CN108752029B - Modified zirconium silicate whisker reinforced alumina ceramic - Google Patents
Modified zirconium silicate whisker reinforced alumina ceramic Download PDFInfo
- Publication number
- CN108752029B CN108752029B CN201810948454.XA CN201810948454A CN108752029B CN 108752029 B CN108752029 B CN 108752029B CN 201810948454 A CN201810948454 A CN 201810948454A CN 108752029 B CN108752029 B CN 108752029B
- Authority
- CN
- China
- Prior art keywords
- zirconium silicate
- mass
- solution
- nano
- stirring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical class [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 title claims abstract description 56
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims description 49
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 25
- 239000003607 modifier Substances 0.000 claims description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 15
- XXAZFSPIXDMVRC-UHFFFAOYSA-N [Na].[Cr].[Fe] Chemical compound [Na].[Cr].[Fe] XXAZFSPIXDMVRC-UHFFFAOYSA-N 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 15
- 239000010439 graphite Substances 0.000 claims description 15
- 229910002804 graphite Inorganic materials 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229920001732 Lignosulfonate Polymers 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 239000000378 calcium silicate Substances 0.000 claims description 10
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 10
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 10
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 10
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 5
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 claims description 5
- 239000000440 bentonite Substances 0.000 claims description 5
- 229910000278 bentonite Inorganic materials 0.000 claims description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 5
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 229910052863 mullite Inorganic materials 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 3
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000919 ceramic Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000000643 oven drying Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 229910052572 stoneware Inorganic materials 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C04B35/803—
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
- C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
- C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
- C04B2235/3472—Alkali metal alumino-silicates other than clay, e.g. spodumene, alkali feldspars such as albite or orthoclase, micas such as muscovite, zeolites such as natrolite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/447—Phosphates or phosphites, e.g. orthophosphate or hypophosphite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a modified zirconium silicate whisker reinforced alumina ceramic, which relates to the technical field of new materials, and comprises 6.40-6.46% of modified zirconium silicate whisker and 3.20-3.23% of sulfhydrylation nanometer hybrid material by mass. The ceramic material prepared from the modified zirconium silicate whisker reinforced alumina ceramic has good bending strength and good hardness.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a modified zirconium silicate whisker reinforced alumina ceramic.
Background
Ceramics are classified into pottery, stoneware and porcelain, which are also commonly called pottery, stoneware and porcelain, in terms of their materials. The alumina ceramic material has the performances of low density, high strength, high wear resistance and chemical stability, stable friction coefficient at high temperature and the like, and has great application potential in the field of friction materials. Aiming at the current increasingly higher use requirements, the wear resistance of the single-phase alumina ceramic needs to be improved, and the ceramic is greatly limited from being applied to more severe environments due to the brittleness of the ceramic.
Disclosure of Invention
The invention aims to provide a modified zirconium silicate whisker reinforced alumina ceramic aiming at the existing problems.
The invention is realized by the following technical scheme:
the modified zirconium silicate whisker reinforced alumina ceramic contains 6.40-6.46% of modified zirconium silicate whisker and 3.20-3.23% of sulfhydrylation nanometer hybrid material by mass, and the mass ratio of the modified zirconium silicate whisker to the sulfhydrylation nanometer hybrid material is 2: 1.
Further, the preparation method of the modified zirconium silicate whisker comprises the following steps:
(1) pretreatment: preparing an aqueous solution with the mass concentration of 6.3% by using iron-chromium sodium lignin sulfonate, adding zirconium silicate whiskers, stirring uniformly, heating to 50 ℃, gradually dropwise adding hydrogen peroxide with the mass concentration of 5%, preserving the temperature for 2 hours in a water bath at 50 ℃, then filtering, cleaning by using deionized water, and drying to constant weight to obtain pretreated zirconium silicate whiskers;
(2) preparing a modifier: adding deionized water into a reaction kettle, then adding phosphoric acid and N, N-dimethylacetamide into the reaction kettle, heating to 88-90 ℃, stirring at the rotating speed of 350r/min for 30min, then adding nano graphite oxide, and continuously stirring for 2 hours to obtain a modifier solution;
(3) modification treatment: adding the pretreated calcium silicate whiskers obtained in the step (1) into the modifier prepared in the step (2), then adjusting the pH of the modifier solution to 10.5 by using a sodium bicarbonate solution, stirring at a rotating speed of 500r/min for 2 hours, filtering, immediately calcining at 430 ℃ for 15min, naturally cooling to room temperature, cleaning by using absolute ethyl alcohol, and drying to constant weight to obtain the calcium silicate whisker.
Further, the mixing ratio of the iron-chromium sodium lignin sulfonate aqueous solution and the zirconium silicate whisker in the step (1) is 250 mL: 85g, wherein the addition amount of hydrogen peroxide is 10% of the mass of the iron-chromium sodium lignosulfonate aqueous solution.
Further, the mixing mass ratio of the deionized water, the phosphoric acid and the N, N-dimethylacetamide in the step (2) is 62:8: 5, the adding amount of the nano graphite oxide is 4.5 percent of the mass of the deionized water.
Further, the particle size of the nano graphite oxide in the step (2) is 75 nm.
Further, the mixing ratio of the pretreated zirconium silicate whisker and the modifier in the step (3) is 120 g: 390 mL.
Further, the pH of the sodium bicarbonate solution in the step (3) is 11.2.
Further, the preparation method of the sulfhydrylation nanometer hybrid material comprises the following steps:
uniformly dispersing nano aluminum into deionized water to obtain a nano aluminum dispersion liquid with the mass fraction of 12%, and mixing the nano aluminum dispersion liquid, a methanol solution containing tetraethoxysilane and an alkali solution according to the ratio of 180 mL: 150mL of: 100mL, stirring and reacting at the rotating speed of 2500r/min for 1.5 hours at 65 ℃, then performing rotary evaporation and drying, grinding for 40 minutes to obtain a nano hybrid material, adding gamma-mercaptopropyltriethoxysilane into an ethanol water solution according to the mass ratio of 1:20 for dissolving to obtain a mixed solution, and mixing the nano hybrid material according to the mass ratio of 55 g: adding 180mL into the mixed solution, treating under ultrasonic for 2min, stirring for 40min, filtering, cleaning, and oven drying to constant weight.
Further, the ethanol water solution accounts for 60% in mass, the ethyl orthosilicate, the methanol and the water in the methanol solution containing the ethyl orthosilicate are mixed according to the mass ratio of 3:5:10, and the alkali solution is sodium hydroxide with the mass fraction of 10%.
Further, the modified zirconium silicate whisker reinforced alumina ceramic also comprises the following components in parts by weight: alpha-alumina powder 102, aluminum dihydrogen phosphate 8, mullite powder 3, bentonite 12 and potassium feldspar 10.
Compared with the prior art, the invention has the following advantages:
according to the alumina ceramic prepared by the invention, under the synergistic effect of the modified zirconium silicate whisker, the sulfhydrylation nano hybrid material and other raw materials, inorganic powder can be uniformly separated under the action of the modified zirconium silicate whisker and the sulfhydrylation nano hybrid material, the fluidity and uniformity of the inorganic powder are enhanced, and in the degumming process, the binder can be uniformly decomposed and diffused from the inside without forming or forming few holes and cracks, so that the compactness of the alumina ceramic is improved; meanwhile, in the firing process, the sulfhydrylation nano hybrid material and the modified zirconium silicate whisker can be melted and decomposed to a certain extent, holes and cracks which are possibly generated are filled, the compactness of the product is improved, the zirconium oxide crystal grains are dispersed on the crystal boundary of the aluminum oxide crystal grains to different degrees, the zirconium oxide existing in the crystal boundary can play a role in fixing and strengthening the crystal boundary, the growth of the aluminum oxide crystal grains is inhibited, the abrasion resistance of the ceramic is favorably improved, and meanwhile, under the induction of the sulfhydrylation nano hybrid material, the binding force between the aluminum oxide and the silicon oxide can be enhanced, so that the hardness and the strength of the aluminum oxide ceramic are improved. The hardness and the strength of the composite material are improved, and simultaneously, the modified zirconium silicate whisker and the sulfhydrylation nanometer hybrid material are matched with each other to jointly inhibit the growth of alumina grains, eliminate pores among the grains, reduce defects, reduce stress concentration points and improve the toughness of the composite material. The alumina ceramic prepared by the invention has uniform size of alumina grains, is uniformly dispersed, further disperses stress and improves toughness.
Detailed Description
Example 1
The modified zirconium silicate whisker reinforced alumina ceramic contains 6.40 wt% of modified zirconium silicate whisker and 3.20 wt% of sulfhydrylation nanometer hybrid material.
Further, the preparation method of the modified zirconium silicate whisker comprises the following steps:
(1) pretreatment: preparing an aqueous solution with the mass concentration of 6.3% by using iron-chromium sodium lignin sulfonate, adding zirconium silicate whiskers, stirring uniformly, heating to 50 ℃, gradually dropwise adding hydrogen peroxide with the mass concentration of 5%, preserving the temperature for 2 hours in a water bath at 50 ℃, then filtering, cleaning by using deionized water, and drying to constant weight to obtain pretreated zirconium silicate whiskers;
(2) preparing a modifier: adding deionized water into a reaction kettle, then adding phosphoric acid and N, N-dimethylacetamide into the reaction kettle, heating to 88-90 ℃, stirring at the rotating speed of 350r/min for 30min, then adding nano graphite oxide, and continuously stirring for 2 hours to obtain a modifier solution;
(3) modification treatment: adding the pretreated calcium silicate whiskers obtained in the step (1) into the modifier prepared in the step (2), then adjusting the pH of the modifier solution to 10.5 by using a sodium bicarbonate solution, stirring at a rotating speed of 500r/min for 2 hours, filtering, immediately calcining at 430 ℃ for 15min, naturally cooling to room temperature, cleaning by using absolute ethyl alcohol, and drying to constant weight to obtain the calcium silicate whisker.
Further, the mixing ratio of the iron-chromium sodium lignin sulfonate aqueous solution and the zirconium silicate whisker in the step (1) is 250 mL: 85g, wherein the addition amount of hydrogen peroxide is 10% of the mass of the iron-chromium sodium lignosulfonate aqueous solution.
Further, the mixing mass ratio of the deionized water, the phosphoric acid and the N, N-dimethylacetamide in the step (2) is 62:8: 5, the adding amount of the nano graphite oxide is 4.5 percent of the mass of the deionized water.
Further, the particle size of the nano graphite oxide in the step (2) is 75 nm.
Further, the mixing ratio of the pretreated zirconium silicate whisker and the modifier in the step (3) is 120 g: 390 mL.
Further, the pH of the sodium bicarbonate solution in the step (3) is 11.2.
Further, the preparation method of the sulfhydrylation nanometer hybrid material comprises the following steps:
uniformly dispersing nano aluminum into deionized water to obtain a nano aluminum dispersion liquid with the mass fraction of 12%, and mixing the nano aluminum dispersion liquid, a methanol solution containing tetraethoxysilane and an alkali solution according to the ratio of 180 mL: 150mL of: 100mL, stirring and reacting at the rotating speed of 2500r/min for 1.5 hours at 65 ℃, then performing rotary evaporation and drying, grinding for 40 minutes to obtain a nano hybrid material, adding gamma-mercaptopropyltriethoxysilane into an ethanol water solution according to the mass ratio of 1:20 for dissolving to obtain a mixed solution, and mixing the nano hybrid material according to the mass ratio of 55 g: adding 180mL into the mixed solution, treating under ultrasonic for 2min, stirring for 40min, filtering, cleaning, and oven drying to constant weight.
Further, the ethanol water solution accounts for 60% in mass, the ethyl orthosilicate, the methanol and the water in the methanol solution containing the ethyl orthosilicate are mixed according to the mass ratio of 3:5:10, and the alkali solution is sodium hydroxide with the mass fraction of 10%.
Further, the modified zirconium silicate whisker reinforced alumina ceramic also comprises the following components in parts by weight: alpha-alumina powder 102, aluminum dihydrogen phosphate 8, mullite powder 3, bentonite 12 and potassium feldspar 10.
Example 2
The modified zirconium silicate whisker reinforced alumina ceramic contains 6.46 wt% of modified zirconium silicate whisker and-3.23 wt% of sulfhydrylation nanometer hybrid material.
Further, the preparation method of the modified zirconium silicate whisker comprises the following steps:
(1) pretreatment: preparing an aqueous solution with the mass concentration of 6.3% by using iron-chromium sodium lignin sulfonate, adding zirconium silicate whiskers, stirring uniformly, heating to 50 ℃, gradually dropwise adding hydrogen peroxide with the mass concentration of 5%, preserving the temperature for 2 hours in a water bath at 50 ℃, then filtering, cleaning by using deionized water, and drying to constant weight to obtain pretreated zirconium silicate whiskers;
(2) preparing a modifier: adding deionized water into a reaction kettle, then adding phosphoric acid and N, N-dimethylacetamide into the reaction kettle, heating to 88-90 ℃, stirring at the rotating speed of 350r/min for 30min, then adding nano graphite oxide, and continuously stirring for 2 hours to obtain a modifier solution;
(3) modification treatment: adding the pretreated calcium silicate whiskers obtained in the step (1) into the modifier prepared in the step (2), then adjusting the pH of the modifier solution to 10.5 by using a sodium bicarbonate solution, stirring at a rotating speed of 500r/min for 2 hours, filtering, immediately calcining at 430 ℃ for 15min, naturally cooling to room temperature, cleaning by using absolute ethyl alcohol, and drying to constant weight to obtain the calcium silicate whisker.
Further, the mixing ratio of the iron-chromium sodium lignin sulfonate aqueous solution and the zirconium silicate whisker in the step (1) is 250 mL: 85g, wherein the addition amount of hydrogen peroxide is 10% of the mass of the iron-chromium sodium lignosulfonate aqueous solution.
Further, the mixing mass ratio of the deionized water, the phosphoric acid and the N, N-dimethylacetamide in the step (2) is 62:8: 5, the adding amount of the nano graphite oxide is 4.5 percent of the mass of the deionized water.
Further, the particle size of the nano graphite oxide in the step (2) is 75 nm.
Further, the mixing ratio of the pretreated zirconium silicate whisker and the modifier in the step (3) is 120 g: 390 mL.
Further, the pH of the sodium bicarbonate solution in the step (3) is 11.2.
Further, the preparation method of the sulfhydrylation nanometer hybrid material comprises the following steps:
uniformly dispersing nano aluminum into deionized water to obtain a nano aluminum dispersion liquid with the mass fraction of 12%, and mixing the nano aluminum dispersion liquid, a methanol solution containing tetraethoxysilane and an alkali solution according to the ratio of 180 mL: 150mL of: 100mL, stirring and reacting at the rotating speed of 2500r/min for 1.5 hours at 65 ℃, then performing rotary evaporation and drying, grinding for 40 minutes to obtain a nano hybrid material, adding gamma-mercaptopropyltriethoxysilane into an ethanol water solution according to the mass ratio of 1:20 for dissolving to obtain a mixed solution, and mixing the nano hybrid material according to the mass ratio of 55 g: adding 180mL into the mixed solution, treating under ultrasonic for 2min, stirring for 40min, filtering, cleaning, and oven drying to constant weight.
Further, the ethanol water solution accounts for 60% in mass, the ethyl orthosilicate, the methanol and the water in the methanol solution containing the ethyl orthosilicate are mixed according to the mass ratio of 3:5:10, and the alkali solution is sodium hydroxide with the mass fraction of 10%.
Further, the modified zirconium silicate whisker reinforced alumina ceramic also comprises the following components in parts by weight: alpha-alumina powder 102, aluminum dihydrogen phosphate 8, mullite powder 3, bentonite 12 and potassium feldspar 10.
Example 3
The modified zirconium silicate whisker reinforced alumina ceramic contains 6.44 wt% of modified zirconium silicate whisker and 3.22 wt% of sulfhydrylation nanometer hybrid material.
Further, the preparation method of the modified zirconium silicate whisker comprises the following steps:
(1) pretreatment: preparing an aqueous solution with the mass concentration of 6.3% by using iron-chromium sodium lignin sulfonate, adding zirconium silicate whiskers, stirring uniformly, heating to 50 ℃, gradually dropwise adding hydrogen peroxide with the mass concentration of 5%, preserving the temperature for 2 hours in a water bath at 50 ℃, then filtering, cleaning by using deionized water, and drying to constant weight to obtain pretreated zirconium silicate whiskers;
(2) preparing a modifier: adding deionized water into a reaction kettle, then adding phosphoric acid and N, N-dimethylacetamide into the reaction kettle, heating to 88-90 ℃, stirring at the rotating speed of 350r/min for 30min, then adding nano graphite oxide, and continuously stirring for 2 hours to obtain a modifier solution;
(3) modification treatment: adding the pretreated calcium silicate whiskers obtained in the step (1) into the modifier prepared in the step (2), then adjusting the pH of the modifier solution to 10.5 by using a sodium bicarbonate solution, stirring at a rotating speed of 500r/min for 2 hours, filtering, immediately calcining at 430 ℃ for 15min, naturally cooling to room temperature, cleaning by using absolute ethyl alcohol, and drying to constant weight to obtain the calcium silicate whisker.
Further, the mixing ratio of the iron-chromium sodium lignin sulfonate aqueous solution and the zirconium silicate whisker in the step (1) is 250 mL: 85g, wherein the addition amount of hydrogen peroxide is 10% of the mass of the iron-chromium sodium lignosulfonate aqueous solution.
Further, the mixing mass ratio of the deionized water, the phosphoric acid and the N, N-dimethylacetamide in the step (2) is 62:8: 5, the adding amount of the nano graphite oxide is 4.5 percent of the mass of the deionized water.
Further, the particle size of the nano graphite oxide in the step (2) is 75 nm.
Further, the mixing ratio of the pretreated zirconium silicate whisker and the modifier in the step (3) is 120 g: 390 mL.
Further, the pH of the sodium bicarbonate solution in the step (3) is 11.2.
Further, the preparation method of the sulfhydrylation nanometer hybrid material comprises the following steps:
uniformly dispersing nano aluminum into deionized water to obtain a nano aluminum dispersion liquid with the mass fraction of 12%, and mixing the nano aluminum dispersion liquid, a methanol solution containing tetraethoxysilane and an alkali solution according to the ratio of 180 mL: 150mL of: 100mL, stirring and reacting at the rotating speed of 2500r/min for 1.5 hours at 65 ℃, then performing rotary evaporation and drying, grinding for 40 minutes to obtain a nano hybrid material, adding gamma-mercaptopropyltriethoxysilane into an ethanol water solution according to the mass ratio of 1:20 for dissolving to obtain a mixed solution, and mixing the nano hybrid material according to the mass ratio of 55 g: adding 180mL into the mixed solution, treating under ultrasonic for 2min, stirring for 40min, filtering, cleaning, and oven drying to constant weight.
Further, the ethanol water solution accounts for 60% in mass, the ethyl orthosilicate, the methanol and the water in the methanol solution containing the ethyl orthosilicate are mixed according to the mass ratio of 3:5:10, and the alkali solution is sodium hydroxide with the mass fraction of 10%.
Further, the modified zirconium silicate whisker reinforced alumina ceramic also comprises the following components in parts by weight: alpha-alumina powder 102, aluminum dihydrogen phosphate 8, mullite powder 3, bentonite 12 and potassium feldspar 10.
Comparative example 1: the only difference from example 1 was that the modified zirconium silicate whiskers were replaced with equivalent amounts of unmodified zirconium silicate whiskers.
Comparative example 2: the only difference from example 1 is that the modified zirconium silicate whiskers were replaced with an equal amount of zirconium silicate powder.
Comparative example 3: the only difference from example 1 is that the thiolated nanohybrid material was replaced with untreated nanohybrid material.
Comparative example 4: the only difference from example 1 is that the thiolated nanohybrid is replaced with an equal amount of nanosilica.
Comparative example 5: the only difference from example 1 is that the thiolated nanohybrid material is replaced with an equal amount of nanoaluminum.
Control group: application No.: 201310647886.4 to be used as a ceramic.
The sample sizes prepared for the examples and comparative examples were 35mm × 35mm × 2.5 mm:
the bending strength of the material is tested by adopting a three-point bending method, the span is 20mm, and the pressing rate of a pressure head is 0.5 mm/min;
TABLE 1 flexural Strength
Flexural strength/MPa | Rockwell hardness/HRA | |
Example 1 | 780.4 | 98 |
Example 2 | 785.7 | 99 |
Example 3 | 783.2 | 98 |
Comparative example 1 | 618.1 | 95 |
Comparative example 2 | 582.6 | 93 |
Comparative example 3 | 605.8 | 93 |
Comparative example 4 | 616.9 | 92 |
Comparative example 5 | 596.4 | 91 |
Control group | 234.6 | 72 |
As can be seen from Table 1, the alumina ceramics prepared by the present invention have good bending strength and hardness.
Placing the sample in an electric furnace at 1380 ℃ for heat preservation for 14 min, taking out for air cooling, placing the sample in the electric furnace for heating, heat preservation and cooling after 30min, repeating the steps for a plurality of times until the sample cracks or breaks, and recording the times of thermal shock before the sample is broken;
TABLE 2 thermal shock resistance
Number of thermal shocks/time | |
Example mean value | 38 |
Comparative example 1 | 33 |
Comparative example 2 | 29 |
Comparative example 3 | 28 |
Comparative example 4 | 30 |
Control group | 11 |
As can be seen from Table 2, the alumina ceramic prepared by the invention has good thermal shock resistance.
Further, the alumina ceramics of the examples had an average porosity of 0.07% and an average fracture toughness of 12.8MPa m1/2。
Claims (1)
1. The modified zirconium silicate whisker reinforced alumina ceramic is characterized by comprising 6.40-6.46% of modified zirconium silicate whiskers and 3.20-3.23% of sulfhydrylation nanometer hybrid materials by mass; the preparation method of the modified zirconium silicate whisker comprises the following steps:
(1) pretreatment: preparing an aqueous solution with the mass concentration of 6.3% by using iron-chromium sodium lignin sulfonate, adding zirconium silicate whiskers, stirring uniformly, heating to 50 ℃, gradually dropwise adding hydrogen peroxide with the mass concentration of 5%, preserving the temperature for 2 hours in a water bath at 50 ℃, then filtering, cleaning by using deionized water, and drying to constant weight to obtain pretreated zirconium silicate whiskers;
(2) preparing a modifier: adding deionized water into a reaction kettle, then adding phosphoric acid and N, N-dimethylacetamide into the reaction kettle, heating to 88-90 ℃, stirring at the rotating speed of 350r/min for 30min, then adding nano graphite oxide, and continuously stirring for 2 hours to obtain a modifier solution;
(3) modification treatment: adding the pretreated calcium silicate whiskers obtained in the step (1) into the modifier prepared in the step (2), then adjusting the pH of the modifier solution to 10.5 by using a sodium bicarbonate solution, stirring at a rotating speed of 500r/min for 2 hours, filtering, immediately calcining at 430 ℃ for 15min, naturally cooling to room temperature, cleaning by using absolute ethyl alcohol, and drying to constant weight to obtain the calcium silicate whisker; the mixing ratio of the iron-chromium sodium lignin sulfonate aqueous solution and the zirconium silicate whisker in the step (1) is 250 mL: 85g, wherein the addition amount of hydrogen peroxide is 10% of the mass of the iron-chromium sodium lignosulfonate aqueous solution; the mixing mass ratio of the deionized water, the phosphoric acid and the N, N-dimethylacetamide in the step (2) is 62:8: 5, and the adding amount of the nano graphite oxide is 4.5% of the mass of the deionized water; the granularity of the nano graphite oxide in the step (2) is 75 nm; the mixing ratio of the pretreated zirconium silicate whisker and the modifier in the step (3) is 120 g: 390 mL; the pH value of the sodium bicarbonate solution in the step (3) is 11.2; the preparation method of the sulfhydrylation nanometer hybrid material comprises the following steps:
uniformly dispersing nano aluminum into deionized water to obtain a nano aluminum dispersion liquid with the mass fraction of 12%, and mixing the nano aluminum dispersion liquid, a methanol solution containing tetraethoxysilane and an alkali solution according to the ratio of 180 mL: 150mL of: 100mL, stirring and reacting at the rotating speed of 2500r/min for 1.5 hours at 65 ℃, then performing rotary evaporation and drying, grinding for 40 minutes to obtain a nano hybrid material, adding gamma-mercaptopropyltriethoxysilane into an ethanol water solution according to the mass ratio of 1:20 for dissolving to obtain a mixed solution, and mixing the nano hybrid material according to the mass ratio of 55 g: adding 180mL of the mixture into the mixed solution, treating for 2min under ultrasonic waves, stirring for reacting for 40min, performing suction filtration, cleaning, and drying to constant weight to obtain the product; the ethanol aqueous solution accounts for 60% in mass, the ethyl orthosilicate, the methanol and the water in the methanol solution containing the ethyl orthosilicate are mixed according to the mass ratio of 3:5:10, and the alkali solution is sodium hydroxide with the mass fraction of 10%; the modified zirconium silicate whisker reinforced alumina ceramic further comprises the following components in parts by weight: alpha-alumina powder 102, aluminum dihydrogen phosphate 8, mullite powder 3, bentonite 12 and potassium feldspar 10.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810948454.XA CN108752029B (en) | 2018-08-20 | 2018-08-20 | Modified zirconium silicate whisker reinforced alumina ceramic |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810948454.XA CN108752029B (en) | 2018-08-20 | 2018-08-20 | Modified zirconium silicate whisker reinforced alumina ceramic |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108752029A CN108752029A (en) | 2018-11-06 |
CN108752029B true CN108752029B (en) | 2021-08-10 |
Family
ID=63967231
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810948454.XA Active CN108752029B (en) | 2018-08-20 | 2018-08-20 | Modified zirconium silicate whisker reinforced alumina ceramic |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108752029B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116177884B (en) * | 2023-03-13 | 2024-06-25 | 爱迪特(秦皇岛)科技股份有限公司 | Glass ceramic matrix and preparation method and application thereof |
CN117865705B (en) * | 2024-03-11 | 2024-05-17 | 山东华信工业科技有限公司 | Preparation method of high-heat-conductivity silicon carbide ceramic |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101182193A (en) * | 2007-11-27 | 2008-05-21 | 清华大学 | Method for preparing in-situ self-toughening alumina ceramics |
CN102258953A (en) * | 2011-07-11 | 2011-11-30 | 北京纳辰科技发展有限责任公司 | Nano aluminum paste and preparation method thereof |
CN104496440A (en) * | 2014-12-26 | 2015-04-08 | 深圳国瓷永丰源股份有限公司 | Formula for high-aluminum hard reinforced ceramic green body and manufacturing process and application thereof |
CN104987113A (en) * | 2015-07-24 | 2015-10-21 | 合肥凯士新材料贸易有限公司 | Zirconium silicate whisker modified tabular alumina porous ceramic used in LED lamp heat dissipation, and preparation method thereof |
CN108249453A (en) * | 2018-03-05 | 2018-07-06 | 西陇科学股份有限公司 | A kind of preparation of modification infusorial earth and its method for being used to prepare high-purity boracic acid |
-
2018
- 2018-08-20 CN CN201810948454.XA patent/CN108752029B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101182193A (en) * | 2007-11-27 | 2008-05-21 | 清华大学 | Method for preparing in-situ self-toughening alumina ceramics |
CN102258953A (en) * | 2011-07-11 | 2011-11-30 | 北京纳辰科技发展有限责任公司 | Nano aluminum paste and preparation method thereof |
CN104496440A (en) * | 2014-12-26 | 2015-04-08 | 深圳国瓷永丰源股份有限公司 | Formula for high-aluminum hard reinforced ceramic green body and manufacturing process and application thereof |
CN104987113A (en) * | 2015-07-24 | 2015-10-21 | 合肥凯士新材料贸易有限公司 | Zirconium silicate whisker modified tabular alumina porous ceramic used in LED lamp heat dissipation, and preparation method thereof |
CN108249453A (en) * | 2018-03-05 | 2018-07-06 | 西陇科学股份有限公司 | A kind of preparation of modification infusorial earth and its method for being used to prepare high-purity boracic acid |
Also Published As
Publication number | Publication date |
---|---|
CN108752029A (en) | 2018-11-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106747541B (en) | Method for in-situ synthesis of mullite whisker self-toughened mullite ceramic | |
CN111848198B (en) | Preparation method of alumina ceramic valve core ceramic chip and product thereof | |
CN108752029B (en) | Modified zirconium silicate whisker reinforced alumina ceramic | |
CN114057467B (en) | High-strength ceramic tile and preparation method thereof | |
CN106673626B (en) | Low-cost alumina powder material for producing self-toughening alumina wear-resistant ceramic | |
CN112110740B (en) | Method for preparing aluminum oxide-based composite biological ceramic material through in-situ reaction and product prepared by method | |
CN105254283A (en) | Preparation method for alumina ceramic matrix material | |
CN113416077B (en) | High-temperature ceramic cutter material with double composite structure and preparation method and application thereof | |
CN113896498B (en) | Preparation method of calcium silicate board | |
CN110040995B (en) | Preparation method of high-temperature light tough mullite aggregate | |
CN110669975A (en) | High-strength ceramic material | |
CN112521169A (en) | High-density ceramic fiber board and preparation method thereof | |
CN112194491A (en) | Pressureless sintering boron carbide ceramic powder and preparation method and application thereof | |
CN106565251B (en) | High-strength light refractory fiber and preparation method thereof | |
CN107540411A (en) | It is a kind of to reduce the method that silicone content is remained in carbon fibre reinforced ceramics based composites | |
CN108329018B (en) | Toughened alumina composite ceramic and preparation method thereof | |
CN114477951B (en) | High-strength high-whiteness ceramic product and processing technology thereof | |
CN104876582A (en) | Silicon carbide ceramic for abrasive medium and preparation method of silicon carbide ceramic | |
RU2664083C1 (en) | Method for obtaining the acid resistant binder | |
CN105601283B (en) | A kind of conductive network structure Si3N4The preparation method of ceramics | |
CN110407546B (en) | Porous autoclaved sand brick | |
CN108546138B (en) | Nano zirconia ceramic material and preparation method thereof | |
CN113582673A (en) | Aluminum oxide/titanium silicon carbon layered composite material and in-situ preparation method thereof | |
CN113149678A (en) | High-performance antibacterial domestic ceramic and preparation method thereof | |
RU2514354C1 (en) | Method of making articles from porous ceramic and fibre materials based on quartz glass |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
TA01 | Transfer of patent application right | ||
TA01 | Transfer of patent application right |
Effective date of registration: 20210714 Address after: 255051 Dongshou, Yuedian village, Nanding Town, Zhangdian District, Zibo City, Shandong Province Applicant after: Zibo new nonmetal material technology Co.,Ltd. Address before: 230000 room 721, Baowen international building, No.1 Zhanxi Road, Yaohai District, Hefei City, Anhui Province Applicant before: HEFEI HANJIA CERAMICS TECHNOLOGY Co.,Ltd. |
|
GR01 | Patent grant | ||
GR01 | Patent grant |