CN109175782A - A kind of novel oxidation-resistant multicomponent alloy solder - Google Patents
A kind of novel oxidation-resistant multicomponent alloy solder Download PDFInfo
- Publication number
- CN109175782A CN109175782A CN201811285339.5A CN201811285339A CN109175782A CN 109175782 A CN109175782 A CN 109175782A CN 201811285339 A CN201811285339 A CN 201811285339A CN 109175782 A CN109175782 A CN 109175782A
- Authority
- CN
- China
- Prior art keywords
- solder
- band
- ingot casting
- multicomponent alloy
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3006—Ag as the principal constituent
-
- 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
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
-
- 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
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Ceramic Products (AREA)
Abstract
The invention discloses a kind of novel oxidation-resistant multicomponent alloy solder, which is made of the element of following weight percent: Ag 49~63.8%, Cu 34~45%, Ni 1~2%, Si 0.2~1.5%, Ge 0.5~1%, Ce 0.2~0.5%, Nd 0.2~0.5%, Hf 0.1~0.5%.Solder processability of the present invention is good, wetability is good, sealing-in strength of joint is high, antioxygenic property is good；Alternative now widely used Ag72Cu28 solder, the sealing-in especially suitable for ceramics and metal in electron tube, it can also be used to the vacuum brazing in other fields and gas protecting soldering.
Description
Technical field
The present invention relates to welding and multicomponent alloy field of material technology, more particularly, to a kind of electron tube sealing-in
Anti-oxidant multicomponent alloy solder.
Background technique
With the fast development of informationization technology, aeronautical and space technology and electric vacuum technology, it is brazed with its unique performance
It is widely used in complicated, fine structure component connection.Significant components-radio tube in electrovacuum encapsulation technology, it is desirable that have
Vacuum degree is high, air-tightness is good, good mechanical property, therefore requires radio tube sealing-in solder relatively high.Silver-base solder tool
There are the performances such as mechanical property is good, conduct electricity very well, corrosion resistance and good, welding point air-tightness are good, is acknowledged as a kind of excellent
Vacuum electronic seal, sealing materials.
The brazing temperature of Ag72Cu28 solder is moderate (about 800 DEG C~850 DEG C), to the wetability and stream of the metals such as copper, nickel
Dynamic property is good, and processing performance is good, and processing performance is good, is easily worked the various shapes such as in blocks, foil, plate, silk, is free of Volatile Elements,
Meet the requirement of electron tube.Therefore, Ag72Cu28 solder is widely used in vacuum switch tube, transmitting tube, microwave device etc.
The welding and sealing-in of electron tube are the solders of electrovacuum industry first choice.However, the silver content of Ag72Cu28 solder is up to
72%.Not only price is high for the high solder of silver content, but also consumes a large amount of noble silver.Therefore, in the work for not changing solder
Under the important performances such as skill, processability and brazing temperature, how to reduce the silver content of Ag72Cu28 solder be electrovacuum industry urgently
A problem to be solved.From disclosed low silver alloy solder patents numerous at present, although being prepared after reducing silver content
Solder welding mechanics performance and welding temperature basically reached the performance of Ag72Cu28 solder, but the antioxygenic property of solder compared with
Difference, face of weld is oxidizable after welding there is macula lutea phenomenon, and the appearance for influencing the weld seam of radio tube is beautiful.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, this application provides a kind of novel oxidation-resistant multicomponent alloy solders.This
The silver-base solder silver content for inventing offer is low, and welding temperature is suitable with Ag72Cu28；Solder processability is good, wetability is good, sealing-in
Strength of joint is high, antioxygenic property is good；Alternative now widely used Ag72Cu28 solder, especially suitable for electron tube
The sealing-in of middle ceramics and metal, it can also be used to the vacuum brazing in other fields and gas protecting soldering.
Technical scheme is as follows:
A kind of novel oxidation-resistant multicomponent alloy solder, the solder are made of the element of following weight percent:
Ag 49~63.8%, Cu 34~45%, Ni 1~2%, Si 0.2~1.5%, Ge 0.5~1%, Ce 0.2
~0.5%, Nd 0.2~0.5%, Hf 0.1~0.5%.
A kind of preparation method of the multicomponent alloy solder, the preparation method include the following steps:
1) raw material A g, Cu, Ni, Si, Ge, Ce, Nd, Hf are put into according to the ratio in vacuum melting furnace, vacuum degree reaches in furnace
After 0.04~0.4Pa, then it will be heated to 1300~1400 DEG C in furnace, keep the temperature 30~40 minutes, ingot casting is made；
(2) ingot casting obtained step (1) advanced driving stripping, to ream the dirty and oxide layer of ingot casting surface, then into
Row milling train cold rolling, when thickness reaches 1~2mm, clot is placed on 600~650 DEG C and keeps the temperature 1~2 hour, then naturally cools to room
Temperature takes out band after annealing；
(3) band after step (3) annealing is continued on through milling train to be cold rolled to a thickness of after 0.04~0.15mm, then will
Its sub-cut is that the band of one fixed width carries out stamping out required shape.
The present invention is beneficial to be had the technical effect that
Silver-based alloy solder brazing temperature of the invention is suitable with Ag72Cu28, and about 830~850 DEG C.
For silver-based alloy solder of the invention in sealing-in ceramics and metal, sealing-in strength of joint is high.
The addition of micro Ge element, Si element, the inoxidizability of solder are mentioned significantly in silver-based alloy solder of the present invention
It rises.
Volume RE elements of Ce is added in silver based soldering alloy of the present invention easily forms the second phase intermetallic compound with Cu,
Disperse phase is distributed among brilliant gap and the fault of crystal is hindered to move, and alloy strength is enhanced；Micro Nd element in alloy
Addition, can greatly improve the air-tightness of sealing-in connector.
The addition of micro Hf, Nd, Ni element, plays solution strengthening to alloy and crystal grain is thin in silver based soldering alloy of the present invention
Change, alloy strength gets a promotion, while the addition of Ni element further improves the wetability and mobility of solder.Silver-colored pricker of the invention
Material silver content is substantially less than Ag72Cu28 solder.
Specific embodiment
Below with reference to embodiment, the present invention is specifically described.
Embodiment 1
A kind of novel oxidation-resistant multicomponent alloy solder, preparation method are as follows: (each raw material dosage is referring to table 1)
1) raw material A g, Cu, Ni, Si, Ge, Ce, Nd, Hf are put into according to the ratio in vacuum melting furnace, vacuum degree reaches in furnace
After 0.04Pa, then it will be heated to 1300 DEG C in furnace, keep the temperature 40 minutes, ingot casting is made；
(2) ingot casting obtained step (1) advanced driving stripping, to ream the dirty and oxide layer of ingot casting surface, then into
Row milling train cold rolling, when thickness reaches 1mm, clot is placed on 600 DEG C and keeps the temperature 2 hours, then naturally cools to room temperature, takes out annealing
Band afterwards；
(3) band after step (2) annealing is continued on through milling train to be cold rolled to a thickness of after 0.04mm, then by its sub-cut
It carries out stamping out required shape for the band of one fixed width.
Embodiment 2
A kind of novel oxidation-resistant multicomponent alloy solder, preparation method are as follows: (each raw material dosage is referring to table 1)
1) raw material A g, Cu, Ni, Si, Ge, Ce, Nd, Hf are put into according to the ratio in vacuum melting furnace, vacuum degree reaches in furnace
After 0.2Pa, then it will be heated to 1350 DEG C in furnace, keep the temperature 35 minutes, ingot casting is made；
(2) ingot casting obtained step (1) advanced driving stripping, to ream the dirty and oxide layer of ingot casting surface, then into
Row milling train cold rolling, when thickness reaches 1.5mm, clot is placed on 620 DEG C and keeps the temperature 1.5 hours, then naturally cools to room temperature, takes out
Band after annealing；
(3) band after step (2) annealing is continued on through milling train to be cold rolled to a thickness of after 0.1mm, then by its sub-cut
It carries out stamping out required shape for the band of one fixed width.
Embodiment 3
A kind of novel oxidation-resistant multicomponent alloy solder, preparation method are as follows: (each raw material dosage is referring to table 1)
1) raw material A g, Cu, Ni, Si, Ge, Ce, Nd, Hf are put into according to the ratio in vacuum melting furnace, vacuum degree reaches in furnace
After 0.4Pa, then it will be heated to 1400 DEG C in furnace, keep the temperature 30 minutes, ingot casting is made；
(2) ingot casting obtained step (1) advanced driving stripping, to ream the dirty and oxide layer of ingot casting surface, then into
Row milling train cold rolling, when thickness reaches 2mm, clot is placed on 650 DEG C and keeps the temperature 1~2 hour, then naturally cools to room temperature, takes out
Band after annealing；
(3) band after step (2) annealing is continued on through milling train to be cold rolled to a thickness of after 0.15mm, then by its sub-cut
It carries out stamping out required shape for the band of one fixed width.
Table 1 (unit: weight %)
| Embodiment | Ag | Cu | Ni | Si | Ge | Ce | Nd | Hf |
| 1 | 49 | 45 | 2 | 1.5 | 1 | 0.5 | 0.5 | 0.5 |
| 2 | 58 | 39 | 0.75 | 0.65 | 0.65 | 0.35 | 0.3 | 0.3 |
| 3 | 63.8 | 34 | 1 | 0.2 | 0.5 | 0.2 | 0.2 | 0.1 |
Each embodiment solder is tested for the property with Ag72Cu28 solder, the results are shown in Table 2.
Ceramic and metal jointing strength of joint (being indicated with connector carrying pulling force) refers to that aluminium oxide ceramics and kovar alloy seal
Banjo fixing butt jointing after connecing carries pulling force, and can cut down pipe diameter is 14mm, and with a thickness of 0.5mm, magnetron connects ceramics with that can cut down sealing-in
The carrying pulling tension requirements of head must not be lower than 3.5KN.
Table 2
| Brazing temperature (DEG C) | Ceramic and metal jointing strength of joint (KN) | |
| Embodiment 1 | 830~850 | 5.2 |
| Embodiment 2 | 830~850 | 5.5 |
| Embodiment 3 | 830~850 | 5.3 |
| Ag72Cu28 | 830~850 | 5.0 |
The solder and Ag72Cu28 solder that Examples 1 to 3 obtains carry out Oxidation Resistance Test, and 4 samples are individually placed to humidify
In insulating box, temperature sets 250 DEG C, and humidity 80%, amount of oxygen 30%, standing time 30 days, the surface oxidation quantity of slag was more, then resisted
Oxidisability is weaker, and the results are shown in Table 3.
Table 3
| Sample | It aoxidizes the quantity of slag (g) |
| Embodiment 1 | 0.51 |
| Embodiment 2 | 0.40 |
| Embodiment 3 | 0.50 |
| Ag72Cu28 | 0.65 |
Claims (2)
1. a kind of novel oxidation-resistant multicomponent alloy solder, which is characterized in that the solder is made of the element of following weight percent:
Ag 49~63.8%, Cu 34~45%, Ni 1~2%, Si 0.2~1.5%, Ge 0.5~1%, Ce 0.2~
0.5%, Nd 0.2~0.5%, Hf 0.1~0.5%.
2. the preparation method of multicomponent alloy solder described in a kind of claim 1, which is characterized in that the preparation method includes as follows
Step:
(1) raw material A g, Cu, Ni, Si, Ge, Ce, Nd, Hf are put into vacuum melting furnace according to the ratio, vacuum degree reaches 0.04 in furnace
After~0.4Pa, then it will be heated to 1300~1400 DEG C in furnace, keep the temperature 30~40 minutes, ingot casting is made；
(2) the advanced driving stripping of the ingot casting obtained step (1), to ream the dirty and oxide layer of ingot casting surface, is then rolled
Machine cold rolling, when thickness reaches 1~2mm, clot is placed on 600~650 DEG C and keeps the temperature 1~2 hour, then naturally cools to room temperature,
Take out band after annealing；
(3) band after step (2) annealing is continued on through milling train to be cold rolled to a thickness of after 0.04~0.15mm, then by its point
The band for being cut to one fixed width carries out stamping out required shape.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811285339.5A CN109175782B (en) | 2018-10-31 | 2018-10-31 | Novel antioxidant multi-element alloy brazing filler metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811285339.5A CN109175782B (en) | 2018-10-31 | 2018-10-31 | Novel antioxidant multi-element alloy brazing filler metal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109175782A true CN109175782A (en) | 2019-01-11 |
| CN109175782B CN109175782B (en) | 2021-02-26 |
Family
ID=64940927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811285339.5A Active CN109175782B (en) | 2018-10-31 | 2018-10-31 | Novel antioxidant multi-element alloy brazing filler metal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109175782B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110170767A (en) * | 2019-06-17 | 2019-08-27 | 无锡日月合金材料有限公司 | A kind of novel oxidation-resistant multicomponent alloy solder and preparation method thereof |
| CN110238559A (en) * | 2019-06-17 | 2019-09-17 | 无锡日月合金材料有限公司 | A kind of novel quaternary alloy solder and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140594A (en) * | 2011-03-11 | 2011-08-03 | 无锡日月合金材料有限公司 | High-strength, high-conductivity and high-toughness copper alloy and preparation method thereof |
| CN106435325A (en) * | 2016-10-10 | 2017-02-22 | 无锡日月合金材料有限公司 | Multielement alloy sealing material and preparation method thereof |
| CN106467941A (en) * | 2016-09-30 | 2017-03-01 | 无锡日月合金材料有限公司 | A kind of radio tube sealing-in low silver multicomponent alloy material and preparation method thereof |
-
2018
- 2018-10-31 CN CN201811285339.5A patent/CN109175782B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140594A (en) * | 2011-03-11 | 2011-08-03 | 无锡日月合金材料有限公司 | High-strength, high-conductivity and high-toughness copper alloy and preparation method thereof |
| CN106467941A (en) * | 2016-09-30 | 2017-03-01 | 无锡日月合金材料有限公司 | A kind of radio tube sealing-in low silver multicomponent alloy material and preparation method thereof |
| CN106435325A (en) * | 2016-10-10 | 2017-02-22 | 无锡日月合金材料有限公司 | Multielement alloy sealing material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110170767A (en) * | 2019-06-17 | 2019-08-27 | 无锡日月合金材料有限公司 | A kind of novel oxidation-resistant multicomponent alloy solder and preparation method thereof |
| CN110238559A (en) * | 2019-06-17 | 2019-09-17 | 无锡日月合金材料有限公司 | A kind of novel quaternary alloy solder and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109175782B (en) | 2021-02-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104526181A (en) | Electric vacuum silver base alloy solder for vacuum electronic device brazing sealing and preparation method thereof | |
| CN106271202B (en) | A kind of composite brazing material and preparation method thereof | |
| CN101475395A (en) | Stainless steel / alumina ceramic low stress hermetic seal solder | |
| CN109175783A (en) | A kind of quaternary alloy solder | |
| CN107838575A (en) | A kind of ceramic and metal jointing low silver content silver solder | |
| CN109175782A (en) | A kind of novel oxidation-resistant multicomponent alloy solder | |
| CN102115834B (en) | Gold-copper-nickel alloy, preparation method and application thereof | |
| CN107617831A (en) | A kind of ceramic and metal jointing oxidation resistant low-silver solder | |
| CN110238559A (en) | A kind of novel quaternary alloy solder and preparation method thereof | |
| CN106381415A (en) | Copper-based silver-free sealing alloy material and preparation method thereof | |
| CN106435325A (en) | Multielement alloy sealing material and preparation method thereof | |
| CN106222478B (en) | A kind of ternary-alloy sealing material and preparation method thereof | |
| CN102626838B (en) | Silver-based cadmium-free medium temperature brazing filler metal and preparation method thereof | |
| CN103014404B (en) | Alloy material for sealing microwave magnetron and preparation method thereof | |
| CN103014406B (en) | Multicomponent alloy material for sealing microwave oven magnetron | |
| KR100620368B1 (en) | Copper phosphorus brazing alloy containing ni-sn element | |
| CN103406684B (en) | A kind of silver-copper-indium-nickel middle temperature brazing material | |
| CN102513727B (en) | Self-fluxing silver solder containing neodymium, zirconium and gallium | |
| CN107760911A (en) | A kind of copper-based anti-oxidant sealing alloy solder and preparation method thereof | |
| CN100463763C (en) | Cu-P-Ag solder containing Ga, In and Ce | |
| CN107838576A (en) | A kind of microwave magnetron sealing alloy solder | |
| CN100377832C (en) | Cd-free silver solder containing Ga and Ce | |
| CN110170767B (en) | Novel antioxidant multi-element alloy brazing filler metal and preparation method thereof | |
| JPS6113916B2 (en) | ||
| CN1037825C (en) | Copper-base solder-silver substituted solder for electrical vacuum with low melting point, low vapour pressure and ductility |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |