CN116354739B - Ceramic connecting piece and preparation method and application thereof - Google Patents
Ceramic connecting piece and preparation method and application thereof Download PDFInfo
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- CN116354739B CN116354739B CN202310269721.1A CN202310269721A CN116354739B CN 116354739 B CN116354739 B CN 116354739B CN 202310269721 A CN202310269721 A CN 202310269721A CN 116354739 B CN116354739 B CN 116354739B
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- 239000000919 ceramic Substances 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 52
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 238000003475 lamination Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000009792 diffusion process Methods 0.000 claims abstract description 10
- 238000005253 cladding Methods 0.000 claims abstract description 4
- 238000010030 laminating Methods 0.000 claims abstract description 4
- 239000003758 nuclear fuel Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims description 46
- 239000011248 coating agent Substances 0.000 claims description 43
- 239000011159 matrix material Substances 0.000 claims description 20
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 15
- 239000007790 solid phase Substances 0.000 claims description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 13
- 238000007733 ion plating Methods 0.000 claims description 12
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 10
- 150000002910 rare earth metals Chemical class 0.000 claims description 9
- 229910052706 scandium Inorganic materials 0.000 claims description 8
- 238000007738 vacuum evaporation Methods 0.000 claims description 8
- XTDAIYZKROTZLD-UHFFFAOYSA-N boranylidynetantalum Chemical compound [Ta]#B XTDAIYZKROTZLD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- LRTTZMZPZHBOPO-UHFFFAOYSA-N [B].[B].[Hf] Chemical compound [B].[B].[Hf] LRTTZMZPZHBOPO-UHFFFAOYSA-N 0.000 claims description 4
- 238000005219 brazing Methods 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 238000003466 welding Methods 0.000 claims description 4
- 238000005304 joining Methods 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052580 B4C Inorganic materials 0.000 claims description 2
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- 229910026551 ZrC Inorganic materials 0.000 claims description 2
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 claims description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 2
- 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 description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 2
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 2
- WHJFNYXPKGDKBB-UHFFFAOYSA-N hafnium;methane Chemical compound C.[Hf] WHJFNYXPKGDKBB-UHFFFAOYSA-N 0.000 claims description 2
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052863 mullite Inorganic materials 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 229910003468 tantalcarbide Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000003647 oxidation Effects 0.000 abstract description 19
- 238000007254 oxidation reaction Methods 0.000 abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 58
- 229910002482 Cu–Ni Inorganic materials 0.000 description 13
- 238000004140 cleaning Methods 0.000 description 10
- 229910052684 Cerium Inorganic materials 0.000 description 9
- 229910052688 Gadolinium Inorganic materials 0.000 description 9
- 229910052765 Lutetium Inorganic materials 0.000 description 9
- 238000000151 deposition Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 230000008021 deposition Effects 0.000 description 8
- 238000005530 etching Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229910052689 Holmium Inorganic materials 0.000 description 5
- 229910052777 Praseodymium Inorganic materials 0.000 description 5
- 229910052772 Samarium Inorganic materials 0.000 description 5
- 229910052771 Terbium Inorganic materials 0.000 description 5
- 230000003064 anti-oxidating effect Effects 0.000 description 5
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HVXCTUSYKCFNMG-UHFFFAOYSA-N aluminum oxygen(2-) zirconium(4+) Chemical compound [O-2].[Zr+4].[Al+3] HVXCTUSYKCFNMG-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910004339 Ti-Si Inorganic materials 0.000 description 1
- 229910010978 Ti—Si Inorganic materials 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
- C04B37/003—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
- C04B41/5105—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal with a composition mainly composed of one or more of the noble metals or copper
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
- C04B41/5133—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal with a composition mainly composed of one or more of the refractory metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
- C04B2237/12—Metallic interlayers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
- C04B2237/12—Metallic interlayers
- C04B2237/122—Metallic interlayers based on refractory metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
- C04B2237/72—Forming laminates or joined articles comprising at least two interlayers directly next to each other
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
Abstract
The invention discloses a ceramic connecting piece and a preparation method and application thereof. The ceramic connector includes: the ceramic substrate comprises at least two ceramic substrates, an intermediate layer and a metal alternate layer lamination, wherein the intermediate layer is used for connecting the ceramic substrates, the metal alternate layer lamination is formed on the surface of the intermediate layer at the joint of the ceramic substrates, and the metal alternate layer lamination is formed by alternately laminating a plurality of metal layers. The ceramic connecting piece provided by the invention has the advantages that the dense mixed oxide layer is formed in the oxidation process by the metal alternate layer lamination, the diffusion of oxygen elements is inhibited, the ceramic connecting piece is ensured to have excellent oxidation resistance, and the obtained connecting piece can be applied to the fields of nuclear fuel cladding, aerospace, electronic components and the like.
Description
Technical Field
The invention belongs to the technical field of ceramic protection, and particularly relates to a ceramic connecting piece and a preparation method and application thereof.
Background
Today, in the fields of nuclear energy, aerospace, magnetism, optics, electronic devices and the like, the ceramic has higher and higher requirements on materials, and ceramics are widely focused due to the excellent performances of chemical stability, high temperature resistance, irradiation resistance, oxidation resistance and the like, so that the ceramic becomes a new generation of materials with great potential. However, the poor workability of ceramics makes it difficult to integrally mold them for use in a specific environment, so that the joining technique of ceramics forms a critical part of the application.
In many connection methods, solid-phase diffusion welding can generate stable intermediate phases and has excellent high-temperature performance, and at present, research is conducted on using a plurality of metal intermediate layers or coatings such as Ti, mo, ta, nb, W, cr, zr, ni, pb to realize the connection between ceramics, but under the neutron irradiation environment, some compounds such as Ti-Si compounds have amorphization tendency and anisotropically expand at high temperature, compared with the compounds, rare earth elements have excellent irradiation resistance, but rare earth elements are rarely reported to be used as intermediate phases of ceramic connection, because most rare earth elements have poor oxidation resistance, and the mechanical properties of the connection part can be greatly reduced under the high-temperature oxygen environment, so that how to improve the oxidation resistance of the connection part is important.
Disclosure of Invention
The invention mainly aims to provide a ceramic connecting piece, and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a ceramic connecting piece, which comprises: the ceramic substrate comprises at least two ceramic substrates, an intermediate layer and a metal alternate layer lamination, wherein the intermediate layer is used for connecting the ceramic substrates, the metal alternate layer lamination is formed on the surface of the intermediate layer at the joint of the ceramic substrates, and the metal alternate layer lamination is formed by alternately laminating a plurality of metal layers.
The embodiment of the invention also provides a preparation method of the ceramic connecting piece, which comprises the following steps:
preparing a rare earth metal coating on the surface of the joint of the ceramic matrix by adopting at least any one of vacuum evaporation, arc ion plating, magnetron sputtering and spraying;
adopting solid-phase diffusion connection treatment to connect the ceramic matrixes;
and preparing a metal alternate layer stack on the surface of the intermediate layer at the joint of the obtained ceramic matrix at least by adopting any one mode of vacuum evaporation, arc ion plating, magnetron sputtering and spraying, thereby preparing the ceramic connecting piece.
The embodiment of the invention also provides application of the ceramic connecting piece in the fields of nuclear fuel cladding, aerospace or electronic components.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, a metal coating is deposited on the surface of a connecting piece which uses rare earth metal as an intermediate layer to connect ceramics for the first time;
(2) The ceramic connecting piece prepared by the invention and taking rare earth metal as the intermediate phase has excellent irradiation resistance;
(3) The metal coating prepared by the invention can generate a compact oxide film on the surface of the coating under the high-temperature vapor oxidation condition, so that the oxidation resistance of the ceramic connecting piece is ensured;
(4) According to the invention, the multi-element rare earth element is adopted as the intermediate layer, so that the corrosion resistance and the irradiation resistance of the joint can be improved under the combined action of a plurality of elements, and then the metal coating is prepared on the surface, so that the oxidation resistance of the high-temperature steam of the connecting piece is further improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a schematic view of the surface Cr-Ti-V-W-Cu-Ni coating on the surface of the antioxidation metal coating on the surface of the titanium carbide ceramic connector in example 1 of the present invention;
FIG. 2 is a schematic illustration of the surface Ti-V-Mo-Zr-Ta-Nb-Ni-Cr-Pt coating on the surface of the oxidation resistant metal coating of the aluminum oxide-zirconium boride ceramic joint of example 2 of the present invention;
FIG. 3 is a schematic illustration of the surface W-Cu-V-Nb-Mo-Ta-Pt-Zr coating on the surface of the oxidation resistant metal coating of the tantalum boride ceramic connector of example 3 of the present invention;
FIG. 4 is a schematic illustration of the surface Ni-Zr-Ta-Zr-Mo coating on the surface of the oxidation resistant metal coating on the surface of the titanium carbide-hafnium boride ceramic connection according to example 4 of the present invention;
FIGS. 5-6 are scanning electron microscope images of a high temperature oxidation test of the presence or absence of a Cr-Ti-V-W-Cu-Ni coating on the surface of a titanium carbide ceramic joint according to comparative example 1 of the present invention.
Detailed Description
In view of the shortcomings of the prior art, the inventor of the present application has long studied and put forward a great deal of practice, and the technical solution of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Specifically, as one aspect of the technical scheme of the invention, the ceramic connecting piece comprises: the ceramic substrate comprises at least two ceramic substrates, an intermediate layer and a metal alternate layer lamination, wherein the intermediate layer is used for connecting the ceramic substrates, the metal alternate layer lamination is formed on the surface of the intermediate layer at the joint of the ceramic substrates, and the metal alternate layer lamination is formed by alternately laminating a plurality of metal layers.
The metal alternate layer lamination of the ceramic connecting piece has a multi-element layered structure, so that a strong chemical bonding interface can be formed with the middle layer in the ceramic connecting piece, and on the other hand, a compact mixed oxide layer is formed in the oxidation process, so that the diffusion of oxygen elements to the connecting piece can be inhibited, and further, excellent oxidation resistance can be obtained; meanwhile, the intermediate layer in the invention reacts with the ceramic matrix in situ under high temperature and high pressure to form a lamellar structure, and forms strong chemical bonding with the surface metal alternate lamination layers, so that the strength and oxidation resistance of the connecting interface are further enhanced.
In some preferred embodiments, the alternating metal layer stack is a metal layer comprising at least two elements.
In some preferred embodiments, the alternating metal layer stack has a multi-layered structure
In some preferred embodiments, the metal layer includes any one of Ti, V, W, cu, zr, mo, ta, nb, ni, pt, cr, and is not limited thereto.
In some preferred embodiments, the intermediate layer comprises a combination of any two or more of Sc, la, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, lu.
In some preferred embodiments, the alternating layers of metal are 5nm to 100 μm thick.
Further, the thickness of the metal alternate layer stack is 50nm to 20 μm.
In some preferred embodiments, the metal layer has a thickness of 1nm to 20 μm.
Further, the thickness of the metal layer is 2 nm-500 nm.
In some preferred embodiments, the thickness of the intermediate layer is from 5nm to 50 μm.
Further, the thickness of the intermediate layer is 50nm to 10 μm.
In some preferred embodiments, the ceramic matrix includes any one or a combination of two or more of boron carbide, zirconium carbide, titanium carbide, tantalum carbide, hafnium carbide, tungsten carbide, silicon nitride, boron nitride, zirconium boride, hafnium boride, titanium boride, tantalum boride, aluminum oxide, zirconium oxide, hafnium oxide, mullite, and is not limited thereto.
Another aspect of the embodiments of the present invention further provides a method for preparing the ceramic connecting piece, which includes:
preparing a rare earth metal coating on the surface of the joint of the ceramic matrix by adopting at least any one of vacuum evaporation, arc ion plating, magnetron sputtering and spraying;
adopting solid-phase diffusion connection treatment to connect the ceramic matrixes;
and preparing a metal alternate layer stack on the surface of the intermediate layer at the joint of the obtained ceramic matrix at least by adopting any one mode of vacuum evaporation, arc ion plating, magnetron sputtering and spraying, thereby preparing the ceramic connecting piece.
In some preferred embodiments, the rare earth metal coating includes a combination of any two or more of Sc, la, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, lu, and is not limited thereto.
In some preferred embodiments, the rare earth metal coating forms the intermediate layer after a solid phase diffusion bonding process.
In some preferred embodiments, the solid phase diffusion bonding process specifically comprises solid phase bonding and/or braze bonding.
Another aspect of an embodiment of the present invention also provides the use of the ceramic connector described above in the field of nuclear fuel cladding, aerospace or electronic components.
The technical scheme of the present invention is further described in detail below with reference to several preferred embodiments and the accompanying drawings, and the embodiments are implemented on the premise of the technical scheme of the present invention, and detailed implementation manners and specific operation processes are given, but the protection scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples described below, unless otherwise specified, were all commercially available from conventional biochemicals.
Example 1
The antioxidant metal coating on the surface of the ceramic connecting piece takes Gd and Lu as an intermediate layer and titanium carbide ceramic as a ceramic matrix, and the surface coating is Cr-Ti-V-W-Cu-Ni, and the preparation method comprises the following specific steps:
(1) The Gd and Lu layers are prepared on the surface of titanium carbide ceramic by adopting arc ion plating, the thickness is controlled to be 10 mu m, and the specific preparation steps are as follows: etching and cleaning the sample in a vacuum chamber, and adjusting the vacuum degree to 8.0X10 -3 Pa, then driven by a radio frequency power supply, negative bias is adjusted to-20V, target current is 30A, the temperature of a sample stage is set to 200 ℃, the rotating speed is set to 20r/min, the deposition rate is controlled to 2 mu m/h, and Gd and Lu are respectively deposited on the connecting surface of the titanium carbide ceramic.
(2) The solid phase connection is adopted to connect the ceramic matrix by taking Gd and Lu as intermediate phases, and the preparation method comprises the following steps: grinding and polishing the material connection surface, placing into acetone, ultrasonic cleaning for 15min, placing into vacuum furnace, and vacuum degree is adjusted to 5.0X10 -3 Pa, controlling the temperature to 1000 ℃, heating up to 30 ℃/min, cooling down to 5 ℃/min, connecting for 2 hours, and controlling the pressure to 25MPa。
(3) A Cr-Ti-V-W-Cu-Ni coating was prepared on the surface of the joint by magnetron sputtering, as shown in FIG. 1, to a thickness of about 5. Mu.m. Finally, the Cr-Ti-V-W-Cu-Ni coating which is resistant to oxidation by high-temperature steam and takes Gd and Lu as intermediate layers on the surface of the titanium carbide ceramic connecting piece is obtained, and the preparation method comprises the following specific steps: etching and cleaning the sample in a vacuum chamber, and adjusting the vacuum degree to 8.0X10 - 3 Pa, driven by a direct current power supply, applying direct current negative bias voltage-30V on the substrate, setting the temperature of a sample stage to 350 ℃, setting the rotating speed of the sample stage to 10r/min, and controlling the deposition rate to 1.5 mu m/h to deposit a Cr-Ti-V-W-Cu-Ni film on the surface of the titanium carbide substrate.
Example 2
The antioxidation metal coating on the surface of the ceramic connecting piece takes Sm and Pr as intermediate layers and aluminum oxide and zirconium boride ceramic as ceramic matrixes, and the surface coating is Ti-V-Mo-Zr-Ta-Nb-Ni-Cr-Pt, and the preparation method comprises the following specific steps:
(1) Vacuum evaporation is adopted to prepare Sm and Pr layers on the surfaces of aluminum oxide and zirconium boride ceramics, the thickness is controlled at 20 mu m, and the specific preparation steps are as follows: transferring the connection sample as substrate into vacuum chamber, placing into quartz crucible as raw material, and adjusting vacuum degree to 1.0X10 -4 Pa, the temperature of the crucible is about 250-300 ℃, and the evaporation rate is kept atThe quartz crucible was heated left and right to evaporate Sm and Pr, and a Sm-Pr film was deposited on the surface of the joined sample.
(2) The brazing connection is adopted to connect the ceramic matrix by taking Sm and Pr as intermediate phases, and the specific preparation steps are as follows: cleaning the materials to be connected, placing the sample into a brazing furnace, preserving heat for 1h at 1450-1550 ℃ for connection, and keeping the vacuum degree at 3.0X10% -4 Pa。
(3) The Ti-V-Mo-Zr-Ta-Nb-Ni-Cr-Pt coating is prepared on the surface of the connecting piece by adopting arc ion plating, and the thickness of the Ti-V-Mo-Zr-Ta-Nb-Ni-Cr-Pt coating is about 2 mu m as shown in figure 2, and finally the Ti-V-Mo-Zr-Ta-Nb-Ni-Cr-Pt coating which takes Sm and Pr as intermediate layers and is oxidized by high-temperature steam is finally obtained on the surface of the aluminum oxide-zirconium boride ceramic connecting piece, wherein the specific preparation steps are as follows: performing sample in vacuum chamberEtching and cleaning, and adjusting the vacuum degree to 8.0x10 -3 Pa, then driven by a radio frequency power supply, negative bias is adjusted to 30V, target current is 30A, the temperature of a sample stage is set to 200 ℃, the rotating speed is set to 15r/min, the deposition rate is controlled to 2.5 mu m/h, and Ti-V-Mo-Zr-Ta-Nb-Ni-Cr-Pt coatings are sequentially deposited on the connecting surface of the ceramic matrix.
Example 3
The antioxidation metal coating on the surface of the ceramic connecting piece takes Ce and Ho as an intermediate layer and tantalum boride ceramic as a ceramic matrix, and the surface coating is W-Cu-V-Nb-Mo-Ta-Pt-Zr, and the preparation method comprises the following specific steps:
(1) Adopting arc ion plating to prepare Ce and Ho layers on the surface of tantalum boride ceramic, controlling the thickness to be 5 mu m, and specifically preparing the following steps: etching and cleaning the sample in a vacuum chamber, and adjusting the vacuum degree to 8.0X10 -3 Pa, then driven by a radio frequency power supply, negative bias is adjusted to 30V, target current 15A, the temperature of a sample stage is set to 200 ℃, the rotating speed is set to 10r/min, the deposition rate is controlled to 2.5 mu m/h, and Ce and Ho are respectively deposited on the connecting surface of zirconium boride ceramics.
(2) Adopts solid phase connection and takes Ce and Ho as intermediate phases to connect ceramic matrixes, and comprises the following specific preparation steps: grinding and polishing the material connection surface, placing into acetone, ultrasonic cleaning for 15min, placing into vacuum furnace, and vacuum degree is adjusted to 5.0X10 -3 Pa, controlling the temperature to 900 ℃, heating up to 25 ℃/min, cooling down to 5 ℃/min, connecting for 2 hours and controlling the pressure to 30MPa.
(3) The W-Cu-V-Nb-Mo-Ta-Pt-Zr coating was prepared on the surface of the connector by arc ion plating, as shown in FIG. 3, to a thickness of about 100nm. Finally, the W-Cu-V-Nb-Mo-Ta-Pt-Zr coating with Ce and Ho as intermediate layers and high-temperature steam oxidation resistance on the surface of the tantalum boride ceramic connecting piece is obtained, and the specific preparation steps are as follows: etching and cleaning the sample in a vacuum chamber, and adjusting the vacuum degree to 8.0X10 -3 Pa, then driven by a radio frequency power supply, negative bias is adjusted to-20V, target current is 15A, the temperature of a sample stage is set to 200 ℃, the rotating speed is set to 25r/min, the deposition rate is controlled to 0.5 mu m/h, and W-Cu-V-Nb-Mo-Ta-Pt-Zr coatings are sequentially deposited on the connecting surface of the ceramic matrix.
Example 4
The antioxidation metal coating on the surface of the ceramic connecting piece takes Pm and Tb as intermediate layers and titanium carbide and hafnium boride ceramic as ceramic matrixes, and the surface coating is Ni-Zr-Ta-Zr-Mo, and the preparation method comprises the following specific steps:
(1) The method adopts magnetron sputtering to prepare Pm and Tb layers on the surfaces of titanium carbide and hafnium boride ceramics, the thickness is controlled at 500nm, and the specific preparation steps are as follows: etching and cleaning the sample in a vacuum chamber, and adjusting the vacuum degree to 8.0X10 -3 Pa, driven by a direct current power supply, applying direct current negative bias voltage-25V on the substrate, setting the temperature of the sample stage to 450 ℃, setting the rotating speed of the sample stage to 20r/min, and controlling the deposition rate to 0.5 mu m/h to deposit Pm and Tb layers on the surface of the ceramic matrix respectively.
(2) Adopts braze welding connection to connect ceramic matrix by using Pm and Tb as intermediate phases, and comprises the following specific preparation steps: cleaning the materials to be connected, placing the sample into a brazing furnace, preserving heat for 1.5h at 1450-1550 ℃ for connection, and keeping the vacuum degree at 3.0X10 - 4 Pa。
(3) A Ni-Zr-Ta-Zr-Mo coating was prepared on the surface of the joint by vacuum evaporation, as shown in FIG. 4, to a thickness of about 15. Mu.m. Finally, the Ni-Zr-Ta-Zr-Mo coating with high temperature resistant vapor oxidation on the surface of the titanium carbide-hafnium boride ceramic connecting piece taking Pm and Tb as intermediate layers is obtained, and the specific preparation steps are as follows: transferring the connection sample as substrate into vacuum chamber, placing into quartz crucible as raw material, and adjusting vacuum degree to 1.0X10 -4 Pa, the temperature of the crucible is about 250-300 ℃, the evaporation rate is kept about 0.5A/s, the quartz crucible is heated to evaporate Ni, zr, ta, zr and Mo respectively, and a Ni-Zr-Ta-Zr-Mo layer film is deposited on the surface of the connected sample.
Comparative example 1
The antioxidant metal coating on the surface of the ceramic connecting piece takes Gd and Lu as an intermediate layer and titanium carbide ceramic as a ceramic matrix, and the surface coating is Cr-Ti-V-W-Cu-Ni, and the preparation method comprises the following specific steps:
(1) Gd and Lu layers were prepared on the surface of titanium carbide ceramic by arc ion plating, and the thickness was controlled to 10 μm, and the same preparation as in example 1 was performed.
(2) The preparation was the same as in example 1 using solid phase connection with Gd and Lu as intermediate phases to connect the ceramic matrix.
(3) The surface morphology of the connection piece without the Cr-Ti-V-W-Cu-Ni layer is shown in figure 5 after oxidizing for 2 hours in the water vapor condition of 1200 ℃.
(4) After the step (2), a Cr-Ti-V-W-Cu-Ni coating layer with a thickness of about 5 μm was prepared on the surface of the connector by magnetron sputtering, and then the connector was oxidized with steam at 1200 ℃ for 2 hours, the surface morphology of which is shown in FIG. 6, and the preparation was the same as that of example 1.
Example 5
The antioxidation metal coating on the surface of the ceramic connecting piece takes Sc, la and Ce as an intermediate layer and tungsten carbide ceramic as a ceramic matrix, and the surface coating is Cr-Ti-V-W-Cu-Ni, and the preparation method comprises the following specific steps:
(1) Arc ion plating is adopted to prepare Sc, la and Ce layers on the surface of tungsten carbide ceramic, the thickness is controlled at 10 mu m, and the specific preparation steps are as follows: etching and cleaning the sample in a vacuum chamber, and adjusting the vacuum degree to 8.0X10 -3 Pa, then driven by a radio frequency power supply, negative bias is adjusted to-20V, target current is 30A, the temperature of a sample stage is set to 200 ℃, the rotating speed is set to 20r/min, the deposition rate is controlled to 2 mu m/h, and Sc, la and Ce are respectively deposited on the connecting surface of the tungsten carbide ceramic.
(2) Adopts solid phase connection and uses Sc, la and Ce as intermediate phases to connect ceramic matrixes, and the specific preparation steps are as follows: grinding and polishing the material connection surface, placing into acetone, ultrasonic cleaning for 15min, placing into vacuum furnace, and vacuum degree is adjusted to 5.0X10 -3 Pa, controlling the temperature to 1000 ℃, heating up to 30 ℃/min, cooling down to 5 ℃/min, connecting for 2 hours and controlling the pressure to 25MPa.
(3) A Cr-Ti-V-W-Cu-Ni coating was prepared on the surface of the joint by magnetron sputtering, as shown in FIG. 1, to a thickness of about 5. Mu.m. Finally, the Cr-Ti-V-W-Cu-Ni coating which is resistant to oxidation by high-temperature steam and takes Gd and Lu as intermediate layers on the surface of the titanium carbide ceramic connecting piece is obtained, and the preparation method comprises the following specific steps: etching and cleaning the sample in a vacuum chamber, and adjusting the vacuum degree to 8.0X10 - 3 Pa, driven by a DC power supply, applying a DC negative bias voltage of-30V on the substrate, setting the temperature of the sample stage to 350 ℃, and setting the rotating speed of the sample stage toAnd (3) depositing a Cr-Ti-V-W-Cu-Ni film on the surface of the titanium carbide substrate at a deposition rate of 1.5 mu m/h at 10 r/min.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
It should be understood that the technical solution of the present invention is not limited to the above specific embodiments, and all technical modifications made according to the technical solution of the present invention without departing from the spirit of the present invention and the scope of the claims are within the scope of the present invention.
Claims (13)
1. A ceramic connector, comprising: the ceramic substrate comprises at least two ceramic substrates, an intermediate layer and a metal alternate layer lamination, wherein the intermediate layer is used for connecting the ceramic substrates, the metal alternate layer lamination is formed on the surface of the intermediate layer at the joint of the ceramic substrates, and the metal alternate layer lamination is formed by alternately laminating a plurality of metal layers;
the intermediate layer is selected from a combination of any two or more of Sc, la, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, lu;
the metal alternate layer is a metal layer containing at least two elements; the metal alternate layer stack has a multi-element layered structure; the metal layer is selected from any one of Ti, V, W, cu, zr, mo, ta, nb, ni, pt, cr.
2. The ceramic connector of claim 1, wherein: the thickness of the metal alternate layer stack is 5 nm-100 μm.
3. The ceramic connector of claim 2, wherein: the thickness of the metal alternate layer stack is 50 nm-20 mu m.
4. The ceramic connector of claim 1, wherein: the thickness of the metal layer is 20 nm-100 mu m.
5. The ceramic connector of claim 4, wherein: the thickness of the metal layer is 50 nm-20 mu m.
6. The ceramic connector of claim 1, wherein: the thickness of the intermediate layer is 1 nm-20 mu m.
7. The ceramic connector of claim 6, wherein: the thickness of the intermediate layer is 2 nm-500 nm.
8. The ceramic connector of claim 1, wherein: the ceramic matrix is selected from any one or more than two of boron carbide, zirconium carbide, titanium carbide, tantalum carbide, hafnium carbide, tungsten carbide, silicon nitride, boron nitride, zirconium boride, hafnium boride, titanium boride, tantalum boride, aluminum oxide, zirconium oxide, hafnium oxide and mullite.
9. A method of producing a ceramic joint according to any one of claims 1 to 8, characterized by comprising:
preparing a rare earth metal coating on the surface of the joint of the ceramic matrix by adopting at least any one of vacuum evaporation, arc ion plating, magnetron sputtering and spraying;
adopting solid-phase diffusion connection treatment to connect the ceramic matrixes;
and preparing a metal alternate layer stack on the surface of the intermediate layer at the joint of the obtained ceramic matrix at least by adopting any one mode of vacuum evaporation, arc ion plating, magnetron sputtering and spraying, thereby preparing the ceramic connecting piece.
10. The method of manufacturing according to claim 9, wherein: the rare earth metal coating is selected from the combination of any two or more of Sc, la, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, lu.
11. The method of manufacturing according to claim 9, wherein: the rare earth metal coating is subjected to solid-phase diffusion welding treatment to form the intermediate layer.
12. The method of manufacturing according to claim 9, wherein: the solid phase diffusion welding process is specifically selected from solid phase joining and/or brazing joining.
13. Use of the ceramic connector of any one of claims 1-8 in the field of nuclear fuel cladding, aerospace or electronic components.
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