CN116618647B - Molybdenum-copper alloy composite material and preparation process thereof - Google Patents
Molybdenum-copper alloy composite material and preparation process thereof Download PDFInfo
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- CN116618647B CN116618647B CN202310896240.3A CN202310896240A CN116618647B CN 116618647 B CN116618647 B CN 116618647B CN 202310896240 A CN202310896240 A CN 202310896240A CN 116618647 B CN116618647 B CN 116618647B
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- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003822 epoxy resin Substances 0.000 claims abstract description 41
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 41
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000853 adhesive Substances 0.000 claims abstract description 23
- 230000001070 adhesive effect Effects 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 239000010949 copper Substances 0.000 claims abstract description 18
- 239000011162 core material Substances 0.000 claims abstract description 17
- 238000005245 sintering Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 238000005096 rolling process Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- 238000005098 hot rolling Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 13
- 239000003292 glue Substances 0.000 claims description 13
- 238000003825 pressing Methods 0.000 claims description 11
- 239000004593 Epoxy Substances 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 238000005097 cold rolling Methods 0.000 claims description 9
- 239000002518 antifoaming agent Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- 238000005121 nitriding Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000000463 material Substances 0.000 abstract description 10
- 239000005022 packaging material Substances 0.000 abstract description 10
- 238000004100 electronic packaging Methods 0.000 abstract description 9
- 238000005204 segregation Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000009700 powder processing Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical group C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical group [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/18—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0425—Copper-based alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/18—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers
- B22F2003/185—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers by hot rolling, below sintering temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/248—Thermal after-treatment
Abstract
The application discloses a molybdenum-copper alloy composite material and a preparation process thereof, belonging to the technical field of metal powder processing, wherein the molybdenum-copper alloy composite material comprises a core material and a copper sheet, the core material comprises copper powder, molybdenum powder and organosilicon modified epoxy resin adhesive, and the mass ratio of the copper powder to the molybdenum powder to the organosilicon modified epoxy resin adhesive is 1:4:2.8-3. According to the application, the separation of copper powder and molybdenum powder can be promoted by adding the organosilicon modified epoxy resin adhesive, so that the problem of component segregation in the molybdenum-copper alloy is effectively solved, and the influence of the component segregation in the molybdenum-copper alloy on the linear expansion coefficient of the electronic packaging material is reduced. Improving the service performance of the material. Compared with the general CIC, CKC, CMC and other planar composite electronic packaging material products, the composite electronic packaging material has the comprehensive properties of better heat conductivity, electric conductivity, low expansion coefficient and low density.
Description
Technical Field
The application belongs to the technical field of metal powder processing, and particularly relates to a molybdenum-copper alloy composite material and a preparation process thereof.
Background
An electronic packaging material is a packaging material with low expansion coefficient and high heat conducting property for the microelectronics industry. At present, molybdenum-copper alloy for electronic packaging materials is generally prepared by adopting an infiltration method, namely, a proper molybdenum skeleton is formed by controlling pressure in the forming process, and copper liquid flows along gaps among molybdenum matrix particles under the action of gravity and capillary force after sintering densification. However, copper cannot be uniformly distributed in the molybdenum skeleton in the method, so that segregation of molybdenum-copper alloy components is caused, the expansion coefficient, heat conduction and electric conduction performance of the molybdenum-copper alloy are further affected, and the operation efficiency and the service life of the chip are finally reduced.
Disclosure of Invention
The application aims to provide a molybdenum-copper alloy composite material and a preparation process thereof, which are used for solving the problems of poor linear expansion coefficient and poor heat conduction performance of an electronic packaging material.
The aim of the application can be achieved by the following technical scheme:
the molybdenum-copper alloy composite material comprises a core material and a copper sheet, wherein the core material comprises copper powder, molybdenum powder and organosilicon modified epoxy resin glue, and the mass ratio of the copper powder to the molybdenum powder to the organosilicon modified epoxy resin glue is 1:4:2.8-3. The grain size of the copper powder is 300-350 meshes, and the grain size of the molybdenum powder is 100-150 meshes.
Further, the organosilicon modified epoxy resin adhesive is prepared by the following steps:
mixing bisphenol A type epoxy resin E51 and epoxy POSS to obtain a component A, and then adding a curing agent and an auxiliary agent to stir and disperse to obtain the organosilicon modified epoxy resin adhesive.
Further, 70-80 parts of bisphenol A type epoxy resin E51, 18-20 parts of epoxy POSS, 21-23 parts of curing agent and 0.7-0.8 part of auxiliary agent by weight.
Wherein, epoxy POSS is prepared by the following steps:
mixing isopropanol and 4% by mass of tetramethyl ammonium hydroxide aqueous solution to obtain a mixed solution, then mixing dimethylbenzene and gamma-glycidoxypropyl trimethoxysilane, adding the mixed solution into the mixed solution, stirring the mixed solution for 10 hours at 20-25 ℃ after the dripping is finished, and heating to 80 ℃ for reflux stirring for 1 hour after the stirring is finished; cooling to 20-25 ℃, regulating the pH value to 7, stirring and reacting for 30-60min, distilling under reduced pressure to remove the solvent, washing with acetone solvent and evaporating to dryness for 3 times, and drying in a vacuum oven at 50 ℃ to obtain epoxy POSS; the dosage ratio of isopropanol, 4% by mass of tetramethyl ammonium hydroxide aqueous solution, xylene and gamma-glycidyl ether oxypropyl trimethoxy silane is 200mL:15g:200mL:60g.
Further, the auxiliary agent comprises a leveling agent and a defoaming agent; the mass ratio of the leveling agent to the defoaming agent is 1:2. the leveling agent is BYK306, the defoamer is BYK-530, and the curing agent is 4, 4-diamino dicyclohexylmethane. The curing agent is 4, 4-diamino dicyclohexylmethane to reduce the viscosity of the organosilicon modified epoxy resin adhesive, so that the subsequent dispersion is facilitated.
Further, the mass ratio of the core material to the copper sheet is 6:1.
a preparation process of a molybdenum-copper alloy composite material comprises the following steps:
s1, filling: mixing copper powder and molybdenum powder, stirring and mixing with organosilicon modified epoxy resin glue, then filling into a mould, and attaching and fixing the copper sheet up and down; carrying out hydraulic pressing tool;
s2, sintering: the method is carried out in a sintering furnace protected by hydrogen, the temperature set values of temperature zones are 8, and the temperature value of each temperature zone is as follows: 450 ℃, 500 ℃, 750 ℃, 800 ℃, 900 ℃, 1100 ℃, 1300 ℃, 1600 ℃; the temperature of each temperature zone is required to be within +/-10 ℃;
s3, hot rolling: heating the sintered product to 900 ℃ and keeping for 20min to start discharging for rolling, wherein the rolling height is adjusted to be 1.2mm plus or minus 0.05mm in the rolling process;
s4, annealing: placing the product in an annealing furnace after hot rolling, placing for 6 hours at 950 ℃, and then cooling to 30+/-10 ℃;
s5, cold rolling: and (3) placing the product at an inlet of a cold rolling mill, and adjusting the rolling height to be 1.0+/-0.05 mm.
Further, the pressure of the hydraulic press-fit was 20kg, and the press-fit time was 30min.
Further, the time value of 1-7 temperature zones set in each temperature zone is 0.5h; the eighth temperature zone time is set to 20min; the speed of sintering movement to the next temperature zone in each temperature zone was controlled to be set at a speed setting of 10mm per second.
Further, after sintering is completed, the temperature is reduced to 30 ℃ through nitriding.
Further, in the hot rolling discharging process, the temperature is set to be 60 ℃ when entering a cooling tank, and the speed is set to be 5mm per second in the running process for cooling discharging.
The application has the beneficial effects that:
according to the application, the separation of copper powder and molybdenum powder can be promoted by adding the organosilicon modified epoxy resin adhesive, so that the problem of component segregation in the molybdenum-copper alloy is effectively solved, and the influence of the component segregation in the molybdenum-copper alloy on the linear expansion coefficient of the electronic packaging material is reduced.
In the application, the organosilicon modified epoxy resin adhesive is selected as a dispersion medium, so that the dispersion effect of copper powder and molybdenum powder is improved, pyrolysis can occur in the sintering process of the organosilicon modified epoxy resin adhesive, deep carbonization and dehydrogenation reaction can occur along with the rise of temperature, micropores are generated, and the density is reduced; the organic silicon modified epoxy resin glue is sintered to generate glassy hard carbon with a graphite-like structure, silicon in the organic silicon modified epoxy resin glue is melted at high temperature and enters carbon particles to react to generate a silicon carbide structure, and the introduction of a silicon carbide component is beneficial to reducing the thermal expansion coefficient of the material, improving the thermal conductivity of the material and further improving the service performance of the material. Compared with the general CIC, CKC, CMC and other planar composite electronic packaging material products, the composite electronic packaging material has the comprehensive properties of better heat conductivity, electric conductivity, low expansion coefficient and low density.
Detailed Description
The technical solutions of the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
The embodiment provides an organosilicon modified epoxy resin adhesive, which is prepared through the following steps:
200mL of isopropyl alcohol and 15g of 4% tetramethylammonium hydroxide aqueous solution by mass fraction are mixed to obtain a mixed solution, 200mL of dimethylbenzene and 60g of gamma-glycidoxypropyl trimethoxy silane are mixed and added into the mixed solution, after the dripping is finished, stirring is carried out for 10h at the temperature of 25 ℃ after the dripping is finished, and after the stirring is finished, the temperature is raised to 80 ℃ and reflux stirring is carried out for 1h; cooling to 25 ℃, regulating the pH value to 7, stirring and reacting for 60min, distilling under reduced pressure to remove the solvent, washing with acetone solvent and evaporating to dryness for 3 times, and drying in a vacuum oven at 50 ℃ to obtain epoxy POSS;
and (3) mixing 70 parts of bisphenol A type epoxy resin E51 and 18 parts of epoxy POSS (polyhedral oligomeric silsesquioxane) by weight to obtain a component A, and then adding 21 parts of curing agent and 0.7 part of auxiliary agent, stirring and dispersing to obtain the organosilicon modified epoxy resin adhesive. The auxiliary agent comprises a leveling agent and an antifoaming agent, wherein the using amount and mass ratio of the leveling agent to the antifoaming agent are 1:2. the leveling agent is BYK306, the defoamer is BYK-530, and the curing agent is 4, 4-diamino dicyclohexylmethane.
Example 2
The embodiment provides an organosilicon modified epoxy resin adhesive, which is prepared through the following steps:
200mL of isopropyl alcohol and 15g of 4% tetramethylammonium hydroxide aqueous solution by mass fraction are mixed to obtain a mixed solution, 200mL of dimethylbenzene and 60g of gamma-glycidoxypropyl trimethoxy silane are mixed and added into the mixed solution, after the dripping is finished, stirring is carried out for 10h at the temperature of 25 ℃ after the dripping is finished, and after the stirring is finished, the temperature is raised to 80 ℃ and reflux stirring is carried out for 1h; cooling to 25 ℃, regulating the pH value to 7, stirring and reacting for 60min, distilling under reduced pressure to remove the solvent, washing with acetone solvent and evaporating to dryness for 3 times, and drying in a vacuum oven at 50 ℃ to obtain epoxy POSS;
80 parts of bisphenol A type epoxy resin E51 and 20 parts of epoxy POSS are mixed according to parts by weight to obtain a component A, and then 23 parts of curing agent and 0.8 part of auxiliary agent are added to be stirred and dispersed to obtain the organosilicon modified epoxy resin adhesive. The auxiliary agent comprises a leveling agent and an antifoaming agent, wherein the using amount and mass ratio of the leveling agent to the antifoaming agent are 1:2. the leveling agent is BYK306, the defoamer is BYK-530, and the curing agent is 4, 4-diamino dicyclohexylmethane.
Comparative example 1
In this comparative example, as compared to example 2, no epoxy POSS was added, and the remaining raw materials and preparation process remained the same as in example 2.
Example 3
The embodiment provides a molybdenum-copper alloy composite material, which comprises a core material and a copper sheet, wherein the core material comprises copper powder, molybdenum powder and the organic silicon modified epoxy resin adhesive prepared in the embodiment 1, and the mass ratio of the copper powder to the molybdenum powder to the organic silicon modified epoxy resin adhesive prepared in the embodiment 1 is 1:4:2.8. the grain size of the copper powder is 300-350 meshes, and the grain size of the molybdenum powder is 100-150 meshes. The mass ratio of the core material to the copper sheet is 6:1. the preparation process of the molybdenum-copper alloy composite material comprises the following steps:
s1, filling: mixing copper powder and molybdenum powder, stirring and mixing with organosilicon modified epoxy resin glue, then filling into a mould, and attaching and fixing the copper sheet up and down; carrying out hydraulic pressing tool, wherein the pressure of hydraulic pressing is 20kg, and the pressing time is 30min;
s2, sintering: the method is carried out in a sintering furnace protected by hydrogen, the temperature set values of temperature zones are 8, and the temperature value of each temperature zone is as follows: 450 ℃, 500 ℃, 750 ℃, 800 ℃, 900 ℃, 1100 ℃, 1300 ℃, 1600 ℃; the temperature of each temperature zone is required to be within +/-10 ℃; the time value of each temperature zone is 1-7, and the time value of each temperature zone is 0.5h; the eighth temperature zone time is set to 20min; the speed of sintering in each temperature zone to move to the next temperature zone is controlled to be set at the speed of 10mm per second, and after sintering is finished, the temperature is reduced to 30 ℃ after nitriding;
s3, hot rolling: heating the sintered product to 900 ℃ and keeping for 20min to start discharging for rolling, wherein the rolling height is adjusted to be 1.2mm plus or minus 0.05mm in the rolling process; in the hot rolling discharging process, the temperature is set to 60 ℃ in a cooling tank, and the speed is set to 5mm per second in the running process for cooling discharging;
s4, annealing: placing the product in an annealing furnace after hot rolling, placing for 6 hours at 950 ℃, and then cooling to 30+/-10 ℃;
s5, cold rolling: and (3) placing the product at an inlet of a cold rolling mill, and adjusting the rolling height to be 1.0+/-0.05 mm.
Example 4
The embodiment provides a molybdenum-copper alloy composite material, which comprises a core material and a copper sheet, wherein the core material comprises copper powder, molybdenum powder and the organic silicon modified epoxy resin adhesive prepared in the embodiment 1, and the mass ratio of the copper powder to the molybdenum powder to the organic silicon modified epoxy resin adhesive prepared in the embodiment 1 is 1:4:2.9. the grain size of the copper powder is 300-350 meshes, and the grain size of the molybdenum powder is 100-150 meshes. The mass ratio of the core material to the copper sheet is 6:1. the preparation process of the molybdenum-copper alloy composite material comprises the following steps:
s1, filling: mixing copper powder and molybdenum powder, stirring and mixing with organosilicon modified epoxy resin glue, then filling into a mould, and attaching and fixing the copper sheet up and down; carrying out hydraulic pressing tool, wherein the pressure of hydraulic pressing is 20kg, and the pressing time is 30min;
s2, sintering: the method is carried out in a sintering furnace protected by hydrogen, the temperature set values of temperature zones are 8, and the temperature value of each temperature zone is as follows: 450 ℃, 500 ℃, 750 ℃, 800 ℃, 900 ℃, 1100 ℃, 1300 ℃, 1600 ℃; the temperature of each temperature zone is required to be within +/-10 ℃; the time value of each temperature zone is 1-7, and the time value of each temperature zone is 0.5h; the eighth temperature zone time is set to 20min; the speed of sintering in each temperature zone to move to the next temperature zone is controlled to be set at the speed of 10mm per second, and after sintering is finished, the temperature is reduced to 30 ℃ after nitriding;
s3, hot rolling: heating the sintered product to 900 ℃ and keeping for 20min to start discharging for rolling, wherein the rolling height is adjusted to be 1.2mm plus or minus 0.05mm in the rolling process; in the hot rolling discharging process, the temperature is set to 60 ℃ in a cooling tank, and the speed is set to 5mm per second in the running process for cooling discharging;
s4, annealing: placing the product in an annealing furnace after hot rolling, placing for 6 hours at 950 ℃, and then cooling to 30+/-10 ℃;
s5, cold rolling: and (3) placing the product at an inlet of a cold rolling mill, and adjusting the rolling height to be 1.0+/-0.05 mm.
Example 5
The embodiment provides a molybdenum-copper alloy composite material, which comprises a core material and a copper sheet, wherein the core material comprises copper powder, molybdenum powder and the organic silicon modified epoxy resin adhesive prepared in the embodiment 2, and the mass ratio of the copper powder to the molybdenum powder to the organic silicon modified epoxy resin adhesive prepared in the embodiment 1 is 1:4:3. the grain size of the copper powder is 300-350 meshes, and the grain size of the molybdenum powder is 100-150 meshes. The mass ratio of the core material to the copper sheet is 6:1. the preparation process of the molybdenum-copper alloy composite material comprises the following steps:
s1, filling: mixing copper powder and molybdenum powder, stirring and mixing with organosilicon modified epoxy resin glue, then filling into a mould, and attaching and fixing the copper sheet up and down; carrying out hydraulic pressing tool, wherein the pressure of hydraulic pressing is 20kg, and the pressing time is 30min;
s2, sintering: the method is carried out in a sintering furnace protected by hydrogen, the temperature set values of temperature zones are 8, and the temperature value of each temperature zone is as follows: 450 ℃, 500 ℃, 750 ℃, 800 ℃, 900 ℃, 1100 ℃, 1300 ℃, 1600 ℃; the temperature of each temperature zone is required to be within +/-10 ℃; the time value of each temperature zone is 1-7, and the time value of each temperature zone is 0.5h; the eighth temperature zone time is set to 20min; the speed of sintering in each temperature zone to move to the next temperature zone is controlled to be set at the speed of 10mm per second, and after sintering is finished, the temperature is reduced to 30 ℃ after nitriding;
s3, hot rolling: heating the sintered product to 900 ℃ and keeping for 20min to start discharging for rolling, wherein the rolling height is adjusted to be 1.2mm plus or minus 0.05mm in the rolling process; in the hot rolling discharging process, the temperature is set to 60 ℃ in a cooling tank, and the speed is set to 5mm per second in the running process for cooling discharging;
s4, annealing: placing the product in an annealing furnace after hot rolling, placing for 6 hours at 950 ℃, and then cooling to 30+/-10 ℃;
s5, cold rolling: and (3) placing the product at an inlet of a cold rolling mill, and adjusting the rolling height to be 1.0+/-0.05 mm.
Comparative example 2
In this comparative example, as compared with example 5, no silicone-modified epoxy resin adhesive was added, and the remaining raw materials and preparation process were the same as in example 5.
Comparative example 3
In this comparative example, as compared with example 5, the silicone-modified epoxy resin adhesive was changed to the sample prepared in comparative example 1, and the remaining raw materials and preparation process were kept the same as in example 5.
Performance tests were performed on examples 3-5 and comparative examples 2-3, and the average linear expansion coefficient represents the average value of the change in the sample length when the temperature increases by 1 ℃ in a certain test temperature interval; the heat conductivity coefficient refers to that 1mm thick material passes through 1mm in 1h under the condition of stable heat transfer when the temperature difference of two side surfaces is 1 DEG C 2 Heat transferred by the area.
The results are shown in Table 1:
TABLE 1
As can be seen from Table 1, the samples prepared by the application have better and better comprehensive properties of heat conductivity, electric conductivity, low expansion coefficient and low density, and the addition of the epoxy resin glue can generate air holes in the subsequent sintering process to reduce the density of the material and is unfavorable for improving the performance of the material, but the application uses the organosilicon modified epoxy resin glue, introduces the silicon carbide component, is favorable for reducing the thermal expansion coefficient of the material, improves the heat conductivity of the material and further improves the service performance of the material.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the application, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The molybdenum-copper alloy composite material comprises a core material and a copper sheet, and is characterized in that the core material comprises copper powder, molybdenum powder and organosilicon modified epoxy resin glue, and the mass ratio of the copper powder to the molybdenum powder to the organosilicon modified epoxy resin glue is 1:4:2.8-3; the organosilicon modified epoxy resin adhesive is prepared through the following steps:
according to the weight portion, 70-80 portions of bisphenol A type epoxy resin E51 and 18-20 portions of epoxy POSS are mixed to obtain a component A, and then 21-23 portions of curing agent and 0.7-0.8 portion of auxiliary agent are added to be stirred and dispersed to obtain the organosilicon modified epoxy resin adhesive.
2. The molybdenum-copper alloy composite material according to claim 1, wherein the auxiliary agent comprises a leveling agent and a defoaming agent; the mass ratio of the leveling agent to the defoaming agent is 1:2.
3. the molybdenum-copper alloy composite according to claim 1, wherein the mass ratio of the core material to the copper sheet is 6:1.
4. a process for preparing a molybdenum-copper alloy composite material according to claim 3, comprising the steps of:
s1, filling: mixing copper powder and molybdenum powder, stirring and mixing with organic silicon modified epoxy resin glue, then filling into a mould, attaching and fixing copper sheets up and down, and carrying out a hydraulic pressing tool;
s2, sintering: the method is carried out in a sintering furnace protected by hydrogen, the temperature set values of temperature zones are 8, and the temperature value of each temperature zone is as follows: 450 ℃, 500 ℃, 750 ℃, 800 ℃, 900 ℃, 1100 ℃, 1300 ℃, 1600 ℃; the temperature of each temperature zone is within +/-10 ℃;
s3, hot rolling: after sintering, heating to 900 ℃ and keeping for 20min to start discharging for rolling, wherein the rolling height is adjusted to be 1.2mm plus or minus 0.05mm in the rolling process;
s4, annealing: after hot rolling, standing for 6 hours at 950 ℃, and then cooling to 30+/-10 ℃;
s5, cold rolling: the adjustment rolling height is 1.0 plus or minus 0.05mm.
5. The process for preparing a molybdenum-copper alloy composite material according to claim 4, wherein the pressure of the hydraulic press is 20kg and the press time is 30min.
6. The process for preparing the molybdenum-copper alloy composite material according to claim 4, wherein the time value set for each temperature zone is 1-7 hours, and the time value is 0.5 hours; the eighth warm zone time was set to 20 minutes.
7. The process for preparing a molybdenum-copper composite material according to claim 4, wherein after sintering, the temperature is reduced to 30 ℃ by nitriding.
8. The process for preparing a molybdenum-copper alloy composite material according to claim 4, wherein the temperature is set to 60 ℃ in a cooling tank during hot rolling discharge, and the speed is set to 5mm per second during operation for cooling discharge.
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