CN111534236A - Graphite-doped high-temperature-resistant heat-conducting phosphate adhesive and preparation method thereof - Google Patents
Graphite-doped high-temperature-resistant heat-conducting phosphate adhesive and preparation method thereof Download PDFInfo
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- CN111534236A CN111534236A CN202010439308.1A CN202010439308A CN111534236A CN 111534236 A CN111534236 A CN 111534236A CN 202010439308 A CN202010439308 A CN 202010439308A CN 111534236 A CN111534236 A CN 111534236A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J1/00—Adhesives based on inorganic constituents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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Abstract
The invention relates to the technical field of adhesives, and discloses a graphite-doped high-temperature-resistant heat-conducting phosphate adhesive and a preparation method thereof. The phosphate adhesive comprises the following components in parts by weight: 70-80 parts of phosphate resin, 5-10 parts of modified graphite, 3-6 parts of alumina, 1-3 parts of zirconia and 1-3 parts of zinc oxide. The preparation method of the phosphate adhesive comprises the following steps: firstly, uniformly mixing alumina, zirconia and zinc oxide to obtain a curing agent, adding the curing agent into phosphate resin, uniformly mixing, then adding modified graphite into the mixture, and uniformly mixing to obtain the modified graphite. The phosphate adhesive has excellent high temperature resistance, heat conductivity and mechanical property.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a high-temperature-resistant heat-conducting phosphate adhesive doped with graphite and a preparation method thereof.
Background
The adhesive is widely applied to various fields of aerospace, automotive electronics, civil use, packaging industry and the like, and can be divided into organic adhesives and inorganic adhesives, wherein the inorganic adhesives have better heat resistance compared with the organic adhesives, and the inorganic adhesives are mainly divided into silicate adhesives and phosphate adhesives. The phosphate adhesive can be cured at room temperature or at elevated temperature, is heat-resistant up to over 1700 ℃, has the characteristics of high bonding strength, good water resistance, low curing shrinkage and the like, is widely applied to the fields of bonding of aerospace heat-resistant materials, encapsulation of heat-resistant sensors and the like, and along with the rapid development of the national defense technology, the used high-temperature-resistant adhesive is required to have the basic properties and also have the functional requirements of good heat conduction and the like. The graphite has good thermal conductivity, and can greatly improve the thermal conductivity of the adhesive when being added into the adhesive. However, under the condition of high temperature and in the presence of oxygen, graphite is oxidized to generate CO and CO2Gas causes the heat-conducting property of the graphite to be reduced, and in addition, the graphite structure becomes loose, thereby influencing the mechanical strength of the adhesive.
The influence of graphite on the performance of phosphate adhesives was published by Cao pioneer, Jia Xinliang et al, who in the publication, the thermal conductivity of the adhesives was improved by doping graphite in the phosphate adhesives, but studies have found that when the processing temperature of the adhesives is higher than 300 ℃, the graphite is oxidized in a large area, and in an environment with oxygen at high temperature, the graphite is easily oxidized to form CO and CO2The gas, as the oxidation proceeds, has a gradually increasing number of pores, causing the graphite and adhesive structure to gradually become loose, thereby reducing the strength of the adhesive material.
Chinese patent publication No. CN108264851A discloses a graphene type high-temperature-resistant phosphate adhesive and a preparation method thereof, the graphene type high-temperature-resistant phosphate adhesive is prepared from modified aluminum dihydrogen phosphate and a curing agent, and comprises the following components: the adhesive is characterized by comprising a phosphoric acid solution, aluminum hydroxide, sodium tungstate, zirconium oxide, a graphene oxide solution and a curing agent, wherein the shear strength of the adhesive does not change at the high temperature of 1300 ℃ after the adhesive is cured, due to the addition of the graphene oxide, the graphene oxide can be reduced into graphene under the anaerobic condition after the temperature of the adhesive exceeds 400 ℃ after the adhesive is cured, the graphene can improve the shear strength of the adhesive under the high-temperature condition, and the curing time can be shortened. However, the adhesive disclosed in this patent document is used in a severe environment, and can be used only in an oxygen-free environment, and graphite is oxidized to CO and CO in an environment where oxygen exists at a high temperature2The graphite and the adhesive structure gradually become loose due to the gas, and the graphite cannot reinforce the adhesive and can reduce the strength of the adhesive.
Disclosure of Invention
The invention aims to overcome the technical problems in the prior art and provides a high-temperature-resistant heat-conducting phosphate adhesive doped with graphite, which has excellent high-temperature resistance, heat-conducting property and mechanical property.
The invention also provides a preparation method of the graphite-doped high-temperature-resistant heat-conducting phosphate adhesive.
In order to achieve the purpose, the invention adopts the following technical scheme:
the high-temperature-resistant heat-conducting phosphate adhesive doped with graphite comprises the following components in parts by weight:
preferably, the preparation method of the phosphate resin comprises the following steps: adding aluminum hydroxide into the phosphoric acid solution, heating to 90-95 ℃ in water bath, and stirring for reaction for 1-5h to obtain the phosphate resin.
Preferably, the preparation method of the modified graphite comprises the following steps: adding titanyl sulfate and urea into deionized water, wherein the mass ratio of titanyl sulfate to urea to deionized water is 1:1-3:20-30, stirring and dissolving to obtain a mixed solution, adjusting the pH value of the mixed solution to 2-3, adding crystalline flake graphite and nano aluminum nitride, performing ultrasonic oscillation and uniform dispersion to obtain a dispersion solution, transferring the dispersion solution into a closed reaction kettle, reacting for 10-15h at the temperature of 170-180 ℃, separating, washing, drying, placing a product obtained by drying in a muffle furnace for calcining, and cooling to obtain modified graphite.
Preferably, the mass ratio of the crystalline flake graphite to the titanyl sulfate is 1: 3-5.
Preferably, the mass ratio of the crystalline flake graphite to the nano aluminum nitride is 1: 0.05-0.1.
Preferably, the scale graphite is pretreated, and the method comprises the following steps:
placing the flake graphite in a microwave oven for microwave treatment to obtain expanded graphite for later use; uniformly mixing methyl pyrrolidone and deionized water to obtain a dispersion solution, adding expanded graphite into the dispersion solution to perform ultrasonic oscillation stripping treatment to obtain a graphene suspension, adding polyethyleneimine into the graphene suspension, uniformly stirring and dispersing, standing for 2-5h, filtering, adding filtered graphene into a trimesoyl chloride solution, heating in a water bath to 40-45 ℃, performing heat preservation reaction for 10-20min, and sequentially filtering, washing and drying to obtain the graphene nano-particles.
Preferably, the ultrasonic oscillation stripping power of the expanded graphite in the dispersion solution is 800-900W.
Preferably, the mass ratio of the expanded graphite to the polyethyleneimine is 1: 0.5-1.
Preferably, the mass concentration of the trimesoyl chloride solution is 0.5-5%.
The preparation method of the high-temperature-resistant heat-conducting graphite-doped phosphate adhesive comprises the following steps: firstly, uniformly mixing alumina, zirconia and zinc oxide to obtain a curing agent, adding the curing agent into phosphate resin, uniformly mixing, then adding modified graphite into the mixture, and uniformly mixing to obtain the modified graphite.
The invention takes phosphate resin as the bonding component of the binder, and the aluminum oxide, the zirconium oxide and the zinc oxide are compounded to be used as the curing agent of the phosphate binder, the phosphate adhesive can be cured at room temperature or under the condition of temperature rise, can resist heat of more than 1700 ℃, has the characteristics of high bonding strength, good water resistance, low curing shrinkage rate and the like, is widely applied to the fields of bonding of aerospace heat-resistant materials, encapsulation of heat-resistant sensors and the like, but the heat conductivity of the phosphate adhesive is poor, and limits the applicable range of the phosphate adhesive, therefore, the invention adds the modified graphite as the heat-conducting agent of the adhesive, the graphite is crystalline carbon and a hexagonal system, has excellent heat-conducting effect, the heat-conducting coefficient can reach 129W/(m.k), and the heat-conducting property of the adhesive is improved by adding the graphite in the phosphate adhesive, thereby providing the phosphate adhesive with good high temperature resistance, however, in the actual high-temperature application process of the adhesive, when the external temperature is higher than 300 ℃, the graphite is oxidized in a large area, and the graphite is easily oxidized to generate CO and CO in the high-temperature oxygen environment2The gas causes the heat conductivity of the graphite to be reduced, and the number of pores is gradually increased along with the oxidation, so that the graphite and the adhesive structure are gradually loosened, and the strength of the adhesive material is reduced. Therefore, the flaky graphite is modified by the method, titanyl sulfate is hydrolyzed to generate nano titanium dioxide, and the nano titanium dioxide is deposited and combined on the surface of the flaky graphite, so that a titanium dioxide protective layer is coated on the surface of the flaky graphite and plays a role in the flaky graphiteThe function of heat insulation and oxygen isolation, thereby avoiding the scale graphite from being oxidized into CO and CO under the high temperature condition2And the gas maintains the heat conduction and the mechanical strength of the phosphate adhesive under the high-temperature condition. In addition, because the surface of the flake graphite is coated with the titanium dioxide protective layer, and the nano titanium dioxide protective layer has the functions of heat insulation and oxygen isolation, but can affect the heat conduction performance of the flake graphite, the nano aluminum nitride is added into the titanyl sulfate solution, and the nano aluminum nitride is partially deposited on the surface of the flake graphite along with the nano titanium dioxide generated by hydrolysis of the titanyl sulfate, so that nano aluminum nitride nano particles are embedded in the titanium dioxide layer coated on the surface of the flake graphite, and the aluminum nitride has excellent heat conduction coefficient, thereby improving the heat conduction performance of the titanium dioxide protective layer, reducing the adverse effect of the titanium dioxide protective layer on the heat conduction performance of the flake graphite and improving the heat conduction performance of the adhesive.
In order to further improve the mechanical property and the heat-conducting property of the phosphate adhesive, the flake graphite is pretreated, the flake graphite is subjected to microwave treatment firstly, so that the flake graphite is expanded, then ultrasonic oscillation stripping treatment is carried out, the flake graphite which is laminated and superposed is stripped and dispersed into flake graphene, and the flake graphene has smaller volume compared with the flake graphite and can be more uniformly dispersed in the phosphate adhesive, so that the mechanical strength and the heat-conducting property of the phosphate adhesive are improved. In order to prevent the re-combination of the stripped and dispersed flake graphene from agglomerating, the polymerization reaction of polyethyleneimine and trimesoyl chloride on the surface of the flake graphene is utilized to organize the surface of the graphene, so that the agglomeration of the flake graphene is avoided; on the other hand, polyethyleneimine and trimesoyl chloride take place polymerization on the surface of flake graphite alkene, thereby make graphite alkene surface load a large amount of amino, in the hydrolysis of titanyl sulfate generates nanometer titanium dioxide in-process, the amino on graphite alkene surface forms the hydrogen bond effort with the hydroxyl on nanometer titanium dioxide surface, thereby make more and quick deposit of nanometer titanium dioxide on graphite alkene surface, form more compact titanium dioxide protective layer, thereby make the titanium dioxide protective layer play better thermal-insulated and oxygen-insulated effect to graphite alkene, avoid graphite alkene to take place the oxidation under the high temperature condition and cause the heat conduction and the mechanical properties decline of adhesive.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. In the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
Flake graphite used in the specific examples: the specification is 45-50 μm, the carbon content is 85-99.9%, and Qingdaosheng Tianshengda graphite company Limited; nano aluminum nitride: model XHMT011, average grain size 40nm, purity 99.9%, specific surface area 70m2G, density 3.5g/m3Shanghai Xiao Huan nanometer science and technology, Inc.; polyethyleneimine: 8300-8900mpa.s viscosity (25 ℃), amine value 19mg eq/g.solid, specific gravity (25 ℃)1.03, pH (5% aq)10-12, Chengdu Jiaye Biotechnology Ltd.
Example 1
The high-temperature-resistant heat-conducting phosphate adhesive doped with graphite comprises the following components in parts by weight:
the preparation method of the phosphate resin comprises the following steps: adding aluminum hydroxide into a phosphoric acid solution with the mass concentration of 80%, wherein the mass ratio of the phosphoric acid solution to the aluminum hydroxide is 1:0.5, heating in a water bath to 95 ℃, and stirring for reacting for 1h to obtain the phosphate resin.
Pretreatment of flake graphite:
placing the crystalline flake graphite into a crucible, placing the crucible into a microwave oven, and performing microwave treatment for 30s under the power of 700W to obtain expanded graphite for later use; uniformly mixing methyl pyrrolidone and deionized water according to the volume ratio of 1:1 to obtain a dispersion solution, adding expanded graphite into the dispersion solution according to the mass volume ratio of 1g/60mL, then carrying out ultrasonic oscillation stripping treatment for 30min under 850W power to obtain a graphene suspension, adding polyethyleneimine into the graphene suspension, wherein the mass ratio of the expanded graphite to the polyethyleneimine is 1:0.8, uniformly stirring and dispersing, standing for 5h, filtering, adding the filtered graphene into a n-hexane solution of trimesoyl chloride with the mass concentration of 3%, heating in a water bath to 40 ℃, carrying out heat preservation reaction for 20min, and sequentially filtering, washing and drying to obtain pretreated crystalline flake graphite.
The preparation method of the modified graphite comprises the following steps:
adding titanyl sulfate and urea into deionized water, wherein the mass ratio of titanyl sulfate to urea to deionized water is 1:2.5:25, stirring and dissolving to obtain a mixed solution, adjusting the pH of the mixed solution to 3, adding the pretreated crystalline flake graphite and the nano aluminum nitride, wherein the mass ratio of the pretreated crystalline flake graphite to the titanyl sulfate is 1:4, and the mass ratio of the pretreated crystalline flake graphite to the nano aluminum nitride is 1:0.08, carrying out ultrasonic oscillation and uniform dispersion to obtain a dispersion liquid, transferring the dispersion liquid into a closed reaction kettle, reacting for 10 hours at 180 ℃, separating, washing, drying, calcining the dried product in a muffle furnace for 1 hour at 600 ℃, and cooling to obtain the modified graphite.
The preparation method of the high-temperature-resistant heat-conducting graphite-doped phosphate adhesive comprises the following steps:
firstly, uniformly mixing alumina, zirconia and zinc oxide according to the proportion to obtain a curing agent, adding the curing agent into phosphate resin, uniformly mixing, then adding modified graphite into the mixture, and uniformly mixing to obtain the modified graphite.
Example 2
The high-temperature-resistant heat-conducting phosphate adhesive doped with graphite comprises the following components in parts by weight:
the preparation method of the phosphate resin comprises the following steps: adding aluminum hydroxide into a phosphoric acid solution with the mass concentration of 80%, wherein the mass ratio of the phosphoric acid solution to the aluminum hydroxide is 1:0.5, heating in a water bath to 90 ℃, and stirring for reacting for 5 hours to obtain the phosphate resin.
Pretreatment of flake graphite:
placing the crystalline flake graphite into a crucible, placing the crucible into a microwave oven, and performing microwave treatment for 30s under the power of 700W to obtain expanded graphite for later use; uniformly mixing methyl pyrrolidone and deionized water according to the volume ratio of 1:1 to obtain a dispersion solution, adding expanded graphite into the dispersion solution according to the mass volume ratio of 1g/60mL, then carrying out ultrasonic oscillation stripping treatment for 30min under 850W power to obtain a graphene suspension, adding polyethyleneimine into the graphene suspension, wherein the mass ratio of the expanded graphite to the polyethyleneimine is 1:0.6, uniformly stirring and dispersing, standing for 2h, filtering, adding the filtered graphene into a n-hexane solution of trimesoyl chloride with the mass concentration of 2%, heating in a water bath to 45 ℃, carrying out heat preservation reaction for 10min, and sequentially filtering, washing and drying to obtain pretreated crystalline flake graphite.
The preparation method of the modified graphite comprises the following steps:
adding titanyl sulfate and urea into deionized water, wherein the mass ratio of titanyl sulfate to urea to deionized water is 1:1.5:25, stirring and dissolving to obtain a mixed solution, adjusting the pH of the mixed solution to 2, adding the pretreated crystalline flake graphite and the nano aluminum nitride, wherein the mass ratio of the pretreated crystalline flake graphite to the titanyl sulfate is 1:3.5, the mass ratio of the pretreated crystalline flake graphite to the nano aluminum nitride is 1:0.06, uniformly dispersing by ultrasonic oscillation to obtain a dispersion liquid, transferring the dispersion liquid into a closed reaction kettle, reacting for 15 hours at 170 ℃, separating, washing, drying, calcining the dried product in a muffle furnace for 1 hour at 600 ℃, and cooling to obtain the modified graphite.
The preparation method of the high-temperature-resistant heat-conducting graphite-doped phosphate adhesive comprises the following steps:
firstly, uniformly mixing alumina, zirconia and zinc oxide according to the proportion to obtain a curing agent, adding the curing agent into phosphate resin, uniformly mixing, then adding modified graphite into the mixture, and uniformly mixing to obtain the modified graphite.
Example 3
The high-temperature-resistant heat-conducting phosphate adhesive doped with graphite comprises the following components in parts by weight:
the preparation method of the phosphate resin comprises the following steps: adding aluminum hydroxide into a phosphoric acid solution with the mass concentration of 80%, wherein the mass ratio of the phosphoric acid solution to the aluminum hydroxide is 1:0.5, heating in a water bath to 93 ℃, and stirring for reacting for 3 hours to obtain the phosphate resin.
Pretreatment of flake graphite:
placing the crystalline flake graphite into a crucible, placing the crucible into a microwave oven, and performing microwave treatment for 30s under the power of 700W to obtain expanded graphite for later use; uniformly mixing methyl pyrrolidone and deionized water according to the volume ratio of 1:1 to obtain a dispersion solution, adding expanded graphite into the dispersion solution according to the mass-volume ratio of 1g/60mL, then carrying out ultrasonic oscillation stripping treatment for 30min under 900W power to obtain a graphene suspension, adding polyethyleneimine into the graphene suspension, wherein the mass ratio of the expanded graphite to the polyethyleneimine is 1:1, uniformly stirring and dispersing, standing for 3h, filtering, adding the filtered graphene into a n-hexane solution of trimesoyl chloride with the mass concentration of 5%, heating in a water bath to 43 ℃, carrying out heat preservation reaction for 15min, and sequentially filtering, washing and drying to obtain the pretreated crystalline flake graphite.
The preparation method of the modified graphite comprises the following steps:
adding titanyl sulfate and urea into deionized water, wherein the mass ratio of titanyl sulfate to urea to deionized water is 1:3:20, stirring and dissolving to obtain a mixed solution, adjusting the pH of the mixed solution to 2.5, adding the pretreated crystalline flake graphite and the nano aluminum nitride, wherein the mass ratio of the pretreated crystalline flake graphite to the titanyl sulfate is 1:5, the mass ratio of the pretreated crystalline flake graphite to the nano aluminum nitride is 1:0.1, uniformly dispersing by ultrasonic oscillation to obtain a dispersion liquid, transferring the dispersion liquid into a closed reaction kettle, reacting for 12 hours at 175 ℃, separating, washing, drying, calcining the dried product in a muffle furnace for 1 hour at 600 ℃, and cooling to obtain the modified graphite.
The preparation method of the high-temperature-resistant heat-conducting graphite-doped phosphate adhesive comprises the following steps:
firstly, uniformly mixing alumina, zirconia and zinc oxide according to the proportion to obtain a curing agent, adding the curing agent into phosphate resin, uniformly mixing, then adding modified graphite into the mixture, and uniformly mixing to obtain the modified graphite.
Example 4
The high-temperature-resistant heat-conducting phosphate adhesive doped with graphite comprises the following components in parts by weight:
the preparation method of the phosphate resin comprises the following steps: adding aluminum hydroxide into a phosphoric acid solution with the mass concentration of 80%, wherein the mass ratio of the phosphoric acid solution to the aluminum hydroxide is 1:0.5, heating in a water bath to 93 ℃, and stirring for reacting for 3 hours to obtain the phosphate resin.
Pretreatment of flake graphite:
placing the crystalline flake graphite into a crucible, placing the crucible into a microwave oven, and performing microwave treatment for 30s under the power of 700W to obtain expanded graphite for later use; uniformly mixing methyl pyrrolidone and deionized water according to the volume ratio of 1:1 to obtain a dispersion solution, adding expanded graphite into the dispersion solution according to the mass volume ratio of 1g/60mL, then carrying out ultrasonic oscillation stripping treatment for 30min under 800W power to obtain a graphene suspension, adding polyethyleneimine into the graphene suspension, wherein the mass ratio of the expanded graphite to the polyethyleneimine is 1:0.5, uniformly stirring and dispersing, standing for 3h, filtering, adding the filtered graphene into a n-hexane solution of trimesoyl chloride with the mass concentration of 0.5%, heating to 43 ℃ in a water bath, carrying out heat preservation reaction for 15min, and sequentially filtering, washing and drying to obtain pretreated crystalline flake graphite.
The preparation method of the modified graphite comprises the following steps:
adding titanyl sulfate and urea into deionized water, wherein the mass ratio of titanyl sulfate to urea to deionized water is 1:1:30, stirring and dissolving to obtain a mixed solution, adjusting the pH of the mixed solution to 2.5, adding the pretreated crystalline flake graphite and the nano aluminum nitride, wherein the mass ratio of the pretreated crystalline flake graphite to the titanyl sulfate is 1:3, the mass ratio of the pretreated crystalline flake graphite to the nano aluminum nitride is 1:0.05, uniformly dispersing by ultrasonic oscillation to obtain a dispersion liquid, transferring the dispersion liquid into a closed reaction kettle, reacting for 12 hours at 175 ℃, separating, washing, drying, calcining the dried product in a muffle furnace for 1 hour at 600 ℃, and cooling to obtain the modified graphite.
The preparation method of the high-temperature-resistant heat-conducting graphite-doped phosphate adhesive comprises the following steps:
firstly, uniformly mixing alumina, zirconia and zinc oxide according to the proportion to obtain a curing agent, adding the curing agent into phosphate resin, uniformly mixing, then adding modified graphite into the mixture, and uniformly mixing to obtain the modified graphite.
Comparative example 1:
comparative example 1 differs from example 1 in that no modified graphite was added to the phosphate binder.
Comparative example 2:
comparative example 2 is different from example 1 in that the flake graphite is not modified.
Comparative example 3:
comparative example 3 differs from example 1 in that the flake graphite was not pretreated.
Testing the performance of the adhesive:
1. and (3) testing the shear strength:
according to the determination of tensile shear strength of adhesive (rigid material to rigid material) of GB/T7124-.
The tensile shear strength of the samples in the examples is gradually increased along with the increase of the temperature, and the tensile shear strength of the samples in the comparative examples 2 is firstly increased along with the increase of the temperature, and the tensile shear strength is gradually reduced after the temperature is higher than 300 ℃ because the graphite in the adhesive is oxidized after the temperature is higher than 300 ℃ to cause the loosening of the graphite structure and further cause the reduction of the tensile shear strength of the adhesive; compared with the embodiment, the tensile shear strength of the sample is slowly increased, because a large amount of amino groups are loaded on the surface of the graphene in the embodiment, and in the process of hydrolyzing titanyl sulfate to generate nano titanium dioxide, the amino groups on the surface of the graphene and the hydroxyl groups on the surface of the nano titanium dioxide form hydrogen bond acting force, so that the nano titanium dioxide is more and rapidly deposited on the surface of the graphene to form a denser titanium dioxide protective layer, and the titanium dioxide protective layer plays a better role in heat insulation and oxygen isolation on the graphene.
2. Adhesive thermal diffusion coefficient determination:
the thermal diffusivity or the thermal conductivity of a test sample is measured according to GB/T22588-. The heat diffusion coefficient (cm) of the adhesives of examples 1-4 and comparative examples 1-3 under the air condition is calculated2The change in/s) with temperature is as follows:
the results recorded in the above table can show that the thermal diffusivity of the adhesive in the example is significantly higher than that of the adhesive without graphite in comparative example 1, and the addition of graphite in the phosphoric acid adhesive can significantly increase the thermal diffusivity of the adhesive. The examples showed less decrease of thermal diffusivity with temperature increase and almost maintained stable compared with comparative example 2, while the thermal diffusivity of the adhesive in comparative example 2 showed sharp decrease after the temperature exceeded 300 ℃, because the graphite in the adhesive was oxidized after the temperature exceeded 300 ℃ and the thermal conductivity of the graphite was decreased. The thermal diffusivity of the adhesive in the comparative example 3 is reduced faster with the increase of temperature compared with that of the adhesive in the example, because a compact titanium dioxide protective layer is not formed on the graphite surface in the comparative example 3, and partial oxidation occurs on the graphite surface under a high temperature condition, so that the heat-conducting property of the graphite is reduced.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The high-temperature-resistant heat-conducting graphite-doped phosphate adhesive is characterized by comprising the following components in parts by weight:
70-80 parts of phosphate resin,
5-10 parts of modified graphite,
3-6 parts of aluminum oxide,
1-3 parts of zirconium oxide, namely,
1-3 parts of zinc oxide.
2. The graphite-doped high-temperature-resistant heat-conductive phosphate adhesive is characterized in that the preparation method of the phosphate resin comprises the following steps: adding aluminum hydroxide into the phosphoric acid solution, heating to 90-95 ℃ in water bath, and stirring for reaction for 1-5h to obtain the phosphate resin.
3. The graphite-doped high-temperature-resistant heat-conductive phosphate adhesive as claimed in claim 1, wherein the preparation method of the modified graphite comprises the following steps: adding titanyl sulfate and urea into deionized water, wherein the mass ratio of titanyl sulfate to urea to deionized water is 1:1-3:20-30, stirring and dissolving to obtain a mixed solution, adjusting the pH value of the mixed solution to 2-3, adding crystalline flake graphite and nano aluminum nitride, performing ultrasonic oscillation and uniform dispersion to obtain a dispersion solution, transferring the dispersion solution into a closed reaction kettle, reacting for 10-15h at the temperature of 170-180 ℃, separating, washing, drying, placing a product obtained by drying in a muffle furnace for calcining, and cooling to obtain modified graphite.
4. The graphite-doped high-temperature-resistant heat-conducting phosphate adhesive as claimed in claim 3, wherein the mass ratio of the crystalline flake graphite to the titanyl sulfate is 1: 3-5.
5. The graphite-doped high-temperature-resistant heat-conductive phosphate adhesive as claimed in claim 3, wherein the mass ratio of the crystalline flake graphite to the nano aluminum nitride is 1: 0.05-0.1.
6. The graphite-doped high-temperature-resistant heat-conductive phosphate adhesive is characterized in that the flake graphite is pretreated, and the method comprises the following steps:
placing the flake graphite in a microwave oven for microwave treatment to obtain expanded graphite for later use; uniformly mixing methyl pyrrolidone and deionized water to obtain a dispersion solution, adding expanded graphite into the dispersion solution to perform ultrasonic oscillation stripping treatment to obtain a graphene suspension, adding polyethyleneimine into the graphene suspension, uniformly stirring and dispersing, standing for 2-5h, filtering, adding filtered graphene into a trimesoyl chloride solution, heating in a water bath to 40-45 ℃, performing heat preservation reaction for 10-20min, and sequentially filtering, washing and drying to obtain the graphene nano-particles.
7. The graphite-doped high-temperature-resistant heat-conducting phosphate adhesive as claimed in claim 6, wherein the ultrasonic vibration stripping power of the expanded graphite in the dispersion solution is 800-900W.
8. The graphite-doped high-temperature-resistant heat-conductive phosphate adhesive is characterized in that the mass ratio of the expanded graphite to the polyethyleneimine is 1: 0.5-1.
9. The graphite-doped high-temperature-resistant heat-conductive phosphate adhesive is characterized in that the mass concentration of the trimesoyl chloride solution is 0.5-5%.
10. A method for preparing a graphite doped high temperature resistant heat conducting phosphate adhesive according to any one of claims 1 to 9, comprising the steps of: firstly, uniformly mixing alumina, zirconia and zinc oxide to obtain a curing agent, adding the curing agent into phosphate resin, uniformly mixing, then adding modified graphite into the mixture, and uniformly mixing to obtain the modified graphite.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142479A (en) * | 2020-09-04 | 2020-12-29 | 华侨大学 | Preparation method of SiC @ Ti (C, N) core-shell structure ceramic powder |
| CN112592664A (en) * | 2020-11-13 | 2021-04-02 | 常州晶泰新材料科技有限公司 | Graphene modified phosphate composite adhesive, preparation method thereof and application of graphene modified phosphate composite adhesive in high-temperature sensor |
-
2020
- 2020-05-22 CN CN202010439308.1A patent/CN111534236A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142479A (en) * | 2020-09-04 | 2020-12-29 | 华侨大学 | Preparation method of SiC @ Ti (C, N) core-shell structure ceramic powder |
| CN112142479B (en) * | 2020-09-04 | 2022-07-29 | 华侨大学 | Preparation method of SiC @ Ti (C, N) core-shell structure ceramic powder |
| CN112592664A (en) * | 2020-11-13 | 2021-04-02 | 常州晶泰新材料科技有限公司 | Graphene modified phosphate composite adhesive, preparation method thereof and application of graphene modified phosphate composite adhesive in high-temperature sensor |
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Application publication date: 20200814 |