CN115927995A - Thermal protection coating of tungsten-copper composite material and preparation method and application thereof - Google Patents
Thermal protection coating of tungsten-copper composite material and preparation method and application thereof Download PDFInfo
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- CN115927995A CN115927995A CN202211679353.XA CN202211679353A CN115927995A CN 115927995 A CN115927995 A CN 115927995A CN 202211679353 A CN202211679353 A CN 202211679353A CN 115927995 A CN115927995 A CN 115927995A
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- SBYXRAKIOMOBFF-UHFFFAOYSA-N copper tungsten Chemical compound [Cu].[W] SBYXRAKIOMOBFF-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000002131 composite material Substances 0.000 title claims abstract description 88
- 238000000576 coating method Methods 0.000 title claims abstract description 74
- 239000011248 coating agent Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title abstract description 22
- WNUPENMBHHEARK-UHFFFAOYSA-N silicon tungsten Chemical compound [Si].[W] WNUPENMBHHEARK-UHFFFAOYSA-N 0.000 claims abstract description 60
- 230000003064 anti-oxidating effect Effects 0.000 claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000010937 tungsten Substances 0.000 claims abstract description 27
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 27
- 230000003647 oxidation Effects 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 25
- 238000009413 insulation Methods 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000005507 spraying Methods 0.000 claims description 72
- 239000000843 powder Substances 0.000 claims description 67
- 239000010949 copper Substances 0.000 claims description 28
- 239000011253 protective coating Substances 0.000 claims description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000011863 silicon-based powder Substances 0.000 claims description 9
- WQJQOUPTWCFRMM-UHFFFAOYSA-N tungsten disilicide Chemical compound [Si]#[W]#[Si] WQJQOUPTWCFRMM-UHFFFAOYSA-N 0.000 claims description 9
- 229910021342 tungsten silicide Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000007750 plasma spraying Methods 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000002679 ablation Methods 0.000 abstract description 15
- 230000008520 organization Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 120
- 239000000395 magnesium oxide Substances 0.000 description 35
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 35
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 35
- 229910000449 hafnium oxide Inorganic materials 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 238000005488 sandblasting Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 9
- NVZBIFPUMFLZLM-UHFFFAOYSA-N [Si].[Y] Chemical compound [Si].[Y] NVZBIFPUMFLZLM-UHFFFAOYSA-N 0.000 description 8
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 8
- UVGLBOPDEUYYCS-UHFFFAOYSA-N silicon zirconium Chemical compound [Si].[Zr] UVGLBOPDEUYYCS-UHFFFAOYSA-N 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 229910000881 Cu alloy Inorganic materials 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229910052727 yttrium Inorganic materials 0.000 description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000010431 corundum Substances 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 229910000640 Fe alloy Inorganic materials 0.000 description 3
- 229910052769 Ytterbium Inorganic materials 0.000 description 3
- ZUZINCHBDVRGPN-UHFFFAOYSA-N [Ba].[Fe].[Si] Chemical compound [Ba].[Fe].[Si] ZUZINCHBDVRGPN-UHFFFAOYSA-N 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 150000002910 rare earth metals Chemical group 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- -1 rare earth silicon oxide Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
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- Coating By Spraying Or Casting (AREA)
Abstract
The invention provides a thermal protection coating of a tungsten-copper composite material and a preparation method and application thereof, the thermal protection coating comprises a tungsten silicon-based anti-oxidation bonding layer and a heat insulation burning-resistant layer which are sequentially arranged on the surface of the tungsten copper composite material; the tungsten silicon-based anti-oxidation bonding layer contains metal components except tungsten, and the metal components comprise any one or combination of at least two of Zr element, cu element or Y element; the heat-insulating burning-resistant layer is Yb 2 O 3 HfO co-doped with MgO 2 A layer of material; the thermal protection coating has good heat insulation performance, high-temperature oxidation resistance, ablation resistance and stable high-temperature organization structure, and can be used for oxidation resistance, heat insulation and ablation resistance protection of ultra-high-temperature components of tungsten-copper composite materials.
Description
Technical Field
The invention relates to the technical field of preparation of ultrahigh-temperature thermal protection coatings, in particular to a thermal protection coating of a tungsten-copper composite material and a preparation method and application thereof.
Background
At present, the tungsten-copper composite material is widely applied to high-temperature parts such as a nozzle throat insert, a gas vane, a nose cone, a balance weight and the like of an aviation and aerospace aircraft, and the working temperature is improved to 2500 ℃ or even higher after a long time. Because the performance of the tungsten-copper composite material without the protective coating is seriously degraded in a high-temperature and aerobic environment, the ultra-high temperature thermal protective coating is very necessary for the ultra-high temperature application of the tungsten-copper composite material.
CN111500967A discloses a tungsten copper alloy surface heat insulation/ablation resistance integrated composite coating, which sequentially comprises a metal bonding layer, a ceramic inner layer, a ceramic transition layer and a ceramic outer layer from bottom to top from the surface of a tungsten copper alloy, wherein the ceramic inner layer is an alumina layer, the ceramic transition layer is an alumina-rare earth zirconate layer, and the ceramic outer layer is a rare earth zirconate layer. As the melting point of the zirconate is below 2300 ℃, the zirconate can be quickly washed away by air flow after overtemperature, and the protective effect on a matrix is lost. The main disadvantage of this coating is therefore its low temperature resistance, which can only be used below 2300 ℃.
CN112662978A discloses a coating for tungsten-copper alloy material and a preparation method thereof, wherein the coating comprises a transition layer and an antioxidation layer which are sequentially formed on the surface of the alloy material, and the transition layer comprises the following raw materials in parts by weight: 15 to 20 parts of nano tin oxide, 10 to 15 parts of strontium fluoride, 0.1 to 0.5 part of tetrabutyl titanate and 1 to 5 parts of polyvinyl alcohol; the anti-oxidation layer comprises the following raw materials in parts by weight: 10-20 parts of nano cerium oxide and 30-50 parts of silicon barium iron alloy powder. Because the melting points of the nano cerium oxide and the silicon-barium-iron alloy are below 2000 ℃, the nano cerium oxide and the silicon-barium-iron alloy can be quickly washed away by air flow after being overtemperature, and the protective effect on a matrix is lost. The main disadvantage of this coating is therefore the low temperature resistance, which can only be used below 2000 ℃.
CN104372192A discloses a nano tungsten-copper composite material and a preparation method thereof, the composite material comprises a base material and a surface coating, the base material is tungsten-copper alloy, wherein the surface of tungsten powder is coated with a nano copper particle layer, and the thickness of the nano copper particle layer is 50-200nm; the surface coating is a resin coating and comprises the following components in percentage by mass: 30-50 parts of epoxy resin and 4-9 parts of nano titanium oxide; 3-8 parts of nano zinc oxide; 3-9 parts of a curing agent. The preparation method of the nano tungsten-copper composite material comprises a chemical vapor deposition method and a coating surface coating material. The patent mainly introduces a tungsten-copper alloy material for the electronic industry and a preparation method of a coating thereof, wherein the thermal protection coating is mainly composed of a resin material with the temperature resistance not higher than 1000 ℃, and is not resistant to high-temperature oxidation.
At present, the surface of a tungsten-copper composite material is provided with a multi-element rare earth silicon oxide, a rare earth silicate thermal protection coating and the like, the working temperature is not higher than 2300 ℃, and the working life is very short, so that the thermal protection coating with longer service life needs to be developed.
Disclosure of Invention
In view of the problems in the prior art, the invention provides the thermal protection coating of the tungsten-copper composite material, and the preparation method and the application thereof, the thermal protection coating has good physical and chemical performance compatibility with the tungsten-copper composite material, is well combined with the tungsten-copper composite material, has the remarkable characteristics of oxidation resistance, heat insulation and ablation resistance, has the working temperature of more than 2700 ℃, and has better application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a thermal protection coating of a tungsten-copper composite material, which comprises a tungsten-silicon-based anti-oxidation bonding layer and a heat-insulation burning-resistant layer which are sequentially arranged on the surface of the tungsten-copper composite material;
the tungsten silicon-based anti-oxidation bonding layer contains metal components except tungsten, and the metal components comprise any one or combination of at least two of Zr element, cu element or Y element;
the heat-insulating burning-resistant layer is Yb 2 O 3 HfO co-doped with MgO 2 A layer of material.
The thermal protection coating provided by the invention is designed into two layers, a tungsten silicon-based anti-oxidation bonding layer is arranged on the surface close to the tungsten-copper composite material, wherein the tungsten silicon-based material is used as a main body, so that the tungsten silicon-based anti-oxidation bonding layer can have better compatibility and matching performance with the tungsten-copper composite material, the slight difference of the thermal expansion coefficients can cause the cutting of each layer at high temperature mainly because the application environment temperature of the tungsten-copper composite material is up to 2200 ℃, and the arrangement of the tungsten silicon-based anti-oxidation bonding layer has better compatibility with the tungsten-copper composite material and the heat-insulation burning-resistant layer on the one hand, and on the other hand, silicon in the tungsten silicon-based anti-oxidation bonding layer is converted into glassy silicate at high temperature, so that oxygen can be prevented from further entering the tungsten-copper composite material, and an anti-oxidation effect is achieved. According to the invention, any one or a combination of at least two of Zr element, cu element or Y element is added into the tungsten-silicon-based anti-oxidation bonding layer, so that the high-temperature viscosity of the bonding layer can be improved, and the stress generated by the mismatch of thermal expansion of the bonding layer and the heat-insulation burning-resistant layer can be reduced.
The invention further arranges a heat-insulating burning-resistant layer on the surface of the tungsten-silicon-based anti-oxidation bonding layer, and Yb is selected 2 O 3 HfO co-doped with MgO 2 Material layer capable of preventing HfO 2 The volume is changed due to the phase change at high temperature, and the condition of poor powder spraying effect in the spraying process can be prevented. Selection of Yb 2 O 3 Co-doping with MgO has a better stabilizing effect.
The metal component comprises any one of Zr element, cu element or Y element or a combination of at least two of the Zr element, the Cu element, the Y element and the Cu element, the Zr element and the Y element, the Zr element and the Cu element, and the Y element, the Zr element and the Cu element, preferably the Y element, the Zr element and the Cu element.
In the present invention, a combination of the Y element, the Zr element, and the Cu element is more preferably used, and the molar ratio of the Y element to the Zr element to the Cu element is preferably 0.9 to 1.
Preferably, the tungsten-silicon-based anti-oxidation bonding layer contains tungsten-based alloy.
Preferably, the tungsten-based alloy comprises tungsten silicide.
Preferably, yb is in the heat-insulating burning-resistant layer 2 O 3 The molar fraction of (b) is 6 to 8%, and may be, for example, 6%, 6.3%, 6.5%, 6.7%, 6.9%, 7.2%, 7.4%, 7.6%, 7.8%, or 8%, etc., but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the mole fraction of MgO in the heat-insulating and burn-resistant layer is 2 to 5%, and may be, for example, 2%, 2.4%, 2.7%, 3%, 3.4%, 3.7%, 4%, 4.4%, 4.7%, or 5%, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, yb is in the heat-insulating burning-resistant layer 2 O 3 And MgO in a molar ratio of 1.5 to 3, for example, 1.5.
Further preferred in the present invention is Yb in the heat-insulating refractory layer 2 O 3 And MgO in the above range, preferably in a molar ratio of 1.5 to 3, and has a more excellent heat-resistant and heat-insulating effect. With HfO 2 Is mainly a heat-insulating and burning-resistant substance, but HfO 2 The crystal phase transformation easily occurs at high temperature, and the transformation of the crystal phase easily causes the volume change to cause the cracking of the heat insulating burning resistant layer, and the like, whereas Yb 2 O 3 The compound of the stabilizer and MgO is used as a stabilizer, the preferable molar ratio is 1.5-3, and the HfO stabilizer is more favorable for stabilizing HfO under the ultrahigh temperature condition 2 And finally, the heat-resistant temperature of the heat-insulating burning-resistant layer is improved.
Preferably, hfO in the heat-insulating burning-resistant layer 2 The molar fraction of (a) is 87 to 92%, and may be, for example, 87%, 87.6%, 88.2%, 88.7%, 89.3%, 89.8%, 90.4%, 90.9%, 91.5%, or 92%, etc., but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the tungsten content in the tungsten-copper composite material is 90 to 95wt%, and may be, for example, 90wt%, 90.6wt%, 91.2wt%, 91.7wt%, 92.3wt%, 92.8wt%, 93.4wt%, 93.9wt%, 94.5wt%, or 95wt%, etc., but is not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the copper content in the tungsten copper composite material is 5 to 10wt%, for example, 5wt%, 5.6wt%, 6.2wt%, 6.7wt%, 7.3wt%, 7.8wt%, 8.4wt%, 8.9wt%, 9.5wt%, or 10wt%, etc., but not limited to the recited values, and other values not recited in this range are also applicable.
The thermal protection coating is preferably more suitable for a tungsten-copper composite material with the copper content of 5-10 wt%, and the tungsten-silicon-based anti-oxidation bonding layer preferably has compatibility with the tungsten-copper composite material with the copper content of 5-10 wt%.
Preferably, the thickness of the tungsten silicon-based oxidation resistant adhesive layer is 0.15 to 0.25mm, for example, 0.15mm, 0.17mm, 0.18mm, 0.19mm, 0.2mm, 0.21mm, 0.22mm, 0.23mm, 0.24mm, or 0.25mm, but is not limited to the values listed, and other values not listed in this range are also applicable.
The thickness of the heat-insulating and burning-resistant layer is preferably 0.6 to 0.8mm, and may be, for example, 0.6mm, 0.63mm, 0.65mm, 0.67mm, 0.69mm, 0.72mm, 0.74mm, 0.76mm, 0.78mm, or 0.8mm, but is not limited to the values listed, and other values not listed in this range are also applicable.
In a second aspect, the invention provides a preparation method of the thermal protection coating of the tungsten-copper composite material, which comprises the following steps:
(1) Spraying a tungsten-silicon-based anti-oxidation bonding layer on the surface of the tungsten-copper composite material;
(2) And spraying a heat-insulating burning-resistant layer on the surface of the tungsten-silicon-based anti-oxidation bonding layer.
The preparation method provided by the second aspect of the invention can prepare the thermal protection coating only by adopting spraying, and has simple preparation process and short flow.
Preferably, the spraying in step (1) comprises atmospheric plasma spraying.
Preferably, the particle size of the tungsten silicon-based oxidation-resistant bonding powder used for the spray coating in the step (1) is 40 to 150 μm, and may be, for example, 40 μm, 53 μm, 65 μm, 77 μm, 89 μm, 102 μm, 114 μm, 126 μm, 138 μm or 150 μm, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the volume fraction of the silicon powder of the metal component other than tungsten in the tungsten silicon-based oxidation resistant bonding layer is 40 to 50%, for example, 40%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, or 50%, etc., but not limited to the enumerated values, and other values not enumerated within this range are also applicable.
The volume fraction of the silicon powder of other metal components except tungsten is further preferably within the range, the high-temperature viscosity of the bonding layer after oxidation is improved, and the effect of reducing the stress generated by mismatching of the thermal expansion of the bonding layer and the heat-insulating burning-resistant layer is achieved.
Preferably, the power of the spraying in step (1) is 25 to 30kW, and may be, for example, 25kW, 25.6kW, 26.2kW, 26.7kW, 27.3kW, 27.8kW, 28.4kW, 28.9kW, 29.5kW or 30kW, etc., but is not limited to the values recited, and other values not recited in the range are also applicable.
Preferably, the powder feeding rate of the spraying in step (1) is 30-40 g/min, such as 30g/min, 32g/min, 33g/min, 34g/min, 35g/min, 36g/min, 37g/min, 38g/min, 39g/min or 40g/min, but not limited to the values listed, and other values not listed in this range are equally applicable.
Preferably, the distance of spraying in step (1) is 80 to 120mm, for example 80mm, 85mm, 89mm, 94mm, 98mm, 103mm, 107mm, 112mm, 116mm or 120mm, but is not limited to the values listed, and other values not listed in this range are equally applicable.
Preferably, the powder for spraying in step (1) includes tungsten silicide powder and silicon powder of other metals.
Preferably, the silicon powder of the other metal comprises any one of silicon copper powder, silicon zirconium powder or silicon yttrium powder or a combination of at least two of the silicon copper powder, the silicon zirconium powder or the silicon yttrium powder.
The tungsten silicide powder and the silicon powder of other metals are preferably adopted for spraying, compared with the tungsten silicide powder and the metal simple substance powder for spraying, the tungsten silicon base is doped with zirconium, copper or yttrium, and the tungsten silicon base is fed and sprayed with the tungsten base powder, so that the tungsten silicon base has better compatibility with tungsten silicide.
Preferably, the spraying manner in step (2) includes atmospheric plasma spraying.
Preferably, the particle size of the powder used for the spraying in step (2) is 40 to 150. Mu.m, and may be, for example, 40 μm, 53 μm, 65 μm, 77 μm, 89 μm, 102 μm, 114 μm, 126 μm, 138 μm or 150 μm, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the power of the spraying in step (2) is 30 to 40kW, and may be, for example, 30kW, 30.6kW, 31.2kW, 31.7kW, 32.3kW, 32.8kW, 33.4kW, 33.9kW, 34.5kW, 35kW, 36kW, 38kW or 40kW, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the powder feeding rate of the spraying in step (2) is 35-45 g/min, such as 35g/min, 37g/min, 38g/min, 39g/min, 40g/min, 41g/min, 42g/min, 43g/min, 44g/min or 45g/min, but not limited to the values listed, and other values not listed in this range are equally applicable.
Preferably, the distance of spraying in step (2) is 100 to 120mm, and may be, for example, 100mm, 103mm, 105mm, 107mm, 109mm, 112mm, 114mm, 116mm, 118mm, or 120mm, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the powder in the powder feeding in the step (2) comprises Yb 2 O 3 Powder, mgO powder and HfO 2 And (3) powder.
Preferably, the preparation method further comprises: and (3) pretreating the spraying surface of the tungsten-copper composite material before spraying the surface of the tungsten-copper composite material.
Preferably, the pretreatment comprises cleaning the spraying surface by using compressed air and then performing sand blasting.
The pressure of the compressed air is preferably 0.35 to 0.45MPa, and may be, for example, 0.35MPa, 0.36MPa, 0.37MPa, 0.38MPa, 0.39MPa, 0.4MPa, 0.41MPa, 0.42MPa, 0.43MPa or 0.45 MPa.
Preferably, the sand blasting treatment adopts 25# brown corundum sand.
Preferably, the blasting angle between the blast gun and the test piece in the blasting treatment is 60 ° to 75 °, and may be, for example, 60 °, 61 °, 62 °, 63 °, 65 °, 68 °, 70 °, 72 °, 74 °, or 75 °.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Spraying a tungsten-silicon-based anti-oxidation bonding layer on the surface of the tungsten-copper composite material by adopting atmospheric plasma, wherein the spraying power is 25-30 kW, the powder feeding rate is 30-40 g/min, and the spraying distance is 80-120 mm;
(2) And spraying a heat-insulating burning-resistant layer on the surface of the tungsten-silicon-based anti-oxidation bonding layer by adopting atmospheric plasma, wherein the spraying power is 30-40 kW, the powder feeding rate is 35-45 g/min, and the spraying distance is 100-120 mm.
In a third aspect, the present invention provides a use of the thermal protective coating of the tungsten copper composite material according to the first aspect in the field of aerospace, aircraft, gas rudders, nose cones or counterweights.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The thermal protection coating of the tungsten-copper composite material provided by the invention has good physical and chemical performance compatibility with the tungsten-copper composite material, is well combined with the tungsten-copper composite material, has oxidation resistance, heat insulation and ablation resistance, can resist temperature up to more than 2700 ℃, can still keep good base body and coating structure integrity after being placed for 350s at 2700 ℃, and has good temperature resistance effect;
(2) The invention provides a thermal protection coating handle of tungsten-copper composite materialThe oxidation-resistant, heat-insulating and ablation-resistant coatings with different functions are combined to exert respective advantages to form a composite coating system with a double-layer structure. The tungsten-silicon-based oxidation-resistant bonding layer added with Zr element, cu element or rare earth Y element improves the interface matching property between the coating and the tungsten-copper composite material, improves the bonding strength between the coating and the tungsten-copper matrix interface, and has the functions of preventing oxygen atoms from diffusing and invading at high temperature and preventing the matrix element from escaping. Ytterbium (Yb) oxide of rare earth 2 O 3 ) Co-doped hafnium oxide (HfO) such as magnesium oxide (MgO) 2 ) The heat insulation and ablation resistance layer reduces the surface temperature of the tungsten-copper composite material, prevents the performance degradation of the tungsten-copper composite material under the high-temperature condition and reduces the ablation loss of the coating in high-speed airflow;
(2) The preparation method of the thermal protection coating of the tungsten-copper composite material provided by the invention is short in flow, simple in preparation process and suitable for large-scale production.
Drawings
Fig. 1 is a schematic structural diagram of a thermal protective coating provided in embodiment 1 of the present invention.
FIG. 2 is a surface view of an ablated thermal protective coating made in accordance with example 1 of the present invention.
In the figure: 1-tungsten copper composite material; 2-tungsten silicon based anti-oxidation bonding layer; 3-heat insulation burning-resistant layer.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
As an embodiment of the invention, a thermal protection coating of a tungsten-copper composite material is provided, as shown in fig. 1, the thermal protection coating comprises a tungsten-silicon-based oxidation-resistant bonding layer and a heat-insulating burning-resistant layer which are sequentially arranged on the surface of the tungsten-copper composite material;
the tungsten silicon-based anti-oxidation bonding layer contains 40-50% of metal components except tungsten, and the metal components comprise any one or combination of at least two of Zr elements, cu elements or Y elements;
the heat-insulating burning-resistant layer is Yb 2 O 3 HfO co-doped with MgO 2 A material layer in the heat-insulating burning-resistant layerYb 2 O 3 The mole fraction of MgO is 6-8%, and the mole fraction of MgO is 2-5%.
The tungsten content in the tungsten-copper composite material is 90-95 wt%, and the copper content is 5-10 wt%.
The thickness of the tungsten silicon-based anti-oxidation bonding layer is 0.15-0.25 mm, and the thickness of the heat-insulation burning-resistant layer is 0.6-0.8 mm.
As another embodiment of the present invention, a method for preparing a thermal protective coating of a tungsten-copper composite material is provided, the method comprising the steps of:
(1) Spraying a tungsten-silicon-based anti-oxidation bonding layer on the surface of the tungsten-copper composite material by adopting atmospheric plasma, wherein the spraying power is 25-30 kW, the powder feeding rate is 30-40 g/min, and the spraying distance is 80-120 mm;
(2) And spraying a heat-insulating burning-resistant layer on the surface of the tungsten-silicon-based anti-oxidation bonding layer by adopting atmospheric plasma, wherein the spraying power is 30-40 kW, the powder feeding rate is 35-45 g/min, and the spraying distance is 100-120 mm.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the appended claims.
Example 1
The embodiment provides a thermal protection coating of a tungsten-copper composite material, as shown in fig. 1, the thermal protection coating comprises a tungsten-silicon-based oxidation-resistant bonding layer 2 and a heat-insulating burning-resistant layer 3 which are sequentially arranged on the surface of a tungsten-copper composite material 1;
the tungsten silicon-based oxidation-resistant bonding layer contains metal components except tungsten, wherein the metal components comprise Zr element, cu element and Y element, and the molar ratio of the Zr element to the Cu element to the Y element is 1;
the heat-insulating burning-resistant layer is Yb 2 O 3 HfO co-doped with MgO 2 A layer of material of Yb in the heat-insulating refractory layer 2 O 3 The molar fraction of MgO was 7% and the molar fraction of MgO was 3.5%.
The tungsten content in the tungsten-copper composite material is 95wt%, and the copper content is 5wt%.
The thickness of the tungsten silicon-based anti-oxidation bonding layer is 0.18mm, and the thickness of the heat-insulation burning-resistant layer is 0.6mm.
The invention also provides a preparation method of the thermal protection coating of the tungsten-copper composite material, which comprises the following steps:
(1) Cleaning the surface of the tungsten-copper composite material by using dry and clean compressed air, performing sand blasting treatment on the material spraying surface by using a suction type dry sand blasting machine, using 25# brown corundum sand, wherein the sand blasting angle between a spray gun and a test piece is 65 degrees, and the pressure of an air compressor is 0.40MPa;
spraying a tungsten silicon-based anti-oxidation bonding layer on the surface of the tungsten-copper composite material by adopting atmospheric plasma, wherein the base powder is tungsten silicide, silicon-zirconium powder (zirconium content is 52 wt%), silicon-copper powder (copper content is 44 wt%) and silicon-yttrium powder (yttrium content is 50 wt%) are doped, the total volume of the silicon-zirconium powder, the silicon-copper powder and the silicon-yttrium powder accounts for 40% of the total volume, the particle size of the powder is 40-100 mu m, the spraying power is 30kW, the powder feeding rate is 35g/min, and the spraying distance is 100mm;
(2) The surface of the tungsten-silicon-based anti-oxidation bonding layer adopts an atmospheric plasma spraying heat-insulation burning-resistant layer, and the powder is 7 percent of Yb 2 O 3 3.5 percent of MgO, and the balance of HfO 2 The mixed powder has the particle size of 40-100 mu m, the spraying power of 38kW, the powder feeding speed of 42g/min and the spraying distance of 100mm.
The ablated surface of the present embodiment is shown in fig. 2, and it can be seen from fig. 2 that after the experiment of 350s plasma ablation at 2700 ℃, the structure of the hafnium oxide coating still remains intact, and the problem of cracking and peeling of the coating due to excessive thermal stress does not occur.
Example 2
The embodiment provides a thermal protection coating of a tungsten-copper composite material, which comprises a tungsten-silicon-based anti-oxidation bonding layer and a thermal insulation burning-resistant layer, wherein the tungsten-silicon-based anti-oxidation bonding layer and the thermal insulation burning-resistant layer are sequentially arranged on the surface of the tungsten-copper composite material;
the tungsten silicon-based oxidation-resistant bonding layer contains metal components except tungsten, wherein the metal components comprise Zr element, cu element and Y element, and the molar ratio of the Zr element to the Cu element to the Y element is 0.9;
the heat-insulating burning-resistant layer is Yb 2 O 3 HfO co-doped with MgO 2 A layer of material of Yb in the heat-insulating refractory layer 2 O 3 The molar fraction of MgO is 6% and the molar fraction of MgO is 4%.
The tungsten content in the tungsten-copper composite material is 90wt%, and the copper content is 10wt%.
The thickness of the tungsten silicon-based anti-oxidation bonding layer is 0.25mm, and the thickness of the heat-insulation burning-resistant layer is 0.8mm.
The invention also provides a preparation method of the thermal protection coating of the tungsten-copper composite material, which comprises the following steps:
(1) Cleaning the surface of the tungsten-copper composite material by using dry and clean compressed air, carrying out sand blasting treatment on a material spraying surface by using a suction type dry sand blasting machine, using 25# brown corundum sand, wherein the sand blasting angle between a spray gun and a test piece is 75 degrees, and the pressure of an air compressor is 0.45MPa;
spraying a tungsten silicon-based anti-oxidation bonding layer on the surface of the tungsten-copper composite material by adopting atmospheric plasma, wherein the base powder is tungsten silicide, silicon-zirconium powder (zirconium content is 48 wt%), silicon-copper powder (copper content is 45 wt%) and silicon-yttrium powder (yttrium content is 52 wt%) are doped, the total volume of the silicon-zirconium powder, the silicon-copper powder and the silicon-yttrium powder accounts for 45%, the particle size of the powder is 50-150 mu m, the spraying power is 25kW, the powder feeding rate is 40g/min, and the spraying distance is 120mm;
(2) The surface of the tungsten-silicon-based anti-oxidation bonding layer adopts an atmospheric plasma spraying heat-insulation burning-resistant layer, and the powder is 6% of Yb 2 O 3 4% of MgO, and the balance of HfO 2 The mixed powder has the particle size of 60-150 mu m, the spraying power of 30kW, the powder feeding speed of 45g/min and the spraying distance of 120mm.
Example 3
The embodiment provides a thermal protection coating of a tungsten-copper composite material, which comprises a tungsten-silicon-based anti-oxidation bonding layer and a thermal insulation burning-resistant layer, wherein the tungsten-silicon-based anti-oxidation bonding layer and the thermal insulation burning-resistant layer are sequentially arranged on the surface of the tungsten-copper composite material;
the tungsten silicon-based oxidation-resistant bonding layer contains metal components except tungsten, wherein the metal components comprise Zr element, cu element and Y element, and the molar ratio of the Zr element to the Cu element to the Y element is 0.9;
the heat-insulating burning-resistant layer is Yb 2 O 3 HfO co-doped with MgO 2 A layer of material of Yb in the heat-insulating refractory layer 2 O 3 The molar fraction of MgO is 8% and the molar fraction of MgO is 5%.
The tungsten content in the tungsten-copper composite material is 93wt%, and the copper content is 7wt%.
The thickness of the tungsten silicon-based anti-oxidation bonding layer is 0.15mm, and the thickness of the heat-insulation burning-resistant layer is 0.7mm.
The invention also provides a preparation method of the thermal protection coating of the tungsten-copper composite material, which comprises the following steps:
(1) Cleaning the surface of the tungsten-copper composite material by using dry and clean compressed air, carrying out sand blasting treatment on a material spraying surface by using a suction type dry sand blasting machine, and using 25# brown corundum sand, wherein the sand blasting angle between a spray gun and a test piece is 60 degrees, and the pressure of an air compressor is 0.35MPa;
spraying a tungsten silicon-based anti-oxidation bonding layer on the surface of the tungsten-copper composite material by adopting atmospheric plasma, wherein the base powder is tungsten silicide, and is doped with silicon-zirconium powder (the zirconium content is 55 wt%), silicon-copper powder (the copper content is 42 wt%) and silicon-yttrium powder (the yttrium content is 52 wt%), the volume ratio of the silicon-zirconium powder, the silicon-copper powder and the silicon-yttrium powder is up to 50%, the particle size of the powder is 50-110 mu m, the spraying power is 30kW, the powder feeding rate is 30g/min, and the spraying distance is 80mm;
(2) The surface of the tungsten-silicon-based anti-oxidation bonding layer adopts an atmospheric plasma spraying heat-insulation burning-resistant layer, and the powder is 8% of Yb 2 O 3 3.5 percent of MgO and the balance of HfO 2 The mixed powder has the particle size of 80-120 mu m, the spraying power of 40kW, the powder feeding speed of 35g/min and the spraying distance of 110mm.
Example 4
This example provides a thermal protective coating of a tungsten-copper composite material, which is the same as in example 1 except that only Zr is added, and the overall content of metal components other than tungsten is kept unchanged.
Example 5
The embodiment provides a thermal protection coating of a tungsten-copper composite material, which is the same as that in the embodiment 1 except that the molar ratio of Zr element, cu element and Y element is 1.5.
Example 6
This example provides a thermal protective coating for a tungsten-copper composite material, which is the same as in example 1 except that the molar ratio of Zr element, cu element, and Y element is 1.
Example 7
This example provides a thermal protective coating of W-Cu composite material, wherein the mole fraction of MgO removed from the thermal protective coating is 2% so that Yb is formed 2 O 3 The molar ratio of MgO to MgO was 3.5.
Example 8
This example provides a thermal protective coating of tungsten copper composite material, wherein the mole fraction of MgO removed from the thermal protective coating is 7% so that Yb is formed 2 O 3 The molar ratio of MgO to MgO was 1, and the rest was the same as in example 1.
Example 9
The embodiment provides a thermal protection coating of a tungsten-copper composite material, and the preparation method is the same as that of embodiment 1 except that copper powder, zirconium powder, yttrium powder and tungsten powder are doped, and silicon powder is supplemented correspondingly, and the element proportion and the element content are kept unchanged.
Comparative example 1
The comparison example provides a thermal protection coating of a tungsten-copper composite material, the thermal protection coating is provided with a thermal insulation burning-resistant layer, no MgO is added, and the content of the thermal protection coating is replaced by Yb 2 O 3 Otherwise, the rest was the same as example 1.
Comparative example 2
This comparative example provides a thermal protective coating of a tungsten copper composite with no Yb addition to the thermal barrier refractory layer 2 O 3 Except for MgO, the contents were the same as in example 1.
Comparative example 3
The comparative example provides a thermal protective coating of a tungsten copper composite material, and the tungsten silicon-based oxidation resistant bonding layer is the same as the example 1 except that metal components except tungsten are not added.
Comparative example 4
The comparative example provides a thermal protective coating of a tungsten-copper composite material, wherein metal components except tungsten in the tungsten silicon-based oxidation-resistant bonding layer are completely replaced by manganese, and the rest is the same as that in the example 1.
Comparative example 5
The comparative example provides a thermal protective coating of a tungsten-copper composite material, wherein metal components except tungsten in the tungsten silicon-based oxidation-resistant bonding layer are replaced by cobalt, and the rest is the same as that in the example 1.
The test method comprises the following steps: the material thus obtained was left at 2700 ℃ for 350 seconds, and the ablated surface was observed.
The test results of the above examples and comparative examples are shown in table 1.
TABLE 1
| Surface topography after ablation | Tolerance situation | |
| Example 1 | Structural integrity of the substrate and coating | Good effect |
| Example 2 | Structural integrity of the substrate and coating | Good effect |
| Example 3 | Structural integrity of the substrate and coating | Good effect |
| Example 4 | Unstable performance of the adhesive layer | Are difficult to tolerate |
| Example 5 | Unstable performance of the adhesive layer | Are difficult to tolerate |
| Example 6 | Unstable performance of the adhesive layer | Are difficult to tolerate |
| Example 7 | The coating is easy to crack | Are difficult to tolerate |
| Example 8 | The coating has insufficient toughness and is easy to fall off | Are difficult to tolerate |
| Example 9 | The bonding layer is seriously oxidized, and the coating is easy to fall off | Are difficult to tolerate |
| Comparative example 1 | Cracking of the coating and slight ablation of the substrate | Intolerance of |
| Comparative example 2 | The coating falls off when the temperature is reduced and the matrix is slightly ablated | Intolerance of |
| Comparative example 3 | The coating is burnt through and falls off, and the ablation of the matrix is serious | Intolerance of |
| Comparative example 4 | The coating is burnt through and falls off, and the ablation of the matrix is serious | Intolerance of |
| Comparative example 5 | The coating is burnt through and falls off, and the ablation of the matrix is serious | Intolerance of |
From table 1, the following points can be seen:
(1) It can be seen from the comprehensive examples 1 to 3 that the thermal protective coating of the tungsten-copper composite material provided by the invention can still keep good structural integrity of the matrix and the coating after being placed at 2700 ℃ for 350 s;
(2) It can be seen from the combination of example 1 and examples 4 to 6 that the adhesion layer performance is unstable due to the Zr element only contained in example 4, and the adhesion layer performance is also unstable due to the fact that the mixture ratio of the three components is not in the preferable range in examples 5 to 6; therefore, zr element, cu element and Y element are preferably added at the same time, the mixture ratio of the Zr element, the Cu element and the Y element is controlled within a specific range, and the structural integrity of the substrate and the coating after ablation at 2700 ℃ can be guaranteed;
(3) It can be seen from a combination of example 1 and examples 7 to 8 that Yb is present in example 7 2 O 3 A molar ratio of 3.5 to MgO of 3.5 results in a coating that is easily cracked and difficult to withstand high temperatures, yb in example 8 2 O 3 The molar ratio of 1 to MgO was 1, which resulted in insufficient toughness of the coating and easy exfoliation, thus indicating that the present invention is prepared by mixing Yb 2 O 3 The mass ratio of the tungsten powder to the MgO is controlled in a specific range, so that the heat resistance of the tungsten-copper composite material can be improved;
(4) It can be seen from the combination of example 1 and example 9 that the direct spraying of the elemental powder and the silicon powder in the preparation method of example 9 results in severe oxidation of the bonding layer and easy peeling of the coating, because silicate capable of playing an anti-oxidation role is not formed during the spraying process and the compatibility of the coating is significantly reduced, which indicates that the heat resistance and oxidation resistance of the coating are improved by selecting silicon powder of other metal components for spraying.
(5) As can be seen from the combination of example 1 and comparative examples 1 to 2, mgO and Yb were simultaneously doped into the heat-insulating and flame-resistant layer 2 O 3 Can resist 2700 ℃ high temperature; similarly, by combining the example 1 and the comparative examples 3 to 5, the situation that the coating directly falls off occurs when Cu, zr and Y are not added into the tungsten-silicon-based oxidation-resistant bonding layer or other elements are replaced, thereby showing that the heat-resistant effect of the thermal protection coating is improved by optimizing the composition of the heat-insulating burning-resistant layer and the silicon-based oxidation-resistant bonding layer.
The present invention is described in detail with reference to the above embodiments, but the present invention is not limited to the above detailed structural features, that is, the present invention is not meant to be implemented only by relying on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The thermal protection coating of the tungsten-copper composite material is characterized by comprising a tungsten-silicon-based anti-oxidation bonding layer and a heat-insulation burning-resistant layer which are sequentially arranged on the surface of the tungsten-copper composite material;
the tungsten silicon-based anti-oxidation bonding layer contains metal components except tungsten, and the metal components comprise any one or combination of at least two of Zr element, cu element or Y element;
the heat-insulating burning-resistant layer is Yb 2 O 3 HfO co-doped with MgO 2 A layer of material.
2. The thermal protective coating according to claim 1, wherein said tungsten silicon based oxidation resistant bonding layer comprises a tungsten based alloy;
preferably, the tungsten-based alloy comprises tungsten silicide.
3. The thermal protective coating of claim 1 or 2, wherein Yb in the thermal insulating refractory layer 2 O 3 The mole fraction of (A) is 6-8%;
preferably, the mole fraction of MgO in the heat-insulating and burning-resistant layer is 2-5%;
preferably, hfO in the heat-insulating burning-resistant layer 2 The molar fraction of (B) is 87-92%.
4. The thermal protective coating according to any one of claims 1 to 3, wherein the tungsten content in the tungsten-copper composite material is 90 to 95wt%;
preferably, the copper content in the tungsten-copper composite material is 5-10 wt%.
5. The thermal protective coating according to any one of claims 1 to 4, wherein the thickness of the tungsten silicon based oxidation resistant bonding layer is 0.15 to 0.25mm;
preferably, the thickness of the heat-insulating burning-resistant layer is 0.6-0.8 mm.
6. A method for preparing a thermal protective coating of a tungsten copper composite material according to any one of claims 1 to 5, characterized in that the method comprises the following steps:
(1) Spraying a tungsten-silicon-based anti-oxidation bonding layer on the surface of the tungsten-copper composite material;
(2) And spraying a heat-insulating burning-resistant layer on the surface of the tungsten-silicon-based anti-oxidation bonding layer.
7. The production method according to claim 6, wherein the manner of spraying in step (1) includes atmospheric plasma spraying;
preferably, the particle size of the tungsten silicon-based anti-oxidation bonding powder adopted in the spraying in the step (1) is 40-150 μm;
preferably, the volume fraction of silicon powder of other metal components except tungsten in the tungsten silicon-based anti-oxidation bonding layer in the step (1) is 40-50%;
preferably, the power of the spraying in the step (1) is 25-30 kW;
preferably, the powder feeding rate of the spraying in the step (1) is 30-40 g/min;
preferably, the distance of the spraying in the step (1) is 80-120 mm.
8. The production method according to claim 7 or 8, wherein the manner of spraying in step (2) includes atmospheric plasma spraying;
preferably, the particle size of the powder adopted in the spraying in the step (2) is 40-150 μm;
preferably, the power of the spraying in the step (2) is 30-40 kW;
preferably, the powder feeding rate of the spraying in the step (2) is 35-45 g/min;
preferably, the distance of the spraying in the step (2) is 100 to 120mm.
9. The production method according to any one of claims 7 to 8, characterized by comprising the steps of:
(1) Spraying a tungsten-silicon-based anti-oxidation bonding layer on the surface of the tungsten-copper composite material by adopting atmospheric plasma, wherein the spraying power is 25-30 kW, the powder feeding rate is 30-40 g/min, and the spraying distance is 80-120 mm;
(2) And spraying a heat-insulating burning-resistant layer on the surface of the tungsten-silicon-based anti-oxidation bonding layer by adopting atmospheric plasma, wherein the spraying power is 30-40 kW, the powder feeding rate is 35-45 g/min, and the spraying distance is 100-120 mm.
10. Use of a thermal protective coating of a tungsten copper composite according to any one of claims 1 to 5 in the field of aerospace, aircraft, gas rudders, nose cones or counterweights.
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