WO2017185195A1 - 表面有珠光和变色效果的资源节约型釉面砖及其制备方法 - Google Patents

表面有珠光和变色效果的资源节约型釉面砖及其制备方法 Download PDF

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WO2017185195A1
WO2017185195A1 PCT/CN2016/000460 CN2016000460W WO2017185195A1 WO 2017185195 A1 WO2017185195 A1 WO 2017185195A1 CN 2016000460 W CN2016000460 W CN 2016000460W WO 2017185195 A1 WO2017185195 A1 WO 2017185195A1
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parts
glaze
powder
frit
weight
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PCT/CN2016/000460
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English (en)
French (fr)
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梁桐灿
余国明
欧家瑞
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广东宏宇新型材料有限公司
广东宏海陶瓷实业发展有限公司
广东宏陶陶瓷有限公司
广东宏威陶瓷实业有限公司
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Publication of WO2017185195A1 publication Critical patent/WO2017185195A1/zh

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    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/132—Waste materials; Refuse; Residues
    • 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
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    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
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Definitions

  • the invention relates to the technical field of preparation of glazed tiles, in particular to a resource-saving glazed tile with pearlescent and color-changing effects on the surface and a preparation method thereof.
  • the tourmaline is also called tourmaline. This gem hidden in the rainbow's foot is called “the rainbow that falls into the world”. It has always been a symbol of happiness and wealth. It is chased by people and used to make precious jewelry, ornaments and art. Products, etc., are expensive, so if you can develop the decorative artwork effect of the inlaid tourmaline gemstone on the ceramic tile technology of large-scale automated production, this precious and inaccessible Art works, through the paving of ordinary wall tiles, can be realized in the interior decoration of ordinary families, so that the home will be completely new and beautiful, and it will inevitably produce obvious technological innovation in the ceramic decoration technology, leading the new development of ceramic decoration technology, with Considerable economic benefits.
  • the object of the present invention is to overcome the above disadvantages, and to provide a resource-saving glazed tile with pearlescent and color-changing effects on the surface thereof and a preparation method thereof, which can pass through the green body without making major changes to the existing glazed tile production process.
  • Formula composition, composition of bottom and surface glaze frit, formulation of bottom and surface glaze, composition of frit of pearlescent printing glaze, formulation of pearlescent printing glaze, formulation of reflective grain granule, printing process and glazing parameters Adjustment and optimization, so that the surface of the glazed tile product with pearlescent and color-changing effect is glazed on the surface of the glazed glazed tile.
  • the finger touch is slightly convex, and the image is inlaid with a grain under the side light or the light.
  • the tourmaline jewels emit the same lustrous radiance, and the pattern color of the printed pearl glaze will appear different colors with the change of the light angle, such as the seven-color rainbow, with unique decorative and artistic, and the glaze quality of the product is good. It is resistant to dirt, pinholes, glaze, etc. At the same time, the technology has strong universality and is easy to promote in the industry.
  • Prime body It is prepared in the following parts by weight:
  • the ceramic polishing waste residue is a filter press sludge after treatment of various waste water generated in the production process of the ceramic polished brick;
  • the glazed brick waste residue is a filter press sludge after treatment of various waste water generated in the production process of the glazed tile;
  • the glaze amount of the bottom glaze is 0.6 ⁇ 0.9kg / m2, the glaze amount is the glaze hydrate weight ;
  • Glaze Prepared in the following parts by weight:
  • frit a 45-65 parts of frit a, 2-10 parts of zirconium silicate, 20-34 parts of kaolin, 2-10 parts of feldspar powder, 2-8 parts of calcined alumina powder, 2-6 parts of talc, plus carboxymethyl fiber 0.06-0.1 parts, 0.4-0.8 parts of sodium tripolyphosphate, 37-45 parts of water, glaze amount of the surface glaze is 0.65-0.95kg/m2, and the glazing amount is the weight of the glaze;
  • the frit a in the bottom glaze and the top glaze is prepared in the following parts by weight:
  • Feldspar powder 24 to 34 parts calcium carbonate 8 to 18 parts, glass powder 4 to 12 parts, zircon powder 3 to 11 parts, lithium porcelain stone powder 8 to 18 parts, talc powder 2 to 6 parts, potassium carbonate 1 to 5 parts , 1 to 5 parts of borax, 17 to 27 parts of quartz powder;
  • the frit b is prepared in the following parts by weight:
  • feldspar powder 25 to 35 parts of feldspar powder, 17 to 23 parts of calcium carbonate, 2 to 6 parts of boric acid, 10 to 16 parts of zinc oxide, 1 to 3 parts of alumina powder, 1 to 3 parts of zirconium silicate, and 1 to 3 parts of barium carbonate. 1 to 4 parts of potassium carbonate, 0.5 to 1.5 parts of cerium oxide, and 29 to 39 parts of quartz powder;
  • Reflective Grain Granules Formulated in the following parts by weight:
  • the frit c pellets are prepared in the following parts by weight:
  • feldspar powder 10 to 16 parts of calcium carbonate, 4 to 8 parts of boric acid, 3 to 7 parts of talc, 8 to 14 parts of zircon powder, 2 to 6 parts of spodumene powder, and 4 to 8 parts of zinc oxide.
  • the invention also relates to a method for preparing a resource-saving glazed tile having a pearlescent and color-changing effect, comprising the following steps:
  • the ceramic polishing waste residue is a filter press sludge after treatment of various waste water generated in the production process of the ceramic polished brick;
  • the glazed brick waste residue is a filter press sludge after treatment of various waste water generated in the production process of the glazed tile;
  • frit a 45-65 parts of frit a, 2-10 parts of zirconium silicate, 20-34 parts of kaolin, 2-10 parts of feldspar powder, 2-8 parts of calcined alumina powder, 2-6 parts of talc, plus carboxymethyl group Cellulose 0.06 ⁇ 0.1 parts, 0.4-0.8 parts of sodium tripolyphosphate, 37-45 parts of water, mixed together to form a glaze slurry with a fineness of 325 mesh sieve and 0.2% to 0.4% by mass of the sieve. Glaze
  • the frit a in the bottom glaze and the top glaze is prepared in the following parts by weight:
  • Feldspar powder 24 to 34 parts calcium carbonate 8 to 18 parts, glass powder 4 to 12 parts, zircon powder 3 to 11 parts, lithium porcelain stone powder 8 to 18 parts, talc powder 2 to 6 parts, potassium carbonate 1 to 5 parts 1 to 5 parts of borax, 17 to 27 parts of quartz powder, the particle size of all components is less than 180 mesh; all the components are mixed together in a mixer, and the melting pool kiln is melted, and the melting temperature ranges from 1500 ° C to 1540. °C, then water quenched into frit particles, drying to obtain a frit a;
  • the frit b is prepared in the following parts by weight:
  • feldspar powder 25 to 35 parts of feldspar powder, 17 to 23 parts of calcium carbonate, 2 to 6 parts of boric acid, 10 to 16 parts of zinc oxide, 1 to 3 parts of alumina powder, 1 to 3 parts of zirconium silicate, and 1 to 3 parts of barium carbonate.
  • the temperature range is 1500 ° C ⁇ 1540 ° C, and then water quenched into frit particles, drying to obtain the frit b;
  • the frit c particles are prepared according to the following parts by weight:
  • the glaze obtained in the step A is first applied to the bottom glaze obtained in the step B, and the glaze amount of the bottom glaze is 0.6-0.9 kg/m2, and the glazing amount is the weight of the glaze glaze; then the glaze obtained in the step C is applied. Glaze The glazing amount is 0.65-0.95kg/m2, and the glazing amount is the weight of the glaze glaze; then the pearl printing glaze obtained by the step D is printed by the screen plate or offset printing according to the design of the pattern, and the pearl embossed glaze pattern is printed.
  • the thickness is 0.6-0.9 mm; the inkjet printing is performed by an inkjet printing machine; and the polishing slurry obtained in the step E is further applied, and the slurry amount of the reflective body slurry is 0.18 to 0.24 kg/m2, and the slurry is applied.
  • the amount is wet slurry, and it is dried by a dryer or after the water trace is not visible on the surface, and then enters the roller kiln to be fired.
  • the highest firing temperature ranges from 1090 ° C to 1130 ° C, and the firing time is 45 to 65 minutes. After edging and grading, the finished product is finally produced.
  • these open pores are the guarantee of uniform water absorption, surface gas permeability and hydrophobicity of the green body, thereby ensuring pearl printing when printing a pearlescent printing glaze with a thickness of 0.6-0.9 mm and applying a reflective grain slurry.
  • the liquid medium in the glaze and the reflective body slurry can quickly penetrate into the surface glaze in a short time, so that the printed pattern can be quickly solidified in a short time, and the original shape is not damaged, and the reflective body particles are firmly adhered to the surface. Glaze, not blown off by the kiln dust blower or the smoking fan of the kiln; at the same time, these holes are the best way to discharge gas during firing.
  • the optimization of the composition of the glaze can also ensure that the glaze has suitable high temperature viscosity and melting properties at high temperatures, thus ensuring the pearlescent printing glaze printed on its surface and applied to it.
  • the reflective particles on the surface remain intact, such as inlaid gemstones and provide a reflective light source; at the same time, it can also ensure that the glaze does not melt at high temperatures due to low temperature viscosity and excessive melting ability, and the pearlescent printing glaze and reflective particles are integrated.
  • the loss of the attractive light of the tourmaline gemstone and the loss of the reflected light by the reflector if the high temperature viscosity is too high, the melting ability is too low, the pearlescent printing glaze and the reflective body and the surface glaze Poor combination, easy to produce defects such as suction, rough surface; pearlescent printing glaze frit formula composition and optimization of the formulation of pearlescent printing glaze, on the one hand to ensure that the pearlescent printing glaze has a suitable surface tension at high temperatures, does not penetrate Into the glaze, to ensure a convex shape like a grain of gemstones; on the other hand, to ensure the high transparency, high gloss and high refractive index of the pearlescent printing glaze, so that the inkjet printing on the surface of the pattern The color changes color depending on the angle of incidence of the light.
  • zinc oxide, titanium dioxide, boric acid, zirconium silicate, and barium carbonate are added to the formulation to adjust the surface tension, transparency, and gloss.
  • a highly transparent glaze that is micro-bumped after the pearl-printing glaze is burned.
  • the highly transparent glaze droplets of these micro-protrusions form a dual effect on the reflection and refraction of light, forming an approximately rainbow Phenomenon, coupled with the interference of the pattern color on the human eye, so that the human eye naturally forms a special effect of discoloration caused by the difference in the angle of the light.
  • the optimization of the composition of the reflective body frit and the reflective grain slurry ensures that it has suitable melting properties and certain stability, otherwise it will not be suitable to be incorporated into the glaze due to its melting property and thus lose the reflection effect on light; Because it is not well bonded to the surface glaze, it is prone to cracking and rough surface, resulting in suction; the glazing process parameters of the glaze, glaze, reflective grain and pearlescent printing glaze and the process adjustment and optimization of the printing can guarantee The integrity of the printed pattern does not adversely affect the reflection and refraction of the light-reflecting grain and the pearl-printing glaze; at the same time, it ensures the proper expansion of the green body, the bottom, the surface glaze and the reflective grain slurry. The coefficient guarantees the flatness of the product.
  • the formulation of the bottom and surface glaze frits Due to the optimization of the formulation of the green body, the formulation of the bottom and surface glaze frits, the formulation of the bottom and surface glaze, the composition of the pearlescent glaze frit, the formulation of the pearlescent glaze, and the composition of the reflective body frit.
  • a large amount of ceramic polishing waste residue and glazed brick waste residue are used in the green body formula, which saves the production cost and saves resources, achieves the purpose of energy saving and emission reduction, and adopts the existing glazed tile production process. Easy to achieve industrial scale.
  • Fig. 1 is a process flow diagram for preparing a resource-saving glazed tile having a pearlescent and color-changing effect on the surface of the present invention.
  • a method for preparing a resource-saving glazed tile having a pearlescent and color-changing effect comprising the following steps:
  • the mixed sand, clay, limestone, wollastonite, ceramic polishing waste, glazed brick waste, and 1 to 2 parts of water glass of potassium feldspar and albite and quartz are respectively weighed.
  • the above raw materials with a particle size of less than 180 mesh are compounded according to the weight of Table 2, uniformly mixed, and melted in a frit furnace.
  • the melting temperature ranges from 1500 ° C to 1540 ° C, and water is quenched into frit particles, and the frit is obtained by drying. ;
  • the frit a, zirconium silicate, feldspar powder, kaolin, burnt talc, alumina powder, quartz powder prepared in the above step B are weighed, and 0.06-0.12 parts of carboxymethyl cellulose is added.
  • the same frit a, silicate silicate, kaolin, feldspar powder, calcined alumina powder, burnt talc, and 0.06-0.1 parts of carboxy group prepared in the above step B are weighed.
  • the composition of the frit b is as follows:
  • the above raw materials having a particle size of less than 180 mesh are compounded according to the weight of Table 5, uniformly mixed and melted in a frit furnace, and the melting temperature ranges from 1500 ° C to 1540 ° C, water is quenched into frit particles, and dried to obtain a frit b ;
  • the frit b, zinc oxide, titanium dioxide and ceramic rubber roller oil are mixed and ground into a glaze slurry with a fineness of 325 mesh and a sieve residue of 0.02% to 0.06% by mass. After sieving iron, pearlescent printing glaze is obtained.
  • the above raw materials having a particle size of less than 180 mesh are compounded according to the weight of Table 7 and uniformly mixed in a frit furnace.
  • the melting temperature ranges from 1500 ° C to 1540 ° C, and then water quenches into frit particles, which are dried and then broken into particle sizes.
  • the frit c is obtained;
  • the c-grain of the frit is weighed, and the ceramic rubber roller ink is mixed and stirred uniformly to obtain the reflective grain slurry.
  • the glaze obtained in the step A is first applied to the bottom glaze obtained in the step B, and the glaze amount of the bottom glaze is 0.6-0.9 kg/m2, and the glazing amount is the weight of the glaze glaze; then the glaze obtained in the step C is applied.
  • the glaze amount of the glaze is 0.65-0.95kg/m2, and the glazing amount is the weight of the glaze glaze; according to the design of the pattern, the pearl lithographic glaze obtained by the step D is printed by the screen or offset printing, and the pearl lithographic printing glaze is printed.
  • the thickness of the pattern is 0.6-0.9 mm; the inkjet printing is performed by an inkjet printing machine; and the slurry of the reflective body obtained by the step E is applied, and the amount of the slurry of the reflective body is 0.18 to 0.24 kg/m2.
  • the amount of slurry is the weight of the wet slurry. After drying in a dryer or after the water trace is not visible on the surface, it enters the roller kiln and is fired. The highest firing temperature is 1090 ° C ⁇ 1130 ° C, and the firing time is 45 ⁇ 65 minutes. After the edging and grading process, the finished product is finally produced.
  • the resource-saving glazed tile product with the pearlescent and color-changing effect prepared by the above method has a slight unevenness on the surface, and the surface is inlaid with a grain of tourmaline gemstone under the side light or the illumination of the light. And these patterns inlaid with tourmaline gemstones will have different colors depending on the angle of light, such as the seven-color rainbow, which looks jewel-like, beautiful, unique and decorative, and has good glaze quality and stain resistance. Defects such as strong sex, no pinholes on the surface, and glaze bubbles break through the deficiencies of the existing glazed tiles.

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Abstract

表面有珠光和变色效果的资源节约型釉面砖及其制备方法，在不对现有釉面砖的生产工艺做出重大改变的基础上，重点对素坯体的配方组成、底、面釉熔块的配方组成、底、面釉的配方组成、珠光印刷釉的熔块组成、珠光印刷釉的配方组成、反光体粒浆的配方组成、施釉参数和印花工艺的调整与优化，从而使制得的釉面砖产品表面呈现微凹凸状，侧光或在灯光照射下，釉面如镶嵌了一粒粒碧玺宝石般发出闪烁诱人的光芒，且印珠光印刷釉处的图案颜色会随着光线角度的不同，呈现出不同的颜色，如七色彩虹，显得珠光宝气、富丽堂皇，具有独特的装饰性和艺术性；同时该技术具备较强的普适性，易于在行业内推广。

Description

表面有珠光和变色效果的资源节约型釉面砖及其制备方法 技术领域：
本发明涉及釉面砖的制备技术领域，尤其是指一种表面有珠光和变色效果的资源节约型釉面砖及其制备方法。
背景技术：
碧玺石也叫电气石，这种藏在彩虹落脚处的宝石，被誊为“落入人间的彩虹”，历来作为幸福和财富的象征，被人们追逐，并用来制作珍贵首饰、装饰品、艺术品等，价格昂贵，因此如能在大规模自动化生产的墙地砖技术上开发出这种将镶嵌碧玺宝石的装饰用艺术品效果复制在陶瓷墙地砖产品上，使这种可遇不可求的珍贵艺术品，通过普通墙地砖的铺贴，实现于普通家庭的室内装饰中，从而使居家焕然一新，富丽堂皇，必然会在陶瓷装饰技术中产生明显的技术革新，引领陶瓷装饰技术的新发展，具有可观的经济效益。
发明内容：
本发明的目的在于克服上述缺点，提供一种表面有珠光和变色效果的资源节约型釉面砖及其制备方法，在不对现有釉面砖生产工艺作出重大改变的基础上，通过对素坯体的配方组成、底、面釉熔块的配方组成、底、面釉的配方组成、珠光印刷釉的熔块组成、珠光印刷釉的配方组成、反光体粒浆的配方组成、印花工艺及施釉参数的调整与优化，从而使制得的釉面砖产品表面有珠光和变色效果的资源节约型釉面砖表面印珠光印刷釉处手指触摸呈微凸状，在侧光或灯光照射下象镶嵌了一粒粒碧玺宝石一样发出闪烁诱人的光芒，且印珠光印刷釉处的图案颜色会随着光线角度的变化出现不同的颜色，如七色彩虹，具有独特的装饰性和艺术性，且产品釉面质量好，耐污强、无针孔、釉泡等缺陷；同时该技术具备较强的普适性，易于在行业内推广。
为解决上述问题，本发明通过以下技术方案实现：
本发明的表面有珠光和变色效果的资源节约型釉面砖，其包括的：
素坯体：按以下重量份组份配制：
钾长石和钠长石及石英的混合砂28～38份，粘土15～25份，石灰石粒5～13份，硅灰石粒2～6份，陶瓷抛光废渣15～25份，釉面砖废渣10～20份，外加水玻璃1～2份，三聚磷酸钠0.1～0.3份，五水偏硅酸钠0.4～0.6份，水50～55份；
其中的陶瓷抛光废渣为陶瓷抛光砖生产过程中产生的各种废水经处理后的压滤泥渣；
其中的釉面砖废渣为釉面砖生产过程中产生的各种废水经处理后的压滤泥渣；
底釉：按以下重量份组份配制：
熔块a 25～35份，硅酸锆3～9份，长石粉3～9份，高岭土15～25份，烧滑石20～30份，氧化铝粉3～9份，石英粉3～9份，外加羧甲基纤维素0.06～0.12份，三聚磷酸钠0.4～0.8份，水37～45份，底釉的施釉量为0.6～0.9㎏/㎡，所述的施釉量为含水釉浆重；
面釉：按以下重量份组份配制：
熔块a 45～65份，硅酸锆2～10份，高岭土20～34份，长石粉2～10份，煅烧氧化铝粉2～8份，烧滑石2～6份，外加羧甲基纤维素0.06～0.1份，三聚磷酸钠0.4～0.8份，水37～45份，面釉的施釉量为0.65～0.95㎏/㎡，所述的施釉量为含水釉浆重；
其中底釉和面釉中的熔块a按以下重量份组份配制：
长石粉24～34份，碳酸钙8～18份，玻璃粉4～12份，锆英粉3～11份，锂瓷石粉8～18份，滑石粉2～6份，碳酸钾1～5份，硼砂1～5份，石英粉17～27份；
珠光印刷釉：按以下重量份组份配制：
熔块b 94～98份，氧化锌1～3份，钛白粉1～3份，陶瓷胶辊印油80～180份，珠光印刷釉印刷图案的厚度为0.6～0.9㎜；
其中熔块b按以下重量份组份配制：
长石粉25～35份，碳酸钙17～23份，硼酸2～6份，氧化锌10～16份，氧化铝粉1～3份，硅酸锆1～3份，碳酸锶1～3份，碳酸钾1～4份，氧化镧0.5～1.5份，石英粉29～39份；
反光体粒浆：按以下重量份组份配制：
熔块c粒35～45份，陶瓷胶辊印油100份，反光体粒浆施浆量为0.18～0.24㎏/㎡，所述的施浆量为湿浆重；
其中熔块c粒按以下重量份组份配制：
长石粉16～22份，碳酸钙10～16份，硼酸4～8份，滑石粉3～7份，锆英粉8～14份，锂辉石粉2～6份，氧化锌4～8份，碳酸锶0.5～3.5份，氧化铈0.5～3.5份，碳酸钾0.5～2.5份，碳酸钠0.5～2.5份，石英粉30～40份。
本发明还涉及一种表面有珠光和变色效果的资源节约型釉面砖的制备方法，其包括以下步骤：
A、素坯体的制备，按重量份制备：
将钾长石和钠长石及石英的混合砂28～38份，粘土15～25份，石灰石粒5～13份，硅灰石粒2～6份，陶瓷抛光废渣15～25份，釉面砖废渣10～20份，外加水玻璃1～2份，三聚磷酸钠0.1～0.3份，五水偏硅酸钠0.4～0.6份，水50～55份，一起混合磨成细度为250目筛的筛余为质量百分比2％～5％的浆料，经除铁过筛喷雾干燥制成含质量百分比6.5％～7.5％水分的粉料，在300～400公斤/厘米2压力范围下用自动液压机压制成型、干燥窑干燥，辊道窑烧成，最高烧成温度范围为1075℃～1140℃，烧成时间40～70分钟，即得素坯体；
其中的陶瓷抛光废渣为陶瓷抛光砖生产过程中产生的各种废水经处理后的压滤泥渣；
其中的釉面砖废渣为釉面砖生产过程中产生的各种废水经处理后的压滤泥渣；
B、底釉的制备，按重量份制备：
将熔块a 25～35份，硅酸锆3～9份，长石粉3～9份，高岭土15～25份，烧滑石20～30份，氧化铝粉3～9份，石英粉3～9份，外加羧甲基纤维素0.06～0.12份，三聚磷酸钠0.4～0.8份，水37～45份，一起混合磨成细度为325目筛的筛余为质量百分比0.2％～0.4％的釉浆，经过筛除铁储存即得底釉；
C、面釉的制备，按重量份制备：
将熔块a 45～65份，硅酸锆2～10份，高岭土20～34份，长石粉2～10份，煅烧氧化铝粉2～8份，烧滑石2～6份，外加羧甲基纤维素0.06～ 0.1份，三聚磷酸钠0.4～0.8份，水37～45份，一起混合磨成细度为325目筛的筛余为质量百分比0.2％～0.4％的釉浆，经过筛除铁储存即得面釉；
其中底釉和面釉中的熔块a按以下重量份组份配制：
长石粉24～34份，碳酸钙8～18份，玻璃粉4～12份，锆英粉3～11份，锂瓷石粉8～18份，滑石粉2～6份，碳酸钾1～5份，硼砂1～5份，石英粉17～27份，所有组分的粒度均小于180目；将所有组分一起放入混合机混合，熔块池窑熔制，熔制温度范围1500℃～1540℃，然后水淬成熔块颗粒，烘干即得熔块a；
D、珠光印刷釉的制备，按重量份制备：
将熔块b 94～98份，氧化锌1～3份，钛白粉1～3份，陶瓷胶辊印油80～180份混合磨成细度为325目筛的筛余为质量百分比0.02％～0.06％的釉浆，经过筛除铁储存即得珠光印刷釉；
其中熔块b按以下重量份组份配制：
长石粉25～35份，碳酸钙17～23份，硼酸2～6份，氧化锌10～16份，氧化铝粉1～3份，硅酸锆1～3份，碳酸锶1～3份，碳酸钾1～4份，氧化镧0.5～1.5份，石英粉29～39份，所有组分的粒度均小于180目；将所有组分一起放入混合机混合，熔块池窑熔制，熔制温度范围1500℃～1540℃，然后水淬成熔块颗粒，烘干即得熔块b；
E、反光体粒浆的制备，按重量份制备：
将熔块c粒35～45份，陶瓷胶辊印油100份混合搅拌均匀即得反光体粒浆；
其中熔块c粒按以下重量份组份制备：
长石粉16～22份，碳酸钙10～16份，硼酸4～8份，滑石粉3～7份，锆英粉8～14份，锂辉石粉2～6份，氧化锌4～8份，碳酸锶0.5～3.5份，氧化铈0.5～3.5份，碳酸钾0.5～2.5份，碳酸钠0.5～2.5份，石英粉30～40份，所有组分的粒度均小于180目；将所有组分一起放入混合机混合，熔块池窑熔制，熔制温度范围1500℃～1540℃，然后水淬成熔块颗粒，烘干再破碎成粒度为70目～180目的细熔块粒即得熔块c粒；
F、产品的制备及烧成：
将步骤A得到的素坯体，先施步骤B得到的底釉，底釉的施釉量为0.6～0.9㎏/㎡，所述的施釉量为含水釉浆重；然后施步骤C得到的面釉，面釉 的施釉量为0.65～0.95㎏/㎡，所述的施釉量为含水釉浆重；再根据图案设计的需要用丝网版或胶印辊印步骤D得到的珠光印刷釉，印刷珠光印刷釉图案的厚度为0.6～0.9㎜；再用喷墨印花机进行喷墨印花；再施步骤E得到的反光体粒浆，反光体粒浆的施浆量为0.18～0.24㎏/㎡，所述的施浆量为湿浆重，经烘干器烘干或待表面看不到水迹后才进入辊道窑烧成，最高烧成温度范围为1090℃～1130℃，烧成时间为45～65分钟，经过磨边、分级工序，最后制成成品。
本发明的表面有珠光和变色效果的资源节约型釉面砖及其制备方法，制造的釉面砖产品在侧光或灯光照射下，表面象镶嵌了一粒粒碧玺宝石一样发出闪烁诱人的光芒，且这些象镶嵌了碧玺宝石处的图案颜色会随着光线角度的变化出现不同的颜色如七色彩虹，显得珠光宝气、富丽堂皇，具有独特的装饰性和艺术性，同时该技术具备较强的普适性，易于在行业内推广。
本发明的表面有珠光和变色效果的资源节约型釉面砖及其制备方法：
通过对素坯体配方组成的优化，在素坯体配方中掺入了大量的陶瓷抛光废渣和釉面砖废渣，一方面这些废渣不但大大降低了生产成本，也达到了节能减排的目的；另一方面，添加这些废渣制造的素坯体，经申请人大量的研究表明，其在高温煅烧过程中由于这些废渣(尤其是陶瓷抛光废渣)中大量气体的排放，在素坯体表面形成大量的开口气孔，这些开口气孔是素坯体吸水率、表面透气性及疏水性均匀优良的保证，从而确保了在印刷图案厚度高达0.6～0.9㎜的珠光印刷釉及施反光体粒浆时，珠光印刷釉及反光体粒浆中的液态介质能够在短时间内快速渗透到面釉中，使印刷的图案在短时间内快速凝固，并保证原状不受到破坏，反光体粒牢牢地粘附在面釉上，而不会被窑头吹尘风机吹掉或窑炉的抽烟风机抽走；同时在烧成时，这些气孔又是气体排放的最佳通道，不会因陶瓷胶辊印油中油性介质量过多使产品在高温中气体排放困难，从而使产品出现针孔、釉泡、桔釉甚至出现爆釉等缺陷。底釉和面釉熔块的配方组成、底釉和面釉配方组成的优化，一方面确保底釉和面釉在高温中透气性良好，使素坯体中的陶瓷废渣在高温中释放的气体能够及时排出，不会因气体过多排放困难而造成对素坯体的破坏；另一方面又能与素坯体形成一个稳固的统一体，不会因三者之间的膨胀系数的差异从而影响产品的平整度及抗热震性；面釉配方组成的优化还可以保证面釉在高温中有合适的高温粘度及熔融性能，从而确保印刷在其面上的珠光印刷釉和施 在其面上的反光体粒保持原状，如镶嵌的宝石和提供反射光源的作用；同时还可以确保面釉不会在高温中因高温粘度过低、熔融能力过强，将珠光印刷釉及反光体粒融入其中，从而失去碧玺宝石闪烁诱人的光芒及反光体失去反射光线的作用；如高温粘度过高，熔融能力过低，则珠光印刷釉及反光体粒与面釉的结合不良，易产生吸污、表面粗糙等缺陷；珠光印刷釉熔块配方组成及珠光印刷釉的配方组成的优化，一方面确保了珠光印刷釉在高温中有合适的表面张力，不会渗透到面釉中，从而保证凸起状如一粒粒镶嵌的宝石；另一方面，又保证了珠光印刷釉的高透明度、高光泽度和高折射率，从而使喷墨印刷在其面上的图案颜色随光线射入角度不同而产生变色的效果，因此在配方组成中添加了适量对表面张力、透明度及光泽度起调节作用的氧化锌、钛白粉、硼酸、硅酸锆、碳酸锶原料，从而使珠光印刷釉烧后成微凸起的高度透明的釉，由于添加了适量含La2O3和TiO2折射率高的材料，再加上反光体形成对光线的反射共同作用，因此当光线以不同角度照射到产品表面上时，这些微凸起的高度透明釉滴形成了对光的反射及折射的双重作用，形成一种近似彩虹的现象，再加上图案颜色对人眼的干扰作用，从而使人眼观看起来自然形成一种图案色彩随着光的角度不同而产生的变色特殊效果。反光体粒熔块和反光体粒浆配方组成的优化，保证了其具有合适的熔融性能及一定的稳定性，否则会因其熔融性能不适宜融入面釉中从而失去对光的反射作用；或因其与面釉粘接不好，易产生开裂及表面粗糙，产生吸污；施底釉、面釉、反光体粒浆和珠光印刷釉的施釉工艺参数及印花的工艺调整与优化，可以保证印花图案的整体性，且不会对反光体粒浆、珠光印刷釉对光线的反射和折射效果产生不利的影响；同时又保证了素坯体、底、面釉、反光体粒浆的合适膨胀系数，保证了产品的平整度。
本发明的表面有珠光和变色效果的资源节约型釉面砖及其制备方法有如下优点：
1、由于优化了素坯体的配方组成、底、面釉熔块的配方组成、底、面釉的配方组成、珠光印刷釉熔块组成、珠光印刷釉的配方组成、反光体粒熔块组成、反光体粒浆的配方组成及施底、面釉、反光体粒浆、印珠光印刷釉的施釉工艺参数及印花工艺的调整与优化等，从而使制造的产品在灯光照射或侧光下，犹如镶嵌了一粒粒如碧玺宝石发出闪烁诱人的光芒。且印珠光印刷釉处的图案颜色会随着光线角度的变化出现如彩虹般的七彩颜色，具有独 特的装饰性和艺术性。
2、该产品表面平整度、断裂模数、抗折强度、耐酸碱性、抗热震性、放射性、铅镉溶出量均达到GB/T4100-2015、GB6566-2011及HJ/T297-2006标准要求。
3、素坯体配方中使用了较大量的陶瓷抛光废渣和釉面砖废渣，使得在降低生产成本的同时又节约了资源，达到了节能减排的目的，且采用现有的釉面砖生产工艺，易于实现产业化规模。
附图说明：
图1是制备本发明的表面有珠光和变色效果的资源节约型釉面砖的工艺流程图。
具体实施方式：
下面结合实施例对本发明作进一步详细说明。
实例1
一种表面有珠光和变色效果的资源节约型釉面砖的制备方法，其包括以下步骤：
A、制备素坯体：
素坯体的配方组份见下表1：
表1、素坯体的组成成份表(重量份)
Figure PCTCN2016000460-appb-000001
按表1素坯体组成成份分别称取钾长石和钠长石及石英的混合砂、粘土、石灰石粒、硅灰石粒、陶瓷抛光废渣、釉面砖废渣、外加1～2份的水玻璃，0.1～0.3份的三聚磷酸钠、0.4～0.6份的五水偏硅酸钠、50～55份的水，入球磨机细碎到250目筛的筛余为质量百分比2％～5％的浆料，经除铁过筛喷雾干燥制成质量百分比6.5％～7.5％水分的粉料，在300～400公斤/厘米2压力范围下用自动液压机压制成型、干燥窑干燥，辊道窑烧成，最高烧成温度 范围为1075℃～1140℃，烧成时间40～70分钟，即得素坯体；所述的陶瓷抛光废渣为陶瓷抛光砖生产过程中产生的各种废水经处理后的压滤泥渣；釉面砖废渣为釉面砖生产过程中产生的各种废水经处理后压滤泥渣。
B、制备底釉：
制备熔块a，熔块a的配方组成成份见表2：
表2、熔块a的组成成份表(重量份)
Figure PCTCN2016000460-appb-000002
将粒度小于180目的上述原料按表2重量份进行配料，混合均匀，在熔块炉内熔制，熔制温度范围1500℃～1540℃，水淬成熔块颗粒，烘干即得熔块a；
制备底釉，底釉的配方组成成份见表3：
表3、底釉配方组成表(重量份)
组份 熔块a 硅酸锆 长石粉 高岭土 烧滑石 氧化铝粉 石英粉
1# 25 9 9 20 28 3 6
2# 30 6 6 25 21 9 3
3# 35 3 3 15 29 6 9
4# 29 5 7 18 30 4 7
5# 33 8 5 23 20 7 4
6# 31 7 4 22 25 5 6
根据表3的底釉配方组成称取上述步骤B制得的熔块a、硅酸锆、长石粉、高岭土、烧滑石、氧化铝粉、石英粉，外加0.06～0.12份的羧甲基纤维素，0.4～0.8份的三聚磷酸钠，37～45份的水，一起入球磨机球磨，磨成细度为325目筛的筛余为质量百分比0.2％～0.4％的釉浆，经过筛除铁储存即得底釉。
C、制备面釉：
面釉的配方组成如下表4：
表4、面釉配方组成表(重量份)
组份 熔块a 硅酸锆 高岭土 长石粉 煅烧氧化铝粉 烧滑石
1# 45 10 34 6 2 3
2# 47 6 27 10 8 2
3# 65 2 20 2 5 6
4# 55 3 22 9 7 4
根据表4的面釉的配方组成称取上述步骤B制成的与底釉相同的熔块a、硅酸锆、高岭土、长石粉、煅烧氧化铝粉、烧滑石，外加0.06～0.1份的羧甲基纤维素，0.4～0.8份的三聚磷酸钠，37～45份的水，一起入球磨机球磨，磨成细度为325目筛的筛余为质量百分比0.2％～0.4％的釉浆，经过筛除铁储存即得面釉。
D、制备珠光印刷釉：
制备熔块b，熔块b的配方组成成份如下表5：
表5、熔块b的配方组成表(重量份)
Figure PCTCN2016000460-appb-000003
将粒度小于180目的上述原料按表5重量份进行配料，混合均匀在熔块炉内熔制，熔制的温度范围1500℃～1540℃，水淬成熔块颗粒，烘干即得熔块b；
制备珠光印刷釉，珠光印刷釉的配方组成成份见下表6：
表6、珠光印刷釉的配方组成表(重量份)
组份 熔块b 氧化锌 钛白粉 陶瓷胶辊印油
1# 94 3 3 80
2# 98 1 1 180
3# 96 2 2 130
根据表6珠光印刷釉的配方组成称取熔块b、氧化锌、钛白粉、陶瓷胶辊印油一起混合磨成细度为325目筛的筛余为质量百分比0.02％～0.06％的釉浆，经过筛除铁即得珠光印刷釉。
E、制备反光体粒浆：
制备熔块c粒，熔块c粒的配方组成成份见下表7：
表7、熔块c粒配方组成表(重量份)
Figure PCTCN2016000460-appb-000004
Figure PCTCN2016000460-appb-000005
将粒度小于180目的上述原料按表7重量份进行配料，混合均匀在熔块炉内熔制，熔制的温度范围1500℃～1540℃，然后水淬成熔块颗粒，烘干再破碎成粒度为70目～180目的细熔块粒即得熔块c粒；
制备反光体粒浆，反光体粒浆的配方组成如下表8：
表8、反光体粒浆的配方组成表(重量份)
组份 熔块c粒 陶瓷胶辊印油
1# 35 100
2# 40 100
3# 45 100
根据表8反光体粒浆的配方组成称取熔块c粒，陶瓷胶辊印油一起混合搅拌均匀即得反光体粒浆。
F、产品的制备及烧成：
将步骤A得到的素坯体，先施步骤B得到的底釉，底釉的施釉量为0.6～0.9㎏/㎡，所述的施釉量为含水釉浆重；然后施步骤C得到的面釉，面釉的施釉量为0.65～0.95㎏/㎡，所述的施釉量为含水釉浆重；再根据图案设计的需要用丝网或胶印辊印步骤D得到的珠光印刷釉，印刷珠光印刷釉图案的厚度为0.6～0.9㎜；再用喷墨印花机进行喷墨印花；再施步骤E得到的反光体粒浆，反光体粒浆的施浆量为0.18～0.24㎏/㎡，所述的施浆量为湿浆重，经烘干器烘干或待表面看不到水迹后才进入辊道窑烧成，最高烧成温度为1090℃～1130℃，烧成时间为45～65分钟，经过磨边、分级工序，最后制成成品。
采用上述方法制备得到的表面有珠光和变色效果的资源节约型釉面砖产品，表面具有微微凹凸感，在侧光或灯光照射下，表面象镶嵌了一粒粒碧玺宝石一样发出闪烁诱人的光芒，且这些像镶嵌了碧玺宝石处的图案颜色会随着光线角度的变化出现不同的颜色，如七色彩虹，显得珠光宝气、富丽堂皇，具有独特的装饰性和艺术性，且釉面质量好、耐污性强、表面无针孔、釉泡等缺陷，突破了现有釉面砖单一釉面装饰的不足。
经检测产品主要指标如下表9：
表9：产品质量检验结果
Figure PCTCN2016000460-appb-000006
综上所述，仅为本发明的较佳实施例而已，并非对本发明作任何形式上的限制；凡本行业的普通技术人员均可按以上所述而顺畅地实施本发明；但是凡熟悉本专业的技术人员在不脱离本发明技术方案范围内，可利用以上所揭示的技术内容而做出的些许变更、修饰与演变的等同变化，均为本发明的等效实施例；同时，凡依据本发明的实质技术对以上实施例所作的任何等同变化的变更、修饰与演变，均仍属于本发明的技术方案的保护范围之内。

Claims (2)

  1. 表面有珠光和变色效果的资源节约型釉面砖，其特征在于：
    素坯体：按以下重量份组份配制：
    钾长石和钠长石及石英的混合砂28～38份，粘土15～25份，石灰石粒5～13份，硅灰石粒2～6份，陶瓷抛光废渣15～25份，釉面砖废渣10～20份，外加水玻璃1～2份，三聚磷酸钠0.1～0.3份，五水偏硅酸钠0.4～0.6份，水50～55份；
    其中的陶瓷抛光废渣为陶瓷抛光砖生产过程中产生的各种废水经处理后的压滤泥渣；
    其中的釉面砖废渣为釉面砖生产过程中产生的各种废水经处理后的压滤泥渣；
    底釉：按以下重量份组份配制：
    熔块a25～35份，硅酸锆3～9份，长石粉3～9份，高岭土15～25份，烧滑石20～30份，氧化铝粉3～9份，石英粉3～9份，外加羧甲基纤维素0.06～0.12份，三聚磷酸钠0.4～0.8份，水37～45份，底釉的施釉量为0.6～0.9㎏/㎡，所述的施釉量为含水釉浆重；
    面釉：按以下重量份组份配制：
    熔块a45～65份，硅酸锆2～10份，高岭土20～34份，长石粉2～10份，煅烧氧化铝粉2～8份，烧滑石2～6份，外加羧甲基纤维素0.06～0.1份，三聚磷酸钠0.4～0.8份，水37～45份，面釉的施釉量为0.65～0.95㎏/㎡，所述的施釉量为含水釉浆重；
    其中底釉和面釉中的熔块a按以下重量份组份配制：
    长石粉24～34份，碳酸钙8～18份，玻璃粉4～12份，锆英粉3～11份，锂瓷石粉8～18份，滑石粉2～6份，碳酸钾1～5份，硼砂1～5份，石英粉17～27份；
    珠光印刷釉：按以下重量份组份配制：
    熔块b94～98份，氧化锌1～3份，钛白粉1～3份，陶瓷胶辊印油80～180份，珠光印刷釉印刷图案的厚度为0.6～0.9㎜；
    其中熔块b按以下重量份组份配制：
    长石粉25～35份，碳酸钙17～23份，硼酸2～6份，氧化锌10～16 份，氧化铝粉1～3份，硅酸锆1～3份，碳酸锶1～3份，碳酸钾1～4份，氧化镧0.5～1.5份，石英粉29～39份；
    反光体粒浆：按以下重量份组份配制：
    熔块c粒35～45份，陶瓷胶辊印油100份，反光体粒浆施浆量为0.18～0.24㎏/㎡，所述的施浆量为湿浆重；
    其中熔块c粒按以下重量份组份配制：
    长石粉16～22份，碳酸钙10～16份，硼酸4～8份，滑石粉3～7份，锆英粉8～14份，锂辉石粉2～6份，氧化锌4～8份，碳酸锶0.5～3.5份，氧化铈0.5～3.5份，碳酸钾0.5～2.5份，碳酸钠0.5～2.5份，石英粉30～40份；
  2. 表面有珠光和变色效果的资源节约型釉面砖的制备方法，其特征在于：
    其包括以下步骤：
    A、素坯体的制备，按重量份制备：
    将钾长石和钠长石及石英的混合砂28～38份，粘土15～25份，石灰石粒5～13份，硅灰石粒2～6份，陶瓷抛光废渣15～25份，釉面砖废渣10～20份，外加水玻璃1～2份，三聚磷酸钠0.1～0.3份，五水偏硅酸钠0.4～0.6份，水50～55份，一起混合磨成细度为250目筛的筛余为质量百分比2％～5％的浆料，经除铁过筛喷雾干燥制成含质量百分比6.5％～7.5％水分的粉料，在300～400公斤/厘米2压力范围下用自动液压机压制成型、干燥窑干燥，辊道窑烧成，最高烧成温度范围为1075℃～1140℃，烧成时间40～70分钟，即得素坯体；
    其中的陶瓷抛光废渣为陶瓷抛光砖生产过程中产生的各种废水经处理后的压滤泥渣；
    其中的釉面砖废渣为釉面砖生产过程中产生的各种废水经处理后的压滤泥渣；
    B、底釉的制备，按重量份制备：
    将熔块a25～35份，硅酸锆3～9份，长石粉3～9份，高岭土15～25份，烧滑石20～30份，氧化铝粉3～9份，石英粉3～9份，外加羧甲基纤维素0.06～0.12份，三聚磷酸钠0.4～0.8份，水37～45份，一起混合磨成细度为325目筛的筛余为质量百分比0.2％～0.4％的釉浆，经过筛除铁储存即得 底釉；
    C、面釉的制备，按重量份制备：
    将熔块a45～65份，硅酸锆2～10份，高岭土20～34份，长石粉2～10份，煅烧氧化铝粉2～8份，烧滑石2～6份，外加羧甲基纤维素0.06～0.1份，三聚磷酸钠0.4～0.8份，水37～45份，一起混合磨成细度为325目筛的筛余为质量百分比0.2％～0.4％的釉浆，经过筛除铁储存即得面釉；
    其中底釉和面釉中的熔块a按以下重量份组份配制：
    长石粉24～34份，碳酸钙8～18份，玻璃粉4～12份，锆英粉3～11份，锂瓷石粉8～18份，滑石粉2～6份，碳酸钾1～5份，硼砂1～5份，石英粉17～27份，所有组分的粒度均小于180目；将所有组分一起放入混合机混合，熔块池窑熔制，熔制温度范围1500℃～1540℃，然后水淬成熔块颗粒，烘干即得熔块a；
    D、珠光印刷釉的制备，按重量份制备：
    将熔块b94～98份，氧化锌1～3份，钛白粉1～3份，陶瓷胶辊印油80～180份混合磨成细度为325目筛的筛余为质量百分比0.02％～0.06％的釉浆，经过筛除铁储存即得珠光印刷釉；
    其中熔块b按以下重量份组份配制：
    长石粉25～35份，碳酸钙17～23份，硼酸2～6份，氧化锌10～16份，氧化铝粉1～3份，硅酸锆1～3份，碳酸锶1～3份，碳酸钾1～4份，氧化镧0.5～1.5份，石英粉29～39份，所有组分的粒度均小于180目；将所有组分一起放入混合机混合，熔块池窑熔制，熔制温度范围1500℃～1540℃，然后水淬成熔块颗粒，烘干即得熔块b；
    E、反光体粒浆的制备，按重量份制备：
    将熔块c粒35～45份，陶瓷胶辊印油100份混合搅拌均匀即得反光体粒浆；
    其中熔块c粒按以下重量份组份制备：
    长石粉16～22份，碳酸钙10～16份，硼酸4～8份，滑石粉3～7份，锆英粉8～14份，锂辉石粉2～6份，氧化锌4～8份，碳酸锶0.5～3.5份，氧化铈0.5～3.5份，碳酸钾0.5～2.5份，碳酸钠0.5～2.5份，石英粉30～40份，所有组分的粒度均小于180目；将所有组分一起放入混合机混合，熔块池窑熔制，熔制温度范围1500℃～1540℃，然后水淬成熔块颗粒，烘干再 破碎成粒度为70目～180目的细熔块粒即得熔块c粒；
    F、产品的制备及烧成：
    将步骤A得到的素坯体，先施步骤B得到的底釉，底釉的施釉量为0.6～0.9㎏/㎡，所述的施釉量为含水釉浆重；然后施步骤C得到的面釉，面釉的施釉量为0.65～0.95㎏/㎡，所述的施釉量为含水釉浆重；再根据图案设计的需要用丝网版或胶印辊印步骤D得到的珠光印刷釉，印刷珠光印刷釉图案的厚度为0.6～0.9㎜；再用喷墨印花机进行喷墨印花；再施步骤E得到的反光体粒浆，反光体粒浆的施浆量为0.18～0.24㎏/㎡，所述的施浆量为湿浆重，经烘干器烘干或待表面看不到水迹后才进入辊道窑烧成，最高烧成温度范围为1090℃～1130℃，烧成时间为45～65分钟，经过磨边、分级工序，最后制成成品。
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