CN115028440A - 一种耐污染瓷砖及其生产工艺 - Google Patents
一种耐污染瓷砖及其生产工艺 Download PDFInfo
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- CN115028440A CN115028440A CN202210603523.XA CN202210603523A CN115028440A CN 115028440 A CN115028440 A CN 115028440A CN 202210603523 A CN202210603523 A CN 202210603523A CN 115028440 A CN115028440 A CN 115028440A
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- ceramic tile
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- 239000000919 ceramic Substances 0.000 title claims abstract description 154
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 30
- 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 23
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 23
- 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 17
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 13
- 239000010453 quartz Substances 0.000 claims abstract description 13
- 239000000440 bentonite Substances 0.000 claims abstract description 11
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 11
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004575 stone Substances 0.000 claims abstract description 11
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- 239000010424 alunite Substances 0.000 claims abstract description 9
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 9
- KPZTWMNLAFDTGF-UHFFFAOYSA-D trialuminum;potassium;hexahydroxide;disulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KPZTWMNLAFDTGF-UHFFFAOYSA-D 0.000 claims abstract description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 40
- 238000011109 contamination Methods 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
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- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 8
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 8
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- BHFJBHMTEDLICO-UHFFFAOYSA-N Perfluorooctylsulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O BHFJBHMTEDLICO-UHFFFAOYSA-N 0.000 claims description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 claims description 6
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- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- CAGIDSBKVZMXMF-UHFFFAOYSA-N 3-[bis(1,1,2,2,2-pentafluoroethoxy)-[1,2,2,2-tetrafluoro-1-(1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctylsulfonyl)ethoxy]silyl]-N,N,1,1,2,2,3,3-octafluoropropan-1-amine Chemical compound FC(C(F)(F)F)(O[Si](OC(C(F)(F)F)(F)F)(OC(C(F)(F)F)(F)F)C(C(C(N(F)F)(F)F)(F)F)(F)F)S(=O)(=O)C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F CAGIDSBKVZMXMF-UHFFFAOYSA-N 0.000 claims description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 230000005855 radiation Effects 0.000 description 2
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- 239000000344 soap Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
- 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 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 239000011777 magnesium Substances 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 239000000725 suspension Substances 0.000 description 1
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- 229910052726 zirconium Inorganic materials 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
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- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
本申请涉及瓷砖技术领域,具体公开了一种耐污染瓷砖及其生产工艺,一种耐污染瓷砖,其包括如下重量份的原料:钾长石粉35‑40份、膨润土3‑6份、滑石粉3‑5份、铝矾石1‑3份、瓷石10‑15份、石英粉16‑18份、釉料1‑3份和表面处理剂0.1‑0.3份;所述表面处理剂为液态纳米二氧化硅。本申请得到的瓷砖单位面积油污残余量最低为0.34g/m2,耐污等级为5级,提高了瓷砖的耐污性。
Description
技术领域
本申请涉及瓷砖技术领域,更具体地说,它涉及一种耐污染瓷砖及其生产工艺。
背景技术
瓷砖,是以耐火的金属氧化物和半金属氧化物,经研磨、混合、压制、施釉、烧结而成的一种耐酸碱瓷质的建筑装饰材料。瓷砖按其工艺可分为釉面砖、通体砖、抛光砖和玻化砖。其中,釉面砖的吸水率较低,防潮性高,经常被应用于卫生间和厨房等场景。但釉面砖在烧制过程中会使砖坯或釉面出现残留的气孔和微观孔洞,在卫生间或厨房等场所使用时,空气中的有机物很容易吸附在瓷砖表面,且当有机物吸附在瓷砖表面后,空气中的无机颗粒更易吸附在瓷砖表面,不易擦除,且容易造成瓷砖吸污变色,影响瓷砖的美观。
相关技术中,通常采用将防污膜材料蒸镀于瓷砖表面,以达到防污的目的,但防污膜与瓷砖表面是通过范德华力连接的,这种作用力较弱,容易被破坏,从而导致防污膜脱落,仍未解决瓷砖的耐污染性较差的问题。
发明内容
为了提高瓷砖的耐污性能,本申请提供了一种耐污染瓷砖及其生产工艺。
第一方面,本申请提供一种耐污染瓷砖,其采用如下技术方案:
一种耐污染瓷砖,其包括如下重量份的原料:钾长石粉35-40份、膨润土3-6份、滑石粉3-5份、铝矾石1-3份、瓷石10-15份、石英粉16-18份、釉料1-3份和表面处理剂0.1-0.3份;所述表面处理剂为液态纳米二氧化硅。
本申请中瓷砖原料选用钾长石粉35-40份、膨润土3-6份、滑石粉3-5份、铝矾石1-3份、瓷石10-15份、石英粉16-18份、釉料1-3份和表面处理剂0.1-0.3份,瓷砖的各性能都是可预期的,且当钾长石粉38份、膨润土4.5份、滑石粉4份、铝矾石2份、瓷石13份、石英粉17份、釉料2份和表面处理剂0.2份,效果最佳。
通过采用上述技术方案,钾长石粉的主要化学成分为氧化钙,既是熔剂原料又是瘠性原料,在坯体中降低烧成温度又可缩短坯体的干燥时间,同时减少坯体干燥时的收缩和变形。另外,钾长石粉在高温下熔化为长石玻璃,填充坯体颗粒间的空隙,粘结颗粒使坯体致密,可改善透明度,有助于提高坯体的机械强度。另外,钾长石粉有利于胚体在高温煅烧时玻璃相的生成,从而提高瓷砖的瓷化程度,降低胚体的气孔率,减少胚体表面开口,吸附污染物的能力降低,从而提高瓷砖的耐污能力。
膨润土增加了胚体的可塑性和强度,使润滑作用大大增大,有利于球磨另外悬浮性和稳定性大大增强,瓷质细腻,抗碰撞,有一定的机械强度。
滑石粉是一种含镁矿物,作为熔剂使用,可有效降低烧成温度,在较低温度下形成液相,促使莫来石晶体的形成,还可扩大体系的烧成温度范围,提高瓷砖白度、热稳定性和力学性能,降低瓷砖的吸湿膨胀;另外滑石粉可有效促进瓷砖的烧结,提高瓷砖内部结构的紧密程度,降低孔隙率,从而提高瓷砖的防污性。
铝矾石中的铝含量较高,可提高坯体中铝的含量,提高瓷砖的硬度、耐磨性和韧性,还可提高坯体的高温抗荷性,具有较高的热稳定性,从而提高瓷砖内部结构的紧密程度,促使原料成分之间的致密性,降低孔隙率,从而避免瓷砖内部渗透污水和油渍,导致瓷砖变色,提高了瓷砖的耐污染性。
瓷石中三氧化二铝的含量一般高达18-19%,可进一步提高瓷砖坯体的可塑性和粘合性。
石英粉是一种非金属矿物质,材质坚硬、耐磨,化学性能稳定,主要矿物成分为二氧化硅,可对瓷砖泥料的可塑性起调剂作用,并能在干燥时降低收缩,缩短干燥时间和防止坯体变形,还可防止坯体在烧成时发生弯曲变形,还可增加坯体结合能力、机械强度和透明度。
涂布在瓷砖表面的表面处理剂为液态纳米二氧化硅,液态纳米二氧化硅可降低瓷砖的表面能,表面能低可以阻止尘埃、微生物、水性物、颗粒等的吸附,在外力作用下易脱附,具有超强的自洁耐沾污性能,同时也能够很好地渗入砖表面缺陷和毛细孔中形成交联网络实现长时间的防污功效。
作为优选:一种耐污染瓷砖,其包括如下重量份原料:钾长石粉37-39份、膨润土3.5-5.5份、滑石粉3.5-4.5份、铝矾石1.5-2.5份、瓷石12-14份、石英粉16.5-17.5份、釉料1.5-2.5份和表面处理剂0.15-0.25份。
作为优选:所述瓷砖原料中还包括2-4重量份的复合防污剂,所述复合防污剂与釉料按体积比1:(0.4-0.8)混合均匀后加入;所述复合防污剂包括如下重量份原料:纳米碳酸钙8-12份、六偏磷酸钠0.5-1.5份、氢氧化钠1-5份、氧化锆1-3份。
通过采用上述技术方案,本申请通过配制复合防污剂,并将复合防污剂与釉料混合均匀使用,使瓷砖表面与水接触后可使水分子活化、降低水的表面张力、减小水在陶瓷表面的接触角、提高乳液的稳定性,使得陶瓷表面具有防污功能。
加入纳米碳酸钙,在瓷砖烧结的过程中年度增加,产生的细小气泡靠表面张力聚集到一起形成大气泡浮上液面排出形成大量的大针孔,在通过表面处理剂填平大针孔,表面处理剂收缩后会形成很浅的凹面,当瓷砖表面遇到污水或油渍时,瓷砖表面受到外力,污水或油渍更易排出,提高瓷砖的耐污性能。六偏磷酸钠可提高纳米碳酸钙的活性和分散均匀性,可进一步提高纳米碳酸钙在瓷砖原料的耐污性。
加入氢氧化钠,可与瓷砖表面的油脂反应生成可溶性的肥皂,使瓷砖表面的油污更易去除。加入氧化锆可提高釉料的红外辐射性能,从而提高瓷砖的烧结效果,使釉料结构更加致密,表面不容易附着污物。
作为优选:所述复合防污剂采用以下步骤制备得到:
将纳米碳酸钙与六偏磷酸钠混合均匀,得到改性后的纳米碳酸钙;
将改性后的纳米碳酸钙、氢氧化钠和氧化锆混合均匀,得到复合防污剂。
通过采用上述技术方案,先将纳米碳酸钙和六偏磷酸钠混合,对纳米碳酸钙进行改性处理,以提高纳米碳酸钙与氢氧化钠和氧化锆之间的分散均匀性。
作为优选:所述表面处理剂还包括如下重量份原料:全氟辛基磺酰氟0.5-0.7份、γ-氨丙基三乙氧基硅烷0.3-0.5份、羟基硅油0.2-0.4份。
通过采用上述技术方案,在瓷砖表面涂布一层表面处理剂,以降低瓷砖的表面能,改善污染物对瓷砖表面的润湿情况,使污染物不易粘附在陶瓷制品表面,提高了瓷砖的耐污性。
将全氟辛基磺酰氟、γ-氨丙基三乙氧基硅烷、液态纳米二氧化硅和羟基硅油混合制备成表面处理剂,可降低瓷砖的表面能,表面能低的瓷砖可阻止尘埃、微生物、水性物、颗粒等的吸附,在外力作用下易脱附,具有超强的自洁耐沾污性能,同时也能够很好地渗入砖表面缺陷和毛细孔中形成交联网络,进一步提高瓷砖的耐污染性。
作为优选:所述表面处理剂采用以下操作步骤制备得到:
将γ-氨丙基三乙氧基硅烷、三乙胺和乙醇按体积比1:(1-2):(2-3)的比例混合均匀,滴加全氟辛基磺酰氟,在60℃搅拌2h,蒸馏除去乙醇和三乙胺,得到全氟辛基磺酰氨丙基三乙氧基硅烷;
将全氟辛基磺酰氨丙基三乙氧基硅烷、羟基硅油和液态纳米二氧化硅混合均匀,得到表面处理剂。
作为优选:所述瓷砖还包括0.4-0.8重量份的十二烷基苯磺酸钠和0.3-0.5重量份的月桂酸钠;所述十二烷基苯磺酸钠和月桂酸钠加入前先与滑石粉混合均匀,并调节pH为11.5。
通过采用上述技术方案,在瓷砖原料中添加滑石粉的基础上,加入十二烷基苯磺酸钠和月桂酸钠,并调节了十二烷基苯磺酸钠、月桂酸钠和滑石粉混合后混合物的pH值为11.5,提高了滑石粉在瓷砖原料中的分散均匀性,使滑石粉均匀的分散在瓷砖内部,在烧结过程中,能够有效促进瓷砖的烧结,提高瓷砖内部结构的紧密程度,降低孔隙率,从而提高瓷砖的防污性,且在防污性提高的同时,还提高了瓷砖的耐磨和防滑等性能。
第二方面,本申请提供一种耐污染瓷砖的制备方法,具体通过以下技术方案得以实现:
一种耐污染瓷砖的制备方法,其包括以下操作步骤:
将瓷砖除釉料和表面处理剂的其余原料混合,球磨,除铁过筛,陈腐均化,喷雾干燥、制粉,压制成型,干燥,得到瓷砖干坯;
将釉料淋釉布施在瓷砖干坯表面,在1120-1130℃条件下煅烧15-18℃,冷却,将表面处理剂均匀的涂布在瓷砖表面,干燥后,打磨瓷砖表面至光泽度>85度,得到耐污染的瓷砖。
通过采用上述技术方案,瓷砖煅烧采用低温快烧的方式,将瓷砖煅烧的温度降至1120-1130℃,且煅烧速度较快,仅用时15-18℃,提高了瓷砖在烧结过程中的紧密程度,在提高瓷砖机械性能的同时,提高了瓷砖的耐污染性。
作为优选:所述球磨过程中同时选用粒径为20mm、30mm、40mm和50mm的研磨球,且粒径20mm、30mm、40mm和50mm研磨球的加入配比为(4-5):(2-3):2:1。
通过采用以上技术方案,采用了不同粒径大小的研磨球来球磨瓷砖原料,且小粒径研磨球的用量占比高于其他粒径的研磨球,提高球磨的细度,以提高瓷砖的致密度,进一步防止污水油渍渗透。
作为优选:所述冷却操作包括极冷期和缓冷期,极冷期温度为煅烧温度至900℃,缓冷期温度为900℃至200℃,煅烧温度降至极冷和极冷降至缓冷的降温速率分别为150℃/min和70℃/min。
通过采用上述技术方案,煅烧后冷却经过了极冷期和缓冷期,控制了煅烧温度降至极冷和极冷降至缓冷分别为150℃/min和70℃/min的降温速率,进一步提高了瓷砖的平整度,使瓷砖表面不易储存污水和油渍,提高了瓷砖的耐污性。
综上所述,本申请包括以下至少一种有益技术效果:
(1)本申请通过控制瓷砖各原料种类和掺量,使瓷砖的单位面积油污残余量分别为0.45g/m2,耐污等级为4级,破坏强度为1069N,吸水率最低为0.29%,在保证瓷砖的机械性能的情况下,提高了瓷砖的耐污性。
(2)本申请通过在瓷砖原料表面活性剂中加入全氟辛基磺酰氟、γ-氨丙基三乙氧基硅烷和羟基硅油,使瓷砖的单位面积油污残余量分别为0.40g/m2,耐污等级为5级,进一步提高了瓷砖的耐污染性。
(3)本申请通过在瓷砖原料中加入复合防污剂,并调节各原料种类和掺量,使瓷砖的单位面积油污残余量分别为0.36g/m2,进一步提高了瓷砖的耐污性。
(4)本申请通过在瓷砖制备球磨过程中同时选用粒径为20mm、30mm、40mm和50mm的研磨球,并控制所加入的研磨球配比;控制煅烧后的冷却经过极冷期和缓冷期,极冷期温度为煅烧温度至900℃,缓冷期温度为900至200℃,煅烧温度降至极冷和极冷降至缓冷的降温速率分别为150℃/min和70℃/min,200℃至完全冷却为自然冷却,使瓷砖的单位面积油污残余量分别为0.34g/m2,进一步提高了瓷砖的耐污染性。
具体实施方式
以下结合具体实施例对本申请作进一步详细说明。
本申请中的如下各原料均为市售产品,均为使本申请的各原料得以公开充分,不应当理解为对原料的来源产生限制作用。具体为:钾长石粉,粒径为100目;膨润土,粒径为325目;滑石粉,粒径为425目;铝矾石,粒径为40-70目;瓷石,粒径为60目;石英粉,粒径为800目;釉料,粒径为325目;液态纳米二氧化硅,型号为SP-10Y/15Y1;纳米碳酸钙,粒径为1250目;六偏磷酸钠,有效物质含量99%;氧化锆,粒径40-50nm;羟基硅油,型号为xld-209。
以下为表面处理剂的制备例
制备例1
制备例1的表面处理剂通过如下操作步骤制得:
按照表1的掺量,将γ-氨丙基三乙氧基硅烷、三乙胺和乙醇按体积比1:1.5:2.5的比例混合均匀,滴加全氟辛基磺酰氟,在60℃搅拌2h,蒸馏除去乙醇和三乙胺,得到全氟辛基磺酰氨丙基三乙氧基硅烷;
将全氟辛基磺酰氨丙基三乙氧基硅烷、羟基硅油和液态纳米二氧化硅混合均匀,得到表面处理剂。
制备例2-3
制备例2-3的表面处理剂与制备例1的制备方法及原料种类完全相同,区别在于各原料掺量不同,具体详见表1所示。
表1制备例1-3表面处理剂的各原料掺量
(单位:kg)
以下为复合防污剂的制备例
制备例4
制备例4的复合防污剂通过如下操作步骤制得:
按照表2的掺量,将纳米碳酸钙与六偏磷酸钠混合均匀,得到改性后的纳米碳酸钙;
将改性后的纳米碳酸钙、氢氧化钠和氧化锆与水混合均匀,过滤,收集固体,清洗干燥,球磨,得到复合防污剂。
制备例5-10
制备例5-10的复合防污剂与制备例4的制备方法及原料种类完全相同,区别在于各原料掺量不同,具体详见表2所示。
表2制备例4-10表面处理剂的各原料掺量
(单位:kg)
实施例1
实施例1的耐污染瓷砖通过如下操作步骤而得:
按照表3的掺量,将钾长石粉、膨润土、滑石粉、铝矾土、瓷石和石英粉混合,选用20mm粒径的研磨球球磨,除铁过筛,陈腐均化,喷雾干燥、制粉,水分控制在6%,压制成型,干燥,得到瓷砖干坯;
将釉料淋釉布施在瓷砖干坯表面,在1120℃条件下煅烧15℃,冷却速率为70℃/min,将表面处理剂(液态纳米二氧化硅)均匀的涂布在瓷砖表面,干燥后,打磨瓷砖表面至光泽度为90度,得到耐污染的瓷砖。
实施例2-5
实施例2-5的耐污染瓷砖与实施例1的制备方法及原料种类完全相同,区别在于各原料掺量不同,具体详见表3所示。
表3实施例1-5耐污染瓷砖的各原料掺量
(单位:kg)
实施例6-9
实施例6-9的耐污染瓷砖与实施例3的制备方法及原料种类完全相同,区别在于各原料掺量不同,具体详见表4所示。
表4实施例6-9耐污染瓷砖的各原料掺量
(单位:kg)
原料 | 实施例6 | 实施例7 | 实施例8 | 实施例9 |
钾长石粉 | 38 | 38 | 38 | 38 |
膨润土 | 4.5 | 4.5 | 4.5 | 4.5 |
滑石粉 | 4 | 5 | 4 | 4 |
铝矾土 | 2 | 2 | 2 | 2 |
瓷石 | 13 | 13 | 13 | 13 |
石英粉 | 17 | 17 | 17 | 17 |
釉料 | 2 | 2 | 2 | 2 |
表面处理剂 | 0.1 | 0.1 | 0.2 | 0.3 |
实施例10-12
实施例10-12的耐污染瓷砖与实施例8的制备方法完全相同,区别在于,耐污染瓷砖原料还选用了制备例1-3制备的复合防污剂,且复合防污剂与釉料按体积比1:0.6混合均匀后加入,其余原料种类和掺量与实施例11相同。
实施例13-19
实施例13-19的耐污染瓷砖与实施例11的制备方法完全相同,区别在于,耐污染瓷砖原料选用的制备例4-10制备的表面处理剂,其余原料种类和掺量与实施例11相同。
实施例20
实施例20的耐污染瓷砖与实施例18的原料种类和掺量完全相同,区别在于,球磨过程中同时选用粒径为20mm、30mm、40mm和50mm的研磨球,且粒径20mm、30mm、40mm和50mm研磨球的加入配比为4:3:2:1,其余制备方法与实施例18完全相同。
实施例21
实施例21的耐污染瓷砖与实施例20的原料种类和掺量完全相同,区别在于,冷却经过极冷期和缓冷期,极冷期温度为煅烧温度至900℃,缓冷期温度为900至200℃,煅烧温度降至极冷和极冷降至缓冷的降温速率分别为150℃/min和70℃/min,200℃至完全冷却为自然冷却,其余制备方法与实施例20完全相同。
对比例1
对比例1的耐污染瓷砖与实施例1的制备方法完全相同,区别在于:耐污染瓷砖原料中的钾长石粉替换为等量的石英粉,其余原料及掺量与实施例1相同。
对比例2
对比例2的耐污染瓷砖与实施例1的制备方法完全相同,区别在于:耐污染瓷砖原料中未添加滑石粉,其余原料及掺量与实施例1相同。
对比例3
对比例3的耐污染瓷砖与实施例1的制备方法完全相同,区别在于:耐污染瓷砖原料中表面处理剂选用甲基高含氢硅油,型号为202,其余原料及掺量与实施例1相同。
性能检测
采用如下检测标准或方法分别对不同的实施例1-21和对比例1-3进行性能检测,检测结果详见表5。
单位面积油污残余量:采用GB/T23764《光催化自清洁材料性能测试方法》检测瓷砖的单位面积油污残余量。
耐污等级:采用GB/T3810.14-2016《陶瓷砖试验方法第14部分:耐污染性的测定》对瓷砖的耐污等级进行测定。
破坏强度:采用GB/T3810.4-2006《陶瓷砖试验方法第4部分:断裂模数和破坏强度的测定》对瓷砖进行弯曲强度的测定。
吸水率:采用GB/T3810.3-2006《陶瓷砖试验方法第3部分:吸水率、显气孔率、表观相对密度和容重的测定》对瓷砖进行吸水率测试。
耐磨等级:按照GB/T3810.7-2006进行耐磨试验。经1200转磨损后,评判耐磨等级,具体评判标准为:(1)若瓷砖表面无可见磨损,则进行耐污测试,污染可擦除为5级,不可擦除为4级;(2)若瓷砖表面有可见磨损,耐磨等级为3级。
表5不同耐污染瓷砖的性能检测结果
由表5的检测结果表明,本申请中得到的耐污染瓷砖的单位面积油污残余量最低为0.34g/m2,耐污等级为5级,提高了瓷砖的耐污性;且瓷砖的破坏强度和耐磨等级最高分别为1130N和5级,具有较高耐磨性和强度;且瓷砖的吸水率最低为0.10%,具有一定的防潮性能。表明本申请瓷砖在保证瓷砖的机械性能的情况下,提高了瓷砖的耐污性。
实施例1-5中,实施例3的耐污染瓷砖的单位面积油污残余量分别为0.45g/m2,均优于实施例1-2和实施例4-5;且实施例3瓷砖的破坏强度为1069N,吸水率最低为0.29%,均优于实施例1-2和实施例4-5,表明实施例3瓷砖原料中钾长石粉和其他各原料的掺量较为合适,提高了瓷砖的耐污性,可能是由于钾长石粉有利于胚体在高温煅烧时玻璃相的生成,从而提高瓷砖的瓷化程度,降低胚体的气孔率,减少胚体表面开口,吸附污染物的能力降低,从而提高瓷砖的耐污能力有关。
实施例6-9中,实施例8的耐污染瓷砖的单位面积油污残余量分别为0.44g/m2,耐污等级为5级,均优于实施例6-7和实施例9;且实施例8瓷砖的破坏强度为1082N,吸水率最低为0.27%,均优于实施例6-7和实施例9,表明实施例8瓷砖原料中滑石粉和表面处理剂的掺量较为合适,提高了瓷砖的耐污性,可能是由于滑石粉可有效促进瓷砖的烧结,提高瓷砖内部结构的紧密程度,降低孔隙率,从而提高瓷砖的防污性以及表面处理剂降低瓷砖的表面能有关。
实施例10-12中,实施例11的耐污染瓷砖的单位面积油污残余量分别为0.40g/m2,均优于实施例10和实施例12;且实施例11瓷砖的破坏强度为1086N,吸水率最低为0.25%,均优于实施例10和实施例12,表明在瓷砖原料中表面处理剂中的液态纳米二氧化硅掺量较为合适,提高了瓷砖的耐污性,可能是由于液态纳米二氧化硅可降低瓷砖的表面能,表面能低可以阻止尘埃、微生物、水性物、颗粒等的吸附,在外力作用下易脱附,具有超强的自洁耐沾污性能有关。
实施例13-15中,实施例14的耐污染瓷砖的单位面积油污残余量分别为0.38g/m2,均优于实施例13和实施例15;且实施例14瓷砖的破坏强度为1110N,吸水率最低为0.17%,均优于实施例13和实施例15,表明在瓷砖原料中复合防污剂中的纳米碳酸钙掺量较为合适,提高了瓷砖的耐污性,可能是由于加入纳米碳酸钙,在瓷砖烧结的过程中年度增加,产生的细小气泡靠表面张力聚集到一起形成大气泡浮上液面排出形成大量的大针孔,在通过表面处理剂填平大针孔,表面处理剂收缩后会形成很浅的凹面,当瓷砖表面遇到污水或油渍时,瓷砖表面受到外力,污水或油渍更易排出,提高瓷砖的耐污性能有关。
实施例16-19中,实施例18的耐污染瓷砖的单位面积油污残余量分别为0.36g/m2,均优于实施例16-17和实施例19;且实施例18瓷砖的破坏强度为1124N,吸水率最低为0.14%,均优于实施例16-17和实施例19,表明在瓷砖原料中复合防污剂中的氢氧化钠和氧化锆的掺量较为合适,提高了瓷砖的耐污性,可能是由于加入氢氧化钠,可与瓷砖表面的油脂反应生成可溶性的肥皂,使瓷砖表面的油污更易去除。加入氧化锆可提高釉料的红外辐射性能,从而提高瓷砖的烧结效果,使釉料结构更加致密,表面不容易附着污物有关。
结合实施例18和实施例20-21瓷砖的性能检测数据发现,实施例20的耐污染瓷砖的单位面积油污残余量分别为0.35g/m2,均优于实施例18;且实施例20瓷砖的破坏强度为1127N,吸水率最低为0.12%,均优于实施例18,表明当在瓷砖制备球磨过程中同时选用粒径为20mm、30mm、40mm和50mm的研磨球,且粒径20mm、30mm、40mm和50mm研磨球的加入配比为4:3:2:1,可进一步提高瓷砖的耐污性。实施例21的耐污染瓷砖的单位面积油污残余量分别为0.34g/m2,均优于实施例20;且实施例21瓷砖的破坏强度为1130N,吸水率最低为0.10%,均优于实施例20,表明当煅烧后冷却经过极冷期和缓冷期,极冷期温度为煅烧温度至900℃,缓冷期温度为900至200℃,煅烧温度降至极冷和极冷降至缓冷的降温速率分别为150℃/min和70℃/min,200℃至完全冷却为自然冷却,可进一步提高瓷砖的烧结性,从而提高瓷砖的耐污染性。
结合对比例1-3和实施例1瓷砖的性能检测数据发现,在瓷砖原料中加入钾长石粉、滑石粉和表面处理剂,均不同程度的提高了瓷砖的耐污染性。
本具体实施例仅仅是对本申请的解释,其并不是对本申请的限制,本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改,但只要在本申请的权利要求范围内都受到专利法的保护。
Claims (10)
1.一种耐污染瓷砖,其特征在于,其包括如下重量份原料:钾长石粉35-40份、膨润土3-6份、滑石粉3-5份、铝矾石1-3份、瓷石10-15份、石英粉16-18份、釉料1-3份和表面处理剂0.1-0.3份;所述表面处理剂为液态纳米二氧化硅。
2.根据权利要求1所述的耐污染瓷砖,其特征在于,其包括如下重量份原料:钾长石粉37-39份、膨润土3.5-5.5份、滑石粉3.5-4.5份、铝矾石1.5-2.5份、瓷石12-14份、石英粉16.5-17.5份、釉料1.5-2.5份和表面处理剂0.15-0.25份。
3.根据权利要求1所述的耐污染瓷砖,其特征在于:所述瓷砖原料中还包括2-4重量份的复合防污剂,所述复合防污剂与釉料按体积比1:(0.4-0.8)混合均匀后加入;所述复合防污剂包括如下重量份原料:纳米碳酸钙8-12份、六偏磷酸钠0.5-1.5份、氢氧化钠1-5份、氧化锆1-3份。
4.根据权利要求3所述的耐污染瓷砖,其特征在于,所述复合防污剂采用以下步骤制备得到:
将纳米碳酸钙与六偏磷酸钠混合均匀,得到改性后的纳米碳酸钙;
将改性后的纳米碳酸钙、氢氧化钠和氧化锆混合均匀,得到复合防污剂。
5.根据权利要求1所述的耐污染瓷砖,其特征在于,所述表面处理剂还包括如下重量份原料:全氟辛基磺酰氟0.5-0.7份、γ-氨丙基三乙氧基硅烷0.3-0.5份、羟基硅油0.2-0.4份。
6.根据权利要求5所述的耐污染瓷砖,其特征在于,所述表面处理剂采用以下操作步骤制备得到:
将γ-氨丙基三乙氧基硅烷、三乙胺和乙醇按体积比1:(1-2):(2-3)的比例混合均匀,滴加全氟辛基磺酰氟,在60℃搅拌2h,蒸馏除去乙醇和三乙胺,得到全氟辛基磺酰氨丙基三乙氧基硅烷;
将全氟辛基磺酰氨丙基三乙氧基硅烷、羟基硅油和液态纳米二氧化硅混合均匀,得到表面处理剂。
7.根据权利要求1所述的耐污染瓷砖,其特征在于:所述瓷砖还包括0.4-0.8重量份的十二烷基苯磺酸钠和0.3-0.5重量份的月桂酸钠;所述十二烷基苯磺酸钠和月桂酸钠加入前先与滑石粉混合均匀,并调节pH为11.5。
8.一种权利要求1-7任一所述的耐污染瓷砖的生产工艺,其特征在于,包括以下操作步骤:
将瓷砖除釉料和表面处理剂的其余原料混合,球磨,除铁过筛,陈腐均化,喷雾干燥、制粉,压制成型,干燥,得到瓷砖干坯;
将釉料淋釉布施在瓷砖干坯表面,在1120-1130℃条件下煅烧15-18℃,冷却,将表面处理剂均匀的涂布在瓷砖表面,干燥后,打磨瓷砖表面至光泽度>85度,得到耐污染的瓷砖。
9.根据权利要求8所述的耐污染瓷砖的生产工艺,其特征在于:所述球磨过程中同时选用粒径为20mm、30mm、40mm和50mm的研磨球,且粒径20mm、30mm、40mm和50mm研磨球的加入配比为(4-5):(2-3):2:1。
10.根据权利要求8所述的耐污染瓷砖的生产工艺,其特征在于:所述冷却操作包括极冷期和缓冷期,极冷期温度为煅烧温度至900℃,缓冷期温度为900℃至200℃,煅烧温度降至极冷和极冷降至缓冷的降温速率分别为150℃/min和70℃/min。
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