CN105385987A - High-temperature anti-oxidation layer on metal tungsten surface and manufacturing method of high-temperature anti-oxidation layer - Google Patents
High-temperature anti-oxidation layer on metal tungsten surface and manufacturing method of high-temperature anti-oxidation layer Download PDFInfo
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- CN105385987A CN105385987A CN201510664159.8A CN201510664159A CN105385987A CN 105385987 A CN105385987 A CN 105385987A CN 201510664159 A CN201510664159 A CN 201510664159A CN 105385987 A CN105385987 A CN 105385987A
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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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/34—Embedding in a powder mixture, i.e. pack cementation
- C23C10/36—Embedding in a powder mixture, i.e. pack cementation only one element being diffused
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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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/34—Embedding in a powder mixture, i.e. pack cementation
- C23C10/36—Embedding in a powder mixture, i.e. pack cementation only one element being diffused
- C23C10/44—Siliconising
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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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/60—After-treatment
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Abstract
The invention discloses a manufacturing method of a high-temperature anti-oxidation layer on the metal tungsten surface. The manufacturing method includes the steps that a metal tungsten base material is polished till the surface is smooth and level, and deoiling and degreasing treatment is conducted on the polished surface; the treated metal tungsten base material is soaked into a molybdenum seeping agent and then subjected to heat treatment in the inertia atmosphere, impurities are removed after cooling, and a semi-finished product with a tungsten and molybdenum solid solution layer on the metal tungsten surface is obtained; the semi-finished product is placed in the nitrogen atmosphere to be subjected to heat treatment, impurities are removed after cooling, and a prefabricated body with a molybdenum nitride and tungsten nitride coating on the metal tungsten surface is obtained; the prefabricated body is soaked into a silicification seeping agent to be subjected to heat treatment in the inertia atmosphere, impurities are removed after cooling, and a finished product with W-Mo-N-Si high-temperature anti-oxidation layer on the metal tungsten base material surface is obtained. The invention further relates to the high-temperature anti-oxidation layer obtained through the method and used on the metal tungsten surface.
Description
Technical field
The present invention relates to a kind of tungsten surface high-temp anti oxidation layer and preparation method thereof.
Background technology
High density tungsten sill is widely used in
national defence troopsthe fields such as work, mechano-electronic, space flight and aviation, metallurgical mine, oil coal, clock and watch ornaments.The tungsten material of non-coating exist not wear-resisting, oxidation-resistance is poor, the corrosion of easy sweat stain, and the defect such as color is dim.
CN101195285 discloses a kind of coating tungsten product, comprise tungsten base material, described tungsten base material is coated with TiN or Cu (surplus)-(15-45) %Zn-(0.1-1.5) %Ni-(0.5-1) %Al that thickness is 3-30 μm
2o
3alloy-coated layer.Described coating tungsten product, can ensure under the relative density condition that tungsten sill is high, effectively improve the comprehensive use properties such as the oxidation-resistance on tungsten sill surface, wear resistance, perspiration resistance corrodibility and property bright in luster.But, described coating tungsten product obtains for using CVD or PVD method, preparation technology is all comparatively complicated, production cost is higher, and poor, between coating and matrix the thermal matching of the compactness that there is coating poor, be difficult to control the problems such as the structure of coating and phase, thus directly affect the high temperature usage life-span of tungsten.Du Zhi adopts by force electroplating technology to obtain coating at tungsten base powder metallurgy material, its technique is electrolytic degreasing-cyanide electroplating-plating bright copper-bright nickel plating, but the bonding force of part and coating is still not high, find that part edge has corrosion phenomenon simultaneously, thickness of coating is uneven, and solidity to corrosion does not reach use standard yet.
Summary of the invention
The invention provides a kind of tungsten surface high-temp anti oxidation layer and preparation method thereof, can effectively solve the problem.
The invention provides a kind of preparation method of tungsten surface high-temp anti oxidation layer, wherein, comprise the following steps:
Tungsten base material is polished to smooth surface smooth, and glazed surface is deoiled skimming treatment;
Tungsten base material after process is imbedded molybdenum penetration enhancer, and then thermal treatment in inert atmosphere, removes impurity after cooling, obtains the work in-process that tungsten surface has tungsten solid solution layer;
Described work in-process are placed in nitrogen atmosphere heat-treat, after cooling, remove impurity, obtain the precast body that tungsten surface is molybdenum nitride and Tungsten nitride coatings; And
Imbedded by precast body in silication penetration enhancer, then thermal treatment in inert atmosphere, removes impurity after cooling, obtains the finished product that tungsten substrate surface is W-Mo-N-Si system high-temperature oxidation resistant layer.
Further, the preparation method of described molybdenum penetration enhancer comprises:
Take the molybdenum powder that mass fraction is 10 ~ 40 parts, mass fraction is the NH of 1 ~ 20 part
4cl, mass fraction is the Al of 40 ~ 89 parts
2o
3, ball milling 1 ~ 10 hour after mixing; And
Under vacuum conditions, temperature 100 ~ 150 DEG C of dryings 10 ~ 30 minutes.
Further, the diameter of described molybdenum powder is that 500 nanometers are to 10 microns.
Further, tungsten base material being imbedded molybdenum penetration enhancer and carries out heat treated temperature is 850 ~ 1100 DEG C, and soaking time is 1 ~ 24 hour.
Further, tungsten base material being imbedded molybdenum penetration enhancer and carries out heat treated temperature is 900 ~ 1000 DEG C, and soaking time is 4 ~ 10 hours.
Further, the described temperature 1000 ~ 1500 DEG C work in-process being placed in nitrogen atmosphere and heat-treating, nitridation time is 1 ~ 24 hour, and the flow velocity of nitrogen is 50 ~ 500mL/min.
Further, the preparation method of described silication penetration enhancer comprises:
Be the silica flour of 10 ~ 50 parts by mass fraction, mass fraction to be the NaF of 1 ~ 10 part and mass fraction the be Al of 40 ~ 89 parts
2o
3, ball milling 1 ~ 10 hour after mixing; And
Under vacuum conditions, temperature 80 ~ 100 DEG C of dryings 10 ~ 60 minutes.
Further, precast body being imbedded heat treated temperature in silication penetration enhancer is 800 ~ 1400 DEG C, and soaking time is 1 ~ 24 hour.
Further, precast body being imbedded heat treated temperature in silication penetration enhancer is 900 ~ 1000 DEG C, and soaking time is 5 ~ 10 hours.
The present invention also provides a kind of tungsten surface high-temp anti oxidation layer, is coated on a tungsten substrate surface, and wherein, described high-temperature oxidation resistant layer is W-Mo-N-Si system protective layer.
Tungsten surface high-temp anti oxidation layer provided by the invention and preparation method thereof, has following beneficial effect:
(1) the present invention adopts the in-situ reaction of molybdenum+nitrogenize+silication.Compared with prior art, its advantage is not need expensive device, and preparation technology is simple, and cost is low, complex-shaped tungsten product can be processed and protective layer structure and phase controlled.
(2) the present invention is formed with (W on tungsten surface by in-situ reaction
xmo
1-x) Si
2solid solution phase is a small amount of Si that advocates peace
3n
4the composite bed of phase.The introducing of Mo element is effectively reduced in Si in high-temperature oxidation process and, to the rate of diffusion of intrinsic silicon, obviously slows down " degeneration " of silicide coating.Compared with prior art, the high-temperature oxidation resistance of coating tungsten product material of the present invention is more excellent, and coat inside defect is less.
(3) antioxidant property of the tungsten surface high-temp anti oxidation layer obtained can reach complete grade of oxidation resistance, thus can solve that tungsten sill oxidation-resistance is poor, easily sweat stain corrosion, and the defect such as color is dim.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.Be understandable that, specific embodiment described herein is only for explaining the present invention, but not limitation of the invention.
The invention provides a kind of preparation method of tungsten surface high-temp anti oxidation layer, comprise the following steps:
S1, is polished to smooth surface by tungsten base material smooth, and to deoil skimming treatment to glazed surface;
S2, the tungsten base material after process is imbedded molybdenum penetration enhancer, and then thermal treatment in inert atmosphere, removes impurity after cooling, obtains the work in-process that tungsten surface has tungsten solid solution layer;
Described work in-process are placed in nitrogen atmosphere and heat-treat, remove impurity after cooling by S3, obtain the precast body that tungsten surface is molybdenum nitride and Tungsten nitride coatings; And
S4, imbedded by precast body in silication penetration enhancer, then thermal treatment in inert atmosphere, removes impurity after cooling, obtains the finished product that tungsten substrate surface is W-Mo-N-Si system high-temperature oxidation resistant layer.
In step sl, described the deoil step of skimming treatment of glazed surface to be comprised:
S11, immerses the tungsten base material after described polishing in a volatile organic solvent and cleans; And
S12, takes out the tungsten base material after cleaning and dries up.
Described volatile organic solvent, for dissolving the grease on substrate surface, can be selected from methyl alcohol, ethanol, propyl alcohol, acetone, ether and composition thereof.
In step s 2, described molybdenum penetration enhancer can be obtained by following steps:
S21, takes the molybdenum powder that mass fraction is 10 ~ 40 parts, and mass fraction is the NH of 1 ~ 20 part
4cl, mass fraction is the Al of 40 ~ 89 parts
2o
3, ball milling 1 ~ 10 hour after mixing, preferably, take the molybdenum powder that mass fraction is 20 ~ 30 parts, mass fraction is the NH of 10 ~ 15 parts
4cl, mass fraction is the Al of 60 ~ 80 parts
2o
3, preferred, take the molybdenum powder that mass fraction is 25 ~ 30 parts, mass fraction is the NH of 12 ~ 15 parts
4cl, mass fraction is the Al of 60 ~ 70 parts
2o
3; And
S22, under vacuum conditions, temperature 100 ~ 150 DEG C of dryings 10 ~ 30 minutes.
In the step s 21, the diameter of described molybdenum powder is preferably 500 nanometers to 10 microns; Preferred, the diameter of described molybdenum powder is preferably 1 micron to 5 microns.Experiment proves, when the diameter of molybdenum powder is excessive, cannot infiltrate tungsten metallic substrate surface, diameter is too small, comparatively easily produces reunion, is also unfavorable for infiltrating tungsten metallic substrate surface.
Described tungsten base material is imbedded molybdenum penetration enhancer and carries out heat treated temperature can be 850 ~ 1100 DEG C, and soaking time is 1 ~ 24 hour, and temperature rise rate is 5 ~ 15 DEG C/min.Preferably, tungsten base material being imbedded molybdenum penetration enhancer and carries out heat treated temperature is 900 ~ 1000 DEG C, and soaking time is 4 ~ 10 hours.Experiment finds, can realize molybdenum and infiltrate fast in 900 ~ 1000 DEG C of temperature ranges.
In step s3, the described temperature 1000 ~ 1500 DEG C work in-process being placed in nitrogen atmosphere and heat-treating, nitridation time is 1 ~ 24 hour, and the flow velocity of nitrogen is 50 ~ 500mL/min, and temperature rise rate is 5 ~ 15 DEG C/min.
In step s 4 which, the preparation method of described silication penetration enhancer comprises:
Mass fraction is the silica flour of 10 ~ 50 parts by S41, mass fraction is the NaF of 1 ~ 10 part and mass fraction is the Al of 40 ~ 89 parts
2o
3, ball milling 1 ~ 10 hour after mixing, is preferably, and mass fraction to be silica flour, the mass fraction of 20 ~ 30 parts the be NaF of 1 ~ 5 part and mass fraction are the Al of 70 ~ 80 parts
2o
3, be more preferably, mass fraction to be silica flour, the mass fraction of 25 ~ 30 parts the be NaF of 2 ~ 4 parts and mass fraction are the Al of 75 ~ 80 parts
2o
3; And
S42, under vacuum conditions, temperature 80 ~ 100 DEG C of dryings 10 ~ 60 minutes.
The diameter of described silica flour is preferably 500 nanometers to 10 microns; Preferred, the diameter of described silica flour is preferably 1 micron to 5 microns.Experiment proves, when the diameter of silica flour is excessive, cannot infiltrate tungsten metallic substrate surface, diameter is too small, comparatively easily produces reunion, is also unfavorable for infiltrating tungsten metallic substrate surface.
Further, precast body being imbedded heat treated temperature in silication penetration enhancer is 800 ~ 1400 DEG C, and soaking time is 1 ~ 24 hour.Preferably, precast body being imbedded heat treated temperature in silication penetration enhancer is 900 ~ 1000 DEG C, and soaking time is 5 ~ 10 hours.
The embodiment of the present invention also provides a kind of and obtains tungsten surface high-temp anti oxidation layer by aforesaid method, be coated on a tungsten substrate surface, and described high-temperature oxidation resistant layer is W-Mo-N-Si system protective layer.Described W-Mo-N-Si system protective layer comprises Mo, N and Si from inside to outside successively.The thickness of described W-Mo-N-Si system protective layer is 500 nanometer ~ 10 micron, and preferably, the thickness of described W-Mo-N-Si system protective layer is 1 micron ~ 5 microns, preferred, and the thickness of described W-Mo-N-Si system protective layer is 2 microns ~ 3 microns.
Embodiment 1:
Tungsten base material sand paper is polished to smooth surface smooth, and puts into dehydrated alcohol and carry out deoiling after skimming treatment, dry up; Pretreated tungsten base material is placed in the alumina crucible filling molybdenum penetration enhancer, molybdenum powder, NH in this molybdenum penetration enhancer
4cl and Al
2o
3mass ratio be 30: 10: 60, alumina crucible is put into process furnace heat, and pass into nitrogen protection, rise to 950 DEG C with the heat-up rate of 10 DEG C/min and be incubated 5 hours, cool to room temperature with the furnace after insulation terminates, take out subsequently and be placed in distilled water and boil 10min, with deionized water rinsing, dehydrated alcohol wiping dries up, and obtains the work in-process that tungsten surface is tungsten solid solution layer; Work in-process are placed in atmosphere furnace, pass into 99.99% nitrogen that flow is 300mL/min, rise to 1000 DEG C of insulations with the heat-up rate of 5 DEG C/min and cool to room temperature with the furnace after 20 hours, take out sample subsequently, use ultrasonic cleaning 10min, dehydrated alcohol wiping dries up, and obtains the precast body that tungsten surface is molybdenum nitride and tungsten nitride layer; Precast body is placed in the alumina crucible filling silication penetration enhancer, silica flour, NaF and Al in this silication penetration enhancer
2o
3mass ratio be 20:5: 75; alumina crucible is put into process furnace heat; and pass into nitrogen protection; rise to 1000 DEG C with the heat-up rate of 15 DEG C/min and be incubated 15 hours; cool to room temperature with the furnace after insulation terminates, take out subsequently and be placed in distilled water and boil 10min, with deionized water rinsing; dehydrated alcohol wiping dries up, and obtains the finished product that tungsten basal body surface is W-Mo-N-Si system protective layer.
Embodiment 2:
Tungsten base material sand paper is polished to smooth surface smooth, and puts into dehydrated alcohol and carry out deoiling after skimming treatment, dry up; Pretreated tungsten base material is placed in the alumina crucible filling molybdenum penetration enhancer, molybdenum powder, NH in this molybdenum penetration enhancer
4cl and Al
2o
3mass ratio be 20:15: 65, alumina crucible is put into process furnace heat, and pass into nitrogen protection, rise to 1000 DEG C with the heat-up rate of 10 DEG C/min and be incubated 5 hours, cool to room temperature with the furnace after insulation terminates, take out subsequently and be placed in distilled water and boil 10min, with deionized water rinsing, dehydrated alcohol wiping dries up, and obtains the work in-process that tungsten surface is tungsten solid solution layer; Work in-process are placed in atmosphere furnace, pass into 99.99% nitrogen that flow is 300mL/min, rise to 1000 DEG C of insulations with the heat-up rate of 5 DEG C/min and cool to room temperature with the furnace after 20 hours, take out sample subsequently, use ultrasonic cleaning 10min, dehydrated alcohol wiping dries up, and obtains the precast body that tungsten surface is molybdenum nitride and tungsten nitride layer; Precast body is placed in the alumina crucible filling silication penetration enhancer, silica flour, NaF and Al in this silication penetration enhancer
2o
3mass ratio be 30:10: 60; alumina crucible is put into process furnace heat; and pass into nitrogen protection; rise to 1400 DEG C with the heat-up rate of 15 DEG C/min and be incubated 15 hours; cool to room temperature with the furnace after insulation terminates, take out subsequently and be placed in distilled water and boil 10min, with deionized water rinsing; dehydrated alcohol wiping dries up, and obtains the finished product that tungsten basal body surface is W-Mo-N-Si system protective layer.
Embodiment 3:
Tungsten base material sand paper is polished to smooth surface smooth, and puts into dehydrated alcohol and carry out deoiling after skimming treatment, dry up; Pretreated tungsten base material is placed in the alumina crucible filling molybdenum penetration enhancer, molybdenum powder, NH in this molybdenum penetration enhancer
4cl and Al
2o
3mass ratio be 40:5: 55, alumina crucible is put into process furnace heat, and pass into nitrogen protection, rise to 1100 DEG C with the heat-up rate of 10 DEG C/min and be incubated 5 hours, cool to room temperature with the furnace after insulation terminates, take out subsequently and be placed in distilled water and boil 10min, with deionized water rinsing, dehydrated alcohol wiping dries up, and obtains the work in-process that tungsten surface is tungsten solid solution layer; Work in-process are placed in atmosphere furnace, pass into 99.99% nitrogen that flow is 300mL/min, rise to 1300 DEG C of insulations with the heat-up rate of 5 DEG C/min and cool to room temperature with the furnace after 20 hours, take out sample subsequently, use ultrasonic cleaning 10min, dehydrated alcohol wiping dries up, and obtains the precast body that tungsten surface is molybdenum nitride and tungsten nitride layer; Precast body is placed in the alumina crucible filling silication penetration enhancer, silica flour, NaF and Al in this silication penetration enhancer
2o
3mass ratio be 40:10: 50; alumina crucible is put into process furnace heat; and pass into nitrogen protection; rise to 1400 DEG C with the heat-up rate of 15 DEG C/min and be incubated 15 hours; cool to room temperature with the furnace after insulation terminates, take out subsequently and be placed in distilled water and boil 10min, with deionized water rinsing; dehydrated alcohol wiping dries up, and obtains the finished product that tungsten basal body surface is W-Mo-N-Si system protective layer.
The phase composite of above-mentioned three embodiment gained high-temperature oxidation resistant silication layers is identical with weave construction, difference is the difference with technique, and the diffraction peak intensity of layer phase composite is different with thickness, but obtained structure all even compacts, combine in metallurgical state between interface, all do not occur the defects such as crackle.Adopt the high-temperature oxidation resistance of cyclic oxidation test W-Mo-N-Si tungsten sill under 1600 DEG C of atmospheric environments to show, tungsten sample oxidation is still intact after 300 hours, and surface forms the glassy membrane of smooth densification.According to the rating scale of GB, W-Mo-N-Si based material reaches complete grade of oxidation resistance at the antioxidant property of 1600 DEG C of atmospheric environments.
Note, above are only preferred embodiment of the present invention and institute's application technology principle.Skilled person in the art will appreciate that and the invention is not restricted to specific embodiment described here, various obvious change can be carried out for a person skilled in the art, readjust and substitute and can not protection scope of the present invention be departed from.Therefore, although be described in further detail invention has been by above embodiment, the present invention is not limited only to above embodiment, when not departing from the present invention's design, can also comprise other Equivalent embodiments more, and scope of the present invention is determined by appended right.
Claims (10)
1. a preparation method for tungsten surface high-temp anti oxidation layer, is characterized in that, comprises the following steps:
Tungsten base material is polished to smooth surface smooth, and glazed surface is deoiled skimming treatment;
Tungsten base material after process is imbedded molybdenum penetration enhancer, and then thermal treatment in inert atmosphere, removes impurity after cooling, obtains the work in-process that tungsten surface has tungsten solid solution layer;
Described work in-process are placed in nitrogen atmosphere heat-treat, after cooling, remove impurity, obtain the precast body that tungsten surface is molybdenum nitride and Tungsten nitride coatings; And
Imbedded by precast body in silication penetration enhancer, then thermal treatment in inert atmosphere, removes impurity after cooling, obtains the finished product that tungsten substrate surface is W-Mo-N-Si system high-temperature oxidation resistant layer.
2. the preparation method of tungsten surface high-temp anti oxidation layer according to claim 1, it is characterized in that, the preparation method of described molybdenum penetration enhancer comprises:
Take the molybdenum powder that mass fraction is 10 ~ 40 parts, mass fraction is the NH of 1 ~ 20 part
4cl, mass fraction is the Al of 40 ~ 89 parts
2o
3, ball milling 1 ~ 10 hour after mixing; And
Under vacuum conditions, temperature 100 ~ 150 DEG C of dryings 10 ~ 30 minutes.
3. the preparation method of tungsten surface high-temp anti oxidation layer according to claim 2, it is characterized in that, the diameter of described molybdenum powder is that 500 nanometers are to 10 microns.
4. the preparation method of tungsten surface high-temp anti oxidation layer according to claim 1, it is characterized in that, tungsten base material being imbedded molybdenum penetration enhancer and carries out heat treated temperature is 850 ~ 1100 DEG C, and soaking time is 1 ~ 24 hour.
5. the preparation method of tungsten surface high-temp anti oxidation layer according to claim 4, it is characterized in that, tungsten base material being imbedded molybdenum penetration enhancer and carries out heat treated temperature is 900 ~ 1000 DEG C, and soaking time is 4 ~ 10 hours.
6. the preparation method of tungsten surface high-temp anti oxidation layer according to claim 1, it is characterized in that, the described temperature 1000 ~ 1500 DEG C work in-process being placed in nitrogen atmosphere and heat-treating, nitridation time is 1 ~ 24 hour, and the flow velocity of nitrogen is 50 ~ 500mL/min.
7. the preparation method of tungsten surface high-temp anti oxidation layer according to claim 1, it is characterized in that, the preparation method of described silication penetration enhancer comprises:
Be the silica flour of 10 ~ 50 parts by mass fraction, mass fraction to be the NaF of 1 ~ 10 part and mass fraction the be Al of 40 ~ 89 parts
2o
3, ball milling 1 ~ 10 hour after mixing; And
Under vacuum conditions, temperature 80 ~ 100 DEG C of dryings 10 ~ 60 minutes.
8. the preparation method of tungsten surface high-temp anti oxidation layer according to claim 7, it is characterized in that, the diameter of described silica flour is that 500 nanometers are to 10 microns.
9. the preparation method of tungsten surface high-temp anti oxidation layer according to claim 1, it is characterized in that, precast body being imbedded heat treated temperature in silication penetration enhancer is 800 ~ 1400 DEG C, and soaking time is 1 ~ 24 hour.
10. a tungsten surface high-temp anti oxidation layer, is coated on tungsten substrate surface, it is characterized in that, described high-temperature oxidation resistant layer is W-Mo-N-Si system protective layer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111996485A (en) * | 2020-07-15 | 2020-11-27 | 深圳艾利门特科技有限公司 | Tungsten-based material with high-temperature insulating coating and preparation method thereof |
| CN112226728A (en) * | 2020-10-15 | 2021-01-15 | 厦门理工学院 | Tungsten product with oxidation-resistant coating and preparation method thereof |
| CN113957438A (en) * | 2021-10-26 | 2022-01-21 | 昆明理工大学 | Preparation method of metal tungsten high-temperature oxidation-resistant gallium-based composite coating |
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| CN104630699A (en) * | 2015-01-27 | 2015-05-20 | 航天材料及工艺研究所 | Method for preparing oxidation resistant coating on surface of niobium alloy material |
| CN104831231A (en) * | 2015-05-11 | 2015-08-12 | 长安大学 | Method for preparing anti-oxidation permeated layer on surface of molybdenum or molybdenum alloy |
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| CN112226728A (en) * | 2020-10-15 | 2021-01-15 | 厦门理工学院 | Tungsten product with oxidation-resistant coating and preparation method thereof |
| CN113957438A (en) * | 2021-10-26 | 2022-01-21 | 昆明理工大学 | Preparation method of metal tungsten high-temperature oxidation-resistant gallium-based composite coating |
| CN113957438B (en) * | 2021-10-26 | 2024-03-12 | 昆明理工大学 | Preparation method of metal tungsten high-temperature oxidation-resistant gallium-based composite coating |
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