CN102581517B - High-temperature soldering solder for soldering inert anode for aluminium electrolysis and metal conductive rod - Google Patents
High-temperature soldering solder for soldering inert anode for aluminium electrolysis and metal conductive rod Download PDFInfo
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- CN102581517B CN102581517B CN201210096861.5A CN201210096861A CN102581517B CN 102581517 B CN102581517 B CN 102581517B CN 201210096861 A CN201210096861 A CN 201210096861A CN 102581517 B CN102581517 B CN 102581517B
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Abstract
The invention relates to a high-temperature soldering solder for soldering an inert anode for aluminium electrolysis and a metal conductive rod. The high-temperature soldering solder is characterized by comprising the following raw materials by mass percent: one or more of 15.00-35.00% of Cr, 5.00-25.00% of Ni and 0.05-10.00% of Si or 0.05-5.00% of B, one or more of 0.50-10.00% of Zr, 0.50-10.00% of Hf, 0.50-10.00% of Ti and 0.50-10.00% of Ta, one or more of 0.01-0.50% of La, 0.01-0.50% of Ce and 0.01-0.50% of Nb, and the balance of Co. The high-temperature soldering solder has the advantages that the high-temperature active solder can be used for directly soldering the ceramic base inert anode and the metal conductive rod without plating a film on the surface of the ceramic base inert anode or carrying out other modification treatment in advance before the soldering, is good in wettability for the ceramic base inert anode and the metal conductive rod, can maintain 60-70% of the room-temperature strength of the joint at 970 DEG C, does not contain a noble metal such as Pd and Au and is low in cost. The powdered solder can meet the needs of soldering all kinds of joints.
Description
Technical field
The invention belongs to technical field of soldering materials, particularly the high temperature active solder of a kind of soldering ceramic-base inert anode used for aluminum electrolysis and metal conducting bar.
Background technology
The Hall-H é orult method that aluminum current electrolytic industry adopts, anode is all carbon annode.Can produce a large amount of bitumen flue gas in carbon anode manufacturing process, in electrolytic process, the oxygen that anode is separated out and carbon anode react, and generate a large amount of CO
2with CO gas, the fluorine simultaneously in electrolyte and carbon anode react and generate CF
4and C
2f
6gas, these gases enter in air, cause severe contamination to environment.Low energy consumption, the production capacity investment of low unit and minimizing greenhouse gas emission etc. require the research and development facilitating aluminium electrolytic industry inert anode.So-called inert anode is exactly the anode not participating in electrochemical reaction in electrolytic process, and substantially do not consume in electrolytic process, reaction product of anode is oxygen, instead of carbon dioxide, while saving ample resources, protects environment.
Aluminium electrolytic temperature is 920 ~ 970 DEG C, and inert anode in use, drawn by anode bus by electric current, by wire and metal conducting bar and anode conducting.Inert anode and metal conducting bar are the materials that two class nature differences are huge, and atom combination fundamental difference, adds the physical and chemical performance that inert anode is special, makes the difficult problem being connected to become aluminium electrolytic industry of inert anode and metal conducting bar.Therefore, can inert anode and metal conducting bar be formed effectively, be connected reliably is guarantee that inert anode successfully realizes the key technology of commercial Application.
Ceramic and metal joining method is a lot, and conventional method has active metal brazing, diffusion welding (DW), PVD metallization, PTLP bonding etc.Wherein active metal brazing is simple with its technique, bonding strength is high, result is reproducible, the wide adaptability of joint dimension and shape becomes the one preferred technique that ceramic/metal is connected with the advantage such as relative cost is low.
At present, the active solder of domestic and international most study is money base and copper base solder, and due to the restriction of fusing point, the serviceability temperature of money base and copper-based active solder is generally lower than 600 DEG C.United States Patent (USP) 7544275, adopts CuZn alloy to do solder (wherein the mass fraction of Cu is 60%, the mass fraction of Zn is 40%), carries out brazing to inert anode and metal conducting bar.The fusing point of this alloy is 870 ~ 900 DEG C, and in brazing process, part Zn is oxidized, and make soldered fitting fusing point higher than 900 DEG C, but high temperature lower contact intensity is lower, can not meets the requirement of aluminium electrolytic industry.And in high temperature brazing filler metal, compare expensive Pd base, Au base solder, Co base solder more has practical value.
In sum, in the prior art of the high temperature active solder of ceramic soldering base inert anode and metal conducting bar, the report of the high temperature active solder of applicable above-mentioned application requirement is not yet seen in.
Summary of the invention
Object of the present invention develops a kind of high-temp solder for ceramic-base inert anode and metal conducting bar soldering just for above-mentioned the deficiencies in the prior art, belonging to Co-Cr-Ni-(Si, B)-(Zr, Hf, Ti, Ta)-(La, Ce, Nb) is high temperature active solder.Solder of the present invention can make ceramic-base inert anode without surface metalation process directly and metal conducting bar form firmly metallurgical binding, bond strength is high and have stable high-temperature performance.
Object of the present invention realizes by following technique measures:
Raw material and the mass percent of the high temperature active solder for soldering ceramic-base inert anode used for aluminum electrolysis and metal conducting bar of the present invention consist of: Cr:15.00 ~ 35.00, Ni:5.00 ~ 25.00, and one or both in Si:0.05 ~ 10.00 or B:0.05 ~ 5.00, one or more in Zr:0.50 ~ 10.00, Hf:0.50 ~ 10.00, Ti:0.50 ~ 10.00 or Ta:0.50 ~ 10.00, one or more in La:0.01 ~ 0.50, Ce:0.01 ~ 0.50 or Nb:0.01 ~ 0.50, surplus is Co.
Raw material of the present invention and mass percent consist of: Cr:18.00 ~ 35.00, Ni:10.00 ~ 25.00, Si:0.50 ~ 10.00, Zr:1.00 ~ 10.00, La:0.02 ~ 0.50, and surplus is Co; Also can: Cr:18.00 ~ 35.00, Ni:10.00 ~ 25.00, Si:1.00 ~ 9.00, Hf:0.50 ~ 8.00, La:0.01 ~ 0.40, Ce:0.01 ~ 0.35, surplus is Co;
Raw material of the present invention and mass percent composition can also be any one in following composition:
Cr:15.00 ~ 32.00, Ni:5.00 ~ 22.00, B:0.05 ~ 4.50, Zr:0.50 ~ 8.00, La:0.01 ~ 0.40, Ce:0.01 ~ 0.50, surplus is Co.
Cr:15.00 ~ 32.00, Ni:8.00 ~ 22.00, B:0.50 ~ 5.00, Zr:1.00 ~ 8.00, La:0.01 ~ 0.40, Ce:0.01 ~ 0.25, Nb:0.01 ~ 0.30, surplus is Co.
Cr:17.00 ~ 35.00, Ni:12.00 ~ 25.00, Si:0.05 ~ 8.00, B:1.00 ~ 4.00, Zr:1.00 ~ 8.00, Hf:0.50 ~ 10.00, La:0.01 ~ 0.45, surplus is Co.
Cr:17.00 ~ 35.00, Ni:12.00 ~ 25.00, Si:1.00 ~ 8.00, B:1.00 ~ 4.00, Zr:0.50 ~ 6.00, Hf:0.50 ~ 8.00, Ti:0.50 ~ 5.00, Ta:0.50 ~ 5.00, Nb:0.02 ~ 0.50, surplus is Co.
Cr:17.00 ~ 35.00, Ni:12.00 ~ 25.00, Si:1.00 ~ 8.00, B:1.00 ~ 4.00, Ti:1.00 ~ 10.00, Ta:0.50 ~ 10.00, Ce:0.01 ~ 0.45, Nb:0.01 ~ 0.35, surplus is Co.
Cr:17.00 ~ 35.00, Ni:12.00 ~ 25.00, Si:0.05 ~ 8.00, B:0.05 ~ 4.00, Zr:0.50 ~ 5.00, Hf:0.50 ~ 6.00, Ti:0.50 ~ 5.00, Ta:0.50 ~ 5.00, La:0.01 ~ 0.30, Ce:0.01 ~ 0.30, Nb:0.01 ~ 0.30, surplus is Co.
The preparation method of high temperature active solder of the present invention is, under gas shield condition, first adopt electric arc melting method that this alloy raw material is smelted into alloy pig, then adopts gas shield powder by atomization equipment to prepare Powdered solder.
Beneficial effect of the present invention is as follows:
High temperature active solder of the present invention can be used for direct ceramic soldering base inert anode and metal conducting bar, does not need to carry out the pre-plated film in surface or other modification to ceramic-base inert anode before weldering.Solder prepared by the present invention and existing solder contrast, for ceramic-base inert anode and metal conducting bar, wetability is good, soldering joint strength is high and high-temperature behavior is more stable, 60% ~ 70% of joint room temperature strength is still maintained at 970 DEG C of temperature, and not containing precious metals pd and Au in solder composition of the present invention, with low cost, pulverous solder can meet the needs of various forms joint brazing.
Detailed description of the invention
The present invention is described further below with reference to embodiment:
Table 1 gives raw material in the embodiment of high temperature active solder described in technical solution of the present invention and each embodiment thereof and mass percent composition.
High-temp solder described in above-described embodiment is prepared according to following process route:
(1) purity is selected to be not less than the raw material of 99.00% by the various embodiments described above to raw material and mass percent requirement;
(2) under argon shield condition, adopt electric arc melting method that this alloy melting is become alloy pig;
(3) argon gas powder by atomization equipment is adopted to prepare alloyed powder powder solder.
Adopt the composition solder of the said embodiment 1-57 of table 1, with Powdered solder form ceramic soldering base inert anode and metal conducting bar, corresponding soldered fitting can maintain more than 95% of joint room temperature strength under 600 DEG C of test conditions, more than 85% ~ 95% of joint room temperature strength can be maintained under 700 DEG C of test conditions, more than 75% ~ 85% of joint room temperature strength can be maintained under 800 DEG C of test conditions, more than 60% ~ 70% of joint room temperature strength can be maintained under 970 DEG C of test conditions.
Claims (7)
1. the high-temp solder of a soldering inert anode for aluminium electrolysis and metal conducting bar, it is characterized in that: its raw material and mass percent consist of: Cr:15.00 ~ 35.00, Ni:5.00 ~ 25.00, and one or both in Si:0.05 ~ 10.00 or B:0.05 ~ 5.00, one or more in Zr:0.50 ~ 10.00, Hf:0.50 ~ 10.00, Ti:0.50 ~ 10.00 or Ta:0.50 ~ 10.00, one or more in La:0.01 ~ 0.50, Ce:0.01 ~ 0.50 or Nb:0.01 ~ 0.50, surplus is Co.
2. the high-temp solder of soldering inert anode for aluminium electrolysis according to claim 1 and metal conducting bar, it is characterized in that: its raw material and mass percent consist of: Cr:18.00 ~ 35.00, Ni:10.00 ~ 25.00, B:0.50 ~ 5.00, Hf:1.50 ~ 10.00, La:0.01 ~ 0.40, surplus is Co.
3. the high-temp solder of soldering inert anode for aluminium electrolysis according to claim 1 and metal conducting bar, it is characterized in that: its raw material and mass percent consist of: Cr:16.00 ~ 32.00, Ni:5.00 ~ 22.00, B:0.05 ~ 4.50, Ta:1.00 ~ 10.00, La:0.01 ~ 0.35, Ce:0.01 ~ 0.40, Nb:0.01 ~ 0.40, surplus is Co.
4. the high-temp solder of soldering inert anode for aluminium electrolysis according to claim 1 and metal conducting bar, it is characterized in that: its raw material and mass percent consist of: Cr:17.00 ~ 35.00, Ni:12.00 ~ 25.00, Si:0.05 ~ 8.00, B:1.00 ~ 5.00, Zr:0.50 ~ 8.00, Hf:0.50 ~ 8.00, La:0.02 ~ 0.50, surplus is Co.
5. the high-temp solder of soldering inert anode for aluminium electrolysis according to claim 1 and metal conducting bar, it is characterized in that: its raw material and mass percent consist of: Cr:17.00 ~ 35.00, Ni:12.00 ~ 25.00, Si:0.05 ~ 8.00, B:1.00 ~ 4.00, Zr:0.50 ~ 8.00, Hf:0.50 ~ 8.00, Ti:0.50 ~ 6.00, Ta:0.50 ~ 9.00, Nb:0.02 ~ 0.50, surplus is Co.
6. the high-temp solder of soldering inert anode for aluminium electrolysis according to claim 1 and metal conducting bar, it is characterized in that: its raw material and mass percent consist of: Cr:17.00 ~ 35.00, Ni:12.00 ~ 25.00, Si:0.50 ~ 8.00, B:0.50 ~ 4.00, Ta:0.50 ~ 8.00, La:0.01 ~ 0.45, Ce:0.01 ~ 0.35, Nb:0.01 ~ 0.40, surplus is Co.
7. the high-temp solder of soldering inert anode for aluminium electrolysis according to claim 1 and metal conducting bar, it is characterized in that: its raw material and mass percent consist of: Cr:17.00 ~ 35.00, Ni:12.00 ~ 25.00, Si:0.05 ~ 8.00, B:0.05 ~ 4.00, Zr:0.50 ~ 5.00, Hf:0.50 ~ 6.00, Ti:0.50 ~ 8.00, Ta:0.50 ~ 8.50, La:0.01 ~ 0.45, Ce:0.01 ~ 0.45, Nb:0.01 ~ 0.45, surplus is Co.
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| CN201210096861.5A CN102581517B (en) | 2012-04-05 | 2012-04-05 | High-temperature soldering solder for soldering inert anode for aluminium electrolysis and metal conductive rod |
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| CN201210096861.5A CN102581517B (en) | 2012-04-05 | 2012-04-05 | High-temperature soldering solder for soldering inert anode for aluminium electrolysis and metal conductive rod |
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| CN102581517B true CN102581517B (en) | 2015-02-11 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US11059132B2 (en) | 2015-09-11 | 2021-07-13 | Siemens Energy, Inc. | Structural braze tape |
| CN105458551B (en) * | 2015-12-28 | 2018-01-30 | 哈尔滨工业大学 | A kind of method of the assistant brazing of high-temp solder containing tantalum of ceramic soldering and metal |
| CN106378506B (en) * | 2016-10-20 | 2018-08-31 | 江苏科技大学 | A kind of technique that SiC based composites are brazed using brazing material |
| CN109909641B (en) * | 2017-12-13 | 2022-03-29 | 中国科学院金属研究所 | Cobalt-based powder brazing filler metal for high-temperature alloy connection and preparation method and application thereof |
| CN108330508B (en) * | 2018-05-16 | 2020-01-07 | 东北大学 | Method for connecting metal ceramic inert anode for aluminum electrolysis and metal conducting rod |
| CN110029249A (en) * | 2019-04-13 | 2019-07-19 | 杭州辰卓科技有限公司 | Welding material between a kind of high Mn content copper-manganese damping alloy and 304 stainless steels |
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| CN1056645A (en) * | 1990-05-18 | 1991-12-04 | 通用电气公司 | Improved high-temperature brazing alloy and method |
| DE19805142A1 (en) * | 1998-02-09 | 1999-08-12 | Siemens Ag | Long life high temperature fuel cell with mechanically and chemically stable joint |
| WO2000071764A2 (en) * | 1999-05-07 | 2000-11-30 | Rolls-Royce Corporation | Cobalt-base composition and method for diffusion braze repair of superalloy articles |
| CN1994656A (en) * | 2005-12-15 | 2007-07-11 | 通用电气公司 | Braze alloy compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1566384A (en) * | 2003-06-18 | 2005-01-19 | 烟台久强纳米材料开发有限公司 | Rare earth element microalloying modified cobalt-base alloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056645A (en) * | 1990-05-18 | 1991-12-04 | 通用电气公司 | Improved high-temperature brazing alloy and method |
| DE19805142A1 (en) * | 1998-02-09 | 1999-08-12 | Siemens Ag | Long life high temperature fuel cell with mechanically and chemically stable joint |
| WO2000071764A2 (en) * | 1999-05-07 | 2000-11-30 | Rolls-Royce Corporation | Cobalt-base composition and method for diffusion braze repair of superalloy articles |
| CN1994656A (en) * | 2005-12-15 | 2007-07-11 | 通用电气公司 | Braze alloy compositions |
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Address after: Fengyang high tech Industrial Development Zone, Henan province Zhengzhou city 450001 Street No. 10 Patentee after: Zhengzhou Machinery Research Institute Co., Ltd. Address before: Fengyang high tech Industrial Development Zone, Henan province Zhengzhou city 450001 Street No. 10 Patentee before: Zhengzhou Research Institute of Mechanical Engineering |
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