as sputtering target, respectively installed at the stations corresponding to DC and RF magnetron sputtering targets;
(3) pre-pumping background vacuum to 10-20 Pa, starting a vacuum heating baking system, setting the baking temperature at 150 ℃, and pumping to the background vacuum of 6 multiplied by 10-4Pa, filling Ar gas into the vacuum chamber, adjusting the throttle valve to vacuum degree and returning to 20Pa, opening the throttle valve after stabilizing for 10min, and pumping to 6 × 10-4Background vacuum of Pa;
(4) closing the baking, heating the substrate to 660 ℃, filling Ar gas to 0.5Pa, applying negative bias of-700V to the substrate, and starting a CrAl target power supply to sputter and clean the surface of the substrate for 15 min;
(5) closing the bias voltage of the substrate, and introducing Ar + O into the gas mixing chamber of the system2Gas, adjusting O2Partial pressure is controlled to be 6%, a throttle valve is controlled to be in a range of 0.6-0.7 Pa, a CrAl sputtering target is opened, and when the target power density is 8W/cm2Then depositing for 20min to obtain Cr + α - (Al, Cr) of about 0.3 μm2O3A substrate bonding layer;
(6) increase the adjustment of O2Partial pressure is 10%, and power density of target is 8W/cm2Then depositing for 60min to obtain α - (Al, Cr) with the particle size of 0.5 mu m2O3A support layer;
(7) the CrAl target power supply is turned off, and the sample is switched to Al + α -Al2O3Target station, adjusting Ar + O2O in the gas mixture2Dividing the voltage to 15%, starting the radio frequency power supply, and when the target power density is 9W/cm2Then depositing for 180min at α - (Al, Cr)2O3Depositing compact α -Al on the surface by reactive sputtering2O3Film, α -Al2O3The thin crystal grain size was 40nm and the thickness was 1.5. mu.m.
(8) Turning off the power supply of the radio frequency target after the deposition is finishedClosing Ar + O2Gas, after the vacuum chamber is pumped to the background vacuum degree, the substrate heating power supply is closed, the substrate is cooled to be lower than 150 ℃ along with the furnace, and then the sample is taken out, thereby obtaining the Cr + α - (Al, Cr) deposited on the surface of the high-speed steel2O3/α-(Al,Cr)2O3/α-Al2O3Three-layer film structure coated samples. The nano-hardness of the coating was 25 GPa.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. The preparation method of the three-layer film structure coating is characterized in that the three-layer film structure coating consists of two phases of Cr + α - (Al, Cr)2O3Substrate bonding layer, Single phase α - (Al, Cr)2O3Support layer and single-phase nano α -Al2O3A surface layer; the preparation method comprises the following preparation steps:
(1) the temperature of the substrate is 550-650 ℃, the sputtering power density of the CrAl alloy target is 8-10W/cm2Range, Ar + O2O in the gas mixture2Under the condition of partial pressure of 6-9%, depositing Cr + α - (Al, Cr) on the surface of the substrate by direct current magnetron sputtering2O3A substrate bonding layer;
(2) the temperature of the substrate is 550-650 ℃, the sputtering power density of the CrAl alloy target is 7-10W/cm2Range, Ar + O2O in the gas mixture2Under the condition of partial pressure of 10-15%, through direct current magnetron sputtering on Cr + α - (Al, Cr)2O3α - (Al, Cr) is obtained by deposition on the surface of the substrate bonding layer2O3A support layer;
(3) the temperature of the substrate is 550-650 ℃, and Al + α -Al2O3The sputtering power density of the composite target is 6-8W/cm2Range, Ar + O2O in the gas mixture2Under the condition of the partial pressure of 12 percent to 15 percent, α is processed by radio frequency magnetron sputtering-(Al,Cr)2O3The surface of the supporting layer is deposited to obtain compact single-phase nano α -Al2O3A surface layer.
2. The method for preparing a three-layer film structure coating according to claim 1, wherein said two-phase Cr + α - (Al, Cr)2O3The thickness of the substrate bonding layer is 0.2-0.3 μm, and the substrate bonding layer is single-phase α - (Al, Cr)2O3The thickness of the supporting layer is 0.3-0.5 mu m, and the single-phase nano α -Al2O3The thickness of the surface layer is 1.0 to 1.5 μm.
3. The method of preparing a three layer film structure coating according to claim 1, wherein: the matrix is high-speed steel, hot-work die steel or a high-temperature alloy matrix.
4. The method of preparing a three layer film structure coating according to claim 1, wherein: the content range of Al in the CrAl alloy target in the step (1) and the step (2) is 35-50 wt.%.
5. The method of preparing a three layer film structure coating according to claim 4, wherein: ar + O in the step (1)2O in the gas mixture2The partial pressure value taking method comprises the following steps: o when the Al content of the CrAl alloy target is 50 wt%2The partial pressure is taken to be 9%, and when the Al content is 35 wt.%, O is present2The partial pressure is 6 percent; ar + O in the step (2)2O in the gas mixture2The partial pressure value taking method is that when the Al content in the CrAl alloy target is 50 wt.%, O2The partial pressure is taken to be 15%, and when the Al content is 35 wt.%, O is present2The partial pressure was 10%.
6. The method of claim 1, wherein Al + α -Al is added in step (3)2O3α -Al in composite target2O3The content of (A) is 10-15 wt.%.
7. According toThe method of preparing a three-layer film structure coating according to claim 6, characterized in that: ar + O in the step (3)2O in the gas mixture2The partial pressure value is obtained when Al + α -Al2O3α -Al in composite target2O3When the content of (B) is 10 wt.%, O2The partial pressure is 15 percent when α -Al2O3When the content of (B) is 15 wt.%, O2The partial pressure was 12%.
8. The method of preparing a three layer film structure coating according to claim 1, wherein: and (3) the distance between the substrate and the target in the direct current magnetron sputtering in the step (1) and the step (2) and the distance between the substrate and the target in the radio frequency magnetron sputtering in the step (3) are within the range of 50-100 mm.
9. The method of preparing a three layer film structure coating according to claim 1, wherein: working air pressure of the direct current magnetron sputtering in the step (1) and the step (2) and working air pressure of the radio frequency magnetron sputtering in the step (3) are 0.4-1.0 Pa.
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| CN109989044B (en) * | 2019-04-03 | 2021-09-21 | 华南理工大学 | AlCr + alpha-Al2O3Sputtering target material and preparation and application thereof |
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