CN103756252A - Thermosetting-resin-based heat-conductive composite material, and preparation method and application thereof - Google Patents
Thermosetting-resin-based heat-conductive composite material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a thermosetting-resin-based heat-conductive composite material, and a preparation method and application thereof. The heat-conductive composite material comprises a base body and a filling material filling the interior of the base body, wherein the base body employs thermosetting resin, and the filling material is modified hollow glass microspheres, and the surface of the hollow glass microspheres is subjected to modification processing by heat-conductive powder and is coated with the heat-conductive powder. The employed thermosetting resin is capable of well dispersing the heat-conductive powder, and the processing performance of the material is guaranteed; because of the reasonable matching of the hollow glass microspheres and the heat-conductive powder, the material has the advantages of being light, resistant to corrosion, good in heat conductivity, good in mechanical properties, free of pollution, low in cost, high in precision, long in service life and the like; and the material can be prepared into heat-radiation parts of electronic products, cooing fins of lamps, and other parts with relatively high heat-radiation requirements.
Description
Technical field
Invention relates to thermal-conductive polymer matrix composites technical field, relate in particular to thermosetting polymer base heat-conductive composite material, be specifically related to thermosetting resin thing base heat-conductive composite material of a kind of filling of the hollow glass micro-ball by conductive powder surface modification and its preparation method and application.
Background technology
Thermally conductive material is widely used in the fields such as heat exchange engineering, heating engineering, electronic information.
Traditional thermally conductive material mostly is the good metallic substance of thermal conductivity, but because the corrosion resistance of metallic substance is poor, electroconductibility is high, density is large, it is high to manufacture energy consumption, has limited its application in fields such as chemical industry, electronics.
Most polymers material has the advantages such as good corrosion resistance nature, quality are light, good insulating, low cost of manufacture, but they are hot poor conductor mostly, thermal conductivity is little, therefore will expand its application in heat conduction and heat radiation field, and it is crucial improving heat conductivility.
Using metal or the Inorganic Fillers Filled polymer materials of high thermal conductivity is at present the method for relatively commonly using, and the easy machine-shaping of thermally conductive material obtaining like this can be applied to a lot of special fields through suitable art breading or formula adjustment.
Thermal-conductive polymer matrix composites refers to take polymer materials as matrix, take thermal conductivity material as filler, through blend, disperses compound obtaining, and has the heterogeneous compound system of certain heat conduction function.Thermal-conductive polymer matrix composites had both had heat conduction function, had again many excellent specific properties of mixture polymer composites, can be again regulates conduction, heat conduction and the mechanical property of material in a big way, thereby was with a wide range of applications.
But the polymeric matrix major part adopting is at present thermoplastics, adopt mechanical blending with the blend of inorganic functional filler, consistency is poor, for having relatively high expectations of heat conduction network.As patent of invention 201110169387.X discloses a kind of thermoplastic polymer based thermal conductive composite, there is higher thermal conductivity, but its heat conduction functional stuffing still could form good heat conduction network up to 30% to 40%, and technique is comparatively complicated, than great.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide a kind of take thermosetting resin as matrix, there is the thermosetting resin thing base heat-conductive composite material of high heat conduction, cost degradation and lighting feature.
Another object of the present invention is to provide the preparation method of above-mentioned thermosetting resin base heat-conductive composite material.
Another object of the present invention is to provide the application of above-mentioned thermosetting resin base heat-conductive composite material.
Above-mentioned purpose of the present invention is achieved by following scheme:
A kind of thermosetting resin thing base heat-conductive composite material, this heat-conductive composite material contains matrix and is filled in the filler in matrix, described matrix is thermosetting resin, described filler is modification hollow glass micro-ball, and described modification hollow glass micro-ball is the coated heat conduction powder in surface being formed after modification is carried out on surface hollow glass micro-ball by heat conduction powder.
In above-mentioned heat-conductive composite material, thermosetting resin can refer to the resin of epoxy resin, unsaturated polyester or urethane resin or other other kinds that can solidify.
In above-mentioned heat-conductive composite material, it is the hollow glass micro-ball of 40 μ m～50 μ m that hollow glass micro-ball adopts particle diameter, so that better and fiber, graphite and other conductive powder bodies build heat conduction network jointly; Described hollow glass micro-ball adopts commercially available prod.
In above-mentioned heat-conductive composite material, heat conduction powder is the mixture of micron-sized nitride, micron-sized carbide, micron-sized heat-conducting metal oxide compound, micron-sized heat conduction carbon dust and micron-sized conductive graphite powder composition, the specific descriptions of each component in this mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized nitride refers to that particle diameter is the aluminium nitride of 1 μ m～2 μ m, and consumption is 10-50 part;
Described micron-sized carbide refers to that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 5-25 part;
Described micron-sized heat-conducting metal oxide compound refers to the aluminium sesquioxide of particle diameter 30 μ m～100 μ m, consumption 10-40 part;
Described micron-sized heat conduction carbon dust refers to that particle diameter is the heat conduction carbon dust of 30 μ m～100 μ m, consumption 5-30 part;
Described micron-sized conductive graphite powder refers to that particle diameter is the conductive graphite powder of 30 μ m～100 μ m, and consumption is 5-30 part;
Above-mentioned aluminium nitride, silicon carbide, aluminium sesquioxide, heat conduction carbon dust and conductive graphite powder are commercially available prod, adopt the heat conductive filler of different-grain diameter and different structure can build better heat conduction network.
In above-mentioned heat-conductive composite material, the inventor finds by research is rear, heat conduction powder is carried out again hollow glass micro-ball being carried out to surface treatment after pre-treatment, can realize better result, its heat conduction powder pre-treatment is: the mixture of micron-sized nitride, micron-sized carbide, micron-sized heat-conducting metal oxide compound, micron-sized heat conduction carbon dust and micron-sized conductive graphite powder composition, after irradiation activation, is uniformly dispersed through acetone is ultrasonic; Processing can make follow-up heat conductive filler and resin matrix build better heat conduction network like this, improves the surface compatability of itself and resin; Described micron-sized nitride, micron-sized carbide, micron-sized heat-conducting metal oxide compound, micron-sized heat conduction carbon dust and the mixture of micron-sized conductive graphite powder composition and the mass ratio of acetone are 1:1.
In above-mentioned heat-conductive composite material, must contain and be filled in matrix and the heat conduction powder in hollow glass and matrix gap.Its effect of heat conduction powder of the present invention is divided into two portions, a part is the mixture that adopts micron-sized nitride, micron-sized carbide, micron-sized heat-conducting metal oxide compound, micron-sized heat conduction carbon dust and micron-sized conductive graphite powder composition as previously mentioned, and its effect is by Hollow Glass Microballoon Surface Improving being coated on to hollow glass micro-ball surface; Another part is to adopt micron order nitride, any one or two or more combination in micron-sized carbide, micron-sized heat-conducting metal oxide compound, micron-sized heat conduction carbon dust or micron-sized conductive graphite powder, its effect is in the gap being filled between matrix and filler, further increases goods heat conductivility.Hollow glass micro-ball is because be filled in matrix, so formed mutually having a common boundary of spherome surface, the heat conduction powder that is coated on hollow glass micro-ball surface is forced to form and interconnects passage of heat.
In above-mentioned heat-conductive composite material, hollow glass micro-ball accounts for 10%～40% of thermosetting resin thing base heat-conductive composite material gross weight, thermosetting resin accounts for 40%～75% of thermosetting resin thing base heat-conductive composite material gross weight, heat conduction powder (described heat conduction powder comprise the heat conduction powder of modification hollow glass micro-ball and be filled in matrix and filler between gap in heat conduction powder) account for 5%～30% of thermosetting resin thing base heat-conductive composite material gross weight; In aforementioned heat conduction powder, for the heat conduction powder consumption of surface modification hollow glass micro-ball, account for 15%～25% of heat conduction powder gross weight, remaining heat conduction powder is all the glass microballon gaps that add with filling substrate and modification for follow-up.
The present invention also provides the preparation method of above-mentioned a kind of thermosetting resin base heat-conductive composite material, and this preparation method comprises the steps:
Step 1.
Micron-sized nitride, micron-sized carbide, micron-sized heat-conducting metal oxide compound, micron-sized heat conduction carbon dust and micron-sized conductive graphite powder are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, take again after the heat conduction powder of surface modification hollow glass micro-ball mixes, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone;
Hollow glass micro-ball is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, silane coupling agent or potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; The consumption of described silane coupling agent or potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
Modification hollow glass micro-ball, the step 1 that thermosetting resin, step 2 are prepared prepare through irradiation activation for being filled in heat conduction powder in the gap between matrix and filler and solidifying agent through physical blending after fixing, prepare a kind of thermosetting resin base heat-conductive composite material required for the present invention.
In above-mentioned steps 1, the more dispersed heat conductive filler of the interaction energy of the ultrasonic dispersion of acetone, so that further surface treatment glass microballon below.
In above-mentioned steps 3, described solidifying agent is to adopt the solidifying agent corresponding with thermosetting resin used.
In above-mentioned steps 3, by thermosetting resin, the modification hollow glass micro-ball that step 2 prepares, step 1 prepare through irradiation activation for being filled in heat conduction powder in the gap between matrix and filler and solidifying agent through physical blending after fixing, described curing operation is specifically divided into two steps to carry out: first by thermosetting resin, the modification hollow glass micro-ball that step 2 prepares and step 1 prepare through irradiation activation for being filled in the heat conduction powder in the gap between matrix and filler, and the corresponding solidifying agent of thermosetting resin used solidifies certain hour at 25 ℃, then at 80 ℃, solidify certain hour, contriver finds by research, solidifies to be divided into as described above two steps and to walk, and can control molding shrinkage goodly, guarantees the physicals of goods:
A kind of thermosetting resin base heat-conductive composite material that above-mentioned preparation method obtains, it not only has good heat conductivility, and mechanical property is also very good, can be used as the heat radiation product of electronic product, the radiator element of light fixture and other environment of having relatively high expectations for heat radiation.
Compared with prior art, the present invention has following beneficial effect:
1. to adopt thermosetting resin be matrix in the present invention, carries out blend synthetic with glass tiny balloon and other functional heat conductive fillers, finally obtains polymer-based carbon heat conduction goods;
2. the dispersion heat conduction powder that the thermosetting resin such as the present invention's epoxy resin used, unsaturated polyester, polyurethane can be good, has guaranteed Drawing abillity; Hollow glass micro-ball can be better by parcels such as heat conduction powders after surface treatment, it add the consumption that has reduced widely heat conduction powder; Due to the filling of hollow glass micro-ball, make material lighting simultaneously; These heat conduction powders cover tiny balloon surface and gap portion, enter in polymeric matrix, to be forced to form and interconnect passage of heat, and the heat conduction network forming, due to the hollow parts without tiny balloon, is directly led away from heat conduction powder, and therefore heat transfer efficiency is higher;
3. the present invention's plastic matrix material used is dispersed in heat conductive filler in matrix by synthetic mode, therefore more efficient with the heat conduction network of functional stuffing formation, the heat producing can be led away as early as possible in materials'use process, improves thermotolerance and working temperature;
4. the present invention has adopted the way that adds greater particle size hollow glass micro-ball, make other function thermally conductive material consumptions greatly less, guarantee that material has the advantages such as lighting, corrosion-resistant, pollution-free, cost is low, precision is high, the life-span is long, can be used for the many aspects of industrial circle.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, but specific embodiment does not do any restriction to the present invention.
embodiment 1
A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:
Step 1.
Be used for the pre-treatment of the heat conduction powder of surface modification hollow glass micro-ball: micron-sized nitride, micron-sized carbide, micron-sized heat-conducting metal oxide compound, micron-sized heat conduction carbon dust and micron-sized conductive graphite powder are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, remix forms mixture, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; The specific descriptions of each component in described mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized nitride is that particle diameter is the aluminium nitride of 1 μ m～2 μ m, and consumption is 30 parts;
Described micron-sized carbide is that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 24 parts;
Described micron-sized heat-conducting metal oxide compound is the aluminium sesquioxide of particle diameter 30 μ m～100 μ m, and consumption is 18 parts;
Described micron-sized heat conduction carbon dust is that particle diameter is the heat conduction carbon dust of 30 μ m～100 μ m, and consumption is 18 parts;
Described micron-sized conductive graphite powder is that particle diameter is the conductive graphite powder of 30 μ m～100 μ m, and consumption is 10 parts;
Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone.
For being filled in the pre-treatment of the heat conduction powder in gap between matrix and filler: be that the aluminium nitride plasma activation instrument of 1 μ m～2 μ m is more than under common plasma treatment pattern, (1.01MPa, 30 ℃) carry out irradiation activation 1h by particle diameter.
The pre-treatment of hollow glass micro-ball: the hollow glass micro-ball that is 40 μ m～50 μ m by particle diameter is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; Total consumption of described Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
Heat conduction powder high speed dispersion clarifixator for being filled in the gap between matrix and filler prepared by the modification hollow glass micro-ball that 80gE-44 epoxy resin, 10g step 2 are prepared and 10g step 1 stirs 5min, then ultrasonic dispersion 15min, add afterwards solidifying agent 650 polymeric amide of 80g and stir at short notice, within working life, be poured in mould, first at 25 ℃, solidify 1h, then at 80 ℃, solidify 3h, make the required thermosetting resin base heat-conductive composite material of the present embodiment.
Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are in Table 1.
embodiment 2
A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:
Step 1.
Be used for the pre-treatment of the heat conduction powder of surface modification hollow glass micro-ball: micron-sized nitride, micron-sized carbide, micron-sized heat-conducting metal oxide compound, micron-sized heat conduction carbon dust and micron-sized conductive graphite powder are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, remix forms mixture, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; The specific descriptions of each component in described mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized nitride is that particle diameter is the aluminium nitride of 1 μ m～2 μ m, and consumption is 30 parts;
Described micron-sized carbide is that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 24 parts;
Described micron-sized heat-conducting metal oxide compound is the aluminium sesquioxide of particle diameter 30 μ m～100 μ m, and consumption is 18 parts;
Described micron-sized heat conduction carbon dust is that particle diameter is the heat conduction carbon dust of 30 μ m～100 μ m, and consumption is 18 parts;
Described micron-sized conductive graphite powder is that particle diameter is the conductive graphite powder of 30 μ m～100 μ m, and consumption is 10 parts;
Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone.
For being filled in the pre-treatment of the heat conduction powder in gap between matrix and filler: be that the aluminium nitride plasma activation instrument of 1 μ m～2 μ m is more than under common plasma treatment pattern, (1.01MPa, 30 ℃) carry out irradiation activation 1h by particle diameter.
The pre-treatment of hollow glass micro-ball: the hollow glass micro-ball that is 40 μ m～50 μ m by particle diameter is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; Total consumption of described Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
Heat conduction powder high speed dispersion clarifixator for being filled in the gap between matrix and filler prepared by the modification hollow glass micro-ball that 70gE-44 epoxy resin, 10g step 2 are prepared and 20g step 1 stirs 5min, then ultrasonic dispersion 15min, add afterwards solidifying agent 650 polymeric amide of 70g and stir at short notice, within working life, be poured in mould, first at 25 ℃, solidify 1h, then at 80 ℃, solidify 3h, make the required thermosetting resin base heat-conductive composite material of the present embodiment.
Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are in Table 1.
embodiment 3
A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:
Step 1.
Be used for the pre-treatment of the heat conduction powder of surface modification hollow glass micro-ball: micron-sized nitride, micron-sized carbide, micron-sized heat-conducting metal oxide compound, micron-sized heat conduction carbon dust and micron-sized conductive graphite powder are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, remix forms mixture, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; The specific descriptions of each component in described mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized nitride is that particle diameter is the aluminium nitride of 1 μ m～2 μ m, and consumption is 30 parts;
Described micron-sized carbide is that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 24 parts;
Described micron-sized heat-conducting metal oxide compound is the aluminium sesquioxide of particle diameter 30 μ m～100 μ m, and consumption is 18 parts;
Described micron-sized heat conduction carbon dust is that particle diameter is the heat conduction carbon dust of 30 μ m～100 μ m, and consumption is 18 parts;
Described micron-sized conductive graphite powder is that particle diameter is the conductive graphite powder of 30 μ m～100 μ m, and consumption is 10 parts;
Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone.
For being filled in the pre-treatment of the heat conduction powder in gap between matrix and filler: be that the aluminium nitride plasma activation instrument of 1 μ m～2 μ m is more than under common plasma treatment pattern, (1.01MPa, 30 ℃) carry out irradiation activation 1h by particle diameter.
The pre-treatment of hollow glass micro-ball: the hollow glass micro-ball that is 40 μ m～50 μ m by particle diameter is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; Total consumption of described Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
Heat conduction powder high speed dispersion clarifixator for being filled in the gap between matrix and filler prepared by the modification hollow glass micro-ball that 60gE-44 epoxy resin, 10g step 2 are prepared and 30g step 1 stirs 5min, then ultrasonic dispersion 15min, add afterwards solidifying agent 650 polymeric amide of 60g and stir at short notice, within working life, be poured in mould, first at 25 ℃, solidify 1h, then at 80 ℃, solidify 3h, make the required thermosetting resin base heat-conductive composite material of the present embodiment.
Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are in Table 1.
embodiment 4
A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:
Step 1.
Be used for the pre-treatment of the heat conduction powder of surface modification hollow glass micro-ball: micron-sized nitride, micron-sized carbide, micron-sized heat-conducting metal oxide compound, micron-sized heat conduction carbon dust and micron-sized conductive graphite powder are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, remix forms mixture, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; The specific descriptions of each component in described mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized nitride is that particle diameter is the aluminium nitride of 1 μ m～2 μ m, and consumption is 30 parts;
Described micron-sized carbide is that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 24 parts;
Described micron-sized heat-conducting metal oxide compound is the aluminium sesquioxide of particle diameter 30 μ m～100 μ m, and consumption is 18 parts;
Described micron-sized heat conduction carbon dust is that particle diameter is the heat conduction carbon dust of 30 μ m～100 μ m, and consumption is 18 parts;
Described micron-sized conductive graphite powder is that particle diameter is the conductive graphite powder of 30 μ m～100 μ m, and consumption is 10 parts;
Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone.
For being filled in the pre-treatment of the heat conduction powder in gap between matrix and filler: be that the aluminium nitride plasma activation instrument of 1 μ m～2 μ m is more than under common plasma treatment pattern, (1.01MPa, 30 ℃) carry out irradiation activation 1h by particle diameter.
The pre-treatment of hollow glass micro-ball: the hollow glass micro-ball that is 40 μ m～50 μ m by particle diameter is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; Total consumption of described Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
Heat conduction powder high speed dispersion clarifixator for being filled in the gap between matrix and filler prepared by the modification hollow glass micro-ball that 50gE-44 epoxy resin, 10g step 2 are prepared and 40g step 1 stirs 5min, then ultrasonic dispersion 15min, add afterwards solidifying agent 650 polymeric amide of 60g and stir at short notice, within working life, be poured in mould, first at 25 ℃, solidify 1h, then at 80 ℃, solidify 3h, make the required thermosetting resin base heat-conductive composite material of the present embodiment.
Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are in Table 1.
embodiment 5
A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:
Step 1.
Be used for the pre-treatment of the heat conduction powder of surface modification hollow glass micro-ball: micron-sized nitride, micron-sized carbide, micron-sized heat conduction carbon dust and micron-sized conductive graphite powder are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, remix forms mixture, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; The specific descriptions of each component in described mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized nitride is that particle diameter is the aluminium nitride of 1 μ m～2 μ m, and consumption is 30 parts;
Described micron-sized carbide is that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 40 parts;
Described micron-sized heat conduction carbon dust is that particle diameter is the heat conduction carbon dust of 30 μ m～100 μ m, and consumption is 20 parts;
Described micron-sized conductive graphite powder is that particle diameter is the conductive graphite powder of 30 μ m～100 μ m, and consumption is 10 parts;
Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone.
For being filled in the pre-treatment of the heat conduction powder in gap between matrix and filler: be that the aluminium nitride plasma activation instrument of 1 μ m～2 μ m is more than under common plasma treatment pattern, (1.01MPa, 30 ℃) carry out irradiation activation 1h by particle diameter.
The pre-treatment of hollow glass micro-ball: the hollow glass micro-ball that is 40 μ m～50 μ m by particle diameter is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; Total consumption of described Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
Heat conduction powder high speed dispersion clarifixator for being filled in the gap between matrix and filler prepared by the modification hollow glass micro-ball that 40gE-44 epoxy resin, 10g step 2 are prepared and 50g step 1 stirs 5min, then ultrasonic dispersion 15min, add afterwards solidifying agent 650 polymeric amide of 60g and stir at short notice, within working life, be poured in mould, first at 25 ℃, solidify 1h, then at 80 ℃, solidify 3h, make the required thermosetting resin base heat-conductive composite material of the present embodiment.
Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are in Table 1.
embodiment 6
A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:
Step 1.
Be used for the pre-treatment of the heat conduction powder of surface modification hollow glass micro-ball: micron-sized nitride, micron-sized carbide, micron-sized heat conduction carbon dust and micron-sized conductive graphite powder are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, remix forms mixture, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; The specific descriptions of each component in described mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized nitride is that particle diameter is the aluminium nitride of 1 μ m～2 μ m, and consumption is 30 parts;
Described micron-sized carbide is that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 40 parts;
Described micron-sized heat conduction carbon dust is that particle diameter is the heat conduction carbon dust of 30 μ m～100 μ m, and consumption is 20 parts;
Described micron-sized conductive graphite powder is that particle diameter is the conductive graphite powder of 30 μ m～100 μ m, and consumption is 10 parts;
Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone.
For being filled in the pre-treatment of the heat conduction powder in gap between matrix and filler: be that the aluminium nitride plasma activation instrument of 1 μ m～2 μ m is more than under common plasma treatment pattern, (1.01MPa, 30 ℃) carry out irradiation activation 1h by particle diameter.
The pre-treatment of hollow glass micro-ball: the hollow glass micro-ball that is 40 μ m～50 μ m by particle diameter is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; Total consumption of described Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
Heat conduction powder high speed dispersion clarifixator for being filled in the gap between matrix and filler prepared by the modification hollow glass micro-ball that 70gE-44 epoxy resin, 20g step 2 are prepared and 10g step 1 stirs 5min, then ultrasonic dispersion 15min, add afterwards solidifying agent 650 polymeric amide of 70g and stir at short notice, within working life, be poured in mould, first at 25 ℃, solidify 1h, then at 80 ℃, solidify 3h, make the required thermosetting resin base heat-conductive composite material of the present embodiment.
Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are in Table 1.
embodiment 7
A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:
Step 1.
Be used for the pre-treatment of the heat conduction powder of surface modification hollow glass micro-ball: micron-sized nitride, micron-sized carbide, micron-sized heat conduction carbon dust and micron-sized conductive graphite powder are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, remix forms mixture, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; The specific descriptions of each component in described mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized nitride is that particle diameter is the aluminium nitride of 1 μ m～2 μ m, and consumption is 30 parts;
Described micron-sized carbide is that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 40 parts;
Described micron-sized heat conduction carbon dust is that particle diameter is the heat conduction carbon dust of 30 μ m～100 μ m, and consumption is 20 parts;
Described micron-sized conductive graphite powder is that particle diameter is the conductive graphite powder of 30 μ m～100 μ m, and consumption is 10 parts;
Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone.
For being filled in the pre-treatment of the heat conduction powder in gap between matrix and filler: be that the aluminium nitride plasma activation instrument of 1 μ m～2 μ m is more than under common plasma treatment pattern, (1.01MPa, 30 ℃) carry out irradiation activation 1h by particle diameter.
The pre-treatment of hollow glass micro-ball: the hollow glass micro-ball that is 40 μ m～50 μ m by particle diameter is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; Total consumption of described Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
Heat conduction powder high speed dispersion clarifixator for being filled in the gap between matrix and filler prepared by the modification hollow glass micro-ball that 60gE-44 epoxy resin, 30g step 2 are prepared and 10g step 1 stirs 5min, then ultrasonic dispersion 15min, add afterwards solidifying agent 650 polymeric amide of 70g and stir at short notice, within working life, be poured in mould, first at 25 ℃, solidify 1h, then at 80 ℃, solidify 3h, make the required thermosetting resin base heat-conductive composite material of the present embodiment.
Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are in Table 1.
embodiment 8
A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:
Step 1.
Be used for the pre-treatment of the heat conduction powder of surface modification hollow glass micro-ball: micron-sized nitride, micron-sized carbide, micron-sized heat conduction carbon dust and micron-sized conductive graphite powder are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, remix forms mixture, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; The specific descriptions of each component in described mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized nitride is that particle diameter is the aluminium nitride of 1 μ m～2 μ m, and consumption is 30 parts;
Described micron-sized carbide is that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 40 parts;
Described micron-sized heat-conducting metal oxide compound is the aluminium sesquioxide of particle diameter 30 μ m～100 μ m, and consumption is 20 parts;
Described micron-sized conductive graphite powder is that particle diameter is the conductive graphite powder of 30 μ m～100 μ m, and consumption is 10 parts;
Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone.
The pre-treatment of hollow glass micro-ball: the hollow glass micro-ball that is 40 μ m～50 μ m by particle diameter is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; Total consumption of described Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
The modification hollow glass micro-ball that 70gE-44 epoxy resin and 30g step 2 are prepared stirs 5min with high speed dispersion clarifixator, then ultrasonic dispersion 15min, add afterwards solidifying agent 650 polymeric amide of 70g and stir at short notice, within working life, be poured in mould, first at 25 ℃, solidify 1h, then at 80 ℃, solidify 3h, make the required thermosetting resin base heat-conductive composite material of the present embodiment.
Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are in Table 1.
embodiment 9
A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:
Step 1.
Be used for the pre-treatment of the heat conduction powder of surface modification hollow glass micro-ball: micron-sized nitride, micron-sized carbide, heat-conducting metal oxide compound and micron-sized conductive graphite powder are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, remix forms mixture, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; The specific descriptions of each component in described mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized nitride is that particle diameter is the aluminium nitride of 1 μ m～2 μ m, and consumption is 30 parts;
Described micron-sized carbide is that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 40 parts;
Described micron-sized heat-conducting metal oxide compound is the aluminium sesquioxide of particle diameter 30 μ m～100 μ m, and consumption is 20 parts;
Described micron-sized conductive graphite powder is that particle diameter is the conductive graphite powder of 30 μ m～100 μ m, and consumption is 10 parts;
Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone.
For being filled in the pre-treatment of the heat conduction powder in the gap between matrix and filler: more than by the aluminium sesquioxide of particle diameter 30 μ m～100 μ m plasma activation instrument, under common plasma treatment pattern, (1.01MPa, 30 ℃) carry out irradiation activation 1h.
The pre-treatment of hollow glass micro-ball: the hollow glass micro-ball that is 40 μ m～50 μ m by particle diameter is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; Total consumption of described Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
Heat conduction powder high speed dispersion clarifixator for being filled in the gap between matrix and filler prepared by the modification hollow glass micro-ball that 80g unsaturated polyester resin resin, 10g step 2 are prepared and 10g step 1 stirs 5min, then ultrasonic dispersion 15min, add afterwards the solidifying agent cobalt naphthenate of 1g and stir at short notice, within working life, be poured in mould, first at 25 ℃, solidify 3h, then at 80 ℃, solidify 2h, make the required thermosetting resin base heat-conductive composite material of the present embodiment.
Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are in Table 1.
embodiment 10
A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:
Step 1.
Be used for the pre-treatment of the heat conduction powder of surface modification hollow glass micro-ball: micron-sized nitride, micron-sized carbide, heat-conducting metal oxide compound and micron-sized conductive graphite powder are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, remix forms mixture, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; The specific descriptions of each component in described mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized nitride is that particle diameter is the aluminium nitride of 1 μ m～2 μ m, and consumption is 30 parts;
Described micron-sized carbide is that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 40 parts;
Described micron-sized heat-conducting metal oxide compound is the aluminium sesquioxide of particle diameter 30 μ m～100 μ m, and consumption is 20 parts;
Described micron-sized conductive graphite powder is that particle diameter is the conductive graphite powder of 30 μ m～100 μ m, and consumption is 10 parts;
Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone.
For being filled in the pre-treatment of the heat conduction powder in the gap between matrix and filler: more than by the aluminium sesquioxide of particle diameter 30 μ m～100 μ m plasma activation instrument, under common plasma treatment pattern, (1.01MPa, 30 ℃) carry out irradiation activation 1h.
The pre-treatment of hollow glass micro-ball: the hollow glass micro-ball that is 40 μ m～50 μ m by particle diameter is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; Total consumption of described Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
Heat conduction powder high speed dispersion clarifixator for being filled in the gap between matrix and filler prepared by the modification hollow glass micro-ball that 70g unsaturated polyester resin resin, 10g step 2 are prepared and 10g step 1 stirs 5min, then ultrasonic dispersion 15min, add afterwards the solidifying agent cobalt naphthenate of 1g and stir at short notice, within working life, be poured in mould, first at 25 ℃, solidify 3h, then at 80 ℃, solidify 2h, make the required thermosetting resin base heat-conductive composite material of the present embodiment.
Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are in Table 1.
embodiment 11
A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:
Step 1.
Be used for the pre-treatment of the heat conduction powder of surface modification hollow glass micro-ball: micron-sized nitride, micron-sized carbide, heat-conducting metal oxide compound and micron-sized conductive graphite powder are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, remix forms mixture, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; The specific descriptions of each component in described mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized nitride is that particle diameter is the aluminium nitride of 1 μ m～2 μ m, and consumption is 30 parts;
Described micron-sized carbide is that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 40 parts;
Described micron-sized heat-conducting metal oxide compound is the aluminium sesquioxide of particle diameter 30 μ m～100 μ m, and consumption is 20 parts;
Described micron-sized conductive graphite powder is that particle diameter is the conductive graphite powder of 30 μ m～100 μ m, and consumption is 10 parts;
Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone.
For being filled in the pre-treatment of the heat conduction powder in the gap between matrix and filler: more than by the aluminium sesquioxide of particle diameter 30 μ m～100 μ m plasma activation instrument, under common plasma treatment pattern, (1.01MPa, 30 ℃) carry out irradiation activation 1h.
The pre-treatment of hollow glass micro-ball: the hollow glass micro-ball that is 40 μ m～50 μ m by particle diameter is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; Total consumption of described Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
Heat conduction powder high speed dispersion clarifixator for being filled in the gap between matrix and filler prepared by the modification hollow glass micro-ball that 60g unsaturated polyester resin resin, 10g step 2 are prepared and 30g step 1 stirs 5min, then ultrasonic dispersion 15min, add afterwards the solidifying agent cobalt naphthenate of 1g and stir at short notice, within working life, be poured in mould, first at 25 ℃, solidify 3h, then at 80 ℃, solidify 2h, make the required thermosetting resin base heat-conductive composite material of the present embodiment.
Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are in Table 1.
embodiment 12
A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:
Step 1.
Be used for the pre-treatment of the heat conduction powder of surface modification hollow glass micro-ball: micron-sized nitride, micron-sized carbide, heat-conducting metal oxide compound and micron-sized conductive graphite powder are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, remix forms mixture, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; The specific descriptions of each component in described mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized nitride is that particle diameter is the aluminium nitride of 1 μ m～2 μ m, and consumption is 30 parts;
Described micron-sized carbide is that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 40 parts;
Described micron-sized heat-conducting metal oxide compound is the aluminium sesquioxide of particle diameter 30 μ m～100 μ m, and consumption is 20 parts;
Described micron-sized conductive graphite powder is that particle diameter is the conductive graphite powder of 30 μ m～100 μ m, and consumption is 10 parts;
Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone.
For being filled in the pre-treatment of the heat conduction powder in the gap between matrix and filler: more than by the aluminium sesquioxide of particle diameter 30 μ m～100 μ m plasma activation instrument, under common plasma treatment pattern, (1.01MPa, 30 ℃) carry out irradiation activation 1h.
The pre-treatment of hollow glass micro-ball: the hollow glass micro-ball that is 40 μ m～50 μ m by particle diameter is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; Total consumption of described Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
Heat conduction powder high speed dispersion clarifixator for being filled in the gap between matrix and filler prepared by the modification hollow glass micro-ball that 50g unsaturated polyester resin resin, 10g step 2 are prepared and 40g step 1 stirs 5min, then ultrasonic dispersion 15min, add afterwards the solidifying agent cobalt naphthenate of 1g and stir at short notice, within working life, be poured in mould, first at 25 ℃, solidify 3h, then at 80 ℃, solidify 2h, make the required thermosetting resin base heat-conductive composite material of the present embodiment.
Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are in Table 1.
embodiment 13
A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:
Step 1.
Be used for the pre-treatment of the heat conduction powder of surface modification hollow glass micro-ball: micron-sized nitride, micron-sized carbide, heat-conducting metal oxide compound and micron-sized heat conduction carbon dust are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, remix forms mixture, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; The specific descriptions of each component in described mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized nitride is that particle diameter is the aluminium nitride of 1 μ m～2 μ m, and consumption is 30 parts;
Described micron-sized carbide is that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 40 parts;
Described micron-sized heat-conducting metal oxide compound is the aluminium sesquioxide of particle diameter 30 μ m～100 μ m, and consumption is 20 parts;
Described micron-sized heat conduction carbon dust is that particle diameter is the heat conduction carbon dust of 30 μ m～100 μ m, and consumption is 10 parts;
Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone.
For being filled in the pre-treatment of the heat conduction powder in gap between matrix and filler: be that the heat conduction carbon dust plasma activation instrument of 30 μ m～100 μ m is more than under common plasma treatment pattern, (1.01MPa, 30 ℃) carry out irradiation activation 1h by particle diameter.
The pre-treatment of hollow glass micro-ball: the hollow glass micro-ball that is 40 μ m～50 μ m by particle diameter is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; Total consumption of described Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
Heat conduction powder high speed dispersion clarifixator for being filled in the gap between matrix and filler prepared by the modification hollow glass micro-ball that 70g unsaturated polyester resin resin, 20g step 2 are prepared and 10g step 1 stirs 5min, then ultrasonic dispersion 15min, add afterwards the solidifying agent cobalt naphthenate of 1g and stir at short notice, within working life, be poured in mould, first at 25 ℃, solidify 3h, then at 80 ℃, solidify 2h, make the required thermosetting resin base heat-conductive composite material of the present embodiment.
Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are in Table 1.
embodiment 14
A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:
Step 1.
Be used for the pre-treatment of the heat conduction powder of surface modification hollow glass micro-ball: micron-sized nitride, micron-sized carbide, heat-conducting metal oxide compound and micron-sized heat conduction carbon dust are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, remix forms mixture, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; The specific descriptions of each component in described mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized nitride is that particle diameter is the aluminium nitride of 1 μ m～2 μ m, and consumption is 30 parts;
Described micron-sized carbide is that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 40 parts;
Described micron-sized heat-conducting metal oxide compound is the aluminium sesquioxide of particle diameter 30 μ m～100 μ m, and consumption is 20 parts;
Described micron-sized heat conduction carbon dust is that particle diameter is the heat conduction carbon dust of 30 μ m～100 μ m, and consumption is 10 parts;
Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone.
For being filled in the pre-treatment of the heat conduction powder in gap between matrix and filler: be that the heat conduction carbon dust plasma activation instrument of 30 μ m～100 μ m is more than under common plasma treatment pattern, (1.01MPa, 30 ℃) carry out irradiation activation 1h by particle diameter.
The pre-treatment of hollow glass micro-ball: the hollow glass micro-ball that is 40 μ m～50 μ m by particle diameter is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; Total consumption of described Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
Heat conduction powder high speed dispersion clarifixator for being filled in the gap between matrix and filler prepared by the modification hollow glass micro-ball that 60g unsaturated polyester resin resin, 30g step 2 are prepared and 10g step 1 stirs 5min, then ultrasonic dispersion 15min, add afterwards the solidifying agent cobalt naphthenate of 1g and stir at short notice, within working life, be poured in mould, first at 25 ℃, solidify 3h, then at 80 ℃, solidify 2h, make the required thermosetting resin base heat-conductive composite material of the present embodiment.
Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are in Table 1.
embodiment 15
A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:
Step 1.
Be used for the pre-treatment of the heat conduction powder of surface modification hollow glass micro-ball: micron-sized nitride, micron-sized carbide, heat-conducting metal oxide compound and micron-sized heat conduction carbon dust are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, remix forms mixture, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; The specific descriptions of each component in described mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized nitride is that particle diameter is the aluminium nitride of 1 μ m～2 μ m, and consumption is 30 parts;
Described micron-sized carbide is that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 40 parts;
Described micron-sized heat-conducting metal oxide compound is the aluminium sesquioxide of particle diameter 30 μ m～100 μ m, and consumption is 20 parts;
Described micron-sized heat conduction carbon dust is that particle diameter is the heat conduction carbon dust of 30 μ m～100 μ m, and consumption is 10 parts;
Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone.
For being filled in the pre-treatment of the heat conduction powder in gap between matrix and filler: be that the heat conduction carbon dust plasma activation instrument of 30 μ m～100 μ m is more than under common plasma treatment pattern, (1.01MPa, 30 ℃) carry out irradiation activation 1h by particle diameter.
The pre-treatment of hollow glass micro-ball: the hollow glass micro-ball that is 40 μ m～50 μ m by particle diameter is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; Total consumption of described Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
100gEP, 200g have been dissolved to the heat conduction powder high speed dispersion clarifixator for being filled in the gap between matrix and filler prepared by the TCM solvent of 20gPC, modification hollow glass micro-ball that 20g step 2 prepares and 20g step 1 and stirred 5min, then ultrasonic dispersion 15min, add afterwards the solidifying agent TEPA of 15g and stir at short notice, within working life, be poured in mould, first at 25 ℃, solidify 6h, then at 80 ℃, solidify 6h, make the required thermosetting resin base heat-conductive composite material of the present embodiment.
Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are in Table 1.
embodiment 16
A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:
Step 1.
Be used for the pre-treatment of the heat conduction powder of surface modification hollow glass micro-ball: micron-sized nitride, micron-sized carbide, heat-conducting metal oxide compound and micron-sized heat conduction carbon dust are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, remix forms mixture, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; The specific descriptions of each component in described mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized nitride is that particle diameter is the aluminium nitride of 1 μ m～2 μ m, and consumption is 30 parts;
Described micron-sized carbide is that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 40 parts;
Described micron-sized heat-conducting metal oxide compound is the aluminium sesquioxide of particle diameter 30 μ m～100 μ m, and consumption is 20 parts;
Described micron-sized heat conduction carbon dust is that particle diameter is the heat conduction carbon dust of 30 μ m～100 μ m, and consumption is 10 parts;
Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone.
For being filled in the pre-treatment of the heat conduction powder in gap between matrix and filler: be that the heat conduction carbon dust plasma activation instrument of 30 μ m～100 μ m is more than under common plasma treatment pattern, (1.01MPa, 30 ℃) carry out irradiation activation 1h by particle diameter.
The pre-treatment of hollow glass micro-ball: the hollow glass micro-ball that is 40 μ m～50 μ m by particle diameter is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; Total consumption of described Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
100gEP, 200g have been dissolved to the heat conduction powder high speed dispersion clarifixator for being filled in the gap between matrix and filler prepared by the TCM solvent of 20gPC, modification hollow glass micro-ball that 10g step 2 prepares and 20g step 1 and stirred 5min, then ultrasonic dispersion 15min, add afterwards the solidifying agent TEPA of 15g and stir at short notice, within working life, be poured in mould, first at 25 ℃, solidify 6h, then at 80 ℃, solidify 6h, make the required thermosetting resin base heat-conductive composite material of the present embodiment.
Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are in Table 1.
embodiment 17
A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:
Step 1.
Be used for the pre-treatment of the heat conduction powder of surface modification hollow glass micro-ball: micron-sized carbide, heat-conducting metal oxide compound, micron-sized heat conduction carbon dust and conductive graphite powder are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, remix forms mixture, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; The specific descriptions of each component in described mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized carbide is that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 30 parts;
Described micron-sized heat-conducting metal oxide compound is the aluminium sesquioxide of particle diameter 30 μ m～100 μ m, and consumption is 40 parts;
Described micron-sized heat conduction carbon dust is that particle diameter is the heat conduction carbon dust of 30 μ m～100 μ m, and consumption is 20 parts;
Described micron-sized conductive graphite powder is that particle diameter is the conductive graphite powder of 30 μ m～100 μ m, and consumption is 10 parts;
Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone.
For being filled in the pre-treatment of the heat conduction powder in gap between matrix and filler: be that the conductive graphite powder plasma activation instrument of 30 μ m～100 μ m is more than under common plasma treatment pattern, (1.01MPa, 30 ℃) carry out irradiation activation 1h by particle diameter.
The pre-treatment of hollow glass micro-ball: the hollow glass micro-ball that is 40 μ m～50 μ m by particle diameter is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; Total consumption of described Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
80gEP, 200g have been dissolved to the heat conduction powder high speed dispersion clarifixator for being filled in the gap between matrix and filler prepared by the TCM solvent of 20gPC, modification hollow glass micro-ball that 20g step 2 prepares and 20g step 1 and stirred 5min, then ultrasonic dispersion 15min, add afterwards the solidifying agent TEPA of 15g and stir at short notice, within working life, be poured in mould, first at 25 ℃, solidify 6h, then at 80 ℃, solidify 6h, make the required thermosetting resin base heat-conductive composite material of the present embodiment.
Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are in Table 1.
embodiment 18
A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:
Step 1.
Be used for the pre-treatment of the heat conduction powder of surface modification hollow glass micro-ball: micron-sized carbide, heat-conducting metal oxide compound, micron-sized heat conduction carbon dust and conductive graphite powder are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, remix forms mixture, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; The specific descriptions of each component in described mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized carbide is that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 30 parts;
Described micron-sized heat-conducting metal oxide compound is the aluminium sesquioxide of particle diameter 30 μ m～100 μ m, and consumption is 40 parts;
Described micron-sized heat conduction carbon dust is that particle diameter is the heat conduction carbon dust of 30 μ m～100 μ m, and consumption is 20 parts;
Described micron-sized conductive graphite powder is that particle diameter is the conductive graphite powder of 30 μ m～100 μ m, and consumption is 10 parts;
Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone.
The pre-treatment of hollow glass micro-ball: the hollow glass micro-ball that is 40 μ m～50 μ m by particle diameter is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; Total consumption of described Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
80gEP, 200g have been dissolved to the TCM solvent of 20gPC and modification hollow glass micro-ball that 40g step 2 prepares high speed dispersion clarifixator stirs 5min, then ultrasonic dispersion 15min, add afterwards the solidifying agent TEPA of 15g and stir at short notice, within working life, be poured in mould, first at 25 ℃, solidify 6h, then at 80 ℃, solidify 6h, make the required thermosetting resin base heat-conductive composite material of the present embodiment.
Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are in Table 1.
embodiment 19
A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:
Step 1.
Be used for the pre-treatment of the heat conduction powder of surface modification hollow glass micro-ball: micron-sized carbide, heat-conducting metal oxide compound, micron-sized heat conduction carbon dust and conductive graphite powder are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, remix forms mixture, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; The specific descriptions of each component in described mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized carbide is that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 30 parts;
Described micron-sized heat-conducting metal oxide compound is the aluminium sesquioxide of particle diameter 30 μ m～100 μ m, and consumption is 40 parts;
Described micron-sized heat conduction carbon dust is that particle diameter is the heat conduction carbon dust of 30 μ m～100 μ m, and consumption is 20 parts;
Described micron-sized conductive graphite powder is that particle diameter is the conductive graphite powder of 30 μ m～100 μ m, and consumption is 10 parts;
Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone.
For being filled in the pre-treatment of the heat conduction powder in gap between matrix and filler: be that the conductive graphite powder plasma activation instrument of 30 μ m～100 μ m is more than under common plasma treatment pattern, (1.01MPa, 30 ℃) carry out irradiation activation 1h by particle diameter.
The pre-treatment of hollow glass micro-ball: the hollow glass micro-ball that is 40 μ m～50 μ m by particle diameter is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; Total consumption of described Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
80gEP, 200g have been dissolved to the heat conduction powder high speed dispersion clarifixator for being filled in the gap between matrix and filler prepared by the TCM solvent of 20gPC and 40g step 1 and stirred 5min, then ultrasonic dispersion 15min, add afterwards the solidifying agent TEPA of 15g and stir at short notice, within working life, be poured in mould, first at 25 ℃, solidify 6h, then at 80 ℃, solidify 6h, make the required thermosetting resin base heat-conductive composite material of the present embodiment.
Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are in Table 1.
embodiment 20
A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:
Step 1.
Be used for the pre-treatment of the heat conduction powder of surface modification hollow glass micro-ball: micron-sized carbide, heat-conducting metal oxide compound, micron-sized heat conduction carbon dust and conductive graphite powder are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, remix forms mixture, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; The specific descriptions of each component in described mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized carbide is that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 30 parts;
Described micron-sized heat-conducting metal oxide compound is the aluminium sesquioxide of particle diameter 30 μ m～100 μ m, and consumption is 40 parts;
Described micron-sized heat conduction carbon dust is that particle diameter is the heat conduction carbon dust of 30 μ m～100 μ m, and consumption is 20 parts;
Described micron-sized conductive graphite powder is that particle diameter is the conductive graphite powder of 30 μ m～100 μ m, and consumption is 10 parts;
Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone.
The pre-treatment of hollow glass micro-ball: the hollow glass micro-ball that is 40 μ m～50 μ m by particle diameter is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; Total consumption of described Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
70gEP, 200g have been dissolved to the TCM solvent of 30gPC and modification hollow glass micro-ball that 40g step 2 prepares high speed dispersion clarifixator stirs 5min, then ultrasonic dispersion 15min, add afterwards the solidifying agent TEPA of 15g and stir at short notice, within working life, be poured in mould, first at 25 ℃, solidify 6h, then at 80 ℃, solidify 6h, make the required thermosetting resin base heat-conductive composite material of the present embodiment.
Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are in Table 1.
embodiment 21
A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:
Step 1.
Be used for the pre-treatment of the heat conduction powder of surface modification hollow glass micro-ball: micron-sized nitride, micron-sized carbide, micron-sized heat-conducting metal oxide compound, micron-sized heat conduction carbon dust and micron-sized conductive graphite powder are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, remix forms mixture, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; The specific descriptions of each component in described mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized nitride is that particle diameter is the aluminium nitride of 1 μ m～2 μ m, and consumption is 30 parts;
Described micron-sized carbide is that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 24 parts;
Described micron-sized heat-conducting metal oxide compound is the aluminium sesquioxide of particle diameter 30 μ m～100 μ m, and consumption is 18 parts;
Described micron-sized heat conduction carbon dust is that particle diameter is the heat conduction carbon dust of 30 μ m～100 μ m, and consumption is 18 parts;
Described micron-sized conductive graphite powder is that particle diameter is the conductive graphite powder of 30 μ m～100 μ m, and consumption is 10 parts;
Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone.
The pre-treatment of hollow glass micro-ball: the hollow glass micro-ball that is 40 μ m～50 μ m by particle diameter is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; Total consumption of described Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
60gEP, 200g have been dissolved to the TCM solvent of 40gPC and modification hollow glass micro-ball that 40g step 2 prepares high speed dispersion clarifixator stirs 5min, then ultrasonic dispersion 15min, add afterwards the solidifying agent TEPA of 15g and stir at short notice, within working life, be poured in mould, first at 25 ℃, solidify 6h, then at 80 ℃, solidify 6h, make the required thermosetting resin base heat-conductive composite material of the present embodiment.
Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are in Table 1.
embodiment 22
A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:
Step 1.
Be used for the pre-treatment of the heat conduction powder of surface modification hollow glass micro-ball: micron-sized nitride, micron-sized carbide, micron-sized heat-conducting metal oxide compound, micron-sized heat conduction carbon dust and micron-sized conductive graphite powder are used respectively to plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 ℃) carry out irradiation activation 1h above after, remix forms mixture, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution; The specific descriptions of each component in described mixture, and the consumption (parts by weight) of this component in mixture is as follows:
Described micron-sized nitride is that particle diameter is the aluminium nitride of 1 μ m～2 μ m, and consumption is 30 parts;
Described micron-sized carbide is that particle diameter is the silicon carbide of 1 μ m～2 μ m, and consumption is 24 parts;
Described micron-sized heat-conducting metal oxide compound is the aluminium sesquioxide of particle diameter 30 μ m～100 μ m, and consumption is 18 parts;
Described micron-sized heat conduction carbon dust is that particle diameter is the heat conduction carbon dust of 30 μ m～100 μ m, and consumption is 18 parts;
Described micron-sized conductive graphite powder is that particle diameter is the conductive graphite powder of 30 μ m～100 μ m, and consumption is 10 parts;
Described is 1:1 for the heat conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone.
The pre-treatment of hollow glass micro-ball: the hollow glass micro-ball that is 40 μ m～50 μ m by particle diameter is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity, the glass microballon obtaining like this can be covered by heat conduction powder better in ensuing treatment step; Total consumption of described Silane coupling agent KH550, silane coupling agent KH570 and potassium titanate coupling agent is 3% of hollow glass micro-ball quality;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
50gEP, 200g have been dissolved to the TCM solvent of 50gPC and modification hollow glass micro-ball that 40g step 2 prepares high speed dispersion clarifixator stirs 5min, then ultrasonic dispersion 15min, add afterwards the solidifying agent TEPA of 15g and stir at short notice, within working life, be poured in mould, first at 25 ℃, solidify 6h, then at 80 ℃, solidify 6h, make the required thermosetting resin base heat-conductive composite material of the present embodiment.
Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are in Table 1.
The performance test results of the thermosetting resin base heat-conductive composite material of table 1 embodiment 1～22 preparation
Table 1 is the performance data of the material of several good embodiment of choosing in patent of the present invention, can find, along with the increase of the consumption of hollow glass micropearl, the proportion of product declines, thermal conductivity also can decline, and therefore selects the hollow glass micropearl of appropriate ratio and heat conductive filler and thermosetting resin can guarantee the mechanical property of material and the stable molding performance of product simultaneously.This product can be used in the higher occasion of accuracy requirement, as the heat radiation product of electric equipment products, and the cooling base of light fixture or heat-dissipating casing use, there is obvious practical value.
Claims (10)
1. a thermosetting resin thing base heat-conductive composite material, it is characterized in that this heat-conductive composite material contains matrix and is filled in the filler in matrix, described matrix is thermosetting resin, described filler is modification hollow glass micro-ball, and described modification hollow glass micro-ball is the coated heat conduction powder in surface being formed after modification is carried out on surface hollow glass micro-ball by heat conduction powder.
2. a kind of thermosetting resin thing base heat-conductive composite material according to claim 1, is characterized in that described thermosetting resin is epoxy resin, unsaturated polyester or urethane resin.
3. a kind of thermosetting resin thing base heat-conductive composite material according to claim 1, is characterized in that it is the hollow glass micro-ball of 40 μ m～50 μ m that described hollow glass micro-ball adopts particle diameter.
4. a kind of thermosetting resin thing base heat-conductive composite material according to claim 1, is characterized in that described heat conduction powder is the mixture of micron-sized nitride, micron-sized carbide, micron-sized heat-conducting metal oxide compound, micron-sized heat conduction carbon dust and micron-sized conductive graphite powder composition.
5. a kind of thermosetting resin thing base heat-conductive composite material according to claim 1, is characterized in that described heat conduction powder will first carry out pre-treatment, and described pre-treatment is that heat conduction powder is first uniformly dispersed through acetone is ultrasonic after irradiation activation again.
6. a kind of thermosetting resin thing base heat-conductive composite material according to claim 1, it is characterized in that described hollow glass micro-ball accounts for 10%～40% of thermosetting resin thing base heat-conductive composite material gross weight, thermosetting resin accounts for 40%～75% of thermosetting resin thing base heat-conductive composite material gross weight.
7. according to a kind of thermosetting resin thing base heat-conductive composite material of any one described in claim 1-6, it is characterized in that described thermosetting resin thing base heat-conductive composite material also contains to be filled in matrix and the heat conduction powder in hollow glass and matrix gap.
8. a preparation method for thermosetting resin thing base heat-conductive composite material described in claim 7, is characterized in that this preparation method comprises the steps:
Step 1.
After micron-sized nitride, micron-sized carbide, micron-sized heat-conducting metal oxide compound, micron-sized heat conduction carbon dust and micron-sized conductive graphite powder are carried out more than irradiation activation 1h with plasma activation instrument respectively under common plasma treatment pattern, take again after the heat conduction powder of surface modification hollow glass micro-ball mixes, be uniformly dispersed through acetone is ultrasonic, obtain mixed solution;
Hollow glass micro-ball is put into sodium hydroxide solution dipping taking-up after 1 hour that concentration is 0.1mol/L, after normal temperature is air-dry, silane coupling agent or potassium titanate coupling agent are sprayed directly on to the bead surface of processing through sodium hydroxide solution, obtain the hollow glass micro-ball of surface irregularity;
Step 2.
The hollow glass micro-ball of surface irregularity prepared by step 1 is put into heat conduction powder mixed solution prepared by step 1, ultrasonic dispersion 1 hour is above until be uniformly dispersed together, after allowing solvent volatilize in air, obtain modification hollow glass micro-ball, namely the hollow glass micro-ball of heat conduction powder has been wrapped up on surface;
Step 3.
Modification hollow glass micro-ball, the step 1 that thermosetting resin, step 2 are prepared prepare through irradiation activation for being filled in heat conduction powder in the gap between matrix and filler and solidifying agent through physical blending after fixing, prepare a kind of thermosetting resin base heat-conductive composite material required for the present invention.
9. a kind of preparation method of thermosetting resin thing base heat-conductive composite material according to claim 8, it is characterized in that in described step 3, prepared by modification hollow glass micro-ball, the step 1 that thermosetting resin, step 2 are prepared is first solidification treatment at 80 ℃ again after solidification treatment at 25 ℃ through irradiation activation for being filled in heat conduction powder in the gap between matrix and filler and solidifying agent.
Described in claim 7 a kind of thermosetting resin thing base heat-conductive composite material in the application of preparing in electronic product radiating product or light fixture radiator element.
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| CN113429924A (en) * | 2021-07-14 | 2021-09-24 | 深圳市汇海鑫科技有限公司 | Epoxy-based heat-conducting adhesive and preparation method thereof |
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