CN113981397B - Cr for titanium alloy 2 O 3 /Al 2 O 3 Gradient antioxidation coating and preparation method thereof - Google Patents
Cr for titanium alloy 2 O 3 /Al 2 O 3 Gradient antioxidation coating and preparation method thereof Download PDFInfo
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 117
- 238000000576 coating method Methods 0.000 title claims abstract description 70
- 239000011248 coating agent Substances 0.000 title claims abstract description 67
- 229910018072 Al 2 O 3 Inorganic materials 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000003064 anti-oxidating effect Effects 0.000 title claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 73
- 238000001035 drying Methods 0.000 claims abstract description 37
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- 230000003647 oxidation Effects 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- 239000011888 foil Substances 0.000 claims abstract description 20
- 239000011159 matrix material Substances 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000005498 polishing Methods 0.000 claims abstract description 19
- 238000004544 sputter deposition Methods 0.000 claims abstract description 16
- 238000007747 plating Methods 0.000 claims abstract description 13
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 6
- 238000003892 spreading Methods 0.000 abstract description 2
- 230000007480 spreading Effects 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 10
- 238000000227 grinding Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 244000137852 Petrea volubilis Species 0.000 description 4
- 230000004584 weight gain Effects 0.000 description 4
- 235000019786 weight gain Nutrition 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000007733 ion plating Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical compound [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
Classifications
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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
-
- 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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
-
- 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
- C23C14/083—Oxides of refractory metals or yttrium
-
- 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
- C23C14/58—After-treatment
- C23C14/5846—Reactive treatment
- C23C14/5853—Oxidation
-
- 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
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
- C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate
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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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
- C23C8/12—Oxidising using elemental oxygen or ozone
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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 relates to Cr for titanium alloy 2 O 3 /Al 2 O 3 The preparation method of the gradient antioxidation coating comprises the following steps: polishing the titanium alloy matrix, polishing, and ultrasonically cleaning; drying the titanium alloy substrate subjected to ultrasonic cleaning in a blast drying oven; placing a matrix on a sample stage of a magnetron sputtering instrument, mounting a Cr target on a target base, and plating a Cr metal layer on the surface of the titanium alloy by adopting a direct current sputtering mode; taking out the titanium alloy substrate, and uniformly spreading a layer of aluminum foil on the surface; placing the prepared titanium alloy substrate in a vacuum furnace, preserving heat at high temperature to enable the titanium alloy substrate to be completely melted, and uniformly coating the titanium alloy substrate on the surface of the titanium alloy substrate; oxidizing the titanium alloy substrate in air to obtain compact Cr 2 O 3 /Al 2 O 3 And (3) coating. The invention can improve the oxidation resistance of the titanium alloy matrix.
Description
Technical Field
The invention belongs to the technical field of metal material surface modification, and in particular relates to Cr for titanium alloy 2 O 3 /Al 2 O 3 A gradient antioxidation coating and a preparation method thereof.
Background
The titanium alloy has high specific strength and small density, and is a novel high-temperature structural material in the fields of aerospace, automobiles and ships. However, titanium alloy has the defects of poor high-temperature oxidation resistance, sharp reduction of oxidation resistance at a high temperature exceeding 650 ℃, and the like, so that the application of the titanium alloy is limited, and the working requirements of hot-end components such as aeroengines, gas turbines and the like cannot be met.
The Al-Cr coating becomes a research hot spot due to the unique design of 'intelligent', and Al obtained after high-temperature oxidation of Al and Cr elements can be utilized 2 O 3 And Cr (V) 2 O 3 The dense protective film prevents further oxidation. At present, the preparation of the Al-Cr coating mainly comprises the processes of powder embedding, arc ion plating, ionic liquid plating, PVD (Physical Vapor Deposition ) and the like. However, the coatings prepared by these processes generally suffer from the problems of high cost, inapplicability to large or complex shaped parts, uneven coating, and peeling of the coating.
The gradient anti-oxidation coating is prepared by combining the magnetron sputtering process and the coating infiltration, and the Cr with smooth and compact surface can be obtained after oxidation 2 O 3 /Al 2 O 3 The film layer solves the problems of rough surface, uneven surface, thin thickness and the like of the film layer prepared by the process, has simple preparation process and low cost, and is more beneficial to practical application and mass production.
Disclosure of Invention
The invention provides Cr for titanium alloy 2 O 3 /Al 2 O 3 A gradient antioxidation coating and a preparation method thereof. The method comprises the steps of taking titanium alloy as a substrate, taking Cr as a target material, firstly sputtering and plating a Cr metal layer on the surface of the titanium alloy by a magnetron sputtering method, then paving a layer of aluminum foil on the surface of the titanium alloy, melting the aluminum foil by high-temperature heat treatment, uniformly coating the aluminum foil on the surface to form an Al layer, and finally oxidizing the aluminum foil at high temperature to obtain Cr 2 O 3 /Al 2 O 3 And the coating is used for improving the oxidation resistance of the titanium alloy matrix.
The invention is realized by adopting the following technical scheme:
cr for titanium alloy 2 O 3 /Al 2 O 3 The preparation method of the gradient antioxidation coating comprises the following steps:
step 1, polishing a titanium alloy matrix, and then polishing;
step 2, sequentially using absolute ethyl alcohol and deionized water to ultrasonically clean the titanium alloy matrix obtained in the step 1;
step 3, drying the titanium alloy matrix obtained in the step 2 in a blast drying oven;
step 4, placing the substrate obtained in the step 3 on a sample stage of a magnetron sputtering instrument, mounting a Cr target on a target base, and plating a Cr metal layer on the surface of the titanium alloy by adopting a direct current sputtering mode;
step 5, taking out the titanium alloy substrate prepared in the step 4, and uniformly paving a layer of aluminum foil on the surface;
step 6, placing the titanium alloy substrate prepared in the step 5 into a vacuum furnace, preserving heat at a high temperature to enable the titanium alloy substrate to be completely melted, and uniformly coating the titanium alloy substrate on the surface of the titanium alloy substrate;
step 7, oxidizing the titanium alloy substrate obtained in the step 6 in air to obtain compact Cr 2 O 3 /Al 2 O 3 And (3) coating.
The invention is further improved in that the 500# sand paper, the 1000# sand paper, the 1500# sand paper and the 2000# sand paper are sequentially polished in the step 1, and polishing treatment is carried out by using the polishing paste.
The invention is further improved in that in the step 2, the ultrasonic cleaning time is 10-30 min.
In the step 3, the drying temperature of the titanium alloy substrate in the blast drying oven is 60-80 ℃ and the drying time is 60-120 min.
A further improvement of the invention is that in step 4, the purity of the Cr target is 99.95 percent, and the background vacuum degree is about 3 multiplied by 10 -4 Pa, deposition temperature of 300-400 ℃, and cavity air pressure of 10 -3 ～10 -2 Pa, bias voltage of 100-300V, argon flow of 20-30 mL/min, and continuous sputtering time of 60-180 min to obtain the Cr plating layer.
The invention is further improved in that in the step 5, the thickness of the paved aluminum foil is 10-100 mu m.
The invention is further improved in the step 6, the temperature of the high-temperature heat treatment is 800-1000 ℃, and the heat preservation time is 2-4 h.
The invention is further improved in that in the step 7, the oxidation temperature in the air is 300-500 ℃ and the time is 1-2 h, thus obtaining compact Cr 2 O 3 /Al 2 O 3 And (3) coating.
Cr for titanium alloy 2 O 3 /Al 2 O 3 The gradient antioxidation coating is prepared by adopting the preparation method.
The invention has at least the following beneficial technical effects:
1. the invention provides Cr for titanium alloy 2 O 3 /Al 2 O 3 A gradient antioxidation coating and a preparation method thereof. The gradient coating is prepared by magnetron sputtering of a Cr layer and spreading of an Al foil, and the coating obtained after high-temperature melting and oxidation is more compact, has strong binding force with a substrate and has more obvious gradient characteristics.
2. The invention provides Cr for titanium alloy 2 O 3 /Al 2 O 3 The preparation method of the gradient antioxidation coating adopts a mode of combining a magnetron sputtering process and coating infiltration to prepare the gradient antioxidation coating, so that a film layer with a flat and compact surface can be obtained, and the problems of rough surface, non-uniformity and thin thickness of the film layer prepared by multi-arc ion plating are solved;
3. cr prepared by the invention 2 O 3 /Al 2 O 3 Gradient antioxidation coating, fully utilizing active chemical properties of Cr and Al and oxidation generated compact protective layer to improve antioxidation of titanium alloy, and single-layer Cr 2 O 3 Compared with coating, cr 2 O 3 /Al 2 O 3 The oxidation weight gain of the gradient coating is reduced by nearly 2 times, which indicates that the high-temperature oxidation resistance is greatly improved.
Drawings
FIG. 1 is a Cr produced by the present invention 2 O 3 /Al 2 O 3 XRD pattern of the gradient oxidation-resistant coating;
FIG. 2 is the presentCr prepared by the invention 2 O 3 /Al 2 O 3 SEM image of the gradient antioxidant coating surface;
FIG. 3 is a Cr produced by the present invention 2 O 3 /Al 2 O 3 SEM image of gradient antioxidant coating cross section
FIG. 4 is a Cr produced by the present invention 2 O 3 /Al 2 O 3 Oxidation weight gain plot of gradient oxidation resistant coating at 800 ℃.
Detailed Description
The invention will be described in detail with reference to specific embodiments,
the invention relates to Cr for titanium alloy 2 O 3 /Al 2 O 3 The preparation method of the gradient antioxidation coating comprises the following steps:
step 1, mechanically polishing a titanium alloy matrix by using 500# abrasive paper, 1000# abrasive paper, 1500# abrasive paper and 2000# abrasive paper in sequence, and polishing by using grinding paste;
step 2, sequentially using absolute ethyl alcohol and deionized water to ultrasonically clean the titanium alloy matrix obtained in the step 1, wherein the ultrasonic cleaning time is 10-30 min;
step 3, drying the titanium alloy substrate obtained in the step 2 in a blast drying oven, wherein the drying temperature of the titanium alloy substrate in the blast drying oven is 60-80 ℃ and the drying time is 60-120 min;
step 4, placing the substrate obtained in the step 3 on a sample stage of a magnetron sputtering instrument, mounting a Cr target on a target base, plating a Cr metal layer on the surface of the titanium alloy by adopting a direct current sputtering mode, wherein the purity of the Cr target is 99.95%, and the background vacuum degree is about 3 multiplied by 10 -4 Pa, deposition temperature of 300-400 ℃, and cavity air pressure of 10 -3 ～10 -2 Pa, bias voltage of 100-300V, argon flow of 20-30 mL/min, and continuous sputtering time of 60-180 min to obtain Cr plating;
step 5, taking out the titanium alloy substrate prepared in the step 4, and uniformly paving a layer of aluminum foil on the surface, wherein the thickness of the paved aluminum foil is 10-100 mu m;
step 6, placing the titanium alloy substrate prepared in the step 5 into a vacuum furnace, preserving heat at a high temperature to enable the titanium alloy substrate to be completely melted, uniformly coating the titanium alloy substrate on the surface of the titanium alloy substrate, and carrying out high-temperature heat treatment at 800-1000 ℃ for 2-4 hours;
step 7, oxidizing the titanium alloy substrate obtained in the step 6 in air to obtain compact Cr 2 O 3 /Al 2 O 3 The coating is oxidized in air at 300-500 ℃ for 1-2 h to obtain compact Cr 2 O 3 /Al 2 O 3 A coating;
example 1
Step 1, mechanically polishing a titanium alloy matrix by using 500# abrasive paper, 1000# abrasive paper, 1500# abrasive paper and 2000# abrasive paper in sequence, and polishing by using grinding paste;
step 2, sequentially using absolute ethyl alcohol and deionized water to ultrasonically clean the titanium alloy matrix obtained in the step 1, wherein the ultrasonic cleaning time is 10min;
step 3, drying the titanium alloy substrate obtained in the step 2 in a blast drying oven, wherein the drying temperature of the titanium alloy substrate in the blast drying oven is 60 ℃, and the drying time is 60min;
step 4, placing the substrate obtained in the step 3 on a sample stage of a magnetron sputtering instrument, mounting a Cr target on a target base, plating a Cr metal layer on the surface of the titanium alloy by adopting a direct current sputtering mode, wherein the purity of the Cr target is 99.95%, and the background vacuum degree is about 3 multiplied by 10 -4 Pa, deposition temperature 300 deg.C, and chamber pressure of 10 -3 Pa, bias voltage 100V, argon flow 20mL/min, and continuous sputtering time 60min to obtain Cr coating;
step 5, taking out the titanium alloy substrate prepared in the step 4, and uniformly paving a layer of aluminum foil on the surface, wherein the thickness of the paved aluminum foil is 10 mu m;
step 6, placing the titanium alloy substrate prepared in the step 5 into a vacuum furnace, preserving heat at a high temperature to enable the titanium alloy substrate to be completely melted, uniformly coating the titanium alloy substrate on the surface of the titanium alloy substrate, wherein the temperature of high-temperature heat treatment is 800 ℃, and the heat preservation time is 2 hours;
step 7, oxidizing the titanium alloy substrate obtained in the step 6 in airTreating to obtain dense Cr 2 O 3 /Al 2 O 3 Coating, oxidizing in air at 300 deg.c for 1 hr to obtain compact Cr 2 O 3 /Al 2 O 3 A coating;
example 2
Step 1, mechanically polishing a titanium alloy matrix by using 500# abrasive paper, 1000# abrasive paper, 1500# abrasive paper and 2000# abrasive paper in sequence, and polishing by using grinding paste;
step 2, sequentially using absolute ethyl alcohol and deionized water to ultrasonically clean the titanium alloy matrix obtained in the step 1, wherein the ultrasonic cleaning time is 30min;
step 3, drying the titanium alloy substrate obtained in the step 2 in a blast drying oven, wherein the drying temperature of the titanium alloy substrate in the blast drying oven is 80 ℃, and the drying time is 120min;
step 4, placing the substrate obtained in the step 3 on a sample stage of a magnetron sputtering instrument, mounting a Cr target on a target base, plating a Cr metal layer on the surface of the titanium alloy by adopting a direct current sputtering mode, wherein the purity of the Cr target is 99.95%, and the background vacuum degree is about 3 multiplied by 10 -4 Pa, deposition temperature 400 ℃, and chamber pressure 10 -2 Pa, bias voltage 300V, argon flow 30mL/min, and sputtering duration 180min to obtain Cr coating;
step 5, taking out the titanium alloy substrate prepared in the step 4, and uniformly paving a layer of aluminum foil on the surface, wherein the thickness of the paved aluminum foil is 100 mu m;
step 6, placing the titanium alloy substrate prepared in the step 5 into a vacuum furnace, preserving heat at a high temperature to enable the titanium alloy substrate to be completely melted, uniformly coating the titanium alloy substrate on the surface of the titanium alloy substrate, wherein the temperature of high-temperature heat treatment is 1000 ℃, and the heat preservation time is 4 hours;
step 7, oxidizing the titanium alloy substrate obtained in the step 6 in air to obtain compact Cr 2 O 3 /Al 2 O 3 Coating, oxidizing in air at 500 deg.c for 2 hr to obtain compact Cr 2 O 3 /Al 2 O 3 A coating;
example 3
Step 1, mechanically polishing a titanium alloy matrix by using 500# abrasive paper, 1000# abrasive paper, 1500# abrasive paper and 2000# abrasive paper in sequence, and polishing by using grinding paste;
step 2, sequentially using absolute ethyl alcohol and deionized water to ultrasonically clean the titanium alloy matrix obtained in the step 1, wherein the ultrasonic cleaning time is 17min;
step 3, drying the titanium alloy substrate obtained in the step 2 in a blast drying oven, wherein the drying temperature of the titanium alloy substrate in the blast drying oven is 66 ℃, and the drying time is 80min;
step 4, placing the substrate obtained in the step 3 on a sample stage of a magnetron sputtering instrument, mounting a Cr target on a target base, plating a Cr metal layer on the surface of the titanium alloy by adopting a direct current sputtering mode, wherein the purity of the Cr target is 99.95%, and the background vacuum degree is about 3 multiplied by 10 -4 Pa, deposition temperature of 330 ℃, and chamber air pressure of 3×10 -3 Pa, bias voltage 160V, argon flow 24mL/min, and sputtering duration 100min to obtain Cr coating;
step 5, taking out the titanium alloy substrate prepared in the step 4, and uniformly paving a layer of aluminum foil on the surface, wherein the thickness of the paved aluminum foil is 40 mu m;
step 6, placing the titanium alloy substrate prepared in the step 5 into a vacuum furnace, preserving heat at a high temperature to enable the titanium alloy substrate to be completely melted, uniformly coating the titanium alloy substrate on the surface of the titanium alloy substrate, wherein the temperature of high-temperature heat treatment is 860 ℃, and the heat preservation time is 2.6h;
step 7, oxidizing the titanium alloy substrate obtained in the step 6 in air to obtain compact Cr 2 O 3 /Al 2 O 3 The coating is oxidized in air at 360 ℃ for 1.3 hours to obtain compact Cr 2 O 3 /Al 2 O 3 A coating;
example 4
Step 1, mechanically polishing a titanium alloy matrix by using 500# abrasive paper, 1000# abrasive paper, 1500# abrasive paper and 2000# abrasive paper in sequence, and polishing by using grinding paste;
step 2, sequentially using absolute ethyl alcohol and deionized water to ultrasonically clean the titanium alloy matrix obtained in the step 1, wherein the ultrasonic cleaning time is 24 minutes;
step 3, drying the titanium alloy substrate obtained in the step 2 in a blast drying oven, wherein the drying temperature of the titanium alloy substrate in the blast drying oven is 72 ℃, and the drying time is 100min;
step 4, placing the substrate obtained in the step 3 on a sample stage of a magnetron sputtering instrument, mounting a Cr target on a target base, plating a Cr metal layer on the surface of the titanium alloy by adopting a direct current sputtering mode, wherein the purity of the Cr target is 99.95%, and the background vacuum degree is about 3 multiplied by 10 -4 Pa, deposition temperature of 360 deg.C, and chamber pressure of 6×10 -3 Pa, bias voltage 220V, argon flow 27mL/min, and continuous sputtering time 140min to obtain Cr coating;
step 5, taking out the titanium alloy substrate prepared in the step 4, and uniformly paving a layer of aluminum foil on the surface, wherein the thickness of the paved aluminum foil is 70 mu m;
step 6, placing the titanium alloy substrate prepared in the step 5 into a vacuum furnace, preserving heat at a high temperature to enable the titanium alloy substrate to be completely melted, uniformly coating the titanium alloy substrate on the surface of the titanium alloy substrate, wherein the temperature of high-temperature heat treatment is 920 ℃, and the heat preservation time is 3.2h;
step 7, oxidizing the titanium alloy substrate obtained in the step 6 in air to obtain compact Cr 2 O 3 /Al 2 O 3 The coating is oxidized in the air at 420 ℃ for 1.6 hours to obtain compact Cr 2 O 3 /Al 2 O 3 A coating;
the titanium alloy Cr prepared by the method of the invention 2 O 3 /Al 2 O 3 XRD patterns of gradient antioxidant coatings, as shown in FIG. 1, cr was detected in the prepared coatings 2 O 3 And Al 2 O 3 Two phases, indicating successful Cr production 2 O 3 /Al 2 O 3 And (3) coating.
The titanium alloy Cr prepared by the method of the invention 2 O 3 /Al 2 O 3 As shown in fig. 2, the SEM image of the gradient oxidation resistant coating surface forms a plurality of oxide particles, but is generally flatter, denser, more uniform,the problem of uneven film layer and thin thickness of the multi-arc ion plating preparation is solved;
the titanium alloy Cr prepared by the method of the invention 2 O 3 /Al 2 O 3 SEM of the cross section of the gradient oxidation-resistant coating, as shown in FIG. 3, can clearly see Cr 2 O 3 、Al 2 O 3 The boundary between the titanium alloy substrate and the substrate is uniform in thickness, and the layers are tightly combined, so that oxygen can be effectively organized to enter the titanium alloy substrate as a protective layer, and the service life of the titanium alloy structural member is greatly prolonged.
Cr prepared by the invention 2 O 3 /Al 2 O 3 As shown in FIG. 4, it can be seen that the weight gain of the coating gradually becomes gentle with the time, as compared with the single-layer Cr 2 O 3 Compared with coating, cr 2 O 3 /Al 2 O 3 The oxidation weight gain of the gradient coating is reduced by nearly 2 times, which indicates that the high-temperature oxidation resistance is greatly improved.
The invention fully utilizes the active chemical properties of Cr and Al and the compact protective layer generated by oxidation to improve the oxidation resistance of the titanium alloy, has simple preparation process and low cost, and is more beneficial to practical application and mass production.
Claims (5)
1. Cr for titanium alloy 2 O 3 /Al 2 O 3 The preparation method of the gradient antioxidation coating is characterized by comprising the following steps:
step 1, polishing a titanium alloy matrix, and then polishing;
step 2, sequentially using absolute ethyl alcohol and deionized water to ultrasonically clean the titanium alloy matrix obtained in the step 1;
step 3, drying the titanium alloy matrix obtained in the step 2 in a blast drying oven;
step 4, placing the substrate obtained in the step 3 on a sample stage of a magnetron sputtering instrument, mounting a Cr target on a target base, and plating a Cr metal layer on the surface of the titanium alloy by adopting a direct current sputtering mode; purity of Cr target material99.95% background vacuum of 3X 10 - 4 Pa, deposition temperature of 300-400 ℃, and cavity air pressure of 10 -3 ～10 -2 Pa, bias voltage of 100-300V, argon flow of 20-30 mL/min, and continuous sputtering time of 60-180 min to obtain Cr plating;
step 5, taking out the titanium alloy substrate prepared in the step 4, and uniformly paving a layer of aluminum foil on the surface; the thickness of the spread aluminum foil is 10-100 mu m;
step 6, placing the titanium alloy substrate prepared in the step 5 into a vacuum furnace, preserving heat at a high temperature to enable the titanium alloy substrate to be completely melted, and uniformly coating the titanium alloy substrate on the surface of the titanium alloy substrate; the temperature of the high-temperature heat treatment is 800-1000 ℃ and the heat preservation time is 2-4 h;
step 7, oxidizing the titanium alloy substrate obtained in the step 6 in air to obtain compact Cr 2 O 3 /Al 2 O 3 The coating is oxidized in air at 300-500 ℃ for 1-2 h to obtain compact Cr 2 O 3 /Al 2 O 3 And (3) coating.
2. Cr for titanium alloy according to claim 1 2 O 3 /Al 2 O 3 The preparation method of the gradient antioxidation coating is characterized in that in the step 1, 500# abrasive paper, 1000# abrasive paper, 1500# abrasive paper and 2000# abrasive paper are sequentially polished, and polishing treatment is carried out by using abrasive paste.
3. Cr for titanium alloy according to claim 1 2 O 3 /Al 2 O 3 The preparation method of the gradient antioxidation coating is characterized in that in the step 2, the ultrasonic cleaning time is 10-30 min.
4. Cr for titanium alloy according to claim 1 2 O 3 /Al 2 O 3 The preparation method of the gradient antioxidation coating is characterized in that in the step 3, the drying temperature of the titanium alloy substrate in a blast drying oven is 60-80 ℃ and the drying time is 60-120 min.
5. Cr for titanium alloy 2 O 3 /Al 2 O 3 A gradient oxidation-resistant coating, characterized in that it is prepared by the preparation method according to any one of claims 1 to 4.
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| CN102732832A (en) * | 2012-06-28 | 2012-10-17 | 南京航空航天大学 | Titanium alloy surface high temperature oxidation resistance and wear resistance oxide gradient coat, and preparation method thereof |
| CN103895282A (en) * | 2012-12-26 | 2014-07-02 | 北京有色金属研究总院 | Composite gradient hydrogen-resistant coating for high-temperature evacuated collector tube and preparation method thereof |
| CN104561891A (en) * | 2015-01-30 | 2015-04-29 | 四川大学 | Double-component gradient hydrogen permeation barrier coating and preparation method thereof |
| CN106939404A (en) * | 2017-02-24 | 2017-07-11 | 华南理工大学 | A kind of nanometer alpha-aluminium oxide/chromium oxide composite coating and preparation method thereof |
| CN107201538A (en) * | 2017-05-22 | 2017-09-26 | 北京科技大学 | A kind of inner wall of metal tube chromium oxide alumina composite coating production |
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| CN102732832A (en) * | 2012-06-28 | 2012-10-17 | 南京航空航天大学 | Titanium alloy surface high temperature oxidation resistance and wear resistance oxide gradient coat, and preparation method thereof |
| CN103895282A (en) * | 2012-12-26 | 2014-07-02 | 北京有色金属研究总院 | Composite gradient hydrogen-resistant coating for high-temperature evacuated collector tube and preparation method thereof |
| CN104561891A (en) * | 2015-01-30 | 2015-04-29 | 四川大学 | Double-component gradient hydrogen permeation barrier coating and preparation method thereof |
| CN106939404A (en) * | 2017-02-24 | 2017-07-11 | 华南理工大学 | A kind of nanometer alpha-aluminium oxide/chromium oxide composite coating and preparation method thereof |
| CN107201538A (en) * | 2017-05-22 | 2017-09-26 | 北京科技大学 | A kind of inner wall of metal tube chromium oxide alumina composite coating production |
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