CN102145978B - Glass solder for connecting SiC ceramics, and preparation method and application thereof - Google Patents
Glass solder for connecting SiC ceramics, and preparation method and application thereof Download PDFInfo
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- CN102145978B CN102145978B CN 201010108339 CN201010108339A CN102145978B CN 102145978 B CN102145978 B CN 102145978B CN 201010108339 CN201010108339 CN 201010108339 CN 201010108339 A CN201010108339 A CN 201010108339A CN 102145978 B CN102145978 B CN 102145978B
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- silicon carbide
- intermediate glass
- glass
- scolder
- carbide ceramics
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Abstract
The invention relates to compositions of a glass interlayer for connecting silicon carbide ceramics, and a process for the compositions serving as an interlayer solder to connect the silicon carbide ceramics. The glass comprises main components of Na2O, B2O3 and SiO2 and a small amount of additive. By regulating a proportion of several oxides, the glass solder with low melting temperature, and coefficient of thermal expansion close to silicon carbide ceramics sintered under normal pressure is obtained, and when the temperature is 1,150DEG C, the glass solder has the wetting angle of less than 10 degrees on the surface of the silicon carbide ceramics, and has high wettability. The connection scheme has the advantages of low connection temperature, simple process, simple operation and low cost, and a silicon carbide connector with good performance can be obtained.
Description
Technical field
The present invention relates to a kind of application that can be used for composition, the preparation method of the glass solder of silicon carbide ceramics connection and connect silicon carbide ceramics as the middle layer scolder.
Background technology
Silicon carbide is a kind of typical covalent bond structure pottery, and its density is low, intensity is large, high-temperature behavior is good, excellent in optical properties etc., all is widely used in the fields such as metallurgy, machinery, chemical industry, building materials, light industry, electronics.Yet for the ceramic component of large size and complicated shape, global formation and difficulty of processing are larger, and cost is higher.For in satisfy using to the requirement of size and the shape of stupalith, the technique that need to take pottery to connect.
At present, the main method of silicon carbide ceramics connection has active metal brazing method, reaction connection, diffusion welding connection and oxide glass middle layer connection method etc.Usually these methods of attachment all are to carry out under vacuum or inert atmosphere conditions, and conditional request and cost are higher.Wherein oxide glass is that the method advantage that the middle layer connects is that its composition is in very large range adjustable, and then can regulate the thermal expansivity in middle layer, the thermal expansivity of the coefficient of expansion in middle layer and matrix is approached and on matrix wettability good.Someone adopts oxide glass to connect the report of thyrite as the middle layer scolder, for example, and the people such as H.L.LEE, (J.Mater.Sci.33 (1998) 5007-5014) and with MgO-Al
2O
3-SiO
2The system mixed oxide is the middle layer, obtains wettability well and the articulamentum of matched coefficients of thermal expansion, and strength of joint is between 342-380MPa; And for example, the people such as Timothy J.Perham, (J.Am.Ceram.Soc.82 (1999) 297-305) do the middle layer with cordierite glass-ceramic and connect, and have also obtained good connection effect.The technological process more complicated such as but the connection temperature surpasses 1450 ℃, and needs vacuum or inert atmosphere protection, crystallization and cost are higher.
Therefore, it is very crucial for reduction cost, raising connection reliability that reduction connects temperature, simplification connects technological process.The present invention intends with Na
2O-B
2O
3-SiO
2(NBS) system is articulamentum, can and connect in normal pressure or air atmosphere under 1000 ℃ to 1150 ℃ relatively lower temps.Relevant middle layer oxide glass scolder composition still rarely has report.
Summary of the invention
The object of the present invention is to provide a kind of glass solder, preparation method and application for connecting the SiC pottery.
The present invention has obtained a kind of thermal expansivity and silicon carbide ceramics and has approached and the good glass solder of wettability by regulating the content of several oxide compounds of frit.And when connecting silicon carbide ceramics take this kind glass solder as the middle layer, obtained good connection effect.
Glass solder involved in the present invention belongs to Na
2O-B
2O
3-SiO
2System.Wherein, Na
2The quality percentage composition of O between 2.0%～20%, B
2O
3The quality percentage composition between 25%～40%, surplus is SiO
2With other compositions, described other consist of Sb
2O
3And As
2O
3The preferential Na that recommends
2O quality percentage composition between 2.0%～8%, B
2O
3The quality percentage composition between 30%～40%, surplus is SiO
2And Sb
2O
3And As
2O
3
Wherein, Na
2O can pass through soda ash (Na
2CO
3), saltcake (Na
2SO
4), the form such as sodium hydroxide (NaOH) introduces;
B
2O
3With boric acid (H
3BO
3) etc. form introduce;
As
2O
3And Sb
2O
3Quality percentage composition＜0.5%.
The preparation method of intermediate glass scolder provided by the present invention comprises
(1) presses above-mentioned composition batching and ball milling mixing 4-24 hour;
(2) mixed powder behind the ball milling was 90～100 ℃ of dryings 4 to 10 hours, and the platinum crucible of then packing into was founded 4 to 6 hours for 1350-1500 ℃ in retort furnace, cooled off being poured on the cold stainless steel plate under the glass solder high temperature after melting clarification;
(3) with the glass solder crushing screening (＜45 μ m) that obtains, be prepared into the intermediate glass scolder.
In order to test the as stated above thermal expansivity curve of the intermediate glass scolder of preparation, to be poured on the cold stainless steel plate at step (2) glass solder, the glass of gained is dropped in the resistance furnace, anneal at a certain temperature and removed thermal stresses in the glass in 30 minutes, be cut into 4 * 4 * 20mm
3The result that tests of size as shown in Figure 1.As can be seen from Figure 1, the thermal elongation curve of this glass and silicon carbide ceramics are very approaching before 410 ℃, connect the low thermophase coupling of middle layer and the carbon/silicon carbide ceramic matrix body heat coefficient of expansion good.
In addition, the glass grinding Cheng Fenhou that obtains is added a certain amount of solvent and binding agent be pressed into the thick disk of 1mm and be placed on the silicon carbide substrate, respectively be incubated 10 minutes in 1000 ℃ to the 1200 ℃ temperature ranges, cooling is measured its wetting angle with sessile drop method.Wetting angle is less than 10 ° when found that temperature to 1150 ℃, and wettability is good.
Glass of the present invention is comprised of following step as the connection technique in the solder application of middle layer:
(1) this intermediate glass scolder is prepared into slurry and also this slurry is evenly coated in silicon carbide ceramics end face to be connected, another silicon carbide ceramics to be connected head to head is pressed in and forms sandwich structure above the middle layer, fixes with anchor clamps.Intermediate layer thickness is controlled between the 10-1000 micron; The binding agent such as the PVB (polyvinyl butyral acetal) that are commonly used during the preparation slurry;
(2) the sandwich structure sample that above-mentioned anchor clamps are fixing is put into resistance furnace, is raised to 1000-1250 ℃ temperature range with the temperature rise rate of 1-10 ℃/min, is incubated 10-180 minute, finishes the connection of silicon carbide ceramics.
Above-mentioned institute all is to carry out under normal pressure and air atmosphere in steps.
The present invention relates to a kind of composition that can be used for the glass middle layer that silicon carbide ceramics connects with and connect the technique of silicon carbide ceramics as the middle layer scolder.This glass main component is Na
2O, B
2O
3, SiO
2And a small amount of additive.The present invention is by regulating the proportioning of several oxide compounds, obtains that a kind of melt temperature is low, thermal expansivity is close with normal pressure-sintered silicon carbide ceramics, and temperature when reaching 1150 ℃ glass solder at silicon carbide ceramics moistened surface angle less than 10 °, wettability is good.Connectivity scenario proposed by the invention connects temperature low, and technique is simple, convenient operation, and cost is low, and can access well behaved silicon carbide linker.
Description of drawings
Fig. 1 is that glass middle layer and silicon carbide ceramic thermal extension curve compare;
Fig. 2 is the interface microtexture take NBS glass as articulamentum.
1 expression SiC matrix among the figure, 2 expressions connect the middle layer.
Embodiment
Further specify the corresponding glass properties that forms of the present invention and be used for connecting the application of silicon carbide ceramics below by concrete example.
Embodiment 1:Na
2O quality percentage composition is 2%-8%, B
2O
3The quality percentage composition is 30%-40%, and surplus is SiO
2When reaching other components, thermal expansion coefficient of glass is 4.29 * 10 between 20-400 ℃
-6K
-1As can be seen from Figure 1, the thermal elongation rate of intermediate glass scolder and sintered sic pottery are close below 410 ℃.
Embodiment 2: sieve the frit grinding that the present invention obtains rear as middle layer scolder connection silicon carbide ceramics, glass middle layer scolder is evenly coated in two blocks of silicon carbide ceramics to be connected surface and forms sandwich structure, temperature rise rate with 5 ℃/min is raised to 1100 ℃, is incubated 1 hour.The three-point bending resistance intensity that obtains material is 111 ± 10MPa.
Embodiment 3: sieve the frit grinding that the present invention obtains rear as middle layer scolder connection silicon carbide ceramics, glass middle layer scolder is evenly coated in two blocks of silicon carbide ceramics to be connected surface and forms sandwich structure, temperature rise rate with 5 ℃/min is raised to 1150 ℃, is incubated 10 minutes.The three-point bending resistance intensity that obtains material is 141 ± 27MPa.Interface pattern such as Fig. 2 of obtaining after the connection.Can find out, the defective such as flawless or bubble at the interface, the interface is better in conjunction with effect, and strength of joint is good.
Claims (5)
1. a method that connects the intermediate glass scolder of usefulness for the preparation of silicon carbide ceramics is characterized in that described intermediate glass scolder is Na
2O-B
2O
3-SiO
2System, wherein Na
2The quality percentage composition of O between 2.0%～20%, B
2O
3The quality percentage composition between 25%～35%, surplus is SiO
2And other compositions, described other consist of Sb
2O
3And As
2O
3, the preparation of intermediate glass scolder comprises following step:
(a) by the composition of aforesaid intermediate glass scolder batching, and ball milling mixing 4-24 hour;
(b) mixed powder behind the ball milling was 90～100 ℃ of dryings 4 to 10 hours, and the platinum crucible of then packing into was founded 4 to 6 hours for 1350-1500 ℃ in retort furnace, cooled off being poured on the cold stainless steel plate under the glass solder high temperature after melting clarification;
(c) with the glass solder crushing screening that obtains, be prepared into the intermediate glass scolder.
2. by method claimed in claim 1, it is characterized in that:
A) use the SiC abrading-ball during step a ball milling, the solvent during ball milling is deionized water, dehydrated alcohol or acetone;
B) Ball-milling Time of step a is 8-16 hour;
C) the frit particle diameter after described step c sieves＜45 μ m.
3. press the application of the intermediate glass scolder of the described method preparation of claim 1, it is characterized in that connecting the SiC pottery and may further comprise the steps:
(1) with described intermediate glass scolder, is modulated into slurry with binding agent;
(2) slurry that step 1 is prepared evenly is coated in two end faces of SiC pottery to be connected, forms sandwich structure, fixes with anchor clamps;
(3) sandwich structure that step 2 anchor clamps are fixing is put into resistance furnace, is warming up to the connection that the SiC pottery is finished in 1000-1250 ℃ of insulation.
4. by application claimed in claim 3, it is characterized in that the thickness of the intermediate glass solder layer of described two end faces that are coated in SiC pottery to be connected of step (2) is 10～1000 microns.
5. by application claimed in claim 3, the temperature rise rate that it is characterized in that step (3) is 1-10 ℃/min; Soaking time is 10-180 minute, and connection technique is implemented in normal pressure and air atmosphere.
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|---|---|---|---|
| CN 201010108339 CN102145978B (en) | 2010-02-10 | 2010-02-10 | Glass solder for connecting SiC ceramics, and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010108339 CN102145978B (en) | 2010-02-10 | 2010-02-10 | Glass solder for connecting SiC ceramics, and preparation method and application thereof |
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| Publication Number | Publication Date |
|---|---|
| CN102145978A CN102145978A (en) | 2011-08-10 |
| CN102145978B true CN102145978B (en) | 2013-01-16 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107021635A (en) * | 2017-04-26 | 2017-08-08 | 苏州融睿电子科技有限公司 | Glass solder and preparation method thereof |
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| CN102603345B (en) * | 2012-03-23 | 2014-01-22 | 内蒙古工业大学 | Method for quickly connecting ceramic materials by adopting high-temperature interlayer material |
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| CN104909795A (en) * | 2015-05-12 | 2015-09-16 | 哈尔滨工业大学 | High-temperature ceramic/metal riveting-glass sealing combination connection method |
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| CN112299869B (en) * | 2020-10-28 | 2021-08-31 | 中国科学院上海硅酸盐研究所 | Laser welding method for silicon carbide and composite material thereof |
| CN114478043B (en) * | 2022-01-12 | 2023-05-09 | 中国科学院上海硅酸盐研究所 | Connecting method of silicon carbide ceramic based on liquid phase sintering |
| CN115259670B (en) * | 2022-07-26 | 2023-11-28 | 冷水江市汇鑫电子陶瓷有限公司 | Glass-based solder and preparation method thereof |
| CN115626776B (en) * | 2022-10-17 | 2024-03-08 | 中国科学院上海硅酸盐研究所 | Glass powder applied to laser-assisted connection of silicon carbide ceramic material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4453305B2 (en) * | 2003-09-03 | 2010-04-21 | 日本電気硝子株式会社 | Fluorescent lamp outer tube and fluorescent lamp |
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2010
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|---|---|---|---|---|
| SU1668326A1 (en) * | 1989-03-10 | 1991-08-07 | Предприятие П/Я Г-4430 | Soldering glass |
| CN1116612A (en) * | 1994-09-10 | 1996-02-14 | 电子工业部第十二研究所 | Glass solder for sealing and its preparing method |
| CN1446767A (en) * | 2002-03-14 | 2003-10-08 | 日本电气硝子株式会社 | Glass preforming blank and its prodn. method |
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| CN107021635A (en) * | 2017-04-26 | 2017-08-08 | 苏州融睿电子科技有限公司 | Glass solder and preparation method thereof |
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| CN102145978A (en) | 2011-08-10 |
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