CN104261886A - Method for vacuum cladding of metal coating on surface of silicon carbide - Google Patents
Method for vacuum cladding of metal coating on surface of silicon carbide Download PDFInfo
- Publication number
- CN104261886A CN104261886A CN201410493272.XA CN201410493272A CN104261886A CN 104261886 A CN104261886 A CN 104261886A CN 201410493272 A CN201410493272 A CN 201410493272A CN 104261886 A CN104261886 A CN 104261886A
- Authority
- CN
- China
- Prior art keywords
- silicon carbide
- vacuum
- metallic coating
- ball
- metal
- 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
Abstract
The invention discloses a method for vacuum cladding of a metal coating on the surface of silicon carbide. The method comprises the main steps: preparing mixed metal powder, preparing a paste, coating the surface of ceramic with the paste and carrying out vacuum cladding, wherein the mixed metal powder comprises 10-40 percentage by mass of Mo, 15-40 percentage by mass of Ni (or Co) and 30-70 percentage by mass of Si; the vacuum cladding temperature and the vacuum cladding time are respectively 1250-1400 DEG C and 10-30 minutes. The method, which is disclosed by the invention, can be used as a preparation process of a transition layer brazed between silicon carbide and a metal, by virtue of the prepared coating, the wettability between the metal and silicon carbide can be significantly improved, the overreaction of silicon carbide ceramic and a brazing filler metal during brazing is reduced or prevented, and thus the interface bonding strength of ceramic and metal brazing is improved.
Description
Technical field
The present invention relates to a kind of preparation method of silicon carbide metallic coating, particularly adopt vacuum cladding technology to prepare the method for metallic coating at silicon carbide, object is the wettability improving metal pair silicon carbide ceramics.
Background technology
Silicon carbide has excellent mechanical property, high thermal conductivity and good thermal shock resistance etc., and these characteristics make them in aerospace, is used widely in the field such as automotive industry and the energy; But the shortcoming of silicon carbide ceramics poor toughness, processing difficulties limits its application, and metal has excellent plasticity, toughness and good processibility, but the high-temperature behavior of most of metal and alloy thereof is poor, if the two to be combined the advantage giving full play to them, very outstanding structure-function integration material will be formed; The interconnection technique of silicon carbide and metal is the gordian technique that the larger application of silicon carbide acquisition must solve; Soldering is connected material by the solder wetting of fusing and forms joint, in connection procedure, be connected mother metal can keep non-fusible, therefore soldering is differing greatly for switching performance and to the advantage having its uniqueness during the material that fusing is responsive, make like this at high technology ceramics with pottery, Ceramic and metal joining technology, method for brazing is most important method of attachment, for Ceramic brazing, it is the prerequisite realizing connecting that the Small angle of solder to pottery soaks.
SiC ceramic is the compound that a kind of covalency key is very strong, shows highly stable electron coordinate, and the basic structural unit of its crystalline structure is SiC
4and CSi
4coordination tetrahedron, is combined by the strong tetrahedron sp bond of orientation, and has polarization to a certain degree; The ion key of the electronegativity of Si to be the electronegativity of 1.8, C be 2.6, Si-C key only accounts for 12%.Huge difference is there is in SiC pottery and metallic substance in process based prediction model, cause SiC pottery be difficult to do not added the liquid metal of interfacial activity metallic element (as Ti, Cr) or alloy soak, this is the essential problem affecting the connection of SiC Ceramic brazing, and by preparing metallic coating to silicon carbide, liquid metal and the wetting of SiC is made to become soaking between liquid metal and metallic coating, thus significantly improve the wettability of metal or alloy melt and SiC pottery, very favourable to the soldering of SiC and metal.
Metallic coating method is formed about thyrite surface, the main of current application and research is exactly by plating, electroless plating or immersed method etc. at SiC ceramic surface formation metal level, as Chinese patent ZL200710035759.3 " a kind of high-performance ceramic surface metallization process " forms metal layer by electroplating and burning nickel at material surface; Chinese patent ZL200510029905.2 " SiC ceramic particle surface electroless copper plating method " and ZL200510029906.7 " SiC ceramic particle surface tangsten plating process " utilizes the method for electroless plating to carry out electroless copper and the process of plating tungsten to ceramic grain surface; Chinese patent ZL200410012575.1 " surface alloying ceramic and preparation method " utilizes composition target to carry out Alloying Treatment to ceramic material surfaces; Chinese patent 200910092748.8 method of attachment of metal " pottery with " is carrying out allowing ceramic surface adhere to one deck aluminum or aluminum alloy film to carry out surface treatment to stupalith by being immersed by pottery in aluminum or aluminum alloy liquation in ceramics-to-metals joining process.But, the metallic diaphragm that these SiC ceramic or particle surface are formed, or in conjunction with undertighten, or follow-up heat treatment process can react with silicon carbide substrate, or can not use in high temperature occasion.
In addition, Chinese patent 201310140262.3 " a kind of method improving metal pair SiC ceramic wettability " is the method adopting the metal ion of ion implantation doses in surface of SiC, improves the wettability of metal on SiC.Chinese patent 201310392098.5 " a kind of side metallization of silicon carbide ceramics and method for metallising " is by being carried out sintering by the mixed powder of pottery (TiC or WC or the mixture both it), Co, Si and B or the method for plasma spraying, preparing metal+ceramic composite coating in SiC ceramic surface.Chinese patent ZL201110211637.1 " SiC ceramic surface treatment method and uses thereof " is then by applying TiH in surface of SiC
2paste, after vacuum heat treatment, forms one in surface of SiC and has metallic Ti (C, Si) composite ceramic coat.
Summary of the invention
The object of the invention is the preparation method providing a kind of silicon carbide ceramics surface superior metal coating, namely form by vacuum cladding the metallic coating that one deck has metallicity, high-temperature stable and high bond strength on silicon carbide ceramics surface, and obvious surface reaction does not occur for coating and silicon carbide substrate, to improve the wettability of metal pair silicon carbide ceramics.
The present invention takes following technical scheme to be achieved, a kind of method of silicon carbide ceramics surface vacuum deposited metals coating, and the method is made up of following steps:
1) one of commercially available Mo, Ni and Co and Si powder are undertaken weighing, mixing by certain mass percent composition, ball milling makes metal mixed powder.
2) above-mentioned metal mixed powder is dried, sieved.
3) get the metal mixed powder that the above-mentioned mistake of part is sieved, add organic binder bond, after fully stirring, obtain even paste.
4) paste is covered the silicon carbide ceramics of clean on the surface by brushing or method for printing screen by hand.
5) by the silicon carbide ceramics sheet of coating, vacuum tightness≤4 × 10 are placed in
-2the vacuum oven of Pa, is heated to certain temperature with 3 ~ 10 DEG C/min, held for some time, makes the complete cladding of metal mixed powder at ceramic surface, then is cooled to room temperature with 3 ~ 5 DEG C/min, forms fine and close metallic coating.
The one of described Mo, Ni and Co and Si powder refer to by certain mass percent composition: the Mo of 10 ~ 40%, Ni or Co of 15 ~ 40%, the Si of 30 ~ 70%.
Described ball milling refers to: in tumbling ball mill, and with sintered carbide ball or agate ball for abrading-ball, alcohol is ball-milling medium, and ball milling makes metal mixed powder in 24 ~ 72 hours.
Described oven dry refers to that being placed in 80 DEG C of vacuum drying ovens dries; Described sieving referred to 200 mesh sieves.
Described organic binder bond is Terpineol 350+ethyl cellulose solution, and Terpineol 350: ethyl cellulose: metal mixed powder=9g:1g:10g.
Described vacuum cladding temperature is 1250 ~ 1400 DEG C, and soaking time is 10 ~ 30 min.
The present invention forms by vacuum cladding the metallic coating that one deck has metallicity, high-temperature stable and high bond strength on silicon carbide ceramics surface, this vacuum cladding technique and thermospray, magnetron sputtering plating, laser plate compares simple process with methods such as plasma coatings, low for equipment requirements, and obvious surface reaction does not occur for this coating and silicon carbide ceramics matrix, metal pair silicon carbide ceramics wettability of the surface significantly can be improved.
Accompanying drawing explanation
Fig. 1 is 1 and No. 2 sample photomacrograph (be contrast coatingsurface color, add uncoated SiC ceramic sample photo) in embodiment.
Fig. 2 be in embodiment No. 1 sample (metallic coating consists of 10Mo+20Co+70S
i) section (a) and Cu be the wetting photo (b) of this No. 1 specimen surface.
Fig. 3 is No. 2 sample (metallic coating consists of 20Mo+15Co+65Si) sections (a) and the wetting photo (b) of Cu at these No. 2 specimen surfaces in embodiment.
embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, and the certain mass percent that is a kind of and Si powder in Mo, Ni or Co of the present invention consists of: the Mo of 10 ~ 40%, Ni or Co of 15 ~ 40%, the Si of 30 ~ 70%.
Organic binder bond of the present invention is Terpineol 350+ethyl cellulose solution, and Terpineol 350: ethyl cellulose: metal mixed powder=9g:1g:10g.
Described vacuum cladding temperature is 1250 ~ 1400 DEG C, and soaking time is 10 ~ 30 min.
A method for silicon carbide ceramics surface vacuum deposited metals coating, the method is made up of following steps:
1) one in commercially available Mo, Ni or Co and Si powder undertaken weighing, mixing by certain mass percent composition, in tumbling ball mill, with sintered carbide ball or agate ball for abrading-ball, alcohol is ball-milling medium, and ball milling makes metal mixed powder in 24 ~ 72 hours.
2) above-mentioned metal mixed powder is placed in 80 DEG C of vacuum drying ovens to dry, and crosses 200 mesh sieves.
3) get the metal mixed powder that the above-mentioned mistake of part is sieved, add organic binder bond, after fully stirring, obtain even paste.
4) paste is covered the silicon carbide ceramics of clean on the surface by brushing or method for printing screen by hand;
5) by the silicon carbide ceramics sheet of coating, vacuum tightness≤4 × 10 are placed in
-2in the vacuum oven of Pa, be heated to certain temperature with 3 ~ 10 DEG C/min, held for some time, make the complete cladding of metal mixed powder at ceramic surface, then be cooled to room temperature with 3 ~ 5 DEG C/min, form fine and close metallic coating.
1) undertaken weighing, mixing by the formula of table 1 by commercially available Mo, Ni, Co and Si powder, in tumbling ball mill, with sintered carbide ball or agate ball for abrading-ball, alcohol is ball-milling medium, and ball milling makes metal mixed powder in 24 ~ 72 hours, specifically fills a prescription in table 1.
Table 1 metallic coating formula
2) above-mentioned metal mixed powder is placed in 80 DEG C of vacuum drying ovens to dry, and crosses 200 mesh sieves,
3) get the metal mixed powder that the above-mentioned mistake of part is sieved, add Terpineol 350+ethyl cellulose solution (Terpineol 350: ethyl cellulose: metal mixed powder=9g:1g:10g), after fully stirring, obtain even paste.
4) paste is covered the silicon carbide ceramics of clean on the surface by coating or method for printing screen by hand.
5) by the silicon carbide ceramics sheet of coating, vacuum tightness≤4 × 10 are placed in
-2in the vacuum oven of Pa, 1250 ~ 1400 DEG C are heated to 3 ~ 10 DEG C/min, insulation 10 ~ 30 min, make the complete cladding of metal mixed powder at ceramic surface, room temperature is cooled to again with 3 ~ 5 DEG C/min, form fine and close metallic coating (Fig. 1 is 1 and No. 2 sample photomacrograph), coating method and the melting and coating process of sample are as shown in table 2.
The coating method of table 2 sample and melting and coating process
6) silicon carbide ceramics will metallized, with diamond saw blade along cutting perpendicular to coating direction, after polishing polishing, under scanning electron microscope, observe the thickness of coating and the thickness of matrix and coating and coating structure pattern (wherein Fig. 2 a and Fig. 3 a is the section of 1 and No. 2 sample), be coated with layer microstructure test result as shown in table 3.
Table 3 is coated with layer microstructure test result
7) wetting angle of high-temperature moisture testing of equipment Cu and Al on different metal ceramic substrate surface is adopted.For Cu, test condition is: 1120 ° of C, be incubated 15 min, heat-up rate 5 ° of C/ minute, and vacuum tightness is 4 × 10
-4pa.For Al, test condition is: 900 ° of C, be incubated 15 min, heat-up rate 5 ° of C/ minute, and vacuum tightness is 4 × 10
-4; The contact angle test result of two kinds of pure metal on different metal pottery is as shown in table 4, and wherein Fig. 2 b and Fig. 3 b is Cu and the wetting photo at 1 and No. 2 specimen surface.
The wetting angle of table 4 two kinds of pure metal on different metal SiC ceramic specimen surface
From Fig. 2 b, Fig. 3 b and table 4 can find out, with Cu or Al, SiC ceramic wettability (wetting angle is about 140o with 110o respectively) compared with non-surface-treated is compared, the SiC ceramic of Cu or Al to the process of the application's vacuum cladding has excellent wettability (contact angle <40o), contributes to follow-up SiC ceramic and the brazing of metal.
The present invention is not limited to above-mentioned specific embodiments, and above-mentioned specific embodiments is only schematic, guiding instead of restrictive.The present invention can be follow-up with embodiment the integrated process such as soldering, Electronic Packaging use.
Claims (7)
1., in a method for silicon carbide vacuum cladding metallic coating, it is characterized in that step is as follows:
1) one of commercially available Mo, Ni and Co and Si powder are undertaken weighing, mixing by certain mass percent composition, ball milling makes metal mixed powder;
2) above-mentioned metal mixed powder is dried, sieved;
3) get the metal mixed powder that the above-mentioned mistake of part is sieved, add organic binder bond, after fully stirring, obtain even paste;
4) paste is covered the silicon carbide ceramics of clean on the surface;
5) by the silicon carbide ceramics sheet of coating, vacuum tightness≤4 × 10 are placed in
-2the vacuum oven of Pa, is heated to certain temperature with 3 ~ 10 DEG C/min, held for some time, makes the complete cladding of metal mixed powder at ceramic surface, then is cooled to room temperature with 3 ~ 5 DEG C/min, forms fine and close metallic coating.
2. a kind of method at silicon carbide vacuum cladding metallic coating as claimed in claim 1, is characterized in that the one of described Mo, Ni and Co and Si powder refer to by certain mass percent composition: the Mo of 10 ~ 40%, Ni or Co of 15 ~ 40%, the Si of 30 ~ 70%.
3. a kind of method at silicon carbide vacuum cladding metallic coating as claimed in claim 1, it is characterized in that: described ball milling refers to: in tumbling ball mill, with sintered carbide ball or agate ball for abrading-ball, alcohol is ball-milling medium, and ball milling makes metal mixed powder in 24 ~ 72 hours.
4. a kind of method at silicon carbide vacuum cladding metallic coating as claimed in claim 1, is characterized in that: described oven dry refers to that being placed in 80 DEG C of vacuum drying ovens dries; Described sieving referred to 200 mesh sieves.
5. a kind of method at silicon carbide vacuum cladding metallic coating as claimed in claim 1, is characterized in that: described organic binder bond is Terpineol 350+ethyl cellulose solution, and Terpineol 350: ethyl cellulose: metal mixed powder=9g:1g:10g.
6. a kind of method at silicon carbide vacuum cladding metallic coating as claimed in claim 1, is characterized in that: described silicon carbide ceramics paste being covered clean is adopt manual brushing or method for printing screen that paste is covered the silicon carbide ceramics of clean on the surface on the surface.
7. a kind of method at silicon carbide vacuum cladding metallic coating as claimed in claim 1, it is characterized in that: described vacuum cladding temperature is 1250 ~ 1400 DEG C, soaking time is 10 ~ 30 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410493272.XA CN104261886B (en) | 2014-09-24 | 2014-09-24 | A kind of method at silicon carbide vacuum cladding metallic coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410493272.XA CN104261886B (en) | 2014-09-24 | 2014-09-24 | A kind of method at silicon carbide vacuum cladding metallic coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104261886A true CN104261886A (en) | 2015-01-07 |
| CN104261886B CN104261886B (en) | 2016-04-27 |
Family
ID=52153508
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410493272.XA Active CN104261886B (en) | 2014-09-24 | 2014-09-24 | A kind of method at silicon carbide vacuum cladding metallic coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104261886B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402533A (en) * | 2014-10-22 | 2015-03-11 | 江苏大学 | Method for vacuum cladding of metal coating layer on silicon carbide surface |
| CN105384469A (en) * | 2015-11-03 | 2016-03-09 | 孝感正华电真空材料有限责任公司 | Nickel burning method for metallized ceramic tube for ceramic gas discharge tube |
| CN108054106A (en) * | 2018-01-11 | 2018-05-18 | 北京大学东莞光电研究院 | A kind of method for preparing high heat dissipation ceramic package substrate |
| CN109467456A (en) * | 2017-09-08 | 2019-03-15 | 核工业西南物理研究院 | A method of it is modified to carbon-based material surface using metal paste |
| CN110604455A (en) * | 2018-06-15 | 2019-12-24 | 佛山市顺德区美的电热电器制造有限公司 | Composite pot and preparation method thereof |
| CN113002915A (en) * | 2017-09-25 | 2021-06-22 | 株式会社东芝 | Fuel-clad pipe and method for closing opening in fuel-clad pipe |
| CN114605170A (en) * | 2022-04-13 | 2022-06-10 | 北航（四川）西部国际创新港科技有限公司 | Infiltration agent with multilayer coating structure and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467140A (en) * | 2013-09-03 | 2013-12-25 | 江苏大学 | Surface metalized layer of silicon carbide ceramic and metalizing method of silicon carbide ceramic |
-
2014
- 2014-09-24 CN CN201410493272.XA patent/CN104261886B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467140A (en) * | 2013-09-03 | 2013-12-25 | 江苏大学 | Surface metalized layer of silicon carbide ceramic and metalizing method of silicon carbide ceramic |
Non-Patent Citations (1)
| Title |
|---|
| 刘桂武等: "Ni-56Si合金对SiC陶瓷的润湿和铺展", 《硅酸盐学报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402533A (en) * | 2014-10-22 | 2015-03-11 | 江苏大学 | Method for vacuum cladding of metal coating layer on silicon carbide surface |
| CN105384469A (en) * | 2015-11-03 | 2016-03-09 | 孝感正华电真空材料有限责任公司 | Nickel burning method for metallized ceramic tube for ceramic gas discharge tube |
| CN109467456A (en) * | 2017-09-08 | 2019-03-15 | 核工业西南物理研究院 | A method of it is modified to carbon-based material surface using metal paste |
| CN113002915A (en) * | 2017-09-25 | 2021-06-22 | 株式会社东芝 | Fuel-clad pipe and method for closing opening in fuel-clad pipe |
| CN108054106A (en) * | 2018-01-11 | 2018-05-18 | 北京大学东莞光电研究院 | A kind of method for preparing high heat dissipation ceramic package substrate |
| CN108054106B (en) * | 2018-01-11 | 2020-03-27 | 北京大学东莞光电研究院 | Method for preparing high-heat-dissipation ceramic packaging substrate |
| CN110604455A (en) * | 2018-06-15 | 2019-12-24 | 佛山市顺德区美的电热电器制造有限公司 | Composite pot and preparation method thereof |
| CN114605170A (en) * | 2022-04-13 | 2022-06-10 | 北航（四川）西部国际创新港科技有限公司 | Infiltration agent with multilayer coating structure and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104261886B (en) | 2016-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104261886B (en) | A kind of method at silicon carbide vacuum cladding metallic coating | |
| CN103467140B (en) | A kind of side metallization of silicon carbide ceramics and method for metallising | |
| CA2627786C (en) | Braze system with matched coefficients of thermal expansion | |
| CN102409299B (en) | Preparation method of oxide ceramic sputtering target | |
| CN102409300B (en) | Oxide ceramic sputtering target and preparation method thereof and used brazing alloy | |
| CN104402533A (en) | Method for vacuum cladding of metal coating layer on silicon carbide surface | |
| CN115153112B (en) | High-efficiency electronic cigarette double-sided heating sheet and preparation method thereof | |
| JPH0561236B2 (en) | ||
| CN109384474B (en) | Paste for ceramic low-temperature active metallization, ceramic metallization method and vacuum electronic device prepared according to method | |
| CN103232257A (en) | Fast connection method of carbon/carbon composite material | |
| US20080131724A1 (en) | Ceramic armor, methods of joining a carbide with a metal-comprising piece, and methods of metallizing carbide-comprising surfaces | |
| RU2665939C1 (en) | Method of ceramics metallization | |
| CN105436643A (en) | Direct aluminum or aluminum alloy brazing method for aluminum oxide ceramics | |
| JP4248944B2 (en) | Conductive paste, circuit pattern forming method, and bump electrode forming method | |
| CN107385439B (en) | Cu-Ag-Ti diamond brazing coating and preparation method thereof | |
| CN107162640B (en) | Manganese oxide-titanium dioxide series activator metallization layer and preparation process thereof | |
| CN109251053B (en) | Air brazing filler material for ceramic metallizing and joining and method for metallizing and joining ceramic surfaces | |
| JPH05105563A (en) | Metal-ceramic joint | |
| CN116354740B (en) | Alumina ceramic-steel composite structure and preparation method thereof | |
| JP7434420B2 (en) | Method for producing metal-ceramic substrates | |
| JPS6111912B2 (en) | ||
| Zhu et al. | Adhesion property of copper paste on ceramic radiator fins | |
| CN110759720B (en) | Stainless steel coating, preparation method of stainless steel coating and preparation method of solid phase component | |
| JPS61174185A (en) | Metallization of carbide base ceramic body | |
| JPS5992979A (en) | Ceramic metallization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200409 Address after: 212400 No.19, Guangming science and Innovation Park, Biancheng Town, Jurong City, Zhenjiang City, Jiangsu Province Patentee after: Jiangsu HONGPU Electronic Material Technology Co., Ltd Address before: Zhenjiang City, Jiangsu Province, 212013 Jingkou District Road No. 301 Patentee before: JIANGSU University |
|
| TR01 | Transfer of patent right |