CN117303741A - High-temperature-resistant glaze - Google Patents
High-temperature-resistant glaze Download PDFInfo
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- CN117303741A CN117303741A CN202311355530.3A CN202311355530A CN117303741A CN 117303741 A CN117303741 A CN 117303741A CN 202311355530 A CN202311355530 A CN 202311355530A CN 117303741 A CN117303741 A CN 117303741A
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- 239000000843 powder Substances 0.000 claims abstract description 108
- 229910018137 Al-Zn Inorganic materials 0.000 claims abstract description 29
- 229910018573 Al—Zn Inorganic materials 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010453 quartz Substances 0.000 claims abstract description 14
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 13
- 229910021532 Calcite Inorganic materials 0.000 claims abstract description 13
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 13
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 claims abstract description 13
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims abstract description 13
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 13
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011521 glass Substances 0.000 claims abstract description 13
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052670 petalite Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 42
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 39
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 33
- 229910021634 Rhenium(III) chloride Inorganic materials 0.000 claims description 28
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- LOIHSHVELSAXQN-UHFFFAOYSA-K trirhenium nonachloride Chemical compound Cl[Re](Cl)Cl LOIHSHVELSAXQN-UHFFFAOYSA-K 0.000 claims description 28
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 27
- 238000005303 weighing Methods 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 21
- 238000000498 ball milling Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000000919 ceramic Substances 0.000 claims description 14
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 13
- 235000006408 oxalic acid Nutrition 0.000 claims description 13
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 12
- 229930182817 methionine Natural products 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 10
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 10
- 239000000080 wetting agent Substances 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 238000011010 flushing procedure Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 3
- 229920002535 Polyethylene Glycol 1500 Polymers 0.000 claims description 3
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 claims description 3
- VUYXVWGKCKTUMF-UHFFFAOYSA-N tetratriacontaethylene glycol monomethyl ether Chemical compound COCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO VUYXVWGKCKTUMF-UHFFFAOYSA-N 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 95
- 239000000463 material Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 13
- 229910052702 rhenium Inorganic materials 0.000 description 13
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- -1 rhenium ions Chemical class 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Dental Preparations (AREA)
Abstract
The invention relates to a high-temperature resistant glaze, which comprises the following components in parts by weight: 65-85 parts of petalite, 4.2-6.8 parts of quartz powder, 3-6 parts of barium carbonate, 2.5-4 parts of calcite, 3.2-4.8 parts of bone powder, 4-6 parts of glass powder, 1.6-3.2 parts of talcum powder, 2.2-4.4 parts of kaolin and 2.5-5.5 parts of Re@Al-Zn powder. Wherein, petalite, quartz powder and kaolin are used as a compound for reducing the thermal expansion coefficient of the glaze; the barium carbonate, calcite and bone powder are used as a compound for enhancing the hardness and strength of the glaze; the glass powder is used for promoting the flow and crystallization of the glaze surface and improving the hardness and the flatness of the glaze surface; the talcum powder is beneficial to reducing the sintering temperature of the glaze and facilitating the forming of the glaze; re@Al-Zn powder is used for providing glossiness, enhancing strength and toughness, and simultaneously enhancing the high temperature resistance of the glaze.
Description
Technical Field
The invention relates to the field of glazes, in particular to a high-temperature-resistant glaze.
Background
The ceramic is various products of materials prepared by crushing, mixing, forming and calcining natural clay and various natural minerals serving as main raw materials. The glaze is a vitreous layer covered on the ceramic surface, generally quartz, feldspar and clay are used as raw materials, and after grinding and water adding modulation, the glaze is coated on the surface of a green body, and is baked at a certain temperature to be molten, and when the temperature is reduced, the vitreous layer on the ceramic surface is formed, so that the effect of protecting the beauty is achieved. The glaze material can increase the mechanical strength, heat stability, dielectric strength, prevent liquid and gas erosion, and promote the beautiful appearance of porcelain, and has no dust adhesion. The glaze material formed by grinding and adding water is used as raw materials for dipping or swinging the glaze, the components and the content of the raw materials need to be strictly controlled in the manufacturing process of the glaze material, and only the proper components and the proper content can be used for improving the quality of the ceramic.
Along with the development of ceramic industry, the types of glaze materials are more and more abundant and various, the types and the application types of the glaze materials used by most daily ceramics are various at present, the glaze materials can be divided into high-temperature glaze materials and low-temperature glaze materials according to the firing temperature, the high-temperature glaze materials have unique points in the development of the glaze materials, and the research on the high-temperature glaze materials is an important research direction of the ceramic industry all the time. The existing high-temperature-resistant composite ceramic glaze still has certain defects, in order to increase the heat resistance and glossiness of the glaze, some metals or metal alloys are added into the glaze to be used as metal pigments, and copper zinc powder, aluminum zinc powder and the like are the most commonly used, however, due to the low melting point of the metals, the high temperature cannot be born under the condition of higher temperature requirements, so that the thermal stability of the glaze is poor, and therefore, the high-temperature-resistant ceramic glaze with higher thermal stability is urgently needed in the market.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a high-temperature resistant glaze.
The aim of the invention is realized by adopting the following technical scheme:
the high temperature resistant glaze comprises the following components in parts by weight:
65-85 parts of petalite, 4.2-6.8 parts of quartz powder, 3-6 parts of barium carbonate, 2.5-4 parts of calcite, 3.2-4.8 parts of bone powder, 4-6 parts of glass powder, 1.6-3.2 parts of talcum powder, 2.2-4.4 parts of kaolin and 2.5-5.5 parts of Re@Al-Zn powder.
Preferably, the petalite, density: 2.3-2.5g/cm 3 Lithium oxide content: 4.2% -4.5%, granularity: 250-350 mesh.
Preferably, the quartz powder has a silica content of: 96.8% -98.9%, density: 2.6g/cm 3 Particle size: 250-350 mesh.
Preferably, the barium carbonate, purity: 99%, density: 4.32-4.43g/cm 3 Particle size: 250-350 mesh.
Preferably, the calcite, density: 2.6-2.8g/cm 3 The CaO mass ratio in the components is 56.0%, the granularity is: 250-350 mesh.
Preferably, the bone powder, namely hydroxyapatite, comprises the following components in percentage by mass: ca:27.5% -32.4%, P:6.4% -7.6%, granularity: 250-350 mesh.
Preferably, the glass frit, density: 2.7-3.6g/cm 3 The components comprise the following components in percentage by mass: siO (SiO) 2 ：65％-70％，Al 2 O 3 :18% -24%, granularity: 250-350 mesh.
Preferably, the talcum powder has the molecular formula of Mg 6 (Si 2 O 5 ) 4 (OH) 4 Particle size: 250-350 mesh.
Preferably, the kaolin comprises the following components in percentage by mass: siO (SiO) 2 46.54 content of Al 2 O 3 ：36.26％，Fe 2 O 3 ：0.65％。
Preferably, the preparation method of the Re@Al-Zn powder comprises the following steps:
s1, weighing aluminum zinc alloy powder, performing ultrasonic treatment in absolute ethyl alcohol for 30min, and drying in an oven for later use;
s2, weighing iminodiacetic acid, oxalic acid and methionine, sequentially mixing into deionized water, continuously stirring at 45-55 ℃ until all iminodiacetic acid, oxalic acid and methionine are uniformly dissolved, then adding a wetting agent, and continuously stirring uniformly to obtain a solution A;
s3, weighing rhenium trichloride into the hydrochloric acid solution, and fully stirring the rhenium trichloride to be uniform at room temperature to obtain a rhenium trichloride solution; gradually dropwise adding the rhenium trichloride solution into the solution A, stirring while dropwise adding, and continuously stirring and dispersing for 15-20min after all dropwise adding to form a solution B;
s4, weighing titanium trichloride, and dissolving the titanium trichloride into deionized water to form a titanium trichloride solution; adding a titanium trichloride solution into the solution B, then adding a sodium carbonate solution into the solution B, regulating the pH of the solution to 9.5-10.0, and fully and uniformly stirring to form a solution C;
s5, adding aluminum zinc alloy powder into the solution C, stirring uniformly at room temperature, heating to 75-95 ℃, continuously stirring to keep the powder in the solution from agglomerating, keeping the temperature and stirring for 3-5h, filtering out the powder after the reaction is finished, filtering and flushing three times by using deionized water under reduced pressure, and drying in an oven to obtain Re@Al-Zn powder.
Preferably, in S1, the purity of the aluminum zinc alloy powder is > 99%, wherein the mass ratio of aluminum to zinc is: al: zn=2:1.
Preferably, in the step S1, the mass-volume ratio of the aluminum zinc alloy powder to the absolute ethyl alcohol is 1g: (5-10) mL.
Preferably, in the step S2, the wetting agent is at least one of polyethylene glycol PEG-1000, polyethylene glycol PEG-1200, polyethylene glycol PEG-1500 and polyethylene glycol PEG-2000.
Preferably, in S2, the mass-to-volume ratio of iminodiacetic acid, oxalic acid, methionine and deionized water is (0.13-0.21) g: (0.09-0.14) g: (0.15-0.22) g:10mL.
Preferably, in the step S3, the concentration of the hydrochloric acid solution is 1.0-2.0mol/L, and the mass volume ratio of the rhenium trichloride to the hydrochloric acid solution is 0.16g: (3-7) mL.
Preferably, in the step S3, the volume ratio of the rhenium trichloride solution to the solution A is 1:5-6.
Preferably, in the titanium trichloride solution of S4, the mass-to-volume ratio of titanium trichloride to deionized water is 0.15g: (5-15) mL.
Preferably, in the step S4, the volume ratio of the titanium trichloride solution to the solution B is 1:3-5.
Preferably, in S5, the mass-to-volume ratio of the aluminum zinc alloy powder to the solution C is 1g: (10-20) mL.
Preferably, the preparation method of the high-temperature resistant glaze comprises the following steps:
(1) Weighing the raw material components according to the weight parts, ball-milling and mixing in a ball mill, wherein the ball-milling medium is water, a small amount of sodium carboxymethylcellulose is added as a lubricant, after ball-milling is completed, washing with water and drying, and sieving with a 200-mesh sieve, wherein the screen residue is less than 0.5%; wherein, the total weight of each raw material: grinding ball: water: the mass ratio of the sodium carboxymethyl cellulose is 1:3-5:1.2-1.5:0.001-0.002;
(2) Spraying the ground raw material mixture on the surface of ceramic by a glaze spraying method, wherein the thickness of the formed glaze is 1-10mm, and thus the preparation of the glaze is completed.
The beneficial effects of the invention are as follows:
1. the glaze material capable of being stable at high temperature is prepared by mixing various raw materials. Wherein, petalite, quartz powder and kaolin are used as a compound for reducing the thermal expansion coefficient of the glaze; the barium carbonate, calcite and bone powder are used as a compound for enhancing the hardness and strength of the glaze; the glass powder is used for promoting the flow and crystallization of the glaze surface and improving the hardness and the flatness of the glaze surface; the talcum powder is beneficial to reducing the sintering temperature of the glaze and facilitating the forming of the glaze; re@Al-Zn powder is used for providing glossiness, enhancing strength and toughness, and simultaneously enhancing the high temperature resistance of the glaze.
2. The rhenium (Re) element is used as a high-temperature resistant metal material and is suitable for being used as a metal pigment, but because the rhenium is relatively expensive and a large amount of rhenium is added at relatively high cost, the invention tries to compound a metal rhenium layer on the surface of some metal alloys, so that the high-temperature stability of rhenium can be realized, and the cost can be further reduced. The Re@Al-Zn powder is prepared by taking high-temperature-resistant aluminum zinc alloy powder as a base material and rhenium ions as a coated metal source. The invention adopts a chemical in-situ reduction method to finish the reduction coating of metal rhenium on the surface of aluminum zinc alloy powder. Compared with the conventional metal coating, the method provided by the invention has the advantages of lower temperature and pressure, and has the advantages of low porosity and uniformity of the coating.
3. In the process of preparing Re@Al-Zn powder, rhenium trichloride is adopted as a source of rhenium element, and the added iminodiacetic acid is used as a complexing agent to complex with rhenium ions so as to prevent the rhenium from hydrolyzing in aqueous solution. The titanium trichloride is used as a reducing agent, so as to promote rhenium ions to generate a rhenium metal simple substance to cover the surface of the alloy powder, and the added oxalic acid is used as a complexing agent to complex with titanium ions so as to prevent the titanium ions from hydrolyzing in an aqueous solution. The wetting agent can prevent the phenomenon of uneven dispersion after the subsequent alloy powder is added into the solution, and the pH value of the solution is adjusted to 9.5-10.0, so that the smooth progress of the reaction can be promoted.
Detailed Description
The technical scheme of the invention is described below through specific examples. It is to be understood that the mention of one or more method steps of the present invention does not exclude the presence of other method steps before and after the combination step or that other method steps may be interposed between these explicitly mentioned steps; it should also be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Moreover, unless otherwise indicated, the numbering of the method steps is merely a convenient tool for identifying the method steps and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention in which the invention may be practiced, as such changes or modifications in their relative relationships may be regarded as within the scope of the invention without substantial modification to the technical matter.
In order to better understand the above technical solution, exemplary embodiments of the present invention are described in more detail below. While exemplary embodiments of the invention are shown, it should be understood that the invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
The raw materials used in the embodiment of the invention are specifically as follows:
petalite, density: 2.3-2.5g/cm 3 Lithium oxide content: 4.2% -4.5%, granularity: 250-350 mesh.
Quartz powder, silica content: 96.8% -98.9%, density: 2.6g/cm 3 Particle size: 250-350 mesh.
Barium carbonate, purity: 99%, density: 4.32-4.43g/cm 3 Particle size: 250-350 mesh.
Calcite, density: 2.6-2.8g/cm 3 In the components ofCaO mass ratio is 56.0%, granularity: 250-350 mesh.
Bone powder, namely hydroxyapatite, comprises the following components in percentage by mass: ca:27.5% -32.4%, P:6.4% -7.6%, granularity: 250-350 mesh.
Glass frit, density: 2.7-3.6g/cm 3 The components comprise the following components in percentage by mass: siO (SiO) 2 ：65％-70％，Al 2 O 3 :18% -24%, granularity: 250-350 mesh.
Talc powder with molecular formula of Mg 6 (Si 2 O 5 ) 4 (OH) 4 Particle size: 250-350 mesh.
Kaolin, the components comprise the following components in percentage by mass: siO (SiO) 2 46.54 content of Al 2 O 3 ：36.26％，Fe 2 O 3 ：0.65％。
The invention is further described with reference to the following examples.
Example 1
The high temperature resistant glaze comprises the following components in parts by weight:
75 parts of petalite, 5.6 parts of quartz powder, 4 parts of barium carbonate, 3.4 parts of calcite, 4 parts of bone powder, 5 parts of glass powder, 2.4 parts of talcum powder, 3.3 parts of kaolin and 3.5 parts of Re@Al-Zn powder.
The preparation method of Re@Al-Zn powder comprises the following steps:
s1, weighing aluminum-zinc alloy powder, and carrying out ultrasonic treatment in absolute ethyl alcohol for 30min, wherein the purity of the aluminum-zinc alloy powder is more than 99%, and the mass ratio of aluminum to zinc is as follows: al: zn=2:1, mass-to-volume ratio of aluminum zinc alloy powder to absolute ethanol is 1g:8mL, drying in an oven for later use;
s2, weighing iminodiacetic acid, oxalic acid and methionine, and sequentially mixing into deionized water, wherein the mass volume ratio of iminodiacetic acid to oxalic acid to methionine to deionized water is 0.18g:0.12g:0.19g:10mL of the solution is continuously stirred at the temperature of 55 ℃ until all the solution is uniformly dissolved, then the polyethylene glycol PEG-1000 serving as a wetting agent is added, the addition amount is 1% of the mass of deionized water, and the solution A is obtained after continuous stirring is uniform;
s3, weighing rhenium trichloride into a 2.0mol/L hydrochloric acid solution, wherein the mass volume ratio of the rhenium trichloride to the hydrochloric acid solution is 0.16g:5mL, fully stirring at room temperature until the mixture is uniform to obtain rhenium trichloride solution; gradually dropwise adding the rhenium trichloride solution into the solution A, wherein the volume ratio of the rhenium trichloride solution to the solution A is 1:5, stirring while dropwise adding, and continuously stirring and dispersing for 20min after all dropwise adding to form a solution B;
s4, weighing titanium trichloride, dissolving the titanium trichloride into deionized water, wherein the mass volume ratio of the titanium trichloride to the deionized water is 0.15g:10mL of a titanium trichloride solution is formed; adding a titanium trichloride solution into the solution B, wherein the volume ratio of the titanium trichloride solution to the solution B is 1:4, then adding a sodium carbonate solution into the solution B, adjusting the pH of the solution to 9.5-10.0, and fully and uniformly stirring to form a solution C;
s5, adding aluminum zinc alloy powder into the solution C, wherein the mass volume ratio of the aluminum zinc alloy powder to the solution C is 1g:15mL, stirring uniformly at room temperature, heating to 85 ℃, continuously stirring to keep the powder in solution from agglomerating, keeping the temperature and stirring for 4 hours, filtering out the powder after the reaction is finished, filtering and flushing three times by using deionized water under reduced pressure, and drying in an oven to obtain Re@Al-Zn powder.
The preparation method of the high-temperature resistant glaze comprises the following steps:
(1) Weighing the raw material components according to the weight parts, ball-milling and mixing in a ball mill, wherein the ball-milling medium is water, a small amount of sodium carboxymethylcellulose is added as a lubricant, after ball-milling is completed, washing with water and drying, and sieving with a 200-mesh sieve, wherein the screen residue is less than 0.5%; wherein, the total weight of each raw material: grinding ball: water: the mass ratio of the sodium carboxymethyl cellulose is 1:4:1.3:0.001;
(2) Spraying the ground raw material mixture on the surface of ceramic by a glaze spraying method, wherein the thickness of the formed glaze is 4mm, and thus the preparation of the glaze is completed.
Example 2
The high temperature resistant glaze comprises the following components in parts by weight:
65 parts of petalite, 6.8 parts of quartz powder, 3 parts of barium carbonate, 4 parts of calcite, 3.2 parts of bone powder, 6 parts of glass powder, 1.6 parts of talcum powder, 4.4 parts of kaolin and 2.5 parts of Re@Al-Zn powder.
The preparation method of Re@Al-Zn powder comprises the following steps:
s1, weighing aluminum-zinc alloy powder, and carrying out ultrasonic treatment in absolute ethyl alcohol for 30min, wherein the purity of the aluminum-zinc alloy powder is more than 99%, and the mass ratio of aluminum to zinc is as follows: al: zn=2:1, mass-to-volume ratio of aluminum zinc alloy powder to absolute ethanol is 1g:5mL, drying in an oven for later use;
s2, weighing iminodiacetic acid, oxalic acid and methionine, and sequentially mixing into deionized water, wherein the mass volume ratio of iminodiacetic acid to oxalic acid to methionine to deionized water is 0.13g:0.09g:0.15g:10mL of the solution is continuously stirred at the temperature of 45 ℃ until all the solution is uniformly dissolved, then a wetting agent polyethylene glycol PEG-1500 is added, the addition amount is 1% of the mass of deionized water, and the solution A is obtained after continuous stirring is uniform;
s3, weighing rhenium trichloride into 1.0mol/L hydrochloric acid solution, wherein the mass volume ratio of the rhenium trichloride to the hydrochloric acid solution is 0.16g:3mL, fully stirring at room temperature until the mixture is uniform to obtain rhenium trichloride solution; gradually dropwise adding the rhenium trichloride solution into the solution A, wherein the volume ratio of the rhenium trichloride solution to the solution A is 1:5, stirring while dropwise adding, and continuously stirring and dispersing for 15min after all dropwise adding to form a solution B;
s4, weighing titanium trichloride, dissolving the titanium trichloride into deionized water, wherein the mass volume ratio of the titanium trichloride to the deionized water is 0.15g:5mL, forming a titanium trichloride solution; adding a titanium trichloride solution into the solution B, wherein the volume ratio of the titanium trichloride solution to the solution B is 1:3, then adding a sodium carbonate solution into the solution B, adjusting the pH of the solution to 9.5-10.0, and fully and uniformly stirring to form a solution C;
s5, adding aluminum zinc alloy powder into the solution C, wherein the mass volume ratio of the aluminum zinc alloy powder to the solution C is 1g:10mL, stirring uniformly at room temperature, heating to 75 ℃, continuously stirring to keep the powder in solution from agglomerating, keeping the temperature and stirring for 3 hours, filtering out the powder after the reaction is finished, filtering and flushing three times by using deionized water under reduced pressure, and drying in an oven to obtain Re@Al-Zn powder.
The preparation method of the high-temperature resistant glaze comprises the following steps:
(1) Weighing the raw material components according to the weight parts, ball-milling and mixing in a ball mill, wherein the ball-milling medium is water, a small amount of sodium carboxymethylcellulose is added as a lubricant, after ball-milling is completed, washing with water and drying, and sieving with a 200-mesh sieve, wherein the screen residue is less than 0.5%; wherein, the total weight of each raw material: grinding ball: water: the mass ratio of the sodium carboxymethyl cellulose is 1:3:1.2:0.001;
(2) Spraying the ground raw material mixture on the surface of ceramic by a glaze spraying method, wherein the thickness of the formed glaze is 2mm, and thus the preparation of the glaze is completed.
Example 3
The high temperature resistant glaze comprises the following components in parts by weight:
85 parts of petalite, 4.2 parts of quartz powder, 6 parts of barium carbonate, 2.5 parts of calcite, 4.8 parts of bone powder, 4 parts of glass powder, 3.2 parts of talcum powder, 2.2 parts of kaolin and 5.5 parts of Re@Al-Zn powder.
The preparation method of Re@Al-Zn powder comprises the following steps:
s1, weighing aluminum-zinc alloy powder, and carrying out ultrasonic treatment in absolute ethyl alcohol for 30min, wherein the purity of the aluminum-zinc alloy powder is more than 99%, and the mass ratio of aluminum to zinc is as follows: al: zn=2:1, mass-to-volume ratio of aluminum zinc alloy powder to absolute ethanol is 1g:10mL, drying in an oven for later use;
s2, weighing iminodiacetic acid, oxalic acid and methionine, and sequentially mixing into deionized water, wherein the mass volume ratio of iminodiacetic acid to oxalic acid to methionine to deionized water is 0.21g:0.14g:0.22g:10mL of the solution is continuously stirred at the temperature of 55 ℃ until all the solution is uniformly dissolved, then a wetting agent polyethylene glycol PEG-2000 is added, the addition amount is 1% of the mass of deionized water, and the solution A is obtained after continuous stirring is uniform;
s3, weighing rhenium trichloride into a 2.0mol/L hydrochloric acid solution, wherein the mass volume ratio of the rhenium trichloride to the hydrochloric acid solution is 0.16g:7mL, fully stirring to be uniform at room temperature to obtain rhenium trichloride solution; gradually dropwise adding the rhenium trichloride solution into the solution A, wherein the volume ratio of the rhenium trichloride solution to the solution A is 1:5-6, stirring while dropwise adding, and continuously stirring and dispersing for 20min after all dropwise adding to form a solution B;
s4, weighing titanium trichloride, dissolving the titanium trichloride into deionized water, wherein the mass volume ratio of the titanium trichloride to the deionized water is 0.15g:15mL, forming a titanium trichloride solution; adding a titanium trichloride solution into the solution B, wherein the volume ratio of the titanium trichloride solution to the solution B is 1:5, then adding a sodium carbonate solution into the solution B, adjusting the pH of the solution to 9.5-10.0, and fully and uniformly stirring to form a solution C;
s5, adding aluminum zinc alloy powder into the solution C, wherein the mass volume ratio of the aluminum zinc alloy powder to the solution C is 1g: and (3) 20mL, uniformly stirring at room temperature, heating to 95 ℃, continuously stirring to keep the powder in solution from agglomerating, keeping the temperature and stirring for 5 hours, filtering out the powder after the reaction is finished, filtering and flushing three times by using deionized water under reduced pressure, and drying in an oven to obtain Re@Al-Zn powder.
The preparation method of the high-temperature resistant glaze comprises the following steps:
(1) Weighing the raw material components according to the weight parts, ball-milling and mixing in a ball mill, wherein the ball-milling medium is water, a small amount of sodium carboxymethylcellulose is added as a lubricant, after ball-milling is completed, washing with water and drying, and sieving with a 200-mesh sieve, wherein the screen residue is less than 0.5%; wherein, the total weight of each raw material: grinding ball: water: the mass ratio of the sodium carboxymethyl cellulose is 1:5:1.5:0.002;
(2) Spraying the ground raw material mixture on the surface of ceramic by a glaze spraying method, wherein the thickness of the formed glaze is 8mm, and thus the preparation of the glaze is completed.
Comparative example 1
The glaze material, and example 1 were different from each other:
the glaze comprises the following components in parts by weight:
75 parts of petalite, 5.6 parts of quartz powder, 4 parts of barium carbonate, 3.4 parts of calcite, 4 parts of bone powder, 5 parts of glass powder, 2.4 parts of talcum powder and 3.3 parts of kaolin.
That is, re@Al-Zn powder was not added to this comparative example.
Comparative example 2
The glaze material, and example 1 were different from each other:
the glaze comprises the following components in parts by weight:
75 parts of petalite, 5.6 parts of quartz powder, 4 parts of barium carbonate, 3.4 parts of calcite, 4 parts of bone powder, 5 parts of glass powder, 2.4 parts of talcum powder, 3.3 parts of kaolin and 3.5 parts of Al-Zn alloy powder.
That is, the Re@Al-Zn powder of comparative example 1 was replaced with an Al-Zn alloy powder having a purity of > 99%, wherein the mass ratio of aluminum to zinc was: al: zn=2:1.
Comparative example 3
The glaze material, and example 1 were different from each other:
the glaze comprises the following components in parts by weight:
75 parts of petalite, 5.6 parts of quartz powder, 4 parts of barium carbonate, 3.4 parts of calcite, 4 parts of bone powder, 5 parts of glass powder, 2.4 parts of talcum powder, 3.3 parts of kaolin and 3.5 parts of Re-Al-Zn powder.
That is, in this comparative example, the Re@Al-Zn powder of comparative example 1 was replaced with an alloy powder of Re-Al-Zn trimetallic, the purity of the Al-Zn powder being > 99%, wherein the mass ratio of rhenium, aluminum and zinc is: re: al: zn=0.16:2:1.
The glazes prepared in example 1 and comparative examples 1 to 3 were compared in high temperature resistance, thermal expansion coefficient, compressive strength and gloss test, the high temperature resistance referring to the critical temperature at which the melting point appears on the surface of the glaze, the thermal expansion coefficient referring to GB/T16535-2008, the compressive strength referring to GB/T3810.2-2006, and the gloss test using a highly polished gloss meter, the results are shown in table 1 below:
table 1 comparison of glaze properties
As can be seen from Table 1, the high temperature resistance of example 1 is as high as 976℃and the thermal expansion coefficient is lower than 4X 10 -6 The compression strength and the glossiness are better at the temperature of/DEG C, and the performance is better than that of comparative example 1. The high temperature resistance of comparative example 1 was also relatively strong, but the coefficient of thermal expansion, compressive strength and gloss were all relatively low; in contrast, comparative example 2 was conducted by adding Al-Zn alloy powder having a low melting pointThe high temperature resistance is reduced, the thermal expansion coefficient is larger than that of comparative example 1, the glossiness is slightly higher than that of example 1, but the overall performance is far lower than that of example 1; comparative example 3 replaces the Re-Al-Zn trimetallic alloy powder, although the performance was slightly improved, the improvement was not large, indicating that it was not satisfactory to use only rhenium metal as an additive.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms should not be understood as necessarily being directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Further, one skilled in the art can engage and combine the different embodiments or examples described in this specification.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. The high temperature resistant glaze is characterized by comprising the following components in parts by weight:
65-85 parts of petalite, 4.2-6.8 parts of quartz powder, 3-6 parts of barium carbonate, 2.5-4 parts of calcite, 3.2-4.8 parts of bone powder, 4-6 parts of glass powder, 1.6-3.2 parts of talcum powder, 2.2-4.4 parts of kaolin and 2.5-5.5 parts of Re@Al-Zn powder.
2. The high temperature resistant glaze according to claim 1, wherein the preparation method of the re@al-Zn powder comprises:
s1, weighing aluminum zinc alloy powder, performing ultrasonic treatment in absolute ethyl alcohol for 30min, and drying in an oven for later use;
s2, weighing iminodiacetic acid, oxalic acid and methionine, sequentially mixing into deionized water, continuously stirring at 45-55 ℃ until all iminodiacetic acid, oxalic acid and methionine are uniformly dissolved, then adding a wetting agent, and continuously stirring uniformly to obtain a solution A;
s3, weighing rhenium trichloride into the hydrochloric acid solution, and fully stirring the rhenium trichloride to be uniform at room temperature to obtain a rhenium trichloride solution; gradually dropwise adding the rhenium trichloride solution into the solution A, stirring while dropwise adding, and continuously stirring and dispersing for 15-20min after all dropwise adding to form a solution B;
s4, weighing titanium trichloride, and dissolving the titanium trichloride into deionized water to form a titanium trichloride solution; adding a titanium trichloride solution into the solution B, then adding a sodium carbonate solution into the solution B, regulating the pH of the solution to 9.5-10.0, and fully and uniformly stirring to form a solution C;
s5, adding aluminum zinc alloy powder into the solution C, stirring uniformly at room temperature, heating to 75-95 ℃, continuously stirring to keep the powder in the solution from agglomerating, keeping the temperature and stirring for 3-5h, filtering out the powder after the reaction is finished, filtering and flushing three times by using deionized water under reduced pressure, and drying in an oven to obtain Re@Al-Zn powder.
3. The high temperature resistant glaze according to claim 2, wherein in S1, the purity of the aluminum zinc alloy powder is > 99%, wherein the mass ratio of aluminum to zinc is: al: zn=2:1, mass-to-volume ratio of aluminum zinc alloy powder to absolute ethanol is 1g: (5-10) mL.
4. The high temperature resistant glaze according to claim 2, wherein in S2, the wetting agent is at least one of polyethylene glycol PEG-1000, polyethylene glycol PEG-1200, polyethylene glycol PEG-1500, polyethylene glycol PEG-2000.
5. The high temperature resistant glaze according to claim 2, wherein in S2, the mass to volume ratio of iminodiacetic acid, oxalic acid, methionine and deionized water is (0.13-0.21) g: (0.09-0.14) g: (0.15-0.22) g:10mL.
6. The high temperature resistant glaze according to claim 2, wherein in S3, the concentration of the hydrochloric acid solution is 1.0-2.0mol/L, and the mass-volume ratio of the rhenium trichloride and the hydrochloric acid solution is 0.16g: (3-7) mL; the volume ratio of the rhenium trichloride solution to the solution A is 1:5-6.
7. The high temperature resistant glaze according to claim 2, wherein in the titanium trichloride solution of S4, the mass to volume ratio of titanium trichloride to deionized water is 0.15g: (5-15) mL.
8. The high temperature resistant glaze according to claim 2, wherein in S4, the volume ratio of the titanium trichloride solution to the solution B is 1:3-5.
9. The high temperature resistant glaze according to claim 2, wherein in S5, the mass-to-volume ratio of the aluminum zinc alloy powder to the solution C is 1g: (10-20) mL.
10. The high temperature resistant glaze according to claim 1, wherein the preparation method of the high temperature resistant glaze comprises the following steps:
(1) Weighing the raw material components according to the weight parts, ball-milling and mixing in a ball mill, wherein the ball-milling medium is water, a small amount of sodium carboxymethylcellulose is added as a lubricant, after ball-milling is completed, washing with water and drying, and sieving with a 200-mesh sieve, wherein the screen residue is less than 0.5%; wherein, the total weight of each raw material: grinding ball: water: the mass ratio of the sodium carboxymethyl cellulose is 1:3-5:1.2-1.5:0.001-0.002;
(2) Spraying the ground raw material mixture on the surface of ceramic by a glaze spraying method, wherein the thickness of the formed glaze is 1-10mm, and thus the preparation of the glaze is completed.
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| US20210221749A1 (en) * | 2019-12-24 | 2021-07-22 | Rolls-Royce Corporation | Silica-rich barrier coatings |
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|---|---|---|---|---|
| WO2011108472A1 (en) * | 2010-03-01 | 2011-09-09 | 株式会社 オハラ | Glass for glaze, glaze, and photocatalyst member |
| CN105906381A (en) * | 2016-03-28 | 2016-08-31 | 河南科技学院 | Making method for purple bronze ceramic artwork |
| CN108892475A (en) * | 2018-08-01 | 2018-11-27 | 江西帮企陶瓷有限公司 | A kind of preparation method of black glaze thermal-resisting ceramic vessel |
| CN109650724A (en) * | 2019-01-23 | 2019-04-19 | 江西省千陶新型材料有限公司 | A kind of Lead-free transparent frit preparing ceramics |
| US20210221749A1 (en) * | 2019-12-24 | 2021-07-22 | Rolls-Royce Corporation | Silica-rich barrier coatings |
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