WO2018000562A1 - Agent opacifiant composé à base de silicate de zirconium, procédé pour sa préparation et application correspondante - Google Patents

Agent opacifiant composé à base de silicate de zirconium, procédé pour sa préparation et application correspondante Download PDF

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Publication number
WO2018000562A1
WO2018000562A1 PCT/CN2016/097194 CN2016097194W WO2018000562A1 WO 2018000562 A1 WO2018000562 A1 WO 2018000562A1 CN 2016097194 W CN2016097194 W CN 2016097194W WO 2018000562 A1 WO2018000562 A1 WO 2018000562A1
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WO
WIPO (PCT)
Prior art keywords
powder
zirconium silicate
slurry
mass
prepared
Prior art date
Application number
PCT/CN2016/097194
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English (en)
Chinese (zh)
Inventor
黎俊豪
陈秀林
易立群
邓广兴
肖飞
Original Assignee
美轲（广州）化学股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 美轲（广州）化学股份有限公司 filed Critical 美轲（广州）化学股份有限公司
Publication of WO2018000562A1 publication Critical patent/WO2018000562A1/fr

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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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
    • 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
    • C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
    • 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

Definitions

  • the invention relates to the field of opacifiers, in particular to a composite zirconium silicate emulsion and a preparation method and application thereof.
  • ceramic raw material glaze or sanitary raw material glaze is added with a large amount of zirconium silicate for pursuing whiteness, which not only makes the production cost of ceramic raw material glaze or sanitary glaze high, but also has high viscosity at high temperature, resulting in poor glaze spreading performance.
  • the problem of product defects, at the same time, is likely to cause high radioactivity of the ceramic product, and the secondary precipitation of zirconium silicate particles is small, so that the opacification of the residual particles cannot be fully exerted.
  • the low-temperature frit is prepared by mass of materials including the following components: potassium feldspar powder 25% to 35%, apatite powder 10% to 20%, fluorite powder 2% to 8%, calcium carbonate 10% to 15%, borax 15% to 18%, zinc oxide 1% to 8%, and quartz powder 2% to 8%.
  • the mass percentage is prepared from materials comprising the following components:
  • the low temperature frit is prepared by mass of materials including the following components: potassium long Stone powder 30% to 35%, apatite powder 15% to 20%, fluorite powder 5% to 8%, calcium carbonate 11% to 14%, borax 15% to 18%, zinc oxide 2% to 6%, quartz powder 6% to 8%.
  • the mass percentage is prepared from materials comprising the following components:
  • the low-temperature frit is prepared by mass of materials including the following components: potassium feldspar powder 34-35%, apatite powder 17-19%, fluorite powder 6-7%, calcium carbonate 12-13 %, borax 15 to 17%, zinc oxide 3 to 5%, quartz powder 7 to 8%.
  • the feldspar, apatite, fluorite, and quartz are all raw materials for ceramic glaze.
  • the invention also discloses a preparation method of the above composite zirconium silicate emulsion, comprising the following steps:
  • the material for preparing the composite zirconium silicate emulsion is compounded according to the above ratio, and is put into a mixer for mixing treatment, and after being uniformly stirred, it is added to a ball mill, and the material is ground to a particle diameter by adding water. Particles less than 5um, obtained slurry 1;
  • the amount of water added in the step (2) is 49 to 51% of the total weight of the material.
  • the dewatering thickening in the step (3) is to dehydrate the slurry 3 to a specific gravity of 2 to 2.4 g/cm 3 .
  • the neutralization in the step (3) is a slurry 3 thickened by dehydration. Neutralize to a pH of 6.5 to 7.5.
  • the drying in step (3) is to dry the neutralized slurry 3 to a moisture content of less than 0.5%.
  • the pickling bleaching time in step (3) is from 2 to 5 hours.
  • the invention also discloses the application of the above composite zirconium silicate emulsion in the preparation of glazes for ceramic tiles, sanitary ceramics and daily-use ceramics.
  • the composite silicic acid high opacifier of the invention can be directly applied to the glaze of ceramic tiles, sanitary ware ceramics and daily-use ceramics, and mainly plays an opaque whitening effect in the glaze.
  • the composite silicic acid high opacifier preferably comprises low-temperature frit in the raw material, including apatite powder, fluorite powder and borax, which can reduce the viscosity in the glaze when the glaze is fired, so that the glaze has good spreading performance, and The solubility of zirconium silicate in the glaze is increased, the amount of residual zirconium silicate particles is reduced, and the chance of secondary precipitation of zirconium silicate is increased.
  • the glaze In the process of glaze cooling, since the glaze contains a variety of network forming bodies, the glaze appears to be phase-separated, resulting in a different glass matrix, and the emulsion effect is enhanced due to the difference in refractive index.
  • a small amount of zinc oxide acts as a fluxing aid and also promotes crystallization.
  • the glazing L value of the composite zirconium silicate emulsion of the invention is substantially above 91, and the emulsion effect is ideal.
  • the composite zirconium silicate emulsion of the present invention reduces about 30% of zircon sand, reduces production costs, and allows the radioactivity of the product to be effectively controlled.
  • the glazed gloss of the product is high, the flatness is good, and the whiteness also meets the requirements for use.
  • Zircon sand trade name: IUKKA MB, purchased from Australia;
  • Calcined alumina trade name: Calcined Alumina, purchased from alteo;
  • Potash feldspar powder trade name: potassium feldspar (special grade), purchased from Foshan Hanyuan Trading Co., Ltd.;
  • Apatite powder trade name: apatite powder, purchased from Foshan Senjun New Ceramic Materials Co., Ltd.;
  • Fluorite powder trade name: flotation fluorite powder, purchased from Guangchang County Dean Industrial Co., Ltd.;
  • Quartz powder trade name: quartz powder, purchased from Guangzhou Hongtu Mining Technology Co., Ltd.;
  • Dispersant trade name: sodium polyacrylate, purchased from Changshu Gaotai Auxiliary Co., Ltd.;
  • Centrifugal vortex classifier model centrifugal 18*28L, purchased from Bird Company, USA;
  • the low temperature frit in the following examples is obtained by mixing 1400 kg of potassium feldspar powder, 720 kg of apatite powder, 260 kg of fluorite powder, 500 kg of calcium carbonate, 640 kg of borax, 160 kg of zinc oxide and 320 kg of quartz powder. At 1500 ° C, the temperature is kept for 1 h, and the transparent frit is obtained by quenching with water, and dried, and then the low-temperature frit is weighed according to the amount of the low-temperature frit required in the specific embodiment.
  • Dehydration thickening dehydration thickening to the normal temperature specific gravity of the slurry 3 is 2.2g/cm 3 ;
  • the product obtained in the step (6) is pulverized to a sieve of 325 mesh, the amount of the residue on the sieve is less than 1 wt% of the total amount of the product;
  • Dehydration thickening dehydration thickening to the normal temperature specific gravity of the slurry 3 is 2.2g/cm 3 ;
  • the product obtained in the step (6) is pulverized to a sieve of 325 mesh, the amount of the residue on the sieve is less than 1 wt% of the total amount of the product;
  • Dehydration thickening dehydration thickening to the normal temperature specific gravity of the slurry 3 is 2.2g/cm 3 ;
  • the product obtained in the step (6) is pulverized to a sieve of 325 mesh, the amount of the residue on the sieve is less than 1 wt% of the total amount of the product;
  • the composite silicate silicate opacifiers obtained in the above Examples 1 to 3 were designated as ##, 2# and 3#, respectively.
  • the composite silicate zirconium opacifiers of 1#, 2# and 3# and the commercially available pure zirconium silicate emulsion (denoted as P#) were subjected to a glaze test.
  • Test procedure Weigh 126.4 grams of base material (Dahong glaze KS-9613), add 14.6 grams of composite zirconium silicate emulsion, add 73 grams of water, and add 0.1% of the additive mass of the base material. Cellulose, ball milled for 25 minutes, glaze test, glaze, put into a muffle furnace for drying, and fired at 1250 ° C, test the brightness of the glaze (L value), the red-green difference of the glaze (a value ) and the yellow-blue difference (b value) of the glaze, the results are shown in Table 1.
  • the L value in the table is the glaze brightness, the a value indicates the red-green difference of the glaze, the range is -120-120, the negative value is greenish, the positive value is reddish, and the b value indicates the yellow-blue difference of the glaze, the range - 120 ⁇ 120, the negative value is bluish, and the positive value is yellowish; from Table 1, it can be seen that the whiteness L value of the composite zirconium silicate emulsion of the invention is substantially above 91, the a and b values are relatively small, and the basic silicic acid is basically The effect of zirconium is comparable, and the gloss of the glaze is not much different. Compared with pure zirconium silicate, the production cost is reduced, and the radioactivity of the product can be effectively controlled.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

L'invention concerne un agent opacifiant composé à base de silicate de zirconium composé, un procédé pour sa préparation et une application correspondante. L'agent opacifiant composé à base de silicate de zirconium est préparé à l'aide des matériaux suivants, comprenant les constituants, en pourcentage en masse : 65 %-84 % de sable de zircone, 1 %-15 % d'alumine calcinée, 15 %-30 % de fritte basse température ; et la fritte basse température est préparée à l'aide des matières premières suivantes, comprenant les constituants, en pourcentage en masse: 25 %-35 % de poudre de feldspath de potassium, 10 %-20 % de poudre d'apatite, 2 %-8 % de poudre de fluorite, 10 %-15 % de carbonate de calcium, 15-18 % de borax, 1-8 % d'oxyde de zinc, 2-8 % de poudre de quartz. Une valeur L de glaçure de l'agent opacifiant composé à base de silicate de zirconium est sensiblement supérieure à 91 et l'effet opacifiant est tel que souhaité. Les coûts de production peuvent être réduits tout en régulant efficacement la radioactivité du produit.
PCT/CN2016/097194 2016-06-28 2016-08-29 Agent opacifiant composé à base de silicate de zirconium, procédé pour sa préparation et application correspondante WO2018000562A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610507426.5 2016-06-28
CN201610507426.5A CN106145664B (zh) 2016-06-28 2016-06-28 复合硅酸锆乳浊剂及其制备方法与应用

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WO2018000562A1 true WO2018000562A1 (fr) 2018-01-04

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111792842A (zh) * 2020-07-21 2020-10-20 萍乡市双华电瓷制造有限公司 一种高压瓷质绝缘子釉料的制备方法
CN113305469A (zh) * 2021-05-13 2021-08-27 中国船舶重工集团公司第七二五研究所 一种奥氏体焊丝埋弧焊用熔炼焊剂及其制备方法
CN113773049A (zh) * 2021-10-08 2021-12-10 江苏脒诺甫纳米材料有限公司 一种锆英砂增白乳浊液及其制备工艺
EP4003936A4 (fr) * 2019-07-24 2023-08-23 Iluka Resources Limited Procédés et compositions de blanchiment
CN117700108A (zh) * 2023-12-06 2024-03-15 景德镇陶瓷大学 一种含氧化锆或氧化锆和硅酸锆共存的高白熔块乳浊釉及其制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107857475A (zh) * 2017-11-24 2018-03-30 广西南山瓷器有限公司 一种白瓷釉料
CN109880402A (zh) * 2019-03-27 2019-06-14 佛山市利德嘉陶瓷制釉有限公司 一种无磁性黑色陶瓷墨水色料及其制备和应用方法
CN110950535A (zh) * 2019-10-31 2020-04-03 佛山市金刚科技有限公司 一种陶瓷增白剂及其制备方法和用途

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CN1126463A (zh) * 1993-06-30 1996-07-10 技术资源有限公司 氧化锆基乳浊剂
US20050209082A1 (en) * 2004-03-18 2005-09-22 Elke Apel Apatite glass ceramic based on siliceous oxyapatites
CN101445398A (zh) * 2008-11-05 2009-06-03 阿斯创钛业（营口）有限公司 固相合成硅酸锆钙复合乳浊剂及其制造方法
CN101983949A (zh) * 2010-11-24 2011-03-09 景德镇陶瓷学院 一种压电陶瓷雾化片用白色乳浊釉及其制备方法
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CN104150961A (zh) * 2014-07-27 2014-11-19 青岛祥海电子有限公司 一种陶瓷增白剂

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4003936A4 (fr) * 2019-07-24 2023-08-23 Iluka Resources Limited Procédés et compositions de blanchiment
CN111792842A (zh) * 2020-07-21 2020-10-20 萍乡市双华电瓷制造有限公司 一种高压瓷质绝缘子釉料的制备方法
CN113305469A (zh) * 2021-05-13 2021-08-27 中国船舶重工集团公司第七二五研究所 一种奥氏体焊丝埋弧焊用熔炼焊剂及其制备方法
CN113305469B (zh) * 2021-05-13 2022-11-08 中国船舶重工集团公司第七二五研究所 一种奥氏体焊丝埋弧焊用熔炼焊剂及其制备方法
CN113773049A (zh) * 2021-10-08 2021-12-10 江苏脒诺甫纳米材料有限公司 一种锆英砂增白乳浊液及其制备工艺
CN117700108A (zh) * 2023-12-06 2024-03-15 景德镇陶瓷大学 一种含氧化锆或氧化锆和硅酸锆共存的高白熔块乳浊釉及其制备方法

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CN106145664A (zh) 2016-11-23

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