CN113684006A - Preparation method of solid-liquid two-phase metal-polymer heat-conducting phase-change composite material - Google Patents
Preparation method of solid-liquid two-phase metal-polymer heat-conducting phase-change composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a solid-liquid two-phase metal-high polymer heat-conducting phase-change composite material, belonging to the technical field of high polymer composite materials. The method utilizes a solid-liquid coexisting region of metal in a metal phase diagram to be compounded with a polymer matrix, and utilizes the high thermal conductivity coefficient and the phase change latent heat of the metal, thereby realizing the high thermal conductivity of the composite material; the composite material utilizes binary, ternary and multi-element phase diagrams of metal, and regulates and controls the solid-liquid phase proportion and the phase change latent heat of the metal through the metal composition and the metal phase diagram lever law, so that the heat conductivity coefficient range of the prepared heat-conducting phase change composite material is 0.2W m‑1K‑1To 30.0W m‑1K‑1And the heat dissipation requirements of various electronic devices are met.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a preparation method of a solid-liquid two-phase metal-polymer heat-conducting phase-change composite material.
Background
Heat conducting phase change materials are one of the important thermal interface materials, because they absorb a large amount of latent heat when undergoing phase change, so as to maintain the system temperature within a narrow temperature range, and have been widely used in the field of heat dissipation of electronic components.
Currently, the most widely used are organic phase change materials such as paraffin, polyols, etc., becauseThey have a wide melting range, namely continuous phase transformation behavior occurs in a melting range interval so as to meet heat dissipation requirements at different temperatures. However, a disadvantage of this class of materials is the low thermal conductivity (0.15-0.3W m)-1K-1) And the heat dissipation effect of the system in the application is seriously reduced. The low-melting-point metal and the alloy thereof as the heat-conducting phase-change material have the advantages of high heat conductivity, large phase-change latent heat and the like, but the phase-change temperature of the metal is fixed, so that the application range of the metal in practical application is greatly limited. For example, liquid metal gallium (Ga) is non-toxic, has high thermal conductivity and low melting point (T)mThe phase change material is used as a novel phase change material for interface heat dissipation of electronic equipment due to the characteristics of 29.8 ℃ and the like. However, as the conventional metal has the defect of single melting point, gallium loses the phase change capability after the melting point (29.8 ℃) of the gallium, and cannot meet the heat dissipation requirement (35-100 ℃) of common electronic products.
The heat-conducting polymer composite material generally refers to a polymer as a matrix, and a metal material, a carbon material and a ceramic material as heat-conducting fillers, such as silver powder, copper nanowires and aluminum oxide (Al)2O3) Zinc oxide (ZnO), graphene, diamond, carbon nanotubes, Boron Nitride (BN) and the like, and the high-thermal-conductivity composite material prepared by a blending method (mechanical stirring, ultrasonic dispersion and the like) can be used as thermal-conductivity grease, thermal-conductivity glue, thermal-conductivity gaskets and the like and widely applied to the fields of microelectronic industry, household appliances, aerospace and the like. The metal filler is widely used due to low cost, simple processing technology and good heat conductivity, however, the traditional metal filler (Ag, Cu, Al and the like) is generally pure solid, and has an obvious phase interface after being blended with a macromolecule, which not only influences the heat transfer efficiency, but also deteriorates the mechanical property of the composite material.
Therefore, if the defects of the heat-conducting phase-change material and the heat-conducting polymer composite material can be simultaneously overcome, a metal filler which is wide in melting range and good in compatibility with a polymer is sought, and the metal-polymer heat-conducting phase-change composite material which is high in heat conductivity coefficient and has continuous phase transformation capability can be prepared by combining the advantages of high heat conductivity and high phase-change latent heat of metal, so that the application range of the heat-conducting phase-change composite material is expanded.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a preparation method of a solid-liquid two-phase metal-high molecular heat conduction phase change composite material, which is simple and convenient in process.
The technical scheme is as follows: in order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the solid-liquid two-phase metal-polymer heat conduction phase change composite material comprises the following steps:
(1) the composition comprises the following components in parts by weight: 10-90 parts of metal and 1-90 parts of high polymer material, and mixing to obtain a mixed material;
(2) heating the mixed materials at the temperature of more than 10 ℃ and less than 300 ℃ to physically mix the metal in the solid-liquid coexisting phase and the polymer material in the molten state to prepare the heat-conducting phase-change polymer composite material;
further, in the step (1), 0-50 parts of a functional additive is further included.
Further, in the step (2), the physical mixing method is at least one of grinding dispersion, ultrasonic dispersion and mechanical stirring dispersion.
Further, the metal has a solid-to-liquid mass fraction ratio (solid fraction) of greater than 2% and less than 99% at 30 ℃.
Further, the mass fraction of the metal in the heat-conducting phase-change polymer composite material is more than 10% and less than 99%; when the mass fraction is equal to 80%, the thermal conductivity exceeds 5W m-1K-1(ii) a When the mass fraction is less than or equal to 10 percent, the heat conductivity coefficient is less than 0.5W m-1K-1(ii) a When the solid fraction of the metal is equal to 60%, the thermal conductivity exceeds 5W m-1K-1(ii) a When the solid fraction of the metal is 2% or less, the thermal conductivity is less than 0.5W m-1K-1When the solid fraction of the metal is 99% or more, the thermal conductivity is less than 0.5W m-1K-1。
Further, the metal is an alloy of at least two of lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, aluminum, gallium, indium, thallium, germanium, tin, lead, antimony, bismuth, polonium, lanthanide, actinide, cerium, praseodymium, neodymium, promethium, samarium, europium, nobileum, californium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, thorium, protactinium, ytterbium, lutetium, uranium, neptunium, thulium, curium, plutonium, americium, californium, and.
Further, the metal is binary or more than binary alloy; when the metal is gallium-zinc alloy; the mass fraction of zinc in the gallium-zinc alloy is more than 2% and less than 80%; when the mass fraction of tin is less than or equal to 2 percent, the heat conductivity coefficient is less than 0.5W m-1K-1When the mass fraction of tin is more than or equal to 80 percent, the heat conductivity coefficient is less than 0.5W m-1K-1(ii) a When the metal is aluminum gallium alloy; the mass fraction of aluminum in the aluminum-gallium alloy is more than 10% and less than 95%; when the mass fraction of the aluminum is less than or equal to 10 percent, the heat conductivity coefficient is less than 0.5W m-1K-1When the mass fraction of aluminum is greater than or equal to 95%, the thermal conductivity is less than 0.5W m-1K-1(ii) a When the metal is gallium indium tin alloy; the mass fraction of tin in the gallium indium tin alloy is more than 1 percent and less than 90 percent; when the mass fraction of tin is less than or equal to 1 percent, the heat conductivity coefficient is less than 0.5W m-1K-1When the mass fraction of tin is more than or equal to 90 percent, the heat conductivity coefficient is less than 0.5W m-1K-1。
Further, the polymer material is acrylic resin, paraffin, polydimethylsiloxane, methyl silicone oil, dimethyl silicone oil, methyl phenyl silicone oil, long-chain alkyl silicone oil, fluorocarbon silicone oil, chlorohydrocarbon modified silicone oil, polydimethylsiloxane, epoxy resin, polyethylene, polybutylene, polystyrene, polypropylene, polyvinyl chloride, chlorinated polyethylene, chlorosulfonated polyethylene, polyimide, polymethyl methacrylate, polyether ether ketone, polyformaldehyde, polycarbonate, thermosetting polyurethane, thermoplastic polyurethane, vinyl resin, silicone resin, alkyd resin, phenolic resin, melamine resin, urea resin, unsaturated polyester resin, cellulose resin, aldehyde ketone resin, fluorocarbon resin, chlorinated polypropylene, polyacrylonitrile, polyphenylene ether ketone, polyphenylene sulfide, polyvinylidene chloride, polybutadiene resin, thermosetting polyimide, polyvinyl chloride, and the like, One or more of butadiene rubber, butyl rubber, natural rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, isoprene rubber, ethylene-propylene-diene monomer rubber, nitrile rubber, silicone rubber, fluororubber, urethane rubber, polysulfide rubber, polyacrylate rubber, epichlorohydrin rubber, nylon and polytetrafluoroethylene.
Further, the metal in the solid-liquid coexisting phase is modified with one or more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent and a bimetallic coupling agent, specifically: mixing a coupling agent, alcohol and water, hydrolyzing to obtain a hydrolysate, and then placing the metal in the hydrolysate, stirring, washing and drying to obtain modified metal; the alcohol comprises one of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol and tert-butanol; the coupling agent is: alcohol: the volume ratio of water is 1-10: 3-50: 10-100; the hydrolysis time is 1-48 h; the drying time is 0.1-4 h.
Further, the functional additive comprises at least one of an anti-settling agent, an antioxidant, a heat stabilizer, a plasticizer, a lubricant, a colorant, a flame retardant, an antistatic agent or a thickener; the anti-settling agent is one or more of organic bentonite, fumed silica, castor oil derivatives, modified hydrogenated castor oil, N-methyl pyrrolidone solution (BYK-410) of modified polyurea, polyolefin wax, titanate coupling agent and polyamide wax; wherein the castor oil derivative comprises at least one of dehydrated castor oil, hydrogenated castor oil, dehydrated castor oil fatty acid, and advanced maleic oil; the polyamide wax series comprises at least one of Heimax P200X, Disparlon 6900-20X, MT6900-20X, ZH 6900-20X, and MT PLUS; the antioxidant is at least one of alkyl monophenol, thiobisphenol, alkyl polyphenol, semi-solid phenol derivatives, aminophenol derivatives, ketoamine, p-phenylenediamine, diaromatic secondary amine, thioester or phosphite ester; wherein the alkyl monophenols comprise antioxidant 264 and/or anti-aging agent SP; the thiobisphenols comprise an anti-aging agent 2246-S and/or an antioxidant 300; the alkyl polyphenols comprise antioxidant 1010 and/or antioxidant 2246; semi-solid phenol derivatives include anti-aging agent DBH; aminophenol derivatives include the antioxidant CMA and/or the antioxidant CEA; the ketoamine comprises at least one of antioxidant RD, antioxidant AW or antioxidant BLE; the p-phenylenediamine comprises at least one of an antioxidant 288, an antioxidant DNP, an antioxidant 4030, an antioxidant 4010NA, an antioxidant 4010 or an antioxidant H; the secondary diarylamine comprises at least one of an antioxidant A, an antioxidant OD or an antioxidant D; the thioester and phosphite ester comprise at least one of antioxidant DLTP, antioxidant DSTP, antioxidant TNP or antioxidant ODP; the heat stabilizer is one or more of stearic acid, oleic acid, lauric acid, thiolate, metal salt, maleate, palmitic acid, fatty acid salt, antimony mercaptide, epoxide, phosphite ester, semisolid alcohol, beta-diketone, dibasic lead stearate, tribasic lead sulfate, solid Ga/Zn composite stabilizer, dibasic lead phthalate, tribasic lead maleate, dibasic lead phosphite and lanthanide rare earth metal elements; the plasticizer is at least one of paraffin, silicone oil, process oil, vaseline, heavy oil, rosin, pine tar, coal tar, asphalt, factice, petroleum resin, coal pitch, terpene resin, nitrile rubber, coumarone resin, aliphatic dibasic acid ester, phenyl alkylsulfonate, tricresyl phosphate, phthalate ester, phosphate ester, chlorinated paraffin, epoxidized soybean oil, dioctyl phthalate, propylene glycol sebacate polyester, dioctyl sebacate, dioctyl adipate, dibutyl phthalate, propylene glycol adipate polyester, diethylene glycol dibenzoate, liquid polybutadiene or liquid polyisobutylene; the lubricant is one or more of paraffin, stearic acid soap, polyethylene glycol, polypropylene glycol, semi-solid alcohol, higher fatty alcohol, oleamide, stearic acid amide, n-butyl stearate, ethylene bis-oleamide, glyceryl tristearate, glyceryl monostearate and ethylene bis-stearamide; the flame retardant is at least one of chlorinated paraffin, chlorinated polyethylene, phosphate ester, phosphite ester, organic salts, oxidized phosphorus, phosphorus-containing polyol and phosphorus-nitrogen compound, antimony trioxide, magnesium hydroxide, aluminum hydroxide, tetrabromobisphenol A, decabromodiphenyl ether, hexabromocyclododecane, octabromodiphenyl ether, bis (tribromophenoxy) ethane, hexabromobenzene and brominated polystyrene; the colorant is at least one of cadmium red, chrome yellow, carbon black, titanium dioxide, gold powder, silver powder, phthalocyanines, azos or fluorescent compounds; the antistatic agent is at least one of trialkyl ammonium salt, tetraalkyl ammonium salt, alkyl sulfonate, alkyl benzene sulfonate, alkyl sulfate, polyacrylate, stearyl trimethyl quaternary ammonium hydrochloride, stearamidopropyl hydroxyethyl quaternary ammonium nitrate, alkyl bis (alpha-hydroxyethyl amine phosphate), sodium p-nonylphenoxy propyl sulfonate, salts of maleic anhydride and other unsaturated monomer copolymers, tetrabromobisphenol A, polystyrene benzene sulfonic acid, alkyl dicarboxymethyl ammonium ethylene lactone, stearic acid monoglyceride and dodecyl dimethyl quaternary ethylene inner salt; the thickener is at least one of starch, gelatin, diatomite, white carbon black, carbon nano tube, organic bentonite, polyisobutylene, ethyl cellulose, carboxyethyl cellulose, nitrocellulose, sodium carboxymethylcellulose, hydroxypropyl methyl cellulose or sodium bentonite silica gel.
The invention principle is as follows: the invention utilizes the metal in the solid-liquid two-phase coexistence area in the metal phase diagram to compound the metal and the polymer matrix above the liquidus temperature of the metal, and the composite material obtained under the condition has high thermal conductivity which is more than the composition of pure solid or pure liquid metal and the polymer material. In the metal-polymer heat-conducting composite material, the traditional metal filler is generally pure solid, and after being blended with polymer, a remarkable phase interface exists, so that the heat conductivity of the composite material is small (<1.5Wm-1K-1). If low-melting-point metal is mixed with high-molecular material, such as pure gallium, the metal in the composite material is liquid at a lower temperature (such as 30 ℃), so that the phenomenon of metal leakage is easy to occur, and the composite material with high metal content cannot be obtained. In the invention, binary, ternary and multi-element phase diagrams of metal are utilized, the solid phase ratio of the metal is regulated and controlled through the metal composition and the metal phase diagram lever law, the solid phase ratio regulates the fluidity and the phase change latent heat of the metal material within a certain temperature range (such as 10-100 ℃), so that the metal can be filled in the high polymer material in a large proportion,and the latent heat of phase change is exerted to the maximum extent, so that high thermal conductivity of the material is realized.
The metal phase diagram lever law means that in a metal phase diagram, a unique phase equilibrium point can be determined through metal composition and temperature, when the phase equilibrium point falls in a solid-liquid two-phase region, a horizontal line passing through the phase equilibrium point is made, and then the solid-liquid phase ratio of the phase equilibrium point is equal to the ratio of the distance from the point to a liquid phase region to the distance from the point to a solid phase region. As shown in fig. 1, the metal phase diagram of the tin-bismuth alloy is taken as an example to explain:
when the metal composition is x and the temperature is T, the phase equilibrium point a (x, T) can be determined and falls in a solid-liquid two-phase region, namely an S + L region, a horizontal straight line is made when the point a passes through and is crossed with the solid-phase region in the x region1The cross-liquid phase region is in x2When the metal is in phase equilibrium a, the solid-liquid phase ratio meets the lever law:
further, from the solid-liquid phase ratio, the solid phase ratio can be calculated:
the solid fraction is a dimensionless number.
Has the advantages that: compared with the prior art, the invention has the following remarkable effects: (1) the metal is compounded with the polymer matrix above the liquidus temperature of the metal by utilizing the solid-liquid two-phase coexistence region of the metal in a metal phase diagram, and the high thermal conductivity and the phase change latent heat of the metal are utilized, so that the high thermal conductivity of the composite material is realized, and the application range of the composite material is expanded; (2) the composite material has high phase change latent heat at the working temperature (30 ℃) of common electronic equipment, and is beneficial to maintaining the working temperature of a system within a normal working range in the using process; (3) the solid phase ratio of metal is regulated and controlled by utilizing a metal phase diagram and the metal composition and the metal phase diagram lever law, so that the thermal conductivity of the composite material is easy to regulate and control, and the metal phase diagram is realized from 0.2W m-1K-1To 30.0W m-1K-1A change in (c); (4) the phase change temperature range of metal is regulated and controlled by utilizing a metal phase diagram and the composition of the metal, so that the phase change melting range of the composite material is more in line with the heat dissipation requirement (35-100 ℃) of most electronic equipment; (5) the thermal conductivity of the material can reach 30.0W m- 1K-1。
Drawings
FIG. 1 is a diagram of a prepared heat-conducting silicone grease;
FIG. 2 is a metal phase diagram of a gallium-zinc alloy;
FIG. 3 is a metallic phase diagram of an aluminum gallium alloy;
FIG. 4 is a metal phase diagram of a gallium indium tin alloy.
Detailed Description
The present invention is described in further detail below.
The preparation method of the solid-liquid two-phase metal-polymer heat conduction phase change composite material comprises the following steps:
(1) the composition comprises the following components in parts by weight: 10-90 parts of metal, 1-90 parts of high polymer material and 0-50 parts of functional additive; respectively weighing metal, high polymer material and functional additive according to the proportion, and mixing to obtain a mixed material;
(2) and heating the mixed materials within the range of more than 10 ℃ and less than 300 ℃ to physically mix the metal in the solid-liquid coexisting phase and the molten polymer material to prepare the heat-conducting phase-change polymer composite material.
The physical mixing method is at least one of grinding dispersion, ultrasonic dispersion and mechanical stirring dispersion.
The ratio of the mass fraction of the solid phase to the liquid phase of the metal at 30 ℃ (solid fraction) is greater than 2% and less than 99%.
The mass fraction of the metal in the heat-conducting phase-change polymer composite material is more than 10% and less than 99%. When the mass fraction is equal to 80%, the thermal conductivity exceeds 5W m-1K-1(ii) a When the mass fraction is less than or equal to 10 percent, the heat conductivity coefficient is less than 0.5W m-1K-1。
When the solid fraction of the metal is 60%, the thermal conductivity exceeds 5Wm-1K-1(ii) a When the solid fraction of the metal is 2% or less, the thermal conductivity is less than 0.5W m-1K-1When the solid fraction of the metal is 99% or more, the thermal conductivity is less than 0.5W m- 1K-1。
The metal is an alloy of at least two of lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, aluminum, gallium, indium, thallium, germanium, tin, lead, antimony, bismuth, polonium, lanthanide, actinide, cerium, praseodymium, neodymium, promethium, samarium, europium, californium, lawrencium, gadolinium, terbium, dysprosium, erbium, thulium, neptunium, protactinium, ytterbium, lutetium, uranium, neptunium, fermium, plutonium, curium, thorium, californium, and stringnium.
The metal is binary or more than binary alloy.
When the metal is gallium-zinc alloy; the mass fraction of zinc in the gallium-zinc alloy is more than 2% and less than 80%. When the mass fraction of tin is less than or equal to 2 percent, the heat conductivity coefficient is less than 0.5W m-1K-1When the mass fraction of tin is more than or equal to 80 percent, the heat conductivity coefficient is less than 0.5W m-1K-1。
When the metal is aluminum gallium alloy; the mass fraction of aluminum in the aluminum-gallium alloy is more than 10% and less than 95%. When the mass fraction of the aluminum is less than or equal to 10 percent, the heat conductivity coefficient is less than 0.5W m-1K-1When the mass fraction of aluminum is greater than or equal to 95%, the thermal conductivity is less than 0.5W m-1K-1。
When the metal is gallium indium tin alloy; the mass fraction of tin in the gallium indium tin alloy is more than 1 percent and less than 90 percent. When the mass fraction of tin is less than or equal to 1 percent, the heat conductivity coefficient is less than 0.5W m-1K-1When the mass fraction of tin is more than or equal to 90 percent, the heat conductivity coefficient is less than 0.5W m-1K-1。
The high polymer material is acrylic resin, paraffin, polydimethylsiloxane, methyl silicone oil, dimethyl silicone oil, methyl phenyl silicone oil, long-chain alkyl silicone oil, fluorocarbon silicone oil, chlorohydrocarbon modified silicone oil, polydimethylsiloxane, epoxy resin, polyethylene, polybutylene, polystyrene, polypropylene, polyvinyl chloride, chlorinated polyethylene, chlorosulfonated polyethylene, polyimide, polymethyl methacrylate, polyether ether ketone, polyformaldehyde, polycarbonate, thermosetting polyurethane, thermoplastic polyurethane, vinyl resin, silicone resin, alkyd resin, phenolic resin, melamine resin, urea resin, unsaturated polyester resin, cellulose resin, aldehyde ketone resin, fluorocarbon resin, chlorinated polypropylene, polyacrylonitrile, polyphenylene ether ketone, polyphenylene sulfide, polyvinylidene chloride, polybutadiene resin, thermosetting polyimide, butadiene rubber, polybutadiene rubber, epoxy resin, epoxy, One or more of butyl rubber, natural rubber, styrene-butadiene rubber, chloroprene rubber, ethylene propylene rubber, isoprene rubber, ethylene propylene diene monomer rubber, nitrile rubber, silicone rubber, fluororubber, urethane rubber, polysulfide rubber, polyacrylate rubber, epichlorohydrin rubber, nylon and polytetrafluoroethylene.
The method is characterized in that metal in a solid-liquid coexisting phase is modified by one or more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent and a bimetallic coupling agent, and the modification method comprises the following steps:
the coupling agent, alcohol and water are mixed according to a certain proportion, hydrolyzed for a plurality of times to obtain hydrolysate, and then the metal is placed in the hydrolysate to be stirred, washed and dried to obtain the modified metal. The alcohol comprises one of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol and tert-butanol; the coupling agent is: alcohol: the volume ratio of water is 1-10: 3-50: 10-100; the hydrolysis time is 1-48 h; the drying time is 0.1-4 h.
The functional additive comprises at least one of an anti-settling agent, an antioxidant, a heat stabilizer, a plasticizer, a lubricant, a colorant, a flame retardant, an antistatic agent or a thickener.
The anti-settling agent is one or more of organic bentonite, fumed silica, castor oil derivatives, modified hydrogenated castor oil, N-methyl pyrrolidone solution (BYK-410) of modified polyurea, polyolefin wax, titanate coupling agent and polyamide wax; wherein the castor oil derivative comprises at least one of dehydrated castor oil, hydrogenated castor oil, dehydrated castor oil fatty acid, and advanced maleic oil; the polyamide wax series comprises at least one of Hessimus P200X, Disparlon 6900-20X, MT6900-20X, ZH 6900-20X, and MT PLUS.
The antioxidant is at least one of alkyl monophenol, thiobisphenol, alkyl polyphenol, semi-solid phenol derivatives, aminophenol derivatives, ketoamine, p-phenylenediamine, diaromatic secondary amine, thioester or phosphite ester; wherein the alkyl monophenols comprise antioxidant 264 and/or anti-aging agent SP; the thiobisphenols comprise an anti-aging agent 2246-S and/or an antioxidant 300; the alkyl polyphenols comprise antioxidant 1010 and/or antioxidant 2246; semi-solid phenol derivatives include anti-aging agent DBH; aminophenol derivatives include the antioxidant CMA and/or the antioxidant CEA; the ketoamine comprises at least one of antioxidant RD, antioxidant AW or antioxidant BLE; the p-phenylenediamine comprises at least one of an antioxidant 288, an antioxidant DNP, an antioxidant 4030, an antioxidant 4010NA, an antioxidant 4010 or an antioxidant H; the secondary diarylamine comprises at least one of an antioxidant A, an antioxidant OD or an antioxidant D; the thioester and phosphite esters include at least one of antioxidant DLTP, antioxidant DSTP, antioxidant TNP or antioxidant ODP.
The heat stabilizer is one or more of stearic acid, oleic acid, lauric acid, thiolate, metal salt, maleate, palmitic acid, fatty acid salt, antimony mercaptide, epoxide, phosphite ester, semisolid alcohol, beta-diketone, dibasic lead stearate, tribasic lead sulfate, solid Ga/Zn composite stabilizer, dibasic lead phthalate, tribasic lead maleate, dibasic lead phosphite and lanthanide rare earth metal elements;
the plasticizer is at least one of paraffin, silicone oil, process oil, vaseline, heavy oil, rosin, pine tar, coal tar, asphalt, factice, petroleum resin, coal pitch, terpene resin, nitrile rubber, coumarone resin, aliphatic dibasic acid ester, phenyl alkylsulfonate, tricresyl phosphate, phthalate ester, phosphate ester, chlorinated paraffin, epoxidized soybean oil, dioctyl phthalate, propylene glycol sebacate polyester, dioctyl sebacate, dioctyl adipate, dibutyl phthalate, propylene glycol adipate polyester, diethylene glycol dibenzoate, liquid polybutadiene, or liquid polyisobutylene.
The lubricant is one or more of paraffin, stearic acid soap, polyethylene glycol, polypropylene glycol, semi-solid alcohol, higher fatty alcohol, oleamide, stearic acid amide, n-butyl stearate, ethylene bis-oleamide, glyceryl tristearate, glyceryl monostearate, and ethylene bis-stearamide.
The fire retardant is at least one of chlorinated paraffin, chlorinated polyethylene, phosphate ester, phosphite ester, organic salt, oxidized phosphorus, phosphorus-containing polyol and phosphorus-nitrogen compound, antimony trioxide, magnesium hydroxide, aluminum hydroxide, tetrabromobisphenol A, decabromodiphenyl ether, hexabromocyclododecane, octabromodiphenyl ether, bis (tribromophenoxy) ethane, hexabromobenzene and brominated polystyrene.
The colorant is at least one of cadmium red, chrome yellow, carbon black, titanium dioxide, gold powder, silver powder, phthalocyanines, azos or fluorescent compounds.
The antistatic agent is at least one of trialkyl ammonium salt, tetraalkyl ammonium salt, alkyl sulfonate, alkyl benzene sulfonate, alkyl sulfate, polyacrylate, stearyl trimethyl quaternary ammonium hydrochloride, stearamidopropyl hydroxyethyl quaternary ammonium nitrate, alkyl bis (alpha-hydroxyethyl amine phosphate), sodium p-nonylphenoxy propyl sulfonate, salts of maleic anhydride and other unsaturated monomer copolymers, tetrabromobisphenol A, polystyrene benzene sulfonic acid, alkyl dicarboxymethyl ammonium ethylene lactone, stearic acid monoglyceride, dodecyl dimethyl quaternary ethylene inner salt.
The thickener is at least one of starch, gelatin, diatomite, white carbon black, carbon nano tube, organic bentonite, polyisobutylene, ethyl cellulose, carboxyethyl cellulose, nitrocellulose, sodium carboxymethylcellulose, hydroxypropyl methyl cellulose or sodium bentonite silica gel.
The obtained composite material is used in various heat dissipation occasions in the forms of heat-conducting silicone grease, heat-conducting glue or heat-conducting gaskets and the like. The photo of the prepared heat-conducting silicone grease object shown in FIG. 1 is gray at room temperature and has certain fluidity.
The solid-liquid ratio of the metal in the composite material can be adjusted according to the phase diagram, so that the thermal conductivity coefficient of the composite material is 0.2W m-1K-1To 30.0W m-1K-1Can be adjusted.
The metal in the composite material has solid-liquid phase conversion capability, so that the composite material absorbs heat due to phase change in heat dissipation application, thereby realizing high-efficiency heat energy management and heat dissipation and being used in a wide temperature range.
Example 1
The invention discloses a preparation method of a metal-polymer heat conduction phase change composite material, which comprises the following steps:
(1) weighing a gallium simple substance, a zinc simple substance, methyl silicone oil, an anti-settling agent BYK-410 and lauric acid according to the mixture ratio in the table 1;
(2) mixing a gallium simple substance and a zinc simple substance with methyl silicone oil, an anti-settling agent BYK-410 and lauric acid;
(3) the mixture is stirred at 150 ℃ for 15min at the rotating speed of 1500r/min by a mechanical stirring method and is uniformly mixed.
Example 2
The basic procedure was the same as in example 1, and the specific parameters are shown in Table 1.
Example 3
The basic procedure was the same as in example 1, and the specific parameters are shown in Table 1.
Example 4
The basic procedure was the same as in example 1, and the specific parameters are shown in Table 1.
TABLE 1
For examples 1 to 4, the zinc content in the gallium-zinc alloy was 11%, 14%, 16%, 20%, and the metal content in the heat-conducting phase-change composite material was 90%, 80%, 50%, 20%, respectively, as calculated from the Ga-Zn binary phase diagram shown in fig. 2: the solid contents of the metals at 30 ℃ were 7%, 10%, 13%, 17%,pure liquid at the processing temperature, corresponding to a thermal conductivity of 7.1W m-1K-1、6.8W m-1K-1、4.9W m-1K-1、3.3W m-1K-1。
Example 5
(1) Weighing the simple substance of aluminum, the simple substance of gallium, epoxy resin, the anti-settling agent BYK-410 and lauric acid according to the mixture ratio in the table 2;
(2) mixing the simple substance of aluminum and gallium with epoxy resin, anti-settling agent BYK-410 and lauric acid;
(3) the mixture is stirred at the rotating speed of 3000r/min for 10min at 180 ℃ by a mechanical stirring method and is uniformly mixed.
Example 6
The basic procedure was the same as in example 5, and is specifically shown in Table 2.
Example 7
The basic procedure was the same as in example 5, and is specifically shown in Table 2.
Example 8
The basic procedure was the same as in example 5, and is specifically shown in Table 2.
TABLE 2
For examples 5 to 8, the aluminum content in the aluminum-gallium alloy was 16%, 12%, 8%, 5%, and the metal content in the heat-conducting phase-change composite material was 90%, 70%, 50%, 20%, respectively, as calculated from the Al-Ga binary phase diagram shown in fig. 3: the solid fraction of the metal at 30 ℃ was 13%, 9%, 5%, 2%, respectively, and the metal was pure liquid at the processing temperature, corresponding to a thermal conductivity of 8.9W m, respectively-1K-1、6.6W m-1K-1、4.2W m-1K-1、2.1W m-1K-1。
Example 9
(1) Weighing a gallium simple substance, an indium simple substance, a tin simple substance, polydimethylsiloxane, an anti-settling agent BYK-410 and lauric acid according to the mixture ratio in the table 3;
(2) mixing a gallium simple substance, an indium simple substance and a tin simple substance with polydimethylsiloxane, an anti-settling agent BYK-410 and lauric acid;
(3) the mixture is stirred at 150 ℃ for 10min at 2000r/min by a mechanical stirring method and is uniformly mixed.
Example 10
The basic procedure was the same as in example 9, and the specific parameters are shown in Table 3.
TABLE 3
For examples 9 to 10, the percentages of tin In the gallium indium tin alloy are 15% and 50%, respectively, and the percentages of metal In the heat-conducting phase-change composite material are 66% and 80%, respectively, which can be calculated according to the Ga-In-Sn ternary phase diagram shown In fig. 4: the solid fraction of the metal at 30 ℃ was 73% and 22%, respectively, and the metal was pure liquid at the processing temperature, corresponding to a thermal conductivity of 7.4W m, respectively-1K-1、8.6W m-1K-1。
Comparative example 1
The basic procedure was the same as in example 1, and is specifically shown in Table 4.
TABLE 4
For comparative example 1, the zinc content of the gallium-zinc alloy was 2%, the metal content of the thermally conductive phase change composite material was 50% by mass, and the composite material was pure liquid at 30 ℃, i.e., solid fraction was 0, pure liquid at the processing temperature, and the corresponding thermal conductivity was 0.4W m-1K-1。
Comparative example 2
The basic procedure was the same as in example 1, and is specifically shown in Table 5.
TABLE 5
For comparative example 2, the percentage of zinc in the gallium-zinc alloy was 34%, the mass fraction of metal in the thermally conductive phase change composite material was 50%, the solid fraction at 30 ℃ was 30%, and the corresponding thermal conductivity was 0.2W m for the non-pure liquid under processing conditions-1K-1。
Comparative example 3
The basic procedure was the same as in example 1, and is specifically shown in Table 6.
TABLE 6
For comparative example 3, the metal was elemental zinc, the metal accounted for 50% by mass of the thermally conductive phase change composite material, the solid fraction was 100% at 30 ℃, the non-pure liquid was not processed under the conditions of processing, the corresponding thermal conductivity was 0.2W m-1K-1。
Comparative example 4
The basic procedure was the same as in example 1, and is specifically shown in Table 7.
TABLE 7
For comparative example 4, the metal was gallium-zinc alloy, the zinc content in the gallium-zinc alloy was 20%, the mass fraction of the metal in the thermally conductive phase change composite was 5%, the solid fraction at 30 ℃ was 17%, the composite was pure liquid under processing conditions, and the corresponding thermal conductivity was 0.4W m-1K-1。
Comparative example 5
The basic procedure was the same as in example 1, and is specifically shown in Table 8.
TABLE 8
For comparative example 5, the metal was gallium-zinc alloy with 84% zinc, 25% metal by mass of the thermally conductive phase change composite, 84% solid fraction at 30 ℃, and non-pure liquid at processing conditions, corresponding to a thermal conductivity of 0.2W m-1K-1。
Comparative example 6
The basic procedure was the same as in example 1, and is specifically shown in Table 9.
TABLE 9
For comparative example 6, the aluminum content in the aluminum-gallium alloy was 4%, the metal content in the thermally conductive phase change composite material was 50% by mass, the solid fraction at 30 ℃ was 1%, the material was pure liquid under processing conditions, and the corresponding thermal conductivity was 0.2W m-1K-1。
Comparative example 7
The basic procedure was the same as in example 1, and is specifically shown in Table 10.
For comparative example 7, the aluminum content in the aluminum-gallium alloy was 30%, the metal content in the thermally conductive phase change composite material was 10% by mass, the solid fraction at 30 ℃ was 28%, and the corresponding thermal conductivity was 0.2W m for the non-pure liquid under the processing conditions-1K-1。
Comparative example 8
The basic procedure was the same as in example 1, and is specifically shown in Table 11.
TABLE 11
For comparative example 8, the aluminum content in the aluminum-gallium alloy was 50%, the metal content was 40% by mass of the thermally conductive phase change composite, the solid fraction was 48% at 30 ℃, and the corresponding thermal conductivity was 0.2W m for a non-pure liquid under processing conditions-1K-1。
Comparative example 9
The basic procedure was the same as in example 1, and is specifically shown in Table 12.
TABLE 12
For comparative example 9, the gallium indium tin alloy had a tin content of 44%, the metal content of 9% by mass of the thermally conductive phase change composite material, a solid fraction of 55% at 30 ℃, and a corresponding thermal conductivity of 0.4W m for a non-pure liquid at processing conditions-1K-1。
The epoxy resin and the functional additive can increase and decrease the mass ratio according to different thermal conductivities, and can realize the thermal conductivity from 0.2W m by controlling the content of the added metal-1K-1To 30.0W m-1K-1A variation within the range; the processing temperature of the metal-macromolecule heat conduction phase change composite material is 10-300 ℃, and the heat conductivity is as high as 30.0W m-1K-1。
Claims (9)
1. The preparation method of the solid-liquid two-phase metal-polymer heat conduction phase change composite material is characterized by comprising the following steps of:
(1) the composition comprises the following components in parts by weight: 10-90 parts of metal and 1-90 parts of high polymer material, and mixing to obtain a mixed material;
(2) and heating the mixed materials within the range of more than 10 ℃ and less than 300 ℃ to physically mix the metal in the solid-liquid coexisting phase and the molten polymer material to prepare the heat-conducting phase-change polymer composite material.
2. The preparation method of the solid-liquid two-phase metal-polymer heat-conducting phase-change composite material according to claim 1, wherein the step (1) further comprises 0-50 parts of a functional additive.
3. The method for preparing the solid-liquid two-phase metal-polymer heat-conducting phase-change composite material according to claim 1, wherein in the step (2), the physical mixing method is at least one of grinding dispersion, ultrasonic dispersion and mechanical stirring dispersion.
4. The method for preparing the solid-liquid two-phase metal-polymer heat-conducting phase-change composite material according to claim 1, wherein the metal can be adjusted to have a solid-liquid mass fraction ratio of more than 2% and less than 99% at 30 ℃ by a phase diagram.
5. The method for preparing the solid-liquid two-phase metal-polymer heat-conducting phase-change composite material according to claim 1, wherein the metal accounts for more than 10% and less than 99% of the heat-conducting phase-change polymer composite material by mass; when the mass fraction is equal to 80%, the thermal conductivity exceeds 5W m-1K-1(ii) a When the mass fraction is less than or equal to 10 percent, the heat conductivity coefficient is less than 0.5W m- 1K-1(ii) a When the solid fraction of the metal is equal to 60%, the thermal conductivity exceeds 5W m-1K-1(ii) a When the solid fraction of the metal is 2% or less, the thermal conductivity is less than 0.5W m-1K-1When the solid fraction of the metal is 99% or more, the thermal conductivity is less than 0.5W m-1K-1。
6. The method according to claim 1, wherein the metal is an alloy of at least two metals selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, aluminum, gallium, indium, thallium, germanium, tin, lead, antimony, bismuth, polonium, lanthanides, actinides, cerium, praseodymium, neodymium, promethium, samarium, europium, neptunium, gadolinium, terbium, dysprosium, erbium, thulium, thorium, protactinium, ytterbium, lutetium, uranium, holmium, plutonium, curium, californium, americium, californium, and trivia.
7. The method for preparing the solid-liquid two-phase metal-polymer heat-conducting phase-change composite material according to claim 1, wherein the polymer material is acrylic resin, paraffin, polydimethylsiloxane, methyl silicone oil, dimethyl silicone oil, methylphenyl silicone oil, long-chain alkyl silicone oil, fluorocarbon-based modified silicone oil, polydimethylsiloxane, epoxy resin, polyethylene, polybutylene, polystyrene, polypropylene, polyvinyl chloride, chlorinated polyethylene, chlorosulfonated polyethylene, polyimide, polymethyl methacrylate, polyether ether ketone, polyformaldehyde, polycarbonate, thermosetting polyurethane, thermoplastic polyurethane, vinyl resin, silicone resin, alkyd resin, phenolic resin, melamine resin, urea resin, unsaturated polyester resin, cellulose resin, aldehyde ketone resin, fluorocarbon resin, epoxy resin, polyvinyl chloride, polyimide, polymethyl methacrylate, polyether ether ketone, polyformaldehyde, polycarbonate, thermosetting polyurethane, thermoplastic polyurethane, vinyl resin, silicone resin, alkyd resin, phenolic resin, melamine resin, urea resin, unsaturated polyester resin, cellulose resin, aldehyde ketone resin, fluorocarbon resin, epoxy resin, or the like, epoxy resin, or the like, epoxy resin, or the like, Chlorinated polypropylene, polyacrylonitrile, polyphenylene ether ketone, polyphenylene sulfide, polyvinylidene chloride, polybutadiene resin, thermosetting polyimide, butadiene rubber, butyl rubber, natural rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, isoprene rubber, ethylene-propylene-diene rubber, nitrile rubber, silicone rubber, fluororubber, urethane rubber, polysulfide rubber, polyacrylate rubber, epichlorohydrin rubber, nylon, polytetrafluoroethylene.
8. The method for preparing the solid-liquid two-phase metal-polymer heat-conducting phase-change composite material according to claim 1, wherein the metal in the solid-liquid coexisting phase is modified with one or more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a bimetallic coupling agent.
9. The method for preparing the solid-liquid two-phase metal-high molecular heat-conducting phase-change composite material according to claim 2, wherein the functional additive comprises at least one of an anti-settling agent, an antioxidant, a heat stabilizer, a plasticizer, a lubricant, a colorant, a flame retardant, an antistatic agent or a thickener; the anti-settling agent is one or more of organic bentonite, fumed silica, castor oil derivatives, modified hydrogenated castor oil, N-methyl pyrrolidone solution (BYK-410) of modified polyurea, polyolefin wax, titanate coupling agent and polyamide wax; wherein the castor oil derivative comprises at least one of dehydrated castor oil, hydrogenated castor oil, dehydrated castor oil fatty acid, and advanced maleic oil; the polyamide wax series comprises at least one of Heimax P200X, Disparlon 6900-20X, MT6900-20X, ZH 6900-20X, and MT PLUS; the antioxidant is at least one of alkyl monophenol, thiobisphenol, alkyl polyphenol, semi-solid phenol derivatives, aminophenol derivatives, ketoamine, p-phenylenediamine, diaromatic secondary amine, thioester or phosphite ester; wherein the alkyl monophenols comprise antioxidant 264 and/or anti-aging agent SP; the thiobisphenols comprise an anti-aging agent 2246-S and/or an antioxidant 300; the alkyl polyphenols comprise antioxidant 1010 and/or antioxidant 2246; semi-solid phenol derivatives include anti-aging agent DBH; aminophenol derivatives include the antioxidant CMA and/or the antioxidant CEA; the ketoamine comprises at least one of antioxidant RD, antioxidant AW or antioxidant BLE; the p-phenylenediamine comprises at least one of an antioxidant 288, an antioxidant DNP, an antioxidant 4030, an antioxidant 4010NA, an antioxidant 4010 or an antioxidant H; the secondary diarylamine comprises at least one of an antioxidant A, an antioxidant OD or an antioxidant D; the thioester and phosphite ester comprise at least one of antioxidant DLTP, antioxidant DSTP, antioxidant TNP or antioxidant ODP; the heat stabilizer is one or more of stearic acid, oleic acid, lauric acid, thiolate, metal salt, maleate, palmitic acid, fatty acid salt, antimony mercaptide, epoxide, phosphite ester, semisolid alcohol, beta-diketone, dibasic lead stearate, tribasic lead sulfate, solid Ga/Zn composite stabilizer, dibasic lead phthalate, tribasic lead maleate, dibasic lead phosphite and lanthanide rare earth metal elements; the plasticizer is at least one of paraffin, silicone oil, process oil, vaseline, heavy oil, rosin, pine tar, coal tar, asphalt, factice, petroleum resin, coal pitch, terpene resin, nitrile rubber, coumarone resin, aliphatic dibasic acid ester, phenyl alkylsulfonate, tricresyl phosphate, phthalate ester, phosphate ester, chlorinated paraffin, epoxidized soybean oil, dioctyl phthalate, propylene glycol sebacate polyester, dioctyl sebacate, dioctyl adipate, dibutyl phthalate, propylene glycol adipate polyester, diethylene glycol dibenzoate, liquid polybutadiene or liquid polyisobutylene; the lubricant is one or more of paraffin, stearic acid soap, polyethylene glycol, polypropylene glycol, semi-solid alcohol, higher fatty alcohol, oleamide, stearic acid amide, n-butyl stearate, ethylene bis-oleamide, glyceryl tristearate, glyceryl monostearate and ethylene bis-stearamide; the flame retardant is at least one of chlorinated paraffin, chlorinated polyethylene, phosphate ester, phosphite ester, organic salts, oxidized phosphorus, phosphorus-containing polyol and phosphorus-nitrogen compound, antimony trioxide, magnesium hydroxide, aluminum hydroxide, tetrabromobisphenol A, decabromodiphenyl ether, hexabromocyclododecane, octabromodiphenyl ether, bis (tribromophenoxy) ethane, hexabromobenzene and brominated polystyrene; the colorant is at least one of cadmium red, chrome yellow, carbon black, titanium dioxide, gold powder, silver powder, phthalocyanines, azos or fluorescent compounds; the antistatic agent is at least one of trialkyl ammonium salt, tetraalkyl ammonium salt, alkyl sulfonate, alkyl benzene sulfonate, alkyl sulfate, polyacrylate, stearyl trimethyl quaternary ammonium hydrochloride, stearamidopropyl hydroxyethyl quaternary ammonium nitrate, alkyl bis (alpha-hydroxyethyl amine phosphate), sodium p-nonylphenoxy propyl sulfonate, salts of maleic anhydride and other unsaturated monomer copolymers, tetrabromobisphenol A, polystyrene benzene sulfonic acid, alkyl dicarboxymethyl ammonium ethylene lactone, stearic acid monoglyceride and dodecyl dimethyl quaternary ethylene inner salt; the thickener is at least one of starch, gelatin, diatomite, white carbon black, carbon nano tube, organic bentonite, polyisobutylene, ethyl cellulose, carboxyethyl cellulose, nitrocellulose, sodium carboxymethylcellulose, hydroxypropyl methyl cellulose or sodium bentonite silica gel.
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