CN109437215B - Micro-nano composite particle and vacuum negative pressure embedding preparation process thereof - Google Patents

Micro-nano composite particle and vacuum negative pressure embedding preparation process thereof Download PDF

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CN109437215B
CN109437215B CN201811605496.XA CN201811605496A CN109437215B CN 109437215 B CN109437215 B CN 109437215B CN 201811605496 A CN201811605496 A CN 201811605496A CN 109437215 B CN109437215 B CN 109437215B
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CN109437215A (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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    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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Abstract

The invention discloses a micro-nano composite particle and a preparation process thereof, wherein the micro-nano composite particle is formed by inserting nano and below-nano scale particles with the diameter smaller than the micropore diameter of a porous micro-nano particle 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 thorn-shaped micro-nano composite particles is 1-100% of the hole volume. The process for embedding nano and below-nano particles under vacuum negative pressure is easy to operate, and the prepared micro-nano composite particles have good dispersibility and are not easy to agglomerate and can be applied to polymers and products thereof. 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 vacuum negative pressure embedding preparation process thereof
Technical Field
The invention relates to the technical field of novel materials, in particular to a novel micro-nano composite particle and a preparation process and a 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 particles with the nanometer and below-nanometer scale. 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. In fact, monodisperse micro-nano and sub-nano particles often generate a very stable aggregate form after synthesis due to drying processes and the like. 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 nano and sub-nano sized particles, small sized particles are less stable than large sized particles due to their low surface energy, and they tend to re-aggregate. However, in general, external forces can still cause good dispersion of the particles by manipulating the chemical composition of the dispersion, such as by adding surfactants, by changing the pH of the matrix, by changing the ionic strength, and by adding certain co-solvents, and by ultimately changing the interactions between particles on a nanometer and sub-nanometer scale, including van der Waals forces, electrostatic double layers, 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 surface-modified micro-nano and nano-sized particle silicon dioxide has a glass transition temperature T. In the room temperature range, 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 and sub-nano scale particle reinforced fiber material, which can be prepared by self-assembly method, micro phase inversion method, sea island template method, electrospinning and other methods. Compared with monodisperse particles, the material has greatly improved mechanical properties even at lower use level. Researchers find that if fiber materials containing nano and below-nano sized particles are woven into a network, materials with high strength, light weight and different properties can be manufactured, and the fiber materials have important application values in the fields of filtering membranes, sensors, micro-electronics, 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 micro-nano 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 micro-nano composite particles on a longer molecular distance through embedding different protruding functional groups, so that the exponential increase of the agglomeration effect caused by too close distance among the particles is avoided, the macro expression is high dispersibility and difficult agglomeration, the composite graphene gel takes porous starch as a substrate material, and the porous starch acts on the raw starch at a temperature lower than the gelatinization temperature to form a porous cellular product, which is general in porosity, incompressibility and chemical stability, especially in 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. In view of the above reasons, the two types of micro-nano composite particles formed above have room for further improvement in high dispersibility and property of being not easy to agglomerate.
Disclosure of Invention
Aiming at the defects existing in the prior background, the micro-nano composite particles have good dispersibility, are not easy to agglomerate, have better 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 micro-nano composite particles, the preparation method is easy to operate, and the micro-nano 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 micro-nano 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 porous micro-nano particles comprise 40-70 wt% of silicon dioxide and 30-60 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 high polymer materials, synthetic rubber high polymer materials, carbon nanotubes, graphene, carbon black, white carbon black, titanium dioxide, ferroferric oxide and metal simple substance nanoparticles.
The invention also provides a first preparation process of the micro-nano composite particle, which is to embed pre-formed nano particles and particles with the size below nano 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 at the temperature of 100 to 300 ℃ in the environment with the vacuum degree of-1000 to 0KPa, preferably-1000 to-800 KPa, and the rotating speed of 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.
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 40-70 wt% of silicon dioxide and 30-60 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.
In addition, the invention also relates to various preparation processes.
The invention also provides a second preparation process of the micro-nano composite particles, which is used for embedding 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 characterized by also comprising a high-speed airflow kinetic energy embedding device for preparing the micro-nano composite particles, wherein the high-speed airflow kinetic energy embedding device is one of a horizontal ring type airflow mill, a circulating pipe type airflow mill, a double-jet type airflow mill, an impact plate type airflow mill or a fluidized bed reverse airflow mill.
According to the third preparation process of the micro-nano composite particles, nano particles and particles with the size below nano are embedded into micropores of 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 a third preparation method of the micro-nano composite particles, wherein a weight-loss feeder is arranged at the feeding dispersion part of a heating section; 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 micro-nano composite particles, pre-formed nano particles and particles with the size below nano 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 micro-nano composite particles, porous micro-nano particles and nano and below-nano particles are placed in a liquid phase polar dispersion system, 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 rotating 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 for 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, ferric nitrate, and ferric sulfate.
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.
According to the sixth preparation process of the micro-nano 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 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 micro-nano composite particles in the technical fields of chemical rubber, medicine manufacturing sustained release agents and the like.
The technical scheme of the invention has the following advantages:
the embodiment of the invention provides a micro-nano 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 in-situ generation method) mode to form a three-dimensional porous and/or spiny micro-nano composite particleParticles; the three-dimensional porous and/or spiny micro-nano composite particles are formed by three micro-nano 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-hole embedding amount is 50-100% of the pore volume, namely most of the nano and below-nano scale particles are inserted or all of the nano and below-nano scale particles are inserted and spiny; when the micro-nano composite particles are prepared, the good dispersibility of the micro-nano monodisperse particles depends on the elimination of interaction force among the monodisperse particles, such as Van der Waals force and the action force of a nucleating agent at the connection points among the particles, and unpredictable phase transition of nano particles and particles with the size below the nano particles, namely unstable aggregation of materials, can not occur due to long-time external stirring, at the moment, the selection of a substrate material has important influence on the adsorption embedding volume and the dispersibility of the prepared micro-nano composite particles, the substrate material during the preparation of the micro-nano 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, and further parameters of the porous micro-nano particles as the substrate material are that the particle size is 100 nm-100 mu m, the pore diameter of a porous structure is 1 nm-500 nm, the pore depth is 2 nm-500 nm, and the pore number is 5000-3 hundred, the BET specific surface area is 0.3 to 300m2The 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 micro-nano composite particles have excellent space mechanical properties, as shown in fig. 4 and 5, which are three-dimensional illustrations of the space mechanical properties of the micro-nano composite particles, the micro-nano composite particles have various surface polarities of different materials due to the fact that a large number of other materials are embedded in a porous structure of the surface, and can be used for strengthening the intermolecular force of polymers under various conditions, and when the micro-nano composite particles are used as reinforcing agents, the reinforcing functions of rubber polymers under different working environments with different temperatures and pressures can be provided, so that the wear resistance, the strength and the wet-skid resistance are improved at the same time. By adding aluminum oxideIncreasing the surface energy of the original porous silica or calcium carbonate. 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 micro-nano composite particles is also greatly reduced without adding the aluminum oxide. Different from the traditional reinforcing particle material, the micro-nano composite particles have certain repulsion force at a longer molecular distance due to the different protruding functional groups embedded in the surfaces of the micro-nano composite particles, so that the exponential increase of the agglomeration effect caused by too close distance between the particles is prevented, and the macro expression is high in dispersity and difficult to agglomerate.
The novel micro-nano composite particles have good dispersibility in polymers, 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 and 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 representations of the space mechanical properties of the micro-nano composite particle of the 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 micro-nano composite particle provided by the embodiment, nano particles with the size smaller than the diameter of the micropores of the porous micro-nano particle and the size below the nano particles 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 micro-nano composite particle state is formed, that is, the nano and sub-nano particles may not be inserted or partially inserted or fully inserted and form a thorn shape, and even a certain degree of nano and sub-nano particles are attached to the surface of the substrate, FIG. 2 shows that the three-dimensional multi-hole/cell is10000x and 100000x scanning electron micrographs of the thorn-shaped micro-nano composite particles.
Specifically, the matrix of the micro-nano composite particle, i.e. the porous micro-nano particle, can be silicon dioxide or calcium carbonate, or a mixture of silicon dioxide and/or calcium carbonate and aluminum oxide; 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 m2And/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, small molecular functional materials, natural rubber polymer materials, synthetic rubber polymer materials, carbon nano tubes, graphene, carbon black, white carbon black, titanium dioxide, ferroferric oxide and metal single substance nanoparticles, wherein the small molecular functional materials are functional molecules with a molecular weight of less than 1000 daltons, and generally are small molecular groups of water, aglycone, xanthogenin, aglycone, alkaloid and the like.
Example 2
The embodiment provides a preparation process of the micro-nano 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 micro-nano 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 micro-nano 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 micro-nano 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 method2Specific surface area in g.
Example 4
The embodiment provides a preparation process of the micro-nano 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 ℃ drying oven for 4h to obtain three-dimensional porous/spine-shaped micro-nano 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 micro-nano 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, and acetone, 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, so that a porous micro-nano particle suspension with the concentration of 13g/ml is obtained; 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 a dispersant sodium polystyrene sulfonate, mixing the solution at room temperature, and magnetically stirring for 1 hour to obtain a uniformly dispersed carbon black 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 an oven at 70 ℃ for 5 hours to obtain three-dimensional porous/spiny micro-nano 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 and below-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, tetrahydropalmiran, azotolidone, diethyl ether, propylene oxide, dichloromethane, chloroform, and triethanolamine; 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/spiny micro-nano composite particles prepared by the method have three structures, and because the inner surface of a hole is far larger than the surface, zinc oxide nano particles and particles with the sizes below nano particles generated in a liquid phase reaction are accumulated in preference to the hole due to the polar diffusion effect, so that the three-dimensional porous/spiny micro-nano composite particles have 3 structures as shown in figure 1, the micro holes are partially embedded with the micro-nano particles as shown in figure 1, or the micro holes are completely filled with the micro-nano particles as shown in figure 1, or zinc oxide particles continue to grow and accumulate to form the spiny micro-nano composite particles as shown in figures 3 and 4, wherein the single-hole embedding amount of the porous micro-nano particles is 5-100% of the total volume of the hole. 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.
Example 6
The embodiment provides a second preparation process of the micro-nano composite particles, 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 BDA0001923485940000171
Example 7
The embodiment provides a second preparation process of the micro-nano composite particles, 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 BDA0001923485940000181
Example 8
The embodiment provides a second preparation process of the micro-nano composite particles, 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 BDA0001923485940000191
Example 9
The embodiment provides a third preparation process of the micro-nano composite particles, namely, inserting nano and below-nano scale particles by a high-temperature reconstruction method.
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 BDA0001923485940000201
Example 10
The embodiment provides a third preparation process of the micro-nano composite particles, namely, inserting nano and below-nano scale particles by a high-temperature reconstruction method.
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 BDA0001923485940000211
Example 11
The embodiment provides a third preparation process of the micro-nano composite particles, namely, inserting nano and below-nano scale particles by a high-temperature reconstruction method.
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 BDA0001923485940000221
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.
Example 12
The embodiment provides a fourth preparation process of micro-nano composite particles, which is to embed micro-nano particles in micropores of porous micro-nano particles through mechanical load, 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 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 micro-nano composite particles, which is to embed micro-nano particles in micropores of porous micro-nano particles through mechanical load, 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 micro-nano composite particles, which is to embed micro-nano particles in micropores of porous micro-nano particles through mechanical load, 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 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.
Example 15
The embodiment provides a fifth preparation process of micro-nano 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 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 material produced by the preparation methodThe thorn-shaped micro-nano composite particles have the thickness of 350m through the test of a BET nitrogen adsorption method2Specific surface area in g.
Example 16
The embodiment provides a fifth preparation process of micro-nano 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 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 micro-nano 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 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.
Example 18
The embodiment provides a sixth preparation process of micro-nano 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/spiny micro-nano composite particles produced by the preparation method have the size of 320m through the test of a BET nitrogen adsorption method2Specific surface area in g.
Example 19
The embodiment provides a sixth preparation process of micro-nano 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 micro-nano 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 micro-nano composite particle powder.
The micro-nano composite particles produced by the preparation method have a particle size of 110m measured by a BET nitrogen adsorption method2Specific surface area in g.
The micro-nano 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 micro-nano composite particles, 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, feeding the mixture into a double-jet type jet mill, grinding for 12 hours at 100m/s at 70 ℃, 100KPa at 1 r/s to prepare micro-nano composite particles.
The micro-nano composite particles produced by the preparation method have a particle size of 130m measured by a BET nitrogen adsorption method2Specific surface area in g.
The micro-nano 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 in water film is improved by 17%.
Comparative example 3
The embodiment provides a preparation process of micro-nano composite particles, namely inserting nano and below-nano scale particles by a high-temperature reconstruction method.
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 micro-nano composite particles produced by the preparation method have a particle size of 133m measured by a BET nitrogen adsorption method2Specific surface area in g.
The micro-nano 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 5%, 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 micro-nano composite particles, which is characterized in that micro-nano particles are embedded in micropores of porous micro-nano particles through mechanical load, and the preparation process 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, 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 micro-nano composite particles produced by the preparation method have a 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 micro-nano 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 vacuum negative pressure acting force, and the 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, mixing ore sand and white carbon black according to the weight ratio of 30: 1, feeding the mixture into a screw-type vacuum mixer, wherein 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, so as to obtain the micro-nano composite particles.
The micro-nano composite particles produced by the preparation method have the size of 100m through the test of 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 (7)

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; adding the micro-nano composite particles into rubber; wherein the single-hole embedding amount of the three-dimensional porous and/or spiny micro-nano composite particles is 50-90% of the pore volume;
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;
the nano and below-nano scale particles are one or more of nano zinc oxide, nano copper oxide, natural rubber high polymer material, synthetic rubber high polymer material, carbon nano tubes, graphene, carbon black, white carbon black, titanium dioxide, ferroferric oxide and metal simple substance nano particles.
2. The composite material according to claim 1, wherein the three-dimensional porous and/or spiny micro-nano composite particles have a single pore embedding amount of 60-90% of pore volume.
3. The composite material according to claim 1 or 2, wherein the porous micro-nano particles are spherical, ellipsoidal, rhombohedral or irregular in shape.
4. The composite material according to claim 1, wherein the porous micro-nano particles have a particle size of 100nm to 100 μm, a pore size of 1nm to 500nm, a pore depth of 2nm to 500nm, a pore number of 5000 to 3 hundred million/g, and a BET specific surface area of 0.3 to 300m2The pH value is 6-8.
5. The composite material according to claim 1, wherein the porous micro-nano particles comprise 30-100 wt% of silica or calcium carbonate and 0-70 wt% of alumina.
6. A preparation process of the composite material according to any one of claims 1 to 5, wherein the micro-nano composite particles are added into rubber to prepare the composite material; the preparation method of the composite particle 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.
7. The process of claim 6, wherein a vacuum negative pressure embedment device is used, said device being 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.
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