CN114395750B - SiO (silicon dioxide) 2 mullite-Al 2 O 3 Multicomponent gradient oxidation-resistant coating and preparation method thereof - Google Patents
SiO (silicon dioxide) 2 mullite-Al 2 O 3 Multicomponent gradient oxidation-resistant coating and preparation method thereof Download PDFInfo
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- CN114395750B CN114395750B CN202111249344.2A CN202111249344A CN114395750B CN 114395750 B CN114395750 B CN 114395750B CN 202111249344 A CN202111249344 A CN 202111249344A CN 114395750 B CN114395750 B CN 114395750B
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- 238000000576 coating method Methods 0.000 title claims abstract description 66
- 239000011248 coating agent Substances 0.000 title claims abstract description 61
- 229910018072 Al 2 O 3 Inorganic materials 0.000 title claims abstract description 56
- 230000003647 oxidation Effects 0.000 title claims abstract description 50
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 title claims description 6
- 239000000377 silicon dioxide Substances 0.000 title claims description 6
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 90
- 239000000758 substrate Substances 0.000 claims abstract description 80
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000003064 anti-oxidating effect Effects 0.000 claims abstract description 19
- 239000011888 foil Substances 0.000 claims abstract description 19
- 238000005498 polishing Methods 0.000 claims abstract description 19
- 230000001590 oxidative effect Effects 0.000 claims abstract description 18
- 239000011159 matrix material Substances 0.000 claims abstract description 16
- 238000004544 sputter deposition Methods 0.000 claims abstract description 16
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000007747 plating Methods 0.000 claims abstract description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 10
- 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
- 239000013077 target material Substances 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 abstract description 6
- 238000003892 spreading Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 22
- 238000000227 grinding Methods 0.000 description 5
- 230000004584 weight gain Effects 0.000 description 5
- 235000019786 weight gain Nutrition 0.000 description 5
- 244000137852 Petrea volubilis Species 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000007733 ion plating Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000007750 plasma spraying Methods 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
- 229910052710 silicon Inorganic materials 0.000 description 1
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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
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
- C04B35/185—Mullite 3Al2O3-2SiO2
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- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- 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
- C23C14/10—Glass or silica
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
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Abstract
The invention relates to SiO 2 mullite-Al 2 O 3 A multi-component gradient anti-oxidation coating and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, mechanically polishing a titanium alloy matrix, then polishing, and ultrasonically cleaning; drying the cleaned titanium alloy substrate in a blast drying oven; plating an Si simple substance layer on the surface of the titanium alloy by adopting a direct current sputtering mode on the dried matrix; oxidizing the Si-plated substrate at a high temperature; taking out the titanium alloy substrate, and uniformly spreading a layer of aluminum foil on the surface; placing the 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 SiO 2 And Al 2 O 3 And the mullite phase is generated by the reaction between the two to obtain SiO 2 mullite-Al 2 O 3 A multi-component gradient oxidation-resistant 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 SiO 2 Mullite (3 Al) 2 O 3 ·2SiO 2 )-Al 2 O 3 A multi-component gradient anti-oxidation coating and a preparation method thereof.
Background
Titanium alloys are important structural materials in the aerospace and industrial fields because of their low density, high specific strength and high specific modulus. However, the weak point of titanium alloy that has poor oxidation resistance at high temperature greatly limits its application at high temperature. The anti-oxidation coating is a common method for improving the service performance of high-temperature structural parts by plating an oxide coating (such as SiO) with good high-temperature stability on the surface of a workpiece 2 、Cr 2 O 3 、Al 2 O 3 Etc.) is an effective way to extend the life of the workpiece.
SiO 2 、Cr 2 O 3 、Al 2 O 3 The oxide coating has been widely used in the field of high temperature oxidation resistant coatings. However, the oxidation resistance of single component coatings is very limited, and the design of coatings has also evolved from simple single layer, single component to multi-component, multi-layer gradients in order to increase the high temperature oxidation resistance and service life of the coating. The dense oxidation protective film formed by the outer active substance (such as Al) at high temperature is used for preventing oxygen from diffusing, and the inner substance is combined with the diffused oxygen to further prevent the oxidation of the titanium alloy matrix, so that the service life of the workpiece is greatly prolonged.
Currently, the methods for preparing the antioxidation coating mainly comprise powder embedding, arc ion plating, ionic liquid plating, PVD (physical vapor deposition), chemical vapor deposition, plasma spraying and other processes. However, the coating prepared by the processes has the problems of non-uniform components and thickness, high cost, inapplicability to large or complex-shaped parts, poor coating binding force, easy peeling and the like.
Disclosure of Invention
The invention provides a SiO 2 mullite-Al 2 O 3 Multicomponent gradient oxidation-resistant coatingThe preparation method. The method uses titanium alloy as a substrate, si is used as a target, a layer of Si simple substance layer is firstly plated on the surface of the titanium alloy by sputtering through a magnetron sputtering method, and the Si simple substance layer is oxidized at high temperature to obtain SiO 2 An oxide layer; spreading a layer of aluminum foil on the surface of the aluminum foil, and uniformly coating the aluminum foil on the surface to form an Al layer after the aluminum foil is melted by vacuum heat treatment; finally oxidizing the mixture at high temperature to obtain SiO 2 And Al 2 O 3 And the mullite phase is generated by the reaction between the two to obtain SiO 2 mullite-Al 2 O 3 The oxidation resistance of the titanium alloy matrix is improved by the multi-component gradient oxidation-resistant coating.
The invention is realized by adopting the following technical scheme:
SiO (silicon dioxide) 2 mullite-Al 2 O 3 The preparation method of the multi-component gradient anti-oxidation coating comprises the following steps:
step 1, mechanically 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 Si target on a target base, and plating an Si simple substance layer on the surface of the titanium alloy by adopting a direct current sputtering mode;
step 5, oxidizing the Si-plated substrate obtained in the step 4 at a high temperature;
step 6, taking out the titanium alloy substrate prepared in the step 5, and uniformly paving a layer of aluminum foil on the surface;
step 7, placing the titanium alloy substrate prepared in the step 6 in 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 8, oxidizing the titanium alloy substrate obtained in the step 7 in air to obtain SiO 2 And Al 2 O 3 And by reaction between the twoForming mullite phase to obtain SiO 2 mullite-Al 2 O 3 A multi-component gradient oxidation-resistant 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 10-20 min.
In the step 3, the drying temperature of the titanium alloy substrate in the blast drying oven is 60-90 ℃ and the drying time is 60-80 min.
The invention is further improved in that in the step 4, the purity of the Si target material is 99.99 percent, and the background vacuum degree is 3 multiplied by 10 -4 Pa, deposition temperature of 300-500 deg.C, and cavity air pressure of 10 -3 ～10 -2 Pa, bias voltage of 200-300V, argon flow of 15-25 mL/min and continuous sputtering time of 60-120 min to obtain the Si simple substance layer.
The invention is further improved in that in the step 5, the oxidation treatment is carried out at a high temperature of 400-600 ℃ for 1-2 hours.
The invention is further improved in that in the step 6, the thickness of the paved aluminum foil is 50-100 mu m.
The invention is further improved in the step 7, the temperature of the high-temperature heat treatment is 750-850 ℃, and the heat preservation time is 1-2 h.
The invention is further improved in that in the step 8, the oxidation temperature in the air is 700-900 ℃ and the time is 2-4 hours, thus obtaining SiO 2 mullite-Al 2 O 3 A multi-component gradient oxidation-resistant coating.
SiO (silicon dioxide) 2 mullite-Al 2 O 3 The multi-component gradient anti-oxidation coating is prepared by adopting the preparation method.
The invention has at least the following beneficial technical effects:
1. the invention provides a SiO 2 mullite-Al 2 O 3 A multi-component gradient anti-oxidation coating and a preparation method thereof. Direct current magnetron sputtering technologyThe gradient anti-oxidation coating is prepared by combining the process with coating infiltration, so that a coating with a flat and compact surface can be obtained, and the problems of rough and uneven surface of a film prepared by multi-arc ion plating are solved; and the preparation process is simple, the cost is low, and the method is more beneficial to practical application and mass production.
2. The invention provides a SiO 2 mullite-Al 2 O 3 The multi-component gradient anti-oxidation coating is prepared by combining a magnetron sputtering process, coating infiltration and in-situ reaction, and the obtained coating is more compact, has strong binding force with a substrate and can effectively prolong the service life of the coating.
3. SiO prepared by the invention 2 mullite-Al 2 O 3 Multicomponent oxidation-resistant coating, simultaneously utilizing SiO generated after oxidation 2 And Al 2 O 3 And the oxidation resistance of the coating is improved by compacting the protective layer and the mullite phase generated by in-situ reaction. With a single layer of Al 2 O 3 Coating phase of SiO 2 mullite-Al 2 O 3 The oxidation weight gain of the coating at 900 ℃ is reduced by nearly 3 times, and the oxidation resistance is greatly improved.
Drawings
FIG. 1 is a SiO produced according to the present invention 2 mullite-Al 2 O 3 XRD pattern of the multicomponent oxidation resistant coating;
FIG. 2 is a SiO produced according to the present invention 2 mullite-Al 2 O 3 SEM image of the surface of the multicomponent antioxidant coating;
FIG. 3 is a SiO produced according to the present invention 2 mullite-Al 2 O 3 SEM images of cross-sections of the multicomponent antioxidant coating;
FIG. 4 is a SiO produced according to the present invention 2 mullite-Al 2 O 3 Oxidation weight gain plot of multi-component oxidation resistant coatings at 900 ℃.
Detailed Description
The invention will be described in detail with reference to specific embodiments,
the invention relates to a SiO 2 Mullite-Al 2 O 3 The preparation method of the multi-component gradient anti-oxidation coating comprises the following steps:
step 1, polishing a titanium alloy substrate 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 ultrasonically cleaning the titanium alloy matrix obtained in the step 1 by using absolute ethyl alcohol and deionized water for 10-20 min;
step 3, drying the titanium alloy substrate obtained in the step 2 in a blast drying oven at the drying temperature of 60-90 ℃ for 60-80 min;
step 4, placing the substrate obtained in the step 3 on a sample stage of a magnetron sputtering instrument, mounting a Si target on a target base, plating a Si simple substance layer on the surface of the titanium alloy by adopting a direct current sputtering mode, wherein the purity of the Si target is 99.99%, and the background vacuum degree is about 3 multiplied by 10 -4 Pa, deposition temperature of 300-500 deg.C, and cavity air pressure of 10 -3 ～10 -2 Pa, bias voltage of 200-300V, argon flow of 15-25 mL/min, and continuous sputtering time of 60-120 min;
step 5, oxidizing the Si-plated substrate obtained in the step 4 at a high temperature, wherein the oxidation temperature is 400-600 ℃ and the time is 1-2 h;
step 6, taking out the titanium alloy substrate prepared in the step 5, and uniformly spreading a layer of aluminum foil on the surface, wherein the thickness of the spread aluminum foil is 50-100 mu m;
step 7, placing the titanium alloy substrate prepared in the step 6 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 750-850 ℃ for 1-2 h;
step 8, oxidizing the titanium alloy substrate obtained in the step 7 in air to obtain SiO 2 And Al 2 O 3 And the mullite phase is generated by the reaction between the two to obtain SiO 2 mullite-Al 2 O 3 The temperature of oxidation is 700-900 ℃ and the time is 2-4 h.
Example 1
Step 1, polishing a titanium alloy substrate 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 ultrasonically cleaning the titanium alloy matrix obtained in the step 1 by using absolute ethyl alcohol and deionized water for 10min;
step 3, drying the titanium alloy substrate obtained in the step 2 in a blast drying oven at a drying temperature of 60 ℃ for 60min;
step 4, placing the substrate obtained in the step 3 on a sample stage of a magnetron sputtering instrument, mounting a Si target on a target base, plating a Si simple substance layer on the surface of the titanium alloy by adopting a direct current sputtering mode, wherein the purity of the Si target is 99.99%, 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 of 200V, argon flow of 15mL/min, and continuous sputtering time of 60min;
step 5, oxidizing the Si-plated substrate obtained in the step 4 at a high temperature, wherein the oxidation temperature is 400 ℃ and the time is 1h;
step 6, taking out the titanium alloy substrate prepared in the step 5, and uniformly paving a layer of aluminum foil on the surface, wherein the thickness of the paved aluminum foil is 50 mu m;
step 7, placing the titanium alloy substrate prepared in the step 6 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 750 ℃, and the heat preservation time is 1h;
step 8, oxidizing the titanium alloy substrate obtained in the step 7 in air to obtain SiO 2 And Al 2 O 3 And the mullite phase is generated by the reaction between the two to obtain SiO 2 mullite-Al 2 O 3 The temperature of oxidation of the multi-component gradient anti-oxidation coating is 700 ℃ and the time is 2h.
Example 2
Step 1, polishing a titanium alloy substrate 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 ultrasonically cleaning the titanium alloy matrix obtained in the step 1 by using absolute ethyl alcohol and deionized water for 20min;
step 3, drying the titanium alloy substrate obtained in the step 2 in a blast drying oven at 90 ℃ for 80min;
step 4, placing the substrate obtained in the step 3 on a sample stage of a magnetron sputtering instrument, mounting a Si target on a target base, plating a Si simple substance layer on the surface of the titanium alloy by adopting a direct current sputtering mode, wherein the purity of the Si target is 99.99%, and the background vacuum degree is about 3 multiplied by 10 -4 Pa, deposition temperature 500 deg.C, and chamber pressure 10 -2 Pa, bias voltage of 300V, argon flow of 25mL/min, and continuous sputtering time of 120min;
step 5, oxidizing the Si-plated substrate obtained in the step 4 at a high temperature, wherein the oxidation temperature is 600 ℃ and the time is 2 hours;
step 6, taking out the titanium alloy substrate prepared in the step 5, and uniformly paving a layer of aluminum foil on the surface, wherein the thickness of the paved aluminum foil is 100 mu m;
step 7, placing the titanium alloy substrate prepared in the step 6 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 850 ℃, and the heat preservation time is 2 hours;
step 8, oxidizing the titanium alloy substrate obtained in the step 7 in air to obtain SiO 2 And Al 2 O 3 And the mullite phase is generated by the reaction between the two to obtain SiO 2 mullite-Al 2 O 3 The temperature of oxidation of the multi-component gradient anti-oxidation coating is 900 ℃ and the time is 4 hours.
Example 3
Step 1, polishing a titanium alloy substrate 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 ultrasonically cleaning the titanium alloy matrix obtained in the step 1 by using absolute ethyl alcohol and deionized water for 15min;
step 3, drying the titanium alloy substrate obtained in the step 2 in a blast drying oven at 80 ℃ for 60min;
step 4, placing the substrate obtained in the step 3 on a sample stage of a magnetron sputtering instrument, mounting a Si target on a target base, plating a Si simple substance layer on the surface of the titanium alloy by adopting a direct current sputtering mode, wherein the purity of the Si target is 99.99%, and the background vacuum degree is about 3 multiplied by 10 -4 Pa, deposition temperature 400 deg.C, chamber pressure 5×10 -3 Pa, bias voltage of 250V, argon flow of 17.5mL/min, and duration of sputtering of 80min;
step 5, oxidizing the Si-plated substrate obtained in the step 4 at a high temperature, wherein the oxidation temperature is 500 ℃ and the time is 1.5h;
step 6, taking out the titanium alloy substrate prepared in the step 5, and uniformly paving a layer of aluminum foil on the surface, wherein the thickness of the paved aluminum foil is 80 mu m;
step 7, placing the titanium alloy substrate prepared in the step 6 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 1.5h;
step 8, oxidizing the titanium alloy substrate obtained in the step 7 in air to obtain SiO 2 And Al 2 O 3 And the mullite phase is generated by the reaction between the two to obtain SiO 2 mullite-Al 2 O 3 The temperature of oxidation of the multi-component gradient anti-oxidation coating is 800 ℃ and the time is 3h.
Example 4
Step 1, polishing a titanium alloy substrate 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 ultrasonically cleaning the titanium alloy matrix obtained in the step 1 by using absolute ethyl alcohol and deionized water for 18min;
step 3, drying the titanium alloy substrate obtained in the step 2 in a blast drying oven at a drying temperature of 75 ℃ for 70min;
step 4, passing throughPlacing the substrate obtained in the step 3 on a sample stage of a magnetron sputtering instrument, mounting a Si target on a target base, plating an Si simple substance layer on the surface of the titanium alloy by adopting a direct current sputtering mode, wherein the purity of the Si target is 99.99%, and the background vacuum degree is about 3 multiplied by 10 -4 Pa, deposition temperature of 350 ℃, and chamber air pressure of 8×10 -3 Pa, bias voltage of 280V, argon flow of 22mL/min, and continuous sputtering time of 100min;
step 5, oxidizing the Si-plated substrate obtained in the step 4 at a high temperature, wherein the oxidation temperature is 550 ℃ and the time is 1.5h;
step 6, taking out the titanium alloy substrate prepared in the step 5, and uniformly paving a layer of aluminum foil on the surface, wherein the thickness of the paved aluminum foil is 60 mu m;
step 7, placing the titanium alloy substrate prepared in the step 6 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 780 ℃, and the heat preservation time is 1.5h;
step 8, oxidizing the titanium alloy substrate obtained in the step 7 in air to obtain SiO 2 And Al 2 O 3 And the mullite phase is generated by the reaction between the two to obtain SiO 2 mullite-Al 2 O 3 The temperature of oxidation of the multi-component gradient anti-oxidation coating is 850 ℃ and the time is 3.5h.
SiO prepared by the method of the invention 2 mullite-Al 2 O 3 XRD patterns of multicomponent gradient oxidation resistant coatings, as shown in FIG. 1, except for SiO detected in the coating 2 、Al 2 O 3 In addition, 3Al was also detected 2 O 3 ·2SiO 2 Phase, indicating successful preparation of SiO 2 mullite-Al 2 O 3 A multi-component coating.
SiO prepared by the method of the invention 2 mullite-Al 2 O 3 As shown in an SEM image of the surface of the multi-component gradient anti-oxidation coating, as shown in fig. 2, the surface of the substrate is relatively flat and compact, and the problems of rough surface and uneven thickness of a film prepared by multi-arc ion plating are solved;
the method of the invention is used for preparingSiO of the preparation 2 mullite-Al 2 O 3 As shown in an SEM image of the cross section of the multi-component gradient oxidation-resistant coating, as shown in fig. 3, an obvious layered structure can be clearly observed, the layers are very tightly combined, and the multi-layer structure can effectively prevent oxygen from entering into the interior to contact with the titanium alloy substrate, so that the oxidation resistance and the service life of the component are greatly improved.
SiO prepared by the method 2 mullite-Al 2 O 3 The oxidation weight gain diagram of the multicomponent oxidation resistant coating at 900 ℃ is shown in fig. 4, and the oxidation weight gain gradually becomes gentle along with the extension of the oxidation time, and is similar to that of a single-layer Al 2 O 3 Coating phase of SiO 2 mullite-Al 2 O 3 The oxidation weight gain of the coating at 900 ℃ is reduced by about 3 times, which indicates that the SiO generated after oxidation is simultaneously utilized 2 And Al 2 O 3 The oxidation resistance of the coating is improved by the compact protective layer and the mullite phase generated by in-situ reaction.
SiO prepared by the invention 2 mullite-Al 2 O 3 The multicomponent antioxidation coating not only utilizes SiO generated after Si and Al are oxidized 2 And Al 2 O 3 The oxidation resistance of the titanium alloy is improved by the compact protective layer; 3Al generated by in-situ reaction 2 O 3 ·2SiO 2 The mullite phase has better high-temperature stability and high-temperature resistance, and can improve the long-time use performance of the alloy at high temperature.
Claims (5)
1. SiO (silicon dioxide) 2 mullite-Al 2 O 3 The preparation method of the multi-component gradient anti-oxidation coating is characterized by comprising the following steps of:
step 1, mechanically 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 (a)4, placing the substrate obtained in the step 3 on a sample stage of a magnetron sputtering instrument, mounting a Si target on a target base, and plating an Si simple substance layer on the surface of the titanium alloy by adopting a direct current sputtering mode; the purity of the Si target material is 99.99 percent, and the background vacuum degree is 3 multiplied by 10 - 4 Pa, deposition temperature of 300-500 deg.C, and cavity air pressure of 10 -3 ～10 -2 Pa, bias voltage of 200-300V, argon flow of 15-25 mL/min, and continuous sputtering time of 60-120 min to obtain an Si simple substance layer;
step 5, oxidizing the Si-plated substrate obtained in the step 4 at a high temperature; the temperature of the oxidation treatment is 400-600 ℃ and the time is 1-2 h;
step 6, taking out the titanium alloy substrate prepared in the step 5, and uniformly paving a layer of aluminum foil on the surface; the thickness of the spread aluminum foil is 50-100 mu m;
step 7, placing the titanium alloy substrate prepared in the step 6 in 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 750-850 ℃, and the heat preservation time is 1-2 h;
step 8, oxidizing the titanium alloy substrate obtained in the step 7 in air to obtain SiO 2 And Al 2 O 3 And the mullite phase is generated by the reaction between the two to obtain SiO 2 mullite-Al 2 O 3 A multi-component gradient oxidation-resistant coating; oxidizing in air at 700-900 deg.c for 2-4 hr to obtain SiO 2 mullite-Al 2 O 3 A multi-component gradient oxidation-resistant coating.
2. A SiO according to claim 1 2 mullite-Al 2 O 3 The preparation method of the multi-component gradient anti-oxidation 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. A SiO according to claim 1 2 mullite-Al 2 O 3 Preparation of multicomponent gradient oxidation-resistant coatingThe method is characterized in that in the step 2, the ultrasonic cleaning time is 10-20 min.
4. A SiO according to claim 1 2 mullite-Al 2 O 3 The preparation method of the multi-component gradient anti-oxidation coating is characterized in that in the step 3, the drying temperature of the titanium alloy substrate in a blast drying oven is 60-90 ℃ and the drying time is 60-80 min.
5. SiO (silicon dioxide) 2 mullite-Al 2 O 3 A multi-component gradient oxidation-preventing coating, characterized in that it is prepared by the preparation method according to any one of claims 1 to 4.
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|---|---|---|---|---|
| US3073770A (en) * | 1961-04-24 | 1963-01-15 | Bell Telephone Labor Inc | Mullite synthesis |
| CN1448534A (en) * | 2002-04-04 | 2003-10-15 | 西北工业大学 | Prep. of alumina---monox composite oxides film |
| CN1448535A (en) * | 2002-04-04 | 2003-10-15 | 西北工业大学 | Prep. of corundum---mullite multiple phase ceramic coating |
| CN101974734A (en) * | 2010-11-30 | 2011-02-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing substrate material with multilayer composite protective film |
| CN102002673A (en) * | 2010-09-17 | 2011-04-06 | 陕西师范大学 | Preparation method of nanocrystalline silicon-aluminum oxide/silicon oxide thermoelectric film material |
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| DE10219812A1 (en) * | 2002-05-02 | 2003-11-13 | Univ Dresden Tech | Components with crystalline coatings of the aluminum oxide / silicon oxide system and process for their production |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3073770A (en) * | 1961-04-24 | 1963-01-15 | Bell Telephone Labor Inc | Mullite synthesis |
| CN1448534A (en) * | 2002-04-04 | 2003-10-15 | 西北工业大学 | Prep. of alumina---monox composite oxides film |
| CN1448535A (en) * | 2002-04-04 | 2003-10-15 | 西北工业大学 | Prep. of corundum---mullite multiple phase ceramic coating |
| CN102002673A (en) * | 2010-09-17 | 2011-04-06 | 陕西师范大学 | Preparation method of nanocrystalline silicon-aluminum oxide/silicon oxide thermoelectric film material |
| CN101974734A (en) * | 2010-11-30 | 2011-02-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing substrate material with multilayer composite protective film |
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