CN114436320A - Preparation method of core-shell structure zinc oxide and zinc oxide obtained by preparation method - Google Patents
Preparation method of core-shell structure zinc oxide and zinc oxide obtained by preparation method Download PDFInfo
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- CN114436320A CN114436320A CN202210088853.XA CN202210088853A CN114436320A CN 114436320 A CN114436320 A CN 114436320A CN 202210088853 A CN202210088853 A CN 202210088853A CN 114436320 A CN114436320 A CN 114436320A
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 216
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 108
- 239000011258 core-shell material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 91
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 76
- 239000011701 zinc Substances 0.000 claims abstract description 76
- 239000011162 core material Substances 0.000 claims abstract description 44
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 239000002270 dispersing agent Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000012670 alkaline solution Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000004113 Sepiolite Substances 0.000 claims abstract description 17
- 239000002244 precipitate Substances 0.000 claims abstract description 17
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 17
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 11
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 239000008117 stearic acid Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011824 nuclear material Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 9
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate 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
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 230000009471 action Effects 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 abstract description 2
- 229920001971 elastomer Polymers 0.000 description 21
- 244000043261 Hevea brasiliensis Species 0.000 description 14
- 229920003052 natural elastomer Polymers 0.000 description 14
- 229920001194 natural rubber Polymers 0.000 description 14
- 239000011257 shell material Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 10
- 238000004073 vulcanization Methods 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 8
- 239000012936 vulcanization activator Substances 0.000 description 8
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000013068 control sample Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960002798 cetrimide Drugs 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a preparation method of core-shell structure zinc oxide and zinc oxide obtained by the same. The invention comprises the following steps: 1) taking a core material, adding a dispersing agent and sepiolite, wherein the dispersing agent is a composite dispersing agent consisting of stearic acid, CTAB, SDBS and KH550 according to the mass ratio of 1-2:0.1-0.3:0.05-0.10:0.5-1.0, and stirring to obtain a primary mixture; 2) taking a zinc-containing solution, adding the primary mixture into the zinc-containing solution, and stirring to obtain a reaction solution; 3) adding an alkaline solution into the reaction solution, stirring for reaction, and removing water to obtain a precipitate; 4) and (4) taking the precipitate, drying and calcining to obtain the core-shell structure zinc oxide. The nuclear material is uniformly dispersed and suspended in the zinc-containing solution under the action of the dispersing agent and the sepiolite, and insoluble substances generated in situ are strongly adsorbed on the surface of the nuclear material, so that the energy consumption is low, and the carbon emission is low; the obtained zinc oxide has small particle size, large specific surface area, high activity and high effective utilization rate.
Description
Technical Field
The invention relates to the technical field of zinc oxide preparation methods, in particular to a preparation method of core-shell zinc oxide and zinc oxide obtained by the preparation method.
Background
Zinc oxide is a white or pale yellow powder, insoluble in water, soluble in strong acids and strong bases, is a vulcanization activator for rubber, and has an irreplaceable effect in the rubber industry. The traditional zinc oxide production method is to gasify zinc metal at high temperature of 1000 ℃ and react with oxygen in the air to generate zinc oxide, and the production method of the zinc oxide has high energy consumption, enlarged carbon emission and serious pollution. In addition, the zinc oxide has low activity, is easy to agglomerate, and is difficult to disperse in rubber; the amount of zinc oxide used in the rubber industry is large, typically 5g per 100g of rubber; however, the effective utilization of zinc oxide is low. Since zinc is also an element close to heavy metal, a large amount of zinc element enters the environment in the use and waste treatment processes of rubber products, thereby causing environmental pollution.
Disclosure of Invention
The invention aims to provide a preparation method of core-shell structure zinc oxide, and aims to solve the problems of high energy consumption, carbon emission amplification, serious pollution, low activity of the obtained zinc oxide, large dosage in the rubber industry and low effective utilization rate of the zinc oxide in the production method of the zinc oxide in the prior art.
In order to solve the technical problem, the technical scheme of the invention is realized as follows:
in one aspect, the preparation method of the core-shell structure zinc oxide comprises the following steps: 1) taking a core material, adding a dispersing agent and sepiolite, wherein the addition amount of the dispersing agent is 5-10% of the mass of the core material, the addition amount of the sepiolite is 1-3% of the mass of the core material, the dispersing agent is a composite dispersing agent consisting of stearic acid, cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate and KH550 according to the mass ratio of 1-2:0.1-0.3:0.05-0.10:0.5-1.0, and stirring to obtain a primary mixture; 2) adding the primary mixture obtained in the step 1) into a zinc-containing solution, wherein the mass ratio of the core material in the primary mixture to zinc in the zinc-containing solution is 1:2-3:1, and stirring to obtain a reaction solution; 3) adding an alkaline solution into the reaction solution obtained in the step 2), wherein the molar ratio of solute in the alkaline solution to zinc in the zinc-containing solution is 2:1-4:1, stirring and reacting for 3-5min at 70-100 ℃, and removing water to obtain a precipitate; 4) taking the precipitate obtained in the step 3), drying, and calcining at the temperature of 300-600 ℃ for 1-4h to obtain the core-shell structure zinc oxide.
In the preparation method of the core-shell structure zinc oxide, the core material can be fully dispersed in the zinc-containing solution under the action of the composite dispersant, so that the dispersion degree of the core material in the zinc-containing solution is improved; under the action of the sepiolite, the core material can be uniformly suspended in the zinc-containing solution, so that the dispersion degree of the core material in the zinc-containing solution is further improved; meanwhile, the sepiolite also has strong adsorption capacity, can absorb more zinc-containing solution around the core material, enables the zinc-containing insoluble substances generated in situ to be strongly adsorbed on the surface of the core material, enhances the connection firmness of the core material and the shell material in the core-shell structure zinc oxide, and improves the structural stability and uniformity of the core-shell structure zinc oxide; the preparation method is a wet precipitation method, has simple operation, mild conditions, low energy consumption and less carbon emission, and greatly reduces the environmental pollution, and the carbon emission is only two thirds of the original carbon emission; the obtained zinc oxide with the core-shell structure has small particle size, large specific surface area, good dispersibility, high activity, small dosage and high effective utilization rate, and maintains good vulcanization performance and mechanical property of rubber. In the present invention, stearic acid is octadecanoic acid; cetyl trimethyl ammonium bromide is a quaternary ammonium salt, namely cetrimide, CTAB, CTMAB and the like; sodium dodecyl benzene sulfonate is an anionic surfactant, referred to as SDBS for short; KH550 is known under the chemical name of APTES and gamma-aminopropyltriethoxysilane.
In a preferred embodiment, the core material is any one of calcium carbonate, barium sulfate, silica, carbon black, alumina, and graphite. The core material is an inert substance, has stable performance, does not participate in any reaction, and has the function of framework support in the core-shell structure zinc oxide.
In a preferred embodiment, the zinc-containing solution is any one of a zinc chloride solution, a zinc nitrate solution and a zinc sulfate solution. The zinc-containing solutions of the present invention are soluble zinc salt solutions, and the role of these zinc-containing solutions is to provide zinc ions, which are uniformly dispersed in the zinc-containing solution.
In a preferred embodiment, the alkaline solution is any one of a sodium carbonate solution, a sodium bicarbonate solution, a sodium hydroxide solution, a potassium carbonate solution, a potassium bicarbonate solution, and a potassium hydroxide solution. The alkaline solution of the invention is used for reacting with zinc ions in the zinc-containing solution to form zinc-containing insoluble substances, and the zinc-containing insoluble substances can generate decomposition reaction in the calcining process, only zinc oxide is left, and thus the core-shell structure zinc oxide is obtained.
As a preferred embodiment, in the step 3), the stirring speed during the stirring reaction is 200-800 r/min. The stirring reaction is carried out at a certain temperature and stirring speed, the reaction temperature can accelerate the reaction process, the reaction efficiency is improved, the stirring speed can ensure that the nuclear material is uniformly dispersed and suspended in the zinc-containing solution all the time, and the uniformity of the obtained core-shell structure zinc oxide is fully ensured.
As a preferred embodiment, in the step 4), the temperature for drying is 140-160 ℃, and the drying time is 8-12 h. The precipitate obtained by the method is dried and then calcined, and the drying is to remove the moisture in the precipitate, so that other impurities are not mixed in the calcining process.
As a preferred embodiment, in the step 2), the molar concentration of the zinc-containing solution is 1-3 mol/L. The invention can control the total amount of zinc in the reaction process by controlling the molar concentration of the zinc-containing solution; the zinc-containing solution has proper concentration, mild reaction between zinc ions and alkaline solution, convenient control and full guarantee of the uniformity of the obtained core-shell structure zinc oxide.
As a preferred embodiment, in the step 3), the molar concentration of the alkaline solution is 1-3 mol/L. In the invention, the alkaline solution is excessive, and zinc ions in the zinc-containing solution can fully react to generate zinc-containing insoluble substances. The invention well controls the calcining temperature, so that only the zinc-containing insoluble substances of the shell layer in the precipitate are subjected to decomposition reaction, and the nuclear material is not subjected to any reaction.
In another aspect, the core-shell zinc oxide is prepared according to any one of the above methods. The zinc oxide has a core-shell structure, the core material is an inert substance, the shell material is zinc oxide, and the zinc oxide can be used as a vulcanization activator in the rubber industry.
As a preferred embodiment, the grain size of the core-shell structure zinc oxide is 0.05-3.00 mu m, and the specific surface area is 10-60m2(ii) in terms of/g. The zinc oxide with the core-shell structure has small particle size, but has large specific surface area, high activity and high effective utilization rate, and when the zinc oxide is used as a vulcanization activator in the rubber industry, the zinc oxide has good dispersibility and processability in rubber, and fully ensures good vulcanization performance and mechanical property of the rubber.
Compared with the prior art, the invention has the beneficial effects that: in the preparation method of the core-shell structure zinc oxide, the core material can be fully dispersed in the zinc-containing solution under the action of the composite dispersant, so that the dispersion degree of the core material in the zinc-containing solution is improved; under the action of the sepiolite, the core material can be uniformly suspended in the zinc-containing solution, so that the dispersion degree of the core material in the zinc-containing solution is further improved; meanwhile, the sepiolite also has strong adsorption capacity, can absorb more zinc-containing solution around the core material, enables the zinc-containing insoluble substances generated in situ to be strongly adsorbed on the surface of the core material, enhances the connection firmness of the core material and the shell material in the core-shell structure zinc oxide, and improves the structural stability and uniformity of the core-shell structure zinc oxide; the preparation method has the advantages of simple operation, mild condition, low energy consumption, less carbon emission and great reduction of environmental pollution; the obtained zinc oxide with the core-shell structure has small particle size, large specific surface area, high activity, small using amount and high effective utilization rate, and when the zinc oxide is used as a vulcanization activator in the rubber industry, the zinc oxide has good dispersibility and processability in rubber, and fully ensures good vulcanization performance and mechanical property of the rubber.
Drawings
FIG. 1 is a scanning electron microscope image of core-shell zinc oxide obtained in the first embodiment of the present invention;
FIG. 2 is a scanning electron microscope image of core-shell zinc oxide obtained in example two of the present invention;
FIG. 3 is a scanning electron microscope image of core-shell zinc oxide obtained in example III of the present invention;
FIG. 4 is a scanning electron microscope photograph of a conventional zinc oxide.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention relates to a preparation method of core-shell structure zinc oxide, which comprises the following steps:
1) taking a core material, adding a dispersing agent and sepiolite, wherein the addition amount of the dispersing agent is 5-10% of the mass of the core material, the addition amount of the sepiolite is 1-3% of the mass of the core material, the dispersing agent is a composite dispersing agent consisting of stearic acid, cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate and KH550 according to the mass ratio of 1-2:0.1-0.3:0.05-0.10:0.5-1.0, and stirring to obtain a primary mixture;
2) adding the primary mixture obtained in the step 1) into a zinc-containing solution, wherein the mass ratio of the core material in the primary mixture to zinc in the zinc-containing solution is 1:2-3:1, and stirring to obtain a reaction solution;
3) adding an alkaline solution into the reaction solution obtained in the step 2), wherein the molar ratio of solute in the alkaline solution to zinc in the zinc-containing solution is 2:1-4:1, stirring and reacting for 3-5min at 70-100 ℃, and removing water to obtain a precipitate;
4) taking the precipitate obtained in the step 3), drying, and calcining at the temperature of 300-600 ℃ for 1-4h to obtain the core-shell structure zinc oxide.
Preferably, the core material is any one of calcium carbonate, barium sulfate, silica, carbon black, alumina, and graphite.
Preferably, the zinc-containing solution is any one of a zinc chloride solution, a zinc nitrate solution and a zinc sulfate solution.
Preferably, the alkaline solution is any one of a sodium carbonate solution, a sodium bicarbonate solution, a sodium hydroxide solution, a potassium carbonate solution, a potassium bicarbonate solution and a potassium hydroxide solution.
Preferably, in the step 3), the stirring speed during the stirring reaction is 200-.
Preferably, in the step 4), the temperature for drying is 140-160 ℃, and the drying time is 8-12 h.
Preferably, in the step 2), the molar concentration of the zinc-containing solution is 1-3 mol/L.
Preferably, in the step 3), the molar concentration of the alkaline solution is 1-3 mol/L.
The core-shell structure zinc oxide is prepared by the preparation method of any one of the core-shell structure zinc oxide.
Preferably, the particle size of the core-shell structure zinc oxide is 0.05-3.00 mu m, and the specific surface area is 10-60m2/g。
Example one
The invention relates to a preparation method of core-shell structure zinc oxide, which comprises the following steps:
1) taking 50g of calcium carbonate as a core material, adding 2g of dispersant and 1g of sepiolite, wherein the dispersant is a composite dispersant consisting of stearic acid, hexadecyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate and KH550 according to the mass ratio of 1:0.1:0.05:0.5, and stirring to obtain a primary mixture;
2) taking 1500mL of zinc chloride as a zinc-containing solution, adding the primary mixture obtained in the step 1) into the zinc-containing solution, wherein the mass ratio of the core material in the primary mixture to the zinc in the zinc-containing solution is 1:2, and stirring to obtain a reaction solution;
3) taking 3000mL of sodium carbonate solution as an alkaline solution, adding the sodium carbonate solution with the molar concentration of 1mol/L into the reaction solution obtained in the step 2), wherein the molar ratio of solute in the alkaline solution to zinc in the zinc-containing solution is 2:1, stirring and reacting for 3min at 70 ℃, and removing water to obtain a precipitate;
4) and (3) drying the precipitate obtained in the step 3) at 140 ℃ for 8h, and calcining at 300 ℃ for 4h to obtain the core-shell structure zinc oxide.
The obtained core-shell structure zinc oxide is placed in a JSM-7500F scanning electrode produced by Japan electronic companyAs can be seen from figure 1, the core-shell zinc oxide obtained by the invention is spherical, has a loose structure and a small particle size, is about 50nm in particle size, is uniformly dispersed, and has a specific surface area of about 50m2/g。
Example two
The invention relates to a preparation method of core-shell structure zinc oxide, which comprises the following steps:
1) taking 100g of calcium carbonate as a core material, adding 5g of dispersant and 1g of sepiolite, wherein the dispersant is a composite dispersant consisting of stearic acid, hexadecyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate and KH550 according to the mass ratio of 2:0.3:0.10:1.0, and stirring to obtain a primary mixture;
2) adding 770mL of zinc nitrate serving as a zinc-containing solution, wherein the molar concentration of the zinc nitrate is 2mol/L, adding the primary mixture obtained in the step 1) into the zinc-containing solution, wherein the mass ratio of the core material in the primary mixture to the zinc in the zinc-containing solution is 1:1, and stirring to obtain a reaction solution;
3) adding 2300mL of sodium hydroxide solution serving as alkaline solution with the molar concentration of 2mol/L into the reaction solution obtained in the step 2), wherein the molar ratio of solute in the alkaline solution to zinc in the zinc-containing solution is 3:1, stirring and reacting for 4min at 80 ℃, and removing water to obtain precipitate;
4) taking the precipitate obtained in the step 3), drying at 160 ℃ for 8h, and calcining at 600 ℃ for 1h to obtain the core-shell structure zinc oxide.
The obtained zinc oxide with the core-shell structure is placed on a scanning electron microscope for observation, and as can be seen from figure 2, the zinc oxide with the core-shell structure is spherical particles, is loose in structure, small in particle size, about 90nm in particle size, uniform in dispersion and about 35m in specific surface area2/g。
EXAMPLE III
The invention relates to a preparation method of core-shell structure zinc oxide, which comprises the following steps:
1) taking 150g of calcium carbonate as a core material, adding 15g of dispersant and 3g of sepiolite, wherein the dispersant is a composite dispersant consisting of stearic acid, hexadecyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate and KH550 according to the mass ratio of 8:1:0.4:4, and stirring to obtain a primary mixture;
2) taking 260mL of zinc nitrate as a zinc-containing solution, adding the primary mixture obtained in the step 1) into the zinc-containing solution, wherein the mass ratio of the core material in the primary mixture to the zinc in the zinc-containing solution is 3:1, and stirring to obtain a reaction solution;
3) 1040mL of potassium carbonate solution is taken as an alkaline solution, the molar concentration of the potassium carbonate solution is 3mol/L, the potassium carbonate solution is added into the reaction liquid obtained in the step 2), the molar ratio of solute in the alkaline solution to zinc in the zinc-containing solution is 4:1, the mixture is stirred and reacted for 4min at the temperature of 80 ℃, and water is removed to obtain a precipitate;
4) taking the precipitate obtained in the step 3), drying at 150 ℃ for 10h, and calcining at 500 ℃ for 2h to obtain the core-shell structure zinc oxide.
The obtained zinc oxide with the core-shell structure is placed on a scanning electron microscope for observation, and as can be seen from figure 3, the zinc oxide with the core-shell structure is spherical particles, is loose in structure, small in particle size, about 70nm in particle size, uniform in dispersion and about 40m in specific surface area2/g。
Referring to fig. 4, it can be seen that the particle size of the conventional zinc oxide is about 2um, and the specific surface area is about 20m2(ii) in terms of/g. The method comprises the steps of respectively using the zinc oxide with the core-shell structure obtained by the invention and the existing zinc oxide as vulcanization activators of natural rubber, placing 100 parts of natural rubber, 66050 parts of carbon black, 5 parts of the vulcanization activators, 1 part of stearic acid, 0.7 part of an accelerator DM and 2.5 parts of sulfur into an internal mixer, internally mixing for 2min at 70 ℃, then adding the vulcanization activators, stearic acid and the accelerator DM, continuously internally mixing for 2min, then adding the carbon black N660, continuously internally mixing for 4min, finally adding the sulfur, continuously mixing for 2min, discharging by an open mill, respectively measuring the vulcanization characteristics on a flat vulcanizing machine according to the method specified by GB/T9869-.
TABLE 1 measurement results of vulcanization characteristics of natural rubber
| Sample name | T10(min) | T90(min) | ML(dN·m) | MH(dN·m) |
| Example one | 3.44 | 12.86 | 1.87 | 18.43 |
| Example two | 3.71 | 13.12 | 1.83 | 17.72 |
| EXAMPLE III | 3.85 | 13.23 | 1.88 | 17.70 |
| Control sample | 4.01 | 13.33 | 1.89 | 18.49 |
As can be seen from Table 1, the scorch time T of the natural rubber articles obtained from the shell-structured zinc oxide of the present invention10About 3.70min, which is equivalent to the scorch time T of the control10Are substantially equal; positive vulcanization time T of Natural rubber articles obtained from Shell Zinc oxide of the invention90About 13.10min, which corresponds to the positive vulcanization time T of the control90As well as substantially the same. Minimum Torque M of Natural rubber articles obtained from Shell-structured Zinc oxide of the inventionLAbout 1.86 dN.m, which is equivalent to the minimum torque M of the controlLAre substantially the same; maximum Torque M of Natural rubber product obtained from Shell-structured Zinc oxide of the inventionHAbout 17.95 dN.m, which is equivalent to the maximum torque M of the controlHThe same is true. Therefore, the shell structure zinc oxide of the invention well maintains the vulcanization characteristic of the rubber product. Moreover, the zinc oxide with a shell structure has low content of zinc oxide, and the zinc oxide with the shell structure with low content of zinc oxide can ensure that the rubber product keeps the same vulcanization characteristic as the existing zinc oxide.
Experiment 2
The natural rubber products were prepared by the method of experiment 1 using the three parts of the core-shell zinc oxide obtained in examples one to three and the existing zinc oxide used in experiment 1. Measuring the mechanical properties of the obtained natural rubber product, wherein the Shore A type hardness is tested according to GB/T531-2008, the tensile property is tested according to the national standard GB/T528-2009 on an electronic tensile machine, the tearing property is tested according to GB/T529-2008 on the electronic tensile machine, and the rebound resilience is tested according to GB/T1681-2009 vulcanized rubber rebound resilience; the results are shown in Table 2.
TABLE 2 measurement results of mechanical properties of natural rubber
| Sample name | Hardness (Shao A) | Tensile Strength (MPa) | Elongation at Break (%) | Rebound resilience (%) |
| Example one | 56 | 27.1 | 576 | 57.9 |
| Example two | 55 | 26.8 | 571 | 57.3 |
| EXAMPLE III | 55 | 26.6 | 570 | 57.1 |
| Control sample | 56 | 26.5 | 579 | 58.8 |
As can be seen from table 2, the hardness (shore a) of the natural rubber product obtained by the shell structure zinc oxide of the present invention is about 56, which is equal to the hardness (shore a) of the control sample; the tensile strength of the natural rubber product obtained by the shell structure zinc oxide of the invention is about 26.8MPa, which is basically consistent with that of a comparison sample; the elongation at break of the natural rubber product obtained by the shell structure zinc oxide of the invention is about 572 percent, which is basically consistent with that of the comparison sample; the shell structure zinc oxide of the present invention gives a natural rubber article having a resiliency of about 57.4%, which is also substantially the same as that of the control. Therefore, the shell structure zinc oxide of the invention well keeps the mechanical property of rubber products.
Therefore, compared with the prior art, the invention has the beneficial effects that: in the preparation method of the core-shell structure zinc oxide, the core material can be fully dispersed in the zinc-containing solution under the action of the composite dispersant, so that the dispersion degree of the core material in the zinc-containing solution is improved; under the action of the sepiolite, the core material can be uniformly suspended in the zinc-containing solution, so that the dispersion degree of the core material in the zinc-containing solution is further improved; meanwhile, the sepiolite also has strong adsorption capacity, can absorb more zinc-containing solution around the core material, enables the zinc-containing insoluble substances generated in situ to be strongly adsorbed on the surface of the core material, enhances the connection firmness of the core material and the shell material in the core-shell structure zinc oxide, and improves the structural stability and uniformity of the core-shell structure zinc oxide; the preparation method has the advantages of simple operation, mild condition, low energy consumption, less carbon emission and great reduction of environmental pollution; the obtained zinc oxide with the core-shell structure has small particle size, large specific surface area, high activity, small using amount and high effective utilization rate, and when the zinc oxide is used as a vulcanization activator in the rubber industry, the zinc oxide has good dispersibility and processability in rubber, and fully ensures good vulcanization performance and mechanical property of the rubber.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The preparation method of the core-shell structure zinc oxide is characterized by comprising the following steps:
1) taking a core material, adding a dispersing agent and sepiolite, wherein the addition amount of the dispersing agent is 5-10% of the mass of the core material, the addition amount of the sepiolite is 1-3% of the mass of the core material, the dispersing agent is a composite dispersing agent consisting of stearic acid, cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate and KH550 according to the mass ratio of 1-2:0.1-0.3:0.05-0.10:0.5-1.0, and stirring to obtain a primary mixture;
2) adding the primary mixture obtained in the step 1) into a zinc-containing solution, wherein the mass ratio of the core material in the primary mixture to zinc in the zinc-containing solution is 1:2-3:1, and stirring to obtain a reaction solution;
3) adding an alkaline solution into the reaction solution obtained in the step 2), wherein the molar ratio of solute in the alkaline solution to zinc in the zinc-containing solution is 2:1-4:1, stirring and reacting for 3-5min at 70-100 ℃, and removing water to obtain a precipitate;
4) taking the precipitate obtained in the step 3), drying, and calcining at the temperature of 300-600 ℃ for 1-4h to obtain the core-shell structure zinc oxide.
2. The preparation method of the core-shell structure zinc oxide according to claim 1, characterized in that:
the nuclear material is any one of calcium carbonate, barium sulfate, silicon dioxide, carbon black, alumina and graphite.
3. The preparation method of the core-shell structure zinc oxide according to claim 1, characterized in that:
the zinc-containing solution is any one of a zinc chloride solution, a zinc nitrate solution and a zinc sulfate solution.
4. The preparation method of the core-shell structure zinc oxide according to claim 1, characterized in that:
the alkaline solution is any one of sodium carbonate solution, sodium bicarbonate solution, sodium hydroxide solution, potassium carbonate solution, potassium bicarbonate solution and potassium hydroxide solution.
5. The method for preparing the core-shell zinc oxide according to any one of claims 1 to 4, wherein:
in the step 3), the stirring speed during the stirring reaction is 200-800 r/min.
6. The method for preparing the core-shell zinc oxide according to any one of claims 1 to 4, wherein:
in the step 4), the temperature during drying is 140-160 ℃, and the drying time is 8-12 h.
7. The method for preparing the core-shell zinc oxide according to any one of claims 1 to 4, wherein:
in the step 2), the molar concentration of the zinc-containing solution is 1-3 mol/L.
8. The method for preparing the core-shell zinc oxide according to any one of claims 1 to 4, wherein:
in the step 3), the molar concentration of the alkaline solution is 1-3 mol/L.
9. The core-shell structure zinc oxide is characterized in that:
the core-shell structure zinc oxide is prepared by the preparation method of the core-shell structure zinc oxide according to any one of claims 1 to 8.
10. The core-shell structure zinc oxide according to claim 9, characterized in that:
the grain size of the core-shell structure zinc oxide is 0.05-3.00 mu m, and the specific surface area is 10-60m2/g。
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