CN105086784A - Graphene modified thermal conductive coating - Google Patents
Graphene modified thermal conductive coating Download PDFInfo
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Abstract
The present invention discloses a graphene modified thermal conductive coating. The high thermal conductivity coating is supplemented with graphene, an auxiliary agent and polydimethylsiloxane. The components in the coating are as below by weight: 27.5-36.5% of base resin, 20-30% of a filler, 20-35% of graphene, 3-5% of an additive, 5-15% of a solvent and 0.5-2.5% of polydimethylsiloxane. The graphene added to the coating makes the coating contact closer to the substrate; the graphene with good lubricating effect can improved friction resistance; graphene with thermal conductivity ten times of copper can improve the thermal conductivity of the coating; the added modified silicone improves the coating leveling and makes the coating smooth and flat; modified silicone reduces air bubbles in the dispersion process, improves the adhesion and corrosion resistance of the coating to the substrate; and the modified polyurethane realizes good acid resistance, high chemical stability and good dispersion of the coating.
Description
Technical field
The invention belongs to chemical technology field, relate to a kind of heat-conductive coating, particularly relate to a kind of thermal conductivity improving coating, the heat-conductive coating of the sticking power of coating and ground, the Graphene modification of self rub resistance.
Background technology
Coating refers to that coating body surface can form film under certain conditions and play protection, the class I liquid I of decoration or other specific functions (insulation, antirust, mildew-resistant, heat-resisting etc.) or solid material.
In recent years, the industrial circle that the develop rapidly of modern industry makes some special such as aerospace, the field such as electric propose higher performance requriements to coating, be mainly manifested in higher heat conductivility, more outstanding toughness etc., but because the thermal conductivity of traditional coating is poor, toughness is not good, poor to the sticking power of ground, rub resistance is poor, limits the application of coating in these fields.
Geim and Novoselov of Man Chesidun university of Britain in 2004 obtains self-existent two-dimensional graphene (Gra-phene by tape stripping high starch breeding, GN), since crystal, Graphene has become one of extremely concerned study hotspot of material science.In fact Graphene is exactly the graphite of monoatomic layer, and it has unique two-dirnentional structure and excellent mechanics, thermodynamics, optics and electric property.
Graphene is at present the thinnest is in the world the hardest nano material also, and it is almost completely transparent, to the light absorbing 2.3%, thermal conductivity up to 5300W/mk, higher than carbon nanotube and diamond.Graphene is a kind of novel material of the individual layer sheet structure be made up of carbon atom, has intensity high, and specific surface area is large, high chemical reactivity, the feature of high fillibility.
Chinese patent publication No. CN102816525A, date of publication on December 12nd, 2012, name is called heat-conductive coating, this application case discloses a kind of heat-conductive coating, mainly be made up of conduction powder and synthetic resins, wherein, the weight percent of conduction powder is about the 4-25% of heat-conductive coating, its inside comprises silicon-dioxide, titanium dioxide, zirconium silicate, boron nitride, separately can add the auxiliary material such as aluminium sesquioxide and silicon carbide, and the weight percent of synthetic resins coordinates the weight percent of conduction powder to form 100%, it is fully mixed by a resin and at least one solvent and formed, this resin is selected from epoxy resin according to demand, polyester, the wherein one of acrylic resin and silicone resin.Its weak point is, although this formula heat-conductive coating solution part of the obtaining defect of traditional coating poor thermal conductivity, its toughness is not good, and poor to the sticking power of ground, rub resistance is poor.
Summary of the invention
The thermal conductivity that the object of the invention is to solve existing coating is poor, toughness is not good, poor to the sticking power of ground, the defect that rub resistance is poor and provide a kind of thermal conductivity improving coating, the heat-conductive coating of the sticking power of coating and ground, the Graphene modification of self rub resistance.
To achieve these goals, the present invention is by the following technical solutions:
A kind of heat-conductive coating of Graphene modification, comprise base resin and filler, add Graphene, auxiliary agent and polydimethylsiloxane in heat-conductive coating, the weight percent of each component shared by coating is respectively: base resin 27.5-36.5%, filler 20-30%, Graphene 20-35%, auxiliary agent 3-5%, solvent 5-15% and polydimethylsiloxane 0.5-2.5%.In the technical program, Graphene is a kind of novel material of the individual layer sheet structure be made up of carbon atom, has intensity high, and specific surface area is large, high chemical reactivity, the feature of high fillibility; In coating, add Graphene makes coating more tight to ground contact, and Graphene high lubricating effect, therefore can improve the rub resistance of coating; Graphene has the thermal conductivity of copper ten times, can improve the thermal conductivity of coating.
As preferably, base resin is the one in Synolac, acrylic resin, aminoresin, epoxy resin, urethane, filler is one or more in aluminum oxide, magnesium oxide, zinc oxide, aluminium nitride, boron nitride, silicon nitride, silicon carbide, titanium oxide, clay, polynite, halloysite or mica powder, and solvent is butyrolactone or epoxy chloropropane.In the technical program, butyrolactone and epoxy chloropropane are conducive to the dispersion of Graphene in system and homogeneity.
As preferably, described auxiliary agent is modified organic silicon, modification silicone and modified polyurethane.In the technical program, modified organic silicon add the levelling property improving coating, make smooth coating smooth; The minimizing of modification silicone produces bubble in dispersion process, improves coating to the sticking power of ground and solidity to corrosion; Adding of modified polyurethane makes coating acid resistance good, and chemical stability is high, good dispersity.
As preferably, the mass ratio of modified organic silicon, modification silicone and modified polyurethane is 1:0.5-0.8:2-5.
As preferably, described Graphene is individual layer sheet structure, or described Graphene be the number of plies at 2-50 layer, be carbon atom sp in layer
2hybridized orbital composition hexagonal honeycomb shape lattice, interlayer are that carbon atom closes with π bond.
As preferably, described Graphene adds with the form of powder or slurry.
As preferably, in described Graphene, carbon and non-carbon mass ratio are greater than 4:1, and non-carbon is selected from one or more in fluorine, nitrogen, oxygen, sulphur, hydrogen, chlorine, bromine, iodine.
As preferably, described Graphene also includes the modified graphene of various functional group, as one or more in hydroxyl, carboxyl, carbonyl, nitrogen base, amino.
As preferably, Graphene before addition, at magneticstrength 5000-5250GS, ultrasonic disperse 30-45min under Ultrasonic Conditions simultaneously.
The invention has the beneficial effects as follows, in coating, add Graphene make coating more tight to ground contact, Graphene high lubricating effect, therefore can improve the rub resistance of coating; Graphene has the thermal conductivity of copper ten times, can improve the thermal conductivity of coating; Modified organic silicon add the levelling property improving coating, make smooth coating smooth; The minimizing of modification silicone produces bubble in dispersion process, improves coating to the sticking power of ground and solidity to corrosion; Adding of modified polyurethane makes coating acid resistance good, and chemical stability is high, good dispersity.
Embodiment
Below in conjunction with specific embodiment, the present invention is further explained:
In the present invention, if not refer in particular to, the raw material adopted all can be buied from market or this area is conventional, and the method in following embodiment, if no special instructions, is the ordinary method of this area.
Raw material needed for the heat-conductive coating related in the present invention is commercially available.
Mica powder believes mineral products processing factory purchased from Lingshou County three, and size is 400 orders; Polydimethylsiloxane is purchased from Guangzhou Fu Yuangui Science and Technology Ltd., and modified polyurethane is purchased from Qi Yixin plastic cement company limited of Shenzhen.
Graphene raw material, Graphene powder, Graphene slurry are commercially available, purchased from Ningbo Mo Xi Science and Technology Ltd..
Graphene is individual layer sheet structure, or described Graphene be the number of plies at 2-50 layer, be carbon atom sp in layer
2hybridized orbital composition hexagonal honeycomb shape lattice, interlayer are that carbon atom closes with π bond; Carbon and non-carbon mass ratio are greater than 4:1, and non-carbon is selected from one or more in fluorine, nitrogen, oxygen, sulphur, hydrogen, chlorine, bromine, iodine.
Graphene also can include the modified graphene of various functional group, as one or more in hydroxyl, carboxyl, carbonyl, nitrogen base, amino.
Embodiment 1
Graphene is at magneticstrength 5000GS, and ultrasonic disperse 30min under Ultrasonic Conditions simultaneously, slowly joins 800-1000 rev/min of stirring 30min in acetone, form Graphene slurry by Graphene powder; Then by Synolac, aluminum oxide, magnesium oxide, zinc oxide, auxiliary agent, polydimethylsiloxane and butyrolactone blending dispersion evenly after, add Graphene slurry agitation 1 hour, obtain the heat-conductive coating of Graphene modification; Wherein, the content of each component is respectively: the mass ratio of Synolac 27.5%, filler 30%, Graphene 20%, auxiliary agent 5%, butyrolactone 15%, polydimethylsiloxane 2.5%, aluminum oxide, magnesium oxide, zinc oxide is 1:1:1, auxiliary agent is modified organic silicon, modification silicone and modified polyurethane, and the mass ratio of modified organic silicon, modification silicone and modified polyurethane is 1:0.5:3.
Embodiment 2
Graphene is at magneticstrength 5100GS, and ultrasonic disperse 35min under Ultrasonic Conditions simultaneously, slowly joins 800-1000 rev/min of stirring 30min in alcohol, form Graphene slurry by Graphene powder; Then by acrylic resin, clay, graphene powder, auxiliary agent, polydimethylsiloxane and epoxy chloropropane blending dispersion evenly after, add Graphene slurry agitation 1 hour, after cooling, obtain the heat-conductive coating of Graphene modification.Wherein, the content of each component is respectively: acrylic resin 30%, filler 25%, Graphene 30%, auxiliary agent 4%, epoxy chloropropane 10%, polydimethylsiloxane 1%, auxiliary agent is modified organic silicon, modification silicone and modified polyurethane, and the mass ratio of modified organic silicon, modification silicone and modified polyurethane is 1:0.6:4.
Embodiment 3
Graphene is at magneticstrength 5250GS, and ultrasonic disperse 45min under Ultrasonic Conditions simultaneously, slowly joins 800-1000 rev/min of stirring 30min in alcohol, form Graphene slurry by Graphene powder; Then by urethane, aluminum oxide, polynite, halloysite, auxiliary agent, polydimethylsiloxane and butyrolactone blending dispersion evenly after, join in Graphene slurry and stir 1.5 hours, obtain the heat-conductive coating of Graphene modification.Wherein, the content of each component is respectively: urethane 36.5%, filler 20%, Graphene 35%, auxiliary agent 3%, butyrolactone 5%, polydimethylsiloxane 0.5%, the mass ratio of aluminum oxide, polynite, halloysite is 1:0.5:2, and auxiliary agent is modified organic silicon, modification silicone and modified polyurethane, and the mass ratio of modified organic silicon, modification silicone and modified polyurethane is 1:0.8:3.
Comparative example 1, purchased from the BN-E10 type anti-oxidation protection heat-conductive coating of Liaoning Peng Da Science and Technology Ltd..
Comparative example 2, formula used is identical with embodiment 1 with method for making, and unique difference does not wherein add Graphene.
The heat-conductive coating of Graphene modification obtained by embodiment 1-3 and the heat-conductive coating of comparative example 1-2 are coated in the metal material surface after existing artistic face process, and carry out contrast test, result is as follows:
Table 1, test result
| Sticking power/MPa | Thermal conductivity/(W/mk) | |
| Embodiment 1 | 2 | 120 |
| Embodiment 2 | 2.3 | 134 |
| Embodiment 3 | 3.1 | 141 |
| Comparative example 1 | 1.5 | 70 |
| Comparative example 2 | 1.8 | 82 |
From table 1, the heat-conductive coating that the present invention obtains Graphene modification is obviously better than the heat-conductive coating of comparative example 1-2 to the sticking power of ground and thermal conductivity, in coating, add Graphene makes coating more tight to ground contact, and Graphene high lubricating effect, therefore can improve the rub resistance of coating; Graphene has the thermal conductivity of copper ten times, can improve the thermal conductivity of coating.
The heat-conductive coating of embodiment 1-3 and comparative example 1-2 is carried out salt spray resistance test, corrosion-resistant test and heat-conducting effect to test, test result is in table 2.
Salt spray resistance is tested: (concentration is 5 % by weight sample to be put into salt fog machine salt solution, pH value is 6.5-7.2) spray 2 hours at 35 DEG C, make sample keep 168 hours in 40 DEG C of environment with relative humidity 93% again, then use the surface energy of Dataphysics company OCA collection of contact angle measuring instrument working sample.
Corrosion-resistant test: the heat-conductive coating of embodiment 1-3 and comparative example 1-2 is coated in carbon steel test piece, then wherein embodiment 2-3 is incited somebody to action, the salpeter solution of 60% is immersed in the test piece of comparative example 1, embodiment 3 in addition, the caustic soda soln of 60% is immersed in the test piece of comparative example 2,2 as a child took out immersed 2 hours again after seasoning after, observe strip.
Heat-conducting effect testing method is as follows:
By 200mL, the pure water of 25 DEG C, be placed in apply embodiment 1-3 and comparative example 1-2 vessel in, be then placed on electrical heater that power is 1KW, start heating and timing, to water temperature 90 DEG C, stop heating and record heating duration, judging heat-conducting effect by heating duration.
Table 2, test result
| Sample name | Surface energy (mN/m) | 60% nitric acid | 60% caustic soda | Heating duration/s |
| Embodiment 1 | 19.8 | Unchanged | Unchanged | 150 |
| Embodiment 2 | 19.6 | Unchanged | Unchanged | 135 |
| Embodiment 3 | 19.5 | Unchanged | Unchanged | 120 |
| Comparative example 1 | 35.7 | Micro-Huang | Micro-Huang | 240 |
| Comparative example 2 | 28.1 | Micro-Huang | Micro-Huang | 220 |
From table 2, the salt spray resistance of the heat-conductive coating that the present invention obtains, corrosion resistance nature are obviously better than existing traditional heat-conductive coating, heat-conducting effect is slightly different due to the add-on difference of Graphene, but compared with common heat-conductive coating, heat-conducting effect of the present invention significantly improves.
Above-described embodiment is a kind of preferred version of the present invention, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.
Claims (9)
1. the heat-conductive coating of a Graphene modification, comprise base resin and filler, it is characterized in that, add Graphene, auxiliary agent and polydimethylsiloxane in heat-conductive coating, the weight percent of each component shared by coating is respectively: base resin 27.5-36.5%, filler 20-30%, Graphene 20-35%, auxiliary agent 3-5%, solvent 5-15% and polydimethylsiloxane 0.5-2.5%.
2. the heat-conductive coating of a kind of Graphene modification according to claim 1, it is characterized in that, base resin is the one in Synolac, acrylic resin, aminoresin, epoxy resin, urethane, filler is one or more in aluminum oxide, magnesium oxide, zinc oxide, aluminium nitride, boron nitride, silicon nitride, silicon carbide, titanium oxide, clay, polynite, halloysite or mica powder, and solvent is butyrolactone or epoxy chloropropane.
3. the heat-conductive coating of a kind of Graphene modification according to claim 1 and 2, is characterized in that, described auxiliary agent is modified organic silicon, modification silicone and modified polyurethane.
4. the heat-conductive coating of a kind of Graphene modification according to claim 3, is characterized in that, the mass ratio of modified organic silicon, modification silicone and modified polyurethane is 1:0.5-0.8:2-5.
5. the heat-conductive coating of a kind of Graphene modification according to claim 1, is characterized in that, described Graphene is individual layer sheet structure, or described Graphene be the number of plies at 2-50 layer, be carbon atom sp in layer
2hybridized orbital composition hexagonal honeycomb shape lattice, interlayer are that carbon atom closes with π bond.
6. the heat-conductive coating of a kind of Graphene modification according to claim 1 or 5, is characterized in that, described Graphene adds with the form of powder or slurry.
7. the heat-conductive coating of a kind of Graphene modification according to claim 1 or 5, is characterized in that, in described Graphene, carbon and non-carbon mass ratio are greater than 4:1, and non-carbon is selected from one or more in fluorine, nitrogen, oxygen, sulphur, hydrogen, chlorine, bromine, iodine.
8. the heat-conductive coating of a kind of Graphene modification according to claim 1 or 5, is characterized in that, described Graphene also includes the modified graphene of various functional group, as one or more in hydroxyl, carboxyl, carbonyl, nitrogen base, amino.
9. the heat-conductive coating of a kind of Graphene modification according to claim 1 or 5, is characterized in that, Graphene before addition, at magneticstrength 5000-5250GS, simultaneously ultrasonic disperse 30-45min under Ultrasonic Conditions.
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