CN102586704B - Preparation method of high thermal conductivity graphite whisker/copper composite - Google Patents
Preparation method of high thermal conductivity graphite whisker/copper composite Download PDFInfo
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Abstract
The invention belongs to the research field of metal matrix composites and relates to a high thermal conductivity graphite whisker/copper composite and a preparation method thereof. The composite comprises two parts, namely matrix pure copper and plated reinforced phase high thermal conductivity graphite whisker, wherein the volume fraction of the pure copper is 40 to 70 percent, and the volume fraction of the plated graphite whisker is 30 to 60 percent. The composite adopts the following production process steps: firstly, the surface of graphite whisker is plated with copper or molybdenum by adopting a chemical plating or salt bath plating method, so as to form a plating with the thickness of 1 to 2 Mum; and secondly, the plated graphite whisker and copper powder are uniformly mixed in the proportion of (30 to 60) to (70 to 40), and then the mixture is sintered at 820 to 980 DEG C by adopting an SPS Spark Plasma Sintering powder metallurgic method, so as to prepare the graphite whisker/copper composite. The invention provides the preparation method of the graphite whisker/copper composite used in the electronic packaging field, and the graphite whisker/copper composite has the advantages of high thermal conductivity, controllable thermal expansion coefficient, high density, easiness in processing and the like, thereby meeting requirements in the modern electronic packaging field.
Description
Technical field
The invention belongs to the metal-base composites technical field, relate to a kind of preparation method of high conductive graphite whisker/carbon/carbon-copper composite material.
Background technology
The exploitation of electronic package material is an important ring of electronics heat management with design all the time, and modern heat management requires electronic package material to have high heat conductance (TC), low-expansion coefficient (CTE), the price that processing characteristics is good and lower.Traditional materials such as Cu/Mo, Cu/W, Al/SiC, AlN are often used in the Electronic Packaging field, these materials each have certain limitation, too high as Cu/Mo, Cu/W density, the CTE of Al/SiC, AlN is higher, and the diamond composite of high thermal conductance then is subject to price and processing characteristics.
A new generation's graphite whisker has low thermal expansivity, high vertical thermal conductivity, and thermal conductivity reaches as high as 1100 W/ (mK), low density, and its good physicals is suitable for the wild phase of METAL-MATRIX MATERIAL FOR ELECTRONIC PACKAGING.Adopt powder metallurgical technique with the matrix material of graphite whisker and the high heat conduction of the compound prepared isotropic of copper base, its heat conductivility excellence, thermal expansivity are low, lightweight and easily processing, preparation technology simply, cost is lower, be with a wide range of applications.
In the preparation process of matrix material, the interface bonding state between wild phase and the matrix has very big influence to performance of composites.Studies show that copper and carbon carry out compound tense, because interface wet ability is poor, make that the heat conductivility of matrix material is not good.Therefore, how to strengthen the interface in conjunction with being the key that improves composite property.
Summary of the invention
The object of the present invention is to provide the high heat conduction of a kind of usefulness, low bulk graphite whisker as wild phase, prepare that thermal expansivity is adjustable, the method for high heat-conducting copper matrix electronic packaging composite material part.
The present invention adopts the method for electroless plating or salt bath plating that whisker is carried out surface metalation, increase the wettability between copper-carbon, effectively improving whisker is combined with the interface of copper, whisker after will handling then evenly mixes with copper powder, the last high performance graphite whisker/Cu-base composites of using plasma spark sintering prepared.
A kind of preparation method of high conductive graphite whisker/carbon/carbon-copper composite material, it is characterized in that using high conductive graphite whisker to make wild phase, method plating layer of copper or molybdenum that elder generation plates with electroless plating or salt bath on the graphite whisker surface, undertaken compoundly then by SPS powder metallurgical technique and copper powder, prepare the high-performance graphite whisker and strengthen Cu-base composites;
Used wild phase is high heat conduction, the graphite whisker of low bulk, length-to-diameter ratio between 10-70, copper or the molybdenum of whisker coating surface thickness 0.1-2 μ m;
The volume ratio of the selected graphite whisker of plating and copper powder is 30-60:70-40, will mix at ball mill before compound, and drum's speed of rotation is 110-150 rev/min, and the time is 1.5-3 hour.
At first carry out the surface metal plating at graphite whisker, copper-plated main technique route is mainly: oil removing-alligatoring-sensitization-activation-electroless plating, the composition of plating bath: cupric sulfate pentahydrate 15g/L, formaldehyde 5g/L, Seignette salt 14g/L, EDTA 19.5g/L, sodium hydroxide 14.5g/L, second bipyridine 0.02g/L, yellow prussiate of potash 0.01g/L.The copper-plating technique condition: plating bath pH is 12.0-12.5, plating temperature 40-50 ℃, plating time 2-15 minute.
The little evaporation plating of vacuum that the main technique route of plating molybdenum is: oil removing-mixing powder-.Graphite whisker after the oil removing put into the NaCl/KCl mixing salt that is added with a certain amount of ammonium paramolybdate mix 30 minutes in the ball mill, the mol ratio of NaCl and KCl is 1:1 in the mixing salt, and the massfraction of ammonium paramolybdate is 10% in the mixing salt.After mixing, mixture is heated to 900 ℃-1100 ℃ under protective atmosphere, forms molybdenum layer on the graphite whisker surface.
Graphite whisker behind the plating and varigrained copper powder according to certain ratio ball mill mixing 1.5-3 hour, drum's speed of rotation is 110-150 rev/min, wherein the volume ratio of graphite whisker and copper powder is 30-60:70-40, and the different grain size copper powder can arbitrarily be arranged in pairs or groups by mass ratio.
At last mixed powder is put into graphite jig, place the SPS sintering oven, adopt the SPS powder metallurgical technique to prepare composite material parts.Sintering temperature is 820-980 ℃, and pressure is 20-70MPa, soaking time 2-5 minute.
The technology of the present invention using plasma spark sintering method (SPS) preparation graphite whisker strengthens the preparation method of Cu-base composites.By adding the middle layer of molybdenum or copper, increase the wettability of whisker and copper, improved the interfacial state between wild phase and the matrix, greatly reduced interface resistance, the particularly adding of molybdenum layer makes mechanical bond weak between script wild phase and the matrix become Chemical bond.Adopt the graphite whisker/composite property excellence of this method preparation, its advantage comprises:
1) has good thermal conductivity, the heat that semi-conductor chip produces when working can be distributed in time;
2) regulatable thermal expansivity is complementary with chip materials such as Si or GaAs, to avoid the thermal stress damage of chip;
3) composite density is little, certain intensity and rigidity;
4) product performance isotropic is easy to processing, and production cost is lower;
5) metal deposition is carried out on the whisker surface and handle, improved the interfacial state between wild phase and the matrix, composite material combination property is greatly enhanced.
Description of drawings
Fig. 1 is the schema of this technology.
Embodiment
Below with reference to example technical solution of the present invention is described in further detail:
Embodiment 1:
Adopt electroless copper at the copper layer of graphite whisker coating surface 1 μ m: after at first graphite whisker being put into 20%NaOH solution and being boiled 15 minutes, with distilled water flushing to neutral.Put into 20%HNO again
3Boiled in the solution 15 minutes, extremely neutral with distilled water flushing.Washed graphite whisker is put into 20ml/LHCl+20g/LSnCl
2The powerful stirring 15 minutes in the solution, explanation reacts completely when being Steel Gray to solution, after the washing graphite whisker is added 20ml/L HCl+0.5g/LPdCl
2Solution is powerful to be stirred 15 minutes, and explanation reacted completely when solution was light brown.Graphite whisker after the sensitization activation is poured in the copper facing plating bath, and electroplate liquid formulation is cupric sulfate pentahydrate 15g/L, Seignette salt 14g/L, EDTA19.5g/L, second bipyridine 0.02g/L, yellow prussiate of potash 0.01g/L.And add formaldehyde [w (HCHO)=36%] 10ml/L and carry out copper coating and handle, plating pH is 12,45 ℃ of temperature, plating time is 3 minutes.Plating finishes back adding distilled water 1000ml with the dilution plating bath.After adopting the method elimination plating bath of vacuum filtration, adding is washed to neutrality with a large amount of distilled water with the copper facing whisker, puts into the loft drier oven dry.Obtaining coating surface has the graphite whisker of the copper of 1 μ m.
The copper powder of getting above-mentioned copper-plated graphite whisker and granularity and the be 40 μ m ratio of 30:70 by volume mixed in planetary ball mill 2 hours, and drum's speed of rotation is 120 rev/mins.After mixing, mixed powder is put into plasma agglomeration stove (SPS) sintering, sintering temperature is 890 ℃, and sintering pressure is 30MPa, is incubated 3 minutes.Namely get graphite whisker/carbon/carbon-copper composite material.
Embodiment 2
Adopting the method for salt bath plating is the molybdenum layer of 1.5 μ m at graphite whisker coating surface one bed thickness.Graphite whisker put into the NaCl/KCl mixing salt that is added with a certain amount of ammonium paramolybdate mix 30 minutes in the ball mill, the mol ratio of NaCl and KCl is 1:1 in the mixing salt, and the massfraction of ammonium paramolybdate is 10% in the mixing salt.After mixing, put into the tube furnace that has protective atmosphere and be heated to 1000 ℃, be incubated furnace cooling after 120 minutes.Sieve after the whisker washing that plating is good, remove redundant impurities, obtain the graphite whisker of surface plating molybdenum.Adopting this technology is the molybdenum layer of 1.5 μ m at uniform plating one layer thickness in the surface of graphite whisker, and reaction generates the carbonization molybdenum layer between graphite whisker and the molybdenum layer.
The copper powder of getting granularity and be 40 μ m and plating molybdenum the graphite whisker ratio of 70:30 by volume mixed in planetary ball mill 2 hours, and drum's speed of rotation is 120 rev/mins.After mixing, mixed powder is put into plasma agglomeration stove (SPS) sintering, sintering temperature is 900 ℃, and sintering pressure is 50MPa, is incubated 5 minutes.Namely get graphite whisker/carbon/carbon-copper composite material.
Embodiment 3
Adopting the method for salt bath plating is the molybdenum layer of 1 μ m at graphite whisker coating surface one bed thickness.Graphite whisker put into the NaCl/KCl mixing salt that is added with a certain amount of ammonium paramolybdate mix 30 minutes in the ball mill, the mol ratio of NaCl and KCl is 1:1 in the mixing salt, and the massfraction of ammonium paramolybdate is 10% in the mixing salt.After mixing, put into the tube furnace that has protective atmosphere and be heated to 1000 ℃, be incubated furnace cooling after 60 minutes.Sieve after the whisker washing that plating is good, remove redundant impurities, obtain the graphite whisker of surface plating molybdenum.Adopting this technology is the molybdenum layer of 1 μ m at uniform plating one layer thickness in the surface of graphite whisker, and reaction generates the carbonization molybdenum layer between graphite whisker and the molybdenum layer.
The copper powder of getting granularity and be 20 μ m and plating molybdenum the graphite whisker ratio of 50:50 by volume mixed in planetary ball mill 2 hours, and drum's speed of rotation is 130 rev/mins.After mixing, mixed powder is put into plasma agglomeration stove (SPS) sintering, sintering temperature is 900 ℃, and sintering pressure is 50MPa, is incubated 5 minutes.Namely get graphite whisker/carbon/carbon-copper composite material.
Embodiment 4
Adopting the method for salt bath plating is the molybdenum layer of 0.5 μ m at graphite whisker coating surface one bed thickness.Graphite whisker put into the NaCl/KCl mixing salt that is added with a certain amount of ammonium paramolybdate mix 30 minutes in the ball mill, the mol ratio of NaCl and KCl is 1:1 in the mixing salt, and the massfraction of ammonium paramolybdate is 10% in the mixing salt.After mixing, put into the tube furnace that has protective atmosphere and be heated to 1000 ℃, be incubated furnace cooling after 40 minutes.Sieve after the whisker washing that plating is good, remove redundant impurities, obtain the graphite whisker of surface plating molybdenum.Adopting this technology is the molybdenum layer of 0.5 μ m at uniform plating one layer thickness in the surface of graphite whisker, and reaction generates the carbonization molybdenum layer between graphite whisker and the molybdenum layer.
The copper powder plating molybdenum graphite whisker of getting copper powder that granularity is 20 μ m, 70 μ m is graphite whisker by volume: copper (20 μ m): the ratio of copper (70 μ m)=50:10:40 was mixed in planetary ball mill 3 hours, and drum's speed of rotation is 150 rev/mins.After mixing, mixed powder is put into plasma agglomeration stove (SPS) sintering, sintering temperature is 890 ℃, and sintering pressure is 30MPa, is incubated 5 minutes.Namely get graphite whisker/carbon/carbon-copper composite material.
Claims (2)
1. the preparation method of a high conductive graphite whisker/carbon/carbon-copper composite material, it is characterized in that using high conductive graphite whisker to make wild phase, method plating layer of copper or molybdenum that elder generation plates with electroless plating or salt bath on the graphite whisker surface, undertaken compoundly then by SPS powder metallurgical technique and copper powder, prepare the high-performance graphite whisker and strengthen Cu-base composites;
Used wild phase is high heat conduction, the graphite whisker of low bulk, length-to-diameter ratio between 10-70, copper or the molybdenum of whisker coating surface thickness 0.1-2 μ m;
The volume ratio of the selected graphite whisker of plating and copper powder is 30-60:70-40, will mix at ball mill before compound, and drum's speed of rotation is 110-150 rev/min, and the time is 1.5-3 hour; Wherein, at first carry out the surface metal plating at graphite whisker, copper-plated operational path is: oil removing-alligatoring-sensitization-activation-electroless plating, the composition of plating bath: cupric sulfate pentahydrate 15g/L, formaldehyde 5g/L, Seignette salt 14g/L, EDTA 19.5g/L, sodium hydroxide 14.5g/L, second bipyridine 0.02g/L, yellow prussiate of potash 0.01g/L; The copper-plating technique condition is: plating bath pH is 12.0-12.5, plating temperature 40-50 ℃, plating time 2-15 minute;
The little evaporation plating of vacuum that the operational path of plating molybdenum is: oil removing-mixing powder-, graphite whisker after the oil removing put into the NaCl/KCl mixing salt that is added with a certain amount of ammonium paramolybdate mix 30 minutes in the ball mill, the mol ratio of NaCl and KCl is 1:1 in the mixing salt, and the massfraction of ammonium paramolybdate is 10% in the mixing salt; After mixing, mixture is heated to 900 ℃-1100 ℃ under protective atmosphere, forms molybdenum layer on the graphite whisker surface; Adopt the SPS powder metallurgical technique that graphite whisker and the copper powder of metal lining coating are carried out compound tense, temperature is that 820-980 ℃, pressure are 20-70MPa, soaking time 2-5 minute.
2. according to the preparation method of the described high conductive graphite whisker/carbon/carbon-copper composite material of claim 1, it is characterized in that: adopt the SPS powder metallurgical technique that graphite whisker and the copper powder of metal lining coating are carried out compound tense, selected copper powder granularity is at 17-80 μ m, and different Cu powder degree volume proportion can be allocated arbitrarily.
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| CN103435373B (en) * | 2013-08-22 | 2015-06-17 | 湖南金博复合材料科技有限公司 | Carbon/carbon composite material connection layer and preparation method |
| CN103911565B (en) * | 2014-04-23 | 2016-02-24 | 北京科技大学 | A kind of high conductive graphite whisker orientation strengthens the preparation method of metal-base composites |
| CN104762614B (en) * | 2015-04-15 | 2017-11-24 | 武汉科技大学 | A kind of high heat conduction graphite fibre surface is without palladium chemical-copper-plating process |
| CN106048286B (en) * | 2016-06-22 | 2017-12-12 | 东北大学 | A kind of process for dispersing of high specific gravity difference constituent element in copper-based melt |
| CN106521230B (en) * | 2016-12-06 | 2018-03-09 | 湖南科技大学 | A kind of graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission and preparation method thereof |
| CN108796258A (en) * | 2018-06-27 | 2018-11-13 | 北京科技大学 | A kind of preparation method of high heat conduction isotropic graphite ball enhancing Cu-base composites |
| CN108893635A (en) * | 2018-06-27 | 2018-11-27 | 北京科技大学 | High thermal conductivity isotropism carbonaceous mesophase spherules enhance Cu-base composites preparation method |
| CN111687417B (en) * | 2020-07-13 | 2022-11-22 | 广东省材料与加工研究所 | Copper-plated graphite-copper-based composite material, and preparation method and application thereof |
| CN114951607B (en) * | 2022-06-09 | 2023-10-31 | 北京科技大学广州新材料研究院 | Method for preparing graphite foam/Cu composite material by vacuum infiltration method |
| CN114921682B (en) * | 2022-06-28 | 2023-03-28 | 北京科技大学广州新材料研究院 | High-thermal-conductivity isotropic graphite nodule-copper-based composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1676640A (en) * | 2005-03-31 | 2005-10-05 | 上海交通大学 | Copper-plated graphite granule reinforced magnesium base composite material |
| CN101545057A (en) * | 2009-05-15 | 2009-09-30 | 北京科技大学 | Method for preparing diamond/Cu composite material with high heat conductivity |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1676640A (en) * | 2005-03-31 | 2005-10-05 | 上海交通大学 | Copper-plated graphite granule reinforced magnesium base composite material |
| CN101545057A (en) * | 2009-05-15 | 2009-09-30 | 北京科技大学 | Method for preparing diamond/Cu composite material with high heat conductivity |
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