CN109326401B - Preparation process of nano zinc oxide composite powder varistor - Google Patents
Preparation process of nano zinc oxide composite powder varistor Download PDFInfo
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- CN109326401B CN109326401B CN201811325969.0A CN201811325969A CN109326401B CN 109326401 B CN109326401 B CN 109326401B CN 201811325969 A CN201811325969 A CN 201811325969A CN 109326401 B CN109326401 B CN 109326401B
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 239000000843 powder Substances 0.000 title claims abstract description 93
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 39
- 238000001354 calcination Methods 0.000 claims description 25
- 229910001868 water Inorganic materials 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- 238000000227 grinding Methods 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 238000004140 cleaning Methods 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 238000005507 spraying Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- 239000011240 wet gel Substances 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004327 boric acid Substances 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 9
- 150000003751 zinc Chemical class 0.000 claims description 9
- 150000001462 antimony Chemical class 0.000 claims description 7
- 150000001621 bismuth Chemical class 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 7
- 150000001844 chromium Chemical class 0.000 claims description 6
- 239000000499 gel Substances 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 16
- 239000002245 particle Substances 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 238000005485 electric heating Methods 0.000 description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 239000004246 zinc acetate Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 238000007605 air drying Methods 0.000 description 3
- PEEDYJQEMCKDDX-UHFFFAOYSA-N antimony bismuth Chemical compound [Sb].[Bi] PEEDYJQEMCKDDX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- JRLDUDBQNVFTCA-UHFFFAOYSA-N antimony(3+);trinitrate Chemical compound [Sb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JRLDUDBQNVFTCA-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 231100000045 chemical toxicity Toxicity 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/006—Apparatus or processes specially adapted for manufacturing resistors adapted for manufacturing resistor chips
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/28—Apparatus or processes specially adapted for manufacturing resistors adapted for applying terminals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/30—Apparatus or processes specially adapted for manufacturing resistors adapted for baking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
- H01C7/105—Varistor cores
- H01C7/108—Metal oxide
- H01C7/112—ZnO type
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (AREA)
Abstract
The invention discloses a preparation process of a nano zinc oxide composite powder varistor, belonging to the technical field of preparation and application of electronic ceramic materials. The preparation method has the advantages of simple process preparation process, cheap and easily-obtained raw materials, simple equipment operation, accurate control of stoichiometric ratio, high product purity, capability of carrying out atom-molecule level mixing, smaller particle size of the obtained zinc oxide composite powder and uniform component distribution.
Description
Technical Field
The invention belongs to the technical field of preparation and application of electronic ceramic materials, and relates to a preparation process of a nano zinc oxide composite powder varistor.
Background
With the progress of modern electronic technology, the commercialized equipment is developed towards the miniaturization of devices. In addition, with the construction of extra-high voltage, the volume and the mass of the zinc oxide valve plate for the lightning arrester are greatly increased. In order to reduce the volume and mass of the zinc oxide valve plate and miniaturize the zinc oxide valve plate, the voltage gradient of the zinc oxide piezoresistor needs to be improved, and the zinc oxide composite powder particles used for preparing the resistor plate need to be nano-sized and the components and the microstructure of the zinc oxide composite powder particles are homogenized.
The prior preparation process method for producing the zinc oxide piezoresistor composite powder is mainly a solid-phase mechanical ball milling method, and although the solid-phase method is simple to operate and low in cost, the composite powder with uniform components and small particle size is difficult to obtain. The research finds that the main reason influencing the current capacity of the resistor is the unevenness of current distribution caused by the microscopic uneven structure of the resistor powder, and the heat generated by the unevenness causes the formation of internal thermal stress, so that the resistor is punctured or cracked. The voltage gradient of the resistive sheet is related to the size of the grain diameter of the grains composing the resistive sheet, and the smaller the grain diameter of the grains is, the larger the voltage gradient of the resistive sheet is.
The production process flow of the existing zinc oxide varistor comprises the following steps: batching, grinding, granulating, hydrating, tabletting, sintering, cleaning a grinding sheet and spraying aluminum on the side surface insulating layer to finally obtain the zinc oxide varistor, and the process is complicated, the production period is long, and the production efficiency is low; the ball milling process is generally adopted, the particle size of the ball milled particles is large, the mixing effect is poor, and nano-scale raw material powder is difficult to obtain; furthermore, it is necessary to add polyvinyl alcohol, which is a binder that is decomposed during sintering, to the slurry during granulationCO2、H2O and carbon black, the porosity of the zinc oxide resistance card is increased, and the uniformity of the internal structure of the resistance card is reduced; meanwhile, the production cost is increased, and the polyvinyl alcohol has chemical toxicity, so that the safety production of operators is not facilitated, and the environment is polluted.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation process of a nano zinc oxide composite powder varistor so as to prepare the zinc oxide composite powder varistor which has small particle size, uniform components, environmental friendliness, high voltage gradient and strong flow capacity.
The invention provides a preparation process of a nano zinc oxide composite powder varistor, which comprises the following steps:
(1) preparing aqueous solution from zinc salt, cobalt salt, chromium salt and boric acid according to a preset proportion, slowly adding aqueous solution of citric acid and glycol solution of bismuth salt and antimony salt, and stirring and dispersing at room temperature to obtain metal salt mixed solution;
(2) carrying out heat preservation treatment on the metal salt mixed solution at a set temperature to obtain wet gel, and drying the wet gel to obtain dry gel;
(3) placing the xerogel in a muffle furnace, calcining at a preset temperature, grinding a calcined product, and then washing and drying to obtain nano zinc oxide composite powder;
(4) water content: adding a predetermined amount of distilled water into the nano zinc oxide composite powder, and fully and uniformly stirring to obtain powder containing water;
(5) tabletting: putting the powder containing water into a tablet press to press into a sheet rough blank;
(6) and (3) sintering: calcining the rough blank in a muffle furnace;
(7) grinding and cleaning: grinding two end faces of the resistance card, and cleaning the resistance card by using distilled water;
(8) spraying aluminum and coating insulating glaze on the side surfaces: and spraying aluminum electrodes on two end surfaces of the resistance chip, and coating insulating glaze on the side surfaces to obtain the nano zinc oxide composite powder varistor.
Preferably, in the metal salt mixed solution, the ratio of zinc salt: 85-95 mol%, 1-5 mol% of cobalt salt, 0-5 mol% of chromium salt, 1-5 mol% of boric acid, 0-5 mol% of bismuth salt and 2-5 mol% of antimony salt, wherein the sum of the mol% of the components is 100 mol%.
Preferably, in the metal salt mixed solution, the molar concentration of the zinc salt is 0.5-3 mol/L, the molar concentration of the citric acid is 0-2 mol/L, and the molar concentration of the ethylene glycol is 2-10 mol/L.
Preferably, the metal salt is one or more of nitrate, acetate and chloride.
Preferably, in the step (2), the metal salt mixed solution is subjected to heat preservation treatment in a water bath at 70-100 ℃, and the heat preservation time is 12-36 hours.
Preferably, in the step (2), the drying temperature of the wet gel is 120-180 ℃, and the drying time is 24-48 h.
Preferably, in the step (3), the calcining temperature is 350-600 ℃, and the heat preservation time is 2-4 h.
Preferably, in the step (3), the calcined product is ground by using a mortar, and the grinding time is 2-10 min.
Preferably, in the step (3), deionized water and absolute ethyl alcohol are adopted for washing, and the volume-to-mass ratio of the usage amount of the deionized water and the absolute ethyl alcohol to the nano zinc oxide composite powder is 10-30 ml/g.
Preferably, in the step (4), 1-1.5% by mass of distilled water is added to the nano zinc oxide composite powder.
Preferably, in the step (6), the calcining temperature is 900-1150 ℃, and the heat preservation time is 1-5 h.
The invention also provides the nano-zinc oxide composite powder varistor prepared according to the preparation process of the nano-zinc oxide composite powder varistor.
The principle of the invention is as follows: the invention adopts an improved Pechini method to prepare the nano zinc oxide composite powder, and the metal salt mixed solution contains boric acid, citric acid and glycol solution, thereby being beneficial to the separation of particlesDispersing to prevent the aggregation and growth of particles, uniformly mixing all components from the molecular layer surface, and nanocrystallizing the particles, so that ball milling is not needed, the gel adopts a lower calcining temperature (350-600 ℃) during calcining, so that partial hydroxyl groups are remained in the composite powder, and the interaction between the powder can be enhanced due to the hydrogen bonds between the hydroxyl groups, so that the adhesive polyvinyl alcohol is not needed to be added, granulation is not needed, the crude blank prepared by directly containing and tabletting the nano zinc oxide composite powder can also keep good strength, cracks can not appear during calcining, and CO can not be generated during sintering due to the absence of the polyvinyl alcohol2、H2And the porosity of the zinc oxide resistance card is reduced by the O and the carbon black, and the distribution uniformity of each component of the resistance card is improved, so that the potential gradient, the through-current capacity and the large-current impact resistance capacity of the zinc oxide resistance card are improved.
Compared with the prior art, the invention has the following beneficial technical effects:
the preparation process of the nano zinc oxide composite powder varistor has the advantages of simple preparation process, cheap and easily-obtained raw materials, simple equipment operation, accurate control of stoichiometric ratio, high product purity, capability of carrying out atom and molecule level mixing, small particle size of the obtained zinc oxide composite powder particles and uniform component distribution.
According to the invention, deionized water and ethylene glycol are used as solvents, citric acid is used as a complexing agent, the citric acid has strong coordination capacity, and carboxyl and hydroxyl in the citric acid can simultaneously form a complex with different metal ions, so that cations can be mixed at a molecular level; the ethylene glycol can also play the roles of a second ligand and a dispersant, and can promote the dissolution and stable complexation of metal ions; the complexation of metal ions is enhanced through the combined action of citric acid and ethylene glycol, and a larger stable network structure is obtained by utilizing the esterification between functional groups of the citric acid and the ethylene glycol and the hydrogen bond between complexing molecules, so that cations are more uniformly and stably distributed in a precursor. Compared with zinc oxide composite powder prepared by other wet chemical methods, the invention has simpler operation and more uniform distribution of components and particle sizes.
Drawings
Fig. 1 is a flow chart of a preparation process of a nano-zinc oxide composite powder varistor in embodiment 1 of the invention.
Fig. 2 is an SEM image of the nano zinc oxide composite powder resistance card obtained in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.
The experimental procedures described in the following examples are conventional unless otherwise specified, and the reagents and materials described therein are commercially available without further specification.
Example 1
The raw materials of this example were prepared according to the following mole percentages, and the specific formulation was as follows:
zinc salt: 90.2 mol%, 2.59 mol% of cobalt salt, 1.93 mol% of boric acid, 1.98 mol% of bismuth salt and 3.3 mol% of antimony salt.
The invention relates to a preparation process of a nano zinc oxide composite powder varistor, which comprises the following steps of:
(1) weighing 165.5g of zinc acetate, 7.5g of cobalt nitrate hexahydrate and 1.2g of boric acid, dissolving in 400ml of deionized water, and stirring to form a red transparent solution; weighing 45.3g of citric acid, dissolving in 350ml of deionized water, and performing ultrasonic dispersion to form a transparent citric acid solution; weighing 7.8g of bismuth nitrate and 7.5g of antimony chloride, dissolving in 250ml of ethylene glycol, and performing ultrasonic dispersion until the solution is transparent; respectively and slowly adding a transparent citric acid solution and a glycol solution of bismuth salt antimony salt into a zinc acetate solution within 20min, and uniformly stirring to form a metal salt mixed solution;
(2) putting the metal salt mixed solution into a constant temperature pot at 80 ℃ for heat preservation for 24h to form stable wet gel, putting the wet gel into an electric heating air blast drying oven, baking for 24h at 120 ℃, and then baking for 24h at 180 ℃ to obtain xerogel;
(3) putting the dry gel into a tube furnace for calcination, wherein the heating rate is 3 ℃/min, the temperature is kept at 200 ℃ for 2h, then, the temperature is continuously raised to 450 ℃ for calcination for 2h, an agate mortar is utilized to grind the calcination product for 5min, the obtained composite powder is washed twice by deionized water and alcohol respectively, the ratio of the usage amount of the deionized water and the absolute ethyl alcohol to the volume-mass ratio of the nano zinc oxide composite powder is 20ml/g, and the specific process comprises the following steps: pouring deionized water into a beaker filled with the zinc oxide composite powder, stirring for 1min by using a glass rod, standing for 4h, pouring the upper layer water, performing suction filtration, pouring deionized water again for cleaning, and repeating the steps;
putting the cleaned zinc oxide composite powder into an electric heating forced air drying oven, and drying for 24 hours at the temperature of 80 ℃ to obtain nano zinc oxide composite powder;
(4) water content: adding 1.5 wt% of distilled water into the nano zinc oxide composite powder, and fully and uniformly stirring to obtain powder containing water;
(5) tabletting: putting the powder containing water into a tablet press to press into a sheet rough blank;
(6) and (3) sintering: calcining the rough blank in a muffle furnace; the heating rate is 2 ℃/h, the temperature is increased to 1050 ℃, the temperature is kept for 2h, and the cooling rate is 3 ℃/h;
(7) grinding and cleaning: grinding two end faces of the resistance card, and cleaning the resistance card by using distilled water;
(8) spraying aluminum and coating insulating glaze on the side surfaces: and spraying aluminum electrodes on two end surfaces of the resistance card, and coating insulating glaze on the side surfaces of the resistance card to obtain the nano zinc oxide composite powder varistor, wherein an SEM image of the nano zinc oxide composite powder varistor is shown in figure 2, and the nano zinc oxide composite powder varistor is uniform in components, flaky in zinc oxide and small in particle size.
In example 1, the specification of the nano-zinc oxide composite powder varistor is a varistor with a phi 70 size (the outer ring diameter is 72mm, the inner ring diameter is 26mm, and the height is 22.5mm), and the voltage gradient, the current capacity, and the large current impact resistance of the obtained varistor are tested, as shown in table 1.
Example 2
The raw materials of this example were prepared according to the following mole percentages, and the specific formulation was as follows:
zinc salt: 89.5mol percent, 1.3mol percent of cobalt salt, 1.1mol percent of chromium salt, 1.6mol percent of boric acid, 3.2mol percent of bismuth salt and 3.3mol percent of antimony salt.
The invention relates to a preparation process of a nano zinc oxide composite powder varistor, which comprises the following steps:
(1) 266.3g of zinc nitrate hexahydrate, 3.8g of cobalt nitrate, 2.6g of chromium nitrate and 1g of boric acid are weighed and dissolved in 400ml of deionized water to be stirred to form a red transparent solution; weighing 50g of citric acid, dissolving in 350ml of deionized water, and performing ultrasonic dispersion to form a transparent citric acid solution; weighing 12.4g of bismuth acetate and 7.53g of antimony chloride, dissolving in 250ml of ethylene glycol, and ultrasonically dispersing until the solution is transparent; respectively and slowly adding a transparent citric acid solution and a glycol solution of bismuth salt antimony salt into a zinc acetate solution within 20min, and uniformly stirring to form a metal salt mixed solution;
(2) putting the metal salt mixed solution into a constant temperature pot at 90 ℃ for heat preservation for 16h to form stable wet gel, putting the wet gel into an electric heating air blast drying oven, baking for 24h at 120 ℃, and then baking for 24h at 180 ℃ to obtain xerogel;
(3) putting the dry gel into a tube furnace for calcination, wherein the heating rate is 3 ℃/min, the temperature is kept at 200 ℃ for 2h, then, the temperature is continuously raised to 400 ℃ for calcination for 3h, an agate mortar is utilized to grind the calcination product for 5min, the obtained composite powder is washed twice by deionized water and alcohol respectively, the ratio of the usage amount of the deionized water and the absolute ethyl alcohol to the volume mass of the nano zinc oxide composite powder is 10ml/g, and the specific process comprises the following steps: pouring deionized water into a beaker filled with the zinc oxide composite powder, stirring for 1min by using a glass rod, standing for 4h, pouring the upper layer water, performing suction filtration, pouring deionized water again for cleaning, and repeating the steps;
putting the cleaned zinc oxide composite powder into an electric heating forced air drying oven, and drying for 24 hours at the temperature of 80 ℃ to obtain nano zinc oxide composite powder;
(4) water content: adding 1.0 wt% of distilled water into the nano zinc oxide composite powder, and fully and uniformly stirring to obtain powder containing water;
(5) tabletting: putting the powder containing water into a tablet press to press into a sheet rough blank;
(6) and (3) sintering: calcining the rough blank in a muffle furnace; the heating rate is 2 ℃/h, the temperature is increased to 1050 ℃, the temperature is kept for 2h, and the cooling rate is 2 ℃/h;
(7) grinding and cleaning: grinding two end faces of the resistance card, and cleaning the resistance card by using distilled water;
(8) spraying aluminum and coating insulating glaze on the side surfaces: and spraying aluminum electrodes on two end surfaces of the resistance chip, and coating insulating glaze on the side surfaces to obtain the nano zinc oxide composite powder varistor.
In example 2, the specification of the nano zinc oxide composite powder varistor is a varistor with a phi 70 size (the outer ring diameter is 72mm, the inner ring diameter is 26mm, and the height is 22.5mm), and the voltage gradient, the current capacity, and the large current impact resistance of the obtained varistor are tested, as shown in table 1.
Example 3
The raw materials of this example were prepared according to the following mole percentages, and the specific formulation was as follows:
zinc salt: 90.2mol percent, 1.1mol percent of cobalt salt, 0.5mol percent of chromium salt, 1.2mol percent of boric acid, 3.1mol percent of bismuth salt and 3.9mol percent of antimony salt.
The invention relates to a preparation process of a nano zinc oxide composite powder varistor, which comprises the following steps:
(1) weighing 165.5g of zinc acetate, 1.9g of cobalt acetate, 1.1g of chromium acetate and 0.7g of boric acid, dissolving in 400ml of deionized water, and stirring to form a red transparent solution; weighing 62g of citric acid, dissolving in 350ml of deionized water, and performing ultrasonic dispersion to form a transparent citric acid solution; weighing 12.2g of bismuth nitrate and 12.0g of antimony nitrate, dissolving in 250ml of ethylene glycol, and performing ultrasonic dispersion until the solution is transparent; respectively and slowly adding a transparent citric acid solution and a glycol solution of bismuth salt antimony salt into a zinc acetate solution within 20min, and uniformly stirring to form a metal salt mixed solution;
(2) putting the metal salt mixed solution into a constant temperature pot at 100 ℃ for heat preservation for 12h to form stable wet gel, putting the wet gel into an electric heating air blast drying oven, baking for 24h at 120 ℃, and then baking for 24h at 180 ℃ to obtain xerogel;
(3) putting the dry gel into a tube furnace for calcination, wherein the heating rate is 3 ℃/min, the temperature is kept at 200 ℃ for 2h, then, the temperature is continuously raised to 500 ℃ for calcination for 2h, an agate mortar is utilized to grind the calcination product for 5min, the obtained composite powder is washed twice by deionized water and alcohol respectively, the ratio of the usage amount of the deionized water and the absolute ethyl alcohol to the volume-mass ratio of the nano zinc oxide composite powder is 30ml/g, and the specific process comprises the following steps: pouring deionized water into a beaker filled with the zinc oxide composite powder, stirring for 1min by using a glass rod, standing for 4h, pouring the upper layer water, performing suction filtration, pouring deionized water again for cleaning, and repeating the steps;
putting the cleaned zinc oxide composite powder into an electric heating forced air drying oven, and drying for 24 hours at the temperature of 80 ℃ to obtain nano zinc oxide composite powder;
(4) water content: adding 1.5 wt% of distilled water into the nano zinc oxide composite powder, and fully and uniformly stirring to obtain powder containing water;
(5) tabletting: putting the powder containing water into a tablet press to press into a sheet rough blank;
(6) and (3) sintering: calcining the rough blank in a muffle furnace; the heating rate is 3 ℃/h, the temperature is raised to 1000 ℃, the temperature is kept for 2h, and the cooling rate is 2 ℃/h;
(7) grinding and cleaning: grinding two end faces of the resistance card, and cleaning the resistance card by using distilled water;
(8) spraying aluminum and coating insulating glaze on the side surfaces: and spraying aluminum electrodes on two end surfaces of the resistance chip, and coating insulating glaze on the side surfaces to obtain the nano zinc oxide composite powder varistor.
In example 3, the specification of the nano zinc oxide composite powder varistor is a varistor with a phi 70 size (the outer ring diameter is 72mm, the inner ring diameter is 26mm, and the height is 22.5mm), and the voltage gradient, the current capacity, and the large current impact resistance of the obtained varistor are tested, as shown in table 1.
Comparative example 1
The preparation method of the zinc oxide-based composite powder resistor disc obtained by adopting a common ball milling method comprises the following steps:
(1) preparing raw materials:
weighing 161.5g of zinc oxide, 4.2g of cobalt oxide, 1.6g of chromium oxide, 0.2g of boron oxide, 21.6g of bismuth oxide and 10.8g of antimony oxide, and putting into a ball mill for grinding for 2 hours to obtain mixed powder;
(2) grinding: adding the mixed powder into distilled water with the mass fraction of 50%, uniformly stirring, and then putting into a sand mill for grinding for 12 hours;
(3) and (3) granulation: adding 5% of polyvinyl alcohol by mass fraction into the ground slurry, and then putting the slurry into a granulator for spray granulation;
(4) water content: adding 1.5 percent of distilled water by mass fraction into the granulated powder, and fully and uniformly stirring;
(5) tabletting: putting the powder containing water into a tablet press to press into a sheet rough blank;
(6) and (3) sintering: calcining the rough blank in a muffle furnace; the heating rate is 2 ℃/h, the temperature is raised to 1100 ℃, the temperature is kept for 2h, and the cooling rate is 3 ℃/h;
(7) grinding and cleaning: grinding two ends of the resistance card, and cleaning the resistance card by using distilled water;
(8) spraying aluminum and coating insulating glaze on the side surfaces: and spraying aluminum electrodes on two ends of the resistance card, and coating insulating glaze on the side surface to obtain the zinc oxide composite powder varistor.
The zinc oxide composite powder varistor in comparative example 1 was a varistor of Φ 70 (outer ring diameter 72mm, inner ring diameter 26mm, height 22.5mm), and the voltage gradient, current capacity, and large current impact resistance of the varistor were measured, as shown in table 1.
TABLE 1 comparison of electrical properties of zinc oxide composite powder varistor
As can be seen from table 1, compared with the resistance card prepared by the common ball milling process (comparative example 1), the zinc oxide composite powder varistor synthesized by the process of the present invention has significantly improved potential gradient, current capacity and large current impact resistance compared with the zinc oxide varistor prepared by the conventional method, which indicates that the nano zinc oxide composite powder synthesized by the process of the present invention has more uniform components and smaller particle size compared with the zinc oxide based composite powder obtained by the common ball milling method; the nano-zinc oxide composite powder varistor provided by the invention does not need ball milling and granulation processes in the process, and does not need to add adhesive polyvinyl alcohol, so that the prepared nano-zinc oxide varistor still has good performance, the production cost is reduced, the production efficiency is improved, and the whole production process is environment-friendly.
Claims (9)
1. A preparation process of a nano zinc oxide composite powder varistor is characterized by comprising the following steps:
(1) preparing aqueous solution from zinc salt, cobalt salt, chromium salt and boric acid according to a preset proportion, slowly adding aqueous solution of citric acid and glycol solution of bismuth salt and antimony salt, and stirring and dispersing at room temperature to obtain metal salt mixed solution;
(2) carrying out heat preservation treatment on the metal salt mixed solution at a set temperature to obtain wet gel, and drying the wet gel to obtain dry gel;
(3) placing the xerogel in a muffle furnace, calcining at a preset temperature, grinding a calcined product, and then washing and drying to obtain nano zinc oxide composite powder;
(4) water content: adding a predetermined amount of distilled water into the nano zinc oxide composite powder, and fully and uniformly stirring to obtain powder containing water;
(5) tabletting: putting the powder containing water into a tablet press to press into a sheet rough blank;
(6) and (3) sintering: calcining the rough blank in a muffle furnace;
(7) grinding and cleaning: grinding two end faces of the resistance card, and cleaning the resistance card by using distilled water;
(8) spraying aluminum and coating insulating glaze on the side surfaces: spraying aluminum electrodes on two end surfaces of the resistance chip, and coating insulating glaze on the side surfaces to obtain the nano zinc oxide composite powder varistor;
in the metal salt mixed solution, 85-95 mol% of zinc salt, 1-5 mol% of cobalt salt, 0-5 mol% of chromium salt, 1-5 mol% of boric acid, 0-5 mol% of bismuth salt and 2-5 mol% of antimony salt are added, and the sum of the mol% of the components is 100 mol%.
2. The preparation process of the nano-zinc oxide composite powder varistor according to claim 1, wherein in the metal salt mixed solution, the molar concentration of zinc salt is 0.5-3 mol/L, the molar concentration of citric acid is 0-2 mol/L, the molar concentration of citric acid is not 0, and the molar concentration of ethylene glycol is 2-10 mol/L.
3. The preparation process of the nano-zinc oxide composite powder varistor as claimed in claim 1, wherein the metal salt is one or more of nitrate, acetate and chloride.
4. The preparation process of the nano-zinc oxide composite powder varistor according to claim 1, wherein in the step (2), the metal salt mixed solution is subjected to heat preservation treatment in a water bath at 70-100 ℃, and the heat preservation time is 12-36 hours.
5. The preparation process of the nano-zinc oxide composite powder varistor as claimed in claim 1, wherein in step (2), the drying temperature of the wet gel is 120-180 ℃ and the drying time is 24-48 h.
6. The preparation process of the nano-zinc oxide composite powder varistor according to claim 1, wherein in the step (3), the calcination temperature is 350-600 ℃ and the calcination time is 2-4 h.
7. The preparation process of the nano-zinc oxide composite powder varistor according to claim 1, wherein in the step (4), 1-1.5% by mass of distilled water is added to the nano-zinc oxide composite powder.
8. The preparation process of the nano-zinc oxide composite powder varistor according to claim 1, wherein in the step (6), the calcination temperature is 900-1150 ℃, and the heat preservation time is 1-5 hours.
9. The nano-zinc oxide composite powder varistor prepared by the preparation process of the nano-zinc oxide composite powder varistor according to any one of claims 1 to 8.
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| CN101125676A (en) * | 2007-09-20 | 2008-02-20 | 上海交通大学 | Method for preparing zinc oxide thin film |
| CN101792307A (en) * | 2010-03-30 | 2010-08-04 | 中国科学院上海硅酸盐研究所 | Preparation method of zinc oxide varistor ceramic composite powder |
| CN102020463A (en) * | 2010-11-10 | 2011-04-20 | 中国科学院宁波材料技术与工程研究所 | Zinc oxide piezoresistor material and preparing method thereof |
| CN108329023A (en) * | 2018-03-05 | 2018-07-27 | 国网湖南省电力有限公司 | A kind of preparation method of zinc oxide base nano composite granule resistor disc |
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| CN101125676A (en) * | 2007-09-20 | 2008-02-20 | 上海交通大学 | Method for preparing zinc oxide thin film |
| CN101792307A (en) * | 2010-03-30 | 2010-08-04 | 中国科学院上海硅酸盐研究所 | Preparation method of zinc oxide varistor ceramic composite powder |
| CN102020463A (en) * | 2010-11-10 | 2011-04-20 | 中国科学院宁波材料技术与工程研究所 | Zinc oxide piezoresistor material and preparing method thereof |
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