CN105585326B - A kind of technique of nanometer of foil diffusion connection carbon/silicon carbide ceramic matrix composite - Google Patents

A kind of technique of nanometer of foil diffusion connection carbon/silicon carbide ceramic matrix composite Download PDF

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CN105585326B
CN105585326B CN201510983420.0A CN201510983420A CN105585326B CN 105585326 B CN105585326 B CN 105585326B CN 201510983420 A CN201510983420 A CN 201510983420A CN 105585326 B CN105585326 B CN 105585326B
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connection
foil
silicon carbide
nanometer
technique
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CN105585326A (en
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熊华平
陈波
李文文
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BEIJING INSTITUTE OF AERONAUTICAL MATERIALS CHINA AVIATION INDUSTRY GROUP Corp
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BEIJING INSTITUTE OF AERONAUTICAL MATERIALS CHINA AVIATION INDUSTRY GROUP Corp
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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
    • C04B37/006—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 consisting of metals 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
    • 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
    • C04B2237/121—Metallic interlayers based on aluminium
    • 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
    • C04B2237/30—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
    • 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
    • C04B2237/30—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
    • C04B2237/363—Carbon
    • 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
    • C04B2237/30—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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Products (AREA)

Abstract

The present invention relates to the techniques of a kind of nanometer of foil diffusion connection carbon/silicon carbide ceramic matrix composite, belong to welding manufacture technical field.Since the processing performance of ceramics and ceramic matric composite is poor, heat-resistant impact ability is weak, both at home and abroad in the connection of ceramics or ceramic matric composite, soldering connection generally is carried out using traditional Ag Cu Ti, Cu Ti systems active solder, but corresponding connector heat resisting temperature is difficult more than 500 DEG C.The present invention provides a kind of low-temperature activation connection, heat safe connection method of connector available for SiC ceramic based composites, the foil being alternately superimposed by using Ti the and Al metal layers of nanometer grade thickness is as solder, by hot-pressing sintering method, realize the connection of carbon/silicon carbide ceramic matrix composite, not only room temperature intensity is high for the jointing of acquisition, but also more than the 75% of room temperature strength of joint can be stablized to 1100 DEG C of high temperature.

Description

A kind of technique of nanometer of foil diffusion connection carbon/silicon carbide ceramic matrix composite
Technical field
The present invention relates to the techniques of a kind of nanometer of foil diffusion connection carbon/silicon carbide ceramic matrix composite, belong to welding manufacture Technical field.
Background technology
Ceramics, ceramic matric composite are the high temperature resistant structure ceramics having very much using future, in recent years especially with carbonization Silicon ceramics (SiC), Ceramic Matrix Composites Reinforced by Carbon Fibers (Cf/ SiC), and silicon carbide fiber reinforced silicon carbide ceramics Based composites (SiCf/ SiC) and silicon/silicon carbide ceramic matric composite (Si/SiC) be in high temperature resistant structure ceramics Than more typical representative.
But since the processing performance of ceramics and ceramic matric composite is poor, heat-resistant impact ability is weak and manufacture size The shortcomings of big and complex-shaped part is more difficult, it usually needs pass through the connection of ceramics and ceramic matric composite itself Realize the manufacture of complex component, and jointing must is fulfilled for heat safe requirement.
It should say, ceramic material belongs to difficult welding material, general both at home and abroad in the connection of ceramics or ceramic matric composite Soldering connection is carried out all over using traditional Ag-Cu-Ti, Cu-Ti system active solder, but corresponding connector heat resisting temperature is difficult to be more than 500℃.Cu-Pd-V, Au-Cu-Pd-V isoreactivity solder can also be used for the company of Ceramic Matrix Composites Reinforced by Carbon Fibers It connects, but the heat resisting temperature of connector is also no more than 800 DEG C.Ceramic joining technology discloses also having for report and uses Ni base solder alloy prickers The result of study of ceramic matric composite is welded, but itself connector room temperature bending strength only has 58 MPa or so, it is female far below by weldering Material.Still lack applicable high temperature conjunction solder and suitable high temperature resistant Joining Technology currently for SiC ceramic based composites.
Also there is the connection that use infiltration in the green body containing carbon enters the reaction method progress silicon carbide ceramics of silicon in recent years Report, but solder early period processing procedure and Joining Technology it is complicated, connection temperature is up to 1400 DEG C or more, on the one hand welds Process energy consumption is big, and the residual quantity that infiltration silicon does not react completely in another aspect connector is uncontrollable, therefore jointing performance It is unstable.In addition, the above method because connection temperature is too high, can not be suitable for the connection of SiC ceramic and metal.Moreover, for Carbon/silicon carbide ceramic matrix composite, such as Cf/ SiC ceramic based composites, SiCf/ SiC ceramic based composites or Si/ SiC ceramic based composites, because the component of composite material is more complicated, their interconnection technique is more multiple compared with SiC ceramic Process that is miscellaneous, being connected currently without simple, practical and quality controllable high temperature resistant.
The content of the invention
The technical problems to be solved by the invention are：For above-mentioned technical need and the deficiencies in the prior art, one kind is provided Low-temperature activation connection, the heat safe connection of connector of SiC ceramic based composites available for carbon/silicon carbide ceramic matrix composite Method.
Here SiC ceramic based composites include SiC ceramic, Cf/ SiC ceramic based composites, SiCf/ SiC ceramic base is answered Condensation material or Si/SiC ceramic matric composites.
The technical solution of the present invention is the work of a kind of nanometer of foil diffusion connection carbon/silicon carbide ceramic matrix composite Skill, the technique comprise the following steps：First, the foil that the Ti and Al metal layers of nanometer grade thickness are alternately superimposed is prepared；Next, with The nanometer foil is placed it between soldered SiC ceramic based composites as solder, using vacuum diffusion welding or Hot-pressing sintering method under the conditions of vacuum-argon gas, temperature are 1000 DEG C~1250 DEG C, and pressure is 10MPa~30MPa, realizes carbon The connection of SiClx ceramic matric composite.
The thickness of each metal layer is 15nm~100nm in the nanometer foil, and overall thickness is 30 μm~100 μm.
The hot pressed sintering is hot pressing discharge plasma sintering.
Hot pressed sintering under the conditions of vacuum diffusion welding or vacuum-argon gas, pyroreaction Connection Time are 3~60 minutes.
The reaction time of hot pressing discharge plasma sintering method is used as 3~10 minutes.
The technique can be also used for the connection between C-C composite.
The present invention can provide the process of the heat-resisting material connection of stable quality for SiC ceramic based composites. Compared with other connection methods, the invention has the advantages that：
1. the solder used is made of the foil that the Ti/Al double-metal layers of nanometer grade thickness alternately change, it has high Activity, for example light the Ti/Al nanometer foils of 30 μm~100 μm of overall thickness at room temperature, its burning in atmospheric conditions Speed reaches 10m/s, therefore high activity causes to realize SiC potteries at a temperature of 150 DEG C~300 DEG C lower than conventional connection methods The connection of porcelain or SiC ceramic based composites, therefore welding procedure is significantly energy saving；
2. due to the high activity for the foil that nanometer grade thickness Ti/Al double-metal layers alternately change, pass through fire-bar Activation diffusion reaction under part, the high-melting-points such as TiC, Ti-Si-C, Ti-Al-C can be being generated with the linkage interface of SiC ceramic Object phase or ceramic phase are closed, not only room temperature intensity is high for the SiC ceramic connector or SiC ceramic based composites jointing of acquisition, I.e. room temperature flexural intensity reaches 220MPa~350MPa, and more than the 75% of room temperature strength of joint can be stablized to 1100 DEG C High temperature；
3. the technical solution in the present invention is not only suitable for above-mentioned 4 class SiC ceramic based composites, in addition C/C composite materials The connection of totally 5 class composite material their owns can be also used for the mutually weldering two-by-two between this 5 class composite material.
Specific embodiment
Nanometer grade thickness double-metal layer Ti/Al alternatings are prepared using the methods of electron beam-physical vapour deposition (PVD) (EB-PVD) The thickness control of the foil of variation, wherein single-layer metal is 15nm~100nm, and the overall thickness control of bimetallic nano foil is 30 μm~100 μm, and this nanometer foil is used to be placed in the SiC ceramic welded or SiC ceramic based composites as solder, It is either either placed between C/C composite materials between the above-mentioned two kinds of materials welded using vacuum diffusion welding or vacuum-argon Hot pressed sintering or hot pressing discharge plasma sintering method under the conditions of gas pass through nanometer foil under 1000 DEG C~1250 DEG C high temperature Exothermic reaction between middle Ti/Al dual elements and they between the SiC ceramic or SiC ceramic based composites welded Activation diffusion reaction realize connection.Apply pressure 10MPa~30MPa during reaction forming.Using vacuum diffusion welding or Hot-pressing sintering method under the conditions of vacuum-argon gas, pyroreaction Connection Time are 3~60 minutes.According to hot pressing electric discharge etc. from Sub- sintering method diffusion connection, then the reaction time is 3~10 minutes.
Embodiment one
Select thickness of the foil that nanometer grade thickness double-metal layer Ti/Al alternately changes as solder, wherein single-layer metal For 15nm~40nm, the overall thickness of bimetallic nano foil is 30 μm~50 μm, using the hot pressed sintering under the conditions of vacuum-argon gas Method, the heating rate in heating process is 15 DEG C~20 DEG C/min, anti-by the diffusion under 1150 DEG C~1200 DEG C high temperature Should, apply pressure 10MPa~15MPa in reaction process, when the reaction time 3~60 is small.After connection the cold of room temperature is down to from high temperature But speed is 2 DEG C~6 DEG C/min.
Embodiment two
Select thickness of the foil that nanometer grade thickness double-metal layer Ti/Al alternately changes as solder, wherein single-layer metal For 30nm~50nm, the overall thickness of bimetallic nano foil is 40 μm~70 μm, is discharged using the hot pressing under the conditions of vacuum-argon gas Plasma agglomeration method, the heating rate in heating process is 40 DEG C~100 DEG C/min, by 1100 DEG C~1200 DEG C high temperature Lower Si and C element reaction in-situ apply pressure 15MPa~30MPa, 4~8 minutes reaction time in reaction process.After connection from The cooling velocity that high temperature is down to room temperature is 30 DEG C~100 DEG C/min.
Embodiment three
Select thickness of the foil that nanometer grade thickness double-metal layer Ti/Al alternately changes as solder, wherein single-layer metal For 40nm~80nm, the overall thickness of bimetallic nano foil is 40 μm~100 μm, using vacuum diffusion welding method, heating process In heating rate for 15 DEG C~20 DEG C/min, by the diffusion reaction under 1150 DEG C~1250 DEG C high temperature, in reaction process Apply pressure 15MPa~25MPa, 3~60 minutes reaction time.The cooling velocity of room temperature is down to after connection from high temperature as 2 DEG C~6 ℃/min。
Above-mentioned three kinds of embodiments, have carried out SiC ceramic, Cf/ SiC ceramic based composites, and SiCf/ SiC ceramic base is answered Condensation material and Si/SiC ceramic matric composites this four major classes materials, and C/C composite materials totally 5 class composite materials they Mutually weldering two-by-two between the connection of itself and this 5 class composite material.
The room temperature flexural intensity of the above-mentioned four classes SiC ceramic based composites their own jointing obtained reaches 220MPa~350MPa, and more than the 75% of room temperature strength of joint can be stablized to 1100 DEG C of high temperature；The C/C of acquisition is compound The room temperature shear strength of material itself jointing reaches 30MPa~45MPa, and more than the 75% of the room temperature intensity can be steady Fixed to 1100 DEG C of high temperature.The room temperature flexural intensity of the dissimilar material joining connector of acquisition reaches materials to be welded self-strength 70%~80%, and more than the 75% of the intensity value can be stablized to 1100 DEG C of high temperature.
Separately it should be noted that, all specific embodiments described in the present invention, title etc. can not used in formula, technique Together.The equivalent or simple change that all constructions based on described in inventional idea of the present invention, feature and principle are done, is included in this hair In bright scope of patent protection.

Claims (5)

1. the technique of a kind of nanometer of foil diffusion connection carbon/silicon carbide ceramic matrix composite, which is characterized in that the technique include with Lower step：First, the Ti metal layers of nanometer grade thickness and Al metal layers are prepared, alternately superposition forms foil to the two；Secondly, with paper tinsel Band is placed it between soldered SiC ceramic based composites, as solder using vacuum diffusion welding or vacuum-argon gas Under the conditions of hot-pressing sintering method, temperature be 1000 DEG C~1250 DEG C, pressure be 10MPa~30MPa, realize carbon/silicon carbide ceramic matrix The connection of composite material；The thickness of each metal layer is 15nm~100nm in foil, and overall thickness is 30 μm~100 μm.
2. technique according to claim 1, it is characterised in that：The hot pressed sintering is hot pressing discharge plasma sintering.
3. technique according to claim 1, it is characterised in that：Hot pressing under the conditions of vacuum diffusion welding or vacuum-argon gas Sintering, pyroreaction Connection Time are 3~60 minutes.
4. technique according to claim 2, it is characterised in that：Using the reaction time of hot pressing discharge plasma sintering method For 3~10 minutes.
5. technique according to claim 1, it is characterised in that：The technique can be also used for the company between C-C composite It connects.
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CN111848226B (en) * 2019-04-24 2022-03-25 成都大学 Nano metal layer ceramic substrate and manufacturing method thereof
DE102019135171A1 (en) * 2019-12-19 2021-06-24 Rogers Germany Gmbh Solder material, method for producing such a solder material and use of such a solder material for connecting a metal layer to a ceramic layer
CN111725085B (en) * 2020-06-16 2022-04-22 杰群电子科技（东莞）有限公司 Semiconductor device and packaging method thereof
CN113385851B (en) * 2021-05-28 2022-11-11 中国科学院上海硅酸盐研究所苏州研究院 High-temperature-resistant corrosion-resistant solder for silicon carbide ceramic connection and preparation method and application thereof
CN115319259B (en) * 2022-08-22 2024-06-07 中国航发北京航空材料研究院 Ti/Nb+V composite intermediate layer for TiAl alloy/steel connection and diffusion welding method
CN115319261A (en) * 2022-08-22 2022-11-11 中国航发北京航空材料研究院 Ti/Al + X composite intermediate layer for TiAl/nickel-based superalloy connection and diffusion welding method

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US20070023489A1 (en) * 2000-05-02 2007-02-01 Swiston Albert J Jr Method of joining components using amorphous brazes and reactive multilayer foil
US7270885B1 (en) * 2001-11-14 2007-09-18 Marlene Rossing, legal representative Method for brazing ceramic-containing bodies, and articles made thereby
CN102814600B (en) * 2012-08-28 2015-05-20 广州有色金属研究院 Amorphous foil brazing filler metal for ceramic braze welding
CN103273155B (en) * 2013-05-10 2015-07-08 山东大学 Diffusion bonding method of silicon carbide ceramics and ferritic stainless steel

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