CN103467889A - Method for preparing heat conductive composite material by mechanical activation and intensification - Google Patents
Method for preparing heat conductive composite material by mechanical activation and intensification Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000004137 mechanical activation Methods 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 46
- 238000002156 mixing Methods 0.000 claims abstract description 35
- 238000000498 ball milling Methods 0.000 claims abstract description 31
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000010439 graphite Substances 0.000 claims abstract description 17
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 16
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 52
- 229920000642 polymer Polymers 0.000 claims description 29
- 239000000654 additive Substances 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 26
- 230000000996 additive effect Effects 0.000 claims description 25
- 238000007731 hot pressing Methods 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000004800 polyvinyl chloride Substances 0.000 claims description 13
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Abstract
The invention relates to the field of heat conductive material processing, and specifically relates to a method for preparing a heat conductive composite material by mechanical activation and intensification. The method comprises the following steps: firstly, uniformly mixing a high molecular base material, a heat conductive additive and a dispersant according to a proportion of (59.5-79.5%):(20-40%):(0.5-1%) to obtain a mixed material; then, placing the mixed material in a high energy ball mill to mix and carrying out ball milling for 40-100 minutes; taking out ball-milled reactants and filling the reactants in a die of a press vulcanizer; and demoulding after hot press at high temperature to obtain the heat conductive material. According to the preparation method, the ball-milling time of the materials is shortened, the reaction efficiency is improved, the reaction is efficient, and energy resources are saved. No industrial wastes are available, and magnesium oxide MgO and graphite used are cheap. The production cost of the heat conductive material is lowered, the heat conductivity is improved, the mechanical property is improved, and the temperature resisting degree is improved.
Description
Technical field
The invention belongs to the thermal conducting material manufacture field, specifically a kind of mechanical activation strengthening prepares the method for heat-conductive composite material.
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 thermal conductivity metallic substance preferably, but has limited its application in fields such as chemical industry because the corrosion resistance of metallic substance is poor.The most polymers material has good corrosion resistance nature and mechanical property, but they are that hot poor conductor is (as PE thermal conductivity 0.33Wm mostly
-1k
-1, PP thermal conductivity 0.24 Wm
-1k
-1, PVC thermal conductivity 0.13 ~ 0.17Wm
-1k
-1, PS thermal conductivity 0.08 Wm
-1k
-1, PB thermal conductivity 0.23Wm
-1k
-1, PA thermal conductivity 0.25Wm
-1k
-1), thermal conductivity is little, therefore will expand its application in the heat conduction field, and it is crucial improving heat conductivility.
Improve at present the polymkeric substance heat conductivility and mainly contain following 2 kinds of approach: first, synthesize and there is the structural polymer that thermal conductivity is high, as there is polyacetylene, polyaniline, polypyrrole of good heat conductive performance etc., or there is complete crystallinity, realize the polymkeric substance of heat conduction by phonon.To its electroconductibility of the more concerns of the research of above highly thermally conductive polymeric, the research of its heat conductivility does not also cause enough attention; And although the height-oriented polymkeric substance of complete crystallization has good heat conductivility, the manufacturing process complexity.The second, metal or the Inorganic Fillers Filled polymer materials of use high thermal conductivity, this method is more commonly used.Cheap, the easy machine-shaping of the thermally conductive material obtained like this, can be applied to some special dimension through suitable art breading or formula adjustment.
Aspect the preparation method, the tradition preparation method be mainly by high polymer monomer with after pretreated additive agent powder fully mixes, mediate through internal mixing and plasticizing instrument or kneader banburying, then put into pair spiral shell mills and repeatedly prolong and mould, compressing tablet after slice, carry out the pressing plate moulding with vulcanizing press.According to processing mode with to the difference of ingredient requirement, working method can be divided into: melting mixing, ground and mixed, solution blending, powder mix.
Melting mixing is that the heat conductive filler powder is mixed by mixing facilities with molten high polymer, then machine-shaping.It is mixing that this method needs high temperature and long period to carry out in the process of melting mixing, therefore has toxic gas as part dioxin and Cl
2emit, be unfavorable for environmental protection, and need the operating process of high temperature highly energy-consuming, consider from economic angle, cost is higher.But the method is widely used in plastic product industry now, its technical maturity, sheet material good mechanical property.
Ground and mixed: the ground and mixed method is that superpolymer and heat conductive filler process are ground, and makes its even mixing, then carries out the fusion-cast moulding.The polishing process means is relatively simple, but each treatment capacity is considerably less, and in process of lapping, error is also high, is unsuitable for industrial production.
Solution blending: this method is that superpolymer is dissolved in suitable solvent, all with disperse, in heat conductive filler and solution, after evaporation, by polymkeric substance and heat conductive filler mixture fusion-cast, to extrude or compression molding.This method is polluted high, and it is very difficult technological difficulties of capturing that the recovery of solvent and nothing poison, and environmental protection effect is poor.
Powder mixes: powder mixes that to send out be the promising utilisation technology of tool at present, and environmental protection effect is strong, there are some researches show by the method for ball milling and draw the composite sheet that thermal conductivity is higher, BN is as the heat conduction additive for Zhou Wenying application boron nitride, high density polyethylene(HDPE) is added to blend, ball milling 5h, obtain the composite sheet of 0.96 W/mK, its method shortcoming is that the blending reaction time is long, and BN is as additive, expensive.
Summary of the invention
The objective of the invention is to overcome existing powder and be mixed with the thermally conductive material method and have the problems such as Ball-milling Time is long, reaction efficiency is low, raw materials cost is high, provide a kind of mechanical activation strengthening to prepare the method for heat-conductive composite material.
The solution of the present invention is by such realization: a kind of mechanical activation strengthening prepares the method for heat-conductive composite material, it is characterized in that, at first the ratio that polymer base-material, heat conduction additive, dispersion agent are 59.5-79.5%:20-40%:0.5-1% according to weight ratio is mixed obtains compound, again compound is put into to high energy ball mill mixing and ball milling 40 ~ 100min, make the strengthening effect of compound generation mechanical activation, reactant after the taking-up ball milling, be filled in the mould of vulcanizing press, after high temperature hot pressing, the demoulding obtains heat-conductive composite material.Utilize this emerging interleaving techniques of mechanical activation to carry out solid state reaction, without the heat conduction additive is carried out to pre-treatment, the heat-conductive composite material reaction times has been shortened in the mechanical activation effect, but still can make the heat conductivility of product improve a lot, and still can keep the outstanding resistance toheat of polymer composite and excellent mechanical property, reaction process is without other chemical additives, and product has retained its high flame retardant, creep-resistant property, acid-alkali-corrosive-resisting performance.
As further restriction of the present invention, be furnished with zirconia balls in described high energy ball mill, the ratio of zirconia balls heap volume and compound weight is 200 ~ 400ml:40～80g, the diameter of zirconia balls is 2 ~ 8mm.
As further restriction of the present invention, described polymer base-material is any or their mixture in polyvinylchloride, polythene PE, polypropylene PP, polymetylmethacrylate, polystyrene PS, nylon Nylon; Described heat conduction additive is any or their mixture in graphite, magnesium oxide; Described dispersion agent is silicon-dioxide.
As further restriction of the present invention, its reaction conditions of described mixing and ball milling is 35 ~ 40 ℃ of rotating speed 100-500rpm, temperature.
As further restriction of the present invention, its condition of described high temperature hot pressing be 5MP with upward pressure, 150-200 ℃ lower hot pressing 5 ~ 20min, mould has been smeared releasing agent.
The know-why that the present invention realizes is: by polymer base-material and heat conduction additive (graphite, magnesium oxide) be placed in high energy ball mill and mix ball milling, utilize the principle of mechanical activation, at first polymer base-material and heat conduction additive (graphite have occurred, magnesium oxide) pulverizing, peeling off of graphite flake layer afterwards, slippage reaches with the polymer base-material of pulverizing and mutually embeds, dispersed, additive (magnesium oxide) is realized the surface parcel to the polymer base-material, powder mixture constantly is subject to the high energy impact of zirconia balls, the collision repeatedly of zirconium ball-powder-zirconium ball-zirconium ball-powder-tank skin occurs, realization is broken, the cold welding effect, final formation is very tiny, the mixed powder particle mixed.
The present invention possesses following good result:
(1) the present invention is improved on the basis that prepared by the conventional powder hybrid system to heat-conductive composite material, by introduce the mechanical activation reaction in the mixing of materials process, powder mixture constantly is subject to the high energy impact of zirconia balls, the collision repeatedly of zirconium ball-powder-zirconium ball-zirconium ball-powder-tank skin occurs, realization is broken, the cold welding effect, finally form mixed powder particle very tiny, that mix, the final shortening material Ball-milling Time of realizing, improve reaction efficiency, reach highly effective reaction and save every energy.
(2) the present invention utilizes preparation method's technique and the formula for a product after optimization, the heat-conductive composite material wherein prepared, and thermal conductivity reaches as high as 1.0420 W/mK, with respect to not improved polymer base-material raw material, has improved 7 times of left and right, and thermal conductivity increases substantially.The product mechanical property is more than 40Mpa according to GB GB1040-1992 and GB9341-2000 test for tensile strength, and flexural strength is more than 70Mpa, product reach and exceed the industrial production needs require 10MPa more than.And the heat decomposition temperature of composite sheet improves more than 2 ℃ than pure heat-conductive composite material, wherein PVC/ graphite heat conducting composite sheet heat decomposition temperature is the highest improves 18 ℃, softening point temperature is substantially constant, and this composite sheet still has the resistant to elevated temperatures excellent properties of polymer base-material.
(3) preparation method's process of the present invention does not have Cl
2discharge, produce without industrial waste, and do not need through processing such as phthalates in process, and environmental protection effect is strong, and magnesium oxide MgO used, graphite are all cheap, and the heat-conductive composite material production cost is reduced.
The accompanying drawing explanation
Fig. 1. mechanical activation strengthening of the present invention prepares the method flow diagram of heat-conductive composite material.
Embodiment
Strengthen below in conjunction with embodiment and a kind of mechanical activation of description the present invention the method for preparing heat-conductive composite material, these descriptions are not that content of the present invention is further limited.
Embodiment 1
Each constitutive material polymer base-material of this heat-conductive composite material in the present embodiment: the heat conduction additive: dispersion agent is 74.5%:25%:0.5% according to weight ratio.Wherein the polymer base-material is polyvinylchloride; The heat conduction additive is magnesium oxide; Dispersion agent is silicon-dioxide.
Each constitutive material is mixed and is obtained compound according to above ratio, again compound is put into to high energy ball mill mixing and ball milling 100min, the reaction conditions of mixing and ball milling is 35 ℃ of rotating speed 150rpm, temperature, is furnished with zirconia balls in high energy ball mill, the ratio of zirconia balls heap volume and compound weight is 400ml:80g, and the diameter of zirconia balls is 6mm.Reactant after the taking-up ball milling, be filled in the mould of vulcanizing press, and after high temperature hot pressing, the demoulding obtains heat-conductive composite material, and its condition of high temperature hot pressing is that 5MP is with upward pressure, 160 ℃ of lower hot pressing 15min.
The product employing conductometer that the present embodiment prepares detects its thermal conductivity and reaches 0.7032W/mK, 4 times have been improved with respect to raw material PVC thermal conductivity 0.14-0.16 W/mK, and be 0.2312 W/mK without the PVC/ magnesium oxide composite material thermal conductivity of mechanical activation, after the mechanical activation strengthening, thermal conductivity has improved 2 times of left and right, the product mechanical property is 42Mpa according to GB GB1040-1992 and GB9341-2000 test for tensile strength, flexural strength is 76Mpa, compare CPVC/ABS/graphite composite plate material test tensile strength 30 MPa, more than the requirement that the present embodiment matrix material reaches industrial production to be needed exceeds 12MPa, heat decomposition temperature improves more than 2 ℃ than pure heat-conductive composite material, softening temperature point improves 2 ℃.
Embodiment 2
Each constitutive material polymer base-material of this heat-conductive composite material in the present embodiment: the heat conduction additive: dispersion agent is 69.5%:30%:0.5% according to weight ratio.Wherein the polymer base-material is polyvinylchloride; The heat conduction additive is graphite; Dispersion agent is silicon-dioxide.
Each constitutive material is mixed and is obtained compound according to above ratio, again compound is put into to high energy ball mill mixing and ball milling 80min, the reaction conditions of mixing and ball milling is 35 ℃ of rotating speed 200rpm, temperature, is furnished with zirconia balls in high energy ball mill, the ratio of zirconia balls heap volume and compound weight is 400ml:80g, and the diameter of zirconia balls is 5mm.Reactant after the taking-up ball milling, be filled in the mould of vulcanizing press, and after high temperature hot pressing, the demoulding obtains heat-conductive composite material, and its condition of high temperature hot pressing is that 5MP is with upward pressure, 165 ℃ of lower hot pressing 15min.
The product employing conductometer that the present embodiment prepares detects its thermal conductivity and reaches 1.042W/mK, 7 times of left and right have been improved with respect to raw material PVC thermal conductivity 0.14-0.16 W/mK, and be 0.32549 W/mK without the PVC/ graphite composite plate material thermal conductivity of mechanical activation, bring up to more than 3 times of simple mixing after activation, the present embodiment product mechanical property is tensile strength 40MPa according to GB GB1040-1992 and GB9341-2000 test, flexural strength is 70MPa, still in the service requirements scope.Heat decomposition temperature improves nearly 18 ℃, and softening temperature has kept 80 ℃ of the softening temperatures of former PVC, illustrates that this composite sheet still has the resistant to elevated temperatures excellent properties of PVC.
Embodiment 3
Each constitutive material polymer base-material of this heat-conductive composite material in the present embodiment: the heat conduction additive: dispersion agent is 79.5%:20%:0.5% according to weight ratio.Wherein the polymer base-material is PE; The heat conduction additive is magnesium oxide; Dispersion agent is silicon-dioxide.
Each constitutive material is mixed and is obtained compound according to above ratio, again compound is put into to high energy ball mill mixing and ball milling 40min, the reaction conditions of mixing and ball milling is 40 ℃ of rotating speed 200rpm, temperature, is furnished with zirconia balls in high energy ball mill, the ratio of zirconia balls heap volume and compound weight is 200ml:40g, and the diameter of zirconia balls is 2.0mm.Reactant after the taking-up ball milling, be filled in the mould of vulcanizing press, and after high temperature hot pressing, the demoulding obtains heat-conductive composite material, and its condition of high temperature hot pressing is that 5MP is with upward pressure, 150 ℃ of lower hot pressing 20min.
The product employing conductometer that the present embodiment prepares detects its thermal conductivity and reaches 0.685W/mK, with respect to raw material PE thermal conductivity, 0.33 W/mK has improved 1 times of left and right, and be 0.454 W/mK without the PE/ magnesium oxide composite sheet thermal conductivity of mechanical activation, bring up to 1.5 times of left and right of simple mixing after activation, the product mechanical property is 36Mpa according to GB GB1040-1992 and GB9341-2000 test for tensile strength, flexural strength is 65Mpa, higher than conventional degree of drawing 30Mpa, sinuousness 55Mpa requires standard, heat decomposition temperature improves more than 3 ℃ than pure heat-conductive composite material, softening temperature point is constant.
Embodiment 4
Each constitutive material polymer base-material of this heat-conductive composite material in the present embodiment: the heat conduction additive: dispersion agent is 59.5%:39.5%:1% according to weight ratio.Wherein the polymer base-material is PMMA; The heat conduction additive is graphite and magnesian mixture, and both blending ratios are the 1:1(weight ratio); Dispersion agent is silicon-dioxide.
Each constitutive material is mixed and is obtained compound according to above ratio, again compound is put into to high energy ball mill mixing and ball milling 80min, the reaction conditions of mixing and ball milling is 37 ℃ of rotating speed 500rpm, temperature, is furnished with zirconia balls in high energy ball mill, the ratio of zirconia balls heap volume and compound weight is 300ml:60g, and the diameter of zirconia balls is 4.0mm.Reactant after the taking-up ball milling, be filled in the mould of vulcanizing press, and after high temperature hot pressing, the demoulding obtains heat-conductive composite material, and its condition of high temperature hot pressing is that 5MP is with upward pressure, 180 ℃ of lower hot pressing 5min.
The product employing conductometer that the present embodiment prepares detects its thermal conductivity and reaches 0.7584W/mK, 4 times of left and right have been improved with respect to raw material PMMA thermal conductivity 0.17-0.25 W/mK, and without mechanical activation PMMA/ graphite/magnesium oxide composite sheet thermal conductivity is 0.3854 W/mK, bring up to 2 times of left and right of simple mixing after activation, the product mechanical property is 38Mpa according to GB GB1040-1992 and GB9341-2000 test for tensile strength, flexural strength is 62Mpa, higher than conventional degree of drawing 30Mpa, sinuousness 55Mpa requires standard, heat decomposition temperature improves more than 5 ℃ than pure heat-conductive composite material, softening temperature point improves more than 2 ℃.
Embodiment 5
Each constitutive material polymer base-material of this heat-conductive composite material in the present embodiment: the heat conduction additive: dispersion agent is 75.5%:24%:0.8% according to weight ratio.The mixture that wherein the polymer base-material is PS and Nylon, both blending ratios are 1:1; The heat conduction additive is magnesium oxide; Dispersion agent is silicon-dioxide.
Each constitutive material is mixed and is obtained compound according to above ratio, again compound is put into to high energy ball mill mixing and ball milling 70min, the reaction conditions of mixing and ball milling is 35 ℃ of rotating speed 400rpm, temperature, is furnished with zirconia balls in high energy ball mill, the ratio of zirconia balls heap volume and compound weight is 300ml:50g, and the diameter of zirconia balls is 2 ~ 4mm.Reactant after the taking-up ball milling, be filled in the mould of vulcanizing press, and after high temperature hot pressing, the demoulding obtains heat-conductive composite material, and its condition of high temperature hot pressing is that 5MP is with upward pressure, 180 ℃ of lower hot pressing 10min.
The product employing conductometer that the present embodiment prepares detects its thermal conductivity and reaches 0.852W/mK, and be 0.5854 W/mK without the PS/Nylon/ magnesium oxide composite sheet thermal conductivity of mechanical activation, bring up to 1.5 times of left and right of simple mixing after activation, the product mechanical property is 35Mpa according to GB GB1040-1992 and GB9341-2000 test for tensile strength, flexural strength is 66Mpa, the standard that requires higher than conventional degree of drawing 30Mpa, sinuousness 55Mpa, heat decomposition temperature improves more than 4 ℃ than pure heat-conductive composite material, and softening temperature point is constant.
Embodiment 6
Each constitutive material polymer base-material of this heat-conductive composite material in the present embodiment: the heat conduction additive: dispersion agent is 69%:30%:1% according to weight ratio.Wherein the polymer base-material is Nylon; The heat conduction additive is graphite; Dispersion agent is silicon-dioxide.
Each constitutive material is mixed and is obtained compound according to above ratio, again compound is put into to high energy ball mill mixing and ball milling 100min, the reaction conditions of mixing and ball milling is 40 ℃ of rotating speed 400rpm, temperature, is furnished with zirconia balls in high energy ball mill, the ratio of zirconia balls heap volume and compound weight is 300ml:80g, and the diameter of zirconia balls is 5mm.Reactant after the taking-up ball milling, be filled in the mould of vulcanizing press, and after high temperature hot pressing, the demoulding obtains heat-conductive composite material, and its condition of high temperature hot pressing is that 5MP is with upward pressure, 200 ℃ of lower hot pressing 5min.
The product employing conductometer that the present embodiment prepares detects its thermal conductivity and reaches 1.053W/mK, with respect to raw material Nylon thermal conductivity, 0.25 W/mK has improved 3 times of left and right, and be 0.4854 W/mK without the Nylon/ graphite composite plate material thermal conductivity of mechanical activation, bring up to 2 times of left and right of simple mixing after activation, the product mechanical property is 40Mpa according to GB GB1040-1992 and GB9341-2000 test for tensile strength, flexural strength is 62Mpa, higher than conventional degree of drawing 30Mpa, sinuousness 55Mpa requires standard, heat decomposition temperature improves more than 7 ℃ than pure heat-conductive composite material, softening temperature point improves more than 2 ℃.
The above embodiment of the present invention scheme is only can not limit the present invention to explanation of the present invention, pointed out the scope of product moiety of the present invention, component proportions, preparation method's parameter in claim, and the scope of parameter of the present invention is not pointed out in above-mentioned explanation, therefore, in the implication suitable with claims of the present invention and any change in scope, all be considered to be in the scope that is included in claims.
The present invention is through multidigit heat-conductive composite material processing staff long term operation experience accumulation, and creates by creative work, has outstanding substantive distinguishing features and significant progressive.The method is base-material by polymer composite (as PVC, PE, PP etc.), utilize this emerging interleaving techniques of mechanical activation to carry out solid state reaction, without additive (graphite, magnesium oxide) is carried out to pre-treatment, can make the heat conductivility of product improve a lot, and still can keep outstanding resistance toheat and the excellent mechanical property of polymer composite; Reaction process is without other chemical additives, and retained its high flame retardant, creep-resistant property, acid-alkali-corrosive-resisting performance.Present method adopts pure physically modified technology, and technique is simple, easy to operate, in production and reaction process, does not have Industrial " three Waste " to produce, and having used the graphite of its cheap market price and magnesium oxide is additive, can realize the doulbe-sides' victory of economic benefit and environment protection.
Claims (5)
1. a mechanical activation is strengthened the method for preparing heat-conductive composite material, it is characterized in that, at first the ratio that polymer base-material, heat conduction additive, dispersion agent are 59.5-79.5%:20-40%:0.5-1% according to weight ratio is mixed obtains compound, again compound is put into to high energy ball mill mixing and ball milling 40 ~ 100min, make the strengthening effect of compound generation mechanical activation, reactant after the taking-up ball milling, be filled in the mould of vulcanizing press, and after high temperature hot pressing, the demoulding obtains heat-conductive composite material.
2. mechanical activation strengthening according to claim 1 prepares the method for heat-conductive composite material, it is characterized in that, is furnished with zirconia balls in described high energy ball mill, the heap volume of zirconia balls and compound part by weight are 200 ~ 400ml:40～80g, and the diameter of zirconia balls is 2-8mm.
3. mechanical activation strengthening according to claim 1 and 2 prepares the method for heat-conductive composite material, it is characterized in that, described polymer base-material is any or their mixture in polyvinylchloride, polythene PE, polypropylene PP, polymetylmethacrylate, polystyrene PS, nylon Nylon; Described heat conduction additive is any or their mixture in graphite, magnesium oxide; Described dispersion agent is silicon-dioxide.
4. mechanical activation strengthening according to claim 3 prepares the method for heat-conductive composite material, it is characterized in that, its reaction conditions of described mixing and ball milling is 35 ~ 40 ℃ of rotating speed 100-500rpm, temperature.
5. mechanical activation strengthening according to claim 4 prepares the method for heat-conductive composite material, it is characterized in that, its condition of described high temperature hot pressing is that 5MP is with upward pressure, 150-200 ℃ lower hot pressing 5 ~ 20min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106492940A (en) * | 2016-12-01 | 2017-03-15 | 东北大学 | A kind of mechanical activation improves the technique that boron concentrate soaks boron rate |
| CN111138832A (en) * | 2019-12-16 | 2020-05-12 | 湖南文理学院 | Method for preparing BN thermal interface material |
| CN112980202A (en) * | 2021-02-07 | 2021-06-18 | 中国科学院合肥物质科学研究院 | Biodegradable biomass-based composite heat conduction material and preparation method thereof |
| CN115716948A (en) * | 2022-11-03 | 2023-02-28 | 盐城海之星车轮有限公司 | Preparation method of graphene-doped high-strength nitrile butadiene rubber |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3756979A (en) * | 1970-01-29 | 1973-09-04 | R Ventres | Method of plasticizing vinyl halide polymers |
| CN103146198A (en) * | 2013-03-12 | 2013-06-12 | 深圳市博恩实业有限公司 | Heat conducting composite material and heat conducting composite sheet prepared by applying same |
-
2013
- 2013-09-16 CN CN201310420987.8A patent/CN103467889B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3756979A (en) * | 1970-01-29 | 1973-09-04 | R Ventres | Method of plasticizing vinyl halide polymers |
| CN103146198A (en) * | 2013-03-12 | 2013-06-12 | 深圳市博恩实业有限公司 | Heat conducting composite material and heat conducting composite sheet prepared by applying same |
Non-Patent Citations (3)
| Title |
|---|
| SANG WOO CHOI等: ""Morphology and thermal conductivity of polyacrylate composites containing aluminum/multi-walled carbon nanotubes"", 《COMPOSITES PART A:APPLIED SCIENCE AND MANUFACTURING》 * |
| 王宝云等: ""PVC/PE基木塑复合材料性能研究"", 《塑料工业》 * |
| 计静琦等: ""机械活化制导热PVC板材研究综述"", 《大众科技》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106492940A (en) * | 2016-12-01 | 2017-03-15 | 东北大学 | A kind of mechanical activation improves the technique that boron concentrate soaks boron rate |
| CN106492940B (en) * | 2016-12-01 | 2018-06-26 | 东北大学 | The technique that a kind of mechanical activation improves boron concentrate leaching boron rate |
| CN111138832A (en) * | 2019-12-16 | 2020-05-12 | 湖南文理学院 | Method for preparing BN thermal interface material |
| CN112980202A (en) * | 2021-02-07 | 2021-06-18 | 中国科学院合肥物质科学研究院 | Biodegradable biomass-based composite heat conduction material and preparation method thereof |
| CN115716948A (en) * | 2022-11-03 | 2023-02-28 | 盐城海之星车轮有限公司 | Preparation method of graphene-doped high-strength nitrile butadiene rubber |
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