CN116120635A - Functionalized surface modifier, modified material and modification method thereof - Google Patents
Functionalized surface modifier, modified material and modification method thereof Download PDFInfo
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- CN116120635A CN116120635A CN202211669636.6A CN202211669636A CN116120635A CN 116120635 A CN116120635 A CN 116120635A CN 202211669636 A CN202211669636 A CN 202211669636A CN 116120635 A CN116120635 A CN 116120635A
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- filler
- liquid metal
- metal
- modified
- containing substance
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- 239000003607 modifier Substances 0.000 title claims abstract description 29
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- 230000004048 modification Effects 0.000 claims abstract description 66
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/6303—Inorganic additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention belongs to the field of material surface modification, and relates to a novel functional surface modifier, a modified material prepared by modification of the novel functional surface modifier and a modification method. The present invention indicates that liquid metal-containing materials can be used as surface modifiers. I.e. it is pointed out that liquid metal-containing substances can act as surface modifiers for materials (including fillers) and can improve the functionality of the materials: electrical conductivity, dielectric conductivity, magnetic conductivity, thermal conductivity, photo-thermal conductivity, medical use and the like, and improves the dispersibility of the related materials when the related materials are used in the composite material. The invention realizes the functional modification of materials (including fillers) through a simple one-step method, has no solvent or byproducts, does not need post treatment, is a novel technology with simple production and strong universality, solves the problem that the traditional surface modification mode can not provide functional gain, and can improve the dispersion of the fillers.
Description
Technical Field
The invention belongs to the field of material surface modification, and relates to a novel functional surface modifier, a modified material prepared by modification of the novel functional surface modifier and a modification method.
Background
The composite material is widely used in the fields of traffic, construction, electronic power and energy. In applications, it is often desirable to surface modify filler particles in a composite in order to obtain good filler dispersion and interfacial bonding to improve the properties of the composite. However, conventional surface modification methods such as plasma treatment, surface oxidation, phosphate modification, silane coupling agent treatment, dopamine treatment, surface grafting, etc., although enhancement of mechanical properties (strength and modulus) of the composite material can be achieved. However, these methods have very limited gains in electrical, magnetic, thermal, acoustic, and optical functions of the composite material. This cannot meet the increasingly abundant demands of functional materials in the fields of electronics, power, energy and environment.
This is mainly due to the intrinsic functionality (electrical, magnetic, thermal, acoustic and optical) of the traditional organically modified layers (organic molecules and groups), the transfer of functions across the interface between the filler/matrix being hindered or even passivated, so that the functionality of the composite material is hardly changed after modification and sometimes also reduced (e.g. conductivity and dielectric constant in polymer composites).
Modification of the second component (such as metallic materials and inorganic ceramic materials) with outstanding functionality to the filler surface holds promise to solve this problem. This generally requires the use of techniques such as deposition and electrostatic assembly which, although addressing the problem of functional enhancement, are not ideal for the versatility and modification of the filler and do not improve the dispersion of the filler.
In summary, currently, there is a few surface modification methods that can solve both the problems of filler function and dispersion, and have good universality and scalability.
Disclosure of Invention
Aiming at the problems in the field of surface modification of the existing filler, the invention aims to provide a more universal functional surface modifier, a modification method thereof and a prepared modified material; the invention uses the substance containing liquid metal (the liquid metal refers to a wide class of low-melting-point metal materials which are liquid at normal temperature or lower temperature, has the functions of intrinsic conduction, dielectric, heat conduction, photo-thermal and the like, and has weak interaction with fillers such as metal, inorganic ceramic and the like) to carry out surface modification on the materials (such as the fillers), the modification method is a mechanical forced mixing method, and the solid phase forced mechanical mixing induced strong shearing force and strong pressure are used for generating strong mechanochemical action to generate strong interface interaction between the liquid metal and the materials (initial fillers), thereby realizing the fixation of the liquid metal on the materials. The obtained liquid metal modified material can improve the dispersibility of materials such as fillers while improving the functionality (such as electric conduction, dielectric conduction, magnetic conduction, heat conduction, photo-thermal, medical use and the like) of the materials (such as fillers), and is a mode which is obviously different from the traditional surface modification; the surface modification is finished by using a one-step method, has no solvent or byproducts, does not need post-treatment, and is a novel technology with simple and convenient production and strong universality.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the present invention is to indicate the use of liquid metal-containing substances as surface modifiers. That is, it is pointed out that the liquid metal-containing substances can be used as surface modifiers for materials (including fillers) and can improve the dispersibility of the relevant materials in composite materials while improving the functionality (electrical conductivity, dielectric conductivity, magnetic conductivity, thermal conductivity, photo-thermal conductivity, medical use, etc.).
Further, the liquid metal-containing substance is used as a surface modifier for the filler.
Further, when the liquid metal-containing substance is used as a surface modifier for a filler, the specific method is as follows: adding a liquid metal-containing substance into the filler, and then adopting a mechanical force mixing processing method to obtain a corresponding modified filler; wherein, the volume ratio of the liquid metal-containing substance to the filler is: 85.00-99.99 parts by volume of filler and 15.00-0.01 part by volume of liquid metal.
Further, the liquid metal-containing substance is used to improve the dispersibility of the filler in the material. Such as in polymeric materials, inorganic ceramic materials or other liquid materials (e.g., small molecule solvents, ionic liquids, etc.).
Further, the liquid metal-containing substance is used for improving the electrical conductivity, dielectric property, electromagnetic property, thermal conductivity, photo-thermal property or rheological stretchability and other functional properties of the filler.
Further, the mechanical force mixing processing method comprises the following steps: the modification of the filler by liquid metal is realized by utilizing shearing force (such as the rotating speed of grinding type mixing equipment is more than 60rpm, the rotating speed of stirring type mixing equipment is more than 600rpm, the distance between a mixing rod and the wall of the mixing equipment is less than 2 cm) and the physical and chemical action induced by pressure during mixing. Auxiliary medium and post-treatment are not needed in the modification process, and the product obtained after one-step strong mechanical mixing is the liquid metal modified filler.
Further, the processing method for performing mechanical mixing employs equipment selected from the group consisting of: the high-speed mixer, the ribbon mixer, the coulter mixer, the gravity-free mixer, the cone mixer, the automatic grinding machine, the automatic ball mill or the sand mill and other equipment with strong mechanical stirring can also be a combination of the above mixing equipment.
Further, the liquid metal-containing substance includes: at least one of gallium, indium, zirconium, rubidium, francium, cesium, tin or bismuth can be liquid metal after secondary modification or multiple modification by chemical reduction, chemical oxidation, grafting of silane coupling agent, polymerization of dopamine, doping and other modification modes.
Further, the filler is selected from: the filler such as ceramic material, metal material, carbon material, etc. may be the above filler after other surface modification, for example, acidified metal, hydrogen peroxide treated ceramic and graphite oxide, or a combination between the above fillers, for example, a combination of carbon graphite oxide and ceramic hexagonal boron nitride.
Still further, the ceramic material is alumina, magnesia, zinc oxide, titanium dioxide, ferric oxide, vanadium pentoxide, silicon dioxide, nickel hydroxide, calcium carbonate, montmorillonite, mica, bentonite, boron nitride, silicon carbide, aluminum nitride, silicon nitride, barium titanate, barium zirconate titanate, barium strontium titanate, mxene, molybdenum disulfide, or the like.
Further, the metal material is structural material metal and functional material metal such as copper, iron, nickel, silver, magnesium, zinc, tungsten, lithium, sodium, manganese, stainless steel, rubidium-iron-boron or samarium-cobalt.
Further, the carbon-based material is expanded graphite, graphene oxide, carbon nanotubes, or the like.
Still further, the morphology of the filler includes 0-dimensional particles, 1-dimensional fibers, 2-dimensional sheets, and 3-dimensional complex shapes.
Furthermore, the initial filler has a size ranging from 1.0nm to 1.0cm, and can be a size monodisperse filler or a size polydisperse filler, such as a size compounded spherical alumina filler in the field of thermal management.
Further, the temperature of the modification process is selected below the melting point of the liquid metal-containing material, so that the liquid metal maintains good fluidity and can be more uniformly dispersed on the filler, for example, when gallium indium tin is used, the mixing temperature should be above 20 ℃.
Further, the mechanical force mixing time is 0.01-10.00 h, and the mixing equipment with high rotating speed can properly shorten the time.
Further, the mechanical force can be controlled by adjusting and controlling the distance between the stirring rod (stirring knife and stirring ball) and the wall of the equipment, and the closer the stirring rod is to the wall of the equipment, the larger the lateral pressure can be applied to the modified filler. The selection of a stirring rod (knife, ball) with a larger modulus helps to reduce the dissipation of force and enhances the modifying effect, such as steel knives over plastic knives. Further, the shearing force during the modification can be increased by greatly increasing the stirring and mixing speed.
Further, the modifying atmosphere may be selected from air, oxygen, nitrogen or inert gases.
The second technical problem to be solved by the invention is to provide a method for improving the dispersibility of filler in a polymer matrix, which comprises the following steps: modifying the filler by adopting a liquid metal-containing substance, and preparing the corresponding modified filler by adopting a machining method of mechanically mixing the filler and the liquid metal-containing substance; then adding the obtained modified filler into a polymer matrix, thereby realizing the improvement of the dispersibility of the filler in the matrix; wherein, the volume ratio of the liquid metal-containing substance to the filler is: 85.00-99.99 parts by volume of filler and 15.00-0.01 part by volume of liquid metal.
Further, the volume ratio of the modified filler to the polymer matrix is as follows: 0.01 to 99.00 parts by volume of modified filler and 99.99 to 1.00 parts by volume of polymer matrix. Preferably, it is: 1 to 99 parts by volume of modified filler and 99 to 1 part by volume of polymer matrix.
Further, the filler is selected from: the filler such as ceramic material, metal material, carbon material, etc. may be the above filler after other surface modification, for example, acidified metal, hydrogen peroxide treated ceramic and graphite oxide, or a combination between the above fillers, for example, a combination of carbon graphite oxide and ceramic hexagonal boron nitride.
The third technical problem to be solved by the invention is to provide a modified material, which is prepared by the following method: adding a liquid metal-containing substance into the filler, and then adopting a mechanical force mixing processing method to obtain a corresponding modified filler; wherein, the volume ratio of the liquid metal-containing substance to the filler is: 85.00-99.99 parts by volume of filler and 15.00-0.01 part by volume of liquid metal.
Further, the liquid metal-containing substance includes: at least one of gallium, indium, zirconium, rubidium, francium, cesium, tin or bismuth can be liquid metal after secondary modification or multiple modification by chemical reduction, chemical oxidation, grafting of silane coupling agent, polymerization of dopamine, doping and other modification modes.
Further, the filler is selected from: the filler such as ceramic material, metal material, carbon material, etc. may be the above filler after other surface modification, for example, acidified metal, hydrogen peroxide treated ceramic and graphite oxide, or a combination between the above fillers, for example, a combination of carbon graphite oxide and ceramic hexagonal boron nitride.
Further, the morphology of the modified material (liquid metal anchored to the material) may be fully wrapped (core-shell structure), partially wrapped (convex structure), lapped (bridging structure) and double-yolk egg (liquid metal wrapped with multiple fillers simultaneously).
Further, the liquid metal modified filler may be modified twice or more after modification, for example, oxidation or reduction is performed on the filler body portion or the liquid metal portion, grafting of a silane coupling agent is performed, polymerization of dopamine is performed, and alloying of liquid metal is performed.
Further, in the modified material, the content of liquid metal is small, and the filler is a main component, which is obviously different from the traditional liquid metal/filler hybrid material, and the surface of the modified filler is only fixed with a small amount of liquid metal, and the volume ratio of the initial filler to the liquid metal is as follows: 85.00-99.99 parts by volume of initial filler and 15.00-0.01 part by volume of liquid metal.
Preferably, in the modified material, the liquid metal-containing substance is gallium indium tin liquid metal, and the filler is: at least one of barium titanate, barium zirconate titanate, barium strontium titanate, mxene, or molybdenum disulfide; the obtained modified material has higher dielectric constant.
Preferably, in the modified material, the liquid metal-containing substance is gallium indium tin liquid metal, and the filler is: at least one of aluminum oxide, magnesium oxide, zinc oxide, titanium dioxide, ferric oxide, vanadium pentoxide, silicon dioxide, nickel hydroxide, calcium carbonate, montmorillonite, mica, bentonite, boron nitride, silicon carbide, aluminum nitride, silicon nitride, barium titanate, barium zirconate titanate, barium strontium titanate, mxene, or molybdenum disulfide; the obtained modified material has higher electromagnetic shielding performance.
The fourth technical problem to be solved by the invention is to provide a method for improving the dielectric constant of a filler, which comprises the following steps: modifying the filler by using a liquid metal-containing substance, and preparing the corresponding modified filler by adopting a mechanical force mixing processing method of the filler and the liquid metal-containing substance; wherein, the volume ratio of the liquid metal-containing substance to the filler is: 0.01 to 15.00:99.99 to 85.00.
Further, the filler is selected from: at least one of barium titanate, barium zirconate titanate, barium strontium titanate, mxene, or molybdenum disulfide.
The fifth technical problem to be solved by the present invention is to provide a method for improving electromagnetic shielding performance of a filler, the method comprising: modifying the filler by using a liquid metal-containing substance, and preparing the corresponding modified filler by adopting a mechanical force mixing processing method of the filler and the liquid metal-containing substance; wherein, the volume ratio of the liquid metal-containing substance to the filler is: 0.01 to 15.00:99.99 to 85.00.
Further, the filler is selected from: at least one of aluminum oxide, magnesium oxide, zinc oxide, titanium dioxide, ferric oxide, vanadium pentoxide, silicon dioxide, nickel hydroxide, calcium carbonate, montmorillonite, mica, bentonite, boron nitride, silicon carbide, aluminum nitride, silicon nitride, barium titanate, barium zirconate titanate, barium strontium titanate, mxene, or molybdenum disulfide.
The sixth technical problem to be solved by the invention is to provide an amphiphilic filler, wherein the raw materials of the amphiphilic filler comprise filler and a surface modifier, and the surface modifier is a substance containing liquid metal; the volume ratio of the liquid metal-containing substance to the filler is as follows: 0.01 to 15.00:99.99 to 85.00; wherein the filler is aluminum oxide, magnesium oxide, zinc oxide, titanium dioxide, ferric oxide, ferroferric oxide, vanadium pentoxide, silicon dioxide, nickel hydroxide, calcium carbonate, montmorillonite, mica, bentonite, boron nitride, silicon carbide, aluminum nitride, silicon nitride, barium titanate, barium zirconate titanate, barium strontium titanate, mxene, expanded graphite, graphene oxide, carbon nanotubes, copper, iron, nickel, silver, magnesium, zinc, tungsten, lithium, sodium, manganese, stainless steel, rubidium-iron-boron or samarium-cobalt.
The seventh technical problem to be solved by the invention is to provide a preparation method of the amphiphilic filler, which comprises the following steps: the filler and the surface modifier are mixed by mechanical force to prepare corresponding modified filler; wherein the volume ratio of the surface modifier to the filler is as follows: 0.01 to 15.00:99.99 to 85.00.
The invention has the beneficial effects that:
the invention realizes the functional modification of materials (including fillers) through a simple one-step method, has no solvent or byproducts, does not need post treatment, is a novel technology with simple production and strong universality, solves the problem that the traditional surface modification mode can not provide functional gain, and is expected to improve the dispersion of the fillers.
The invention firstly points out that the liquid metal material (liquid metal-containing substance) can be used as a surface modifier of the material by a method of carrying out strong mechanical mixing processing on the liquid metal material and the material through strong interaction induced by mechanochemistry; preparing a modified material with a structure of anchoring a small amount of liquid metal on the surface of a filler; the obtained modified material is particularly suitable for being used as a raw material in the fields of electronics, electromagnetism, electric power, energy, photo-heat, environment, biomedical and the like. In the application, the modified material can be directly used as a raw material, or can be assembled and sintered to be used as a framework, or can be prepared into a dispersion liquid, or can be amplified to be used for modifying the surface of a macroscopic block material, or can be directly added into a matrix material (polymer, ceramic, metal and the like) to be mixed to prepare a composite material.
Description of the drawings:
FIG. 1 shows a liquid metal-modified alumina filler (LM-Al) having a liquid metal content of 4.0vol% in example 1 prepared after forced mixing by a strong shear machine 2 O 3 ) And the liquid metal modified boron nitride filler (LM-BN) of example 3.
FIG. 2a is LM-BaTiO in example 2 3 Dielectric constant (1 kHz) as a function of liquid metal content FIG. 2b is LM-Al in example 1 2 O 3 Electromagnetic shielding efficiency varies with liquid metal content.
FIG. 3 is a liquid metal-modified gallium indium tin barium titanate (LM-BaTiO) of example 2 3 ) With liquid metal content, hydrophilicity (H 2 O wettability) and lipophilicity (diiodomethane wettability, abbreviated CH) 2 I 2 ) Is a changing picture of (1); and Silane-modified barium titanate (Silane-BaTiO) obtained in comparative example 3 3 ) And dopamine-modified barium titanate (PDA-BaTiO) obtained in comparative example 4 3 ) Is a comparison of (c).
FIG. 4a is a liquid metal-modified gallium indium tin barium titanate (LM-BaTiO) of example 2 3 ) Variation of contact angle with liquid metal content; fig. 4b is a comparison of example 2 with silane modification (comparative example 3) and dopamine modification (comparative example 4).
FIG. 5 is a drawing showing the hydrophilicity (H) of gallium indium tin liquid metal modified boron nitride filler (LM@BN) of example 5 2 O wettability) and lipophilicity (diiodomethane wettability, abbreviated CH) 2 I 2 ) Is a picture of the change in (c).
Fig. 6 is a scanning electron microscope cross-sectional profile of polymer composites prepared with polypropylene (PP), polymethyl methacrylate (PMMA) and polyvinylidene fluoride (PVDF) before and after modification of BN with liquid metal in example 5 and comparative example 5, showing improved filler dispersion by liquid metal modification.
FIG. 7 shows BaTiO in example 6 and comparative example 6 3 The cross-sectional morphology of a scanning electron microscope of a polymer composite prepared from the polymer composite and polyvinylidene fluoride (PVDF) before and after modification by liquid metal shows improved filler dispersion by liquid metal modification.
Fig. 8 is a scanning electron microscope cross-sectional morphology of polymer composites prepared with Polydimethylsiloxane (PDMS) before and after modification of the alumina filler with liquid metal in example 7 and comparative example 7, showing improved filler dispersion with liquid metal modification.
Fig. 9 is a scanning electron microscope cross-sectional morphology of polymer composites prepared with polyvinylidene fluoride (PVDF) before and after modification of rubidium-iron-boron (NdFeB) with liquid metal in example 8 and comparative example 8, showing improved filler dispersion for liquid metal modification.
FIG. 10 is a comparison of macroscopic rheological properties of the composites obtained in inventive example 7 and comparative example 7.
Detailed Description
Aiming at the problem that the functionality is difficult to enhance in the prior filler surface modification, the invention aims to provide a functional surface modifier, a functional surface modification method and a modified material thereof. The modification method is characterized in that the mechanochemical reaction induced by strong mechanical force causes the initial filler to generate strong interaction with the liquid metal, thereby realizing the liquid metal modified filler; the method of the invention does not require solvents, post-treatments and large amounts of liquid metal. The obtained modified filler has the characteristics that the macroscopic shape is consistent with that of the initial filler (such as powder, fiber, and the like), and the microscopic surface of the modified filler has the characteristic of anchoring by a small amount of liquid metal. The modified filler obtained by surface modification of the invention improves the functionality of the initial filler by liquid metal on one hand, reduces association between the initial fillers by adhesion of flowing liquid metal on the other hand, improves the hydrophilicity and lipophilicity of the filler, and improves the dispersibility of the filler.
In the modification method of the filler, when in modification, the fluidity of liquid metal firstly enables the liquid metal to easily infiltrate the surface of the initial filler tightly without gaps. Secondly, the strong shearing force and the strong pressure induced mechanochemical action induced by the solid-phase mechanical mixing enable the liquid metal and the initial filler to generate strong interface interaction, so that the fixing of the liquid metal is realized, and the liquid metal modified filler is prepared. For ceramic fillers, the interaction results from the strong coordination of the empty orbitals of the liquid metal (e.g., heavy metal atoms such as Ga atoms of the gallium indium tin liquid metal, rich empty orbitals) with lone pair electrons (e.g., electron-rich O atoms in alumina, electron-rich N atoms in boron nitride, O atoms in barium titanate) on the surface of the ceramic filler. For some carbon-based fillers this interaction may also exist, which may result from interactions of empty orbitals of the liquid metal with lone pair electrons of the oxide layer on the surface of the carbon-based filler (e.g. graphene oxide and O atoms in the acidified carbon tubes). For some metal fillers, this interaction results from the interaction that, when mixed with the metal, the reactivity of the liquid metal with the metal filler after mechanical activation of the metal filler surface causes diffusion of the interface element and interfacial alloying (in fact, the active metal such as aluminum may react directly with the liquid metal to form an alloy), and the presence of lone pair electrons between the empty orbitals of the liquid metal and the trace oxide O atoms on the metal filler surface.
In the preparation of the liquid metal modified filler, controllable factors include the equipment of mechanical mixing, the time of modification, the magnitude of mechanical force, the modified atmosphere and the modified temperature.
The invention also provides a modified material, which is prepared by adopting the method. The material with the modified surface by the functionalization is obtained by modifying an initial material (such as a filler) by liquid metal, and a small amount of liquid metal is fixed on the surface of the material. On the one hand, the liquid metal can endow the modified material with stronger functions by virtue of good functional characteristics. On the other hand, the liquid metal can reduce association (such as covalent bond, hydrogen bond, hydrophobic interaction, dipole interaction, conjugation and the like) among materials, influence the surface energy and wettability of the modified materials, and the oxide layer of the liquid metal can also interact with the polar matrix materials, so that the liquid metal modified filler hopefully improves the dispersion of the filler in different matrix materials (polymer, ceramic, metal and the like).
The morphology of the obtained modified material (liquid metal anchoring filler) can be full-wrapped (core-shell structure), partial-wrapped (convex structure), lap-jointed (bridging structure) and double-yolk egg (liquid metal simultaneously wraps a plurality of fillers). For example, by regulating the environmental temperature and the force/time/frequency of forced mixing of the strong shearing machine, the mechanochemical action can be regulated, so that the anchoring degree of the liquid metal and the filler is regulated, and the transition of partial wrapping/full wrapping of the surface of the filler is realized; the liquid metal surface modification is carried out by selecting filler particles with multiple particle sizes, and the liquid metal can bridge small-size fillers to the surface of large-size fillers; by selecting nano-scale (1 nm-10 nm) filler particles with extremely small particle sizes for surface modification of liquid metal, the liquid metal can coat a plurality of small particle fillers to form double-egg-shaped coating structure modification, which is probably due to the high surface energy of the liquid metal, so that the liquid metal tends to coat rather than spread on the surfaces of the nano-particles with extremely small particle sizes to form a coating.
The technical scheme is further described below in connection with the specific embodiments. It is to be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, since numerous insubstantial modifications and variations will become apparent to those skilled in the art in light of the disclosure herein.
Example 1: preparing gallium indium tin liquid metal modified alumina filler:
adding 4.0vol%,8.0vol% gallium indium tin liquid metal (purchased from Hunan middling material Cheng Te new material) and 96.0vol% aluminum oxide (purchased from hundred-picture technology, particle size 1 μm) into an automatic ball mill to prepare four modified fillers with different liquid metal contents, wherein the atmosphere is air, the temperature is 25 ℃, the rotating speed is 300rpm, and grinding is carried out for 10min, thus obtaining the liquid metal modified aluminum oxide filler (LM-Al) with different liquid metal contents 2 O 3 )。
Example 2: preparing gallium indium tin liquid metal modified barium titanate filler:
adding 0.5vol%,1.0vol%,3.0vol%,6.0vol% of gallium indium tin liquid metal (purchased from Hunan middle material Cheng Te new material) and 99.5vol%,99.0vol%,97.0vol%,94.0vol% of barium titanate (purchased from Shanghai Ala dine, particle size of 1 μm) into an automatic grinding machine to prepare four modified fillers with different liquid metal contents, wherein the atmosphere is air, the temperature is 25 ℃, the rotating speed is 100rpm, and grinding is carried out for 10min, so that the liquid metal modified materials with different liquid metal contents can be obtained Barium titanate filler (named 0.5 LM-BaTiO) 3 ，1LM-BaTiO 3 ，3LM-BaTiO 3 ，6LM-BaTiO 3 )。
Example 3: preparing gallium indium tin liquid metal modified boron nitride filler:
3vol% of gallium indium tin liquid metal (purchased from Hunan medium Cheng Te new material) and 97vol% of boron nitride (purchased from Qinhuang island Yinuo with the particle size of 10-15 mu m) are added into an automatic grinding machine, the atmosphere is air, the temperature is 25 ℃, the rotating speed is 200rpm, and the grinding is carried out for 10min, so that the liquid metal modified boron nitride filler (LM-BN) can be obtained.
Example 4: preparing gallium indium tin liquid metal modified silicon dioxide:
5vol% of gallium indium tin liquid metal (purchased from Hunan medium Cheng Te new material) and 95vol% of silicon dioxide (purchased from Yingzhang, particle size <50 nm) are added into a high-speed stirrer, the atmosphere is air, the temperature is 25 ℃, the rotating speed is 1500rpm, and the liquid metal modified silicon dioxide filler can be obtained after mixing for 6 minutes.
Example 5: preparing a liquid metal modified boron nitride nanosheet polymer composite material:
step one, 15vol% gallium indium tin liquid metal (new material from Hunan Medium Cheng Te) and 85vol% boron nitride nanoplatelets (particle size 200nm from Sigma-Aldrich) were added to an automatic ball mill under nitrogen at 25℃at 300rpm for 1min. And then the product is put into a coulter mixer to be ground for 1min, the temperature is 25 ℃, the atmosphere is air, and the rotating speed is 100rpm, so that the liquid metal modified boron nitride nano-sheet can be obtained.
Step two, respectively melt blending the liquid metal modified boron nitride nano-sheet with polypropylene (PP), polymethyl methacrylate (PMMA) and polyvinylidene fluoride (PVDF) to prepare three polymer composite materials (PP/LM-BN, PMMA/LM-BN and PVDF/LM-BN), wherein the volume part ratio of the modified filler to the polymer matrix is 4:96, the mixing equipment is a micro mixing rheometer, the mixing temperature is 195 ℃,225 ℃ and 200 ℃, the mixing rotating speed is 120rpm, the mixing time is 10min, and the extruded product is cooled and pelletized to obtain the liquid metal modified boron nitride nano-sheet polymer composite material.
Example 6: preparation of a liquid metal modified barium titanate polymer composite material:
step one, adding 3vol% of gallium indium tin liquid metal (purchased from Hunan medium Cheng Te new material) and 97vol% of barium titanate (purchased from Shanghai Ala, particle size <100 nm) into an automatic ball mill, wherein the atmosphere is air, the temperature is 25 ℃, the rotating speed is 300rpm, and grinding is carried out for 5min, so that the liquid metal modified barium titanate filler can be obtained.
Secondly, preparing a polymer composite material by melt blending liquid metal modified barium titanate filler and polyvinylidene fluoride (PVDF), wherein the volume part ratio of the modified filler to the polymer matrix is 5:95, the mixing equipment is a micro mixing rheometer, the mixing temperature is 195 ℃, the mixing rotating speed is 120rpm, the mixing time is 10min, and the extruded product is cooled and granulated to obtain the liquid metal modified barium titanate polymer composite material.
Example 7: preparation of a liquid metal modified alumina polymer composite material:
firstly, adding 1vol% of gallium indium tin liquid metal (a new material purchased from Hunan China material Cheng Te) and 99vol% of aluminum oxide (purchased from hundred-picture technology, the particle size is less than 500 nm) into a mortar, wherein the atmosphere is air, the temperature is 25 ℃, the rotating speed is 120rpm, and grinding is carried out for 20 minutes, so that the liquid metal modified silicon dioxide filler can be obtained.
Blending liquid metal modified alumina filler and Polydimethylsiloxane (PDMS) to prepare a polymer composite material, wherein the volume part ratio of the modified filler to the polymer matrix is 50:50, the mixing equipment is a planetary mixer, the mixing temperature is room temperature, the mixing rotating speed is 300rpm, the mixing time is 2min, and the product is the liquid metal modified alumina polymer composite material.
Example 8: preparing a liquid metal modified rubidium-iron-boron polymer composite material:
firstly, adding 5vol% of gallium indium tin liquid metal (purchased from a novel material of a Hunan medium Cheng Te) and 95vol% of rubidium iron boron (purchased from a Galaxa magnet, with the particle size of about 10 mu m, abbreviated as NdFeB) into an automatic ball mill, wherein the atmosphere is air, the temperature is 25 ℃, the rotating speed is 300rpm, and grinding is carried out for 5 minutes, so that the liquid metal modified rubidium iron boron filler (abbreviated as LM-NdFeB) can be obtained.
Secondly, preparing a polymer composite material by melt blending liquid metal modified rubidium-iron-boron filler and polyvinylidene fluoride (PVDF), wherein the volume part ratio of the modified filler to the polymer matrix is 10:90, the mixing equipment is a micro mixing rheometer, the mixing temperature is 195 ℃, the mixing rotating speed is 120rpm, the mixing time is 10min, and the extrusion product is cooled and granulated to obtain the liquid metal modified rubidium-iron-boron polymer composite material.
Example 9: preparation of a liquid metal modified silicon dioxide polymer composite material:
step one, adding 5vol% of gallium indium tin liquid metal (purchased from Hunan medium Cheng Te new material) and 95vol% of silicon dioxide (purchased from Yingzhang, particle size <50 nm) into a high-speed stirrer, wherein the atmosphere is air, the temperature is 25 ℃, the rotating speed is 1500rpm, and mixing for 6min to obtain the liquid metal modified silicon dioxide filler.
Secondly, melt blending liquid metal modified silicon dioxide filler and polypropylene (PP) to prepare a polymer composite material, wherein the volume part ratio of the modified filler to the polymer matrix is 40:60, the mixing equipment is a micro mixing rheometer, the mixing temperature is 195 ℃, the mixing rotating speed is 120rpm, the mixing time is 10min, and the extruded product is cooled and granulated to obtain the liquid metal modified silicon dioxide polymer composite material.
Comparative example 1: alumina filler (from hundred-picture technology, particle size 1 μm) was not modified at all.
Comparative example 2: barium titanate filler (available from Shanghai Ala with particle size 1 μm) was not modified at all.
Comparative example 3 preparation of silane-modified barium titanate filler:
2g of gamma-methacryloxypropyl trimethoxysilane (silane coupling agent KH 570, available from Shanghai Ala-dine) was mixed with 4g of deionized water, 2g of absolute ethanol under magnetic stirring at 200rpm for 1.0h at 60 ℃. Spraying the solution onto 200g of uniformly dispersed barium titanate filler solid powder surface, and drying in a vacuum oven at 60 ℃ for 8 hours to obtain silane modified barium titanate filler (named asSilane-BaTiO 3 )。
Comparative example 4 preparation of dopamine-modified barium titanate filler:
0.3g of dopamine hydrochloride (from Macklin) and 30g of barium titanate filler were added to Tris-HCl buffer solution and mixed at room temperature under magnetic stirring at 200rpm for 24 hours. The suspension was then centrifuged at 10000rpm for 5 minutes and the precipitate was collected. Stirring with deionized water, and repeating the centrifugal stirring process twice to remove unreacted dopamine. Finally, the mixture was dried in a vacuum oven at 60℃for 8 hours to obtain a dopamine-modified barium titanate filler (designated PDA-BaTiO) 3 )。
Comparative example 5: preparation of boron nitride nanosheet polymer composite material
Three polymer composites (PP/BN, PMMA/BN and PVDF/BN) were prepared by melt blending boron nitride nanoplatelets (purchased from Sigma-Aldrich, particle size 200 nm) with polypropylene (PP), polymethyl methacrylate (PMMA) and polyvinylidene fluoride (PVDF), the ratio of filler to polymer matrix by volume was 4:96, the mixing equipment is a micro mixing rheometer, the mixing temperature is 195 ℃,225 ℃ and 200 ℃, the mixing rotating speed is 120rpm, the mixing time is 10min, and the extruded product is cooled and pelletized to obtain the boron nitride nanosheet polymer composite material.
Comparative example 6: preparation of barium titanate polymer composite material:
the polymer composite material is prepared by melt blending barium titanate (purchased from Shanghai Allatin and with the particle size of <100 nm) and polyvinylidene fluoride (PVDF), and the volume part ratio of the filler to the polymer matrix is 5:95, the mixing equipment is a micro mixing rheometer, the mixing temperature is 195 ℃, the mixing rotating speed is 120rpm, the mixing time is 10min, and the extruded product is cooled and granulated to obtain the barium titanate polymer composite material.
Comparative example 7 preparation of alumina polymer composite:
the polymer composite material is prepared by blending alumina filler (purchased from hundred-picture technology, particle size <500 nm) with Polydimethylsiloxane (PDMS), and the volume fraction ratio of the filler to the polymer matrix is 50:50, the mixing equipment is a planetary mixer, the mixing temperature is room temperature, the mixing rotating speed is 300rpm, the mixing time is 2min, and the product is the alumina polymer composite material.
Comparative example 8 preparation of rubidium-iron-boron polymer composite material:
the rubidium-iron-boron (purchased from Galaxy magnet, particle size about 10 mu mB) and polyvinylidene fluoride (PVDF) are melt blended to prepare a polymer composite material, and the volume part ratio of filler to polymer matrix is 10:90, the mixing equipment is a micro mixing rheometer, the mixing temperature is 195 ℃, the mixing rotating speed is 120rpm, the mixing time is 10min, and the extrusion product is cooled and granulated to obtain the rubidium-iron-boron polymer composite material.
Comparative example 9 preparation of silica polymer composite:
the polymer composite material is prepared by melt blending silicon dioxide (purchased from Yingzhang, particle size <50 nm) and polyvinylidene fluoride (PVDF), and the volume part ratio of filler to polymer matrix is 40:60, the mixing equipment is a micro mixing rheometer, the mixing temperature is 195 ℃, the mixing rotating speed is 120rpm, the mixing time is 10min, and the extruded product is cooled and pelletized to obtain the silicon dioxide polymer composite material.
Structure and performance characterization
The invention characterizes the microscopic morphology of the liquid metal modified filler. The liquid metal modified alumina morphology and liquid metal modified boron nitride morphology (test equipment FESEM, hitachi, S-4800) in examples 1 and 3 are shown in fig. 1. Comparison with the initial filler and elemental distribution of gallium prove that gallium indium tin liquid metal can be coated on the surface of the filler in a convex shape under strong shearing.
The invention tests the improvement of the liquid metal modified filler to the intrinsic function of the filler. The dielectric constant (test equipment Novo control concept 60) and the electromagnetic shielding efficiency (test equipment Agilent N5244 Avector) are described below. As shown in fig. 2a, a comparison of example 2 and comparative example 2 shows that the dielectric constant of the liquid metal modified barium titanate filler increases with an increase in the content of gallium indium tin liquid metal, and at 6vol%, the dielectric constant increases to 510 approximately 1.6 times that of the unmodified initial filler (unmodified barium titanate dielectric constant 320). As shown in fig. 2b, a comparison of example 1 and comparative example 1 shows that the electromagnetic shielding performance of the liquid metal modified alumina filler increases significantly with an increase in the content of gallium indium tin liquid metal, and at 8vol%, the electromagnetic shielding reflection efficiency of the liquid metal modified alumina increases to 4.1dB, which is approximately 2.8 times (1.5 dB) that of the unmodified initial filler.
The invention tests the improvement of the liquid metal modified filler on the filler dispersibility by the hydrophilic-lipophilic characterization of the filler (optical contact angle measuring instrument, KRUSS DSA 25) and the section morphology judgment of the modified filler in the composite material (FESEM, hitachi, S-4800). Taking the modified barium titanate filler as an example, as shown in fig. 3, a comparison of example 2 and comparative examples 2,3 and 4 shows that the wettability of the liquid metal modified barium titanate filler to oil and water increases with the content of the gallium indium tin liquid metal, showing improvement of amphiphilicity, while the silane modified barium titanate and the dopamine modified barium titanate only increase in lipophilicity/hydrophobicity.
Fig. 4a calculates the change in contact angle in fig. 3, and at 6vol% liquid metal, the oil contact angle of the liquid metal modified barium titanate filler drops to about 55 ° and the water contact angle drops to 14 °, which represents the modified filler having excellent hydrophilicity and good lipophilicity. Fig. 4b shows that even with the same 1vol% modification content, the liquid metal modification shows a more pronounced amphiphilicity than the dopamine modification and the silane modification, which suggests that the liquid metal modified filler is hopefully able to achieve an improvement of the dispersibility in the matrix material of the different composites. As shown in fig. 5, the oil contact angle and water contact angle of the liquid metal modified boron nitride filler (example 5) were also reduced compared to the original boron nitride filler, indicating that the improvement in the liquid metal modified filler for filler amphiphilicity was true for different types of filler.
As shown in fig. 6, a comparison of example 5 and comparative example 5 shows that the initial boron nitride nano-platelet filler is highly susceptible to agglomeration in polypropylene (PP), polymethyl methacrylate (PMMA) and polyvinylidene fluoride (PVDF), while the liquid metal modification is effective in improving the dispersion of the boron nitride nano-platelet filler, indicating that the improvement effect of the liquid metal modification filler on the filler dispersion is established in different types of matrix.
In additionAs shown in FIGS. 7 to 9, comparison of examples 6 to 8 with comparative examples 6 to 8 shows that liquid metal-modified barium titanate (LM-BaTiO 3 ) Liquid metal modified alumina (LM-Al) 2 O 3 ) And liquid metal modified rubidium-iron-boron (LM-NdFeB) dispersion in a matrix compared to unmodified barium titanate (BaTiO) 3 ) Alumina (Al) 2 O 3 ) Rubidium-iron-boron (NdFeB) is also improved, which suggests that the improved effect of liquid metal modified fillers on dispersion is true for different types of fillers.
In addition, the invention also examines the macro rheological property of the composite material, and the invention uses the slope flow distance test to evaluate the change of the macro extrusion fluidity of the alumina polymer composite material before and after the modification of the liquid metal, as shown in figure 10, the liquid metal modified composite material (PDMS/LM-Al in the test time of 30s is shown in the figure 7 2 O 3 ) Before modification (PDMS/Al) 2 O 3 ) About 30% increase, it can be seen that the modified filler of the present invention improves the flow workability of the composite.
The invention also verifies that the functionality of the composite material can be enhanced by the liquid metal modified filler, and the comparison of the embodiment 9 and the comparative embodiment 9 shows that the electromagnetic shielding efficiency of the liquid metal modified silicon dioxide polymer composite material can be improved from 0.5dB of the unmodified silicon dioxide polymer composite material in the comparative embodiment to 6.1dB after modification, and 1120 percent improvement is achieved.
Claims (10)
1. The liquid metal-containing material is used as a surface modifier.
2. The use of a liquid metal-containing substance as claimed in claim 1 as a surface modifier, characterized in that the liquid metal-containing substance is used as a surface modifier for a filler; and/or:
when the liquid metal-containing substance is used for the surface modifier of the filler, the modification method comprises the following steps: adding a liquid metal-containing substance into the filler, and then adopting a mechanical force mixing processing method to obtain a corresponding modified filler; wherein, the volume ratio of the liquid metal-containing substance to the filler is: 85.00 to 99.99 parts by volume of filler and 15.00 to 0.01 part by volume of liquid metal; and/or:
when the liquid metal-containing substance is used as a surface modifier, the dispersibility of the filler in the material can be improved;
further, the material is a high molecular material, an inorganic ceramic material or other liquid materials.
3. The use of a liquid metal-containing substance as claimed in claim 1 or 2 as a surface modifier, characterized in that the mechanical force mixing process is: modifying the filler by utilizing physical and chemical actions induced by shearing force and pressure during mixing; and/or:
the processing method for carrying out mechanical force mixing adopts equipment selected from the following: at least one of a high speed mixer, a ribbon mixer, a coulter mixer, a gravity-free mixer, a cone mixer, an automatic grinding mill, an automatic ball mill, or a sand mill; and/or:
The liquid metal-containing substance comprises: at least one of gallium metal, indium metal, zirconium metal, rubidium metal, francium metal, cesium metal, tin metal or bismuth metal, and liquid metal after secondary modification or multiple modification by chemical reduction, chemical oxidation, silane coupling agent grafting, dopamine polymerization or doping modification; and/or:
in the process of obtaining the corresponding modified filler by adopting the mechanical force mixing processing method, the temperature is below the melting point of the liquid metal-containing substance; and/or:
in the process of obtaining the corresponding modified filler by adopting the mechanical mixing processing method, the modified atmosphere can be selected from air, oxygen, nitrogen or inert gas; and/or:
the filler is selected from: at least one of a ceramic material, a metal material, a carbon-based material, and a modified material thereof, wherein the modification treatment refers to an acidification treatment or a hydrogen peroxide treatment;
further, the ceramic material is aluminum oxide, magnesium oxide, zinc oxide, titanium dioxide, ferric oxide, vanadium pentoxide, silicon dioxide, nickel hydroxide, calcium carbonate, montmorillonite, mica, bentonite, boron nitride, silicon carbide, aluminum nitride, silicon nitride, barium titanate, barium zirconate titanate, barium strontium titanate, mxene or molybdenum disulfide;
Further, the metal material is copper, iron, nickel, silver, magnesium, zinc, tungsten, lithium, sodium, manganese, stainless steel, rubidium-iron-boron or samarium-cobalt;
further, the carbon-based material is expanded graphite, graphene oxide or carbon nanotubes;
further, the morphology of the filler includes 0-dimensional particles, 1-dimensional fibers, 2-dimensional sheets, and 3-dimensional complex shapes;
further, the particle size of the filler is in the range of 1.0nm to 1.0cm.
4. A method for improving the dispersibility of a filler in a polymeric matrix, the method comprising: modifying the filler by adopting a liquid metal-containing substance, and preparing the corresponding modified filler by adopting a machining method of mechanically mixing the filler and the liquid metal-containing substance; then adding the obtained modified filler into a polymer matrix, thereby realizing the improvement of the dispersibility of the filler in the matrix; wherein, the volume ratio of the liquid metal-containing substance to the filler is: 85.00 to 99.99 parts by volume of filler and 15.00 to 0.01 part by volume of liquid metal;
further, the volume ratio of the modified filler to the polymer matrix is as follows: 0.01 to 99.00 parts by volume of modified filler and 99.99 to 1.00 parts by volume of polymer matrix;
further, the filler is selected from: at least one of ceramic material, metal material, carbon-based material and modified material thereof, wherein the modification treatment refers to acidification treatment or hydrogen peroxide treatment.
5. A modified material, characterized in that the modified material is prepared by the following method: adding a liquid metal-containing substance into the filler, and then adopting a mechanical force mixing processing method to obtain a corresponding modified material; wherein, the volume ratio of the liquid metal-containing substance to the filler is: 85.00-99.99 parts by volume of filler and 15.00-0.01 part by volume of liquid metal.
6. A modified material as claimed in claim 5, wherein,
the liquid metal-containing substance comprises: at least one of gallium metal, indium metal, zirconium metal, rubidium metal, francium metal, cesium metal, tin metal or bismuth metal, and liquid metal after secondary modification or multiple modification by chemical reduction, chemical oxidation, silane coupling agent grafting, dopamine polymerization or doping modification; and/or:
the filler is selected from: at least one of a ceramic material, a metal material, a carbon-based material, and a modified material thereof, wherein the modification treatment refers to an acidification treatment or a hydrogen peroxide treatment; and/or:
the morphology of the modified material is a core-shell structure, a convex structure, a bridging structure or a double-yolk egg structure;
preferably, in the modified material, the liquid metal-containing substance is gallium indium tin liquid metal, and the filler is: at least one of barium titanate, barium zirconate titanate, barium strontium titanate, mxene, or molybdenum disulfide;
Preferably, in the modified material, the liquid metal-containing substance is gallium indium tin liquid metal, and the filler is: at least one of aluminum oxide, magnesium oxide, zinc oxide, titanium dioxide, ferric oxide, vanadium pentoxide, silicon dioxide, nickel hydroxide, calcium carbonate, montmorillonite, mica, bentonite, boron nitride, silicon carbide, aluminum nitride, silicon nitride, barium titanate, barium zirconate titanate, barium strontium titanate, mxene, or molybdenum disulfide.
7. A method of increasing the dielectric constant of a filler, the method comprising: modifying the filler by using a liquid metal-containing substance, and preparing the corresponding modified filler by adopting a mechanical force mixing processing method of the filler and the liquid metal-containing substance; wherein, the volume ratio of the liquid metal-containing substance to the filler is: 0.01 to 15.00:99.99 to 85.00;
further, the filler is selected from: at least one of barium titanate, barium zirconate titanate, barium strontium titanate, mxene, or molybdenum disulfide.
8. A method for improving electromagnetic shielding performance of a filler, the method comprising: modifying the filler by using a liquid metal-containing substance, and preparing the corresponding modified filler by adopting a mechanical force mixing processing method of the filler and the liquid metal-containing substance; wherein, the volume ratio of the liquid metal-containing substance to the filler is: 0.01 to 15.00:99.99 to 85.00;
Further, the filler is selected from: at least one of aluminum oxide, magnesium oxide, zinc oxide, titanium dioxide, ferric oxide, vanadium pentoxide, silicon dioxide, nickel hydroxide, calcium carbonate, montmorillonite, mica, bentonite, boron nitride, silicon carbide, aluminum nitride, silicon nitride, barium titanate, barium zirconate titanate, barium strontium titanate, mxene, or molybdenum disulfide.
9. The amphiphilic filler is characterized in that raw materials of the amphiphilic filler comprise filler and a surface modifier, and the volume ratio of the liquid metal-containing substance to the filler is as follows: 0.01 to 15.00:99.99 to 85.00; wherein the surface modifier is a liquid metal-containing substance; the filler is aluminum oxide, magnesium oxide, zinc oxide, titanium dioxide, ferric oxide, ferroferric oxide, vanadium pentoxide, silicon dioxide, nickel hydroxide, calcium carbonate, montmorillonite, mica, bentonite, boron nitride, silicon carbide, aluminum nitride, silicon nitride, barium titanate, barium zirconate titanate, barium strontium titanate, mxene, expanded graphite, graphene oxide, carbon nanotubes, copper, iron, nickel, silver, magnesium, zinc, tungsten, lithium, sodium, manganese, stainless steel, rubidium-iron-boron or samarium-cobalt.
10. The method for preparing the amphiphilic filler according to claim 9, wherein the method comprises the steps of: the filler and the surface modifier are mixed by mechanical force to prepare corresponding modified filler; wherein the volume ratio of the surface modifier to the filler is as follows: 0.01 to 15.00:99.99 to 85.00.
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