US20070235122A1 - Process for the low-deformation diffusion welding of ceramic components - Google Patents

Process for the low-deformation diffusion welding of ceramic components Download PDF

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US20070235122A1
US20070235122A1 US11/224,296 US22429605A US2007235122A1 US 20070235122 A1 US20070235122 A1 US 20070235122A1 US 22429605 A US22429605 A US 22429605A US 2007235122 A1 US2007235122 A1 US 2007235122A1
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components
component
joined
particularly preferably
ceramic
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Frank Meschke
Ursula Kayser
Andreas Rendtel
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ESK Ceramics GmbH and Co KG
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ESK Ceramics GmbH and Co KG
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Assigned to ESK CERAMICS GMBH & CO., KG reassignment ESK CERAMICS GMBH & CO., KG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KAYSER, URSULA, MESCHKE, FRANK, RENDTEL, ANDREAS
Publication of US20070235122A1 publication Critical patent/US20070235122A1/en
Priority to US12/385,608 priority Critical patent/US8087567B2/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
    • B23K20/02—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating by means of a press ; Diffusion bonding
    • B23K20/021—Isostatic pressure welding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
    • B23K20/02—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating by means of a press ; Diffusion bonding
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
    • C04B35/575—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained by pressure sintering
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C04B35/645—Pressure sintering
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • 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
    • C04B37/001—Joining burned ceramic articles with other burned ceramic articles or other articles by heating directly with other burned ceramic articles
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D25/00—Component parts, details, or accessories, not provided for in, or of interest apart from, other groups
    • F01D25/28—Supporting or mounting arrangements, e.g. for turbine casing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2101/00—Articles made by soldering, welding or cutting
    • B23K2101/001—Turbines
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3821—Boron carbides
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/782—Grain size distributions
    • C04B2235/783—Bimodal, multi-modal or multi-fractional
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
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    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/36—Non-oxidic
    • C—CHEMISTRY; METALLURGY
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    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/36—Non-oxidic
    • C04B2237/365—Silicon carbide
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    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/36—Non-oxidic
    • C04B2237/368—Silicon nitride
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    • 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
    • C04B2237/66—Forming laminates or joined articles showing high dimensional accuracy, e.g. indicated by the warpage
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]

Definitions

  • the invention relates to a process for the low-deformation diffusion welding of ceramic components, to the monoliths produced by this process and to their applications.
  • Ceramic components are in general use in plant and mechanical engineering where wear, corrosion and high thermal loads occur.
  • the hardness, chemical stability and high-temperature stability of ceramics is far superior to the corresponding properties of steels.
  • silicon carbide as a representative of industrial ceramics, has the particular advantage of an extremely good thermal conductivity (four times better than that of steel). This predestines the material not only for use in nozzles, valves, axial face seals and sliding-contact bearings but also for use in reactors, such as for example tube bundle heat exchangers or diesel particulate filters.
  • the ceramic components have to be of very complex shape for design reasons. The design is often incompatible with available ceramic shaping processes, which makes it necessary to join individual constituents.
  • U.S. Pat. No. 4,925,608 (1990) describes as a process the diffusion welding of slightly pre-sintered SiC components based on hot isostatic pressing in order to obtain a cohesive, seamless SiC bond.
  • particular emphasis is placed on the ⁇ -modification of SiC and the higher sintering activity of the components, which are still up to 85% porous.
  • Temperatures of >1700° C. and pressures of greater than 150 MPa are preferred. Since densification of the porous components still occurs during the joining, correspondingly high degrees of plastic deformation occur.
  • the object is achieved by virtue of the fact that the components that are to be joined are brought into contact with one another in a diffusion-welding process in the presence of a shielding gas atmosphere and are joined with little deformation, under the application of a temperature of at least 1600° C., and if appropriate a load, to form a monolith, the components which are to be joined experiencing plastic deformation in the direction in which force is introduced of less than 5%, preferably less than 1%.
  • the diffusion welding is preferably a hot-pressing process.
  • FIG. 1 is a graph, illustrating creep rate of SiC materials as a function of temperature.
  • FIG. 2 is a photomicrograph showing a microreactor formed in a joining cycle, formed of a coarse-grained SSiC.
  • FIG. 3 is a photomicrograph showing a polished ground section of a monolith joined from 6 components.
  • FIG. 4 is a photomicrograph showing coarse-grained SSiC components, in which the grains of the two plates grow into one another and thereby dissolve the component interface.
  • FIG. 5 is a photomicrograph showing a polished section of the microstructure.
  • FIG. 6 is a photomicrograph showing the polished ground section of the component.
  • FIG. 7 is a photomicrograph showing a plane of adjacent grain boundaries after an etching treatment to uncover interfaces.
  • the resistance to plastic deformation in the high-temperature range is referred to as the high-temperature creep resistance.
  • What is known as the creep rate is used as a measure of the creep resistance.
  • the creep rate of the materials to be joined can be used as a central parameter for minimizing the plastic deformation in a joining process for the seamless joining of sintered ceramic components.
  • SSiC sintered SiC materials
  • the creep resistance of ceramic materials can generally be increased considerably by two strategies:
  • Both strategies are equally suitable for producing creep-resistant materials with a sintering activity and to allow low-deformation joining of components produced therefrom.
  • At least one of the components that are to be joined consist of a material whereof the creep rate in the joining process is always lower than 2 ⁇ 10 ⁇ 4 -1/s, preferably always lower than 8 ⁇ 10 ⁇ 5 1/s, particularly preferably always lower than 2 ⁇ 10 ⁇ 5 1/s.
  • the ceramic material is preferably selected from the group consisting of titanium diboride, boron carbide, silicon nitride, silicon carbide and mixtures thereof.
  • the material may contain further material components amounting to up to 35% by volume, preferably less than 15%, particularly preferably less than 5%, such as for example graphite, boron carbide or other ceramic particles, preferably nanoparticles.
  • Sintered SiC with a bimodal grain size distribution which is particularly suitable for the process according to the invention is SSiC with a mean grain size of greater than 5 ⁇ m, preferably greater than 20 ⁇ m, particularly preferably greater than 50 ⁇ m.
  • the mean grain size of the material is therefore higher by a factor of 10-100 than that of conventionally sintered, fine-grained SiC with a mean grain size of just approx. 5 ⁇ m.
  • What is known as coarse-grained sintered silicon carbide (SSiC) for this reason has a considerably higher creep resistance than fine-grained SSiC.
  • the literature does not give any details as to creep rates of modern SiC materials of this type.
  • FIG. 1 illustrates the lower creep rate of a coarse-grained SSiC (mean grain size approx. 200 ⁇ m) for various temperatures and compares it under identical load conditions to a fine-grained SSiC variant (mean grain size 5 ⁇ m), which is marketed, for example, under the name EKasic® F by ESK Ceramics GmbH & Co. KG.
  • the process according to the invention is preferably carried out at a temperature of >1600° C., in particular >1800° C., particularly preferably >2000° C.
  • the process is preferably carried out at a pressure of >10 kPa, preferably >1 MPa, particularly preferably >10 MPa.
  • the temperature-holding time is preferably at least 10 min, particularly preferably at least 30 min.
  • the process according to the invention can be used to produce ceramic components of complex shape to form near net shape components for plant and mechanical engineering with an extremely high thermal stability, corrosion resistance or wear resistance. Reactors in which the seals or solder seams have hitherto formed the weak points can now be produced as a seamless monolith.
  • the process can be used, for example, to produce plate-type heat exchangers from sintered SiC ceramic with an extremely high thermal stability and corrosion resistance.
  • Plate-type heat exchangers have already been produced by reaction bonding from Si-infiltrated SiC ceramic (Si—SiC).
  • Si—SiC Si-infiltrated SiC ceramic
  • the corrosion resistance which is not universal, however, constitutes a considerable restriction on the possible applications.
  • Filters and in particular ceramic microreactors can now likewise be produced as a monolith from sintered SiC ceramic.
  • microreactors with channels designed for cross-current can now also be formed as a SSiC monolith.
  • heating elements made from electrically conductive SSiC ceramic, for example for furnaces and reactors.
  • Linings, impact protection means or first wall components for fusion reactors are also conceivable.
  • Other highly creep-resistant components of complex shape for high-temperature technology such as furnace rolls, furnace holding means and burner components, can also be formed.
  • More or less complex structural components, such as deformation tools, plates, tubes, flanges or hermetically sealed containers, can in this way be joined from insulating or electrically conductive nonoxide ceramic.
  • the invention also relates to components made from a nonoxide ceramic with at least one seamless join.
  • the component prefferably has a bending rupture strength of >150 MPa, particular preferably >250 MPa, measured using the 4-point method, at the seamless join.
  • the bending rupture strength of the components according to the invention is particularly preferably just as high in the region of the seamless join as in the base material of the component.
  • the component is preferably a structural component or functional component, preferably a container, tube, reactor, lining, valve, heat exchanger, heating element, plating, a wearing component, such as a sliding-contact bearing or an axial face seal, a brake, a clutch, a nozzle or a deformation tool.
  • a wearing component such as a sliding-contact bearing or an axial face seal, a brake, a clutch, a nozzle or a deformation tool.
  • the invention also relates to the use of components produced by the process according to the invention as structural components and functional components, including containers, reactors, linings, valves, heat exchangers, deformation tools, nozzles, platings.
  • said components consist of particularly coarse-grained SSiC-ceramic (mean grain size >50 ⁇ m). Not only is the low-deformation joining then easier, but also the corrosion resistance of the components is considerably improved as a result.
  • Polished plates with dimensions of 50 ⁇ 35 ⁇ 5 mm made from sintered coarse-grained SiC (mean grain size approx. 200 ⁇ m) are put on top of one another in a hot press to form a stack.
  • a joining cycle using a nitrogen atmosphere, a temperature of 2150° C., a load of 11.4 MPa and a holding time of 45 min leads to plastic deformation in the direction in which force is introduced at less than 1%.
  • the joined component represents a seamless monolith.
  • the creep rate of this SSiC material is less than 2 ⁇ 10 ⁇ 5 1/s at 2150° C.
  • This joining cycle can be used, for example, to produce a microreactor as shown in FIG. 2 as a monolith.
  • the ground section at 45° to the channel direction reveals that the monolith consists homogeneously of a coarse-grained SSiC, the channels do not have any deformation and there are no seams.
  • Polished plates with dimensions of 50 ⁇ 35 ⁇ 5 mm made from different sintered SiC grades are placed on top of one another in a hot press to form a stack.
  • 2 plates made from coarse-grained (mean grain size approx. 200 ⁇ m), fine-grained SSiC material (mean grain size approx. 5 ⁇ m) and 2 plates made from an SSiC composite material with an initial medium grain size (approx. 50 ⁇ m) are used for the monolith that is to be joined.
  • the stack is subjected to a load of 11.4 MPa for 45 min under a nitrogen atmosphere at a temperature of 2150° C.
  • FIG. 3 shows the polished ground section of the monolith joined from 6 components.
  • Plastic deformation of approx. 15% parallel to the direction in which force is introduced is present in the component only where fine-grained SiC material was initially present (2 plates in the left-hand part of the figure).
  • the coarse-grained SiC material (2 plates in the right-hand part of the figure) and also the SSiC material with a medium grain size (2 plates in the middle) remain dimensionally stable (deformation ⁇ 1%) during joining.
  • This example demonstrates that even components made from selected different SiC grades can be joined to one another seamlessly and with little deformation to form a monolith.
  • the polished ground section shown does not reveal a boundary under the microscope at any of the joins. Even etching of the ground section, which uncovers the grain boundaries, does not reveal a seam. Instead, as can be seen in FIG. 4 on the basis of the coarse-grained SSiC components, the grains of the two plates grow into one another and thereby dissolve the component interface. The same phenomenon occurs at the joins formed between pairs of the same material and at the joins between SiC components of different types. A very high mechanical strength results from the good joining. The strength of a bending bar produced from the component exceeds 290 MPa in the 4-point bending test.
  • FIG. 3 illustrates that the microstructures of all three SSiC materials become coarser during this joining cycle at a very high temperature.
  • polished plates with dimensions of 50 ⁇ 35 ⁇ 5 mm made from different sintered SiC grades were placed on top of one another in a hot press to form a stack.
  • 2 plates of coarse-grained (mean grain size approx. 200 ⁇ m), fine-grained SSiC material (mean grain size approx. 5 ⁇ m) and 2 plates of an SSiC composite material with an initial medium grain size of approx. 50 ⁇ m are used for the monolith that is to be joined.
  • the stack is subjected to a lower temperature of 1800° C. under a nitrogen atmosphere, once again using a load of 11.4 MPa for 45 min.
  • the creep rate of the fine-grained SSiC at this temperature is sufficiently low for low-deformation joining of all the SSiC components to one another.
  • All the SSiC grades, including the fine-grained SSiC have a plastic deformation in the direction in which force is introduced of less than 1%.
  • the creep rate of all the SSiC materials is less than 2 ⁇ 10 ⁇ 5 1/s at 1800° C.
  • Polished plates with dimensions of 50 ⁇ 35 ⁇ 5 mm made from fine-grained, sintered SSiC (mean grain size approx. 5 ⁇ m) are placed on top of one another in a hot press to form a stack.
  • the creep rate of this SSiC material which has been coarsened in situ is less than 2 ⁇ 10 ⁇ 5 1/s at 2150° C.
  • Polished plates (50*50*6 mm) made from a particle-reinforced boron carbide are placed on top of one another in a hot press to form a stack.
  • the creep rate of this material at 2150° C. is less than 8 ⁇ 10 ⁇ 5 1/s.
  • FIG. 6 shows the polished ground section of the component. Microscopic examination does not reveal any seams at the join. The grains of components facing one another do not grow together. Instead, the joining cycle converts the component interfaces into a grain boundary which forms part of a polycrystalline monolith. A plane of adjacent grain boundaries can be seen after an etching treatment to uncover interfaces ( FIG. 7 ).
  • Polished plates made from sintered SiC (mean grain size approx. 5 ⁇ m) with dimensions of 50 ⁇ 35 ⁇ 5 mm are placed on top of one another in a hot press to form a stack.
  • the creep rate of this SiC material is approx. 2 ⁇ 10 ⁇ 4 1/s at 2150° C.

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US8998268B2 (en) 2012-03-22 2015-04-07 Saint-Gobain Ceramics & Plastics, Inc. Sinter bonded ceramic articles
CN104741615A (zh) * 2015-04-08 2015-07-01 华北电力大学（保定） 一种超细晶双峰铜的制备方法
US9290311B2 (en) 2012-03-22 2016-03-22 Saint-Gobain Ceramics & Plastics, Inc. Sealed containment tube
US9995417B2 (en) 2012-03-22 2018-06-12 Saint-Gobain Ceramics & Plastics, Inc. Extended length tube structures
CN113185315A (zh) * 2021-03-29 2021-07-30 岭东核电有限公司 核用碳化硅包壳快速连接方法、SiC包壳及其应用
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US20100322829A1 (en) * 2007-02-27 2010-12-23 Boostec S.A. Process for manufacturing a device of heat exchanger type made of ceramic, and devices obtained by the process
US8998268B2 (en) 2012-03-22 2015-04-07 Saint-Gobain Ceramics & Plastics, Inc. Sinter bonded ceramic articles
US9290311B2 (en) 2012-03-22 2016-03-22 Saint-Gobain Ceramics & Plastics, Inc. Sealed containment tube
US9751686B2 (en) 2012-03-22 2017-09-05 Saint-Gobain Ceramics & Plastics, Inc. Sinter bonded containment tube
US9995417B2 (en) 2012-03-22 2018-06-12 Saint-Gobain Ceramics & Plastics, Inc. Extended length tube structures
CN104741615A (zh) * 2015-04-08 2015-07-01 华北电力大学（保定） 一种超细晶双峰铜的制备方法
US11390566B2 (en) 2017-12-19 2022-07-19 Tokai Carbon Korea Co., Ltd Bonded ceramic and manufacturing method therefor
CN113185315A (zh) * 2021-03-29 2021-07-30 岭东核电有限公司 核用碳化硅包壳快速连接方法、SiC包壳及其应用

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ATE509727T1 (de) 2011-06-15
WO2006029741A1 (de) 2006-03-23
CN1827279A (zh) 2006-09-06
US20090239007A1 (en) 2009-09-24
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US8087567B2 (en) 2012-01-03

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