CN112059470A - Active brazing filler metal for brazing titanate microwave dielectric ceramic and metal and preparation method thereof - Google Patents
Active brazing filler metal for brazing titanate microwave dielectric ceramic and metal and preparation method thereof Download PDFInfo
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- CN112059470A CN112059470A CN202010937192.4A CN202010937192A CN112059470A CN 112059470 A CN112059470 A CN 112059470A CN 202010937192 A CN202010937192 A CN 202010937192A CN 112059470 A CN112059470 A CN 112059470A
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- microwave dielectric
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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
- 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
- B23K35/302—Cu 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
- B23K35/40—Making wire or rods for soldering or welding
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Abstract
The invention provides an active solder for soldering titanate microwave dielectric ceramics and metals and a preparation method thereof, wherein the mass fraction content ranges are respectively Cu: 60-85%, tin: 5-15%, titanium: 8-15%, nickel: 3-8% of fluorine-containing potassium borate. The material is prepared by ball milling and mixing, compression molding, vacuum sintering, annealing, rolling and other processes. The melting point of the Cu-Sn-Ti-Ni active solder provided by the invention is 930-1100 ℃, the requirement on silver in the active solder for brazing the traditional ceramics and metals is reduced, the metallization cost of the ceramics is greatly reduced, and the problem that the non-oxide ceramics and the metals are difficult to braze is solved.
Description
Technical Field
The invention belongs to the technical field of brazing, and particularly relates to an active brazing filler metal for brazing titanate microwave dielectric ceramics and metals and a preparation method thereof.
Background
With the advent of the 5G era, by 8 months of 2020, over 70 million 5G base stations have been established globally, with a projected end of year reaching 150 million. Each base station consists of 3 antennas, and each antenna needs 64 filters on average, so that the total quantity of medium filters can reach 10 hundred million, the number of the filters needed is huge, and the filters for the domestic base stations have wide application and market prospects in the period of 5G. The ceramic filter is made of ceramic materials into a sheet shape, silver is coated on two surfaces of the ceramic filter to serve as electrodes, the piezoelectric effect is achieved after direct-current high-voltage polarization, the filtering effect is achieved, the ceramic filter has the advantages of being high in Q value, good in amplitude-frequency and phase-frequency characteristics, small in size, high in signal-to-noise ratio and the like, the conversion of electric signals → mechanical vibration → electric signals is achieved by the piezoelectric effect, the traditional LC filter network is gradually replaced, and the ceramic filter has very important value in the construction of a radio frequency processing unit RRU of a 5G base station
The metallization process is an essential link in the preparation process of the ceramic filter, whether the ceramic filter can be produced on a large scale or not is determined, the metallization process adopted by the existing ceramic filter is mainly to coat silver on the surface to generate a metal surface layer, and finally, metal (silver, copper, nickel and the like) is plated on the surface.
The brazing is to use one or several metal materials with lower melting point than the base metal as brazing filler metal, the brazing filler metal between the ceramic and the metal base metal is melted into liquid state at high temperature, the active components in the brazing filler metal and the ceramic are chemically reacted to form a stable reaction gradient layer, and the stable reaction gradient layer and the base metal are mutually diffused to realize connection.
Common solder is divided into soft solder and hard solder according to the melting point, and the soft solder is mainly divided into zinc-based alloy, gallium-based alloy and tin-based alloy; brazing filler metal mainly refers to copper-based, silver-based, aluminum-based and nickel-based alloys, and is commonly used for brazing dissimilar materials of ceramics and metals. The technical difficulty is as follows:
(1) the brazing filler metal is non-infiltrative to the metal ceramic, namely metallurgical incompatibility, and the surface wettability of the ceramic can be obviously improved by adding transition group metal elements such as Si, Nb and the like into the brazing filler metal, so that the brazing filler metal has higher affinity to the silicate ceramic; (2) the difference between the thermal expansion coefficients of ceramic and metal is large, and thermal stress is easy to appear at the joint, namely, the physical properties are not matched.
At present, the ceramic-metal brazing studied at home and abroad mainly relates to a brazing method and solder preparation between oxide ceramic (such as alumina ceramic) and metal, but the brazing research on non-metal ceramic such as titanate and the like and metal is less, and most of the microwave dielectric ceramic filters are non-oxide ceramic at present, so the research on the brazing method of titanate ceramic and metal has very important significance, and the development of active brazing solder with good wettability with the surface of ceramic is very important for realizing the large-scale production of the metallization of titanate microwave dielectric ceramic.
Disclosure of Invention
The invention aims to provide an active solder capable of being directly used for soldering titanate microwave dielectric ceramics and metals and a preparation method thereof, which make up the defects of the existing soldering technology of non-metal oxide ceramics and metals, realize the large-scale production of metallization of titanate ceramics and reduce the production cost of ceramic filters. The active welding flux can realize the brazing between titanate and most metals (silver, copper, nickel and the like), the obtained joint has clean surface, stable shape and size and little change of the structural properties of a weldment, and the metalized filter has excellent electrical performance and application performance and stable conduction performance.
The purpose of the invention is realized as follows: the mass fraction content ranges of the components (alloy powder) are respectively Cu: 60-85%, tin: 5-15%, titanium: 8-15%, nickel: 3-8% of fluorine-containing potassium borate.
The purity of the silver powder is 99.99%, and the silver powder is 100-300 meshes.
The purity of the copper powder is 99.9%, and the copper powder is 100-300 meshes.
The purity of the titanium powder is 99.99%, and the titanium powder is 100-300 meshes.
The fluorine-containing potassium borate is used as a welding flux, is mainly used for removing oxides and redundant brazing filler metal on the surface of a base material, and can be removed by boiling in water or in 10% citric acid hot water.
The preparation method of the active solder for soldering the titanate microwave dielectric ceramic and the metal comprises the following steps:
step 1, adjusting the proportion of each component in the range according to the brazing requirement of titanate microwave dielectric ceramic and metal (silver, copper, nickel and the like);
step 2, putting the four alloy powders into a ball-milling mixer according to the proportion, fully and uniformly mixing, and pressing the mixture into a block-shaped blank on a quick oil press;
step 3, putting the pressed block blank into a vacuum induction heating furnace, and keeping the vacuum degree not lower than 10 at 650-1000 DEG C-3Sintering for 0.5-1.5 hours under the condition of Pa; the vacuum sintering is carried out when the inert protective atmosphere is filled to 2.5-3.5 Pa; annealing the sintered blank at 550-750 ℃ for 2-10 hours;
step 4, taking the annealed blank out of the vacuum induction heating furnace, rolling in a hot rolling mill, adjusting the temperature of the rolling mill to 550-650 ℃, and repeating the steps of hot rolling, annealing and hot rolling for a plurality of times until the blank is thinned to sheets, namely brazing material sheets with the thickness of 1.2-1.8 mm;
and 5, firstly, pickling the brazing material sheet formed by hot rolling, washing off an oxide film on the surface, and then preparing an ultrathin sheet with the thickness of 0.10-0.16 on a cold rolling mill to obtain the Cu-Sn-Ti-Ni active brazing material with the melting point of 930-1100 ℃.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.
Example 1
The invention prepares an active solder for brazing magnesium titanate microwave dielectric ceramic and metallic nickel. The mass percentages of the raw materials (alloy powder) are respectively as follows: cu: 75%, tin: 10%, titanium: 10%, nickel: 5 percent of fluorine-containing potassium borate in proper amount.
The purity of the silver powder is 99.99%, and the silver powder is 100-300 meshes.
The purity of the copper powder is 99.9 percent and 100-300 meshes.
The purity of the titanium powder is 99.99 percent and 100-300 meshes.
The fluorine-containing potassium borate is used as a welding flux, is mainly used for removing oxides and redundant brazing filler metal on the surface of a base material, and can be removed by boiling in water or in hot water of 10 percent citric acid.
The preparation method of the active solder for brazing the magnesium titanate microwave dielectric ceramic and the metallic nickel comprises the following steps:
step 1, weighing alloy powder according to the ratio of each component determined in the range according to the brazing requirement of magnesium titanate ceramics and metallic nickel;
step 2, putting the four alloy powders into a ball-milling mixer according to the proportion, fully grinding the four alloy powders, uniformly mixing the four alloy powders in a dry mode, and pressing the mixture into a block-shaped blank on a quick oil press;
step 3, the pressed block blank is put into a vacuum induction heating furnace, and the temperature and the vacuum degree are 950 ℃ and 10-3Sintering for 1 hour under the condition of Pa; vacuum sintering is carried out when inert protective atmosphere is filled to 3 Pa; annealing the sintered blank at 650 ℃ for 5 hours;
step 4, taking the annealed blank out of the vacuum induction heating furnace, rolling in a hot rolling mill, adjusting the temperature of the rolling mill to 600 ℃, and repeating the steps of hot rolling, annealing and hot rolling for a plurality of times until the blank is thinned to a brazing sheet with the thickness of 1.6 mm;
and 5, firstly, pickling the brazing material sheet formed by hot rolling, washing off an oxide film on the surface, and then preparing an ultrathin sheet with the thickness of 0.15 on a cold rolling mill to obtain the Cu-Sn-Ti-Ni active brazing material with the melting point of 950-1100 ℃.
Example 2
The invention prepares an active solder for soldering tin titanate microwave dielectric ceramics and metal copper. The raw materials comprise the following components (alloy powder) in percentage by mass: cu: 80%, tin: 8%, titanium: 9%, nickel: 3 percent of fluorine-containing potassium borate in proper amount.
The purity of the silver powder is 99.99%, and the silver powder is 100-300 meshes.
The purity of the copper powder is 99.9 percent and 100-300 meshes.
The purity of the titanium powder is 99.99 percent and 100-300 meshes.
The fluorine-containing potassium borate is used as a welding flux, is mainly used for removing oxides and redundant brazing filler metal on the surface of a base material, and is removed in hot water of 10 percent citric acid.
The preparation method of the active solder for soldering the tin titanate microwave dielectric ceramic and the metallic nickel comprises the following steps:
step 1, weighing alloy powder according to the proportion of each component determined in the range according to the brazing requirement of magnesium titanate ceramics and metal copper;
step 2, putting the four alloy powders into a ball-milling mixer according to the proportion, fully grinding the four alloy powders, uniformly mixing the four alloy powders in a dry mode, and pressing the mixture into a block-shaped blank on a quick oil press;
step 3, the pressed block blank is put into a vacuum induction heating furnace, and the temperature and the vacuum degree are 950 ℃ and 10-3Sintering for 1 hour under the condition of Pa; vacuum sintering is carried out when inert protective atmosphere is filled to 3 Pa; annealing the sintered blank at 650 ℃ for 5 hours;
step 4, taking the annealed blank out of the vacuum induction heating furnace, rolling in a hot rolling mill, adjusting the temperature of the rolling mill to 600 ℃, and repeating the steps of hot rolling, annealing and hot rolling for a plurality of times until the blank is thinned to a brazing sheet with the thickness of 1.5 mm;
and 5, firstly, pickling the brazing material sheet formed by hot rolling, washing off an oxide film on the surface, and then preparing an ultrathin sheet with the thickness of 0.14 on a cold rolling mill to obtain the Cu-Sn-Ti-Ni active brazing material with the melting point of 800-950 ℃.
The Cu-Sn-Ti-Ni active solder is suitable for brazing of non-metal oxide titanate ceramics and metals, and the active solder added with Ni has good wettability on the surface of the titanate ceramics, so that high-strength connection of the titanate ceramics and the metals can be realized.
Claims (6)
1. Titanate microwave dielectric ceramic and metal braze welding are with active brazing filler metal, its characterized in that: the alloy powder is an alloy powder, and the mass fraction content ranges of the components are respectively Cu: 60-85%, tin: 5-15%, titanium: 8-15%, nickel: 3-8% of fluorine-containing potassium borate.
2. The active solder for soldering titanate microwave dielectric ceramics and metals as claimed in claim 1, wherein: the purity of the silver powder is 99.99%, and the silver powder is 100-300 meshes.
3. The active solder for soldering titanate microwave dielectric ceramics and metals as claimed in claim 1, wherein: the purity of the copper powder is 99.9 percent and 100-300 meshes.
4. The active solder for soldering titanate microwave dielectric ceramics and metals as claimed in claim 1, wherein: the purity of the titanium powder is 99.99 percent and 100-300 meshes.
5. The active solder for soldering titanate microwave dielectric ceramics and metals as claimed in claim 1, wherein: fluorine-containing potassium borate is used as a welding flux.
6. The method for preparing the active solder for brazing the titanate microwave dielectric ceramic and the metal as claimed in claim 1, which is characterized by comprising the following steps:
step 1, adjusting the proportion of each component according to the requirements of soldering titanate microwave dielectric ceramics and metals;
step 2, putting the four alloy powders into a ball-milling mixer according to the proportion, fully and uniformly mixing, and pressing the mixture into a block-shaped blank on a quick oil press;
step 3, putting the pressed block blank into a vacuum induction heating furnace, and keeping the vacuum degree not lower than 10 at 650-1000 DEG C- 3Sintering for 0.5-1.5 hours under the condition of Pa; the vacuum sintering is carried out when the inert protective atmosphere is filled to 2.5-3.5 Pa; annealing the sintered blank at 550-750 ℃ for 2-10 hours;
step 4, taking the annealed blank out of the vacuum induction heating furnace, rolling in a hot rolling mill, adjusting the temperature of the rolling mill to 550-650 ℃, and carrying out hot rolling, annealing and hot rolling repeatedly for a plurality of times until the blank is thinned to sheets, namely brazing material sheets with the thickness of 1.2-1.8 mm;
and 5, firstly, pickling the brazing material sheet formed by hot rolling, washing off an oxide film on the surface, and then preparing an ultrathin sheet with the thickness of 0.10-0.16 on a cold rolling mill to obtain the Cu-Sn-Ti-Ni active brazing material with the melting point of 930-1100 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010937192.4A CN112059470A (en) | 2020-09-08 | 2020-09-08 | Active brazing filler metal for brazing titanate microwave dielectric ceramic and metal and preparation method thereof |
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| CN202010937192.4A CN112059470A (en) | 2020-09-08 | 2020-09-08 | Active brazing filler metal for brazing titanate microwave dielectric ceramic and metal and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112635949A (en) * | 2020-12-14 | 2021-04-09 | 江苏宝利金材科技有限公司 | Method for metallizing surface of ceramic filter |
| CN115028467A (en) * | 2022-06-20 | 2022-09-09 | 昆明冶金研究院有限公司北京分公司 | Low-voidage ceramic copper-clad plate and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112635949A (en) * | 2020-12-14 | 2021-04-09 | 江苏宝利金材科技有限公司 | Method for metallizing surface of ceramic filter |
| CN112635949B (en) * | 2020-12-14 | 2022-04-01 | 江苏宝利金材科技有限公司 | Method for metallizing surface of ceramic filter |
| CN115028467A (en) * | 2022-06-20 | 2022-09-09 | 昆明冶金研究院有限公司北京分公司 | Low-voidage ceramic copper-clad plate and preparation method thereof |
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