CN103865234B - The preparation method of micro-, nano inorganic particle/epoxy resin trielement composite material - Google Patents
The preparation method of micro-, nano inorganic particle/epoxy resin trielement composite material Download PDFInfo
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- CN103865234B CN103865234B CN201410138599.5A CN201410138599A CN103865234B CN 103865234 B CN103865234 B CN 103865234B CN 201410138599 A CN201410138599 A CN 201410138599A CN 103865234 B CN103865234 B CN 103865234B
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Abstract
A kind of preparation method of micro-, nano inorganic particle/epoxy resin trielement composite material of technical field of composite materials, process and emulsification through milling after epoxy resin-base material is mixed with nano inorganic particle, then add solidifying agent and micron inorganic particle and stir, obtaining tri compound solution; Through carrying out vacuum defoamation after fixing to tri compound solution; Finally remove surperficial epoxy resin portion both to obtain.The gap place of the present invention in micron or epoxide resin nano adds nanometer again can blind preferably, and the amount of high heat conduction particle is increased, and therefore proposes to prepare trielement composite material.Make inorganic particle sink to the bottom of matrix material by the method for precipitation, make bottom concentration very high, thus realize the preparation of high-content inorganic particle and epoxy resin composite material.
Description
Technical field
What the present invention relates to is a kind of method of technical field of composite materials, specifically a kind of preparation method of micro-, nano inorganic particle/epoxy resin trielement composite material with high thermal conductivity, high-content.
Background technology
Along with the development of power industry, for material low cost, high dielectric property and high heat conductance propose more and more higher requirement.Because alumina ceramic material has high thermal diffusivity, high heat conductance coefficient, the difference of metastable electrical property and thermal diffusivity small between chip and packaged material, device for high-power power electronic selects alumina ceramic material as substrate insulating material.But, alumina ceramic material has embrittlement, the shortcomings such as the complicacy be shaped, and the cost that sintered ceramic material needs cost higher, and epoxy resin is easy to solidifying formation, there is the advantages such as higher metal adhesion and low cost, therefore propose to adopt the epoxy resin composite material of high heat conductance to substitute the substrate insulating material of pottery as power electronic devices.The power electronic devices working hour is longer, and insulated substrate can produce very high temperature.If this heat does not does not scatter and disappear in time, the life-span of device will reduce significantly.Therefore, epoxy resin needs to have high thermal conductance and could replace pottery and insulate as substrate.Because aluminum oxide has high heat conductance, alumina particle be used as improve epoxy resin thermal conductivity mix particle.In order to obtain significantly improving of thermal conductance, theoretical according to bruggman, the particle of high-content must be added into epoxy resin.
But prepare high-content inorganic particle/epoxy resin composite material not a duck soup, when micron particle content reaches 70wt%, matrix material just has higher thermal conductivity.A large amount of interpolation inorganic particles can make itself and epoxy resin be difficult to stir, and is not easy dispersion and curing molding because viscosity is too high.
Through finding the retrieval of prior art, open (bulletin) the day 2011.05.25 of Chinese patent literature CN102076767A, discloses a kind of method be dispersed in by organic nanometer granule in non-aqueous resin medium.The method comprises the following steps: resin dispersion/emulsion a) be prepared in water, and wherein, described resin contains unsaturated functional group in polymer chain; B) by adding monomer and initiator or by adding initiator, making described resin dispersion solidify; C) during the synthesis step of resin medium, add the dispersion/emulsion of described solidification.The amount of the organic nanometer granule in resin medium can be 2 ~ 30 % by weight.But because the compound of nano particle and polymkeric substance needs certain shearing force, do not relate to the improvement of the party's surface technology in this technology, the agglomeration therefore easily producing nano particle is relatively more serious, can make the degradation of matrix material when there being reunion.
Open (bulletin) the day 2013.04.24 of Chinese patent literature CNCN103059699A, discloses a kind of rust-inhibiting paint and preparation method thereof.Conversion and prevention paint of rust of the present invention comprises the component organosilicon crylic acid latex 28 ~ 42 parts of following weight part ratio, Sodium hexametaphosphate 99 0.1 ~ 0.7 part, alcohol ester 12 ~ 2.2 parts, trolamine 0.9 ~ 2.1 part, aluminium triphosphate 2.5 ~ 4 parts, titanium dioxide 5.6 ~ 8.2 parts, barium metaborate 5.6 ~ 8.2 parts, silicon sol 1.8 ~ 4.1 parts, potassium silicate 1.6 ~ 4.3 parts, rust-preventive agent 0.15 ~ 0.35 part of part, vinyl ester resin 20 ~ 30 parts; First its preparation method for prepare vinyl ester resin; Take each component again; Each for other except vinyl ester resin component is placed in stirrer for mixing to stir 15 ~ 40 minutes, obtains mixture I; Mixture I is ground, until the particle diameter fineness of mixture is 20 ~ 40 microns, adds vinyl ester resin, then after stirring 30 ~ 50 minutes, with 300 ~ 350 order filter-cloth filterings.But in vinyl ester resin mixing after particulate matter grinds by this technology, by filter-cloth filtering dregs, operational means is comparatively complicated and be difficult to enhance productivity.
Summary of the invention
The present invention is directed to prior art above shortcomings, a kind of preparation method of micro-, nano inorganic particle/epoxy resin trielement composite material is proposed, gap place in micron or epoxide resin nano adds nanometer again can blind preferably, the amount of high heat conduction particle is increased, therefore proposes to prepare trielement composite material.Make inorganic particle sink to the bottom of matrix material by the method for precipitation, make bottom concentration very high, thus realize the preparation of high-content inorganic particle and epoxy resin composite material.
The present invention is achieved by the following technical solutions, and the present invention, by processing and emulsification through milling after being mixed with nano inorganic particle by epoxy resin-base material, then adding solidifying agent and micron inorganic particle and stirring, obtaining tri compound solution; Through carrying out vacuum defoamation after fixing to tri compound solution; Finally remove surperficial epoxy resin portion both to obtain.
Described micro-, nano inorganic particle adopt but be not limited to following any one: Al
2o
3, BaTiO
3.
Described epoxy resin-base material adopt but be not limited to following any one: 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexyl manthanoate.
Described solidifying agent adopt but be not limited to following any one: methyl hexahydrophthalic anhydride.
Described process of milling refers to: adopt runner milling, and be preferably three roller runner millings and carry out at least twice mill, three roller runner milling roller spacing are set to 100 microns, makes nanoparticle agglomerates obtain extruding dispersion.
Described emulsification refers to: adopt mulser, is preferably the emulsification that Nanomizer carries out at least three times, and each Nanomizer arranges ejection pressure-controlling at more than 100MPa, and ejection aperture is 150 microns.
Described stirring refers to: planetary alr mode, be specially and adopt but be not limited to have the planetary mixing equipment that revolution and autobiography combine, turn 3 minutes with 500 turns/min respectively, 1000 turns/min turns 3 minutes, and the process that 2000 turns/min turns 3 minutes completes mix and blend.Make micron particle in a liquid dispersed, thus obtain the tri compound solution of homodisperse micro-, nano inorganic particle/epoxy resin.
Described vacuum defoamation refers to: adopt the mode vacuumized to carry out deaeration to tri compound solution, outgassing rate is controlled by controlling vacuum tightness in de-aeration, avoid outgassing rate too high and make composite solution occur the boiling of eruption shape, and then producing the phenomenon accelerating solidification.
Described solidification treatment refers to: poured into by tri compound solution in grinding tool and leave standstill 24 hours at normal temperatures, utilize the action of gravity of granule particles to make it precipitate downwards; After precipitation, put into baking oven solidify 48 hours at the temperature of 80 DEG C.
The present invention relates to the trielement composite material that aforesaid method prepares, its component and content are: 5wt% nano aluminium oxide or barium titanate, 80wt% micrometer alumina or barium titanate and 15wt% epoxy resin.
Technique effect
Compared with prior art, the present invention increases the pellet density of epoxy resin composite material by tri compound, and the inorganic particle of high heat conduction is dispersed in the middle of matrix material as much as possible.By controlling to adopt set time gravitational settling method to make inorganic particle sink to reaching high-density, having solved too high amount inorganic particle, to add stickiness in epoxy resin to too high and make to mix and be difficult to the problem of carrying out with dispersion.
Accompanying drawing explanation
Fig. 1 is solid-liquid delamination schematic diagram before the solidification of prepared trielement composite material sample;
In figure: left side is the liquid composite solids precipitation sample drawing (far clapping) before solidification in beaker; Right side for left side be the front liquid composite solids precipitation sample drawing (close-perspective recording) in beaker of solidification.
Fig. 2 is that high thermal conductivity is micro-, nano inorganic particle/epoxy resin trielement composite material preparation flow figure.
Embodiment
Elaborate to embodiments of the invention below, the present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
As shown in Figure 2, the present embodiment comprises the following steps:
1) adopt 150 grams of epoxy resin, mix with nano aluminium oxide 50 grams, hand operated mixing, adopt three roller runner milling roller spacing to be set to 100 microns, mix twice.
2) disperseed by Nanomizer equipment, arrange ejection pressure-controlling at 100MPa/pass, ejection aperture is 150 microns.Mixing number of times is three times.
3) 800 grams of micrometer alumina particles are poured into before in nano particle/epoxy resin composition of mixing, hand operated mixing, makes liquid all be covered by solid.
4) adopt and have revolution and the planetary mixing equipment that combines of autobiography disperses, turn 3 minutes with 500 turns/min respectively, 1000 turns/min turns 3 minutes, and the process that 2000 turns/min turns 3 minutes completes mix and blend.Thus obtain homodisperse micro-, nano inorganic particle/epoxy resin tri compound solution.
4) tri compound solution adopts the mode vacuumized to carry out deaeration, controlling outgassing rate, avoiding outgassing rate too high and making composite solution occur the boiling of eruption shape, and then producing the phenomenon accelerating solidification in de-aeration by controlling vacuum tightness.Tri compound solution after deaeration completes is poured in grinding tool, leaves standstill at normal temperatures, utilizes the action of gravity of granule particles to make it precipitate downwards.And put into baking oven at 24 hours and solidify 48 hours at the temperature of 80 DEG C, to strengthen its solidification effect after precipitation.
5) in the trielement composite material after solidification there is the phenomenon that concentration from top to bottom increases gradually in micro-nano inorganic particle, epoxy resin lower for upper strata concentration is cut away, can obtain micro-, the nano inorganic particle/epoxy resin trielement composite material of high thermal conductivity, proportioning is 80wt% micrometer alumina+5wt% nano aluminium oxide+15wt% epoxy resin.
The component proportion that the present embodiment relates to is as follows:
Claims (3)
1. the preparation method of micro-, nano inorganic particle/epoxy resin trielement composite material, it is characterized in that, the component of this trielement composite material and content are: 5wt% nano aluminium oxide or barium titanate, 80wt% micrometer alumina or barium titanate and 15wt% epoxy resin;
Described preparation method, processes and emulsification through milling after being mixed with nano inorganic particle by epoxy resin-base material, then adds solidifying agent and micron inorganic particle and stirs, obtaining tri compound solution; Through carrying out vacuum defoamation after fixing to tri compound solution; Finally remove surperficial epoxy resin portion both to obtain;
Described micro-, nano inorganic particle adopt Al
2o
3or BaTiO
3;
Described epoxy resin-base material adopts 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexyl manthanoate;
Described solidifying agent adopts methyl hexahydrophthalic anhydride;
Described emulsification refers to: adopt Nanomizer mulser to carry out the emulsification of at least three times, and each Nanomizer arranges ejection pressure-controlling at more than 100MPa, and ejection aperture is 150 microns;
Described vacuum defoamation refers to: adopt the mode vacuumized to carry out deaeration to tri compound solution, outgassing rate is controlled by controlling vacuum tightness in de-aeration, avoid outgassing rate too high and make composite solution occur the boiling of eruption shape, and then producing the phenomenon accelerating solidification;
Described solidification treatment refers to: poured into by tri compound solution in grinding tool and leave standstill 24 hours at normal temperatures, utilize the action of gravity of granule particles to make it precipitate downwards; After precipitation, put into baking oven solidify 48 hours at the temperature of 80 DEG C.
2. method according to claim 1, is characterized in that, described process of milling refers to: adopt three roller runner millings to carry out at least twice mill, three roller runner milling roller spacing are set to 100 microns, makes nanoparticle agglomerates obtain extruding dispersion.
3. method according to claim 1, it is characterized in that, described stirring refers to: planetary alr mode, adopt and there is revolution and the planetary mixing equipment that combines of autobiography, 3 minutes are turned respectively with 500 turns/min, 1000 turns/min turns 3 minutes, and the process that 2000 turns/min turns 3 minutes completes mix and blend.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104893247A (en) * | 2015-05-27 | 2015-09-09 | 合肥卓元科技服务有限公司 | Heat conduction transparent modification process of epoxy resin for LED packaging |
| CN105440584B (en) * | 2015-12-10 | 2017-12-15 | 上海复合材料科技有限公司 | A kind of low shrinkage epoxy resin system and preparation method thereof |
| CN105860437A (en) * | 2016-04-19 | 2016-08-17 | 西安思坦电气技术有限公司 | Micron-nano modified epoxy matrix temperature resisting, heat conducting and insulating composite and preparation method thereof |
| CN109943021A (en) * | 2019-03-25 | 2019-06-28 | 电子科技大学 | A kind of method of nano inorganic filler modified epoxy resin composite |
| CN113336978B (en) * | 2021-05-28 | 2023-07-25 | 西安交通大学 | Preparation method of epoxy micro-nano co-doped composite material |
| TWI786761B (en) * | 2021-08-05 | 2022-12-11 | 臺灣塑膠工業股份有限公司 | Method of manufacturing resin composition |
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| CN101790561A (en) * | 2007-07-18 | 2010-07-28 | 洛德公司 | thermally conductive underfill formulations |
| CN101792573A (en) * | 2010-02-09 | 2010-08-04 | 广东生益科技股份有限公司 | Halogen-free high heat-conducting resin composition and resin coated copper foil |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101790561A (en) * | 2007-07-18 | 2010-07-28 | 洛德公司 | thermally conductive underfill formulations |
| CN101792573A (en) * | 2010-02-09 | 2010-08-04 | 广东生益科技股份有限公司 | Halogen-free high heat-conducting resin composition and resin coated copper foil |
Non-Patent Citations (2)
| Title |
|---|
| The role of nano and micro particles on partial discharge and breakdown strength in epoxy composities;Zhe Li etc;《IEEE Transcctions on dielectrics and Electrical Insulation》;20110630;第18卷(第3期);676页2实验过程和3实验结果 * |
| 微/纳米氧化铝/环氧树脂复合材料热导率和击穿强度的研究;王旗等;《绝缘材料》;20130420;第46卷(第2期);第50页1实验1.1-1.2 * |
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