CN118283939B - A processing technology of ceramic copper clad plate - Google Patents
A processing technology of ceramic copper clad plate Download PDFInfo
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- CN118283939B CN118283939B CN202410559008.5A CN202410559008A CN118283939B CN 118283939 B CN118283939 B CN 118283939B CN 202410559008 A CN202410559008 A CN 202410559008A CN 118283939 B CN118283939 B CN 118283939B
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000010949 copper Substances 0.000 title claims abstract description 72
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 71
- 239000000919 ceramic Substances 0.000 title claims abstract description 61
- 238000005516 engineering process Methods 0.000 title claims abstract description 19
- 238000012545 processing Methods 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 151
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 113
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 113
- 238000007747 plating Methods 0.000 claims abstract description 96
- 238000001035 drying Methods 0.000 claims abstract description 39
- 238000005245 sintering Methods 0.000 claims abstract description 37
- 238000005406 washing Methods 0.000 claims abstract description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 24
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims abstract description 20
- JTTIOYHBNXDJOD-UHFFFAOYSA-N 2,4,6-triaminopyrimidine Chemical compound NC1=CC(N)=NC(N)=N1 JTTIOYHBNXDJOD-UHFFFAOYSA-N 0.000 claims abstract description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 14
- 239000011651 chromium Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 238000005219 brazing Methods 0.000 claims abstract description 11
- 238000005097 cold rolling Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000005098 hot rolling Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 9
- 239000010937 tungsten Substances 0.000 claims abstract description 9
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 7
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 71
- 239000000243 solution Substances 0.000 claims description 58
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 25
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 17
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 17
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 17
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 16
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 16
- OWMVSZAMULFTJU-UHFFFAOYSA-N bis-tris Chemical compound OCCN(CCO)C(CO)(CO)CO OWMVSZAMULFTJU-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 10
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 9
- ICYJJTNLBFMCOZ-UHFFFAOYSA-J molybdenum(4+);disulfate Chemical compound [Mo+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ICYJJTNLBFMCOZ-UHFFFAOYSA-J 0.000 claims description 9
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 9
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 9
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 8
- 239000004310 lactic acid Substances 0.000 claims description 8
- 235000014655 lactic acid Nutrition 0.000 claims description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 206010070834 Sensitisation Diseases 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 230000008313 sensitization Effects 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- 239000001119 stannous chloride Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- PXZLYPLSGXGBMZ-UHFFFAOYSA-N 3,5-dihydroxy-3-(2-hydroxyethyl)-2-(hydroxymethyl)pentanamide Chemical compound OCCC(O)(C(C(O)=N)CO)CCO PXZLYPLSGXGBMZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims 3
- 239000002253 acid Substances 0.000 claims 1
- 229960001484 edetic acid Drugs 0.000 claims 1
- 239000002109 single walled nanotube Substances 0.000 claims 1
- 238000012986 modification Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 7
- 238000007781 pre-processing Methods 0.000 description 7
- 239000005751 Copper oxide Substances 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 nitrogen-containing heterocyclic compound Chemical class 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229910018565 CuAl Inorganic materials 0.000 description 1
- 229910017945 Cu—Ti Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000001476 sodium potassium tartrate Substances 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Carbon And Carbon Compounds (AREA)
- Chemically Coating (AREA)
Abstract
本发明涉及陶瓷覆铜板领域，具体公开了一种陶瓷覆铜板的加工工艺；包括以下步骤：S1：取碳纳米管，表面改性，得碳纳米管A；镀覆铬和镍，得碳纳米管B；镀覆钼和钨，得碳纳米管C；镀覆氧化亚铜，得改性碳纳米管；S2：将改性碳纳米管与铜粉混合，烧结，得坯料；将坯料依次进行挤压、热轧、冷轧，制得铜板；S3：将铜板预处理，得预处理铜片；将预处理铜片与氮化铝陶瓷基板进行活性金属钎焊，真空烧结，得陶瓷覆铜板。碳纳米管A的制备具体包括以下步骤：取碳纳米管、DMF、三羟甲基丙烷三缩水甘油醚，升温搅拌，加入二(2‑羟乙基)亚氨基三(羟甲基)甲烷、2,4,6‑三氨基嘧啶，升温搅拌，过滤、干燥、洗涤，得碳纳米管A。The present invention relates to the field of ceramic copper-clad laminates, and specifically discloses a processing technology for ceramic copper-clad laminates; comprising the following steps: S1: taking carbon nanotubes, surface modification, and obtaining carbon nanotubes A; plating chromium and nickel to obtain carbon nanotubes B; plating molybdenum and tungsten to obtain carbon nanotubes C; plating cuprous oxide to obtain modified carbon nanotubes; S2: mixing the modified carbon nanotubes with copper powder, sintering, and obtaining a blank; extruding, hot rolling, and cold rolling the blank in sequence to obtain a copper plate; S3: pretreating the copper plate to obtain a pretreated copper sheet; performing active metal brazing of the pretreated copper sheet with an aluminum nitride ceramic substrate, and vacuum sintering to obtain a ceramic copper-clad laminate. The preparation of carbon nanotube A specifically comprises the following steps: taking carbon nanotubes, DMF, trimethylolpropane triglycidyl ether, heating and stirring, adding di(2-hydroxyethyl)iminotri(hydroxymethyl)methane, 2,4,6-triaminopyrimidine, heating and stirring, filtering, drying, and washing to obtain carbon nanotubes A.
Description
Technical Field
The invention relates to the field of ceramic copper-clad plates, and particularly discloses a processing technology of a ceramic copper-clad plate.
Background
When ceramic is used as a packaging substrate material, copper coating treatment is required on the surface of the ceramic, and the type of the ceramic substrate and the combination stability of the substrate and a copper layer are closely related to the stability of a power electronic device during operation, so that the ceramic-based packaging substrate is a hot spot for research in recent years.
However, the problem of thermal stress of a joint interface caused by different thermal expansion coefficients of the ceramic substrate and the copper layer still exists, and the combination of the ceramic substrate and the copper layer is not tight enough, so that the stability, the reliability and the service life of the whole power module are affected. Therefore, research on the ceramic copper-clad plate with high reliability, high stability, durability and excellent performance has important significance.
Disclosure of Invention
The invention aims to provide a processing technology of a ceramic copper-clad plate, which aims to solve the problems in the background technology.
In order to solve the technical problems, the invention provides a processing technology of a ceramic copper-clad plate, which comprises the following steps:
S1, taking a carbon nano tube, carrying out surface modification to obtain a carbon nano tube A, plating chromium and nickel to obtain a carbon nano tube B, plating molybdenum and tungsten to obtain a carbon nano tube C, and plating cuprous oxide to obtain a modified carbon nano tube;
s2, mixing the modified carbon nano tube with copper powder, and sintering to obtain a blank, and sequentially extruding, hot-rolling and cold-rolling the blank to obtain a copper plate;
S3, pretreating the copper plate to obtain a pretreated copper plate, performing active metal brazing on the pretreated copper plate and the aluminum nitride ceramic substrate, and performing vacuum sintering to obtain the ceramic copper-clad plate.
Preferably, the copper powder is prepared by adopting an air atomization powder preparation technology, the powder preparation temperature is 1200 ℃, the heat preservation time is 30min, the flow rate of atomization gas is 30m/min, and the pressure of the atomization gas is 5.0MPa.
Preferably, the active metal solder Ag-Cu-Ti is used in the active metal brazing, and contains 25.5% of Cu, 5.0% of Ti and the balance of Ag.
Preferably, the addition of the modified carbon nano tube and the copper powder is 6-10% by mass of the modified carbon nano tube, and the balance is the copper powder.
Preferably, the preparation of the carbon nano tube A specifically comprises the following steps of taking a carbon nano tube, DMF and trimethylolpropane triglycidyl ether, heating to 130-140 ℃, stirring for 4-6 hours, adding di (2-hydroxyethyl) iminotris (hydroxymethyl) methane and 2,4, 6-triaminopyrimidine, keeping the temperature of 130-140 ℃ and stirring for 6-8 hours, filtering, drying and washing to obtain the carbon nano tube A.
Preferably, the carbon nano tube A comprises, by mass, 15-20 parts of carbon nano tubes, 150-200 parts of DMF, 4-8 parts of trimethylolpropane triglycidyl ether, 6-10 parts of bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane and 10-15 parts of 2,4, 6-triaminopyrimidine, wherein the carbon nano tubes are hydroxylated single-arm carbon nano tubes.
The preparation method of the carbon nano tube B specifically comprises the following steps of pretreating the carbon nano tube A, plating chromium and nickel on the surface through chemical plating, washing and drying to obtain the carbon nano tube B, wherein the chemical plating process specifically comprises the steps of placing the pretreated carbon nano tube A in chemical plating solution A with the pH value of 11-12 for 50-60 min and the temperature of 75-80 ℃, and the chemical plating solution A comprises the raw materials of 6-10 g/L of chromium sulfate, 6-10 g/L of nickel sulfate, 20-25 g/L of disodium ethylenediamine tetraacetate, 10-15 g/L of potassium sodium tartrate and 15-20 ml/L of hydrazine hydrate according to concentration.
The pretreatment method specifically comprises the following steps of sensitization for 25-30 min and activation for 10-12 min, wherein the raw materials of the sensitization liquid comprise 15-20 g/L stannous chloride, 60-70 ml/L hydrochloric acid and the balance of water according to concentration, and the raw materials of the activation liquid comprise 0.05-0.08 g/L palladium chloride, 8-9 ml/L hydrochloric acid and the balance of water according to concentration.
Preferably, the pretreatment specifically comprises the following steps of sensitization for 30min and activation for 10min, wherein the raw materials of the sensitization liquid comprise 20g/L stannous chloride, 60ml/L hydrochloric acid and the balance of water in terms of concentration, and the raw materials of the activation liquid comprise 0.05g/L palladium chloride, 8ml/L hydrochloric acid and the balance of water in terms of concentration.
The preparation method of the carbon nanotube C specifically comprises the steps of plating molybdenum and tungsten on the surface of the carbon nanotube B through chemical plating, washing and drying to obtain the carbon nanotube C, wherein the chemical plating process specifically comprises the steps of placing the carbon nanotube B in chemical plating solution B with the pH value of 11-12 for 50-60 min and the temperature of 75-80 ℃, and the chemical plating solution B comprises 15-20 g/L of sodium tungstate, 6-10 g/L of molybdenum sulfate, 20-25 g/L of disodium ethylenediamine tetraacetate, 10-15 g/L of potassium sodium tartrate and 15-20 ml/L of hydrazine hydrate according to concentration.
The preparation method of the modified carbon nanotube specifically comprises the steps of plating cuprous oxide on the surface of a carbon nanotube C through chemical plating, washing and drying to obtain the modified carbon nanotube, wherein the chemical plating process specifically comprises the steps of placing the carbon nanotube C in a chemical plating solution C for 50-60 min at 75-80 ℃, and preparing the chemical plating solution C by taking 15-20 parts of copper sulfate pentahydrate, 45-50 parts of lactic acid, 5-8 parts of disodium ethylenediamine tetraacetate and 1-2 parts of formaldehyde, stirring uniformly, diluting to 1L by adding water, and adding sodium hydroxide to adjust pH to 11-12 to obtain the chemical plating solution C.
The copper plate is preferably pretreated by placing the copper plate in acetone for ultrasonic cleaning, drying, placing in a chain furnace, introducing nitrogen as a protective gas, introducing oxygen, and treating for 20-25 min at 750-800 ℃, wherein the oxygen concentration in the chain furnace is 300ppm, pickling for 8-10 s by using 5wt% sulfuric acid aqueous solution, washing with water, and drying to obtain pretreated copper sheets.
The copper plate is preferably pretreated by placing the copper plate in acetone, ultrasonically cleaning for 60min, blow-drying, placing in a chain furnace, introducing nitrogen as a protective gas, introducing oxygen, and treating for 20min at 800 ℃, wherein the oxygen concentration in the chain furnace is 300ppm, pickling for 8s by using 5wt% sulfuric acid aqueous solution, washing with water, and drying to obtain pretreated copper sheet.
Preferably, the vacuum sintering process is that the temperature is kept at 850-950 ℃ for 0.5-1 h.
Compared with the prior art, the copper-clad plate has the beneficial effects that the copper plate is prepared by using the modified carbon nano tube and copper powder, and is compounded with the aluminum nitride ceramic substrate to obtain the ceramic copper-clad plate after pretreatment, wherein the modified carbon nano tube is prepared by carrying out surface modification, chromium and nickel plating, molybdenum and tungsten plating and cuprous oxide plating on the hydroxylated single-arm carbon nano tube;
The specific steps of surface modification are that firstly, trimethylolpropane triglycidyl ether is used for modifying a carbon nano tube with hydroxyl groups, so that the carbon nano tube is provided with epoxy groups, meanwhile, ether bonds have good wettability, interfacial tension can be reduced, uniformity and stability of a subsequent plating metal layer are improved, then bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane and 2,4, 6-triaminopyrimidine are added, the bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane contains a plurality of hydroxyl groups, the smoothness and stability of the plating layer are improved through hydrogen bonds and Van der Waals force, and the 2,4, 6-triaminopyrimidine is a nitrogen-containing heterocyclic compound, the molecular planarity of the nitrogen-containing heterocyclic compound is favorable for orderly adsorbing the plating layer on the surface of the carbon nano tube, so that a flat plating layer is obtained, wherein a plurality of amino groups play a complexation role, and the bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane play a synergistic role, so that the plating layer is assisted;
after the surface modification is finished, firstly plating chromium and nickel, wherein the chromium has the effect of inhibiting abnormal growth of crystal grains and improving the sintering yield;
The thermal expansion coefficients of molybdenum and tungsten are similar to those of an aluminum nitride ceramic substrate, internal stress between a copper layer and the ceramic substrate can be reduced, conductivity, corrosion resistance and the like of a carbon nano tube material can be improved, meanwhile, migration resistance of the molybdenum and tungsten is good, migration of chromium and nickel can be prevented, the conductivity and electrochemical properties of the copper layer can be influenced if the migration of the chromium and the nickel occurs, and the process is complex and the cost is increased when the copper layer is subjected to a subsequent etching step due to the strong corrosion resistance of the chromium, so that the chromium and the nickel are coated on the innermost layer of a plating layer;
Copper oxide is plated outside molybdenum and tungsten, the copper oxide can be mixed with Al in an aluminum nitride ceramic substrate to generate spinel substances of CuAlO 2 and CuAl 2O4, the bonding strength of ceramics and copper sheets is improved, in the process of directly oxidizing the copper sheets and compounding the copper sheets with the ceramic substrate, enough copper oxide is difficult to obtain in the oxidation process, a formed oxide layer is often a mixture of CuO and copper oxide, and if the CuO is too much, the CuO releases oxygen at high temperature to form tiny pores, so that the bonding strength is affected.
Detailed Description
What follows is a preferred implementation of the embodiments of the invention, it being apparent that the described embodiments are only some, but not all, of the embodiments of the invention. All other embodiments, which are apparent to those of ordinary skill in the art without undue burden, are within the scope of the invention, as would be within the skill of one of ordinary skill in the art without departing from the principles of the embodiments of the present invention.
The following parts are mass parts unless specified;
Example 1S 1, taking 20 parts of carbon nano tube, 200 parts of DMF and 6 parts of trimethylolpropane triglycidyl ether, heating to 140 ℃, stirring for 4 hours, adding 8 parts of bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane and 12 parts of 2,4, 6-triaminopyrimidine, keeping the temperature of 140 ℃ and stirring for 7 hours, filtering, drying and washing to obtain carbon nano tube A;
S2, pretreating the carbon nano tube A, placing the pretreated carbon nano tube A in the chemical plating solution A with the pH value of 12 for 60min, washing at 80 ℃, and drying to obtain a carbon nano tube B;
The chemical plating solution A comprises 10g/L of chromium sulfate, 6g/L of nickel sulfate, 25g/L of disodium ethylenediamine tetraacetate, 15g/L of potassium sodium tartrate and 18ml/L of hydrazine hydrate according to concentration;
S3, placing the carbon nano tube B in the chemical plating solution B with the pH value of 12 for 60min and the temperature of 80 ℃, washing and drying to obtain the carbon nano tube C;
The chemical plating solution B comprises 18g/L of sodium tungstate, 8g/L of molybdenum sulfate, 25g/L of disodium ethylenediamine tetraacetate, 15g/L of potassium sodium tartrate and 18ml/L of hydrazine hydrate according to concentration;
S4, taking the carbon nano tube C, placing the carbon nano tube C in the chemical plating solution C with the pH value of 12 for 60min and the temperature of 80 ℃, washing and drying to obtain the modified carbon nano tube;
The preparation of the chemical plating solution C comprises the following steps of taking 20 parts of copper sulfate pentahydrate, 50 parts of lactic acid, 5 parts of disodium ethylenediamine tetraacetate and 1-2 parts of formaldehyde, uniformly stirring, adding water to dilute to 1L, and adding sodium hydroxide to adjust the pH to 12 to obtain the chemical plating solution C;
S5, mixing the modified carbon nano tube with copper powder, and sintering in a sintering furnace to obtain a blank, wherein the addition amount of the modified carbon nano tube and the copper powder is 8% by mass percent, and the balance is copper powder;
The method comprises the steps of sequentially extruding, hot rolling and cold rolling blanks to obtain a copper plate with the thickness of 0.3mm, preprocessing the copper plate to obtain a preprocessed copper plate, carrying out active metal brazing on the preprocessed copper plate and a 1mm aluminum nitride ceramic substrate, putting the preprocessed copper plate and the 1mm aluminum nitride ceramic substrate into a vacuum furnace for sintering, and preserving heat for 1h at the sintering temperature of 870 ℃ to obtain the ceramic copper-clad plate.
Example 2S 1, taking 20 parts of carbon nano tube, 200 parts of DMF and 8 parts of trimethylolpropane triglycidyl ether, heating to 140 ℃, stirring for 4 hours, adding 10 parts of bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane and 15 parts of 2,4, 6-triaminopyrimidine, keeping the temperature of 140 ℃ and stirring for 7 hours, filtering, drying and washing to obtain carbon nano tube A;
S2, pretreating the carbon nano tube A, placing the pretreated carbon nano tube A in the chemical plating solution A with the pH value of 12 for 60min, washing at 80 ℃, and drying to obtain a carbon nano tube B;
the chemical plating solution A comprises 10g/L of chromium sulfate, 10g/L of nickel sulfate, 25g/L of disodium ethylenediamine tetraacetate, 15g/L of sodium potassium tartrate and 20ml/L of hydrazine hydrate according to concentration;
S3, placing the carbon nano tube B in the chemical plating solution B with the pH value of 12 for 60min and the temperature of 80 ℃, washing and drying to obtain the carbon nano tube C;
The chemical plating solution B comprises 20g/L of sodium tungstate, 10g/L of molybdenum sulfate, 25g/L of disodium ethylenediamine tetraacetate, 15g/L of potassium sodium tartrate and 20ml/L of hydrazine hydrate according to concentration;
S4, taking the carbon nano tube C, placing the carbon nano tube C in the chemical plating solution C with the pH value of 12 for 60min and the temperature of 80 ℃, washing and drying to obtain the modified carbon nano tube;
the preparation of the chemical plating solution C comprises the following steps of taking 20 parts of copper sulfate pentahydrate, 50 parts of lactic acid, 8 parts of disodium ethylenediamine tetraacetate and 2 parts of formaldehyde, uniformly stirring, adding water to dilute to 1L, and adding sodium hydroxide to adjust the pH to 12 to obtain the chemical plating solution C;
S5, mixing the modified carbon nano tube with copper powder, and sintering in a sintering furnace to obtain a blank, wherein the addition of the modified carbon nano tube and the copper powder is 10% by mass percent of the modified carbon nano tube, and the balance is the copper powder;
The method comprises the steps of sequentially extruding, hot rolling and cold rolling blanks to obtain a copper plate with the thickness of 0.3mm, preprocessing the copper plate to obtain a preprocessed copper plate, carrying out active metal brazing on the preprocessed copper plate and a 1mm aluminum nitride ceramic substrate, putting the preprocessed copper plate and the 1mm aluminum nitride ceramic substrate into a vacuum furnace for sintering, and preserving heat for 1h at the sintering temperature of 870 ℃ to obtain the ceramic copper-clad plate.
S1, taking 15 parts of carbon nano tubes, 150 parts of DMF (dimethyl formamide) and 4-8 parts of trimethylolpropane triglycidyl ether, heating to 140 ℃, stirring for 4 hours, adding 6 parts of bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane and 10 parts of 2,4, 6-triaminopyrimidine, keeping the temperature of 140 ℃ and stirring for 7 hours, filtering, drying and washing to obtain carbon nano tubes A;
S2, pretreating the carbon nano tube A, placing the pretreated carbon nano tube A in the chemical plating solution A with the pH value of 12 for 60min, washing at 80 ℃, and drying to obtain a carbon nano tube B;
the chemical plating solution A comprises 6g/L of chromium sulfate, 6g/L of nickel sulfate, 20g/L of disodium ethylenediamine tetraacetate, 10g/L of potassium sodium tartrate and 15ml/L of hydrazine hydrate according to concentration;
S3, placing the carbon nano tube B in the chemical plating solution B with the pH value of 12 for 60min and the temperature of 80 ℃, washing and drying to obtain the carbon nano tube C;
the chemical plating solution B comprises 20g/L of sodium tungstate, 10g/L of molybdenum sulfate, 20g/L of disodium ethylenediamine tetraacetate, 10g/L of potassium sodium tartrate and 15ml/L of hydrazine hydrate according to concentration;
S4, taking the carbon nano tube C, placing the carbon nano tube C in the chemical plating solution C with the pH value of 12 for 60min and the temperature of 80 ℃, washing and drying to obtain the modified carbon nano tube;
The preparation of the chemical plating solution C comprises the following steps of taking 15 parts of copper sulfate pentahydrate, 45 parts of lactic acid, 5 parts of disodium ethylenediamine tetraacetate and 1 part of formaldehyde, uniformly stirring, adding water to dilute to 1L, and adding sodium hydroxide to adjust the pH to 12 to obtain the chemical plating solution C;
s5, mixing the modified carbon nano tube with copper powder, and sintering in a sintering furnace to obtain a blank, wherein the addition amount of the modified carbon nano tube and the copper powder is 6% by mass percent, and the balance is copper powder;
The method comprises the steps of sequentially extruding, hot rolling and cold rolling blanks to obtain a copper plate with the thickness of 0.3mm, preprocessing the copper plate to obtain a preprocessed copper plate, carrying out active metal brazing on the preprocessed copper plate and a 1mm aluminum nitride ceramic substrate, putting the preprocessed copper plate and the 1mm aluminum nitride ceramic substrate into a vacuum furnace for sintering, and preserving heat for 1h at the sintering temperature of 870 ℃ to obtain the ceramic copper-clad plate.
Comparative example 1 (carbon nanotubes were used instead of carbon nanotubes A, the remaining method steps were identical to those of example 1) S1, pretreating carbon nanotubes, placing pretreated carbon nanotubes A in electroless plating solution A having pH value of 12 for 60min at 80deg.C, washing, and drying to obtain carbon nanotubes B;
The chemical plating solution A comprises 10g/L of chromium sulfate, 6g/L of nickel sulfate, 25g/L of disodium ethylenediamine tetraacetate, 15g/L of potassium sodium tartrate and 18ml/L of hydrazine hydrate according to concentration;
S2, placing the carbon nano tube B in the chemical plating solution B with the pH value of 12 for 60min and the temperature of 80 ℃, washing and drying to obtain the carbon nano tube C;
The chemical plating solution B comprises 18g/L of sodium tungstate, 8g/L of molybdenum sulfate, 25g/L of disodium ethylenediamine tetraacetate, 15g/L of potassium sodium tartrate and 18ml/L of hydrazine hydrate according to concentration;
s3, taking the carbon nano tube C, placing the carbon nano tube C in the chemical plating solution C with the pH value of 12 for 60min and the temperature of 80 ℃, washing and drying to obtain the modified carbon nano tube;
The preparation of the chemical plating solution C comprises the following steps of taking 20 parts of copper sulfate pentahydrate, 50 parts of lactic acid, 5 parts of disodium ethylenediamine tetraacetate and 1-2 parts of formaldehyde, uniformly stirring, adding water to dilute to 1L, and adding sodium hydroxide to adjust the pH to 12 to obtain the chemical plating solution C;
S4, mixing the modified carbon nano tube with copper powder, and sintering in a sintering furnace to obtain a blank, wherein the addition amount of the modified carbon nano tube and the copper powder is 8% by mass percent, and the balance is copper powder;
The method comprises the steps of sequentially extruding, hot rolling and cold rolling blanks to obtain a copper plate with the thickness of 0.3mm, preprocessing the copper plate to obtain a preprocessed copper plate, carrying out active metal brazing on the preprocessed copper plate and a 1mm aluminum nitride ceramic substrate, putting the preprocessed copper plate and the 1mm aluminum nitride ceramic substrate into a vacuum furnace for sintering, and preserving heat for 1h at the sintering temperature of 870 ℃ to obtain the ceramic copper-clad plate.
Comparative example 2 (increasing the addition amount of modified carbon nanotubes, and the rest method steps are the same as in example 1), S1, taking 20 parts of carbon nanotubes, 200 parts of DMF and 6 parts of trimethylolpropane triglycidyl ether, heating to 140 ℃ and stirring for 4 hours, adding 8 parts of bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane and 12 parts of 2,4, 6-triaminopyrimidine, keeping 140 ℃ and stirring for 7 hours, filtering, drying and washing to obtain carbon nanotubes A;
S2, pretreating the carbon nano tube A, placing the pretreated carbon nano tube A in the chemical plating solution A with the pH value of 12 for 60min, washing at 80 ℃, and drying to obtain a carbon nano tube B;
The chemical plating solution A comprises 10g/L of chromium sulfate, 6g/L of nickel sulfate, 25g/L of disodium ethylenediamine tetraacetate, 15g/L of potassium sodium tartrate and 18ml/L of hydrazine hydrate according to concentration;
S3, placing the carbon nano tube B in the chemical plating solution B with the pH value of 12 for 60min and the temperature of 80 ℃, washing and drying to obtain the carbon nano tube C;
The chemical plating solution B comprises 18g/L of sodium tungstate, 8g/L of molybdenum sulfate, 25g/L of disodium ethylenediamine tetraacetate, 15g/L of potassium sodium tartrate and 18ml/L of hydrazine hydrate according to concentration;
S4, taking the carbon nano tube C, placing the carbon nano tube C in the chemical plating solution C with the pH value of 12 for 60min and the temperature of 80 ℃, washing and drying to obtain the modified carbon nano tube;
The preparation of the chemical plating solution C comprises the following steps of taking 20 parts of copper sulfate pentahydrate, 50 parts of lactic acid, 5 parts of disodium ethylenediamine tetraacetate and 1-2 parts of formaldehyde, uniformly stirring, adding water to dilute to 1L, and adding sodium hydroxide to adjust the pH to 12 to obtain the chemical plating solution C;
s5, mixing the modified carbon nano tube with copper powder, and sintering in a sintering furnace to obtain a blank, wherein the addition of the modified carbon nano tube and the copper powder is 15% by mass percent, and the balance is copper powder;
The method comprises the steps of sequentially extruding, hot rolling and cold rolling blanks to obtain a copper plate with the thickness of 0.3mm, preprocessing the copper plate to obtain a preprocessed copper plate, carrying out active metal brazing on the preprocessed copper plate and a 1mm aluminum nitride ceramic substrate, putting the preprocessed copper plate and the 1mm aluminum nitride ceramic substrate into a vacuum furnace for sintering, and preserving heat for 1h at the sintering temperature of 870 ℃ to obtain the ceramic copper-clad plate.
Comparative example 3 (carbon nanotube C was used instead of modified carbon nanotube, the remaining method steps were identical to example 1) S1, taking 20 parts of carbon nanotube, 200 parts of DMF, 6 parts of trimethylolpropane triglycidyl ether, heating to 140 ℃ and stirring for 4 hours, adding 8 parts of bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane, 12 parts of 2,4, 6-triaminopyrimidine, keeping 140 ℃ and stirring for 7 hours, filtering, drying and washing to obtain carbon nanotube A;
S2, pretreating the carbon nano tube A, placing the pretreated carbon nano tube A in the chemical plating solution A with the pH value of 12 for 60min, washing at 80 ℃, and drying to obtain a carbon nano tube B;
The chemical plating solution A comprises 10g/L of chromium sulfate, 6g/L of nickel sulfate, 25g/L of disodium ethylenediamine tetraacetate, 15g/L of potassium sodium tartrate and 18ml/L of hydrazine hydrate according to concentration;
S3, placing the carbon nano tube B in the chemical plating solution B with the pH value of 12 for 60min and the temperature of 80 ℃, washing and drying to obtain the carbon nano tube C;
The chemical plating solution B comprises 18g/L of sodium tungstate, 8g/L of molybdenum sulfate, 25g/L of disodium ethylenediamine tetraacetate, 15g/L of potassium sodium tartrate and 18ml/L of hydrazine hydrate according to concentration;
S4, mixing the carbon nano tube C with copper powder, and sintering in a sintering furnace to obtain a blank, wherein the addition of the modified carbon nano tube C and the copper powder is 8% by mass percent, and the balance is copper powder;
The method comprises the steps of sequentially extruding, hot rolling and cold rolling blanks to obtain a copper plate with the thickness of 0.3mm, preprocessing the copper plate to obtain a preprocessed copper plate, carrying out active metal brazing on the preprocessed copper plate and a 1mm aluminum nitride ceramic substrate, putting the preprocessed copper plate and the 1mm aluminum nitride ceramic substrate into a vacuum furnace for sintering, and preserving heat for 1h at the sintering temperature of 870 ℃ to obtain the ceramic copper-clad plate.
Comparative example 4 (without chromium plating and nickel, the remaining method steps are the same as example 1) S1, taking 20 parts of carbon nano tube, 200 parts of DMF, 6 parts of trimethylolpropane triglycidyl ether, heating to 140 ℃ and stirring for 4 hours, adding 8 parts of bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane, 12 parts of 2,4, 6-triaminopyrimidine, keeping 140 ℃ and stirring for 7 hours, filtering, drying and washing to obtain carbon nano tube A;
s2, pretreating the carbon nano tube A, placing the pretreated carbon nano tube A in the chemical plating solution B with the pH value of 12 for 60min, washing at 80 ℃, and drying to obtain a carbon nano tube C;
The chemical plating solution B comprises 18g/L of sodium tungstate, 8g/L of molybdenum sulfate, 25g/L of disodium ethylenediamine tetraacetate, 15g/L of potassium sodium tartrate and 18ml/L of hydrazine hydrate according to concentration;
s3, taking the carbon nano tube C, placing the carbon nano tube C in the chemical plating solution C with the pH value of 12 for 60min and the temperature of 80 ℃, washing and drying to obtain the modified carbon nano tube;
The preparation of the chemical plating solution C comprises the following steps of taking 20 parts of copper sulfate pentahydrate, 50 parts of lactic acid, 5 parts of disodium ethylenediamine tetraacetate and 1-2 parts of formaldehyde, uniformly stirring, adding water to dilute to 1L, and adding sodium hydroxide to adjust the pH to 12 to obtain the chemical plating solution C;
S4, mixing the modified carbon nano tube with copper powder, and sintering in a sintering furnace to obtain a blank, wherein the addition amount of the modified carbon nano tube and the copper powder is 8% by mass percent, and the balance is copper powder;
The method comprises the steps of sequentially extruding, hot rolling and cold rolling blanks to obtain a copper plate with the thickness of 0.3mm, preprocessing the copper plate to obtain a preprocessed copper plate, carrying out active metal brazing on the preprocessed copper plate and a 1mm aluminum nitride ceramic substrate, putting the preprocessed copper plate and the 1mm aluminum nitride ceramic substrate into a vacuum furnace for sintering, and preserving heat for 1h at the sintering temperature of 870 ℃ to obtain the ceramic copper-clad plate.
In the above examples, the test methods used, unless otherwise specified, were all conventional; all the raw materials used were obtained from commercial sources, without any particular explanation, and were derived from carbon nanotubes (CF 2023122, hubei Chemie Co., ltd.), DMF (CAS: 68-12-2), trimethylolpropane triglycidyl ether (CAS: 30499-70-8, cat# S64328, shanghai Source leaf), bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane (CAS: 6976-37-0, cat# PA07636, shanghai Yi vast chemical technology Co., ltd.), 2,4, 6-triaminopyrimidine (CAS: 1004-38-2), stannous chloride (S24125, shanghai Source leaf), palladium chloride (V900829, VETEC), chromium sulfate (cat# 145916, kelamal), nickel sulfate (CAS: 656895, ALDRICH), disodium ethylenediamine tetraacetate (CAS: 139-33-3), sodium tartrate (S30441, shanghai Source leaf), BD (CAS: 7803-57), sodium tungstate (CAS: 1004-38), sodium nitrate (CAS: 35-34), MARZ-35, WA-50, WA source leaf, WASHI, UK-50, WASHUI-0, WASHUI, or WASHUI-0.
The test comprises the steps of taking the ceramic copper clad laminate prepared in the examples 1-3 and the comparative examples 1-4, (1) testing the cycle times of high and low temperature, namely, after the temperature is kept at-50 ℃ for 15min, the temperature is raised to 150 ℃ for 15min, and then the temperature is lowered to-50 ℃ for one cycle, recording the cycle times until the ceramic copper clad laminate cracks or the copper layer is peeled off, (2) testing the peeling strength on a universal tensile testing machine, manufacturing a peeling spline graph by etching before the peeling strength test, and measuring the peeling strength at 90 DEG vertically, wherein the specific data are shown in the following table;
The conclusion is that the carbon nanotube is used for replacing the carbon nanotube A in the comparative example 1, the surface treatment is not carried out, the high-low temperature cycle times and the peeling strength are obviously reduced, the adding amount of the modified carbon nanotube is increased in the comparative example 2, the performance is reduced instead, so that the importance of controlling the adding amount can be known, the carbon nanotube C is used for replacing the modified carbon nanotube, namely, cuprous oxide is not plated, the peeling strength is obviously reduced, the chromium plating and the nickel are not carried out in the comparative example 4, the high-low temperature cycle times and the peeling strength are obviously reduced, and in conclusion, the ceramic copper-clad plate prepared by the invention has good reliability, good durability and high peeling strength.
It should be noted that the above description is only a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions easily conceivable by those skilled in the art within the technical scope of the present application should be covered within the scope of the present application, and the embodiments and features of the embodiments of the present application may be combined with each other without conflict. Therefore, the protection scope of the application is subject to the protection scope of the claims.
Claims (9)
1. The processing technology of the ceramic copper-clad plate is characterized by comprising the following steps of S1, taking a carbon nano tube, DMF and trimethylolpropane triglycidyl ether, heating to 130-140 ℃, stirring for 4-6 hours, adding di (2-hydroxyethyl) iminotris (hydroxymethyl) methane and 2,4, 6-triaminopyrimidine, keeping 130-140 ℃ and stirring for 6-8 hours, filtering, drying and washing to obtain the carbon nano tube A, plating chromium and nickel to obtain the carbon nano tube B, plating molybdenum and tungsten to obtain the carbon nano tube C, and plating cuprous oxide to obtain the modified carbon nano tube;
s2, mixing the modified carbon nano tube with copper powder, and sintering to obtain a blank, and sequentially extruding, hot-rolling and cold-rolling the blank to obtain a copper plate;
S3, pretreating the copper plate to obtain a pretreated copper plate, performing active metal brazing on the pretreated copper plate and the aluminum nitride ceramic substrate, and performing vacuum sintering to obtain the ceramic copper-clad plate.
2. The processing technology of the ceramic copper-clad plate is characterized in that the addition amount of the modified carbon nano tube and the copper powder is 6-10% by mass of the modified carbon nano tube, and the balance is the copper powder.
3. The processing technology of the ceramic copper-clad plate according to claim 1, wherein the carbon nano tube A comprises, by mass, 15-20 parts of carbon nano tubes, 150-200 parts of DMF, 4-8 parts of trimethylolpropane triglycidyl ether, 6-10 parts of bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane and 10-15 parts of 2,4, 6-triaminopyrimidine, and the carbon nano tubes are hydroxylated single-walled carbon nano tubes.
4. The processing technology of the ceramic copper-clad plate is characterized by comprising the following steps of pretreating a carbon nanotube A, plating chromium and nickel on the surface through chemical plating, washing and drying to obtain the carbon nanotube B, wherein the chemical plating process comprises the steps of placing the pretreated carbon nanotube A in chemical plating solution A with pH value of 11-12 for 50-60 min and temperature of 75-80 ℃, and the chemical plating solution A comprises the raw materials of 6-10 g/L of chromium sulfate, 6-10 g/L of nickel sulfate, 20-25 g/L of disodium ethylenediamine tetraacetate, 10-15 g/L of potassium sodium tartrate and 15-20 ml/L of hydrazine hydrate according to concentration.
5. The processing technology of the ceramic copper-clad plate according to claim 4, which is characterized by comprising the following steps of sensitization for 25-30 min and activation for 10-12 min, wherein the sensitization liquid comprises 15-20 g/L stannous chloride, 60-70 ml/L hydrochloric acid and the balance of water in terms of concentration, and the activation liquid comprises 0.05-0.08 g/L palladium chloride, 8-9 ml/L hydrochloric acid and the balance of water in terms of concentration.
6. The processing technology of the ceramic copper-clad plate is characterized by comprising the following steps of taking a carbon nano tube B, plating molybdenum and tungsten on the surface through chemical plating, washing and drying to obtain the carbon nano tube C, wherein the chemical plating technology is characterized in that the carbon nano tube B is placed in a chemical plating solution B with a pH value of 11-12 for 50-60 min, the temperature is 75-80 ℃, and the raw materials of the chemical plating solution B are calculated according to the concentration of 15-20 g/L of sodium tungstate, 6-10 g/L of molybdenum sulfate, 20-25 g/L of disodium ethylenediamine tetraacetate, 10-15 g/L of potassium sodium tartrate and 15-20 ml/L of hydrazine hydrate.
7. The processing technology of the ceramic copper-clad plate is characterized by comprising the following steps of taking a carbon nano tube C, plating cuprous oxide on the surface through chemical plating, washing and drying, wherein the chemical plating process comprises the steps of placing the carbon nano tube C in a chemical plating solution C for 50-60 min at the temperature of 75-80 ℃, and the preparation of the chemical plating solution C comprises the steps of taking 15-20 parts of copper sulfate pentahydrate, 45-50 parts of lactic acid, 5-8 parts of ethylene diamine tetraacetic acid and 1-2 parts of formaldehyde, stirring uniformly, adding water to dilute to 1L, and adding sodium hydroxide to adjust the pH to 11-12, thus obtaining the chemical plating solution C.
8. The processing technology of the ceramic copper clad laminate is characterized by comprising the steps of placing the copper clad laminate in acetone, conducting ultrasonic cleaning, drying, placing in a chain furnace, introducing nitrogen as a protective gas, introducing oxygen, and conducting treatment for 20-25 min at 750-800 ℃, wherein the oxygen concentration in the chain furnace is 300ppm, using 5wt% sulfuric acid aqueous solution to conduct acid cleaning for 8-10 s, conducting water cleaning and drying, and obtaining the pretreated copper sheet.
9. The processing technology of the ceramic copper-clad plate according to claim 1, wherein the vacuum sintering technology is that the temperature is kept at 850-950 ℃ for 0.5-1 h.
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