CN100427437C - High temperature solder in use for braze welding ceramics of silicon nitride and composite materials based on ceramics of silicon nitride - Google Patents

High temperature solder in use for braze welding ceramics of silicon nitride and composite materials based on ceramics of silicon nitride Download PDF

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CN100427437C
CN100427437C CNB2007100872927A CN200710087292A CN100427437C CN 100427437 C CN100427437 C CN 100427437C CN B2007100872927 A CNB2007100872927 A CN B2007100872927A CN 200710087292 A CN200710087292 A CN 200710087292A CN 100427437 C CN100427437 C CN 100427437C
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silicon nitride
solder
nitride ceramics
surplus
soldering
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CN101050127A (en
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熊华平
陈波
毛唯
郭万林
李晓红
程耀永
叶雷
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Beijing Institute of Aeronautical Materials China Aviation Industry No 1 Group Corp
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Abstract

This invention discloses a high-temperature brazing filler metal for brazing silicon nitride ceramic or silicon nitride ceramic-based composite. The brazing filler metal is composed of: Co 18.0-45.0 wt.%, Au 0.0-33 wt.%, Ni 0.0-12.0 wt.%, V 1.5-22.0 wt.%, Si 0.0-3.9 wt.%, B 0.0-2.9 wt.%, and Pd as balance. Si3N4 ceramic/Si3N4 ceramic joint with a bending strength of 250-370 MPa at room temperature can be obtained at 1140-1296 deg.C with the brazing filler metal. The brazing filler metal can be used for brazing silicon nitride ceramic or silicon nitride ceramic-based composite at high temperatures.

Description

The high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites
Technical field
The present invention is a kind of high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites, belongs to welding technology field.
Background technology
Si 3N 4Pottery and Si 3N 4Ceramic matric composite is that the high temperature resistant structure ceramics of using future is arranged very much.But because the poor processability of stupalith, heat-resistant impact ability is weak and manufacturing dimension is big and complex-shaped part shortcoming such as difficulty comparatively, need form that composite structure is used with metallic substance usually or the manufacturing that realizes complex component that is connected by pottery self.
At Si 3N 4During the soldering of pottery connects, use morely traditional Ag-Cu-Ti (A P Xian, Z Y Si.Journal of Materials Science.1992,27:1560), Cu-Ti (Zhai Yang, Ren Jialie, Zhuan Lijun, Cao Yuqing, Sun Lijun. Acta Metallurgica Sinica .1995,31 (9): B423) be active solder etc., though some brazed joint intensity is higher, the high-temperature behavior of joint is poor, thereby has restricted the performance of structural ceramics high-temperature behavior.
Be connected in the new type high temperature solder of usefulness with metal at the research pottery since external more than ten years recently, design morely and contain noble metal or be the solder composition of base with noble metal Au, Pd, Pt, Ag-Pd, goal in research is that joint after the soldering can be worked under 650 ℃ or higher temperature, and what wherein obtain better result has Au-base solder such as Au-33~35Ni-3~4.5Cr-1~2Fe-1~2Mo (wt%) and Au-36.6Ni-4.7V-1Mo solders such as (at.%).Use above-mentioned Au-Ni-Cr-Fe-Mo solder brazing Si 3N 4/ Incoloy909 (iron-based low expansion alloy) though the joint intensity level under 650 ℃ of temperature that obtains is higher, (the S Kang and H J Kim that descends occurred compared with room temperature, Wel ding Journal, 1995,74 (9): 289-s), and use this solder Si before soldering 3N 4Surface palpus preplating Ti film, strict to technology controlling and process, corresponding ceramic/metal joint heat resisting temperature is also not high enough.The Si that the Au-36.6Ni-4.7V-1Mo solder obtains 3N 4/ Si 3N 4Joint, its room temperature four-point bending intensity be up to 393MPa, but intensity level 40% (S DPeteves, M Paulasto, G Ceccone and V Stamos.Acta Mater., 1998,46 (7): 2407 of not enough room temperature 700 ℃ the time; M Paulasto, G Ceccone, S D Peteves, R Voitovich andN Eustathopoulos.Ceramic Transactions, 1997,77:91).Also have document announcement design Au-Pd-V solder carry out Si 3N 4/ Si 3N 4The result of study that connects, the content of Pd is near 8wt% in the solder, V content is 3~4wt%, the at room temperature average four-point bending intensity of corresponding joints reaches 350MPa, but in the time of 600 ℃ intensity level during 60%, 800 ℃ of not enough room temperature intensity level dropped to 50% (RE Loehman.Key Engineering Materials, 1999 of room temperature, 161-163:657), this solder long term operation temperature even very difficult above 600 ℃ is described.
In addition, also there is design Ni-20.35Cr-10.04Si (at.%) solder to carry out Si abroad 3N 4/ Si 3N 4Research report (the Ali Mohammad Hadian and Robin A.L.Drew..J.Am.Ceram.Soc. that connects, 1996,79 (3): 659), joint room temperature flexural strength is obviously on the low side (only being 118MPa), though joint four-point bending intensity under 700 ℃~900 ℃ high temperature can be brought up to 200~220MPa, but the low and very big characteristics of fragility of the joint room temperature strength of considering this solder correspondence, the solder practicality is very poor, also can not be used for Si substantially 3N 4Pottery and being connected of metal (follow-up also do not see use this solder to carry out pottery be connected the report of studying with metal).
In sum, also lack both at home and abroad at present and can be directly used in Si 3N 4Pottery connects and joint is being not less than the practical solder that has stable high-temperature behavior under 700 ℃ of temperature.
Summary of the invention
Purpose of the present invention designs at above-mentioned the deficiencies in the prior art just a kind of high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites is provided, and belonging to Pd-Co-Au-Ni-V-Si-B is the high temperature active solder.Both can be used for soldering Si 3N 4Pottery and Si 3N 4Ceramic matric composite can be used for connecting corresponding Si again 3N 4Pottery is connected with other stupaliths or metal (as superalloy) combination sub.Strength of ceramic soldered joint is high and have stable high-temperature performance,
The objective of the invention is to realize by following measure:
This kind is used for the high-temp solder of silicon nitride ceramics and the soldering of silicon nitride ceramics based composites, and its composition and weight percent consist of: Co:18.0~45.0, Au:0.0~33, Ni:0.0~12.0, V:1.5~22.0, Si:0.0~3.9, B:0.0~2.9, the Pd surplus.
According to the requirement of above-mentioned total technical scheme, can further propose following multiple weight percent and form:
1.Co:20.0~45.0, V:1.5~22.0, Pd surplus.
2.Co:20.0~45.0, V:1.5~22.0, Si:0.2~3.9, Pd surplus.
3.Co:20.0~45.0, V:1.5~22.0, B:0.2~2.9, Pd surplus.
4.Co:20.0~45.0, V:1.5~22.0, Si:0.2~3.5, B:0.2~2.5, Pd surplus.
5.Co:20.0~45.0, Ni:1.0~12.0, V:1.5~22.0, Pd surplus.
6.Co:20.0~45.0, Ni:1.0~12.0, V:1.5~22.0, Si:0.2~3.5, Pd surplus.
7.Co:20.0~45.0, Ni:1.0~12.0, V:1.5~22.0, B:0.2~2.9, Pd surplus.
8.Co:20.0~45.0, Ni:1.0~12.0, V:1.5~22.0, Si:0.2~3.5, B:0.2~2.5, Pd surplus.
9.Co:20.0~45.0, Au:2.0~33, V:1.5~22.0, Pd surplus.
10.Co:20.0~45.0, Au:2.0~33, V:1.5~22.0, Si:0.1~3.5, Pd surplus.
11.Co:20.0~45.0, Au:2.0~33, V:1.5~22.0, B:0.2~2.9, Pd surplus.
12.Co:20.0~45.0, Au:2.0~33, V:1.5~22.0, Si:0.1~3.0, B:0.2~2.0, Pd surplus.
13.Co:18.0~45.0, Au:2.0~33, Ni:0.5~12.0, V:1.5~22.0, Pd surplus.
14.Co:18.0~45.0, Au:2.0~33, Ni:0.5~12.0, V:1.5~22.0, Si:0.2~3.5, Pd surplus.
15.Co:18.0~45.0, Au:2.0~33, Ni:0.5~12.0, V:1.5~22.0, B:0.2~2.9, Pd surplus.
16.Co:18.0~45.0, Au:2.0~33, Ni:0.5~12.0, V:1.5~22.0, Si:0.2~3.0, B:0.2~2.0, Pd surplus.
17.Co:18.0~45.0, Au:0.0~33, Ni:0.0~12.0, V:3.0~22.0, Si:0.0~3.9, B:0.0~2.9, Pd surplus.
18.Co:18.0~45.0, Au:0.0~33, Ni:0.0~12.0, V:4.0~22.0, Si:0.0~3.9, B:0.0~2.9, Pd surplus.
19.Co:18.0~45.0, Au:0.0~33, Ni:0.0~12.0, V:5.5~22.0, Si:0.0~3.9, B:0.0~2.9, Pd surplus.
20.Co:18.0~45.0, Au:0.0~33, Ni:0.0~12.0, V:1.5~4.6, Si:0.0~3.9, B:0.0~2.9, Pd surplus.
21.Co:18.0~45.0, Au:0.0~33, Ni:0.0~12.0, V:4.7~7.8, Si:0.0~3.9, B:0.0~2.9, Pd surplus.
22.Co:18.0~45.0, Au:0.0~33, Ni:0.0~12.0, V:7.9~14.8, Si:0.0~3.9, B:0.0~2.9, Pd surplus.
23.Co:18.0~45.0, Au:0.0~33, Ni:0.0~12.0, V:14.9~22.0, Si:0.0~3.5, B:0.0~2.5, Pd surplus.
The method for preparing above-mentioned high-temp solder is at first to adopt the arc melting method that this alloy raw material is smelted into alloy pig under the argon shield condition; Use one of following method preparation solder then:
(1) adopt argon gas powder by atomization equipment to prepare Powdered solder;
(2) under the argon shield condition, adopt chilling attitude foil to prepare equipment and prepare chilling paper tinsel band solder;
(3) adopt electric spark wire cutting method to cut out thin slice, again with thin slice pros and cons mechanical polishing from alloy pig.
(4) be rolled into solder alloy composite band by two or three kind of simple alloy thin band of composition with design mix.
The method of using above-mentioned high-temp solder to carry out soldering is:
(1) assembling is carried out Si according to the requirement of jointing 3N 4Pottery/Si 3N 4Pottery or Si 3N 4The assembling of ceramic/metal is at Si 3N 4The linkage interface of pottery/pottery or Si 3N 4Adding chilling paper tinsel band solder of the present invention or alloy powder powder solder between pottery and the adjacent slow release layer in the ceramic/metal joint, or the solder thin slice that cuts out from alloy pig;
(2) heating, vacuum furnace is put into together with anchor clamps in weldment assembling back, cools to room temperature after the insulation again with the furnace.
The advantage of technical solution of the present invention is: high-temp solder of the present invention can be used for direct soldering Si 3N 4Pottery need be to Si before weldering 3N 4Pottery carries out the pre-plated film in surface or other modification is handled; The Si of solder correspondence of the present invention 3N 4Pottery self jointing intensity height and high temperature (700 ℃~900 ℃) stable performance.In addition, solder of the present invention can also be used to connecting corresponding Si 3N 4Pottery (or Si 3N 4Ceramic matric composite)/metal (as superalloy etc.) combination sub.
Embodiment
Below with reference to embodiment technical solution of the present invention is further described:
Table 1 has provided embodiment and the composition among each embodiment and the weight percent composition of the described high-temp solder of technical solution of the present invention.
Figure C20071008729200091
Figure C20071008729200101
Figure C20071008729200111
The described high-temp solder of the foregoing description prepares by following operational path:
(1) selection purity is not less than 99.0% high-purity Pd, Ni, Au, V, Si, B, Co, and wherein the B element can add with the form of Ni-B under situation with good conditionsi, and weighing by weight ratio;
(2) under the argon shield condition, adopt the arc melting method that this alloy melting is become alloy pig.
(3) adopt one of following method preparation solder:
A, employing argon gas powder by atomization equipment prepare alloy powder powder solder;
B, under the argon shield condition, adopt chilling attitude foil to prepare equipment to prepare chilling attitude paper tinsel band solder.For the single-roller method rapid solidification, single roller needs the high-speed rotation with 1000~10000r/min, and the fusing of solder ingot bar forms liquid postcooling speed between 10 3~10 6Between the K/s.
C, adopt electric spark wire cutting method to cut out thin slice from alloy pig to use behind the pros and cons mechanical polishing again.
D, be rolled into solder alloy composite band with design mix by two or three kind of simple alloy thin band of composition.
Solder of the present invention also can or mix the back by high purity elements by proportioning and directly use with alloy block.Si is carried out in requirement according to jointing 3N 4Pottery/Si 3N 4Pottery or Si 3N 4The assembling of ceramic/metal is at Si 3N 4The linkage interface of pottery/pottery and Si 3N 4Add chilling paper tinsel band solder of the present invention or alloy powder powder solder in the ceramic/metal joint between pottery and the adjacent slow release layer, or the solder thin slice that cuts out from alloy pig, or solder alloy composite rolling band, vacuum furnace is put into together with anchor clamps in the assembling back, by cooling to room temperature again with the furnace after the processing requirement insulation.
Adopt the embodiment 1-7 shown in the table 1,12-32,35-37,41, the composition solder of 72-82 uses with the form of alloy powder powder solder form, solder alloy composite rolling band respectively, embodiment 3-6,8-11, the composition solder of 30-41, make chilling paper tinsel band solder form and use embodiment 1-3,9-22,24-25,27-30,33-37, the composition solder of 72-82 cuts out the solder thin slice from the solder alloy ingot, has carried out Si 3N 4The connection of pottery/pottery; The composition solder of embodiment 42-51, the form of the solder thin slice that cuts out with alloy powder powder solder form, from the solder alloy ingot is used respectively, has carried out Si 3N 4The connection of pottery/pottery; With the composition solder of the embodiment 52-71 shown in the table 1, carried out Si with the form of alloy powder powder solder form, chilling paper tinsel band solder respectively 3N 4The connection of pottery/pottery.All obtain high-quality ceramic soldered joint, joint average room temperature three-point bending strength reaches 250~370MPa.
According to actual needs, the form of the alloy block that solder of the present invention also can obtain with melting is used, or mixes directly use of back by high purity elements powder (200 order) by proportioning.
Use palladium cobalt-based high-temperature active solder, the Si of acquisition 3N 4/ Si 3N 4Close Si in the joint 3N 4Form vanadium-nitrogen, vanadium-pasc reaction layer, joint central tissue is characterized as palladium cobalt base superalloy phase.The room temperature three-point bending strength of corresponding brazed joint reaches 250~370MPa, wherein uses to contain the Si that the Au solder obtains 3N 4/ Si 3N 4Joint reaches more than 80% of room temperature strength 700 ℃ of lower sub intensity; Use the joint that does not contain the acquisition of Au solder 700 ℃ of room temperature strengths that can keep joint down fully, reach more than 80% of room temperature strength at 800 ℃~900 ℃ strength of joints.Solder not only is suitable for Si 3N 4Pottery (or Si 3N 4Ceramic matric composite) soldering of self also is suitable for Si 3N 4Pottery (or Si 3N 4Ceramic matric composite) with being connected of other stupalith or metallic substance combination sub.Use this solder, adopt composite slow release layer structure, carry out Si 3N 4The vacuum brazing of/GH3044 nickel base superalloy, the highest three-point bending strength of joint reaches 112MPa.

Claims (24)

1, a kind of high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites, it is characterized in that, its composition and weight percent consist of: Co:18.0~45.0, Au:0.0~33, Ni:0.0~12.0, V:1.5~22.0, Si:0.0~3.9, B:0.0~2.9, the Pd surplus.
2, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:20.0~45.0, V:1.5~22.0, Pd surplus.
3, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:20.0~45.0, V:1.5~22.0, Si:0.2~3.9, Pd surplus.
4, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:20.0~45.0, V:1.5~22.0, B:0.2~2.9, Pd surplus.
5, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:20.0~45.0, V:1.5~22.0, Si:0.2~3.5, B:0.2~2.5, the Pd surplus.
6, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:20.0~45.0, Ni:1.0~12.0, V:1.5~22.0, Pd surplus.
7, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:20.0~45.0, Ni:1.0~12.0, V:1.5~22.0, Si:0.2~3.5, the Pd surplus.
8, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:20.0~45.0, Ni:1.0~12.0, V:1.5~22.0, B:0.2~2.9, the Pd surplus.
9, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:20.0~45.0, Ni:1.0~1 2.0, V:1.5~22.0, Si:0.2~3.5, B:0.2~2.5, the Pd surplus.
10, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:20.0~45.0, Au:2.0~33, V:1.5~22.0, Pd surplus.
11, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:20.0~45.0, Au:2.0~33, V:1.5~22.0, Si:0.1~3.5, the Pd surplus.
12, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:20.0~45.0, Au:2.0~33, V:1.5~22.0, B:0.2~2.9, the Pd surplus.
13, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:20.0~45.0, Au:2.0~33, V:1.5~22.0, Si:0.1~3.0, B:0.2~2.0, the Pd surplus.
14, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:18.0~45.0, Au:2.0~33, Ni:0.5~12.0, V:1.5~22.0, the Pd surplus.
15, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:18.0~45.0, Au:2.0~33, Ni:0.5~12.0, V:1.5~22.0, Si:0.2~3.5, the Pd surplus.
16, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:18.0~45.0, Au:2.0~33, Ni:0.5~12.0, V:1.5~22.0, B:0.2~2.9, the Pd surplus.
17, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:18.0~45.0, Au:2.0~33, Ni:0.5~1 2.0, V:1.5~22.0, Si:0.2~3.0, B:0.2~2.0, Pd surplus.
18, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:18.0~45.0, Au:0.0~33, Ni:0.0~12.0, V:3.0~22.0, Si:0.0~3.9, B:0.0~2.9, Pd surplus.
19, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:18.0~45.0, Au:0.0~33, Ni:0.0~12.0, V:4.0~22.0, Si:0.0~3.9, B:0.0~2.9, Pd surplus.
20, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:18.0~45.0, Au:0.0~33, Ni:0.0~12.0, V:5.5~22.0, Si:0.0~3.9, B:0.0~2.9, Pd surplus.
21, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:18.0~45.0, Au:0.0~33, Ni:0.0~12.0, V:1.5~4.6, Si:0.0~3.9, B:0.0~2.9, Pd surplus.
22, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:18.0~45.0, Au:0.0~33, Ni:0.0~12.0, V:4.7~7.8, Si:0.0~3.9, B:0.0~2.9, Pd surplus.
23, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:18.0~45.0, Au:0.0~33, Ni:0.0~12.0, V:7.9~14.8, Si:0.0~3.9, B:0.0~2.9, Pd surplus.
24, the high-temp solder that is used for silicon nitride ceramics and the soldering of silicon nitride ceramics based composites according to claim 1, it is characterized in that: its composition and weight percent consist of: Co:18.0~45.0, Au:0.0~33, Ni:0.0~12.0, V:14.9~22.0, Si:0.0~3.5, B:0.0~2.5, Pd surplus.
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CN102584312B (en) * 2012-03-01 2013-07-03 哈尔滨工业大学 Carbon-nanotube-assisted brazing method of ceramic matrix fibre-woven composite and metal material
CN103331499B (en) * 2013-06-24 2015-06-10 哈尔滨工业大学 Method for brazing ZrB2-SiC composite ceramic material by using Pd-Co-Ni brazing filler metals
CN108188520B (en) * 2017-12-01 2020-06-09 浙江工业大学 Method for braze welding of DD98M single crystal high-temperature alloy by adopting Pd-Si composite solder

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