CN109608699B - Micro-nano composite particle and preparation process and device thereof - Google Patents

Micro-nano composite particle and preparation process and device thereof Download PDF

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CN109608699B
CN109608699B CN201811605490.2A CN201811605490A CN109608699B CN 109608699 B CN109608699 B CN 109608699B CN 201811605490 A CN201811605490 A CN 201811605490A CN 109608699 B CN109608699 B CN 109608699B
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CN109608699A (en
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王友善
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Harbin Taiming Technology Co ltd
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Taiming Technology Co ltd Harbin Institute Of Technology
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The invention discloses a micro-nano composite particle, wherein nano and below-nano scale particles smaller than the diameter of a micropore of a porous micro-nano particle are inserted into the porous micro-nano particle to form a three-dimensional porous and/or thorn-shaped micro-nano composite particle; the single-hole embedding amount of the three-dimensional porous and/or spiny micro-nano composite particles is 1-100% of the hole volume; meanwhile, the invention also discloses six preparation processes of the micro-nano composite particles, which comprise a liquid phase method insertion method, a high-speed airflow kinetic energy insertion method, a high-temperature reconstruction insertion method, a mechanical load insertion method, a vacuum negative pressure insertion method and a multi-rotor physical continuous modification method. The rubber has better reinforcing effect in rubber and products thereof, shows excellent mechanical property, and shows synergistic improvement effect of reinforcing, low heat generation and wet skid resistance in tire rubber.

Description

Micro-nano composite particle and preparation process and device thereof
Technical Field
The invention relates to the technical field of novel materials, in particular to novel composite particles and a preparation process and a preparation device thereof.
Background
At present, micro-nano-scale (10-1000nm) particles play an important role in the fields of modern industry, medicine, bioengineering and the like. Obvious surface interaction exists between particles and between the particles and a polymer matrix, so that the performance of the material can be improved to a certain degree by selecting proper particles and a polymer resin matrix and using a certain material compounding process.
The morphology of the particles directly influences the properties of the material, such as cohesiveness, mechanical strength, transparency and the like, and is directly related to the compatibility of the filler and the matrix in the composite material and the effective dispersibility of the nanoparticles. Most research has therefore focused on obtaining homogeneous mixtures, for example by chemically or physically modifying the particle surface to alter its interaction with the matrix.
Good dispersion of monodisperse particles requires deaggregation of the inorganic fine powder to the most primitive, most primary, smallest-scale particle morphology, otherwise a polydisperse particle distribution morphology will be present that does not achieve the material properties of the monodisperse particles. Actually, after the monodisperse micro-nano particles are synthesized, a very stable aggregate form is often generated due to drying processes and other reasons. The interparticle junctions often act as "nucleating agents" for random powders to form extremely stable, large-scale structures. This interparticle interaction is partially re-dispersed by certain external forces, such as stirring, milling, ultrasound, etc. However, when the particle size is 500nm or less, the polishing or the external force requires a longer polishing time and higher polishing strength, which easily introduces foreign substances and unpredictable phase transition (aggregation of material instability). For nanoparticles, small scale particles are less stable than large scale particles due to their low surface energy, and they tend to re-aggregate again. However, in general, external forces can still cause good dispersion of the particles by manipulating the chemical composition of the dispersion, such as adding surfactants, changing the pH of the matrix, ionic strength, and adding certain co-solvents, and ultimately changing the nanoparticle interactions, including van der Waals forces, electrostatic double layer and rigid interactions. However, this also causes the application of micro-nano particles to be limited.
The function of the highly dispersed micro-nano particles is in certain correlation with the concentration thereof. The use of lower filler content can reduce the reduction of binding power caused by the filler; at the same time, the filler is dispersed more uniformly in the matrix. In general, the weight fraction of filler should be less than 10%. However, the amount of the filler is too small to exert its effect. Therefore, many researchers have studied the aggregation or multidimensional assembly structure of inorganic fillers, such as particle crystallites, glassy aggregates, mixed with high molecular materials. Research shows that the structures have more excellent value on the property improvement of the material. For example, the glassy aggregate of the surface-modified micro-nano particle silicon dioxide has a glass transition temperature in a room temperature range, so that the material has extremely strong bonding performance at a specific temperature; this property has been used to develop many excellent products and put them on the market. Another material that has been more studied is a fibrous material with a bead chain structure; or nano particle reinforced fiber material, which may be prepared through self-assembling process, micro phase reversal process, sea island template process, electric spinning process, etc. Compared with monodisperse particles, the material has greatly improved mechanical properties even at lower use level. Researchers find that materials with high strength, light weight and different properties can be manufactured by weaving fiber materials containing nano particles into a network, and the fiber materials have important application values in the fields of filtering membranes, sensors, microelectronics, optical elements, biomedicine, safety protection and the like.
Patent CN2016101110205 discloses a composite graphene gel for rubber filler and a preparation method thereof, wherein the obtained graphene is dispersed in a porous starch solution, so that the graphene is uniformly distributed in pores of the porous starch, the stability of the graphene is improved, the aggregation of the graphene is prevented, and the graphene is directly added into a rubber base material as a filler, and the graphene gel has good dispersibility and is not easy to aggregate; patent CN2017110853377 also discloses a modified carbon black composite material and a preparation method and application thereof, inorganic nano materials are tightly attached to the rugged surface of a carbon black microcrystal area and/or embedded into micropores and mesopores of carbon black, the reinforcing performance of the modified carbon black composite material in rubber materials is improved, the two patents select porous starch and carbon black as base materials respectively, the selection of the base materials substantially plays a decisive role in the dispersion performance of composite particles, such as the performances on porosity, incompressibility and chemical stability, the adsorption performance and the surface energy of the final base particles are directly influenced, and further, certain repulsion can exist between the composite particles at a longer molecular distance by embedding different protruding functional groups, the exponential increase of the agglomeration effect caused by too close particles is avoided, the macroscopic expression is high dispersibility, the carbon black composite material has high strength, and the composite material has high strength and good dispersion performance, The composite graphene gel is not easy to agglomerate, the porous starch is used as a substrate material, the porous starch acts on raw starch at a temperature lower than the gelatinization temperature to form a porous cellular product, and the porous cellular product has common porosity, incompressibility and chemical stability, particularly chemical stability; the carbon black is excellent in porosity and chemical stability, but in the carbon black, the arrangement of carbon atoms is similar to that of graphite, a hexagonal plane is formed, generally 3-5 layers form a microcrystal, and the structure is unstable under the action of external force due to the layered structure. For the above reasons, there is room for further improvement in the properties of high dispersibility and less tendency to agglomerate of the two types of composite particles formed as described above.
Disclosure of Invention
Aiming at the defects existing in the prior background, the composite particles have good dispersibility, are not easy to agglomerate, have good reinforcing effect in rubber and products thereof, show excellent mechanical property, and show synergistic improvement effect of reinforcing, low heat generation and wet skid resistance in tire rubber.
Meanwhile, the invention also provides a preparation process of various composite particles, the preparation method is easy to operate, and the composite particles obtained by each method comprise three-dimensional porous micro-nano particles and three-dimensional porous spiny micro-nano particles.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a composite particle is characterized in that nano and below-nano particles smaller than the diameter of a micropore of a porous micro-nano particle are inserted into the porous micro-nano particle to form a three-dimensional porous and/or thorn-shaped micro-nano composite particle.
Optionally, the single-hole embedding amount of the three-dimensional porous and/or spiny micro-nano composite particles is 5-100% of the pore volume, and the BET nitrogen adsorption specific surface area is 30m2/g~350m2/g。
Optionally, the single-hole embedding amount of the three-dimensional porous and/or spiny micro-nano composite particles is 50-100% of the pore volume,
optionally, the porous micro-nano particles are spherical, ellipsoidal, rhombohedral or irregular.
Optionally, the particle size of the porous micro-nano particle is 100 nm-100 μm, the pore diameter of the porous structure is 1 nm-500 nm, the pore depth is 2 nm-500 nm, the number of pores is 5000-3 hundred million/g, and the BET specific surface area is 0.3-300 m2The pH value is 6-8.
Optionally, the porous micro-nano particles are silicon dioxide or calcium carbonate or composite porous micro-nano particles of silicon dioxide and/or calcium carbonate and aluminum oxide.
Optionally, the porous micro-nano particles comprise 20-95 wt% of silicon dioxide or calcium carbonate and 5-80 wt% of aluminum oxide.
Optionally, the porous micro-nano particles comprise 30-80 wt% of silicon dioxide and 20-70 wt% of aluminum oxide.
Optionally, the nano and sub-nano scale particles are one or more of nano zinc oxide, nano copper oxide, small molecule functional materials, natural rubber polymer materials, synthetic rubber polymer materials, carbon nanotubes, graphene, carbon black and white carbon black.
The invention also provides a first preparation process of the composite particles, which comprises the steps of placing the porous micro-nano particles and nano and below-nano particles in a liquid-phase polar dispersion system, wherein the pH value of a solution is 6-8, the temperature is 50-80 ℃, an electric field of 100-8000V/m is added, the stirring time is 0.1-2 hours, and the stirring speed is 30-200 r/min.
Optionally, the input weight ratio of the porous micro-nano particles to nano and sub-nano particles is 20: 1-1: 1.
Optionally, the nano-scale and sub-nano-scale particles are pre-generated or generated in situ in a liquid phase reaction.
Optionally, the raw material in the in-situ generation is one or more of zinc chloride, zinc sulfate, zinc nitrate, copper chloride, copper sulfate, copper nitrate, sodium silicate, silicone, ferric chloride and ferric nitrate.
Optionally, the porous micro-nano particles comprise 20-95 wt% of silicon dioxide or calcium carbonate and 5-80 wt% of aluminum oxide.
Optionally, the porous micro-nano particles comprise 30-80 wt% of silicon dioxide and 20-70 wt% of aluminum oxide.
Optionally, the porous micro-nano particles are obtained by alternately coating a silicon dioxide film layer and an aluminum oxide film layer on the core body to form a porous composite layer and then crushing and screening the porous composite layer.
Alternatively, the silica or calcium carbonate is derived from a silicon/calcium containing material comprising: alunite, rice hull ash, straw ash, montmorillonite, talc, yellow clay, mica, wollastonite, bauxite, protein shale, diatomaceous earth, diatom shale, opal.
Optionally, the solvent used in the liquid-phase polar dispersion system is one or more of water, methanol, ethanol, glycerol, trifluoroethanol, formic acid, triethanolamine, acetic acid, acetone, ethyl acetate, tetrahydrofuran, N-methylpyrrolidone, diethyl ether, propylene oxide, dichloromethane, trichloromethane and triethanolamine.
The invention also provides a second preparation process of the composite particles, which is to embed nano and below-nano particles into the porous micro-nano particles under the action of high-speed airflow kinetic energy.
Optionally, the porous micro-nano particles and the preformed nano and below-nano scale particles in the weight ratio of 20: 1-1: 1 are mixed in advance, blown in or dispersed and synchronously fed, the air flow speed is 300-1200 m/s, the temperature is 80-200 ℃, and the pressure is 100-1000 KPa.
The device is one of a horizontal ring type air flow mill, a circulating pipe type air flow mill, a double-jet type air flow mill, an impact plate type air flow mill or a fluidized bed reverse air flow mill.
According to the third preparation process of the composite particles, the particles with the size of nanometer or below nanometer are embedded into micropores of the porous micro-nano particles at the high temperature of 500-3500 ℃.
Optionally, the nano-and sub-nano-scale particles are pre-formed or generated in situ in a high temperature reaction.
Optionally, the method comprises the following steps:
in the temperature-rising reaction stage, the airflow speed at the tail end is 5-15 m/s, and the temperature is 500-2000 ℃;
an airflow acceleration stage, wherein the airflow speed is 20-100 m/s, and the temperature is 600-3500 ℃;
and in the reaction stage, the temperature at the outlet of the reaction section is lower than 800 ℃.
Optionally, the reaction reconstruction time of the in-situ production reaction raw material of the nano and below-nano particles in the reaction stage is 0.05 s-5 s.
Optionally, the high temperature reaction furnace comprises: the temperature raising section part, the gas flow accelerating section part, the reaction section part and the collecting section part are provided with one or more feeding dispersing devices.
The invention provides a preparation device of the third preparation method of the composite particles, wherein a weight-loss feeder is arranged as a feeding dispersing device at a temperature rising section part; the feeding dispersing devices in the gas flow accelerating section part, the reaction section part and the collecting section part are atomizing dispersing devices.
Optionally, the distance between the nozzle of the atomization dispersion device and the center line of the high-temperature reaction furnace is 0-D/2, D is the diameter of the cavity where the nozzle is located, the distance between the atomization dispersion device arranged on the airflow acceleration section part and the inlet of the airflow acceleration section part is 0-L, the distance between the atomization dispersion device arranged on the reaction section part and the inlet of the reaction section part is 0-L, and L is the length of the cavity where the nozzle is located.
Optionally, the diameter of the nozzle orifice of the atomization and dispersion device is 0.5 mm-5 mm.
Optionally, the nozzle of the atomization and dispersion device sprays in a reverse airflow at an angle of 0-90 degrees.
Optionally, the length-diameter ratio of the temperature rising section part is 1: 1-5: 1, the length-diameter ratio of the airflow accelerating section part is 5: 1-10: 1, and the length-diameter ratio of the reaction section part is 2: 1-15: 1.
According to the fourth preparation process of the composite particles, the preformed nano particles and particles with the size below the nano size are embedded into micropores of the porous micro-nano particles in a grinding mode.
Optionally, a mechanical load embedding device is adopted for continuous or step-by-step feeding, the grinding temperature is 50-100 ℃, and the rotating speed is 0.5-5 r/s.
Optionally, the discharging mouth winnowing classifier of the mechanical load embedding device has a rotor frequency of 10 Hz-50 Hz and a wind speed of 10 m/s-200 m/s.
According to the fifth preparation process of the composite particles, the preformed nano particles and particles with the size below the nano size are embedded into micropores of the porous micro-nano particles through vacuum negative pressure acting force.
Optionally, the treatment is carried out for 4 to 48 hours under the environment with the vacuum degree of-1000 KPa to 0KPa and the temperature of 100 to 300 ℃, and the rotating speed is 0.5 to 5 revolutions per second.
Alternatively, the vacuum negative pressure embedment device is one of a ribbon type vacuum mixer, a double star vacuum mixer, a planetary vacuum mixer, a vacuum disperser, and an all negative pressure mixer.
According to the sixth preparation process of the composite particles, the preformed nano and below-nano particles are embedded into micropores of the porous micro-nano particles through multi-rotor physical continuous modification.
Optionally, the treatment time is 4-48 hours, the vacuum degree in the vacuum negative pressure ball milling chamber is-1000 KPa-0 KPa, the rotation speed of the ball milling chamber is 0.5-5 r/s, the temperature is 50-300 ℃, the air flow speed in the airflow milling chamber is 300-1200 m/s, the rotation speed is 0.5-5 r/s, the temperature is 80-200 ℃, and the pressure is 100 KPa-1000 KPa.
Optionally, the multi-rotor physical continuous modification device comprises two or more mixing methods of mechanical ball milling, vacuum negative pressure mixing and high-speed gas flow mixing.
The invention also comprises the application of the composite particles in the technical fields of chemical rubber, medicine manufacturing of sustained release agents and the like.
The technical scheme of the invention has the following advantages:
the embodiment of the invention provides a composite particle, which takes a porous micro-nano particle as a matrix, and embeds nano and below-nano scale particles into micropores of the porous micro-nano particle in a physical or chemical (including an in-situ generation method) mode to form a three-dimensional porous and/or thorn-shaped micro-nano composite particle; the three-dimensional porous and/or spiny micro-nano composite particles are composed of three composite particle states as shown in figure 1, nano and below-nano scale particles are inserted into micropores of the porous micro-nano particles, the single-pore embedding amount is 50-100% of the pore volume, namely most of the nano and below-nano scale particlesInserted separately or completely and in a thorn shape; when the composite particles are prepared, the good dispersibility of the micro-nano monodisperse particles depends on the elimination of the interaction force among the monodisperse particles, such as van der Waals force and the acting force of a nucleating agent at the connection points between particles, and cannot cause unpredictable phase transformation of the nanoparticles due to long-time external stirring, namely the unstable aggregation of the material, at the moment, the selection of the substrate material has important influence on the adsorption embedding volume and the dispersibility of the prepared composite particles, the substrate material during the preparation of the composite particles selects silicon dioxide or calcium carbonate or porous micro-nano composite particles formed by the silicon dioxide or the calcium carbonate and aluminum oxide, further parameters of the porous micro-nano particles used as the substrate material are that the particle size is 100 nm-100 mu m, the pore diameter of the porous structure is 1 nm-500 nm, the pore depth is 2 nm-500 nm, the number of pores is 5000-3 hundred million/g, and the BET specific surface area is 0.3-300 m.2The pH value is 6-8, porous micro-nano composite particles formed by silicon dioxide or calcium carbonate and aluminum oxide are used as substrate materials, the prepared substrate particles have porosity, incompressibility and chemical stability, the porosity of the porous micro-nano particles can reach over 90 percent, which is 5000-6000 times of that of activated carbon, and is just the outstanding molecular sieve structure, so that the porous micro-nano composite particles have extremely strong physical adsorption performance; meanwhile, the obtained composite particle has excellent space mechanical properties, as shown in fig. 4 and 5, which are three-dimensional representations of the space mechanical properties of the composite particle, the composite particle has a plurality of surface polarities of different materials due to the fact that a large amount of other materials are embedded in a porous structure of the surface, so that the intermolecular force of the polymer can be strengthened under various conditions, and when the composite particle is used as a reinforcing agent, the reinforcing function under different working environments with different temperatures and pressures can be provided for the rubber polymer, so that the wear resistance, the strength and the wet skid resistance are improved at the same time. The surface energy of the original porous silica or calcium carbonate can be increased by adding the aluminum oxide. Taking zinc oxide nano-columns as an example: the quantity of the nano zinc oxide columns which can be embedded by the pure porous silicon dioxide substrate is only 40% of that of the modified substrate (added with the aluminum oxide), and the stability of the space three-dimensional structure formed by the composite particles is also greatly reduced without adding the aluminum oxide. With conventional reinforcing particlesDifferent materials are adopted, and different functional groups which are embedded into the surfaces of the composite particles are protruded, so that certain repulsion can exist between the composite particles at a longer molecular distance, the exponential increase of an agglomeration effect caused by too close distance between the particles is prevented, and the macroscopic expression is high in dispersity and difficult to agglomerate.
The composite particles can construct a stable space network structure in a polymer, and the novel composite particles are obtained through a plurality of tests, have good dispersibility in the polymer, are not easy to agglomerate, particularly have a good reinforcing effect in rubber and products thereof, and have the synergistic improvement effects of reinforcement, low heat generation and wet skid resistance in tire rubber.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic diagram of a micro-nano particle of the invention partially, completely embedded and forming a thorn-shaped micro-nano composite particle;
FIG. 2 shows scanning electron micrographs of 10000x and 100000x of three-dimensional porous/spiny micro-nano composite particles prepared by the invention;
FIG. 3 is a schematic diagram of a high-temperature reaction furnace production device used for preparing three-dimensional porous/spiny micro-nano composite particles according to the invention;
wherein, 1-7 are 7 feed inlets at different positions of a heating reaction section, an airflow acceleration section, a reaction section and a collection section of the high-temperature reaction furnace;
a-a temperature-rising reaction section; b-an airflow acceleration section; c-reaction section; d-a collection section; e-a cooler.
Fig. 4 and 5 are three-dimensional graphical representations of the mechanical properties of the composite particles of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. 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.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
According to the composite particle provided by the embodiment, nanoparticles smaller than the diameter of micropores of the porous micro-nano particle are inserted into the porous micro-nano particle to form a three-dimensional porous and/or spiny micro-nano composite particle, the single-hole embedding amount of the three-dimensional porous and/or spiny micro-nano composite particle is 5-100% of the pore volume, and the BET nitrogen adsorption specific surface area is 30m2/g~350m2(g), referring to fig. 1, the composite particle state is formed, that is, the nanoparticle may not be inserted or partially inserted or completely inserted and form a thorn shape, and even a certain degree of nanoparticles are attached to the surface of the substrate, and fig. 2 is a scanning electron micrograph of 10000x and 100000x three-dimensional porous/thorn-shaped micro-nano composite particles.
Specifically, the matrix of the composite particle, i.e., the porous micro-nano particle, may be silica or calcium carbonate, or a mixture of silica and/or calcium carbonate and alumina; the particle size of the porous micro-nano particles is 100 nm-100 mu m, the pore diameter of the porous structure is 1 nm-500 nm, the pore depth is 2 nm-500 nm, the number of pores is 5000-3 hundred million/g, and the specific surface area of a BET method is 0.3-300 m2/g,The porous micro-nano particles are spherical, ellipsoidal, rhombohedral or other irregular shapes.
Specifically, the nano-sized and sub-nano-sized particles are one or more of nano-zinc oxide, nano-copper oxide, a small molecular functional material, a natural rubber polymer material, a synthetic rubber polymer material, a carbon nanotube, graphene, carbon black and white carbon black, wherein the small molecular functional material is a functional molecule with a molecular weight of less than 1000 daltons, and is generally a small molecular group of water, aglycone, flavochrome, aglycone, alkaloid and the like.
Examples 2 to 5 below are first preparation processes of composite particles.
Example 2
The embodiment provides a preparation process of the composite particle, which comprises the following steps:
s1, dissolving zinc nitrate hexahydrate in deionized water to form a zinc nitrate solution with the concentration of 10g/ml, and stirring for 2 minutes for later use;
s2, mixing the silicon dioxide and aluminum oxide porous micro-nano composite substrate with methanol to obtain a solution of porous micro-nano particles, and placing the solution in an ultrasonic instrument for ultrasonic dispersion, wherein the ultrasonic frequency is 60Hz, the temperature is below 50 ℃, and the ultrasonic time is 0.1h to obtain a porous micro-nano particle suspension liquid with the concentration of 20 g/ml; in the embodiment, the composite substrate is prepared by 20% of silicon dioxide and 80% of aluminum oxide in parts by weight;
s3, dissolving ammonia water into deionized water to prepare ammonia water with the concentration of 30% for later use;
s4, mixing the porous micro-nano particle suspension prepared in the S2 with the zinc nitrate solution prepared in the S1 according to a mass ratio of 1:1, adding an external fixed or rotating electric field of 100V/m, rotating the rotating speed of the rotating electric field by 10 r/min, and magnetically stirring for 0.1 hour at the rotating speed of 200 r/min;
s5, dropwise adding the ammonia water solution prepared in the step S3 into the mixed solution, controlling the pH within the range of 6, keeping the temperature of 50 ℃ for constant-temperature water bath heating, and stirring for about 1 hour;
s6, after the reaction is finished, carrying out suction filtration, washing with distilled water for 1 time, and washing with absolute ethyl alcohol for 2 times;
s7, drying the washed powder in a 50 ℃ oven for 8h to obtain three-dimensional porous/spine-shaped composite particle powder.
The three-dimensional porous/spiny micro-nano composite particles produced by the preparation method have a particle size of 331m measured by a BET nitrogen adsorption method2The specific surface area in terms of/g and the scanning electron microscope test photograph are shown in FIG. 2.
Example 3
The embodiment provides a preparation process of the composite particle, which comprises the following steps:
s1, dissolving copper sulfate in deionized water to form a copper sulfate solution with the concentration of 20g/ml, and stirring for 2 minutes for later use;
s2, mixing the calcium carbonate and aluminum oxide porous micro-nano composite substrate with ethanol to obtain a solution of porous micro-nano particles, and placing the solution in an ultrasonic instrument for ultrasonic dispersion, wherein the ultrasonic frequency is 30Hz, the temperature is below 80 ℃, and the ultrasonic time is 2 hours to obtain a porous micro-nano particle suspension liquid with the concentration of 1 g/ml; in the embodiment, the composite substrate is prepared by 95% of calcium carbonate and 5% of aluminum oxide in parts by weight;
s3, dissolving urea in deionized water, and preparing a buffer solution with the concentration of 50% for later use (ammonium radicals and copper ions can generate a complex compound which cannot be precipitated, so that the buffer solution is prepared by urea);
s4, mixing the porous micro-nano particle suspension prepared in the S2 with the copper sulfate solution prepared in the S1 according to a mass ratio of 20:1, adding an external fixed or rotating electric field with the rotating speed of 50 r/min and magnetic stirring for 2 hours at the rotating speed of 30 r/min, wherein the external fixed or rotating electric field is 8000V/m;
s5, dropwise adding the buffer solution prepared in the step S3 into the mixed solution, controlling the pH value within 8, keeping the temperature of 80 ℃ for heating in a constant-temperature water bath, and stirring for about 1 hour;
s6, after the reaction is finished, carrying out suction filtration, washing with distilled water for 5 times, and washing with absolute ethyl alcohol for 1 time;
s7, drying the washed powder in a 70 ℃ oven for 4h to obtain three-dimensional porous/spine-shaped composite particle powder.
The three-dimensional porous/spiny micro-nano composite particles produced by the preparation method have the size of 310m through the test of a BET nitrogen adsorption method2In terms of/gSpecific surface area.
Example 4
The embodiment provides a preparation process of the composite particle, which comprises the following steps:
s1, dissolving zinc sulfate in deionized water to form a zinc sulfate solution of 15g/ml, and stirring for 1 minute for later use;
s2, mixing a porous micro-nano particle solution obtained by mixing a silicon dioxide and aluminum oxide porous micro-nano composite substrate with ethanol and a porous micro-nano particle solution obtained by mixing ethanol, and placing the porous micro-nano particle solution in an ultrasonic instrument for ultrasonic dispersion, wherein the ultrasonic frequency is 50Hz, the temperature is below 60 ℃, and the ultrasonic time is 2 hours, so that a porous micro-nano particle suspension with the concentration of 12g/ml is obtained; in the embodiment, the composite substrate is prepared by 30% of silicon dioxide and 70% of aluminum oxide in parts by weight;
s3, dissolving ammonia water into deionized water to prepare ammonia water with the concentration of 40% for later use;
s4, mixing the porous micro-nano particle suspension prepared in the S2 with the zinc sulfate solution prepared in the S1 according to a mass ratio of 13: 1, adding 5000V/m external fixed or rotating electric field, rotating at 30 r/min for magnetic stirring for 1.5h at 100 r/min;
s5, dropwise adding the ammonia water solution prepared in the step S3 into the mixed solution, controlling the pH within the range of 7, keeping the temperature of 60 ℃ for constant-temperature water bath heating, and stirring for about 1.5 hours;
s6, after the reaction is finished, carrying out suction filtration, washing with distilled water for 3 times, and washing with absolute ethyl alcohol for 2 times;
s7, drying the washed powder in a 60 ℃ oven for 4h to obtain three-dimensional porous/spine-shaped composite particle powder.
The three-dimensional porous/spiny micro-nano composite particle produced by the preparation method has the size of 325m after being tested by a BET nitrogen adsorption method2Specific surface area in g.
Example 5
The embodiment provides a preparation process of the composite particle, which comprises the following steps:
s1, mixing porous micro-nano particles obtained by mixing a silicon dioxide and aluminum oxide porous micro-nano composite substrate with ethanol with isopropanol, and placing the mixture in an ultrasonic instrument for ultrasonic dispersion, wherein the ultrasonic frequency is 40Hz, the temperature is below 50 ℃, and the ultrasonic time is 1h to obtain a porous micro-nano particle suspension liquid with the concentration of 13 g/ml; in the embodiment, the composite substrate is prepared by 80% of silicon dioxide and 20% of aluminum oxide in parts by weight;
s2, mixing nano copper oxide according to the mass ratio of 1: 10, adding the solution into polystyrene sodium sulfonate serving as a dispersing agent, mixing the solution at room temperature, and magnetically stirring for 1 hour to obtain uniformly dispersed nano copper oxide suspension;
s3, mixing the porous micro-nano particle suspension and the nano copper oxide suspension in a ratio of 18: 1, adding 5000V/m of external fixed or rotating electric field, stirring for 2 hours at the rotating speed of the rotating electric field of 35 revolutions per minute;
s4, carrying out suction filtration on the solution, washing the solution for 3 times by using distilled water, and washing the solution for 2 times by using absolute ethyl alcohol.
S5, drying the washed powder in a 70 ℃ oven for 5 hours to obtain three-dimensional porous/spine-shaped composite particle powder.
The particles of example 2 to example 4, which are of nanometer or even smaller size, are all produced by the liquid phase original method, or the particles of nanometer or even smaller size, which are previously molded and mixed, may be inserted by the liquid phase method, as in example 5; the prepared nano particle solution can be one or more of zinc chloride, copper nitrate, sodium silicate and silicone besides zinc nitrate, copper sulfate and zinc sulfate; the solvent can be one or more of trifluoroethanol, formic acid, triethanolamine, acetic acid, acetone, ethyl acetate, tetrahydrofuran, N-methyl pyrrolidone, diethyl ether, propylene oxide, dichloromethane, chloroform, and triethanolamine in addition to methanol and ethanol; the ammonia water may also be one or more of urea, sodium bicarbonate, sodium carbonate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, barbital sodium, and borax.
The three-dimensional porous/thorn-shaped micro-nano composite particles prepared by the method have three structures, and because the inner surface of the hole is far larger than the surface, the zinc oxide nano particles generated in the liquid phase reaction can be subjected to polar diffusionThe single-hole embedding amount of the porous micro-nano particles is 5-100% of the total volume of the holes, as shown in figure 1, the generated three-dimensional porous/thorn-shaped micro-nano composite particles can have 3 structures, as shown in figure 1, micro-holes are partially embedded into the micro-nano particles, as shown in figure 1, 2, the micro-holes are completely filled with the micro-nano particles, or as shown in figures 1, 3 and 4, zinc oxide particles continue to grow and are stacked to form the thorn-shaped micro-nano composite particles. The test shows that the three-dimensional porous/spiny micro-nano composite particles produced by the preparation method have 345m after being tested by a BET nitrogen adsorption method2The specific surface area of the zinc oxide particles is/g, which shows that most of the zinc oxide particles are partially or completely embedded into the porous micro-nano particles.
Examples 6 to 8 below are second preparation processes of composite particles.
Example 6
The embodiment provides a second preparation process of the composite particle, namely a high-speed airflow kinetic energy embedding method, which specifically comprises the following steps:
s1, adding diatomite ore into a hammer crusher, and crushing to 100-mesh ore sand;
s2, putting the ore sand into a Raymond mill for grinding, and carrying out vacuum mechanical ball milling for 4 hours at the grinding temperature of 80 ℃ and the rotating speed of 2 revolutions per second, wherein the grain size after grinding is less than 150 mu m;
s4, respectively preparing the silicon dioxide particles obtained after grinding and aluminum oxide powder into spraying liquid, and alternately spraying the spraying liquid on the core body layer by layer to form a porous composite layer, and then crushing and screening to obtain porous micro-nano particles; the composite substrate is prepared by 50 percent of silicon dioxide and 50 percent of aluminum oxide in parts by weight;
s5, mixing the ground powder and the carbon nano tube in a ratio of 1:1, grinding for 12 hours and 300m/s in a double-jet type jet mill at the temperature of 200 ℃, the pressure of 100KPa and the rotating speed of 1 r/s to prepare powder with the particle size of 10-20 mu m, wherein the obtained powder part comprises three-dimensional porous/spiny micro-nano composite particles.
When the three-dimensional porous/spiny micro-nano composite particles produced by the preparation method are applied to tread rubber, the performance is improved as shown in the table. The three-dimensional porous/thorn-shaped micro-nano composite particles with the mass fraction of 20% are added into the standard tread rubber, so that Tb property of the original tread rubber at 151 ℃ is improved by 9%, tg property at 60 ℃ is optimized by 38%, compression temperature rise is reduced by 19%, Akron abrasion is reduced by 4%, and anti-wet skid property under a water film condition of 1mm is improved by 45%.
Table: tread rubber application test data
Figure BDA0001923486010000161
Example 7
The embodiment provides a second preparation process of the composite particle, namely a high-speed airflow kinetic energy embedding method, which specifically comprises the following steps:
s1, adding yellow clay ore into a hammer crusher, and crushing to 200-mesh ore sand;
s2, putting the ore sand into a Raymond mill for grinding, and performing vacuum mechanical ball milling for 24 hours at the grinding temperature of 80 ℃ and the rotating speed of 2 revolutions per second, wherein the grain size after grinding is less than 150 mu m;
s3, respectively preparing the silicon dioxide particles obtained after grinding and aluminum oxide powder into spraying liquid, and alternately spraying the spraying liquid on the core body layer by layer to form a porous composite layer, and then crushing and screening to obtain porous micro-nano particles; the composite substrate is prepared by using 450% of silicon dioxide and 55% of aluminum oxide in parts by weight;
s4, mixing the porous micro-nano particles with carbon black or carbon nano tubes in a proportion of 20:1, grinding for 12 hours and 1200m/s in a double-jet type jet mill at the temperature of 80 ℃, the pressure of 1000KPa and the rotating speed of 5 r/s to prepare powder with the particle size of 10-20 mu m, wherein the obtained powder part comprises three-dimensional porous/spiny micro-nano composite particles.
When the three-dimensional porous/spiny micro-nano composite particles produced by the preparation method are applied to tread rubber, the performance is improved as shown in the table. The addition of 20% by mass of three-dimensional porous/thorn-shaped micro-nano composite particles into the standard tread rubber can improve the Tb property of the original tread rubber at 151 ℃ by 10%, optimize the tg property at 60 ℃ by 46%, reduce the compression temperature rise by 22%, reduce the Akron abrasion by 9% and improve the anti-wet skid property at 1mm water film by 48%.
Table: tread rubber application test data
Figure BDA0001923486010000171
Example 8
The embodiment provides a second preparation process of the composite particle, namely a high-speed airflow kinetic energy embedding method, which specifically comprises the following steps:
s1, adding montmorillonite ore into a hammer crusher, and crushing to 200-mesh ore sand;
s2, putting the ore sand into a Raymond mill for grinding, and performing vacuum mechanical ball milling for 24 hours at the grinding temperature of 80 ℃ and the rotating speed of 2 revolutions per second, wherein the grain size after grinding is less than 150 mu m;
s3, respectively preparing spraying liquid from the ground silicon dioxide, calcium carbonate particles and aluminum oxide powder, and alternately spraying the spraying liquid on the core body layer by layer to form a porous composite layer and then crushing and screening to obtain porous micro-nano particles; the composite substrate is prepared by 35% of silicon dioxide and 65% of aluminum oxide in parts by weight;
s4, mixing the porous micro-nano particles with carbon black or carbon nano tubes in a proportion of 12: 1, grinding for 12 hours and 1000m/s in a circulating tubular jet mill at 130 ℃, 600KPa and 3 r/s of rotation speed to prepare powder with the particle size of 10-20 mu m, wherein the obtained powder part comprises three-dimensional porous/spiny micro-nano composite particles.
When the three-dimensional porous/spiny micro-nano composite particles produced by the preparation method are applied to tread rubber, the performance is improved as shown in the table. The three-dimensional porous/thorn-shaped micro-nano composite particles with the mass fraction of 20% are added into the standard tread rubber, so that Tb property of the original tread rubber at 151 ℃ is improved by 16%, tg property at 60 ℃ is optimized by 23%, compression temperature rise is reduced by 23%, Akron abrasion is reduced by 6%, and anti-wet skid property under a 1mm water film is improved by 47%.
Table: tread rubber application test data
Figure BDA0001923486010000181
Examples 9 to 11 below are third processes for preparing composite particles.
Example 9
This example provides a third preparation process of the composite particles, namely, high temperature reconstruction method for inserting nano and sub-nano sized particles.
The high-temperature reaction furnace shown in FIG. 3 comprises a temperature-rising reaction section A, a gas flow acceleration section B, a reaction section C, a collection section D and 7 feeding ports at different positions. Wherein the length-diameter ratio of the heating reaction section is 1:1, the length-diameter ratio of the airflow acceleration section is 10:1, and the length-diameter ratio of the reaction section is 2: 1. In this embodiment, the diameter of the cavity of the temperature-rising reaction section is 1m, the diameter of the cavity of the airflow acceleration is 0.6m, and the diameter of the cavity of the reaction section is 1.5 m.
Adding nano zinc oxide into a No. 1 feeding hole, blowing the nano zinc oxide into a heating reaction section through a weight-loss feeder, and simultaneously ensuring that carrier gas is excessive so that natural gas introduced into an inlet of the heating section is completely combusted. The air flow speed at the tail end of the combustion section reaches 5m/s and the temperature is 500 ℃ by adjusting the natural gas feeding rate; then the air flow speed of the fuel entering the air flow acceleration section is increased to 20m/s due to the compression effect, the temperature reaches 600 ℃, and under the action of the high-speed air flow, the high-temperature reconstruction reaction of the composite substrate prepared by the porous alunite entering through the feed inlet 4 and the nano zinc oxide can only last for about 1 s; spraying cooling water with the temperature of below 100 ℃ into the tail end of the reaction section through a cooler E to cool the reaction product to below 800 ℃; and (3) allowing the reaction product after temperature reduction to enter a cyclone separator of a collecting section to complete gas-solid separation, wherein the obtained raw material is porous/thorn-shaped micro-nano composite particles, and the micropores of the porous/thorn-shaped micro-nano composite particles are partially or completely embedded with nano zinc oxide.
When the three-dimensional porous/spiny micro-nano composite particles produced by the preparation method are applied to tread rubber, the performance is improved as shown in the following table, 20% of the three-dimensional porous/spiny micro-nano composite particles are added into standard tread rubber in mass fraction, so that the Tb property of the original tread rubber at 151 ℃ is improved by 5%, the tg property of the original tread rubber at 60 ℃ is optimized by 17%, the compression temperature rise is reduced by 15%, the Akron abrasion is reduced by 3%, and the anti-wet-skid property of the original tread rubber at 1mm under the water film condition is improved by 32%.
Table: tread rubber application test data
Figure BDA0001923486010000191
Figure BDA0001923486010000201
Example 10
This example provides a third preparation process of the composite particles, namely, high temperature reconstruction method for inserting nano and sub-nano sized particles.
The high-temperature reaction furnace shown in FIG. 3 comprises a temperature-rising reaction section, a gas flow acceleration section, a reaction section, a collection section and 7 feeding ports at different positions. Wherein the length-diameter ratio of the heating reaction section is 5:1, the length-diameter ratio of the airflow acceleration section is 5:1, and the length-diameter ratio of the reaction section is 15: 1. In this embodiment, the diameter of the cavity of the temperature-rising reaction section is 1.1m, the diameter of the cavity of the airflow acceleration is 0.8m, and the diameter of the cavity of the reaction section is 2.0 m.
Adding nano zinc oxide into a No. 1 feeding hole, blowing the nano zinc oxide into a heating reaction section through a weight-loss feeder, and simultaneously ensuring that carrier gas is excessive so that natural gas introduced into an inlet of the heating section is completely combusted. The air flow speed at the tail end of the combustion section reaches 15m/s and the temperature reaches 2000 ℃ by adjusting the natural gas feeding rate; then the air flow speed of the fuel entering the air flow acceleration section is increased to 100m/s due to the compression effect, the temperature reaches 3500 ℃, and under the action of the high-speed air flow, the high-temperature reconstruction reaction of the composite substrate prepared by the porous alunite entering through the feed inlet 4 and the nano zinc oxide can only last for about 5 s; spraying cooling water with the temperature of below 100 ℃ into the tail end of the reaction section through a cooler to cool the reaction product to below 800 ℃; and (3) allowing the reaction product after temperature reduction to enter a cyclone separator of a collecting section to complete gas-solid separation, wherein the obtained raw material is porous/thorn-shaped micro-nano composite particles, and the micropores of the porous/thorn-shaped micro-nano composite particles are partially or completely embedded with nano zinc oxide.
When the three-dimensional porous/spiny micro-nano composite particles produced by the preparation method are applied to tread rubber, the performance is improved as shown in the following table, 20% of the three-dimensional porous/spiny micro-nano composite particles are added into standard tread rubber in mass fraction, so that the Tb property of the original tread rubber at 151 ℃ is improved by 8%, the tg property of the original tread rubber at 60 ℃ is optimized by 13%, the compression temperature rise is reduced by 21%, the Akron abrasion is reduced by 3%, and the anti-slippery property of the original tread rubber at 1mm under the water film condition is improved by 33%.
TABLE tread rubber application test data
Figure BDA0001923486010000211
Example 11
This example provides a third preparation process of the composite particles, namely, high temperature reconstruction method for inserting nano and sub-nano sized particles.
The high-temperature reaction furnace shown in FIG. 3 comprises a temperature-rising reaction section, a gas flow acceleration section, a reaction section, a collection section and 7 feeding ports at different positions. Wherein the length-diameter ratio of the heating reaction section is 2:1, the length-diameter ratio of the airflow acceleration section is 6:1, and the length-diameter ratio of the reaction section is 8: 1. In this embodiment, the diameter of the cavity of the temperature-rising reaction section is 1.3m, the diameter of the cavity of the airflow acceleration is 1.0m, and the diameter of the cavity of the reaction section is 1.8 m.
Adding nano zinc oxide into a No. 1 feeding hole, blowing the nano zinc oxide into a heating reaction section through a weight-loss feeder, and simultaneously ensuring that carrier gas is excessive so that natural gas introduced into an inlet of the heating section is completely combusted. The air flow speed at the tail end of the combustion section reaches 10m/s and the temperature is 1500 ℃ by adjusting the natural gas feeding rate; then the air flow speed of the fuel entering the air flow acceleration section is increased to 70m/s due to the compression effect, the temperature reaches 2000 ℃, and under the action of the high-speed air flow, the high-temperature reconstruction reaction of the composite substrate prepared by the porous alunite entering through the feed inlet 4 and the nano zinc oxide can only last for about 5 s; spraying cooling water with the temperature of below 100 ℃ into the tail end of the reaction section through a cooler to cool the reaction product to below 800 ℃; and (3) allowing the reaction product after temperature reduction to enter a cyclone separator of a collecting section to complete gas-solid separation, wherein the obtained raw material is porous/thorn-shaped micro-nano composite particles, and the micropores of the porous/thorn-shaped micro-nano composite particles are partially or completely embedded with nano zinc oxide.
When the three-dimensional porous/spiny micro-nano composite particles produced by the preparation method are applied to tread rubber, the performance is improved as shown in the following table, 20% of the three-dimensional porous/spiny micro-nano composite particles are added into standard tread rubber in mass fraction, so that the Tb property of the original tread rubber at 151 ℃ is improved by 11%, the tg property of the original tread rubber at 60 ℃ is optimized by 46%, the compression temperature rise is reduced by 8%, the Akron abrasion is reduced by 3%, and the anti-slippery property of the original tread rubber at 1mm under the water film condition is improved by 42%.
Table: tread rubber application test data
Figure BDA0001923486010000221
It should be noted that during the reaction, one or more of porous micro-nano particles and/or zinc chloride, zinc sulfate, zinc nitrate, copper chloride, copper sulfate, copper nitrate, ferric chloride, ferric nitrate, ferric sulfate, sodium silicate, methane, acetylene, propyne, butane, natural gas, liquid hydrocarbon, clarified oil, heavy oil, kerosene, coal tar, pyrolysis oil, anthracene oil, silicone, and silane, which are put through a feed inlet No. 1-5, complete the high-temperature reconstitution reaction, the duration of the high-temperature reconstitution reaction is 0.05-5s, and then the reaction product is immediately cooled to below 800 ℃ by cooling water of 0-50 ℃ sprayed by a cooler at the end of the reaction section.
The feed inlet No. 1-5 can also be one or more of porous micro-nano particles and/or pre-formed silicon carbide, carbon nano tubes, graphene oxide, nano zinc oxide, nano copper oxide, carbon black, acetylene black and white carbon black.
The reaction product after temperature reduction enters a cyclone separator of the collecting section to complete gas-solid separation, and porous micro-nano particles can be further added at the front end (a feed inlet 6) or the tail end (a feed inlet 7) of the collecting section to simply embed nano and below-nano scale particles.
The feeding of the method is not limited to 7 feeding holes, and all positions of the temperature-rising reaction section, the airflow acceleration section, the reaction section and the collection section can comprise one or more porous micro-nano particle feeding holes; each feed port allows porous micro-nano particles to be dispersed in a liquid feed, in a separate gaseous stream, or in a separate aqueous stream into the furnace.
Feeding porous micro-nano particles into a furnace along with fuel gas by adopting a weight-loss Feeder of a SchenckAccuRate MC Feeder manufactured by the existing Schenck Process, ChagrinFalls and OH in a temperature-rising section feeding mode; the feeding mode of the airflow acceleration section, the reaction section and the collection section is an atomization dispersion device, the diameter of a spray hole of the atomization dispersion device is 0.5-3 mm, raw materials are sprayed into the airflow acceleration section or the reaction section in a reverse airflow mode at an angle of 0-90 degrees, optimally, the diameter of the spray hole of the embodiment is 2mm, the raw materials are sprayed into the airflow acceleration section and the reaction section in a reverse airflow mode at an angle of 90 degrees, micro-nano particles and dispersing agents can be uniformly mixed, nozzles of all the atomization dispersion devices are 2m away from a center line D/2(D is the diameter of a reaction cavity where the atomization dispersion devices are located) of the reaction furnace, the atomization dispersion devices of the airflow acceleration section are 2m away from an inlet of the airflow acceleration section, and the atomization dispersion devices of the reaction.
The dispersant used for atomization is one or more of sodium polystyrene sulfonate, hexadecyl trimethyl sniffing hinge, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate and polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer.
Examples 12 to 14 below are fourth preparation processes of composite particles.
Example 12
The embodiment provides a fourth preparation process of composite particles, which is to embed micro-nano particles in micropores of porous micro-nano particles through mechanical loading, and specifically comprises the following steps:
s1, putting an opal ore raw material into a hammer crusher, and crushing to 75-mesh ore sand;
s2, preparing spraying liquid from the ground silicon dioxide particles and aluminum oxide powder respectively to alternately spray the silicon dioxide particles and the aluminum oxide powder layer by layer on a core body, forming a porous composite layer, and crushing and screening to obtain porous micro-nano particles; the composite substrate is prepared by 70% of silicon dioxide and 30% of aluminum oxide in parts by weight;
s3, mixing the obtained porous micro-nano particles with carbon black in a ratio of 10:1, grinding the mixture in a vertical mill for 48 hours at 50 ℃ at a rotation speed of 0.5 r/s, wherein the particle size after grinding is less than 100 mu m;
and S4, feeding the ground particles into an air separation classifier, wherein the rotor frequency of the classifier is 50Hz, the wind speed is 10m/s, and the obtained powder part contains three-dimensional porous/thorn-shaped micro-nano composite particles.
The three-dimensional porous/spiny micro-nano composite particle produced by the preparation method has the size of 325m after being tested by a BET nitrogen adsorption method2Specific surface area in g.
Example 13
The embodiment provides a fourth preparation process of composite particles, which is to embed micro-nano particles in micropores of porous micro-nano particles through mechanical loading, and specifically comprises the following steps:
s1, putting opal ore and alunite raw materials into a hammer crusher, and crushing to 75-mesh ore sand;
s2, preparing spraying liquid from the ground silicon dioxide particles and aluminum oxide powder respectively to alternately spray the silicon dioxide particles and the aluminum oxide powder layer by layer on a core body, forming a porous composite layer, and crushing and screening to obtain porous micro-nano particles; the composite substrate is prepared by 40% of silicon dioxide and 60% of aluminum oxide in parts by weight;
s3, obtaining the porous micro-nano particles and carbon black, wherein the ratio of the porous micro-nano particles to the carbon black is 20:1, grinding the mixture in a vertical mill for 48 hours at 100 ℃ at a rotation speed of 5 revolutions per second, wherein the particle size after grinding is less than 100 mu m;
and S4, feeding the ground particles into an air separation classifier, wherein the rotor frequency of the classifier is 10Hz, the wind speed is 200m/s, and the obtained powder part contains three-dimensional porous/thorn-shaped micro-nano composite particles.
The three-dimensional porous/spiny micro-nano composite particles produced by the preparation method have a particle size of 330m measured by a BET nitrogen adsorption method2Specific surface area in g.
Example 14
The embodiment provides a fourth preparation process of composite particles, which is to embed micro-nano particles in micropores of porous micro-nano particles through mechanical loading, and specifically comprises the following steps:
s1, putting mica ore and alunite raw materials into a hammer crusher, and crushing to 75-mesh ore sand;
s2, preparing spraying liquid from the ground silicon dioxide particles and aluminum oxide powder respectively to alternately spray the silicon dioxide particles and the aluminum oxide powder layer by layer on a core body, forming a porous composite layer, and crushing and screening to obtain porous micro-nano particles; the composite substrate is prepared by 50 percent of silicon dioxide and 50 percent of aluminum oxide in parts by weight;
s3, mixing the obtained porous micro-nano particles with carbon black in a ratio of 1:1, grinding the mixture in a vertical mill for 48 hours at 80 ℃ at a rotating speed of 3 r/s, wherein the particle size after grinding is less than 100 mu m;
and S4, feeding the ground particles into an air separation classifier, wherein the rotor frequency of the classifier is 120Hz, the wind speed is 100m/s, and the obtained powder part contains three-dimensional porous/thorn-shaped micro-nano composite particles.
The three-dimensional porous/spiny micro-nano composite particle produced by the preparation method has a particle size of 350m tested by a BET nitrogen adsorption method2Specific surface area in g.
Examples 15 to 17 below are fifth preparation processes of composite particles.
Example 15
The embodiment provides a fifth preparation process of composite particles, which is to embed pre-formed nano particles and particles with the size below nano into micropores of porous micro-nano particles through vacuum negative pressure acting force, and the fifth preparation process comprises the following specific steps:
s1, putting a kaolinite ore raw material into a hammer crusher, and crushing to 75-mesh ore sand;
s2, preparing spraying liquid from the ground silicon dioxide particles and aluminum oxide powder respectively to alternately spray the silicon dioxide particles and the aluminum oxide powder layer by layer on a core body, forming a porous composite layer, and crushing and screening to obtain porous micro-nano particles; the composite substrate is prepared by 30 weight percent of silicon dioxide and 70 weight percent of aluminum oxide;
s3, mixing the obtained porous micro-nano particles with white carbon black according to the proportion of 1:1, the powder is fed into a screw-strip type vacuum mixer, the vacuum degree is-1000 KPa, the temperature is 300 ℃, the rotating speed is 0.5 r/s, the processing time is 48 hours, and the obtained powder part can contain three-dimensional porous/thorn-shaped micro-nano composite particles.
The three-dimensional porous/spiny micro-nano composite particle produced by the preparation method has a particle size of 350m tested by a BET nitrogen adsorption method2Specific surface area in g.
Example 16
The embodiment provides a fifth preparation process of composite particles, which is to embed pre-formed nano particles and particles with the size below nano into micropores of porous micro-nano particles through vacuum negative pressure acting force, and the fifth preparation process comprises the following specific steps:
s1, putting a kaolinite ore raw material into a hammer crusher, and crushing to 75-mesh ore sand;
s2, preparing spraying liquid from the ground silicon dioxide particles and aluminum oxide powder respectively to alternately spray the silicon dioxide particles and the aluminum oxide powder layer by layer on a core body, forming a porous composite layer, and crushing and screening to obtain porous micro-nano particles; the composite substrate is prepared by 70% of silicon dioxide and 30% of aluminum oxide in parts by weight;
s3, mixing the obtained porous micro-nano particles and white carbon black by the following steps of: 1, feeding the powder into a double-star vacuum mixer, wherein the vacuum degree is 0KPa, the temperature is 100 ℃, the rotating speed is 5 r/s, the processing time is 4 hours, and the obtained powder part can contain three-dimensional porous/spiny micro-nano composite particles.
The three-dimensional porous/spiny micro-nano composite particles produced by the preparation method have a particle size of 330m measured by a BET nitrogen adsorption method2Specific surface area in g.
Example 17
The embodiment provides a fifth preparation process of composite particles, which is to embed pre-formed nano particles and particles with the size below nano into micropores of porous micro-nano particles through vacuum negative pressure acting force, and the fifth preparation process comprises the following specific steps:
s1, putting a kaolinite ore raw material into a hammer crusher, and crushing to 75-mesh ore sand;
s2, preparing spraying liquid from the ground silicon dioxide particles and aluminum oxide powder respectively to alternately spray the silicon dioxide particles and the aluminum oxide powder layer by layer on a core body, forming a porous composite layer, and crushing and screening to obtain porous micro-nano particles; the composite substrate is prepared by 40% of silicon dioxide and 60% of aluminum oxide in parts by weight;
s3, mixing the obtained porous micro-nano particles with white carbon black by the following ratio of 10:1, the mixture is fed into a planetary vacuum mixer, the vacuum degree is-800 KPa, the temperature is 200 ℃, the rotating speed is 3 r/s, the processing time is 36 hours, and the obtained powder part can contain three-dimensional porous/spiny micro-nano composite particles.
The three-dimensional porous/spiny micro-nano composite particle produced by the preparation method has 340m measured by a BET nitrogen adsorption method2Specific surface area in g.
Examples 18 to 20 below are sixth preparation processes of composite particles.
Example 18
The embodiment provides a sixth preparation process of composite particles, which is characterized in that pre-formed nano particles and particles with the size below the nano particles are embedded into micropores of porous micro-nano particles through multi-rotor physical continuous modification, and the preparation process comprises the following specific steps:
s1, crushing talc ore and opal raw material ore, and grinding for 8 hours to 40 mu m particle size by using a vertical ball mill;
s2, preparing spraying liquid from the ground silicon dioxide particles and aluminum oxide powder respectively to alternately spray the silicon dioxide particles and the aluminum oxide powder layer by layer on a core body, forming a porous composite layer, and crushing and screening to obtain porous micro-nano particles; the composite substrate is prepared by 30 weight percent of silicon dioxide and 70 weight percent of aluminum oxide;
s3, mixing sodium polystyrene sulfonate and carbon black according to the mass ratio of 10:1, mixing the solution at room temperature, and stirring to obtain a uniformly dispersed carbon black suspension;
s4, mixing the carbon black suspension and the porous micro-nano particles with the particle size of 300-2500 meshes prepared in the step one according to the ratio of 1: 20 weight percent of the mixture is sent into a multi-rotor physical continuous modification device to be subjected to vacuum mechanical ball milling with the vacuum degree of 4 hours to 1000KPa, the ball milling temperature is 300 ℃, and the rotating speed of a ball milling chamber is 0.5 r/s;
s5, feeding the obtained powder into an airflow milling chamber in a multi-rotor physical continuous modification device, and performing high-pressure airflow milling at the temperature of 80 ℃, the pressure of 100KPa and the rotating speed of 5 revolutions per second for 24 hours and 1200 m/s.
The three-dimensional porous/thorn-shaped micro-nano composite particles produced by the preparation methodBET nitrogen adsorption test of 320m2Specific surface area in g.
Example 19
The embodiment provides a sixth preparation process of composite particles, which is characterized in that pre-formed nano particles and particles with the size below the nano particles are embedded into micropores of porous micro-nano particles through multi-rotor physical continuous modification, and the preparation process comprises the following specific steps:
s1, crushing talc ore and opal raw material ore, and grinding for 8 hours to 40 mu m particle size by using a vertical ball mill;
s2, preparing spraying liquid from the ground silicon dioxide particles and aluminum oxide powder respectively to alternately spray the silicon dioxide particles and the aluminum oxide powder layer by layer on a core body, forming a porous composite layer, and crushing and screening to obtain porous micro-nano particles; the composite substrate is prepared by 40% of silicon dioxide and 60% of aluminum oxide in parts by weight;
s3, mixing sodium polystyrene sulfonate and carbon black according to the mass ratio of 10:1, mixing the solution at room temperature, and stirring to obtain a uniformly dispersed carbon black suspension;
s4, mixing the carbon black suspension and the porous micro-nano particles with the particle size of 300-2500 meshes prepared in the step one according to the ratio of 1:1, sending the mixture into a multi-rotor physical continuous modification device, and carrying out vacuum mechanical ball milling for 48 hours at a vacuum degree of 0KPa, wherein the ball milling temperature is 50 ℃, and the rotating speed of a ball milling chamber is 5 r/s;
s5, feeding the obtained powder into an airflow milling chamber in a multi-rotor physical continuous modification device, and performing 24-hour 300m/s high-pressure airflow milling at the temperature of 200 ℃, the pressure of 1000KPa and the rotating speed of 0.5 r/s.
The three-dimensional porous/spiny micro-nano composite particle produced by the preparation method has 340m measured by a BET nitrogen adsorption method2Specific surface area in g.
Example 20
The embodiment provides a sixth preparation process of composite particles, which is characterized in that pre-formed nano particles and particles with the size below the nano particles are embedded into micropores of porous micro-nano particles through multi-rotor physical continuous modification, and the preparation process comprises the following specific steps:
s1, crushing talc ore and opal raw material ore, and grinding for 9 hours to 40 mu m particle size by using a vertical ball mill;
s2, preparing spraying liquid from the ground silicon dioxide particles and aluminum oxide powder respectively to alternately spray the silicon dioxide particles and the aluminum oxide powder layer by layer on a core body, forming a porous composite layer, and crushing and screening to obtain porous micro-nano particles; the composite substrate is prepared by 80% of silicon dioxide and 20% of aluminum oxide in parts by weight;
s3, mixing sodium polystyrene sulfonate and carbon black according to the mass ratio of 10:1, mixing the solution at room temperature, and stirring to obtain a uniformly dispersed carbon black suspension;
s4, mixing the carbon black suspension and the porous micro-nano particles with the particle size of 300-2500 meshes prepared in the step one according to the ratio of 1: 15, sending the mixture into a multi-rotor physical continuous modification device, and carrying out vacuum mechanical ball milling at the vacuum degree of 4-500 KPa for 4 hours at the ball milling temperature of 80 ℃ and at the ball milling chamber rotating speed of 3 r/s;
s5, feeding the obtained powder into an airflow milling chamber in a multi-rotor physical continuous modification device, and performing high-pressure airflow milling for 24 hours at 800m/s, wherein the temperature is 135 ℃, the pressure is 200KPa, and the rotating speed is 4 r/s.
The three-dimensional porous/spiny micro-nano composite particle produced by the preparation method has the size of 325m after being tested by a BET nitrogen adsorption method2Specific surface area in g.
Comparative example 1
S1, dissolving zinc nitrate hexahydrate in deionized water to form a zinc nitrate solution with the concentration of 10g/ml, and stirring for 2 minutes for later use;
s2, mixing silicon dioxide and methanol to obtain a solution of porous micro-nano particles, and placing the solution in an ultrasonic instrument for ultrasonic dispersion, wherein the ultrasonic frequency is 50Hz, the temperature is below 30 ℃, and the ultrasonic time is 2 hours, so that a porous micro-nano particle suspension with the concentration of 20g/ml is obtained;
s3, dissolving ammonia water into deionized water to prepare ammonia water with the concentration of 30% for later use;
s4, mixing the porous micro-nano particle suspension prepared in the S2 with the zinc nitrate solution prepared in the S1 according to a mass ratio of 30: 1, adding an external fixed or rotating electric field of 80V/m, rotating the rotating speed of the rotating electric field by 10 r/min, and magnetically stirring for 0.1 hour at the rotating speed of 200 r/min;
s5, dropwise adding the ammonia water solution prepared in the step S3 into the mixed solution, controlling the pH within the range of 6, keeping the temperature of 80 ℃ for heating in a constant-temperature water bath, and stirring for about 1 hour;
s6, after the reaction is finished, carrying out suction filtration, washing with distilled water for 1 time, and washing with absolute ethyl alcohol for 1 time;
s7, drying the washed powder in a 50 ℃ oven for 8h to obtain composite particle powder.
The composite particles produced by the preparation method have the particle size of 110m measured by a BET nitrogen adsorption method2Specific surface area in g.
The composite particles produced by the preparation method are applied to tread rubber, 20% of three-dimensional porous/thorn-shaped micro-nano composite particles in mass fraction are added into standard tread rubber, so that Tb property of the original tread rubber at 151 ℃ is improved by 2%, tg property of the original tread rubber at 60 ℃ is optimized by 9%, compression temperature rise is reduced by 8%, Akron abrasion is reduced by 1%, and anti-slippery property of the original tread rubber at 1mm water film is improved by 16%.
Comparative example 2
The embodiment provides a preparation process of the composite particle, namely a high-speed airflow kinetic energy embedding method, which specifically comprises the following steps:
s1, adding diatomite ore into a hammer crusher, and crushing to 100-mesh ore sand;
s2, respectively preparing spraying liquid from the ground silicon dioxide particles and aluminum oxide powder, and alternately spraying the spraying liquid on the core body layer by layer to form a porous composite layer and then crushing and screening the porous composite layer to obtain porous micro-nano particles, wherein the composite substrate is prepared from 5% of silicon dioxide and 95% of aluminum oxide in parts by weight;
s3, putting the ore sand into a Raymond mill for grinding, and performing vacuum mechanical ball milling for 1 hour at the grinding temperature of 60 ℃ at the rotating speed of 1 r/s;
s4, mixing the ground powder and the carbon nano tube in a ratio of 25: 1, grinding for 12 hours and 100m/s in a double-jet type jet mill at 70 ℃, 100KPa pressure and 1 r/s of rotation speed to prepare composite particles.
The composite particles produced by the preparation method have the particle size of 130m measured by a BET nitrogen adsorption method2Ratio of/gSurface area.
The composite particles produced by the preparation method are applied to tread rubber, 20% of three-dimensional porous/thorn-shaped micro-nano composite particles in mass fraction are added into standard tread rubber, so that Tb property of the original tread rubber at 151 ℃ is improved by 2%, tg property of the original tread rubber at 60 ℃ is optimized by 11%, compression temperature rise is reduced by 9%, Akron abrasion is reduced by 1%, and anti-slippery property of the original tread rubber at 1mm water film is improved by 17%.
Comparative example 3
This example provides a process for preparing composite particles, i.e., particles with dimensions of nanometers and below by high temperature reconstruction.
The high-temperature reaction furnace shown in FIG. 3 comprises a temperature-rising reaction section A, a gas flow acceleration section B, a reaction section C, a collection section D and 7 feeding ports at different positions. Wherein the length-diameter ratio of the heating reaction section is 7:1, the length-diameter ratio of the airflow acceleration section is 2:1, and the length-diameter ratio of the reaction section is 2: 1. In this embodiment, the diameter of the cavity of the temperature-rising reaction section is 1m, the diameter of the cavity of the airflow acceleration is 0.6m, and the diameter of the cavity of the reaction section is 1.5 m.
Adding nano zinc oxide into a No. 1 feeding hole, blowing the nano zinc oxide into a heating reaction section through a weight-loss feeder, and simultaneously ensuring that carrier gas is excessive so that natural gas introduced into an inlet of the heating section is completely combusted. The air flow speed at the tail end of the combustion section reaches 5m/s and the temperature is 300 ℃ by adjusting the natural gas feeding rate; then the air flow speed of the fuel entering the air flow acceleration section is increased to 10m/s due to the compression effect, the temperature reaches 400 ℃, and under the action of the high-speed air flow, the high-temperature reconstruction reaction of the porous alunite powder entering through the feeding hole 4 and the nano zinc oxide only lasts for about 8 s; spraying cooling water with the temperature of below 100 ℃ into the tail end of the reaction section through a cooler E to cool the reaction product to below 800 ℃; and (3) allowing the reaction product after temperature reduction to enter a cyclone separator of a collecting section to complete gas-solid separation, wherein the obtained raw material is porous/thorn-shaped micro-nano composite particles, and the micropores of the porous/thorn-shaped micro-nano composite particles are partially or completely embedded with nano zinc oxide.
The composite particles produced by the preparation method have 133m measured by a BET nitrogen adsorption method2Specific surface area in g.
The composite particles produced by the preparation method are applied to tread rubber, 20% of three-dimensional porous/thorn-shaped micro-nano composite particles in mass fraction are added into standard tread rubber, so that Tb property of the original tread rubber is improved by 5% at 151 ℃, tg property is optimized by 118% at 60 ℃, compression temperature rise is reduced by 7%, Akron abrasion is reduced by 1%, and anti-wet skid property is improved by 19% at 1mm water film.
Comparative example 4
The embodiment provides a preparation process of composite particles, which embeds micro-nano particles in micropores of porous micro-nano particles through mechanical load, and specifically comprises the following steps:
s1, putting an opal ore raw material into a hammer crusher, and crushing to 75-mesh ore sand;
s2, mixing ore sand and carbon black in a ratio of 25: 1, grinding in a vertical mill at 30 ℃ for 48 hours at 6 rpm/s.
The composite particles produced by the preparation method have the particle size of 80m measured by a BET nitrogen adsorption method2Specific surface area in g.
Comparative example 5
The embodiment provides a preparation process of composite particles, which is characterized in that particles with nanometer sizes and below nanometer sizes which are formed in advance are embedded into micropores of porous micro-nano particles through vacuum negative pressure acting force, and the preparation process comprises the following specific steps:
s1, putting a bauxite ore raw material into a hammer crusher, and crushing the bauxite ore raw material into ore sand with a granularity of 75 meshes;
s2, mixing ore sand and white carbon black according to the weight ratio of 30: 1 is fed into a screw-type vacuum mixer, the vacuum degree is-1500 KPa, the temperature is 80 ℃, the rotating speed is 0.5 r/s, and the processing time is 48 hours, thus obtaining the composite particles.
The composite particles produced by the preparation method have the size of 100m tested by a BET nitrogen adsorption method2Specific surface area in g.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (34)

1. The composite material of the micro-nano composite particles and rubber is characterized in that the micro-nano composite particles are particles with the size of nanometers and below nanometers, which are smaller than the diameter of micropores of the porous micro-nano particles, inserted into the porous micro-nano particles so as to form three-dimensional porous and/or thorn-shaped micro-nano composite particles; and adding the micro-nano composite particles into rubber.
2. The composite material according to claim 1, wherein the single-hole embedding amount of the three-dimensional porous and/or spiny micro-nano composite particles is 1-100% of the pore volume, and the BET nitrogen adsorption specific surface area is 30m2/g~350 m2/g。
3. The composite material according to claim 1 or 2, wherein the single-pore embedding amount of the three-dimensional porous and/or spiny micro-nano composite particles is 30-100% of the pore volume.
4. The composite material of claim 1, wherein the porous micro-nano particles are spherical, ellipsoidal, rhombohedral, or irregular in shape.
5. The composite material according to claim 4, wherein the porous micro-nano particles have a particle size of 100 nm-100 μm, a pore size of 1 nm-500 nm, a pore depth of 2 nm-500 nm, a pore number of 5000-3 hundred million/g, and a BET specific surface area of 0.3-300 m2The pH value is 6-8.
6. The composite material according to claim 4 or 5, wherein the porous micro-nano particles are silica or calcium carbonate or composite porous micro-nano particles of silica and/or calcium carbonate and aluminum oxide.
7. The composite material of claim 6, wherein the porous micro-nano particles comprise 20-95 wt% of silica or calcium carbonate and 5-80 wt% of alumina.
8. The composite material of claim 1, wherein the nano and sub-nano sized particles are one or more of nano zinc oxide, nano copper oxide, small molecule functional material, natural rubber polymer material, synthetic rubber polymer material, carbon nanotube, graphene, carbon black, white carbon black, titanium dioxide, ferroferric oxide, and metal simple substance nanoparticles.
9. The composite material according to claim 6, wherein the porous micro-nano particles of silica, calcium carbonate or alumina are derived from a silicon/calcium containing material comprising: one or more of alunite, rice hull ash, straw ash, montmorillonite, talc, yellow clay, mica, wollastonite, bauxite, protein shale, diatomite, and opal.
10. The preparation process of the composite material according to any one of claims 1 to 9, wherein the micro-nano composite particles are added into rubber to prepare the composite material; the preparation method of the micro-nano composite particles comprises the following steps: placing the porous micro-nano particles and nano and below-nano particles in a liquid phase polar dispersion system, wherein the pH of a solution is 6-8, the temperature is 50-80 ℃, an electric field with the voltage of 100-8000V/m is added, the stirring time is 0.1-2 h, and the stirring speed is 30-200 r/min.
11. The preparation process according to claim 10, wherein the input weight ratio of the porous micro-nano particles to the nano and sub-nano particles is 20: 1-1: 1.
12. The process according to claim 10, wherein the nano-sized and sub-nano-sized particles are pre-formed or formed in situ in a liquid phase reaction.
13. The process of claim 12, wherein the raw material for in situ formation is one or more of zinc chloride, zinc sulfate, zinc nitrate, copper chloride, copper sulfate, copper nitrate, sodium silicate, silicone, ferric chloride, ferric nitrate, and ferric sulfate.
14. The preparation process of claim 10, wherein the porous micro-nano particles comprise 20-95 wt% of silicon dioxide or calcium carbonate and 5-80 wt% of aluminum oxide.
15. The preparation process of the composite material according to any one of claims 1 to 9, wherein the micro-nano composite particles are added into rubber to prepare the composite material; the preparation method of the micro-nano composite particles comprises the following steps: under the action of high-speed airflow kinetic energy, nano and below-nano particles are embedded into the holes of the porous micro-nano particles.
16. The preparation process of claim 15, wherein the porous micro-nano particles and the preformed nano and sub-nano particles in a weight ratio of 20:1 to 1:1 are mixed, blown or dispersed in advance and fed synchronously, and the air flow rate is 300m/s to 1200m/s, the temperature is 80 ℃ to 200 ℃, and the pressure is 100KPa to 1000 KPa.
17. The preparation process of claim 15, wherein the micro-nano composite particles are prepared by using a high-speed airflow kinetic energy embedding device, wherein the high-speed airflow kinetic energy embedding device is one of a horizontal circular ring airflow mill, a circulating pipe airflow mill, a double-jet airflow mill, an impact plate airflow mill or a fluidized bed reverse airflow mill.
18. The preparation process of the composite material according to any one of claims 1 to 9, wherein the micro-nano composite particles are added into rubber to prepare the composite material; the preparation method of the micro-nano composite particles comprises the following steps: embedding nano and below-nano sized particles into micropores of the porous micro-nano particles at a high temperature of 500-3500 ℃.
19. The process of claim 18, wherein the nano-sized and sub-nano-sized particles are pre-formed or generated in situ in a high temperature reaction.
20. The process according to claim 18, comprising the steps of:
in the temperature-raising reaction stage, the air flow speed at the tail end is 5-15 m/s, and the temperature is 500-2000 ℃;
an airflow acceleration stage, wherein the airflow speed is 20-100 m/s, and the temperature is 600-3500 ℃;
and in the reaction stage, the temperature at the outlet of the reaction section is lower than 800 ℃.
21. The process of claim 20, wherein the in situ reaction of the nano-sized or sub-nano-sized particles is carried out for a reaction reconfiguration time of 0.05s to 5 s.
22. The preparation process according to claim 18, wherein the micro-nano composite particles are prepared by using a high-temperature reaction furnace, and the high-temperature reaction furnace comprises: the temperature raising section part, the gas flow accelerating section part, the reaction section part and the collecting section part are provided with one or more feeding dispersing devices.
23. The process of claim 22, wherein the feed distribution in the temperature rising section is a loss-in-weight feeder; the feeding dispersing devices in the gas flow accelerating section part, the reaction section part and the collecting section part are atomizing dispersing devices.
24. The preparation process according to claim 22, wherein the distance between the nozzle of the atomization dispersion device and the center line of the high-temperature reaction furnace is 0-D/2, D is the diameter of the cavity where the nozzle is located, the distance between the atomization dispersion device arranged on the gas flow acceleration section part and the inlet of the gas flow acceleration section part is 0-L, the distance between the atomization dispersion device arranged on the reaction section part and the inlet of the reaction section is 0-L, and L is the length of the cavity where the nozzle is located.
25. The preparation process according to claim 23 or 24, wherein the diameter of the nozzle orifice of the atomization and dispersion device is 0.5 mm-5 mm.
26. The preparation process of claim 25, wherein the nozzle of the atomization and dispersion device is sprayed at an angle of 0-90 ° against the airflow.
27. The preparation process of claim 22, wherein the length-to-diameter ratio of the temperature rising section part is 1:1 to 5:1, the length-to-diameter ratio of the gas flow accelerating section part is 5:1 to 10:1, and the length-to-diameter ratio of the reaction section part is 2:1 to 15: 1.
28. The preparation process of the composite material according to any one of claims 1 to 9, wherein the micro-nano composite particles are added into rubber to prepare the composite material; the preparation method of the micro-nano composite particles comprises the following steps: and embedding the preformed nano and below-nano particles into micropores of the porous micro-nano particles in a grinding way.
29. The preparation process of claim 28, wherein the mechanical load embedding device is used for continuous or step-by-step feeding, the grinding temperature is 50 ℃ to 100 ℃, and the rotating speed is 0.5 to 5 revolutions per second.
30. The preparation process according to claim 29, wherein the porous micro-nano particles are silica or calcium carbonate or composite porous micro-nano particles of silica and/or calcium carbonate and aluminum oxide.
31. The preparation process of the composite material according to any one of claims 1 to 9, wherein the micro-nano composite particles are added into rubber to prepare the composite material; the preparation method of the micro-nano composite particles comprises the following steps: and embedding the pre-formed nano and below-nano particles into micropores of the porous micro-nano particles through vacuum negative pressure acting force.
32. The preparation process of claim 31, wherein the micro-nano composite particles are prepared by using a vacuum negative pressure embedding device, wherein the vacuum negative pressure embedding device is one of a screw type vacuum mixer, a double star vacuum mixer, a planetary vacuum mixer, a vacuum disperser and a full negative pressure mixer.
33. The preparation process of the composite material according to any one of claims 1 to 9, wherein the micro-nano composite particles are added into rubber to prepare the composite material; the preparation method of the micro-nano composite particles comprises the following steps: and embedding the preformed nano and below-nano particles into micropores of the porous micro-nano particles through multi-rotor physical continuous modification.
34. The preparation process of claim 33, wherein the micro-nano composite particles are prepared by using a multi-rotor physical continuous modification device, wherein the multi-rotor physical continuous modification device comprises two or more mixing methods selected from mechanical ball milling, vacuum negative pressure mixing and high-speed airflow mixing.
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