CN103508737B - 氧化铝在陶瓷产品且特别是面砖的制造中作为遮光剂的用途 - Google Patents

氧化铝在陶瓷产品且特别是面砖的制造中作为遮光剂的用途 Download PDF

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CN103508737B
CN103508737B CN201310190397.0A CN201310190397A CN103508737B CN 103508737 B CN103508737 B CN 103508737B CN 201310190397 A CN201310190397 A CN 201310190397A CN 103508737 B CN103508737 B CN 103508737B
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aluminium oxide
granule
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weight
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CN103508737A (zh
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纳塔莉·马丁内斯
埃里克·帕潘
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Alteo Gardanne SAS
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Abstract

本发明涉及氧化铝颗粒在经受陶瓷产品制造中的烧结操作的组合物中的用途,以便在所述陶瓷产品中获得遮光效果,其特征在于所用的氧化铝颗粒表现出小于96%的α‑氧化铝重量百分比,以及通过Brunauer,Emmett和Teller(BET)技术在氮气下测得的大于或等于1平方米/克的比表面积。

Description

氧化铝在陶瓷产品且特别是面砖的制造中作为遮光剂的用途
技术领域
本发明涉及陶瓷领域并特别涉及面砖(tiling)。更具体而言,本发明的主题是特定氧化铝在陶瓷产品制作过程中为获得令人满意的遮光效果的用途。
背景技术
在众多陶瓷产品,也就是说通过热处理不同的氧化物混合物且特别是金属氧化物和/或二氧化硅获得的产品中,出于多种原因必须使用遮光材料。这特别是用于制作瓷器(porcelain)、浴室釉料和面砖且特别是诸如炻器(stoneware)、瓷炻器(porcelainstoneware)和瓷砖(porcellanato)的面砖(其主要应用于地面砖和墙面砖)的情况。
面砖通常由三部分组成:充当支承面砖的砖体、沉积在砖体上的釉底料、以及沉积在釉底料上的釉料。釉底料具有双重作用:遮光,以遮盖支撑面砖的颜色,以及赋予面砖不可渗透性,以防止水出现到面砖的表面。釉底料还构成中间层,所述中间层能够防止在釉料与砖体之间发生化学相互作用。
釉料就其本身而言对装饰具有至关重要的作用。构成面砖上表面的釉料除了有助于装饰之外,还特别要耐受污渍、磨损和机械冲击。
某些面砖仅由砖体组成。在这种情况下,砖体还必须特别要耐受污渍、磨损和机械冲击。
在所有的情况下,遮光剂用于面砖的所有组成部分中。
在仅由砖体组成的面砖中,遮光剂还具有赋予面砖白度的作用。在釉底料中,遮光剂的基本作用是遮光。在釉料中,遮光剂的基本作用是遮光和贡献白度。
目前用于陶瓷产品,如面砖的主要遮光剂是锆石ZrSiO4。锆石的极高折射率(1.92)使其成为遮光剂的选择。炻器类型的面砖具有基于粘土、基于长石和基于石英的组成。使用如锆石的遮光剂对白色炻器而言是首先必须的,该白色炻器也经常包含本身对白度有贡献的高岭土。例如,“超白(ultrawhite)”面砖包含5至8%的锆石,“极白(superwhite)”面砖包含3至5%的锆石,“白”面砖包含1至3%的锆石。在釉底料与釉料中,组成通常可以包含8至15%的锆石。
锆石类型的遮光剂的使用在用于浴室装置和陶瓷餐具的陶瓷釉料中也是必需的。
但是,由于锆石的价格,其在供需不平衡的作用下已经变得非常高,如今使用锆石被强烈质疑。作为举例说明,该价格在四年中提高了三倍,并代表陶瓷产品制造商的主要制约因素。由此在寻找替代解决方案方面存在着非常强大的优势。
因其折射率,已经设想到作为遮光剂的另一种氧化物是二氧化钛。但是,二氧化钛在市场上同样短缺,其成本非常高。
至于在陶瓷组合物中使用氧化铝,应当提及专利申请WO2011/030366,其描述了从阴极管回收玻璃的方法,其中将该玻璃引入到陶瓷组合物中。由于添加玻璃的结果是提高了该组合物的可熔性和提高其透明度,推荐使用氧化铝作为遮光剂以补偿这两种现象。在这些具体组合物中,其包含10至50重量%的来自于阴极管的玻璃,遮光剂的优选含量为15至25重量%。该专利申请没有以任何方式描述所用的氧化铝,也没有明确记载为获得所需的遮光效应其应当具备的优选特性。
氧化铝还没有用于充当遮光剂,而是充当颜料。这特别是在文献GB1286003中和在出版物Journal of the European Ceramic Society,第22卷,第5期,,2002,第631-633页和Dyes and Pigments,第76卷,第1期,2007,第179-186页中的情况。
发明内容
在本发明中,发明人已着手研究在陶瓷产品如面砖的制作中使用氧化铝Al2O3作为遮光剂。
氧化铝的折射率(其为1.7)并不能使氧化铝成为遮光剂的好的候选,但是本发明人已经证明,通过选择特定的氧化铝,可能改善其遮光功率,甚至在某些情况下获得可与锆石相当的遮光效果。
在本文中,本发明涉及氧化铝Al2O3颗粒在经受陶瓷产品制造中的烧结操作的组合物中的用途,以便在所述陶瓷产品中获得遮光效果,所用的所述氧化铝Al2O3颗粒表现出小于96%的α-氧化铝的重量百分比和大于或等于1平方米/克的通过Brunauer、Emmett和Teller(BET)技术在氮气下测得的比表面积。
本发明针对的氧化铝作为遮光剂的用途与化合物作为颜料的用途不同。
这是因为颜料将陶瓷染色,然而在本发明中,氧化铝用于对陶瓷产品遮光并由此赋予其不透明性,也就是说其能够阻止光的通过。
在本发明中可以使用的氧化铝可以有利地通过采用下列主要阶段并因其发明人姓名而被称作Bayer法的方法来制备:
-用氢氧化钠在温度与压力下化学侵蚀铝土矿以溶解铝土矿中存在的氧化铝,
-将溶解在氢氧化钠溶液中的氧化铝与其它组分分离,
-由溶解在氢氧化钠溶液中的氧化铝沉淀水合氧化铝,
-在相对高的温度下煅烧获得的水合氧化铝。在该煅烧阶段中,氧化铝脱水,残余氢氧化钠的含量降低,并且氧化铝根据以所用的温度与煅烧时间为函数的不同结晶相结晶,
-如果需要的话,研磨以降低晶粒的尺寸。
此类方法的进一步细节可参考例如“Alumina Chemicals,Science&TechnologyHandbook”,L.D.Hart编辑,2006年3月和B.Castel,“Les alumines et leursapplications”[氧化铝和它们的应用],Aluminium Pechiney,Techno Nathan,1990。
α-氧化铝是氧化铝的最稳定的结晶相。α-氧化铝相应于氢氧化铝(无论它们是何种氢氧化铝)热分解以得到纯的结晶氧化物Al2O3的最终阶段。其通过它的结晶结构来限定,其中氧原子安置在六方密堆积(compact hexagonal stack)中,并容易地通过X射线衍射表征。特别地,α-氧化铝在X射线衍射(XRD)中通过存在以下峰来表征,其主峰对应于等于以下值的2θ值: 在ASTM10-173表格中对α-氧化铝进一步给出了这些2θ值,进一步的细节可以参考。α-氧化铝的含量基本上取决于煅烧温度。其还在较低程度下取决于通常使用的煅烧添加剂,如氟。
特别地,表现出所需的α-氧化铝含量和高比表面积的氧化铝可以通过在大约900℃至1300℃的温度范围下进行煅烧10分钟至2小时的时间来获得。在高于1300℃的温度下煅烧氧化铝特别是多于30分钟,表现出更大的α-氧化铝含量。
在本发明中使用的氧化铝表现出高α-氧化铝含量,剩余部分由同样具有式Al2O3但是为非晶态形式或为表现出另一种晶体或弱结晶结构的“过渡”形式的氧化铝构成。在本发明中,所用氧化铝有利地包含20至96重量%的α-氧化铝Al2O3,优选50至90重量%,这些重量百分比相对于所用氧化铝的总重量给出。采用此α-氧化铝含量,对制得的陶瓷产品所获得的不透明外观非常令人满意。
α-氧化铝的重量百分比可以通过X射线衍射测定。该百分数可以由2θ=29.8°和2θ=67.9°的角度下α-氧化铝的(002)晶格面的峰面积来获得。特别是可以使用实施例中详细描述的方法。
在陶瓷产品上获得的遮光效果可以由使用分光光度计测得的色度坐标(L*、a*、b*)评估。此类色度坐标特别定义在CIELAB标准(Commission Internationale de l’Eclairage,1976)中,其定义了通过L*、a*、b*坐标表示颜色的模式。如果获得的陶瓷产品的L*值大于76,优选L*值大于80,则遮光效果将被认为是令人满意的。
优选地,所用的氧化铝Al2O3颗粒表现出通过BET技术在氮气下测得的1至80平方米/克和优选3至15平方米/克的比表面积。对于所用氧化铝具有此比表面积,氧化铝晶粒是细分散的,并分散在组合物中,这有促进了它们作为遮光剂的效力;此外,经受烧结操作的组合物更易于使用。用于测量比表面积的参考技术是标准NF X11621中描述的技术。
在本发明中,能够在陶瓷产品制造中经受烧结操作的现有技术已知的现有组合物中使用氧化铝取代锆石而不改变尤其是烧结温度是有利的。当采用Mie理论通过激光衍射由颗粒的体积粒径分布获得的所用氧化铝颗粒的D90小于45微米时,这尤其是可能的。就D50而言,优选小于10微米。可以由在蒸馏水中的悬浮液获得粒径分布,所述悬浮液包含1体积%的分散剂,如丙烯酸共聚物(例如Coatex GX)和使得能够获得5至15%的遮蔽程度的一定量的氧化铝,该溶液经受超声处理以获得令人满意的分散。可以采用下列折射率:分散介质的折射率为1.33,氧化铝为1.760,虚数指数(imaginary index)为0.1。可以使用例如装有632.8纳米下的He-Ne激光器的Malvern Mastersizer S设备。进一步的细节可以参照实施例中详细描述的技术。
优选使用氧化物粉末,其D90小于25微米。就D50而言,优选小于5微米。
为了获得此粒径,根据本发明使用的氧化铝可以通过根据本领域技术人员已知的任何常规技术的研磨与筛分操作来获得。
本发明尤其可用于制造面砖、制造浴室水槽、浴盆或厕所类型的浴室部件、或制造陶瓷餐具、制造碟或盘类型等等。特别地,本发明特别适于选自炻器、瓷炻器和瓷砖的面砖。本文中所述的氧化铝的用途特别适用于地面砖和用于墙壁的面砖。
可以使用氧化铝Al2O3颗粒以便在面砖的砖体中获得遮光效果。在这种情况下,在经受面砖砖体制造中的烧结操作的组合物中,所用的氧化铝Al2O3颗粒通常与粘土、长石和石英混合。由于遮光效果对轻质面砖(light tilings)或白面砖而言通常是非常需要的,经受面砖砖体制造中的烧结操作的组合物除粘土、长石和石英之外还包含高岭土。
通常,相对于组合物总重量以重量%表示,此类组合物包含30至40%的粘土、45至60%的长石、3至15%的石英和5至20%的高岭土。
在本发明中,还可使用氧化铝Al2O3颗粒以便在面砖的釉底料和/或面砖的釉料中获得遮光效果。在这种情况下,在经受面砖的釉底料和/或面砖的釉料制造中的烧结操作的组合物中,所用的氧化铝Al2O3颗粒与粘土、长石、玻璃料和高岭土混合。玻璃料通常包含SiO2、B2O3、Al2O3、CaO、MgO、ZnO和ZrO2的混合物。
有利地,在本发明中,为获得遮光效果而使用的氧化铝颗粒占经受烧结操作的组合物的超过5重量%,通常为组合物的5至15重量%。作为比较,在现有技术的面砖中,在经受烧结的组合物中常规上以3至15重量%的比例使用遮光剂(其通常排它地由锆石组成)。
还已经发现,在制造面砖和特别是制造面砖砖体的情况下,对于经受烧结操作的组合物来说优选的是包含比现有技术中使用的锆石重量大至少50重量%的氧化铝颗粒。
最经济的方案使用包含锆石ZrSiO4的组合物(该组合物将经受陶瓷产品制造中的烧结操作),该锆石ZrSiO4相对于该组合物总重量以重量%为单位为少于0.5重量%,并且所述组合物优选根本不包含锆石。
根据本发明的备选实施方式,为获得遮光效果而使用的氧化铝Al2O3颗粒在混入经受烧结操作(在陶瓷产品的制造过程中)的组合物之前与选自TiO2、ZnO、锆石(ZrSiO4)和ZrO2的白色颜料混合。为此,氧化铝和白色颜料可经受共研磨阶段,该阶段使得能够获得紧密混合物。当使用氧化铝Al2O3颗粒以便在面砖的釉底料和/或面砖的釉料或其它陶瓷釉料中获得遮光效果时,此备选形式是特别合适的。有利地,在将氧化铝Al2O3颗粒混入经受烧结操作(在制造陶瓷产品的过程中)的组合物之前,将为获得遮光效果而使用的氧化铝Al2O3颗粒与TiO2混合,按重量计的TiO2/氧化铝含量为0.05至5%。
按照本发明的另一备选实施方式,其可以与前述实施方式结合,为获得遮光效果而使用的氧化铝Al2O3颗粒在经受烧结操作的组合物中与有机分散剂混合,所述有机分散剂选自例如聚丙烯酸、铵或钠的聚丙烯酸盐和聚甲基丙烯酸盐、油酸甘油酯、聚乙烯亚胺、磷酸酯、鱼油、或铵或钠的三聚磷酸盐和偏硅酸盐。优选使用三聚磷酸钠和/或偏硅酸钠。将氧化铝颗粒并入到陶瓷产品制造过程中经受烧结操作的组合物之前,可以将氧化铝颗粒与此类分散剂混合。
在制造面砖的情况下,本发明中描述的氧化铝颗粒的使用可用于仅仅在砖体中,或仅仅在面砖的釉底料和/或釉料中,或同时在砖体中、在所述面砖的釉料中和在釉底料中获得遮光效果。
通常,对本文中所述的包含氧化铝的组合物施以在950℃至1250℃的温度范围下进行的烧结操作。常规上,此类操作在通过空气中的热处理逐渐升温至所选的烧结温度后进行特别是5分钟至2小时的时间,该时间特别是作为固结的陶瓷产品的厚度的函数。
在烧结操作之前,该组合物可以以含水悬浮液形式制备,在制造面砖类型的整块产品的情况下,其可以雾化和压实,或者在制造釉底料或釉料的情况下,其可以散布在载体上。
已经以应用的形式描述了本发明,但是应当理解的是,给出的描述,以所有能想到的备选形式,还涉及通过烧结包含氧化铝Al2O3颗粒的组合物制造陶瓷产品的方法,所述氧化铝Al2O3颗粒表现出小于96%的α-氧化铝重量比和大于1平方米/克的通过Brunauer、Emmett和Teller(BET)技术在氮气下测得的比表面积,并且给出的描述还涉及能够通过此类方法获得的陶瓷产品。此类氧化铝用作遮光剂。
本发明中描述的不同的备选实施方式同样出色地应用于所述氧化铝的用途、应用于使用此类氧化铝制备陶瓷产品的方法和应用于用此类氧化铝获得的陶瓷产品。
具体实施方式
下面的实施例能够例示本发明但不具有任何限制性。
表征方法
I.通过X射线衍射测量α相的含量
原理:测量在2θ=29.8°和2θ=67.9°的角度下被α-氧化铝的(002)晶格面衍射的X射线束的积分净强度。
在选择的方法中,关于6点校正曲线测定α相的含量。用100%的α-氧化铝与不同含量的水合氧化铝的混合物进行选择以构建校正曲线。α相的含量以重量%表示,并通过下式给出:
α含量=a×Sn+b,
其中Sn是在2θ=29.36-30.18和2θ=67.32-68.55的范围内的衍射峰面积,
a是校正曲线的斜率,
b是原点处的纵坐标。
α相的含量对应于两次计算的平均。
设备:装有X射线管的Philips X’型号Pert MPD X射线衍射仪,具有发射波长的射线的钴对阴极。
II.通过BET法测量比表面积
一般原理:BET(Brunauer,Emmett,Teller)方法。参考标准:NF X11621。
样品在200℃下在减压下脱气。设定样品脱气的持续时间,直到测得的降低的压力低于或等于50毫托。
所用装置是全自动的Micromeritics Tristar3000。所用试剂是氮气。引入的粉末的量为大约2克,并用精密天平测量。
III.通过激光衍射测量粒径分布
设备:Malvern Mastersizer S,装有632.8纳米下的He-Ne激光器。
运行参数:
-湿路线(蒸馏水),
-泵速度和搅拌速度:设定在标度的70%,
-分散剂:在蒸馏水中以1体积%添加Coatex GX(丙烯酸共聚物)分散剂+超声(100%功率,持续时间30秒),
-测量时间:30000次扫描,
-5至15%的遮蔽度,
-光学模型:根据Mie理论并入装置的数学模型,分散介质的折射率为1.33,氧化铝的折射率为1.760,虚数指数为0.1。
结果的表示:%是指体积%,
D10<X微米:表示颗粒的10%具有小于X微米的直径,
D50<Y微米:表示颗粒的50%具有小于Y微米的直径,
D90<Z微米:表示颗粒的90%具有小于Z微米的直径。
IV.色度测量
使用具有Minolta CM3610D商品名的分光光度计进行这些测量。
所用产品
氧化铝A:由Rio Tinto Alcan以AC34为名销售,
氧化铝B:由Rio Tinto Alcan以AC44为名销售,
氧化铝C:通过在1150℃下煅烧水合氧化铝合成,固定期(stationary phase)为30分钟,不使用添加剂,
氧化铝D:由Rio Tinto Alcan以AR75为名销售,
“Ukraine clay”粘土,由Imerys供应,
“Turkish floated feldspar”长石,由Esan供应,
高岭土,由Imerys供应,
锆石(用于对比试验),由Endeka供应。
砖体/面砖
实施例1:
试验了已经经受不同煅烧的不同的氧化铝。特性显示在下表1中。
表1
所用的面砖砖体的组成(重量%):
粘土: 30%
长石: 50%
高岭土: 15%
遮光剂(氧化铝或用于对比试验的锆石):5%
制造方法:
在行星式球磨机中混合粘土与高岭土原材料,直到混合物通过筛目开口为1毫米的筛。
接着,在包含氧化铝球的旋转罐中,除了遮光剂以外的所有原材料,以及分散剂以有效的比例在蒸馏水中(50%干物质)混合,直到采用40微米筛达到1%的最大筛上物。在研磨结束前1分钟,加入遮光剂(氧化铝或锆石)。分散剂是在水中以75%的干物质制备的包含25重量%的三聚磷酸钠和75重量%的偏硅酸钠的混合物,相对于无机物总量以0.3重量%引入。在这阶段,测量悬浮液的粘度。使用Gallenkamp粘度计测量粘度。通过粘度的测量绘制反絮凝曲线,引入不同含量的分散剂的混合物(25%的三聚磷酸钠和75%的偏硅酸钠)。
将悬浮液干燥。粉末随后压缩,以达到大约1.9克/立方厘米的未焙烧状态下的密度。
面砖随后在静电炉(static electric furnace)中以25℃/分钟的升温速率在各种情况下烧结至不同的烧结温度,并保持6分钟。最佳烧结温度对应于最大密度。与密度测量值耦合的温度扫描给出了表2中显示的下列最佳温度:
表2
粉末 A B C D 锆石
温度(℃) 1219 1219 1222 1226 1215
对这些条件下制备的面砖进行色度坐标测量。
遮光剂的效力通过在成品面砖上使用分光光度计测得的色度坐标(L*、a*、b*)来测定。
所述氧化铝颗粒A、B、C和D的遮光效果相应于CIELAB标准(CommissionInternationale de l’Eclairage,1976)中定义的L*值如下所示:
A B C D 锆石
L*值 79 79 83.1 82.8 83.6
结果:
-高度煅烧类型的氧化铝A和B并未贡献足以与锆石竞争的遮光效果。
-氧化铝D的遮光贡献令人满意,但是表现出加工困难,悬浮液的流变特性非常不同并且难以解决。其还存在压缩的问题。这可能与其极高的比表面积有关。
-氧化铝C贡献与锆石相当的遮光效果,同时具有类似的加工特性;其因此符合最佳选择。由于微细颗粒的良好分散,其高遮光效果是确定无疑的。
确定的副作用:
用氧化铝取代锆石导致燃烧温度(firing temperature)的变化,其变得更高,这一现象是由于氧化铝更大的耐火性。在实施例2中,进行研究以试图避免这一变化,因为燃烧温度的变化对陶瓷产品制造商来说会导致面砖、釉底料和釉料的特性的变化,还会带来相容性的问题。例如,如果燃烧温度改变,难以控制面砖的平坦度。由于面砖/釉底料/釉料组件的开发非常复杂,当用氧化铝取代锆石时保持燃烧温度尽可能接近是关键的,从而避免改变特别是组合物中使用的组分与比例。此外,燃烧温度的改变会导致相应于更高孔隙率的较低的烧成后密度,这会产生渗透性和对污渍的耐受性的问题。
实施例2:
已经比较了由表现出不同研磨程度,由此表现出不同的粒径分布(以微米为单位)的类型C的氧化铝形成的几种粉末。在表3中给出了在各种情况下获得的D10、D50、D90和D97值。
表3
所用的面砖砖体的组成:
-使用锆石作为遮光剂(对比试验):与实施例1中相同的组成,
-使用氧化铝作为遮光剂:重量百分比形式的组成
粘土: 29.2%
长石: 48.7%
高岭土: 14.6%
氧化铝: 7.5%
制造方法:与实施例1的制造方法相同,使用表4中给出的下列最佳烧结温度。
表4
粉末 温度(℃)
C1 1225
C2 1216
C3 1207
C4 1207
C5 1208
C6 1208
锆石 1208
获得的结果表明:
-能够获得最大密度并由此获得最小孔隙率的所用燃烧温度与粉末的粒径直接相关,
-关键之处在于限制最大的颗粒(D90和低D97),其导致在压缩结束时的大的孔隙,这难以在燃烧过程中除去。
釉底料和釉料
实施例1:
试验了上文用于制备面砖砖体并已经经受不同的煅烧的不同氧化铝,其特性在下表5中重新描述。
表5
制备方法:
以70%的干物质在30%的水中(相对于悬浮液总重量的重量百分比)通过湿研磨在包括氧化铝球的旋转罐中制备悬浮液。设定研磨时间以达到采用40微米筛最多1%的筛上物。
相对于组合物的干物质总含量以重量百分比表示的组成(由于分散剂是在燃烧时消失的有机材料,作为无机材料的组合物对应于100%,并且分散剂的含量相对于无机材料的总重量来表示):
-80%的透明玻璃料,
-7%的高岭土,
-13%的氧化铝,
-0.3%(相对于无机材料含量按重量计)的羧甲基纤维素钠,
-0.3%(相对于无机材料含量按重量计)的三聚磷酸钠。
所用玻璃料按重量百分比计包含58.1%的SiO2、8.1%的Al2O3、8.6%的B2O3、7.5%的CaO、2.7%的MgO、4.7%的Na2O、3.1%的K2O、6.45%的ZrO2和0.15%的ZnO作为主要成分。
使用刮刀将悬浮液沉积在未燃烧的(因此是多孔的)支承面砖上,调节至沉积500微米厚度。样品随后在电炉中在110℃干燥,并随后以25℃/分钟的升温速率在所需温度下烧结,在所选的最终温度下的静止期为6分钟。在测试氧化铝A、B、C和D的情况下,测试的燃烧温度分别为1080、1100、1120和1140℃。
结果:
-氧化铝A和B的遮光能力太低以致于无法与锆石竞争,
-氧化铝D能够获得比氧化铝A和B更好的遮光效果,但是获得了外观非常暗淡的多孔釉料,
-氧化铝C表现出在遮光效果方面的良好结果,并构成了最佳的妥协。
确定的副作用:
获得的白色比使用锆石的白色“更冷”,也就是说略带蓝色,而锆石获得更温的颜色,偏黄色。
实施例2:
将氧化铝C的使用与氧化铝C’比较,所述氧化铝C’通过将氧化铝C与加入的0.35重量%(相对于组合物干物质总含量按重量百分比计)的TiO2共同研磨而制备。
结果:
在两种情况下,获得的遮光效果相同。另一方面,在使用氧化铝C’的情况下,获得的白色更好地符合用锆石获得的白色。

Claims (26)

1.氧化铝Al2O3颗粒在经受陶瓷产品制造中的烧结操作的组合物中的用途,以便在所述陶瓷产品中获得遮光效果,其特征在于所用的氧化铝Al2O3颗粒由氧化铝组成并且表现出小于96%的α-氧化铝重量百分比,以及通过Brunauer,Emmett和Teller(BET)技术在氮气下测得的大于或等于1平方米/克的比表面积;并且其特征在于使用所述氧化铝颗粒以便在获得的陶瓷产品上获得遮光效果,所述遮光效果是指CIELAB标准(Commission Internationalede l’Eclairage,1976)中定义的L*值大于76。
2.如权利要求1所述的用途,其特征在于所用的氧化铝Al2O3包含20至96重量%的α-氧化铝。
3.如权利要求1所述的用途,其特征在于所用的氧化铝Al2O3包含50至90重量%的α-氧化铝。
4.如前述权利要求之一所述的用途,其特征在于所用的氧化铝Al2O3颗粒表现出1至80平方米/克的通过BET技术在氮气下测得的比表面积。
5.如权利要求4所述的用途,其特征在于所用的氧化铝Al2O3颗粒表现出3至15平方米/克的通过BET技术在氮气下测得的比表面积。
6.如权利要求1-3和5中任一项所述的用途,其特征在于采用Mie理论通过激光衍射由所述颗粒的体积粒径分布获得的所用的氧化铝颗粒的D90小于45微米。
7.如权利要求1-3和5中任一项所述的用途,其特征在于采用Mie理论通过激光衍射由所述颗粒的体积粒径分布获得的所用的氧化铝颗粒的D50小于10微米。
8.如权利要求1-3和5中任一项所述的用途,其特征在于采用Mie理论通过激光衍射由所述颗粒的体积粒径分布获得的所用的氧化铝颗粒的D90小于25微米,采用Mie理论通过激光衍射由所述颗粒的体积粒径分布获得的所用的氧化铝颗粒的D50小于5微米。
9.如权利要求1-3和5中任一项所述的用途,其特征在于所述陶瓷产品选自面砖、浴室组件和陶瓷餐具。
10.如权利要求1-3和5中任一项所述的用途,其特征在于所述陶瓷产品是面砖,所述面砖选自炻器、瓷炻器和瓷砖。
11.如权利要求1-3和5中任一项所述的用途,其特征在于使用所述氧化铝Al2O3颗粒以便在面砖砖体中获得遮光效果。
12.如权利要求1-3和5中任一项所述的用途,其特征在于在经受面砖砖体制造中的烧结操作的组合物中,所述氧化铝Al2O3颗粒作为与粘土、长石和石英的混合物使用。
13.如权利要求1-3和5中任一项所述的用途,其特征在于在经受面砖砖体制造中的烧结操作的组合物中,所述氧化铝Al2O3颗粒作为与粘土、长石、石英和高岭土的混合物使用。
14.如权利要求13所述的用途,其特征在于相对于组合物的总重量以重量%表示,所述组合物包含30至40%的粘土、45至60%的长石、3至15%的石英和5至20%的高岭土。
15.如权利要求1-3、5和14中任一项所述的用途,其特征在于使用所述氧化铝Al2O3颗粒以便在面砖的釉底料和/或面砖的釉料中获得遮光效果。
16.如权利要求15所述的用途,其特征在于在经受面砖的釉底料和/或面砖的釉料制造中的烧结操作的组合物中,所述氧化铝Al2O3颗粒作为与粘土、长石、玻璃料和高岭土的混合物使用。
17.如权利要求1-3、5、14和16中任一项所述的用途,其特征在于所用的氧化铝颗粒占经受烧结操作的组合物的超过5重量%。
18.如权利要求17所述的用途,其特征在于所用的氧化铝颗粒占经受烧结操作的组合物的5至15重量%。
19.如权利要求1-3、5、14、16和18中任一项所述的用途,其特征在于在为获得遮光效果而使用的氧化铝颗粒混入陶瓷产品制造过程中经受烧结操作的组合物之前,将所述氧化铝颗粒与选自TiO2、ZnO、锆石和ZrO2的白色颜料混合。
20.如权利要求1-3、5、14、16和18中任一项所述的用途,其特征在于为获得遮光效果而使用的氧化铝颗粒混入陶瓷产品制造过程中经受烧结操作的组合物之前,将所述氧化铝颗粒与TiO2混合,按重量计,TiO2/氧化铝含量为0.05至5%。
21.如权利要求1-3、5、14、16和18中任一项所述的用途,其特征在于为获得遮光效果而使用的氧化铝Al2O3颗粒混入陶瓷产品制造过程中经受烧结操作的组合物之前,将所述氧化铝Al2O3颗粒与有机分散剂混合,所述有机分散剂选自聚丙烯酸、铵或钠的聚丙烯酸盐和聚甲基丙烯酸盐、油酸甘油酯、聚乙烯亚胺、磷酸酯、鱼油、或铵或钠的三聚磷酸盐和偏硅酸盐。
22.如权利要求1-3、5、14、16和18中任一项所述的用途,其特征在于使用所述的氧化铝Al2O3颗粒以便同时在面砖的砖体中、釉料中和釉底料中获得遮光效果。
23.如权利要求1-3、5、14、16和18中任一项所述的用途,其特征在于相对于组合物的总重量以重量百分比表示,经受陶瓷产品制造中的烧结操作的组合物包含小于0.5重量%的锆石。
24.如权利要求1-3、5、14、16和18中任一项所述的用途,其特征在于经受陶瓷产品制造中的烧结操作的组合物不包含锆石。
25.如权利要求1-3、5、14、16和18中任一项所述的用途,其特征在于所述烧结操作在950至1250℃的温度范围内进行。
26.如权利要求1-3、5、14、16和18中任一项所述的用途,其特征在于所用的氧化铝Al2O3颗粒由α-氧化铝和非晶态形式或表现出另一种晶体或更弱结晶结构的“过渡”形式的氧化铝的混合物构成。
CN201310190397.0A 2012-05-21 2013-05-21 氧化铝在陶瓷产品且特别是面砖的制造中作为遮光剂的用途 Expired - Fee Related CN103508737B (zh)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1286003A (en) * 1968-10-30 1972-08-16 Grace W R & Co Process for preparing aluminium oxide

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2474636A (en) * 1946-07-12 1949-06-28 Oesterle Henry Vitreous enamel opacification and process
FR1407140A (fr) * 1964-06-15 1965-07-30 Pechiney Saint Gobain Peintures à base d'alumine
IT1399600B1 (it) 2009-09-11 2013-04-26 Gruppo Concorde Spa Impasto ceramico per piastrelle comprendente vetro crt e piastrella ottenuta con detto impasto

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1286003A (en) * 1968-10-30 1972-08-16 Grace W R & Co Process for preparing aluminium oxide

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Ceramic pigments obtained by sol-gel techniques and by mechanochemical insertion of color centers in Al2O3 host matrix;Riccardo Ricceri et.al.;《Journal of the European Ceramic Society》;20021231;第22卷;629-637 *
Grayeblue Al2O3eMoOx ceramic pigments: Crystal structure,colouring mechanism and performance;Michele Dondi et.al.;《Dyes and Pigments》;20061010;第76卷;179-186 *

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