CN114989641A - Modified carbon microsphere/zinc oxide hybrid and preparation method and application thereof - Google Patents
Modified carbon microsphere/zinc oxide hybrid and preparation method and application thereof Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 172
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 150000001721 carbon Chemical class 0.000 title claims abstract description 133
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920001971 elastomer Polymers 0.000 claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 24
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims abstract description 19
- 229940007718 zinc hydroxide Drugs 0.000 claims abstract description 19
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims abstract description 19
- 150000003751 zinc Chemical class 0.000 claims abstract description 18
- 239000000945 filler Substances 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007900 aqueous suspension Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 230000020477 pH reduction Effects 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 239000002131 composite material Substances 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 5
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- 239000011248 coating agent Substances 0.000 abstract description 3
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- 229910021392 nanocarbon Inorganic materials 0.000 abstract description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 23
- 229920003052 natural elastomer Polymers 0.000 description 23
- 229920001194 natural rubber Polymers 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000463 material Substances 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 7
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
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- 238000005336 cracking Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 238000010587 phase diagram Methods 0.000 description 4
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- 238000001291 vacuum drying Methods 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 238000005169 Debye-Scherrer Methods 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
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- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 229910003472 fullerene Inorganic materials 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
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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
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- C08K3/22—Oxides; Hydroxides of metals
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
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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
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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
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- C08K9/02—Ingredients treated with inorganic substances
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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
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- C08K9/04—Ingredients treated with organic substances
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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
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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
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- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
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- C09C3/06—Treatment with inorganic compounds
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/00—Crystal-structural characteristics
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention relates to the technical field of nano carbon materials, and provides a modified carbon microsphere/zinc oxide hybrid and a preparation method and application thereof. The invention firstly carries out acid treatment on the carbon microspheres to obtain modified carbon microspheres, increases the active sites of the carbon microspheres, then carries out in-situ coating reaction on the modified carbon microspheres by adopting zinc salt and hydroxide to ensure that zinc hydroxide is combined on the active sites on the surfaces of the carbon microspheres, and finally obtains the modified carbon microspheres/zinc oxide hybrid by calcining. According to the invention, ZnO is loaded on the surface of the modified carbon microsphere, the agglomeration of the carbon microsphere is greatly reduced by utilizing the isolation effect of ZnO, and the modified carbon microsphere/zinc oxide hybrid is filled into a rubber product as a filler, so that the obtained rubber composite material has excellent comprehensive performance.
Description
Technical Field
The invention relates to the technical field of nano carbon materials, in particular to a modified carbon microsphere/zinc oxide hybrid and a preparation method and application thereof.
Background
The carbon microsphere is a spherical nano carbon material, and can be used as a diamond film material, a lubricating material, a catalyst, a stealth material, a lithium ion battery cathode material and the like due to the excellent performance similar to fullerene.
The carbon microsphere has good chemical stability, high stacking density, easy graphitization, good thermal stability and excellent electric and thermal conductivity, and is a high-quality precursor for preparing high-performance carbon and graphite materials. In order to further expand the application field of the carbon microspheres, the method for improving the performance of the rubber product by filling the carbon microspheres serving as the filler into the rubber becomes a means for expanding the application field of the rubber product. However, after the carbon microspheres are filled into rubber, the carbon microsphere particles are easy to agglomerate and have poor dispersibility, and the performance of rubber products is reduced, so that the application of the carbon microspheres in the rubber products is hindered. Therefore, how to improve the dispersibility of the carbon microspheres in the rubber becomes a technical problem to be solved urgently.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a modified carbon microsphere/zinc oxide hybrid, a preparation method and an application thereof, the modified carbon microsphere/zinc oxide hybrid provided by the present invention has excellent dispersion performance, and can be used as a filler in a rubber composite material, and the obtained rubber composite material has excellent performance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a modified carbon microsphere/zinc oxide hybrid, which comprises the following steps:
(1) mixing the carbon microspheres with acid, and then acidifying to obtain modified carbon microspheres;
(2) dispersing the modified carbon microspheres in water to obtain modified carbon microsphere aqueous suspension;
(3) mixing the modified carbon microsphere aqueous suspension and a zinc salt, then carrying out first heat treatment, adjusting the obtained first heat treatment liquid to be alkaline by adopting hydroxide, and carrying out second heat treatment to obtain a modified carbon microsphere/zinc hydroxide hybrid;
(4) and calcining the modified carbon microsphere/zinc hydroxide hybrid to obtain the modified carbon microsphere/zinc oxide hybrid.
Preferably, the particle size of the carbon microsphere is less than 100 nm.
Preferably, the acid comprises an inorganic acid; the mass of the carbon microspheres and the volume ratio of the acid are 3 g: 30-80 mL; the acidification temperature is 50-100 ℃, and the time is 1-3 h.
Preferably, the ratio of the mass of the modified carbon microspheres to the volume of water in the modified carbon microsphere aqueous suspension is 3 g: 200-500 mL.
Preferably, the molar weight ratio of the mass of the modified carbon microspheres to the zinc salt is 3 g: 0.0366-0.0854 mol; the temperature of the first heat treatment is 60-100 ℃, and the time is 1-3 h.
Preferably, the zinc salt comprises one or more of zinc acetate dihydrate, zinc sulfate and zinc chloride.
Preferably, the hydroxide comprises one or both of sodium hydroxide or potassium hydroxide; adding the hydroxide in the form of hydroxide solution, wherein the addition amount of the hydroxide is based on the adjustment of the pH value of the first heat treatment liquid to 9-11; the mass fraction of the hydroxide solution is 0.5-2%; the temperature of the second heat treatment is 60-100 ℃, and the time is 1-3 h.
Preferably, the calcining temperature is 150-180 ℃, and the time is 1-3 h.
The invention also provides a modified carbon microsphere/zinc oxide hybrid prepared by the preparation method in the technical scheme, wherein the modified carbon microsphere/zinc oxide hybrid comprises modified carbon microspheres and zinc oxide particles loaded on the surfaces of the modified carbon microspheres.
The invention also provides the application of the modified carbon microsphere/zinc oxide hybrid in the technical scheme as a rubber filler.
The invention provides a preparation method of a modified carbon microsphere/zinc oxide hybrid, which comprises the following steps: (1) mixing the carbon microspheres with acid, and then acidifying to obtain modified carbon microspheres; (2) dispersing the modified carbon microspheres in water to obtain modified carbon microsphere aqueous suspension; (3) mixing the modified carbon microsphere aqueous suspension and zinc salt, carrying out first heat treatment, adjusting the obtained first heat treatment liquid to be alkaline by adopting hydroxide, and carrying out second heat treatment to obtain a modified carbon microsphere/zinc hydroxide hybrid; (4) and calcining the modified carbon microsphere/zinc hydroxide hybrid to obtain the modified carbon microsphere/zinc oxide hybrid. The invention firstly carries out acid treatment on the carbon microspheres to obtain modified carbon microspheres, increases the active sites of the carbon microspheres, then carries out in-situ coating reaction on the modified carbon microspheres by adopting zinc salt and hydroxide to ensure that zinc hydroxide is combined on the active sites on the surfaces of the carbon microspheres, and finally obtains the modified carbon microspheres/zinc oxide hybrid by calcining. According to the invention, ZnO is loaded on the surface of the modified carbon microsphere, the agglomeration of the carbon microsphere is greatly reduced by utilizing the isolation effect of ZnO, and the modified carbon microsphere/zinc oxide hybrid is filled into a rubber product as a filler, so that the obtained rubber composite material has excellent comprehensive performance.
Drawings
FIG. 1 is a flow chart of the preparation of a modified carbon microsphere/zinc oxide hybrid;
FIG. 2 is a scanning electron micrograph of the modified carbon microspheres and the modified carbon microsphere/zinc oxide hybrid and zinc oxide prepared in example 1;
FIG. 3 is a transmission electron micrograph of the modified carbon microsphere/zinc oxide hybrid prepared in example 1;
FIG. 4 is an X-ray diffraction pattern of modified carbon microspheres and modified carbon microsphere/zinc oxide hybrids and zinc oxide prepared in example 1;
FIG. 5 is an atomic force microscope photograph of the modified carbon microsphere/zinc oxide hybrid prepared in example 1 and the CZ/NR composite prepared in application example 1 and the CM/NR composite prepared in comparative example 2;
FIG. 6 is a Raman spectrum of the modified carbon microspheres and the modified carbon microsphere/zinc oxide hybrid and zinc oxide prepared in example 1;
FIG. 7 is a graph of dynamic mechanical analysis tests using the CZ/NR prepared in example 1, the N330/NR prepared in comparative example 1, and the CM/NR prepared in comparative example 2;
FIG. 8 is a graph showing the static mechanical property test using CZ/NR prepared in example 1, N330/NR prepared in comparative example 1, and CM/NR prepared in comparative example 2.
Detailed Description
The invention provides a preparation method of a modified carbon microsphere/zinc oxide hybrid, which comprises the following steps:
(1) mixing the carbon microspheres with acid, and then acidifying to obtain modified carbon microspheres;
(2) dispersing the modified carbon microspheres in water to obtain modified carbon microsphere aqueous suspension;
(3) mixing the modified carbon microsphere aqueous suspension and zinc salt, carrying out first heat treatment, adjusting the obtained first heat treatment liquid to be alkaline by adopting hydroxide, and carrying out second heat treatment to obtain a modified carbon microsphere/zinc hydroxide hybrid;
(4) and calcining the modified carbon microsphere/zinc hydroxide hybrid to obtain the modified carbon microsphere/zinc oxide hybrid.
In the present invention, unless otherwise specified, each of the substances is a commercially available product well known to those skilled in the art.
The invention mixes the carbon microsphere and acid and then acidifies the mixture to obtain the modified carbon microsphere. In the invention, the particle size of the carbon microsphere is preferably less than 100nm, more preferably less than 90nm, and further preferably 80-90 nm; the acid preferably comprises inorganic acid, the inorganic acid preferably comprises one or more of nitric acid, hydrochloric acid and sulfuric acid, and the nitric acid, hydrochloric acid and sulfuric acid preferably comprise undiluted commercially available concentrated nitric acid, concentrated hydrochloric acid and concentrated sulfuric acid; the volume ratio of the mass of the carbon microspheres to the volume of the acid is preferably 3 g: 30-80 mL, more preferably 3 g: 50-80 mL, more preferably 3 g: 50 mL; the invention has no special requirements on the mixing mode and can be mixed uniformly; the acidification temperature is preferably 50-100 ℃, more preferably 80-100 ℃, and the time is preferably 1-3 hours, more preferably 2-3 hours; after the acidification, the feed liquid obtained by acidification is preferably subjected to suction filtration and drying in sequence, deionized water is preferably adopted for washing during the suction filtration, and the suction filtration is preferably carried out until filtrate is neutral.
The source of the carbon microspheres is not particularly limited in the present invention, and those known to those skilled in the art can be used, specifically, those commercially available or prepared by themselves.
In the embodiment of the invention, the carbon microspheres are obtained by cracking acetylene serving as a carbon source under a high-temperature nitrogen or argon environment by using a CVD method, and specifically comprise the following steps:
a. introducing nitrogen or argon into the tubular furnace, wherein the speed of the nitrogen or argon is 80-120 mL/min, and heating to 600-700 ℃ at the heating speed of 3-7 ℃/min;
b. stopping introducing nitrogen or argon, introducing acetylene gas into the tubular furnace for cracking, wherein the acetylene speed is 80-120 mL/min, the cracking time is 0.5-1.5 h, stopping introducing the acetylene gas after cracking is finished, and cooling to normal temperature under the condition of introducing the nitrogen or argon to obtain the carbon microspheres, wherein the nitrogen or argon speed is 20-150 mL/min.
After the modified carbon microspheres are obtained, the modified carbon microspheres are dispersed in water to obtain the modified carbon microsphere aqueous suspension. In the invention, the ratio of the mass of the modified carbon microspheres to the volume of water in the modified carbon microsphere aqueous suspension is 3 g: 200-500 mL, more preferably 3 g: 300-500 mL; the dispersing mode has no special requirements, and the dispersing is uniform.
After the modified carbon microsphere aqueous suspension is obtained, the modified carbon microsphere aqueous suspension and zinc salt are mixed and then subjected to first heat treatment, then the obtained first heat treatment liquid is adjusted to be alkaline by adopting hydroxide, and then second heat treatment is carried out, so that the modified carbon microsphere/zinc hydroxide hybrid is obtained. In the present invention, the ratio of the mass of the modified carbon microspheres to the molar weight of the zinc salt is preferably 3 g: 0.0366-0.0854 mol, more preferably 3 g: 0.061-0.0854 mol; the zinc salt preferably comprises one or more of zinc acetate dihydrate, zinc sulfate and zinc chloride, and more preferably zinc acetate dihydrate; the zinc salt is preferably added in a form of a zinc salt aqueous solution, the concentration of the zinc salt aqueous solution is preferably 0.305-1.22 mol/L, more preferably 0.61mol/L, the adding mode of the zinc salt aqueous solution is preferably dropwise adding, the dropwise adding speed is preferably 60-180 drops/min, more preferably 120 drops/min, after the dropwise adding is completed, stirring and ultrasonic processing are preferably continued for 0.5-1 h, more preferably 1h, so as to obtain a uniform suspension; the temperature of the first heat treatment is preferably 60-100 ℃, more preferably 80-100 ℃, and the time is preferably 1-3 hours, more preferably 1-2 hours. In the invention, the hydroxide preferably comprises one or two of sodium hydroxide or potassium hydroxide, the hydroxide is preferably added in the form of hydroxide solution, the addition amount of the hydroxide is preferably based on the adjustment of the pH value of the first heat treatment liquid to 9-11, more preferably to 10-11, the mass fraction of the hydroxide solution is preferably 0.5-2%, more preferably 1-2%, the addition manner of the hydroxide solution is preferably dropwise addition, and the dropwise addition rate is preferably 60-180 drops/min, more preferably 120 drops/min; the second heat treatment temperature is preferably 60-100 ℃, more preferably 80-90 ℃, and the time is preferably 1-3 hours, more preferably 2-3 hours; after the second heat treatment, preferably filtering the second heat treatment liquid, and then preferably washing and drying the obtained solid in sequence to obtain a modified carbon microsphere/zinc hydroxide hybrid; the washing frequency is preferably 3-5 times, more preferably 5 times, the washing liquid for washing is preferably deionized water, the drying is preferably vacuum drying, the drying temperature is preferably 40-60 ℃, more preferably 50-60 ℃, and the drying time is preferably 12-36 hours, more preferably 12-24 hours.
After the modified carbon microsphere/zinc hydroxide hybrid is obtained, the modified carbon microsphere/zinc hydroxide hybrid is calcined to obtain the modified carbon microsphere/zinc oxide hybrid. In the invention, the calcining temperature is preferably 150-180 ℃, more preferably 150-160 ℃, and the time is preferably 1-3 h, more preferably 2-3 h; the atmosphere for the calcination is preferably an air atmosphere.
The invention also provides the modified carbon microsphere/zinc oxide hybrid prepared by the preparation method in the technical scheme, the modified carbon microsphere/zinc oxide hybrid preferably comprises modified carbon microspheres and zinc oxide particles loaded on the surfaces of the modified carbon microspheres, and the mass fraction of the zinc oxide particles in the modified carbon microsphere/zinc oxide hybrid is preferably 50-75%. In the invention, the particle size of the zinc oxide particles is preferably 14-17 nm. According to the invention, ZnO is loaded on the surface of the modified carbon microsphere, and the agglomeration of the carbon microsphere is greatly reduced by utilizing the isolation effect of ZnO.
The invention also provides the application of the modified carbon microsphere/zinc oxide hybrid in the technical scheme as a rubber filler. In the invention, the application specifically comprises the steps of preparing the natural rubber composite material by using the modified carbon microsphere/zinc oxide hybrid as a rubber filler; the rubber mixing method of the natural rubber composite material preferably implements an open mill method in the carbon black national standard GB/T3780.18-2007, and the modified carbon microsphere/zinc oxide hybrid, sulfur and an accelerator are preferably added simultaneously. In a specific embodiment of the invention, the natural rubber composite material comprises the following components in parts by mass: the rubber comprises, by mass, 100 parts of natural rubber, 50 parts of carbon black N33050 parts, 3 parts of stearic acid, 6-10 parts of modified carbon microsphere/zinc oxide hybrid, 0.6 part of accelerator DM and 2.5 parts of sulfur.
In order to further illustrate the present invention, the following examples are provided to describe the modified carbon microsphere/zinc oxide hybrid and the preparation method and application thereof in detail, but they should not be construed as limiting the scope of the present invention.
FIG. 1 is a flow chart of a preparation process of a modified carbon microsphere/zinc oxide hybrid, which comprises the steps of firstly carrying out acid treatment on carbon microspheres to obtain modified carbon microspheres, increasing active sites of the carbon microspheres, then carrying out in-situ coating reaction on the modified carbon microspheres by adopting zinc salt and hydroxide to enable zinc hydroxide to be combined on the active sites on the surfaces of the carbon microspheres, and finally calcining to obtain the modified carbon microsphere/zinc oxide hybrid.
Example 1
Preparing carbon microspheres:
a. introducing nitrogen into the tubular furnace at the speed of 100mL/min, and heating to 600 ℃ at the heating speed of 5 ℃/min;
b. stopping introducing nitrogen, introducing acetylene gas into the tubular furnace for cracking at the acetylene speed of 100mL/min for 1h, stopping introducing the acetylene gas after cracking is finished, and cooling to normal temperature under the condition of introducing nitrogen to obtain the carbon microspheres, wherein the nitrogen speed is 100 mL/min.
The method for preparing the modified carbon microsphere/zinc oxide hybrid by using the prepared carbon microsphere comprises the following steps:
placing 3g of carbon microspheres in an oil bath kettle at 80 ℃ for stirring, adding 50mL of undiluted concentrated nitric acid, reacting for 2h at constant temperature, washing the obtained acid solution with deionized water after the reaction is finished until the obtained acid solution is subjected to suction filtration to be neutral, and naturally drying the obtained solid to obtain modified carbon microspheres (marked as CM);
dispersing 3g of modified carbon microspheres in 300mL of deionized water in a three-neck flask to obtain modified carbon microsphere aqueous suspension;
dropwise adding a zinc acetate dihydrate water solution into the modified carbon microsphere solution, wherein the dropwise adding speed is 2 drops/s, and the mass ratio of the modified carbon microsphere to the zinc acetate dihydrate is 3: 13.48, the concentration of the zinc acetate dihydrate water solution is 0.61mol/L, and the obtained suspension is continuously stirred and ultrasonically treated for 1h to obtain uniform suspension; then putting the suspension into an oil bath pan, starting heating, setting the temperature at 80 ℃, and heating for 1h to obtain a first heat treatment liquid;
dropwise adding 1 wt% of sodium hydroxide solution into the first heat treatment solution at a dropping rate of 2 drops/s, adjusting the addition amount of the sodium hydroxide solution to 10 according to the pH value of the first heat treatment solution, then reacting for 2 hours at 80 ℃ to obtain a second heat treatment solution, washing and filtering the second heat treatment solution for 5 times by using deionized water, and drying the obtained solid for 24 hours at 50 ℃ in a vacuum oven to obtain a modified carbon microsphere/zinc hydroxide hybrid;
calcining the obtained modified carbon microsphere/zinc hydroxide hybrid in an oven at 150 ℃ for 2h in air atmosphere to obtain the modified carbon microsphere/zinc oxide hybrid (marked as CZ).
Application example 1
The rubber mixing method of the natural rubber composite material implements an open mill method in the carbon black national standard GB/T3780.18-2007, and the used natural rubber, carbon black N330, stearic acid, accelerator DM and sulfur implement the requirements of Table 1 in the GB/T3780.18-2007 standard.
The natural rubber composite material comprises the following components in parts by mass: 100 parts of natural rubber, 50 parts of carbon black N33050, 3 parts of stearic acid, 8 parts of CZ prepared in example 1, 0.6 part of accelerator DM and 2.5 parts of sulfur.
Before mixing, placing the carbon black raw material in a drying oven for drying at 125 ℃ for 1h, and placing in a clean environment for later use after drying. The rubber mixing method of the natural rubber composite material adopts an open mill method in the carbon black national standard GB/T3780.18-2007, and comprises the following specific preparation steps: the operation distance between two baffles is (200 +/-10) mm during mixing, the temperature of a radial cylinder is controlled to be (70 +/-5) DEG C, the mixing distance of an open mill is adjusted to be 0.8mm, and raw rubber is not wrapped and mixed and broken for 1 time; adjusting the wheel tread of the open mill to 1.4mm, adding a natural rubber bag, mixing in the front, and cutting for 2 times. The width of the cutting knife is 3/4 of the mixing cylinder, 1 time of cutting knife from two ends is 1 knife alternately, and the interval time of each knife is about 20 s; adjusting the wheel track to 1.65mm, adding stearic acid, and cutting for 1 time; adding sulfur, accelerator DM and CZ, and cutting for 2 times; all the carbon black N330 was added and freely dispersed into the tray. Cutting knife twice after no obvious powder on the surface of the rubber material, adjusting the wheel track to 1.9mm, and cutting knife 3 times after all the carbon black N330 scattered in the material receiving disc is mixed (when obvious powder exists on the mixed rubber material, the cutting knife is not accurate, and the materials falling into the material receiving disc are ensured to be mixed into the rubber material completely). Adjusting the roller spacing to be 0.8mm, and vertically passing the rolled sizing material through the roller gap for 6 times without wrapping the roller; adjusting the roller distance to enable the thickness of the rubber sheet to be 6-8 mm, and enabling the folded rubber sheet to pass through the roller gap for 4 times. The above operation time was (17.0 seconds 0.5) min. The gum weight was rechecked and recorded. If the mass of the rubber compound after mixing exceeds the range of (480.9-485.7) g, the roller rubber compound is discarded, and the roller rubber compound with qualified quality is a natural rubber composite material (marked as CZ/NR).
According to the test method GB/T9869, the vulcanization characteristic of the natural rubber composite material is measured, enough rubber materials are cut out from the mixed rubber materials, and the wheel track is adjusted to be about 2.2mm according to the thickness of the rubber material sheet. The method comprises the steps of placing a film on a flat, dry and clean metal plate, placing the film for 1-24 hours at the temperature of 23 +/-3 ℃, controlling the relative humidity to be 50 +/-5%, and storing the film in a cool and sealed container to prevent moisture absorption if the humidity does not meet the requirement.
The vulcanizing mould is designed according to the test piece size of 150mm multiplied by 2mm, the rubber compound pieces are cut into rubber compound test pieces with the length and width smaller than 3mm of each vulcanizing mould, the name, the number and the rolling direction of the sample are marked, and the weight of each rubber compound piece is (54 +/-1). The temperature of a vulcanizing machine (GB 6038) flat plate is adjusted to (145 +/-1) DEG C.
Placing the mold at a proper position of a vulcanizing flat plate (GB 6038), preheating for 20min, and quickly filling the mold for vulcanization. After the mold is filled, when the pressure applied to the mold reaches the requirement (GB 6038), timing is carried out immediately, the allowable error of the vulcanization time is 20s, and the vulcanization time: and (3) 30 min. And standing the vulcanized rubber test piece at 23 +/-3 ℃ for 1-96 hours according to the requirement of GB/T2941.
Comparative example 1
A natural rubber composite (denoted as N330/NR) was prepared according to the procedure of application example 1, except that:
changing 8 parts of CZ into 5 parts of zinc oxide;
the preparation method of the zinc oxide comprises the following steps: adding 1mmol of zinc acetate dihydrate into a three-neck flask, pouring 1000mL of deionized water into the flask, placing the device in an oil bath kettle, heating and stirring at 80 ℃, adjusting the pH value of the solution to 10 by using a sodium hydroxide solution with the mass fraction of 1%, filtering feed liquid in the flask, washing the obtained solid with deionized water for 5 times, and performing vacuum drying at 50 ℃ for 24 hours to obtain a zinc hydroxide solid. And calcining the zinc hydroxide solid for 2 hours at 150 ℃ in an air atmosphere to obtain a zinc oxide solid.
Comparative example 2
A natural rubber composite (noted as CM/NR) was prepared with reference to the procedure of application example 1, except that:
And (3) performance characterization:
the surface morphology of the modified carbon microspheres, ZnO and CZ was observed by SEM, and the results are shown in fig. 2, where (a) in fig. 2 is the modified carbon microspheres, (b) is zinc oxide, (c) is CZ (magnification of 10K), and (d) is CZ (magnification of 7K). As can be seen from (a), the shapes of the modified carbon microspheres are all similar to spheres, the dispersibility is better, and the shapes are regular. In (b), the ZnO particles are mostly spherical with some agglomeration. In (c) and (d), it can be seen that ZnO is loaded on the surface of the modified carbon microsphere, and the dispersion is relatively uniform.
The morphology of CZ was observed by TEM, and the results are shown in FIG. 3, in which (a) is on a 0.5 μm scale, (b) is on a 100nm scale, and (c) is a high-resolution transmission electron micrograph of CZ. According to the (a) and the (b), the modified carbon microspheres are amorphous carbon, have good dispersibility, are all spherical-like in shape, and have more defects on the surface of the material. Meanwhile, ZnO is well adsorbed on the surface of the modified carbon microspheres, and the agglomeration of the carbon microspheres is greatly reduced due to the isolation effect of ZnO, so that the ZnO-based carbon microspheres have an important effect on improving the dispersion degree of CZ in a rubber matrix in the rubber mixing process. Meanwhile, it can be seen from (c) that the lattice fringes of zinc oxide are clear, and the crystallinity of zinc oxide is known to be excellent, which is consistent with the analysis result of XRD. The spacing between adjacent lattice fringes was found to be 0.26nm, corresponding to the spacing of wurtzite zinc oxide (002) crystal planes.
Fig. 4 is an X-ray diffraction pattern of the modified carbon microsphere prepared in example 1, CZ and zinc oxide, and it can be seen from the curve (a) in the figure that reference peaks of carbon appear at 2 θ ═ 25.4 ° (002 crystal face) and 41.9 ° (100 crystal face), which are characteristic diffraction peaks of microcrystalline graphite on the surface of the modified carbon microsphere. In the curve (b), the characteristic peaks at 31.6 °, 34.3 °, 36.1 °, 47.4 °, 56.4 °, 62.6 ° and 67.8 ° are typical hexagonal wurtzite ZnO structures (JCPDS card No. 36-1451). In curve (c), the characteristic peaks of ZnO were all present, while the characteristic peaks of the modified carbon microsphere at 2 θ of 25.4 ° disappeared, probably due to the ZnO particles supported on the surface of the modified carbon microsphere. According to the Debye-Scherrer formula, the sizes of ZnO crystal grains loaded on the pure ZnO and CZ surfaces are 16.9nm and 14.2nm respectively. The reduction in grain size indicates that the presence of the modified carbon microspheres inhibited the growth of ZnO grains.
In order to further observe the internal distribution of the composite material, the natural rubber composite materials prepared in application example 1 and comparative example 2 were subjected to frozen ultra-thin slicing, and then the smooth surfaces thereof were subjected to AFM characterization, and the results are shown in fig. 5. In FIG. 5, (a), (b) represent the morphology and phase diagram, respectively, of CM/NR prepared in comparative example 2, (c), (d) represent the morphology and phase diagram, respectively, of CZ/NR prepared in application example 1 (the scale on the abscissa is 0 to 5 μm), and (e) and (f) represent the morphology and phase diagram, respectively, of CZ/NR prepared in application example 1 (the scale on the abscissa is 0 to 2 μm). In the AFM image, bright spots in the morphology graph indicate protruded carbon black particles, which correspond to the corresponding positions of the phase diagram, respectively, and it can be seen from (a), (b), (c) and (d) that CZ in application example 1 has more hard spots in the rubber, better dispersion and more uniformity than those in comparative example 2; from (e) and (f), ZnO is relatively uniformly loaded on the surface of the modified carbon microsphere.
In order to confirm the interfacial interaction between the modified carbon microspheres and ZnO in CZ, raman spectroscopy tests were performed on the modified carbon microspheres, ZnO, and CZ, respectively, and the results are shown in fig. 6. In curve (a) of FIG. 6, 2E of ZnO 2 (M) and E 2 (high) mode absorption peaks respectively located at 333cm -1 And 440cm -1 To (3). In curve (b), at 1322cm -1 With the occurrence of D-band, which is in contrast to the modified carbon microspheresDisordered structure is related and is 1578cm -1 The G band, usually I, appears nearby D And I G The relative ratio of (A) is to express the disorder degree and defect condition of the sample, so that the I of the modified carbon microsphere can be obtained D /I G The value is about 0.84, in curve (c), E of CZ 2 (high) mode occurrence 15cm -1 The bathochromic shift, which is due to the modified carbon microspheres, limits the growth of ZnO crystals in CZ, while the small size of the crystals leads to the space-limiting effect of the optical phonons. Meanwhile, D bands and G bands of CZ are respectively appeared at 1332cm -1 And 1581cm -1 Obtaining I of CZ D /I G The value was about 1.41, indicating that the surface structure of the modified carbon microspheres was changed due to the surface loading of ZnO and the destruction of the regular structure of part of the modified carbon microspheres. This indicates that there is some interfacial interaction between ZnO and modified carbon microspheres.
In order to investigate the interfacial interaction between the filler and the natural rubber matrix, DMA characterization was performed on the CZ/NR prepared in example 1, the N330/NR prepared in comparative example 1, and the CM/NR prepared in comparative example 2, with the results shown in FIG. 7. In FIG. 7, (a) is a storage modulus-temperature curve of the above three natural rubber composites, (b) is a loss tangent-temperature curve of the above three natural rubber composites, and (c) is a loss modulus-temperature curve of the above three natural rubber composites. In (a), E 'represents the magnitude of the stored energy of the material, E' is mainly related to the filler-rubber network and the filler-filler network, if the degree of networking of the filler is large, the part of the produced occlusion rubber (rubber adsorbed in the filler network) is large, the effective volume of the filler is larger than the actual part filled, and the larger the degree of networking is, the larger the modulus is at the same filling amount. (a) The medium CZ/NR has the largest storage modulus and the smallest storage modulus of CM/NR, which shows that under the influence of CZ, the acting force of carbon black and rubber molecules is strong, the rubber molecules can enter a carbon black network more easily to form a new network structure, and a larger amount of bonding glue is generated. As can be seen from (b), the addition of the modified carbon microspheres did not significantly affect the peak position of tan. delta. but significantly reduced itThe peak value is the lowest CZ/NR peak value, so that some rubber molecules are adsorbed on the surface of the modified carbon microsphere, and the physical performance of the composite material is improved. Meanwhile, (c) shows the relationship between the loss modulus of the filler and the temperature, and the glass transition temperature T is also shown in some documents by this peak value g As can be seen from (c), CZ/NR and CM/NR did not change much compared to N330/NR.
Static mechanical property tests were performed on CZ/NR prepared in application example 1, N330/NR prepared in comparative example 1 and CM/NR prepared in comparative example 2, and 100% stress at definite elongation, 200% stress at definite elongation, 300% stress at definite elongation, tensile strength and elongation at break were recorded, respectively, and the results are shown in FIG. 8 and Table 1. As can be seen, compared with N330/NR, the CZ/NR has the advantages that the 100% stress at definite elongation, the 200% stress at definite elongation, the 300% stress at definite elongation and the tensile strength are respectively improved by 40.3%, 30.6%, 23.3% and 9.6%, and meanwhile, the elongation at break of the composite material is hardly influenced, and the rigidity of the composite material is improved.
TABLE 1 mechanical Properties of Natural rubber composites
In view of the direct influence of ZnO dispersion in the natural rubber matrix on the crosslinking rate of the natural rubber matrix, the vulcanization characteristics of CZ/NR prepared in example 1, N330/NR prepared in comparative example 1 and CM/NR prepared in comparative example 2 were respectively tested, and the results are shown in Table 2. The better the dispersity of the rubber accelerator is, the better the rubber accelerator can accelerate the vulcanization of the rubber, and the shorter the time for achieving the best vulcanization effect is, as can be seen from table 2, the shortest T90 (positive vulcanization time) and the shortest T10 (scorching time) of CZ/NR indicate that CZ accelerates the vulcanization of the rubber, and CZ is more favorable for accelerating the vulcanization of the rubber than CM and N330; m H The higher the MH, the higher the hardness, which corresponds to the results of the crosslink density, which is characteristic of the shear modulus, hardness, tensile strength and crosslink density of the compound, M of CZ compared to CM/NR and N330/NR H The highest value indicates that CZ is more favorable for promoting rubber and filler than CM and N330In the form of a bond between them.
TABLE 2 crosslinking Properties of Natural rubber composites
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that modifications and adaptations can be made by those skilled in the art without departing from the principle of the present invention, and should be considered as within the scope of the present invention.
Claims (10)
1. A preparation method of a modified carbon microsphere/zinc oxide hybrid is characterized by comprising the following steps:
(1) mixing the carbon microspheres with acid and then acidifying to obtain modified carbon microspheres;
(2) dispersing the modified carbon microspheres in water to obtain modified carbon microsphere aqueous suspension;
(3) mixing the modified carbon microsphere aqueous suspension and zinc salt, carrying out first heat treatment, adjusting the obtained first heat treatment liquid to be alkaline by adopting hydroxide, and carrying out second heat treatment to obtain a modified carbon microsphere/zinc hydroxide hybrid;
(4) and calcining the modified carbon microsphere/zinc hydroxide hybrid to obtain the modified carbon microsphere/zinc oxide hybrid.
2. The method of claim 1, wherein the carbon microspheres have a particle size of less than 100 nm.
3. The method of claim 1, wherein the acid comprises an inorganic acid; the mass of the carbon microspheres and the volume ratio of the acid are 3 g: 30-80 mL; the acidification temperature is 50-100 ℃, and the time is 1-3 h.
4. The method according to claim 1, wherein the mass-to-water volume ratio of the modified carbon microspheres in the aqueous suspension of modified carbon microspheres is 3 g: 200-500 mL.
5. The preparation method of claim 1, wherein the molar weight ratio of the mass of the modified carbon microsphere to the zinc salt is 3 g: 0.0366-0.0854 mol; the temperature of the first heat treatment is 60-100 ℃, and the time is 1-3 h.
6. The method according to claim 1 or 5, wherein the zinc salt comprises one or more of zinc acetate dihydrate, zinc sulfate and zinc chloride.
7. The method of claim 1, wherein the hydroxide comprises one or both of sodium hydroxide or potassium hydroxide; adding the hydroxide in the form of hydroxide solution, wherein the addition amount of the hydroxide is based on the adjustment of the pH value of the first heat treatment liquid to 9-11; the mass fraction of the hydroxide solution is 0.5-2%; the temperature of the second heat treatment is 60-100 ℃, and the time is 1-3 h.
8. The preparation method according to claim 1, wherein the calcination is carried out at a temperature of 150 to 180 ℃ for 1 to 3 hours.
9. The modified carbon microsphere/zinc oxide hybrid prepared by the preparation method of any one of claims 1 to 8, which comprises modified carbon microspheres and zinc oxide particles loaded on the surfaces of the modified carbon microspheres.
10. Use of the modified carbon microsphere/zinc oxide hybrid of claim 9 as a rubber filler.
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