CN102086118A - Aluminum oxide ceramic prone to Mo-Mn metallization and preparation method of aluminum oxide ceramic - Google Patents
Aluminum oxide ceramic prone to Mo-Mn metallization and preparation method of aluminum oxide ceramic Download PDFInfo
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- CN102086118A CN102086118A CN 201010585204 CN201010585204A CN102086118A CN 102086118 A CN102086118 A CN 102086118A CN 201010585204 CN201010585204 CN 201010585204 CN 201010585204 A CN201010585204 A CN 201010585204A CN 102086118 A CN102086118 A CN 102086118A
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Abstract
The invention discloses an aluminum oxide ceramic prone to Mo-Mn metallization and a preparation method of the aluminum oxide ceramic. The preparation method comprises the following steps: taking and evenly mixing the following raw materials in percentage by weight: 92%-94% of aluminum oxide, 3%-5% of silica, 0.75%-1.2% of calcium oxide, 1.12%-1.2% of barium oxide and 0.49%-0.7% of magnesium oxide; ball-milling; sintering green bodies for 4-6 hours at the temperature of 1650-1680 DEG C; and naturally cooling to room temperature. In the technical scheme of the invention, a glass phase with a proper viscosity at a certain temperature exists in the aluminum oxide ceramic, so that the diffusion and migration of the glass phase between the ceramic and a metalized layer can be achieved, thereby achieving a better sealing effect.
Description
Technical field
The present invention relates to a kind of alumina-ceramic and preparation method thereof, more particularly, relate to a kind of metallized alumina-ceramic of Mo-Mn and preparation method thereof that is easy to realize.
Background technology
Because 95% left and right sides aluminum oxide (Al
2O
3) pottery has good electric property under high frequency, its dielectric loss is little, and specific volume resistance is big, intensity is high, hardness is big, thermal expansivity is little, and advantage, the present main insulating material that has become in the electron tube such as wear-resisting and resistance to sudden heating is good.But since alumina-ceramic can't with metal solder, when reality is used, need promptly metallize at ceramic surface sintering layer of metal film.Present 95% alumina-ceramic factory mostly adopts Mo-Mn to metallize, but for different technology, there is bigger difference in the metal layer that obtains, and different metal layer microstructures directly has influence on bonding strength and resistance to air loss between alumina-ceramic-metallic substance.In general, metal layer has the microstructure of even compact, is the basis that obtains the high sealing property of ceramic-metal.
For obtaining the preferred metal effect, Chinese invention patent application " a kind of compoistion and method of use that is used for ceramic metallization " (application number 200910116273.1, March 4 2009 applying date, open day on September 23rd, 2009) disclose in composition, add titanium dioxide powder, magnesia powder has improved the infiltration of the composition of ceramic metallization to pottery, has improved the sealing strength of pottery with metal sealing spare.But lack at aluminum oxide (Al
2O
3) improvement of ceramic composition, to satisfy the metallized requirement of Mo-Mn.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, metallized alumina-ceramic of a kind of Mo-Mn of being easy to and preparation method thereof is provided, having at a certain temperature in the alumina-ceramic, the glassy phase of proper viscosity exists, enable to realize diffusion, the migration of glassy phase between pottery and metal layer, reach sealing-in preferably.
Purpose of the present invention is achieved by following technical proposals:
A kind of metallized alumina-ceramic of Mo-Mn that is easy to, adopt following raw material to prepare as follows:
(1) takes by weighing raw material according to following mass percent, mix the back ball milling
Aluminium sesquioxide 92%-94%
Silicon-dioxide 3%-5%
Calcium oxide 0.75%-1.2%
Barium oxide 1.12%-1.2%
Magnesium oxide 0.49%-0.7%
(2) add tackiness agent in the raw material powder behind ball milling, make green compact, then with green compact after 1650-1680 ℃ of following sintering 4-6 hour, naturally cool to room temperature.
In the described step (1), preferably mixed raw material wet-milling is reached 3-4 μ m to powder diameter index D50.
In the described step (1), can preferably adjust calcium oxide in described mass percent scope and magnesian mass ratio is 1.5-2, the mass ratio of barium oxide and calcium oxide is 1.0-1.5.
In the described step (2), preferably add the tackiness agent of 1-3% of its mass percent in the raw material powder behind ball milling after, spraying drying; Described tackiness agent is polyvinyl alcohol, Walocel MT 20.000PV or Natvosol.
In the described step (2), behind the employing isostatic pressing, car is made base.
In the described step (2), preferably with green compact 1650-1680 ℃ of following sintering 4 hours.
A kind of preparation is easy to the method for the metallized alumina-ceramic of Mo-Mn, carries out according to following step: (1) takes by weighing raw material according to following mass percent, mixes the back ball milling
Aluminium sesquioxide 92%-94%
Silicon-dioxide 3%-5%
Calcium oxide 0.75%-1.2%
Barium oxide 1.12%-1.2%
Magnesium oxide 0.49%-0.7%
(2) add tackiness agent in the raw material powder behind ball milling, make green compact, then with green compact after 1650-1680 ℃ of following sintering 4-6 hour, naturally cool to room temperature.
In the described step (1), preferably mixed raw material wet-milling is reached 3-4 μ m to powder diameter index D50.
In the described step (1), can preferably adjust calcium oxide in described mass percent scope and magnesian mass ratio is 1.5-2, the mass ratio of barium oxide and calcium oxide is 1.0-1.5.
In the described step (2), preferably add the tackiness agent of 1-3% of its mass percent in the raw material powder behind ball milling after, spraying drying; Described tackiness agent is polyvinyl alcohol, Walocel MT 20.000PV or Natvosol.
In the described step (2), behind the employing isostatic pressing, car is made base.
In the described step (2), preferably with green compact 1650-1680 ℃ of following sintering 4 hours.
According to the Twentyman theory, glassy phase migration, dispersal direction depend on the relative size of glassy phase capillary force in glassy phase in the pottery and the metal layer.In technical scheme of the present invention, for 95% alumina-ceramic is realized metallization better, add magnesium, calcium and barium component ratio by adjusting, final realization 95% alumina-ceramic can be under suitable temperature, by suitably form, the glassy phase of viscosity exists, and then realizes the Mo-Mn metallization better.Wherein the increase of BaO, CaO is intended to adjust behind the sintering glassy phase in the pottery and forms and viscosity, and the increase of CaO, MgO is intended to adjust the size of ceramic crystalline grain, and then the capillary force of influence pottery in the Mo-Mn metallization, can reduce metallizing temperature.Like this, in the Production of Ceramics process, can realize by forming control, burning till control, adjust, control well the size and the homogeneity of crystal grain, so that in pottery at a certain temperature by suitably form, the glassy phase of viscosity exists, suitably size and inhomogeneity crystal grain, realizes the metallized connection of Mo-Mn better.
Embodiment
Further specify technical scheme of the present invention below in conjunction with specific embodiment.
Embodiment 1
Adopt following raw material to carry out the preparation of 95% alumina-ceramic: Al
2O
3, SiO
2, CaO, BaO and MgO purity 〉=99.0%.
Take by weighing each constituent mass according to following mass percent, wet-milling is to powder diameter index D50:3～4 μ m, then to the polyvinyl alcohol that wherein adds raw materials quality summation 1% (being 1g), after the spraying drying powder is passed through isostatic pressing (as 180MPa), car is made green compact, at last in tunnel furnace with 1650～1680 ℃, sintering naturally cooled to room temperature after 4 hours.
Embodiment 2
Adopt following raw material to carry out the preparation of 95% alumina-ceramic: Al
2O
3, SiO
2, CaO, BaO purity 〉=99.0%; The technical grade potter's clay that uses in the ceramic industry (the quality percentage composition of potter's clay: SiO
2Be 53.4%, Al
2O
3Be 43.97%) and (the steatitic quality percentage composition: SiO of technical grade talcum
2Be 65.2%, MgO is 33.1%) provide part A l for system
2O
3, SiO
2And MgO.
Take by weighing each constituent mass according to following mass percent, wet-milling is to powder diameter index D50:3～4 μ m, then to the Walocel MT 20.000PV that wherein adds raw materials quality summation 2% (being 2g), after the spraying drying powder is passed through isostatic pressing (as 180MPa), car is made green compact, at last in tunnel furnace with 1650～1680 ℃, sintering naturally cooled to room temperature after 6 hours.
Adopt three kinds of metallizing formulas shown in the following table sample 1-6 of embodiment 1 and 2 preparations to be metallized (selecting metallizing temperature is 1300-1450 ℃) test of the line correlation performance of going forward side by side:
1. according to standard GB/T5593-1996, the method for GB/T2413-86 is tested its volume density (g/cm
3), the average-volume density of sample 1-6 is 3.7, GB regulation 3.6 on
2. according to standard GB/T5593-1996, the GB5594.1-85 method is tested its resistance to air loss and (is adopted the helium mass analyzer blowing process, use Britain Ying Fukang helium leak check instrument UL1000 type, leak helium speed, Pam
3/ s), the mean value of sample 1-6≤5 * 10
-12, be better than GB regulation≤1 * 10
-10
3. according to standard GB/T5593-1996, use the microcomputer control electronics universal testing machine CSS44020 of Changchun Inst of Testing Machine type, test its folding strength, the mean value of sample 1-6 is 316.8MPa
4. according to standard GB/T5593-1996, the GB5594.4-85 method is tested dielectric properties, uses the accurate high resistance analyser of 4294A type of U.S. Agilent company, and it is 9.4 that the dielectric of sample 1-6 is counted mean value, and dielectric loss angle tangent mean number is 1.8 * 10
-4
5. according to standard GB/T5593-1996, adopt 100KV type high-voltage breakdown device to test dc breakdown intensity (KV/mm), the mean value of sample 1-6 is 39
6. according to standard GB/T5593-1996, GB5594.5-85 method test volume resistivity (Ω cm), use the Shanghai ZC36 of instrument plant type megger, the volume specific resistance mean value of sample 1-6 is 5.7 * 10
14(100 ℃), 1.2 * 10
11(300 ℃), 4.1 * 10
9(500 ℃)
7. according to the method for industry standard SJ/T3326-2001 and SJ/T11246-2001, use German universal testing machine ZDM10T/51 type test ceramic-metal encapsulation performance, the sealing-in area is 1.22cm
2The sealing strength of sample 1-6 and metallizing formula 1 (MPa) mean value is 130.8, with sealing strength (MPa) mean value of metallizing formula 2 be 145.9, with sealing strength (MPa) mean value of metallizing formula 3 be 138.4, all be higher than the requirement of SJ/T11246 〉=90, and present and to hang down the performance that all can realize good sealing strength under the metallizing temperature with the metallizing formula of multiple different components, demonstrated fully in 95% pottery of the present invention and added magnesium by adjusting, calcium and barium component, pottery is made up of suitable under metallizing temperature, the glassy phase of viscosity exists, and then realizes the Mo-Mn metallization better.
More than the present invention has been done exemplary description; should be noted that; under the situation that does not break away from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (10)
1. one kind is easy to the metallized alumina-ceramic of Mo-Mn, it is characterized in that, adopts following raw material to prepare as follows:
(1) takes by weighing raw material according to following mass percent, mix the back ball milling
Aluminium sesquioxide 92%-94%
Silicon-dioxide 3%-5%
Calcium oxide 0.75%-1.2%
Barium oxide 1.12%-1.2%
Magnesium oxide 0.49%-0.7%
(2) add tackiness agent in the raw material powder behind ball milling, make green compact, then with green compact after 1650-1680 ℃ of following sintering 4-6 hour, naturally cool to room temperature.
2. a kind of metallized alumina-ceramic of Mo-Mn that is easy to according to claim 1 is characterized in that, in the described step (1), mixed raw material wet-milling is reached 3-4 μ m to powder diameter index D50.
3. a kind of metallized alumina-ceramic of Mo-Mn that is easy to according to claim 1 is characterized in that, in described step (1), adjusting calcium oxide and magnesian mass ratio is 1.5-2, and the mass ratio of barium oxide and calcium oxide is 1.0-1.5.
4. a kind of metallized alumina-ceramic of Mo-Mn that is easy to according to claim 1 is characterized in that, in the described step (2), adds the tackiness agent of the 1-3% of its mass percent in the raw material powder behind ball milling; Described tackiness agent is polyvinyl alcohol, Walocel MT 20.000PV or Natvosol.
5. a kind of metallized alumina-ceramic of Mo-Mn that is easy to according to claim 1 is characterized in that, in the described step (2), with green compact 1650-1680 ℃ of following sintering 4 hours.
6. prepare the method for the metallized alumina-ceramic of the Mo-Mn of being easy to as claimed in claim 1, it is characterized in that, prepare according to following step:
(1) takes by weighing raw material according to following mass percent, mix the back ball milling
Aluminium sesquioxide 92%-94%
Silicon-dioxide 3%-5%
Calcium oxide 0.75%-1.2%
Barium oxide 1.12%-1.2%
Magnesium oxide 0.49%-0.7%
(2) add tackiness agent in the raw material powder behind ball milling, make green compact, then with green compact after 1650-1680 ℃ of following sintering 4-6 hour, naturally cool to room temperature.
7. preparation according to claim 6 is easy to the method for the metallized alumina-ceramic of Mo-Mn, it is characterized in that, in the described step (1), mixed raw material wet-milling is reached 3-4 μ m to powder diameter index D50.
8. preparation according to claim 6 is easy to the method for the metallized alumina-ceramic of Mo-Mn, it is characterized in that, in described step (1), adjusting calcium oxide and magnesian mass ratio is 1.5-2, and the mass ratio of barium oxide and calcium oxide is 1.0-1.5.
9. preparation according to claim 6 is easy to the method for the metallized alumina-ceramic of Mo-Mn, it is characterized in that, in the described step (2), adds the tackiness agent of the 1-3% of its mass percent in the raw material powder behind ball milling; Described tackiness agent is polyvinyl alcohol, Walocel MT 20.000PV or Natvosol.
10. preparation according to claim 6 is easy to the method for the metallized alumina-ceramic of Mo-Mn, it is characterized in that, in the described step (2), with green compact 1650-1680 ℃ of following sintering 4 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103732558A (en) * | 2012-06-25 | 2014-04-16 | 京瓷株式会社 | Alumina ceramic, and ceramic wiring substrate and ceramic package using same |
| FR3058256A1 (en) * | 2016-11-02 | 2018-05-04 | Thales | ALUMINA CERAMIC-BASED ELECTRICAL INSULATION, METHOD FOR PRODUCING THE INSULATOR, AND VACUUM TUBE COMPRISING THE INSULATION |
| CN109761589A (en) * | 2019-03-15 | 2019-05-17 | 沈阳君威新能科技有限公司 | A kind of ceramics thermal battery inertia block ring and preparation method thereof |
| CN113173797A (en) * | 2021-06-01 | 2021-07-27 | 湖南新华源科技有限公司 | Al (aluminum)2O3Base ceramic welding sealing component and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250057A (en) * | 2007-12-14 | 2008-08-27 | 陈国安 | CaO-Al2O3-MgO-ZrO2-SiO2 series aluminum oxide electronic ceramics |
-
2010
- 2010-12-10 CN CN 201010585204 patent/CN102086118B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250057A (en) * | 2007-12-14 | 2008-08-27 | 陈国安 | CaO-Al2O3-MgO-ZrO2-SiO2 series aluminum oxide electronic ceramics |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103732558A (en) * | 2012-06-25 | 2014-04-16 | 京瓷株式会社 | Alumina ceramic, and ceramic wiring substrate and ceramic package using same |
| CN103732558B (en) * | 2012-06-25 | 2016-03-30 | 京瓷株式会社 | Aluminum oxide pottery and use its ceramic wiring board and ceramic package |
| CN110168695A (en) * | 2016-11-02 | 2019-08-23 | 塔莱斯公司 | Electrical insulator based on aluminium oxide ceramics, the method for manufacturing the insulator and the vacuum tube including the insulator |
| WO2018083194A1 (en) * | 2016-11-02 | 2018-05-11 | Thales | Alumina-ceramic-based electrical insulator, method for producing the insulator, and vacuum tube comprising the insulator |
| KR20190080906A (en) * | 2016-11-02 | 2019-07-08 | 탈레스 | ALUMINA-CERAMIC ELECTRIC INSULATOR, METHOD FOR MANUFACTURING THE INSULATOR, AND VACUUM TUBE CONTAINING THE INSULATOR |
| FR3058256A1 (en) * | 2016-11-02 | 2018-05-04 | Thales | ALUMINA CERAMIC-BASED ELECTRICAL INSULATION, METHOD FOR PRODUCING THE INSULATOR, AND VACUUM TUBE COMPRISING THE INSULATION |
| KR102254085B1 (en) | 2016-11-02 | 2021-05-18 | 탈레스 | Alumina-ceramic electrical insulator, method for manufacturing the insulator, and vacuum tube containing the insulator |
| CN110168695B (en) * | 2016-11-02 | 2021-10-15 | 塔莱斯公司 | Alumina ceramic-based electrical insulator, method for producing same, and vacuum tube |
| AU2017353417B2 (en) * | 2016-11-02 | 2021-12-09 | Thales | Alumina-ceramic-based electrical insulator, method for producing the insulator, and vacuum tube comprising the insulator |
| US11538604B2 (en) | 2016-11-02 | 2022-12-27 | Thales | Alumina-ceramic-based electrical insulator, method for producing the insulator, and vacuum tube comprising the insulator |
| CN109761589A (en) * | 2019-03-15 | 2019-05-17 | 沈阳君威新能科技有限公司 | A kind of ceramics thermal battery inertia block ring and preparation method thereof |
| CN113173797A (en) * | 2021-06-01 | 2021-07-27 | 湖南新华源科技有限公司 | Al (aluminum)2O3Base ceramic welding sealing component and preparation method thereof |
| CN113173797B (en) * | 2021-06-01 | 2021-12-07 | 湖南新华源科技有限公司 | Al (aluminum)2O3Base ceramic welding sealing component and preparation method thereof |
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