CN113480828A - Aluminum nitride nanoflower/polymer composite material and preparation method thereof - Google Patents
Aluminum nitride nanoflower/polymer composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of preparation of electronic packaging heat management materials, in particular to an aluminum nitride nanoflower/polymer composite material and a preparation method thereof. The preparation method comprises the following steps: A) mixing aluminum powder with a salt solution, and performing ultrasonic cavitation corrosion; B) carrying out suction filtration on the product solution obtained in the step A) to obtain a filter cake; C) crushing the filter cake, uniformly mixing the filter cake with a solid nitrogen source, and performing nitridation reaction in a nitrogen-containing atmosphere; D) decarbonizing the product after the nitridation reaction to obtain the aluminum nitride nanoflower; E) uniformly mixing the aluminum nitride nanoflower, the sintering aid and the additive in a solvent to form a suspension, performing directional freeze forming, freeze drying, and sintering to obtain a porous aluminum nitride three-dimensional network framework; F) and (3) under the vacuum condition, impregnating the resin into the porous aluminum nitride three-dimensional network framework, and then curing to obtain the aluminum nitride nanoflower/polymer composite material. The aluminum nitride nanoflower/polymer composite material has excellent thermal conductivity.
Description
Technical Field
The invention relates to the technical field of preparation of electronic packaging heat management materials, in particular to an aluminum nitride nanoflower/polymer composite material and a preparation method thereof.
Background
Since this century, with the rapid development of science and technology, electronic components are smaller and smaller, and the computation load of chips is greatly increased, which leads to a corresponding substantial increase in the heat productivity of electronic components per unit volume. The problem of overheating of electronic components caused by rapid power increase greatly affects the service performance, service life and safety of the electronic components. Therefore, efficient heat dissipation of electronic components is an urgent problem to be solved. The polymer material has the advantages of low cost, light weight, good processability, low water absorption, high resistivity, corrosion resistance and the like, so the polymer material is widely applied to heat management materials. However, most polymers exhibit poor thermal conductivity, which limits their use in many applications where high thermal conductivity is required. For this reason, a common solution is to add a highly thermally conductive inorganic filler to the polymer, thereby improving its thermal conductivity. At present, the heat conductive filler of the polymer matrix composite material is mainly oxide, carbide, nitride, graphene, carbon nanotube and the like. The aluminum nitride has low thermal expansion coefficient and excellent electrical insulation, the room temperature thermal conductivity is only lower than that of beryllium oxide in ceramics, and the aluminum nitride is nontoxic, so the aluminum nitride is the preferred filler of the heat-conducting polymer matrix composite material and has wide application prospect in heat management materials.
The following methods are mainly used for preparing aluminum nitride: (1) the direct aluminum powder nitriding process is one combining aluminum powder and nitrogen gas in nitrogen atmosphere at 800-1200 deg.c. (2) A carbothermic reduction process in which a mixed powder of alumina powder and carbon powder is carbothermally nitrided in a nitrogen atmosphere to produce aluminum nitride powder at a reaction temperature of generally not lower than 1600 ℃. (3) A self-spreading high-temp synthesis method features that after aluminium powder is ignited by external heat source in high-pressure nitrogen gas, the self-maintaining reaction is carried out by high-chemical reaction heat until the aluminium powder is completely converted into aluminium nitride powder. (4) Chemical vapour deposition processes, which are based on the chemical reaction of volatile compounds of aluminium with ammonia or nitrogen, deposit aluminium nitride powders from the vapour phase.
At present, the carbothermic method is mostly adopted for preparing the nano aluminum nitride, but the method also has some defects, such as higher cost of the nano aluminum oxide raw material, difficulty in fully and uniformly mixing the raw material, higher reaction temperature and longer reaction time, and the cost for synthesizing the nano aluminum nitride is higher due to the factors. Moreover, the research field of nano aluminum nitride is generally limited to zero-dimensional aluminum nitride powder, one-dimensional aluminum nitride nanowires, etc., and the research on the nano structure of aluminum nitride with more than one dimension is less. Schering et al, in patent CN 101798071, disclose a combustion synthesis method for preparing aluminum nitride with flower-like structure, but this method requires the use of high-pressure nitrogen and the use of a large current, which increases the risk of experiment, and the submicron rather than the nano flower-like aluminum nitride powder is obtained.
Disclosure of Invention
In view of this, the invention provides an aluminum nitride nanoflower/polymer composite material and a preparation method thereof.
The invention provides a preparation method of an aluminum nitride nanoflower/polymer composite material, which comprises the following steps:
A) uniformly mixing aluminum powder and a salt solution, and performing ultrasonic cavitation corrosion on the mixed liquid;
B) carrying out suction filtration on the solution obtained in the step A) to obtain a filter cake;
C) crushing the filter cake, uniformly mixing the filter cake with a solid nitrogen source, and performing a nitridation reaction in a nitrogen-containing atmosphere;
D) decarbonizing the product after the nitridation reaction to obtain the aluminum nitride nanoflower;
E) uniformly mixing the aluminum nitride nanoflower, the sintering aid and the additive in a solvent to form a suspension, performing directional freeze forming, freeze drying, and sintering to obtain a porous aluminum nitride three-dimensional network framework and a porous aluminum nitride three-dimensional network framework;
F) and (3) under the vacuum condition, impregnating resin into the porous aluminum nitride three-dimensional network framework, and then curing to obtain the aluminum nitride nanoflower/polymer composite material.
Preferably, in the step a), the salt solution includes at least one of a sodium chloride solution, a potassium chloride solution, a calcium chloride solution, a sodium nitrate solution, a potassium nitrate solution, a sodium sulfate solution and a potassium sulfate solution;
the mass concentration of the salt solution is 2.5-5%.
Preferably, in the step A), the mass ratio of the aluminum powder to the salt solution is 1-10: 100;
the pH value of the mixed material liquid is 4-10;
the pH value of the mixed feed liquid is adjusted by a chemical reagent;
the chemical reagent comprises at least one of hydrochloric acid, acetic acid, citric acid, nitric acid, sulfuric acid, ammonia water, ammonium chloride, sodium hydroxide and potassium hydroxide;
the ultrasonic power of the ultrasonic cavitation corrosion is 180-500W, and the time is 1-6 h.
Preferably, in step C), the solid nitrogen source comprises at least one of urea, cyanamide, dicyandiamide, melamine and ammonium chloride;
the mass ratio of the filter cake to the solid nitrogen source is 1: 1-6;
the uniformly mixed liquid medium is ethanol;
the mass ratio of the solid nitrogen source to the ethanol is 1-3: 5.
Preferably, in step C), the gas forming the nitrogen-containing atmosphere comprises at least one of nitrogen and ammonia;
the gas flow rate for forming the nitrogen-containing atmosphere is 90-100 sccm;
the temperature of the nitridation reaction is 800-1000 ℃, and the time is 30-180 min;
the nitridation reaction is carried out at normal pressure.
Preferably, in the step D), the temperature for carbon removal is 600-700 ℃, and the time is 60-120 min;
preferably, in step E), the sintering aid is CaF2、Y2O3、CaO、La2O3And YF3At least one of;
in the nano aluminum nitride suspension, the volume fraction of the sintering aid is 0.5-5%.
Preferably, in step E), the additives in the raw materials for preparing the suspension include a dispersant and a binder;
the dispersing agent is at least one of citric acid, sodium tartrate and potassium citrate, and the binder is at least one of sodium carboxymethyl cellulose and polyvinyl alcohol.
Preferably, the solvent comprises at least one of deionized water, tert-butanol and camphene;
in the suspension, the volume fraction of the nano aluminum nitride is 10-40%;
preferably, in the step E), the temperature of the directional freezing forming is-80 to-120 ℃;
the sintering temperature is 800-1300 ℃, and the sintering time is 5-120 min.
Preferably, in step F), the resin comprises at least one of a phenolic resin and an epoxy resin;
the volume ratio of the porous aluminum nitride three-dimensional network framework to the resin is 5-50: 100;
the vacuum infiltration time is 1-2 h; the vacuum degree is required to be less than 10-1Pa。
Preferably, in step F), the curing comprises:
curing for 1-2 h at 70-90 ℃, and then curing for 1-2 h at 110-130 ℃.
The invention also provides the aluminum nitride nanoflower/polymer composite material prepared by the preparation method.
The invention provides a preparation method of an aluminum nitride nanoflower/polymer composite material, which comprises the following steps: A) mixing aluminum powder with a salt solution, and performing ultrasonic cavitation corrosion on the obtained mixed feed liquid; B) carrying out suction filtration on the product solution obtained in the step A) to obtain a filter cake; C) crushing the filter cake, uniformly mixing the filter cake with a solid nitrogen source, and performing nitridation reaction in a nitrogen-containing atmosphere; D) decarbonizing the product after the nitridation reaction to obtain the aluminum nitride nanoflower; E) uniformly mixing the aluminum nitride nanoflower, the sintering aid and the additive in a solvent to form a suspension, performing directional freeze forming, freeze drying, and sintering to obtain a porous aluminum nitride three-dimensional network framework; F) and (3) under the vacuum condition, impregnating resin into the porous aluminum nitride three-dimensional network framework, and then curing to obtain the aluminum nitride nanoflower/polymer composite material. Compared with the traditional nano aluminum oxide used as the raw material for preparing nano aluminum nitride, the method has the advantages of low raw material cost and low reaction temperature, the prepared nano flower aluminum nitride has good shape, the surfaces of the nano flower aluminum nitride are in an overlapped nano petal shape, the specific surface area is large, the sintering activity is high, after the vertically arranged aluminum nitride nano flower three-dimensional network framework is constructed by freezing according to the ice template law, the resin is impregnated in vacuum, and finally the polymer-based composite material with excellent thermal conductivity can be obtained.
Drawings
FIG. 1 is an XRD (X-ray diffraction) pattern of aluminum powder selected in example 1 of the invention after ultrasonic cavitation corrosion;
FIG. 2 is an SEM image of the aluminum powder selected in example 1 of the present invention after ultrasonic cavitation corrosion;
FIG. 3 is an XRD pattern of the aluminum nitride nanoflower prepared in example 1 of the present invention;
FIG. 4 is an SEM image of the aluminum nitride nanoflower prepared in example 1 of the present invention at a magnification of 25 k;
FIG. 5 is an SEM image of the aluminum nitride nanoflower prepared in example 1 of the present invention at a magnification of 100 k;
FIG. 6 is an SEM image of a cross section of a porous aluminum nitride three-dimensional network skeleton prepared in example 1 of the present invention;
fig. 7 is an SEM image of a cross-section of the aluminum nitride nanoflower/polymer composite prepared in example 1 of the present invention after polishing.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of an aluminum nitride nanoflower/polymer composite material, which comprises the following steps:
A) mixing aluminum powder with a salt solution, and performing ultrasonic cavitation corrosion on the mixed liquid;
B) carrying out suction filtration on the product solution obtained in the step A) to obtain a filter cake;
C) crushing the filter cake, uniformly mixing the filter cake with a solid nitrogen source, and performing nitridation reaction in a nitrogen-containing atmosphere;
D) decarbonizing the product after the nitridation reaction to obtain the aluminum nitride nanoflower;
E) uniformly mixing the aluminum nitride nanoflower, the sintering aid and the additive in a solvent to form a suspension, performing directional freeze forming, freeze drying, and sintering to obtain a porous aluminum nitride three-dimensional network framework;
F) and (3) under the vacuum condition, impregnating resin into the porous aluminum nitride three-dimensional network framework, and then curing to obtain the aluminum nitride nanoflower/polymer composite material.
The invention firstly mixes the aluminum powder and the salt solution, and carries out ultrasonic cavitation corrosion on the obtained mixed feed liquid.
In some embodiments of the present invention, the aluminum powder has a particle size of 0.5 to 3 μm. In some embodiments, the aluminum powder has a particle size of 0.5 to 1 μm, 2 to 3 μm, 1 to 3 μm, or 1 to 2 μm.
In certain embodiments of the present invention, the salt solution comprises at least one of a sodium chloride solution, a potassium chloride solution, a calcium chloride solution, a sodium nitrate solution, a potassium nitrate solution, a sodium sulfate solution, and a potassium sulfate solution. In certain embodiments of the invention, the solvent of the salt solution is water. In certain embodiments of the invention, the salt solution has a mass concentration of 2.5% to 5%.
In some embodiments of the invention, the mass ratio of the aluminum powder to the salt solution is 1-10: 100.
In some embodiments of the present invention, the pH of the mixed solution is 4 to 10. In certain embodiments, the pH of the mixed liquor is 7, 10, 4, 9, or 5. In certain embodiments of the invention, the pH of the mixed liquor is adjusted by chemical agents. In certain embodiments of the invention, the chemical agent comprises at least one of hydrochloric acid, acetic acid, citric acid, nitric acid, sulfuric acid, ammonia, ammonium chloride, sodium hydroxide, and potassium hydroxide.
In some embodiments of the invention, the ultrasonic power of the ultrasonic cavitation corrosion is 180-500W, and the time is 1-6 h. In certain embodiments, the ultrasonic power of the ultrasonic cavitation erosion is 180W, 300W. In certain embodiments, the ultrasonic cavitation erosion time is 6h or 5 h. In certain embodiments of the invention, the ultrasonic cavitation erosion is performed in an ultrasonic generator. In some embodiments of the present invention, during the ultrasonic cavitation erosion, the mixed feed liquid is magnetically stirred. In some embodiments of the invention, the rotation speed of the magnetic stirring is 50 to 200 r/min. The ultrasonic cavitation corrosion process is the corrosion process of the aluminum powder.
And after the ultrasonic cavitation corrosion is finished, carrying out suction filtration on the product solution subjected to the ultrasonic cavitation corrosion to obtain a filter cake.
The method of suction filtration is not particularly limited in the present invention, and a method of suction filtration known to those skilled in the art may be used. After suction filtration, a white filter cake was obtained.
In some embodiments of the present invention, after the suction filtering, the method further comprises: vacuum drying is carried out to obtain a filter cake. The method and parameters of the vacuum drying are not particularly limited in the present invention, and those known to those skilled in the art can be used.
After a filter cake is obtained, the filter cake is crushed and mixed with a solid nitrogen source uniformly, and then the nitriding reaction is carried out in a nitrogen-containing atmosphere. The nitrogen-containing atmosphere serves as a reaction gas as well as a gaseous nitrogen source.
In certain embodiments of the present invention, the solid nitrogen source comprises at least one of urea, cyanamide, dicyandiamide, melamine, and ammonium chloride.
In some embodiments of the invention, the mass ratio of the filter cake to the solid nitrogen source is 1: 1-6. In certain embodiments, the mass ratio of the filter cake to the solid nitrogen source is 1: 6 or 1: 4.
In certain embodiments of the invention, the homogenized liquid medium is ethanol. In some embodiments of the invention, the mass ratio of the solid nitrogen source to the ethanol is 1-3: 5. In certain embodiments, the mass ratio of the solid nitrogen source to ethanol is 1: 5, 2: 5, or 3: 5.
In certain embodiments of the invention, after blending with the solid nitrogen source, drying is also included. The method of drying is not particularly limited in the present invention, and a drying method known to those skilled in the art may be used.
In certain embodiments of the present invention, the gas forming the nitrogen-containing atmosphere comprises at least one of nitrogen and ammonia. In some embodiments of the present invention, the flow rate of the gas forming the nitrogen-containing atmosphere is 90-100 sccm. In some embodiments, the nitrogen-containing atmosphere is formed at a gas flow rate of 90sccm or 100 sccm.
In some embodiments of the present invention, the temperature of the nitridation reaction is 800-1000 ℃ for 30-180 min. In certain embodiments, the temperature of the nitridation reaction is 900 ℃ or 1000 ℃. In certain embodiments, the time for the nitridation reaction is 180min, 30min, or 60 min. In certain embodiments of the invention, the nitridation reaction is performed at atmospheric pressure. In certain embodiments of the invention, the nitriding reaction is performed in a vacuum carbon tube furnace, a vacuum sintering furnace, a vacuum tube furnace, a microwave sintering furnace, or a spark plasma sintering furnace.
In some embodiments of the invention, after the filter cake is crushed, mixed with a solid nitrogen source uniformly and dried, the obtained mixture is heated to the nitriding reaction temperature at a heating rate of 5-100 ℃/min. In certain embodiments, the rate of heating the resulting mixture to the nitridation reaction temperature is 5 deg.C/min, 100 deg.C/min, 7 deg.C/min, or 50 deg.C/min.
In certain embodiments of the present invention, cooling is also included after the nitridation reaction. In some embodiments of the present invention, the cooling rate is 2-20 ℃/min. In certain embodiments, the rate of cooling is 2 ℃/min or 20 ℃/min. In certain embodiments, the method of cooling is furnace cooling. In certain embodiments, cooling to room temperature.
And (3) decarbonizing the product after the nitridation reaction to obtain the aluminum nitride nanoflower.
In certain embodiments of the invention, the method of carbon removal comprises: and (3) preserving the heat for 60-120 min at 600-700 ℃ in an air atmosphere.
In certain embodiments of the invention, the carbon removal is performed in a muffle furnace. And removing carbon to obtain a white substance, namely the aluminum nitride nanoflower. The thickness of the aluminum nitride nanoflower prepared by the method is nano-scale, and in some embodiments of the invention, the thickness of petals of the aluminum nitride nanoflower is 10-20 nm. In some embodiments, the petal thickness of the aluminum nitride nanoflower is 14-16 nm.
After the aluminum nitride nanoflower is obtained, uniformly mixing the aluminum nitride nanoflower, the sintering aid and the additive in a solvent to form a suspension, performing directional freeze forming, freeze drying, and sintering to obtain the porous aluminum nitride three-dimensional network framework.
The porous aluminum nitride three-dimensional network framework prepared by the method adopts an ice template method.
In certain embodiments of the invention, the sintering aid is CaF2、Y2O3、CaO、La2O3、YF3At least one of (1). In some embodiments of the invention, the volume fraction of the sintering aid in the suspension is 0.5% to 5%. In some embodiments, the volume fraction of sintering aid in the suspension is 5%, 2%, 0.5%, 1%, or 3%.
In certain embodiments of the present invention, the solvent comprises at least one of deionized water, t-butanol, and camphene. In some embodiments of the present invention, the volume fraction of the nano aluminum nitride in the suspension is 10% to 40%. In some embodiments, the volume fraction of nano aluminum nitride in the suspension is 20%, 15%, 10%, 30%, or 40%.
In certain embodiments of the invention, the additives in the raw materials for preparing the suspension include a dispersant and a binder. The dispersing agent is at least one of citric acid, sodium tartrate and potassium citrate, and the binder is at least one of sodium carboxymethyl cellulose and polyvinyl alcohol. In some embodiments of the invention, the volume fraction of the dispersant is 0.5% to 5% and the volume fraction of the binder is 0.5% to 5% in the suspension. In certain embodiments, the volume fraction of dispersant in the suspension is 2%, 3%, or 4%. In certain embodiments, the volume fraction of binder in the suspension is 0.5%, 2%, 3%, or 4%.
In certain embodiments of the invention, the temperature of the directional freeze-forming is in the range of-80 to-120 ℃. In certain embodiments, the temperature of the directional freeze forming is-80 ℃. In certain embodiments of the invention, the cooling medium for directional freeze forming is liquid nitrogen.
In some embodiments of the invention, the freeze-drying time is 20-24 h. In certain embodiments, the freeze-drying time is 24 hours. In certain embodiments of the invention, the freeze-drying is performed in a freeze-drying oven.
In some embodiments of the present invention, the sintering temperature is 800-1300 ℃ and the sintering time is 5-120 min. In certain embodiments, the temperature of the sintering is 1200 ℃ or 1100 ℃. In certain embodiments, the sintering time is 5 min. In certain embodiments of the invention, the sintering is performed in a vacuum carbon tube furnace, a vacuum sintering furnace, a vacuum tube furnace, a microwave sintering furnace, or a spark plasma sintering furnace.
In some embodiments of the present invention, the porous aluminum nitride three-dimensional network framework has vertically arranged columnar pores distributed therein.
After obtaining the porous aluminum nitride three-dimensional network framework, impregnating resin into the porous aluminum nitride three-dimensional network framework under a vacuum condition, and then curing to obtain the aluminum nitride nanoflower/polymer composite material.
The vacuum degree of the invention is required to be less than 10 under the vacuum condition-1Pa。
In certain embodiments of the present invention, the resin comprises at least one of a phenolic resin and an epoxy resin.
In some embodiments of the invention, the volume ratio of the porous aluminum nitride three-dimensional network skeleton to the resin is 5-50: 100. In certain embodiments, the volume ratio of the porous aluminum nitride three-dimensional network framework to the resin is 20: 100, 15: 100, 10: 100, 30: 100, 25: 100, or 40: 100.
In some embodiments of the invention, the resin is impregnated into the porous aluminum nitride three-dimensional network framework for 1 to 2 hours.
In certain embodiments of the present invention, the curing is a secondary curing comprising:
curing for 1-2 h at 70-90 ℃, and then curing for 1-2 h at 110-130 ℃.
The source of the above-mentioned raw materials is not particularly limited, and the raw materials may be generally commercially available.
The invention also provides an aluminum nitride nanoflower/polymer composite material prepared by the preparation method.
The nitrogen source used in the invention is mainly a solid nitrogen source, the decomposition temperature is low, and compared with a nitrogen source, the decomposed nitrogen has high activity; compared with ammonia nitrogen source, the method is safer in experiment. Therefore, the solid nitrogen source is utilized to cause low reaction temperature and low pressure of the nitrogen-containing gas required by the whole reaction, thereby being beneficial to improving the production safety and reducing the production cost, and the method has simple process, good repeatability and high purity of the obtained aluminum nitride product.
According to the invention, an aluminum source is corroded by using an ultrasonic cavitation corrosion technology, and the technology can obtain a corrosion product of nanoparticles, so that the reaction activity of the aluminum source can be greatly improved. Furthermore, the prepared nano flower aluminum nitride material has good shape, the surface is in an overlapped nano petal shape, the specific surface area is large, and the sintering activity is high.
The vertically arranged three-dimensional porous aluminum nitride three-dimensional network framework is constructed by an ice template method, so that the thermal conductivity of the subsequent polymer matrix composite material is improved, and under the condition that the porous aluminum nitride three-dimensional network framework with the volume fraction of 20% is added, the thermal conductivity is 8.3 times higher than that of the normal state and can reach 2.26W/m.k.
The aluminum nitride nanoflower prepared by the method only needs to be operated under normal pressure, and does not need to use large current, so that the experimental safety is well guaranteed.
In order to further illustrate the present invention, the following will describe in detail an aluminum nitride nanoflower/polymer composite and a method for preparing the same in connection with the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
1. Selecting 5g of aluminum powder (the particle size range of the aluminum powder is 0.5-1 mu m), putting the aluminum powder into 500g of 2.5 wt% sodium chloride solution, adjusting the pH value to 7 by using dilute hydrochloric acid and sodium hydroxide, corroding the solution by using an ultrasonic generator, setting the ultrasonic power to be 180W, and simultaneously stirring by using magnetic force (50 r/min);
2. after 6h of corrosion, carrying out suction filtration on the solution after reaction to obtain a white filter cake;
3. vacuum drying the white filter cake, crushing the dried filter cake, uniformly mixing the crushed filter cake and melamine with ethanol, and drying, wherein the mass ratio of the melamine to the ethanol is 1: 5; the mass ratio of the dried filter cake to the melamine is 1: 6;
4. putting the mixed material obtained in the step (3) into a tubular furnace, heating to 900 ℃ at the speed of 5 ℃/min, supplying gas by adopting flowing nitrogen, setting the pressure of the nitrogen to be normal pressure and the flow to be 100sccm, reacting for 3 hours at 900 ℃, cooling after the reaction is finished, setting the cooling rate to be 2 ℃/min, and cooling to room temperature;
5. and after cooling, opening the furnace cover, taking out the crucible, then putting the crucible into a muffle furnace, keeping the temperature at 700 ℃ for 1h, and removing carbon to obtain a white substance, namely the aluminum nitride nanoflower.
6. Mixing the aluminum nitride nanoflower with tert-butyl alcohol, using potassium citrate as a dispersing agent, CMC as a bonding agent, and adding CaF2Using the nano aluminum nitride suspension as a sintering aid to obtain a nano aluminum nitride suspension (the volume fraction is 20%, the volume fraction of the sintering aid is 5%, the volume fraction of the dispersing agent is 2% and the volume fraction of the binding agent is 0.5%), using liquid nitrogen as a cooling medium, carrying out directional freezing molding on the suspension at-80 ℃, placing the obtained sample in a freezing drying oven for 24h for freezing drying, and drying to obtain the nano aluminum nitride suspensionThen placing the porous aluminum nitride into a discharge plasma sintering furnace, and sintering at high temperature of 1200 ℃ for 5min to obtain a porous aluminum nitride three-dimensional network framework;
7. and infiltrating the porous aluminum nitride three-dimensional network framework and epoxy resin according to the volume ratio of 20: 100 for 2h under the vacuum condition, curing for 2h at 90 ℃, and then curing for 2h at 120 ℃ to obtain the aluminum nitride nanoflower/polymer composite material.
The X-ray phase analysis of the cavitated and corroded aluminum powder in example 1 is shown in FIG. 1. FIG. 1 is an XRD pattern of the aluminum powder selected in example 1 of the present invention after ultrasonic cavitation corrosion. The XRD pattern shows that the diffraction peak of the aluminum powder completely disappears, and AlOOH and Al (OH) appear newly3And Al2O3The characteristic diffraction peak of the aluminum powder shows that the surface corrosion of the aluminum powder is relatively complete. The shape analysis of the cavitation erosion aluminum powder in the embodiment 1 is carried out by a scanning electron microscope, and the result is shown in figure 2. FIG. 2 is an SEM image of the aluminum powder selected in example 1 of the present invention after ultrasonic cavitation erosion. As can be seen from FIG. 2, the surface of the raw spherical aluminum powder is very smooth (the top right corner of FIG. 2 is inserted into the SEM image), but many petal-shaped nanostructures appear on the surface of the cavitation erosion aluminum powder.
The present invention carried out X-ray phase analysis of the aluminum nitride nanoflower obtained in example 1, and the results are shown in FIG. 3. Fig. 3 is an XRD pattern of the aluminum nitride nanoflower prepared in example 1 of the present invention. The XRD pattern shows that only the characteristic diffraction peak of the aluminum nitride is present, which indicates that the nitridation reaction is relatively complete and all cavitation corrosion aluminum powder is reacted.
The aluminum nitride nanoflower obtained in example 1 was subjected to scanning electron microscopy morphology analysis, and the results are shown in fig. 4 and 5. Fig. 4 is an SEM image of the aluminum nitride nanoflower prepared in example 1 of the present invention at a magnification of 25 k. As can be seen from FIG. 4, the spherical morphology of the raw aluminum powder was maintained while the powder was petaloid. Fig. 5 is an SEM image of the aluminum nitride nanoflower prepared in example 1 of the present invention at a magnification of 100 k. As is clear from fig. 5, the synthesized aluminum nitride powder had a petaloid shape, and the specific surface area of the powder was greatly increased, thereby improving the sintering activity of the powder. In FIG. 5, the top right corner is an SEM image of petals of the aluminum nitride nanoflower prepared in example 1 of the present invention at a magnification of 500 k. As can be seen, the petal thickness of the produced aluminum nitride nanoflower was 14 to 16 nm.
The microstructure analysis of the cross section of the porous aluminum nitride three-dimensional network skeleton obtained in example 1 is performed, and the result is shown in fig. 6, and fig. 6 is an SEM image of the cross section of the porous aluminum nitride three-dimensional network skeleton prepared in example 1 of the present invention. As can be seen from fig. 6, the cross section of the three-dimensional porous aluminum nitride network skeleton constructed by freezing according to the ice template law is distributed with vertically arranged columnar pores, which are pores left after the aluminum nitride nanoflowers are repelled and extruded to the outside of the ice crystals by the growth of the ice crystals in the freezing process, and then the ice crystals are sublimated in the freeze drying process. Moreover, after the short-time sintering in a discharge plasma system, no high polymer materials such as adhesive, dispersant and the like added in the process of preparing the nano aluminum nitride suspension exist in the aluminum nitride porous framework, so that the high purity of the aluminum nitride is ensured, and the thermal conductivity of the polymer-based composite material prepared subsequently is favorably improved.
The cross section of the aluminum nitride nanoflower/polymer composite obtained in example 1 is polished and then subjected to microstructure analysis, and the result is shown in fig. 7, and fig. 7 is an SEM image of the cross section of the aluminum nitride nanoflower/polymer composite prepared in example 1 of the present invention after polishing. As can be seen from fig. 7, after the three-dimensional porous aluminum nitride network framework is impregnated in the liquid epoxy resin mixture for 2 hours, the columnar pores in the framework are completely filled with the epoxy resin. After the composite material is heated and cured for the second time, the preformed three-dimensional porous aluminum nitride network frameworks are not damaged or are arranged in the vertical direction, so that the anisotropy of the epoxy resin-based composite material in the aspect of heat conductivity is caused, and the heat diffusion is facilitated by virtue of continuous network channels formed by the aluminum nitride nanoflowers in the vertical direction. The thermal conductivity of the aluminum nitride nanoflower/polymer composite material in the vertical direction can reach 2.26W/m.k measured by a laser heat dissipation method.
Example 2
1. Selecting 10g of aluminum powder (the particle size range of the aluminum powder is 2-3 mu m), putting the aluminum powder into 500g of 3.2 wt% sodium chloride solution, adjusting the pH value to 10 by using sodium hydroxide, corroding the solution by using an ultrasonic generator, setting the ultrasonic power to be 300W, and simultaneously stirring by using magnetic force (50 r/min);
2. after 5h of corrosion, carrying out suction filtration on the solution after reaction to obtain a white filter cake;
3. vacuum drying the white filter cake, crushing the dried filter cake, uniformly mixing the crushed filter cake and urea with ethanol, and drying, wherein the mass ratio of urea to ethanol is 2: 5; the mass ratio of the dried filter cake to the urea is 1: 4;
4. putting the mixed material obtained in the step (3) into a tubular furnace, heating to 900 ℃ at the speed of 100 ℃/min, supplying gas by adopting flowing nitrogen, setting the pressure of the nitrogen to be normal pressure and the flow to be 100sccm, reacting for 30min at 900 ℃, cooling after the reaction is finished, setting the cooling rate to be 20 ℃/min, and cooling to room temperature;
5. and after cooling, opening the furnace cover, taking out the crucible, then putting the crucible into a muffle furnace, keeping the temperature at 650 ℃ for 1h, and removing carbon to obtain a white substance, namely the nanoflower aluminum nitride.
6. Mixing the aluminum nitride nanoflower with tert-butyl alcohol, using citric acid as a dispersing agent, using carboxymethyl cellulose as an adhesive, adding CaO as a sintering aid to obtain a nano aluminum nitride suspension (the volume fraction is 15%; in the nano aluminum nitride suspension, the volume fraction of the sintering aid is 2%, the volume fraction of the dispersing agent is 2%, and the volume fraction of the adhesive is 2%), using liquid nitrogen as a cooling medium, performing directional freezing molding on the suspension at-80 ℃, putting the obtained sample in a freezing and drying box for 24h of freeze drying, putting the sample in a discharge plasma sintering furnace after drying, and performing high-temperature sintering at the high temperature of 800 ℃ for 5min to obtain a porous aluminum nitride three-dimensional network framework;
7. and (2) impregnating the porous aluminum nitride three-dimensional network framework and epoxy resin for 1h according to the volume ratio of 15: 100 under the vacuum condition, curing for 2h at 70 ℃, and curing for 2h at 130 ℃ to obtain the aluminum nitride nanoflower/polymer composite material. The thermal conductivity of the aluminum nitride nanoflower/polymer composite material in the vertical direction can reach 1.28W/m.k measured by a laser heat dissipation method.
Example 3
1. Selecting 15g of aluminum powder (the particle size range of the aluminum powder is 1-3 mu m), putting the aluminum powder into 500g of 2.5 wt% sodium chloride solution, adjusting the pH value to be 4 by adopting citric acid, corroding the solution by adopting an ultrasonic generator, setting the ultrasonic power to be 180W, and simultaneously stirring by adopting magnetic force (50 r/min);
2. after 6h of corrosion, carrying out suction filtration on the solution after reaction to obtain a white filter cake;
3. vacuum drying the white filter cake, crushing the dried filter cake, uniformly mixing the crushed filter cake and dicyandiamide with ethanol, and drying, wherein the mass ratio of dicyandiamide to ethanol is 1: 5; the mass ratio of the dried filter cake to the dicyandiamide is 1: 6;
4. putting the mixed material obtained in the step (3) into a tubular furnace, heating to 1000 ℃ at the speed of 7 ℃/min, supplying gas by adopting flowing nitrogen, setting the pressure of the nitrogen to be normal pressure and the flow to be 90sccm, reacting for 3 hours at 1000 ℃, cooling along with the furnace after the reaction is finished, and cooling to room temperature;
5. and after cooling, opening the furnace cover, taking out the crucible, then putting the crucible into a muffle furnace, and keeping the temperature at 600 ℃ for 2h to remove carbon, wherein a white substance is the nanoflower aluminum nitride after carbon removal.
6. Mixing the aluminum nitride nanoflower with tert-butyl alcohol, adding La by using sodium tartrate as a dispersing agent and carboxymethyl cellulose as a bonding agent2O3Using the nano aluminum nitride suspension as a sintering aid to obtain a nano aluminum nitride suspension (the volume fraction of the nano aluminum nitride suspension is 10%, the volume fraction of the sintering aid is 0.5%, the volume fraction of the dispersing agent is 3% and the volume fraction of the binding agent is 3%), using liquid nitrogen as a cooling medium to perform directional freezing and molding on the suspension at-80 ℃, placing an obtained sample in a freezing and drying box to perform freezing and drying for 24 hours, placing the sample in a discharge plasma sintering furnace after drying is completed, and performing high-temperature sintering at the high temperature of 1200 ℃ for 5min to obtain a porous aluminum nitride three-dimensional network framework;
7. and (3) impregnating the porous aluminum nitride three-dimensional network framework and epoxy resin for 1h according to the volume ratio of 10: 100 under the vacuum condition, curing for 2h at 80 ℃, and curing for 2h at 120 ℃ to obtain the aluminum nitride nanoflower/polymer composite material. The thermal conductivity of the aluminum nitride nanoflower/polymer composite material in the vertical direction can reach 0.80W/m.k measured by a laser heat dissipation method.
Example 4
1. Selecting 20g of aluminum powder (the particle size range of the aluminum powder is 1-2 mu m), putting the aluminum powder into 500g of 2.5 wt% sodium chloride solution, adjusting the pH value to 9 by using ammonia water, corroding the solution by using an ultrasonic generator, setting the ultrasonic power to be 180W, and simultaneously stirring by using magnetic force (50 r/min);
2. after 6h of corrosion, carrying out suction filtration on the solution after reaction to obtain a white filter cake;
3. vacuum drying the white filter cake, crushing the dried filter cake, uniformly mixing the crushed filter cake and ammonium chloride with ethanol, and drying, wherein the mass ratio of the ammonium chloride to the ethanol is 3: 5; the mass ratio of the dried filter cake to the ammonium chloride is 1: 4;
4. putting the mixed material obtained in the step (3) into a tubular furnace, heating to 1000 ℃ at a speed of 50 ℃/min, supplying gas by adopting flowing nitrogen, setting the pressure of the nitrogen to be normal pressure, setting the flow to be 100sccm, reacting for 1h at 1000 ℃, cooling along with the furnace after the reaction is finished, and cooling to room temperature;
5. and after cooling, opening the furnace cover, taking out the crucible, then putting the crucible into a muffle furnace, keeping the temperature at 650 ℃ for 2h, and removing carbon to obtain a white substance, namely the nanoflower aluminum nitride.
6. Mixing the aluminum nitride nanoflowers and camphene, adding YF (YF) by using potassium citrate as a dispersing agent and polyvinyl alcohol as an adhesive3Using the nano aluminum nitride suspension as a sintering aid to obtain a nano aluminum nitride suspension (the volume fraction of the nano aluminum nitride suspension is 30%, the volume fraction of a sintering aid is 1%, the volume fraction of a dispersing agent is 4% and the volume fraction of a binding agent is 4%), using liquid nitrogen as a cooling medium, carrying out directional freezing molding on the suspension at-80 ℃, putting an obtained sample in a freezing drying box for 24h freezing drying, putting the sample in a discharge plasma sintering furnace after drying is finished, and carrying out high-temperature sintering at the high temperature of 1100 ℃ for 5min to obtain a porous aluminum nitride three-dimensional network framework;
7. and (3) impregnating the porous aluminum nitride three-dimensional network framework and epoxy resin for 1h according to the volume ratio of 25: 100 under the vacuum condition, curing for 2h at 80 ℃, and curing for 2h at 110 ℃ to obtain the aluminum nitride nanoflower/polymer composite material. The thermal conductivity of the aluminum nitride nanoflower/polymer composite material in the vertical direction can reach 4.23W/m.k measured by a laser heat dissipation method.
Example 5
1. Selecting 25g of aluminum powder (the particle size range of the aluminum powder is 1-3 mu m), putting the aluminum powder particles into 500g of 2.5 wt% sodium chloride solution, adjusting the pH value to 5 by using nitric acid, corroding the solution by using an ultrasonic generator, setting the ultrasonic power to be 180W, and simultaneously stirring by using magnetic force (50 r/min);
2. after 6h of corrosion, carrying out suction filtration on the solution after reaction to obtain a white filter cake;
3. vacuum drying the white filter cake, crushing the dried filter cake, uniformly mixing the crushed filter cake and cyanamide with ethanol, and drying, wherein the mass ratio of the cyanamide to the ethanol is 1: 5; the mass ratio of the dried filter cake to the cyanamide is 1: 6;
4. putting the mixed material obtained in the step (3) into a tubular furnace, heating to 1000 ℃ at a speed of 5 ℃/min, supplying gas by adopting flowing nitrogen, setting the pressure of the nitrogen to be normal pressure, setting the flow to be 100sccm, reacting for 3 hours at 1000 ℃, cooling along with the furnace after the reaction is finished, and cooling to room temperature;
5. and after cooling, opening the furnace cover, taking out the crucible, then putting the crucible into a muffle furnace, keeping the temperature at 700 ℃ for 2h, and removing carbon to obtain a white substance, namely the nanoflower aluminum nitride.
6. Mixing the aluminum nitride nanoflower with tert-butyl alcohol, using citric acid as a dispersing agent, using polyvinyl alcohol as an adhesive, and adding Y2O3Using the suspension as a sintering aid to obtain a nano aluminum nitride suspension (the volume fraction is 40%, the volume fraction of the sintering aid in the nano aluminum nitride suspension is 3%, the volume fraction of the dispersing agent is 2% and the volume fraction of the binding agent is 2%), using liquid nitrogen as a cooling medium, carrying out directional freeze forming on the suspension at-80 ℃, putting the obtained sample in a freeze drying oven for 24h for freeze drying, putting the sample in the freeze drying oven after the drying is finished, and then putting the sample in the freeze drying ovenSintering at high temperature of 1000 ℃ for 5min in a discharge plasma sintering furnace to obtain a porous aluminum nitride three-dimensional network framework;
7. and (3) impregnating the porous aluminum nitride three-dimensional network framework and epoxy resin for 1h according to the volume ratio of 40: 100 under the vacuum condition, curing for 2h at 80 ℃, and curing for 2h at 120 ℃ to obtain the aluminum nitride nanoflower/polymer composite material. The thermal conductivity of the aluminum nitride nanoflower/polymer composite material in the vertical direction can reach 6.91W/m.k measured by a laser heat dissipation method.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (13)
1. A preparation method of an aluminum nitride nanoflower/polymer composite material comprises the following steps:
A) uniformly mixing aluminum powder and a salt solution, and performing ultrasonic cavitation corrosion on the mixed liquid;
B) carrying out suction filtration on the solution obtained in the step A) to obtain a filter cake;
C) crushing the filter cake, uniformly mixing the filter cake with a solid nitrogen source, and performing a nitridation reaction in a nitrogen-containing atmosphere;
D) decarbonizing the product after the nitridation reaction to obtain the aluminum nitride nanoflower;
E) uniformly mixing the aluminum nitride nanoflower, the sintering aid and the additive in a solvent to form a suspension, performing directional freeze forming, freeze drying, and sintering to obtain a porous aluminum nitride three-dimensional network framework;
F) and (3) under the vacuum condition, impregnating resin into the porous aluminum nitride three-dimensional network framework, and then curing to obtain the aluminum nitride nanoflower/polymer composite material.
2. The method according to claim 1, wherein in the step a), the salt solution includes at least one of a sodium chloride solution, a potassium chloride solution, a calcium chloride solution, a sodium nitrate solution, a potassium nitrate solution, a sodium sulfate solution, and a potassium sulfate solution;
the mass concentration of the salt solution is 2.5-5%.
3. The preparation method of claim 1, wherein in the step A), the mass ratio of the aluminum powder to the salt solution is 1-10: 100;
the pH value of the mixed material liquid is 4-10;
the pH value of the mixed feed liquid is adjusted by a chemical reagent;
the chemical reagent comprises at least one of hydrochloric acid, acetic acid, citric acid, nitric acid, sulfuric acid, ammonia water, ammonium chloride, sodium hydroxide and potassium hydroxide;
the ultrasonic power of the ultrasonic cavitation corrosion is 180-500W, and the time is 1-6 h.
4. The method according to claim 1, wherein in step C), the solid nitrogen source comprises at least one of urea, cyanamide, dicyandiamide, melamine, and ammonium chloride;
the mass ratio of the filter cake to the solid nitrogen source is 1: 1-6;
the uniformly mixed liquid medium is ethanol;
the mass ratio of the solid nitrogen source to the ethanol is 1-3: 5.
5. The production method according to claim 1, wherein in step C), the gas forming the nitrogen-containing atmosphere includes at least one of nitrogen gas and ammonia gas;
the gas flow rate for forming the nitrogen-containing atmosphere is 90-100 sccm;
the temperature of the nitridation reaction is 800-1000 ℃, and the time is 30-180 min;
the nitridation reaction is carried out at normal pressure.
6. The method according to claim 1, wherein the temperature for carbon removal in step D) is 600-700 ℃ for 60-120 min.
7. The method according to claim 1, wherein in step E), the sintering aid is CaF2、Y2O3、CaO、La2O3And YF3At least one of;
in the nano aluminum nitride suspension, the volume fraction of the sintering aid is 0.5-5%.
8. The method according to claim 1, wherein in step E), the additives in the raw materials for preparing the suspension include a dispersant and a binder;
the dispersing agent is at least one of citric acid, sodium tartrate and potassium citrate, and the binder is at least one of sodium carboxymethyl cellulose and polyvinyl alcohol.
9. The method of claim 1, wherein in step E), the solvent comprises at least one of deionized water, t-butanol, and camphene;
in the suspension, the volume fraction of the nano aluminum nitride is 10-40%.
10. The preparation method according to claim 1, wherein the temperature of the directional freeze-forming in the step E) is-80 to-120 ℃;
the sintering temperature is 800-1300 ℃, and the sintering time is 5-120 min.
11. The method according to claim 1, wherein in step F), the resin comprises at least one of a phenol resin and an epoxy resin;
the volume ratio of the porous aluminum nitride three-dimensional network framework to the resin is 5-50: 100;
the vacuum infiltration time is 1-2 h; the vacuum degree is required to be less than 10-1Pa。
12. The method according to claim 1, wherein in step F), the curing comprises:
curing for 1-2 h at 70-90 ℃, and then curing for 1-2 h at 110-130 ℃.
13. The aluminum nitride nanoflower/polymer composite material prepared by the preparation method of any one of claims 1 to 11.
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