CN116143507B - Zirconium-free super-white light-transmitting green body material and application thereof - Google Patents
Zirconium-free super-white light-transmitting green body material and application thereof Download PDFInfo
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- CN116143507B CN116143507B CN202310144516.2A CN202310144516A CN116143507B CN 116143507 B CN116143507 B CN 116143507B CN 202310144516 A CN202310144516 A CN 202310144516A CN 116143507 B CN116143507 B CN 116143507B
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- zirconium
- transmitting
- white light
- free
- green body
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- 239000000463 material Substances 0.000 title abstract description 55
- 239000002994 raw material Substances 0.000 claims abstract description 34
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 21
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 21
- 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 21
- 229910052656 albite Inorganic materials 0.000 claims abstract description 18
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 15
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 15
- 235000011010 calcium phosphates Nutrition 0.000 claims abstract description 15
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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 abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 14
- 239000010456 wollastonite Substances 0.000 claims abstract description 12
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 12
- 239000011787 zinc oxide Substances 0.000 claims abstract description 11
- 239000010433 feldspar Substances 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 48
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 229910052742 iron Inorganic materials 0.000 claims description 24
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 12
- 239000011591 potassium Substances 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 10
- 239000004575 stone Substances 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 239000011435 rock Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- 238000009718 spray deposition Methods 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 abstract description 31
- 238000002834 transmittance Methods 0.000 abstract description 17
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 abstract description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 abstract description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract description 4
- 239000007844 bleaching agent Substances 0.000 abstract description 2
- 239000011449 brick Substances 0.000 description 25
- 239000010410 layer Substances 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 13
- 238000010304 firing Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 230000002087 whitening effect Effects 0.000 description 5
- 239000003086 colorant Substances 0.000 description 4
- 239000010977 jade Substances 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 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 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000124033 Salix Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000010427 ball clay Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IDONSVYZWGSKOA-UHFFFAOYSA-L calcium zinc hydrogen phosphate oxygen(2-) Chemical compound P(=O)(O)([O-])[O-].[Ca+2].[O-2].[Zn+2] IDONSVYZWGSKOA-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940024464 emollients and protectives zinc product Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 235000012041 food component Nutrition 0.000 description 1
- 239000005417 food ingredient Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005392 opalescent glass Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009700 powder processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
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- 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
- C04B35/16—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 silicates other than clay
- C04B35/18—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 silicates other than clay rich in aluminium oxide
- C04B35/19—Alkali metal aluminosilicates, e.g. spodumene
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- 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
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- C04B2235/3436—Alkaline earth metal silicates, e.g. barium silicate
- C04B2235/3454—Calcium silicates, e.g. wollastonite
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- 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
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- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
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Abstract
The invention discloses a zirconium-free super-white light-transmitting green body material, which takes kaolin, potassium feldspar, albite, lithium feldspar, wollastonite, calcium phosphate and zinc oxide as raw materials, wherein the whiteness of a zirconium-free super-white light-transmitting ceramic tile prepared from the zirconium-free super-white light-transmitting green body material can reach 73-81 ℃, the light transmittance is about 6.5% under the condition of 65mm thickness, and the light transmittance is more than 1.5% under the condition of 8mm thickness, and the precedent that the super-white ceramic tile can be obtained without adding zirconium silicate, zirconium oxide and other zirconium-containing whitening agents is created.
Description
Technical Field
The invention belongs to the technical field of ceramic production, and particularly relates to a zirconium-free super-white light-transmitting blank material, and also relates to application of the zirconium-free super-white light-transmitting blank material, which can be used for manufacturing ceramic tiles and rock plates and can also be used for producing regenerated stone.
Background
The ceramic tile is a plate-shaped or block-shaped ceramic product produced by clay and other inorganic nonmetallic raw materials through processes such as molding, sintering and the like, and is widely applied to decoration of families, offices and business places due to the characteristics of wear resistance, water resistance, attractive and various surface patterns and the like. Today, the ceramic industry is continuously developed and is greatly improved along with the development of social economy and the improvement of the living standard of people, people put higher requirements on the material of ceramic bricks, the layering of patterns or the colors, wherein a novel green body material with certain light transmittance (namely commonly called as a 'light-transmitting brick') can generate a full body and a changing effect under the action of lamplight, so that the novel green body material becomes a new pet in the market.
CN208122161U discloses a transparent marble tile, which comprises a green body layer and a glaze layer covering the surface of the green body layer, wherein the green body layer consists of a transparent area, a semi-transparent area and an opaque area.
CN109369165a discloses a light-transmitting jade brick, which comprises a primer layer, a fabric layer compounded on the primer layer and a protective layer compounded on the fabric layer; the base material layer is made of light-transmitting base materials with different colors and light transmittance, the surface material layer is a light-transmitting pattern layer, and the light-transmitting pattern layer is made of light-transmitting base materials with different colors and light transmittance and milk candles; the protective layer is made of a light-transmitting protective frit. According to the invention, the three-layer structure of the light-transmitting jade brick is transparent by improving the formula of the primer layer, the formula of the fabric layer and the formula of the protective layer, so that the light-transmitting jade brick has a light-transmitting function; the light-transmitting bottom material with light-transmitting property is adopted as a matrix in the surface material layer, and zirconium silicate and aluminum oxide are added to increase the texture contrast of the patterns, so that the texture of the brick body is improved; finally, the protective layer plays a role in protection and decoration. However, the light-transmitting primer of the light-transmitting jade brick is prepared from 80-90% of light-transmitting frit, 8-20% of clay, 0.1-3% of binder and 0-4% of colorant, and the light-transmitting primer contains a large amount of light-transmitting frit, so that the cost is high, zirconium silicate is added, the risk of exceeding the standard of radiation is generated, the light-transmitting primer is possibly harmful to human bodies, along with the tightening of environmental protection policies, the energy consumption of a frit kiln is high, the treatment requirements of generated flue gas and waste water are high, and the light-transmitting frit cannot be produced in many areas, so that the technology is widely popularized in a large range.
In summary, how to obtain a novel transparent green body material with low cost and simplicity and easiness on the basis of meeting the environmental protection becomes a research and development hot spot for researchers in the ceramic industry.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a zirconium-free super-white light-transmitting green body material, which takes kaolin, potassium feldspar, albite, lithium feldspar, wollastonite, calcium phosphate and zinc oxide as raw materials, and the raw materials are subjected to ball milling, spray drying, forming and sintering to obtain the super-white light-transmitting green body, wherein the whiteness of the obtained super-white light-transmitting green body can reach 73-81 ℃, the light transmittance is 6.5% under the condition of 6mm in thickness and 1.5% under the condition of 8mm in thickness, and the precedent that the super-white ceramic tile can be obtained without adding zirconium silicate, zirconium oxide and other zirconium-containing whitening agents is created.
According to a first aspect of the invention, the invention provides a zirconium-free super white light-transmitting green body material, which is prepared from the following raw materials in percentage by weight:
wherein the weight percentages of the components are based on the total weight of the raw materials.
At present, the whiteness of the ceramic tile in the ceramic industry is generally controlled between 45-50 ℃, the whiteness can reach 65 degrees, namely 'fish maw white', 'snow white' which is promoted by very individual ceramic manufacturers, and the ceramic tile with the whiteness of more than 70 degrees basically adopts zirconium-containing compounds such as zirconium silicate, zirconium oxide and the like as a whitening agent and simultaneously adds clinker to reach the light transmittance performance, but the zirconium compounds have the risk of exceeding the standard of radiation. However, the invention obtains a zirconium-free super-white light-transmitting green body material by carrying out a great deal of research on the existing light-transmitting bricks and combining the process experience of the prior light-transmitting bricks, and selecting the components through creative labor and controlling the components within a reasonable range.
Preferably, in the zirconium-free super white light-transmitting green body material, the weight percentage of the kaolin is 12-15%, and the particle size is below 100 meshes. The kaolin can form a large amount of mullite crystal phase in the firing process, so that the bending strength and toughness of the ceramic tile are improved, the maturation temperature is too high when the kaolin content is too high, and the expansion coefficient is smaller. The kaolin contains a certain amount of free quartz, so that the fineness of the kaolin is controlled below 100 meshes, and the kaolin can remove the harmful free quartz in a granular state after passing through a 100-mesh screen, thereby being beneficial to the toughness and strength of ceramic tiles.
Preferably, in the zirconium-free super white light-transmitting blank material, the sintering whiteness of the kaolin is more than or equal to 70 degrees, the weight percentage of iron, namely the iron content is less than 0.5 weight percent, the iron content is important, and when the iron content is too high, such as the iron content is more than 0.5 percent, the obtained blank cannot be super white, and even the common whiteness of 60 degrees cannot be realized.
Preferably, in the zirconium-free super white light-transmitting blank material, the weight percentage of aluminum in the kaolin, namely the aluminum content, is more than or equal to 38%. The aluminum content in the kaolin is a major source of aluminum oxide in the entire light transmitting tile and if the aluminum content is insufficient, it is detrimental to the formation of mullite crystal phases.
It should be noted that the kaolin may be either virgin kaolin or calcined kaolin, as long as the above requirements are satisfied.
Preferably, in the zirconium-free super white light transmitting green body material, the potassium feldspar or the albite is used in a conventional amount in the field, but the weight percentage of potassium in the potassium feldspar or the albite, namely the potassium content, is more than or equal to 3.0%, the weight percentage of sodium, namely the sodium content, is more than or equal to 3.0%, and the weight percentage of iron, namely the iron content, is less than or equal to 0.2%. Because the iron content is required to be strictly controlled to be less than or equal to 0.2 percent due to the requirement on whiteness, otherwise, the whiteness is directly influenced, the potassium content and the sodium content can reduce the sintering temperature, and the potassium content can widen the sintering range, so that the content is required to be controlled.
Particularly preferably, in the zirconium-free super white light transmitting green body material, the potassium feldspar is water-washed potassium feldspar and/or potassium albite, and the albite is water-washed albite and/or potassium albite.
Preferably, in the zirconium-free super white light-transmitting green body material, the weight percentage of lithium in the lithium feldspar, namely the lithium content, is more than or equal to 1.0 percent, and the weight percentage of iron, namely the iron content, is less than or equal to 0.5 percent. The lithium feldspar is a fluxing raw material, and has the advantages of low-temperature fluxing and wide firing range, and is favorable for stabilizing the ceramic bricks in a low-temperature quick firing state.
Preferably, in the zirconium-free super white light-transmitting green body material, the wollastonite is needle-shaped wollastonite. The wollastonite belongs to a triclinic system of single-chain silicate minerals, is usually in a flake, radial or fibrous aggregate, and is white and slightly gray.
Preferably, in the zirconium-free super-white light-transmitting green body material, the calcium phosphate is calcium phosphate with the whiteness of more than or equal to 85 degrees after being burned at 1160 ℃, the calcium phosphate is white crystal or amorphous powder, and is commonly used for manufacturing opalescent glass, and generally, the conventional ceramic products do not use the calcium phosphate, so that the whitening effect is achieved by utilizing the mordant dyeing performance of the zirconium-free super-white light-transmitting green body material, and the whitening effect of the calcium phosphate with the whiteness of more than or equal to 85 degrees after being burned is the best.
Preferably, in the zirconium-free super white light-transmitting green body material, the weight percentage of the calcium phosphate based on the total weight of the raw materials is 10-15%. If the weight percentage of calcium phosphate is less than 10%, the whitening effect is poor, and if it is more than 15%, pinholes may occur in the obtained green body.
Preferably, in the zirconium-free super white light-transmitting green body, the weight percentage of the zinc oxide based on the total weight of the raw materials is 0.3-1.2%. The zinc oxide has the characteristics of high energy band gap and exciton binding energy, high transparency and excellent normal-temperature luminous performance, so that the ceramic tile is easy to transmit light. In addition, since the rest raw materials are inevitably mixed with trace sulfate, sulfur dioxide is easy to generate, zinc sulfide is generated by the reaction of the sulfate and zinc oxide, the zinc sulfide is white, and the whiteness of the obtained product is further improved, so that if the weight percentage of the zinc oxide is lower than 0.3%, the light transmittance is poor, and if the weight percentage of the zinc oxide is higher than 1.2%, the cost is obviously increased.
Preferably, in the zirconium-free super white light-transmitting green body material, the weight percentage of iron in the raw material, namely the iron content is less than 0.5%, the iron content in the raw material is critical, and if the iron content exceeds the standard, particularly more than 1.0%, the obtained product cannot be super white, and even the whiteness of 60 degrees is difficult to realize. Also for example if the iron content is > 3.0%, the color of the product obtained is blackish.
In addition, the invention also provides application of the zirconium-free super-white light-transmitting blank material, wherein the zirconium-free super-white light-transmitting blank material is used as a blank material for manufacturing ceramic tiles and rock plates, or is applied to production of regenerated stone.
It should be noted that the preparation process of the regenerated stone material is not different from the existing preparation process in the ceramic tile and the rock plate involved in the application process of the zirconium-free super white light-transmitting blank material. However, the transparent green body material obtained by the method has super white requirement, so that strict requirements on site management are required, and the cleanness and sanitation are ensured so as to avoid the introduction of a large amount of impurities.
Compared with the prior art, the invention has the following advantages.
(1) The zirconium-free super-white light-transmitting green body material can exist in a composite form or in a form of independently packaging and storing all components, and the existing production equipment is not required to be modified in a large scale during preparation, and only the cleanliness of a production line is required to reach an industrial 'clean production' evaluation index, so that the pollution caused by external environment is reduced as much as possible.
(2) The zirconium-free super-white light-transmitting green body material has rich raw material sources and low cost, provides an economic basis for large-scale application, has the whiteness reaching 73-81 degrees, has the light transmittance of 6.5% under the condition of 5mm thickness and the light transmittance of 1.5% under the condition of 8mm thickness, creates a precedent of no zirconium-containing whitening agent such as zirconium silicate, zirconium oxide and the like, and fully meets the diversified requirements of ceramic tiles.
(3) The zirconium-free super white light-transmitting green body material is inexhaustible in raw materials or replaced, and the raw materials are jointly acted to obtain the zirconium-free super white light-transmitting brick without changing the existing production line.
Detailed Description
The following describes the invention in more detail.
The invention takes the production of the zirconium-free super white light-transmitting brick as an example to explain the application of the zirconium-free super white light-transmitting blank material, the preparation process flow of the zirconium-free super white light-transmitting brick is the same as that of other ceramic production, and the process is not different, but the zirconium-free super white light-transmitting blank material, namely the raw material formula, is adopted. However, because the zirconium-free super white light-transmitting brick has super white requirements, the requirements on field management are relatively strict, and the requirements are specifically as follows.
(1) The cleanliness of the production line is required to reach the evaluation index of industrial clean production, and the pollution caused by the external environment is reduced as much as possible.
(2) Before each production, the slurry pipeline needs to be cleaned and washed once, so that the pollution caused by the rust of the equipment is reduced as much as possible.
(3) The equipment involved in the manufacturing process is selected as much as possible from materials that do not rust or are difficult to rust. For example, the slurry conveying pipeline adopts a stainless steel pipeline, the ball mill lining adopts a high-alumina lining, the ball stone adopts a high-alumina ball stone, the underground slurry tank lining adopts vitrified ceramic tiles, the ground slurry tank adopts a stainless steel or glass fiber reinforced plastic lining, the spray drying tower adopts a stainless steel lining, the powder bin adopts a stainless steel material and the like.
(4) Under the condition of ensuring normal slurry and powder in the production process, the cleanness and sanitation of a powder conveying system and a forming system are ensured, a conveying belt is cleaned, and the scraping materials of the belt are polluted and cannot be recovered; the material distribution system needs to be cleaned comprehensively, and each batch of raw materials need to be cleaned, especially when the whole pigment is added to align and distribute materials, the material distribution system and the mould need to be cleaned comprehensively so as to avoid color confusion, and the powder falling onto the ground cannot be directly recycled after being polluted.
It is apparent that the zirconium-free ultra-white light transmitting brick strictly limits the sanitary condition and the waste recycling condition of the production line only due to the requirement of "ultra-white", and does not relate to the improvement of the whole production line or the improvement of the existing ceramic tile production method, and therefore, the manufacturing method of the zirconium-free ultra-white light transmitting brick is not different from the manufacturing method of the existing ceramic tile.
In the following examples, all the raw materials used were commercial products, and the following are specific.
The kaolin is purchased from Hebei Shijia Zhengyu new material limited company, the grain diameter is 100 meshes, the firing whiteness is 71.5 degrees, the iron content is 0.46 percent, and the aluminum content is 42.33 percent.
The potassium feldspar is purchased from a water washing potassium feldspar of a mineral powder processing plant of the Lingshu county Feng Xin, the potassium content is 10.64%, the sodium content is 2.87%, and the iron content is 0.16%.
The albite is purchased from water-washed albite in a mineral processing plant of the earth-transported mineral products in the Ming county of the Shangshou, the potassium content is 0.98%, the sodium content is 4.69%, and the iron content is 0.11%.
The lithium feldspar was purchased from Rong Heng mining Co.Ltd in Yichun, and had a lithium content of 1.5% and an iron content of 0.09%.
The wollastonite is purchased from Jiangxi Guangdong chemical industry Limited liability company and is of needle-shaped structure.
The calcium phosphate was purchased from the company, limited to food ingredients in the hongkongensis, and burned at 1160 c to a whiteness of 85.3 °.
The zinc oxide was purchased from willow zinc products limited liability company.
Preparation example
Preparation examples 1 to 9
The zirconium-free superwhite light-transmitting bricks in preparation examples 1 to 9 were identical in production method, except that the amounts of the respective components in the raw materials were different, and specifically, the prepared zirconium-free superwhite light-transmitting bricks were designated as P1, P2, P3, P4, P5, P6, P7, P8, and P9, respectively, as shown in the following table. The preparation process is as follows.
(1) And (3) blank material preparation: weighing all the raw materials of the zirconium-free super white light-transmitting brick according to the invention as shown in the following table 1;
(2) Blank processing: mixing the raw materials weighed in the step (1) uniformly, and then placing the raw materials in a ball mill for ball milling until the processing fineness of the slurry is 0.8% of the 250-mesh screen residue and the specific gravity is 1.670g/ml, wherein the lining of the ball mill adopts a high-alumina lining, and the ball stone adopts a high-alumina ball stone;
(3) Spray pulverizing: atomizing the material obtained in the step (2) by a high-pressure plunger pump, and then dehydrating and drying in a spray tower at 120 ℃ to obtain powder with the water content of 7%;
(4) And (5) press forming: conveying the powder obtained in the step (3) to a 33000 ton roll forming press for press forming, wherein the press pressure is 370bar, and obtaining a green body, and the thickness of the green body is 8mm;
(5) Firing: and (3) placing the green body obtained in the step (4) into a sintering kiln, and sintering for 70 minutes at the sintering temperature of 1200 ℃ to obtain the zirconium-free super white light-transmitting brick.
TABLE 1 amounts of the respective raw materials (in kg) in preparation examples 1 to 9
Comparative examples
Comparative examples 1 to 9
The ceramic tiles of comparative examples 1 to 9 were produced in the same manner as in the production examples except that the amounts of the respective components in the raw materials were different, and specifically, the ceramic tiles produced were designated as C1, C2, C3, C4, C5, C6, C7, C8, C9, respectively, as shown in the following tables. The preparation process is as follows.
(1) And (3) blank material preparation: weighing the raw materials according to the following table 1;
(2) Blank processing: mixing the raw materials weighed in the step (1) uniformly, and then placing the raw materials in a ball mill for ball milling until the processing fineness of the slurry is 0.8% of the 250-mesh screen residue and the specific gravity is 1.667g/ml, wherein the lining of the ball mill adopts a high-alumina lining, and the ball stone adopts a high-alumina ball stone;
(3) Spray pulverizing: atomizing the material obtained in the step (2) by a high-pressure plunger pump, and then dehydrating and drying in a spray tower at 120 ℃ to obtain powder with the water content of 7%;
(4) And (5) press forming: conveying the powder obtained in the step (3) to a 33000 ton roll forming press for press forming, wherein the press pressure is 370bar, and the green body is obtained, and the thickness of the green body is 8mm;
(5) Firing: and (3) placing the green body obtained in the step (4) into a firing kiln, and firing for 70 minutes at the firing temperature of 1200 ℃ to obtain the ceramic tile.
TABLE 2 amounts of the respective raw materials (in kg) in comparative examples 1 to 9
| Kaolin clay | Potassium feldspar | Albite feldspar | Lithium feldspar | Ball clay | Wollastonite | Calcium phosphate | Zinc oxide | |
| C1 | 10 | 30 | 10 | 30 | 15 | 3 | 0 | 2 |
| C2 | 10 | 20 | 33 | 10 | 25 | 0 | 1 | 1 |
| C3 | 5 | 25 | 15 | 30 | 20 | 2 | 1 | 2 |
| C4 | 20 | 10 | 20 | 20 | 27 | 1 | 1 | 1 |
| C5 | 20 | 25 | 32 | 10 | 10 | 0 | 0 | 3 |
| C6 | 20 | 15 | 10 | 32 | 20 | 0 | 0 | 3 |
| C7 | 25 | 15 | 25 | 20 | 10 | 0 | 0 | 5 |
| C8 | 10 | 30 | 15 | 10 | 20 | 10 | 5 | 0 |
| C9 | 25 | 10 | 25 | 30 | 5 | 1 | 4 | 0 |
Test examples
The zirconium-free superwhite light-transmitting bricks prepared in preparation examples 1 to 9 and the ceramic bricks prepared in comparative examples 1 to 9 were subjected to whiteness detection using SBDY-1 whiteness meter of Shanghai yuefeng instruments and meters, inc., and the results of the whiteness detection are shown in table 3 below. The light transmittance is detected by using a light transmittance tester of a LH-230 densimeter of Shenzhen Chengcheng technology Co.
TABLE 3 Performance test results (thickness of 8mm each)
| Project | Whiteness degree | Transmittance of light | Project | Whiteness degree | Transmittance of light |
| P1 | 73.1 | 1.514％ | C1 | 56.3 | 0.000％ |
| P2 | 77.5 | 1.541％ | C2 | 51.8 | 0.000％ |
| P3 | 76.0 | 1.603％ | C3 | 59.6 | 0.000％ |
| P4 | 75.3 | 1.527％ | C4 | 54.2 | 0.000％ |
| P5 | 80.1 | 1.623％ | C5 | 51.4 | 0.000％ |
| P6 | 73.2 | 1.516％ | C6 | 52.5 | 0.000％ |
| P7 | 76.5 | 1.635％ | C7 | 51.9 | 0.000％ |
| P8 | 72.9 | 1.439％ | C8 | 50.3 | 0.000％ |
| P9 | 77.2 | 1.539％ | C9 | 52.5 | 0.000％ |
Therefore, the whiteness and the transmittance of the zirconium-free super-white light-transmitting brick prepared from the zirconium-free super-white light-transmitting material meet the current aesthetic requirements and personalized requirements, when the thickness of the brick body reaches 8mm, the transmittance is about 1.5%, and in the practical application process, the thickness of the brick body can be adjusted according to the requirements of a user, so that the corresponding transmittance is obtained. It is emphasized that the zirconium-free super-white light-transmitting green body material provided by the invention is subjected to a large number of experiments, and each raw material is screened and tested, so that the material capable of realizing super-white and light transmission is finally obtained. In addition, wollastonite is rarely used in the common ceramic formula, calcium phosphate is not used, zinc oxide is not used, the whiteness cannot reach 70 ℃, and light transmission is not caused.
Variations and modifications to the above would be obvious to persons skilled in the art to which the invention pertains from the foregoing description and teachings. Therefore, the invention is not limited to the specific embodiments disclosed and described above, but some modifications and changes of the invention should be also included in the scope of the claims of the invention. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.
Claims (6)
1. The zirconium-free super-white light-transmitting green body is characterized by being prepared from the following raw materials in percentage by weight:
10-15% of kaolin;
10-25% of potassium feldspar;
10-30% of albite;
10-30% of lithium feldspar;
10-20% of wollastonite;
10-15% of calcium phosphate;
zinc oxide 0.1-1.5%, and trace amount of sulfate is mixed in the rest raw materials;
wherein the weight percentages of the raw materials are based on the total weight of the raw materials of the zirconium-free super white light-transmitting green body, the grain diameter of the kaolin is less than 100 meshes, the sintering whiteness is more than or equal to 70 ℃, and the weight percentage of iron, namely the iron content, is less than 0.5 wt%; the weight percentage of potassium in the potassium feldspar or the albite, namely the potassium content is more than or equal to 3.0 percent, the weight percentage of sodium is more than or equal to 3.0 percent, and the weight percentage of iron is less than or equal to 0.2 percent; the weight percentage of lithium in the lithium feldspar, namely the lithium content, is more than or equal to 1.0 percent, and the weight percentage of iron, namely the iron content, is less than or equal to 0.5 percent; the calcium phosphate is calcium phosphate with whiteness not less than 85 degrees after being burned at 1160 ℃,
the zirconium-free super-white light-transmitting green body is prepared from kaolin, potassium feldspar, albite, lithium feldspar, wollastonite, calcium phosphate and zinc oxide serving as raw materials through ball milling, spray drying, forming and sintering.
2. The zirconium-free super white light transmitting blank according to claim 1, wherein the kaolin clay is 12-15% by weight.
3. The zirconium-free super white light-transmitting blank according to claim 1, wherein the weight percentage of aluminum in the kaolin, namely the aluminum content, is more than or equal to 38 percent.
4. The zirconium-free super white light transmitting green body according to claim 1, wherein the potassium feldspar is water-washed potassium feldspar and/or potassium albite, and the albite is water-washed albite and/or potassium albite.
5. The zirconium-free ultra-white light-transmitting blank according to claim 1, wherein the wollastonite is needle-like structured wollastonite.
6. Use of the zirconium-free superwhite light-transmitting blank according to any of claims 1-5, characterized in that the zirconium-free superwhite light-transmitting blank is used as a blank for the manufacture of tiles and rock boards or the zirconium-free superwhite light-transmitting blank is used for the production of reclaimed stone.
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