CN104276839B - The method for sealing of glass-ceramic - Google Patents
The method for sealing of glass-ceramic Download PDFInfo
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- CN104276839B CN104276839B CN201310293875.0A CN201310293875A CN104276839B CN 104276839 B CN104276839 B CN 104276839B CN 201310293875 A CN201310293875 A CN 201310293875A CN 104276839 B CN104276839 B CN 104276839B
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Abstract
The present invention relates to a kind of method for sealing of glass-ceramic, comprise: preparation and the glass dust of ceramic matrix matched coefficients of thermal expansion: preparing in borosilicate glass process, in base furnish, add the component of described ceramic matrix and for regulating the adjusting component of thermal coefficient of expansion, ball milling mixes, and carries out melting, cooling, ball milling makes described glass dust; Prepare glass-ceramic closure: make described glass-ceramic closure by being modulated into after described glass dust and binding agent, solvent to form vitreous coating layer and heat-treat on the sealing surface that is evenly coated on described ceramic matrix after paste under air atmosphere; And by described glass-ceramic closure with after sealing-in metal parts is worked good, under inert atmosphere, carry out sealing-in.
Description
Technical field
The present invention relates to a kind of by glass-ceramic, and then the method for carrying out sealing-in with metal.
Background technology
The application of the process for sealing of pottery and metal in modern industrial technology has very important meaning. Be not only vacuumCritical process in electronic device, and its range of application is more and more wider, is also widely used at present integrated antenna package, atomThe fields such as energy, high-energy physics, the energy, Medical Devices, chemical industry, auto industry, science and techniques of defence. Ceramic and metal jointing technologyDouble to grow up along with multi-disciplinary intersection, it is the extension of material application, is that a manufacturability and practicality are all very strongBasic technology. Along with vacuum electron device day by day opening up to high-power future development and ceramic and metal jointing process application fieldExhibition, to the quality of seal interface, as reliability, air-tightness, intensity, stability etc. are had higher requirement.
Traditional ceramic and metal jointing, all first metallizes crunch seal face, is then undertaken by scolder and metalSealing-in. Ceramic metallization technology is exactly that the surface being connected with metalwork at ceramic member applies by specific refractory metal (molybdenum, tungstenDeng) and the paste of metal oxide (aluminium oxide, calcium oxide, silica etc.) composition, and in reducing atmosphere high temperature(1300-1600 DEG C) sintering curing, makes ceramic member surface attachment one deck have the coating of metalline, so that and metal partsWeld, form ceramic-metal closure. First, ceramic metalizing process need to be consolidated by high temperature sintering in reducing atmosphereChange, the control of atmosphere is had to certain requirement, this has increased cost and the difficulty of operation undoubtedly; Secondly, utilize ceramic metallizationThe closure that technique obtains when metal molybdenum or tungsten are had to certain corrosive environment, the air-tightness of seal interface, stabilityAnd reliability will be difficult to be guaranteed; In addition the closure that, utilizes ceramic metalizing process to obtain contains multiple boundaries in sealing-in placeSurface layer (as the interface between ceramic component and metal layer, the interface between metal layer and scolder, scolder and metal parts itBetween interface), and boundary layer is the weakest place of whole closure, thereby ceramic metallization sealing technology is to process for sealing mistakeThe control of journey is had higher requirement.
Summary of the invention
The object of this invention is to provide a kind of new approaches of ceramic and metal jointing, to overcome the deficiencies in the prior art. ThisBright inventor finds after deliberation, first by the position surface vitrification of crunch seal part sealed portion, crunch seal face apply one deck byThe paste of glass dust furnishing carries out high-temperature heat treatment under air atmosphere, utilizes the phase counterdiffusion of glass ingredient and ceramic composition,Particularly ceramic composition, to the diffusion in glass under concentration difference effect, forms component at crunch seal face and has the knot that gradient distributesClose firmly vitrifying layer, then direct and metal carries out sealing-in by vitrifying layer, can realize this purpose.
At this, the invention provides a kind of method for sealing of glass-ceramic, comprising:
(1) preparation and the glass dust of ceramic matrix matched coefficients of thermal expansion: preparing in borosilicate glass process, in base furnishIn add the component of described ceramic matrix and for regulating the adjusting component of thermal coefficient of expansion, ball milling mixes, carry out melting,Cooling, ball milling makes described glass dust;
(2) prepare glass-ceramic closure: after being modulated into paste after described glass dust and binding agent, solvent, evenly applyOn the sealing surface of described ceramic matrix, form vitreous coating layer and heat-treat under air atmosphere and make described glass-ceramicClosure; And
(3) by described glass-ceramic closure with after sealing-in metal parts is worked good, under inert atmosphere, carry out sealing-in.
The present invention is first by the position surface vitrification of crunch seal part sealed portion, and then direct and metal seals by vitrifying layerConnect. Glass-ceramic is to apply the paste of one deck by glass dust furnishing at crunch seal face, carries out high warm place under air atmosphereReason, the phase counterdiffusion, particularly ceramic composition that utilizes glass ingredient and ceramic composition under concentration difference effect to the expansion in glassLoose, form component at crunch seal face and there is the firmly vitrifying layer of combination that gradient distributes. Envelope with traditional ceramic metallizationThe method of connecing is compared, and in the method for sealing of glass-ceramic of the present invention, the effect by chemical bond between pottery and glass is combined in oneRise, make both combinations very firm, interface stability is high, and air-tightness is good; Adjustable due to the thermal coefficient of expansion of glass dustWide ranges, makes common pottery all can select the seal glass that thermal coefficient of expansion and component match with it, thereby realizes potteryThe vitrifying on surface, closure sealed portion position, this has greatly expanded the range of application of glass-ceramic sealing technology.
Preferably, in described step (1), the component of described ceramic matrix can be Al2O3、ZrO2、SiO2、MgO or its any mixture. Described base furnish comprises SiO2、B2O3Or H3BO3、Al2O3, and R2O orR2CO3, wherein R2O is Li2O、Na2O and K2In O at least one.
Again, described adjusting component can be MgO, Bi2O3、ZrO2And TiO2In at least one. By selecting differenceAdjusting component can make the thermal coefficient of expansion of described glass dust regulate within a large range, thereby conventional pottery is all optionalSelect out the seal glass that thermal coefficient of expansion and component match with it, thereby realize the glass on surface, crunch seal part sealed portion positionChange, this has greatly expanded the range of application of glass-ceramic sealing technology.
Again, preferably, in described step (1), each component in the molal quantity of described adjusting component and described base furnishThe mol ratio of total mole number can be (0.02～0.2): 1.
One preferred embodiment in, in described step (1), described melting can be molten at 1200～1600 DEG CRefine 0.5～6 hour.
Preferably, the particle diameter of described glass dust can be 2～200 μ m, is preferably 5～20 μ m.
Preferably, in described step (2), described binding agent can be polyvinyl butyral resin, ethyl cellulose, pinePerfume (or spice) and/or nitrocellulose.
Again, described solvent can be ethanol, acetone, terpinol, butyl acetate, n-butanol and/or cyclohexanone.
Again, the weight ratio of glass dust, binding agent, solvent can be (40wt%～80wt%): (2wt%～10wt%): （15wt%～55%）。
Preferably, in described step (2), described coating is to apply by dip-coating, spraying or serigraphy.
The thickness of the vitreous coating layer forming in described step (2) again, can be 0.5～3mm.
One preferred embodiment in, in described step (2), described heat treatment can be at 600～1200 DEG CProcess 0.5～24 hour. Through this heat treatment, between pottery and vitrifying layer, by the phase counterdiffusion of component, form componentThe boundary layer of graded, combines pottery and glass by the effect of chemical bond, makes both combinations very firmGu interface stability is high, air-tightness is good.
And compared with the technique of ceramic metallization, glass-ceramic just can carry out under air atmosphere, and heat treatment temperatureDegree (not higher than 1200 DEG C), well below the heat treatment temperature (1300～1600 DEG C) of ceramic metallization, becomes Technology for Heating ProcessingMust be more easy to operate, reduced energy consumption simultaneously, effectively reduce cost.
Another preferred embodiment in, in described step (3), described sealing-in can be at Ar or N2AtmosphereUnder in 600～1200 DEG C of sealing-ins 30～120 minutes. Can be directly after glass-ceramic and metal carry out sealing-in, do not need additionally to addAdd scolder, simplified process for sealing, reduced seal interface simultaneously, improved the reliability and stability of process for sealing.
Brief description of the drawings
Fig. 1 is the principle schematic of glass-ceramic method for sealing of the present invention.
Detailed description of the invention
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that following embodiment is only for sayingBright the present invention, and unrestricted the present invention.
The object of this invention is to provide a kind of new approaches of ceramic and metal jointing, to overcome the deficiencies in the prior art. ThisThe bright method for sealing that discloses a kind of glass-ceramic, first by the position surface vitrification of crunch seal part sealed portion, then directly with goldenBelong to and carry out sealing-in by vitrifying layer. Fig. 1 is the principle schematic of glass-ceramic method for sealing of the present invention, referring to Fig. 1,Glass-ceramic is exactly to apply the paste of one deck by glass dust furnishing at crunch seal face, carries out high warm place under air atmosphereReason, the phase counterdiffusion, particularly ceramic composition that utilizes glass ingredient and ceramic composition under concentration difference effect to the expansion in glassLoose, form component at crunch seal face and there is the firmly vitrifying layer of combination that gradient distributes.
As example, the method for sealing of glass-ceramic of the present invention can comprise the steps.
(1) preparation of the glass dust of matched coefficients of thermal expansion
Taking traditional borosilicate glass as basis, basic components is SiO2、B2O3Or H3BO3、Al2O3、R2O or R2CO3（R2O is Li2O、Na2O、K2One or more in O, R2CO3For Li2CO3、Na2CO3、K2CO3In oneOr several), and according to the component of ceramic matrix and thermal coefficient of expansion, add MgO, Bi2O3、ZrO2、TiO2Deng to glassComponent and thermal coefficient of expansion regulate and control, make it to match with ceramic matrix; All raw materials are at the high temperature of 1200～1600 DEG CLower melting 30～360 minutes; After quick cooling, obtain glass dregs; Glass dregs obtains glass dust through ball milling, after sieving, preferably glassThe particle diameter of glass powder is 2～200 μ m.
(2) will after the glass dust in step (1) and binding agent, solvent, be modulated into paste. Described binding agent bagDraw together but be not limited to polyvinyl butyral resin (PVB), ethyl cellulose (EC), rosin and/or nitrocellulose. Described solvent bagDraw together but be not limited to ethanol, acetone, terpinol, butyl acetate, n-butanol and/or cyclohexanone. Glass dust, binding agent, solventWeight ratio be (40wt%～80wt%): (2wt%～10wt%): (15wt%～55%).
(3) by the sealing surface of even paste in step (2) coating and ceramic matrix
Described ceramic matrix is Al2O3、ZrO2、SiO2, MgO and contain in these components one or more compound; ApplyMethod includes but not limited to that dip-coating, spraying, serigraphy, machinery apply. The thickness of vitreous coating layer forming is 0.5～3mm。
(4) pottery that is coated with glass dust of step (3) gained is placed in to for example Muffle furnace of firing equipment, at airIn atmosphere, heat-treat
Described heat treatment temperature is 600～1200 DEG C, and heat treatment time is 0.5～24 hour.
(5) by the parts of step (4) gained with after the metal parts sealing is worked good, under inert atmosphere, carry out sealing-inDescribed sealing temperature is 600～1200 DEG C, and the sealing-in time is 30～120 minutes; Described inert atmosphere is Ar or N2。
The sealing technology of glass-ceramic of the present invention has the following advantages:
1, between pottery and vitrifying layer, pass through the phase counterdiffusion of component, formed the boundary layer that composition gradient changes, pass through chemical bondEffect pottery and glass are combined, make both combinations very firm, interface stability is high, air-tightness is good;
2, because the thermal coefficient of expansion of glass dust can regulate within a large range according to the difference of its component, thereby conventional potteryPorcelain all can be selected the seal glass that thermal coefficient of expansion and component match with it, thereby realizes surface, crunch seal part sealed portion positionVitrifying, this has greatly expanded the range of application of glass-ceramic sealing technology;
3, compared with the technique of ceramic metallization, glass-ceramic just can carry out under air atmosphere, and heat treatment temperature (not higher than1200 DEG C) well below the heat treatment temperature (1300～1600 DEG C) of ceramic metallization, make Technology for Heating Processing become more easily behaviourDo, reduced energy consumption simultaneously, effectively reduced cost;
4, can be directly after glass-ceramic and metal carry out sealing-in, do not need additionally to add scolder, simplified process for sealing, subtract simultaneouslyLack seal interface, improved the reliability and stability of process for sealing.
Embodiment further give an example below to describe the present invention in detail. Should be understood that equally following examples are only for to thisBright being further described, and can not be interpreted as limiting the scope of the invention, those skilled in the art is according to the present inventionSome nonessential improvement of making of foregoing and adjust and all belong to protection scope of the present invention. The reaction that following example is concrete, those skilled in the art can be by herein temperature, time, inventory etc. are only also examples in OK range,Illustrate to do in suitable scope and select, and do not really want to be defined in the below concrete numerical value of example.
Embodiment 1
(a) preparation of the glass dust of matched coefficients of thermal expansion
beta-Al2O3Thermal coefficient of expansion be 6～7 × 10-6K-1(25～300 DEG C), select thermal coefficient of expansion match and component in containThere is Al2O3Borosilicate glass as seal glass. By SiO2、Al2O3、H3BO3、Na2CO3、K2CO3、Li2CO3、Bi2O3According to component S iO2：Al2O3：B2O3：Na2O：K2O：Li2O：Bi2O3=40:3:18:3:3:1:32Prepare burden; Taking absolute ethyl alcohol as medium, ball milling 4 hours, dries; Sintering 2 hours at 800 DEG C, then at the height of 1400 DEG CThe lower melting of temperature 2 hours; After quick cooling, obtain glass dregs; Glass dregs obtains glass dust, preferred glass powder through ball milling, after sievingParticle diameter be 10～20 μ m. This glass dust is 6.2 × 10 at the thermal coefficient of expansion of 25～300 DEG C-6K-1。
(b) preparation of glass paste
Make solvent with absolute ethyl alcohol, the PVB that weight ratio is 3% makes binding agent, the glass dust of gained in (a) is modulated into component equalEven paste.
(c) paste being modulated into by glass dust in (b) is evenly coated on to beta-Al2O3Crunch seal part sealing-in positionSurface, coating method is manual, the thickness of coat is 2mm.
(d) vitrifying on surface, crunch seal part sealed portion position
Parts in (c) are placed in to Muffle furnace, in air atmosphere in 900 DEG C, heat treatment 2 hours.
(e) sealing-in of pottery and metal
By the crunch seal part in (d) with after the metal parts sealing is worked good, under Ar atmosphere, carry out sealing-in, sealing temperature is1000 DEG C, the sealing-in time is 50 minutes.
The testing result of helium mass spectrometer leak detector shows, the helium leak rate of closure is less than 10-11Pa·m3·s-1; Mechanics Performance Testing knotReally show, the sealing strength of closure is about 85MPa.
Embodiment 2
(a) preparation of the glass dust of matched coefficients of thermal expansion: with embodiment 1;
(b) preparation of glass paste: the mixture (1:4) with ethanol and terpinol is made solvent, and the EC that weight ratio is 3% bondsAgent, is modulated into the uniform paste of component by the glass dust of gained in (a);
(c) with embodiment 1;
(d) vitrifying on surface, crunch seal part sealed portion position: with embodiment 1;
(e) sealing-in of pottery and metal: with embodiment 1;
The testing result of helium mass spectrometer leak detector shows, the helium leak rate of closure is 10-11Pa·m3·s-1; Mechanical experimental results shows,The sealing strength of closure is about 91MPa.
Embodiment 3
(a) preparation of the glass dust of matched coefficients of thermal expansion: the particle diameter of preferred glass powder is 5～15 μ m, the same embodiment of all the other conditions1；
(b) preparation of glass paste: with embodiment 1;
(c) paste being modulated into by glass dust in (b) is evenly coated on to beta-Al2O3The surface at crunch seal part sealing-in position,Coating method is serigraphy, and the thickness of coat is 1.5mm;
(d) vitrifying on surface, crunch seal part sealed portion position: with embodiment 1;
(e) sealing-in of pottery and metal: with embodiment 1;
The testing result of helium mass spectrometer leak detector shows, the helium leak rate of closure is 1.8 × 10-10Pa·m3·s-1; Mechanical experimental results tableBright, the sealing strength of closure is about 69MPa.
Embodiment 4
(a) preparation of the glass dust of matched coefficients of thermal expansion
ZrO2Thermal coefficient of expansion be 9～10 × 10-6K-1(25～300 DEG C), select thermal coefficient of expansion match and component in containZrO2Borosilicate glass as seal glass. By SiO2、Al2O3、H3BO3、Na2CO3、K2CO3、Bi2O3、ZrO2According to component S iO2：Al2O3：B2O3：Na2O：K2O：Bi2O3：ZrO2=10:3:18:1:5:60:3 prepares burden;Taking absolute ethyl alcohol as medium, ball milling 4 hours, dries; Sintering 2 hours at 800 DEG C, then melting 1 under the high temperature of 1500 DEG CHour; After quick cooling, obtain glass dregs; Glass dregs obtains glass dust through ball milling, after sieving, and the particle diameter of preferred glass powder is10～20 μ m. This glass dust is 9～10 × 10 at the thermal coefficient of expansion of 25～300 DEG C-6K-1
(b) preparation of glass paste: with embodiment 1;
(c) paste being modulated into by glass dust in (b) is evenly coated on to ZrO2The surface at crunch seal part sealing-in position, appliesMode is that machinery applies, and the thickness of coat is 2mm;
(d) vitrifying on surface, crunch seal part sealed portion position: with embodiment 1;
(e) sealing-in of pottery and metal: with embodiment 1;
The testing result of helium mass spectrometer leak detector shows, the helium leak rate of closure is less than 10-11Pa·m3·s-1; Mechanical experimental results tableBright, the sealing strength of closure is about 88MPa.
Embodiment 5
(a) preparation of the glass dust of matched coefficients of thermal expansion: with embodiment 4;
(b) preparation of glass paste: with embodiment 4;
Make solvent with acetone, the nitrocellulose that weight ratio is 2.5% is made binding agent, and glass dust is modulated into the uniform paste of component;
(c) with embodiment 4;
(d) vitrifying on surface, crunch seal part sealed portion position
Parts in (c) are placed in to Muffle furnace, in air atmosphere in 800 DEG C, heat treatment 4 hours;
(e) sealing-in of pottery and metal
By the crunch seal part in (d) with after the metal parts sealing is worked good, under Ar atmosphere, carry out sealing-in, sealing temperature is900 DEG C, the sealing-in time is 120 minutes;
The testing result of helium mass spectrometer leak detector shows, the helium leak rate of closure is less than 10-11Pa·m3·s-1; Mechanical experimental results tableBright, the sealing strength of closure is about 86MPa.
Embodiment 6
(a) preparation of the glass dust of matched coefficients of thermal expansion: with embodiment 4;
(b) preparation of glass paste: with embodiment 4;
(c) with embodiment 4;
(d) vitrifying on surface, crunch seal part sealed portion position: with embodiment 4;
(e) sealing-in of pottery and metal
By the crunch seal part in (d) with after the metal parts sealing is worked good in N2Under atmosphere, carry out sealing-in, sealing temperature is1050 DEG C, the sealing-in time is 30 minutes;
The testing result of helium mass spectrometer leak detector shows, the helium leak rate of closure is less than 10-11Pa·m3·s-1; Mechanical experimental results tableBright, the sealing strength of closure is about 93MPa.
Industrial applicability: in the method for sealing of glass-ceramic of the present invention, between pottery and glass by the effect of chemical bondCombine, make both combinations very firm, interface stability is high, and air-tightness is good; Due to the thermal expansion system of glass dustThe adjustable extent of number is wide, makes common pottery all can select the seal glass that thermal coefficient of expansion and component match with it, therebyRealize the vitrifying on surface, crunch seal part sealed portion position, and then carry out sealing-in with metal, can be applied to integrated antenna package,The fields such as atomic energy, high-energy physics, the energy, Medical Devices, chemical industry, auto industry, science and techniques of defence.
Claims (11)
1. a method for sealing for glass-ceramic, is characterized in that, comprising:
(1) preparation and the glass dust of ceramic matrix matched coefficients of thermal expansion: preparing in borosilicate glass process, in base furnish, add the component of described ceramic matrix and for regulating the adjusting component of thermal coefficient of expansion, ball milling mixes, carry out melting, cooling, ball milling makes described glass dust, described adjusting component is MgO, Bi2O3、ZrO2And TiO2In at least one, in the molal quantity of described adjusting component and described base furnish, the mol ratio of each component total mole number is (0.02～0.2): 1;
(2) prepare glass-ceramic closure: make described glass-ceramic closure by being modulated into after described glass dust and binding agent, solvent to form vitreous coating layer and heat-treat on the sealing surface that is evenly coated on described ceramic matrix after paste under air atmosphere; And
(3) by described glass-ceramic closure with after sealing-in metal parts is worked good, under inert atmosphere, carry out sealing-in.
2. method for sealing according to claim 1, is characterized in that, in described step (1), the component of described ceramic matrix is Al2O3、ZrO2、SiO2, MgO or its any mixture, described base furnish comprises SiO2、B2O3Or H3BO3、Al2O3, and R2O or R2CO3, wherein R2O is Li2O、Na2O and K2In O at least one.
3. method for sealing according to claim 1, is characterized in that, in described step (1), described melting is 1200～1600 DEG C of meltings 0.5～6 hour.
4. method for sealing according to claim 1, is characterized in that, the particle diameter of glass dust prepared by described step (1) is 2～200 μ m.
5. method for sealing according to claim 1, is characterized in that, in described step (2), described binding agent is polyvinyl butyral resin, ethyl cellulose, rosin and/or nitrocellulose.
6. method for sealing according to claim 1, is characterized in that, in described step (2), described solvent is ethanol, acetone, terpinol, butyl acetate, n-butanol and/or cyclohexanone.
7. method for sealing according to claim 1, is characterized in that, in described step (2), the weight ratio of glass dust, binding agent, solvent is (40wt%～80wt%): (2wt%～10wt%): (15wt%～55%).
8. according to the method for sealing described in claim 1, it is characterized in that, in described step (2), described coating is to apply by dip-coating, spraying or serigraphy.
9. method for sealing according to claim 1, is characterized in that, the thickness of the vitreous coating layer forming in described step (2) is 0.5～3mm.
10. method for sealing according to claim 1, is characterized in that, in described step (2), described heat treatment is to process 0.5～24 hour at 600～1200 DEG C.
11. according to the method for sealing described in any one in claim 1～10, it is characterized in that, in described step (3), described sealing-in is at Ar or N2Under atmosphere in 600～1200 DEG C of sealing-ins 30～120 minutes.
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| CN110028246B (en) * | 2019-05-08 | 2021-08-03 | 哈尔滨工业大学 | Glass solder and preparation method and application thereof |
| CN116495992A (en) * | 2023-04-26 | 2023-07-28 | 华东理工大学 | Glass ceramic slurry for temperature sensor and preparation method thereof |
| CN116854500A (en) * | 2023-07-03 | 2023-10-10 | 优钢新材料科技(湖南)有限公司 | Method for coating high expansion coefficient film on ZTA particle surface |
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| EP0922682A1 (en) * | 1997-12-12 | 1999-06-16 | FINMECCANICA S.p.A. AZIENDA ANSALDO | Method of forming a joint between a ceramic substrate and a metal component |
| CN101103478A (en) * | 2004-12-28 | 2008-01-09 | 丹麦科技大学 | Method of producing metal to glass, metal to metal or metal to ceramic connections |
| CN101439982A (en) * | 2007-11-22 | 2009-05-27 | 曾松 | Process for sealing ceramic-stainless steel |
| CN101857457A (en) * | 2010-05-19 | 2010-10-13 | 中国电子科技集团公司第四十三研究所 | Transition layer for combination of ceramic composite substrate and metal and preparation method thereof |
| CN103596903A (en) * | 2011-09-05 | 2014-02-19 | 三井金属矿业株式会社 | Bonded ceramic and process for producing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0922682A1 (en) * | 1997-12-12 | 1999-06-16 | FINMECCANICA S.p.A. AZIENDA ANSALDO | Method of forming a joint between a ceramic substrate and a metal component |
| CN101103478A (en) * | 2004-12-28 | 2008-01-09 | 丹麦科技大学 | Method of producing metal to glass, metal to metal or metal to ceramic connections |
| CN101439982A (en) * | 2007-11-22 | 2009-05-27 | 曾松 | Process for sealing ceramic-stainless steel |
| CN101857457A (en) * | 2010-05-19 | 2010-10-13 | 中国电子科技集团公司第四十三研究所 | Transition layer for combination of ceramic composite substrate and metal and preparation method thereof |
| CN103596903A (en) * | 2011-09-05 | 2014-02-19 | 三井金属矿业株式会社 | Bonded ceramic and process for producing same |
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