CN106800800B - 用于陶瓷物品的装饰的颜料和墨水 - Google Patents
用于陶瓷物品的装饰的颜料和墨水 Download PDFInfo
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- 239000000049 pigment Substances 0.000 title claims abstract description 66
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- 238000005034 decoration Methods 0.000 title claims abstract description 16
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- 238000009472 formulation Methods 0.000 claims abstract description 16
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims abstract description 4
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000003801 milling Methods 0.000 claims description 27
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 7
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 3
- 238000010348 incorporation Methods 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
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- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 229910052572 stoneware Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 239000003086 colorant Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
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- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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Abstract
本发明公开用于陶瓷物品的装饰的颜料和墨水,在它们的配方中包括与氧化锂结合的氧化铁和氧化磷,氧化锂的存在是给予颜料被研磨(呈溶剂基中悬浮物的形式)到能够获得墨水的点的能力,特征在于具有非常窄PSD以及小于1μm的上限。由于该PSD,使用这些颜料制备的墨水能够应用在标准打印头中以对陶瓷物品上釉料,从而在所述陶瓷物品承受烧制工艺之后能够获得金属光泽度和外观。获得的墨水具有低黏性,从而允许增加颜料的浓度,因而增加其产量,优化成品陶瓷物品的光泽度和金属外观。
Description
技术领域
本发明的领域是用于陶瓷工业的材料,尤其具有金属效果的煅烧颜料和墨水,旨在用于工业陶瓷工业的应用,用于瓷砖、结构陶瓷以及卫生陶瓷,目的是获得金属光泽度或者金属外观(metallic appearance)。
背景技术
粉末、粒状产品或者液体中散布的颗粒的粒度分布(PSD)是一系列值,该值定义了根据颗粒尺寸定级的存在的颗粒按质量或者体积的相对量。
d(v,n)通常表示为Dn,是允许PSD为特征的参数的集合,其定义为颗粒的当量直径,使得控制样本的体积的量n(表示以每单元基础表示)具有的当量直径小于所述值。例如:d(v,0.50)还表示为D50,将对应于PSD的中值。
分布宽度是WPSD,其是给予我们中值周围数据的分散程度的测量的值。其根据以下表达式计算:
d(v,0.97)还表示为D97,是这样一个参数,其通常用作悬浮物和粉末的PSD的上限。
金属外观(光泽度)。其是材料的质量或者效果,特征在于这样的事实:材料的光泽度和颜色根据观察角度而改变,使得人眼将它们关联于金属产品(而不是它们必须具有基于金属键的原子结构)。也即,光学外观不是始终相关于产品的化学或者结构成分。具有金属外观的材料(它们不是实际是金属)的典型例子是车用油漆以及通常由塑料制成的很多日常用品的涂层。
考虑到这是视觉外观效果,不易于以数字表示。虽然如此,由于金属外观相关于取决于观察角度所产生的颜色和光泽度的改变,因此能够建立基于根据角度的光学测量对所述金属外观的测量。在文献中能够发现用于估计金属外观的各种提议。例如,方程2通常使用在汽车工业中。
其中,L* 15°、L* 45°、L* 110°是利用多角度分光光度计色度计确定的亮度值。
陶瓷的金属效果已经公知几百年,已经用不同的技术来获得该金属效果,范围包括热降低处理,陶瓷釉中的贵金属的颗粒悬浮,在它们的成分中具有高浓度过渡族金属氧化物的硅酸盐釉料,墨水包含晶体平面颜料(类似于使用在车用油漆中的那些)。除了在最后一种情形下金属效果是基于包含反光层颜料的涂层的应用,通常来说陶瓷金属效果是由于在对应热处理期间釉料中高反射率的析晶的微晶体的存在,这取决于角度而生成光泽变化,在中间角度(60°)具有高强度波峰。此外,在该情况下必须补充的是,金属光泽装饰施加在能够是亚光或者光泽的釉料中,从而影响墨水涂层的光泽度测量。基于该原因,在该情况下,根据方程3,基于利用标准多角度光泽仪确定的光泽度测量来估计金属外观指数θM:
θM=θ60°-θ85° (3)
其中,θ60°和θ85°是在对应角度处涂层的光泽度值。
所测量的表面的金属外观越大,该参数的值是越高以及越积极的。
分辨率。在喷墨术语中,该术语指的是在打印时获得的清晰度,也即每单位长度中打印的点的数量,通常表示为每英寸的点数(dpi)。陶瓷装饰中使用的大多数打印头具有的分辨率容量在360dpi至400dpi之间。
由于其是一个经济的高灵活性的工艺,因此通过使用喷墨机器进行数字打印瓷砖装饰的技术已经变成惯例。通常采用的是依靠应用颜料墨水来装饰陶瓷瓷砖,一旦陶瓷瓷砖烧制时,颜料墨水给予瓷砖它们的颜色。
起初,使用的墨水是溶解在不同类型有机溶剂(异链烷烃、乙二醇等)中的金属阳离子的可溶性盐,通常具有无极性质,以防止打印头的短路问题,诸如EP1272574中涉及的“用于使用在釉料陶瓷物件以及表面的彩色喷墨打印中的各墨水以及各组墨水”。但是,考虑到这些墨水施加在未烧制的釉料中,也即是说,它们是多孔基板,由于难以控制基板中墨水的渗透,使用可溶性盐会引起打印再现性的严重问题。
当用具有陶瓷性质的固体颜料替换可溶性盐时,不可控制的墨水渗透问题随后被最小化,这些固体颜料比起可溶性盐非常不易于渗透多孔基板。因而,在溶剂介质中制备颜料的悬浮物,颜料随后被研磨以获得粒度分布(PSD),该粒度分布足够小以使用在陶瓷中通常采用的打印头中。总之,大多数打印头的规格(由喷射器确定)要求的是,使用的墨水具有限制在其上限的固体PSD。大多数打印头限制是使用D97<1μm的墨水,仅少数打印头对墨水的限制是D97<3μm。
但是,重要的不仅是要限制墨水悬浮物的PSD的上限。而且还基本的是要防止形成过多的颜料的细粒,这是由于固体的比表面积以与颗粒直径成反比的比率变化,当比表面积过度增加时,会发生颗粒的再聚集。因而,具有非常小宽度PSD的墨水在一段时间内改善了它们的稳定性(通过防止再聚集)并且允许达到更高浓度的颜料。
在现有技术中能够发现涉及陶瓷墨水打印的不同方法,诸如,专利ES2131466“用于装饰陶瓷基板的自动方法”,其概括的描述了陶瓷中喷墨***的使用,以及还有专利ES2289916“陶瓷颜料的胶体分散系”,其概括地描述了用于喷墨应用的墨水的制造。这些方法和墨水仅能够通过喷射用不同颜色产生质感,但是不可能获得具有金属外观的质感。
此外,获得金属质感通常关联于要使用相当厚的特殊釉料,诸如专利ES2246166“金属釉料成分”描述的,其创建充分厚的金属化基底,期望的颜色装饰能够随后施加至该金属化基底上。该方法具有的缺陷是,金属化釉料必须施加在整个瓷砖表面上。此外,如果瓷砖要用有色墨水装饰,那么中间非常不透明的白色釉料层必须并入要装饰的区域以防止在金属釉料和装饰之间发生化学反应使颜色扭曲或者失光。这理论上涉及更高经济成本并且浪费材料。此外,该技术要求非常厚的涂层,这是使用用于喷墨陶瓷装饰通常采用的高分辨率(300-400dpi)打印头不能够获得的。实际上,金属效果主要是通过用淋釉法(waterfall)、喷釉器或者盘类施釉线应用施加釉料层而使用的,固体的每单位表面积的重量在300至500g/m2之间。但是,高分辨率喷射头仅能够提供所施加的固体6-75g/m2之间的重量,这大大小于所需要的。因此,现有技术上认为在技术上不能够通过喷墨在陶瓷瓷砖中获得金属效果。
发明内容
本发明涉及一种用以制造墨水的陶瓷颜料,当其使用在用于陶瓷物品的装饰的工艺方法中时产生获得光泽度或者金属外观,该工艺方法由以下阶段组成:
对陶瓷产品上釉料。
使用本发明的墨水进行喷墨装饰(通过喷射墨水)。
完成常规烧制工艺。
因而,本发明首先涉及一种陶瓷颜料,其特征在于,在其配方中其包括以下物质作为基本氧化物:氧化磷和氧化铁,作为晶体的去玻作用的前体,用于获得金属光泽度;以及氧化锂,作为颜料的结构的改性剂,允许改善其研磨。此外,颜料能够包含少量其他氧化物以改进其可溶性以及晶体生长的属性。
已经确定出的是,相比于标准磷酸铁(III)颜料的作用,其原始分子式为FePO4(或者陶瓷记号中的Fe2O3·P2O5),磷酸铁和锂颜料此后称为P-Fe-Li颜料,其更易于精确研磨(在制备墨水的工艺中作为溶剂基中的悬浮),这是由于其在成分中包括氧化锂的事实。
本发明的第二目的是基于先前提到的P-Fe-Li颜料通过研磨制备墨水,P-Fe-Li颜料的配方包括对应于P-Fe-Li颜料的固体部分、分散剂和溶剂部分。
本发明的优势
在颜料配方中以特定浓度并入氧化锂Li2O,惊喜地引起墨水研磨时间的显著降低。该时间降低意味着能够获得更窄的PSD,也即是说,能够获得具有较小宽度值的PSD。这意味着,墨水将具有更低浓度的微细粒,这将防止墨水重新聚集的趋势,防止固体成分的结块以及因而损失可滤性(其能够被确定为在通常2巴的特定压力下通过孔隙直径5μm的标准Teflon过滤器的过滤速度、墨水流动)。
此外,本发明的新颜料改善了现有技术,这是由于克服了当前磷酸铁的有限过滤能力的技术问题,改善了研磨效率,降低了达到目标PSD所需的时间,以及降低了墨水黏性,这允许增加墨水中的颜料浓度,优化最终结果。因此,总之,一般来讲,用更浓缩的墨水装饰的瓷砖或者陶瓷物品在它们的金属外观(光泽度)方面改善了光学属性。
附图说明
为了获得对本发明的更好理解,附图中,
图1示出了颜料中的锂含量(公式4中表示为[x+y])和墨水研磨的PSD之间的关系的图形。
图2示出了墨水的PSD(D97)相对于4个研磨操作消耗的比功的进展的图形。
图3示出了对于底部釉料1和金属墨水2取决于角度产生的光泽度变化的图形。
具体实施方式
本发明涉及一种用以制造墨水的陶瓷颜料,当其使用在用于陶瓷物品的装饰的工艺方法中时其导致获得光泽度或者金属外观,该工艺方法由以下阶段组成:
对陶瓷产品上釉料。
使用本发明的墨水进行喷墨装饰。
完成常规烧制处理。
因而,本发明首先涉及一种陶瓷颜料,其特征在于,在其配方中其包括以下物质作为基本氧化物:氧化磷和氧化铁,作为晶体的去玻作用的前体,用于获得金属光泽度;以及氧化锂,作为颜料的结构的改性剂,允许改善其研磨。此外,颜料能够包含少量其他氧化物以改进其可溶性以及晶体生长的属性。
已经确定出的是,相比于标准磷酸铁(III)颜料的作用,其原始分子式为FePO4(或者陶瓷记号中的Fe2O3·P2O5),新型颜料更易于研磨(在制备墨水的工艺中作为溶剂基中的悬浮),该新型颜料在其化学组成中包括氧化锂,根据公式(4)以摩尔数表示为:
(1-x)Fe2O3·(1-y)P2O5·(x+y)Li2O (4)
其中:
x在-0.10至0.30之间。
y在-0.10至0.30之间。
x和y的总和在0.20至0.60之间。
事实上,根据公式(4),在新P-Fe-Li颜料的配方中并入氧化锂Li2O,基于特定浓度(表示为:x+y≥0.20摩尔)惊喜地引起降低墨水的研磨时间。该时间降低意味着能够获得非常窄的PSD,也即是说,能够获得具有较小宽度值的PSD。这意味着,墨水将具有较低浓度的微细粒,这将防止墨水重新聚集的趋势,防止固体成分的结块因而损失可滤性(其能够被确定为在通常2巴的特定压力下通过孔隙直径5μm的标准Teflon过滤器的过滤速度、墨水流动)。
因此,利用本发明的新型P-Fe-Li颜料改善了现有技术,这是通过克服了当前磷酸铁墨水的有限过滤容量的技术问题,改善了研磨效率,降低了达到目标PSD所需的时间,以及获得墨水黏性的降低,这允许增加墨水中颜料的浓度,并且优化了最终结果。因此,总之,一般来讲,利用该更加浓缩的墨水装饰的瓷砖或者陶瓷物品在它们的金属外观(光泽度)方面改善了光学属性。
除了三个基本氧化物,P-Fe-Li颜料的组分能够包含其他少量氧化物,SiO2、SnO2、Al2O3、Na2O、K2O、MgO或者CaO,它们添加至公式(4),始终具有的总含量(表示为所述氧化物的总和)小于0.10摩尔。
本发明的第二目的是基于前述P-Fe-Li颜料通过研磨制备墨水,前述P-Fe-Li颜料的配方包括对应于P-Fe-Li的固体部分、分散剂以及溶剂部分(其中,溶剂能够选自乙二醇、异链烷烃碳氢化合物以及羧酸酯),根据以下组分,表示为%重量比,表格1:
表格1 墨水组分的范围
由于颜料的特殊配方,在优选实施例中,被研磨的墨水具有的墨水粒度分布确定为值D97<3μm,使得其能够使用在DIMATIX1024L、XAAR1002GS40或者SEIKORC1536打印头中,除此之外,使得允许能够使用粒径高达3μ的墨水。
在尤其优选实施例中,被研磨的墨水具有的PSD的特征在于其具有的值D97<1μm,这使得除了用于装饰陶瓷产品,其适用于所有类型的打印头。
到目前为止,涉及的陶瓷物品的装饰的工艺:
通过选自由钟罩式淋釉器(bell)、喷釉枪、旋转式施釉器(rotary)、盘类施釉线(disc)或者水刀式喷釉器(waterfall)形成的组中的处理,执行对陶瓷基底上釉料的阶段。
使用通常使用在陶瓷装饰中的喷射头优选执行利用金属墨水进行装饰的阶段。
通过正常陶瓷循环执行烧制阶段,范围为900℃的传统二次烧制至1300℃的高温炻瓷砖烧制。
示例
例子1 颜料配方和获得的PSD之间的关系
使用原料的混合物:磷酸一铵、碳酸锂以及氧化铁(在提供氧化物P2O5、Li2O以及Fe2O3的不同可选物中选择),利用表格2指示的化学组分来制备颜料P1至P8,表示为摩尔公式,基于摩尔公式以及根据公式(4)确定x和y系数。
这些混合物P1至P8在860°下进行煅烧,在最大温度下逗留时间为2小时,以产生对应颜料。
随后,通过在实验室间歇操作式研磨机中研磨设定时间(240min)来制备墨水,使用0.3-0.4mm直径的Zr-Y球作为研磨材料,为此目的使用表格3的配方。在研磨之后,通过激光衍射来测量墨水的PSD,从而确定表格2的结尾指示的D97值。
表格2 颜料P1至P8的配方以及在研磨之后获得的PSD(D97)
表格3 墨水配方
基于表格2的数据,示出的D97值相关于因子x和y的总和,从而获得图1示出的图形,在该图形中可见的是,当x和y参数的总和达到大于0.20的值时,颗粒尺寸存在惊人的降低,获得的晶粒尺寸D97<1,这适合于使用在用于陶瓷装饰的标准打印头的墨水中。因而,惊奇的是,颜料中锂的浓度允许所述的降低尺寸。
例子2。连续研磨中的墨水研磨
为了确定在颜料中并入锂的效果,在可扩展生产的研磨机中使用其,在连续研磨中准备4个研磨操作,在每个情况下利用0.3-0.4mm直径的Ce-Y球执行循环,见表格4。利用标准纯磷酸铁颜料执行前两个研磨操作M1和M2,不并入锂(也即是说,公式(4)中x=0并且y=0)。
表格4。连续研磨中研磨操作的颜料和墨水的成分。
对于四个研磨操作,在时间方面采集数据,PSD(D97[μm])和相对于所研磨颜料重量的单位能量消耗(W/M[kWh/kg])。
正如可见于图2的图形,利用使用不含锂的标准磷酸铁颜料执行的两个研磨操作M1和M2中的任一个,均未实现D97<1μm的目标,尽管感觉上利用墨水中颜料浓度的降低能够实现,但是具有极高单位消耗。这是由于通过热煅烧制备的磷酸铁颜料获取一个层状结构,使得将它们研磨为墨水极其复杂:正如能够看见的,研磨时间增加,并且最后的墨水的粒度分布在很大程度上受限制,这制约着墨水的使用。事实上,在较长研磨过程之后,勉强达到颗粒分布参数D97<3μm,这迫使使用非标准打印头。而且,考虑到颜料的层状结构,墨水具有非常有限的过滤能力,使得利用打印头会产生问题。
但是,在M3研磨操作中,用P-Fe-Li颜料制备,在该情况下x=0.0且y=0.2,实现了追求的目标。为了确定分散剂浓度是否合适,使用相同P-Fe-Li颜料和较低浓度的分散剂(见表格4)执行第四研磨操作M4,产生甚至更有效的研磨,并且获得的目标是颜料的单位消耗为2.9kWh/kg。
例子3。制造使用具有P-Fe-Li颜料的墨水所装饰的具有金属光泽度的陶瓷瓷砖。
使用具有适用于它们使用的釉料对陶瓷白瓷炻瓷铺地瓷砖进行上釉,具有的重量约为350g/m2。随后,为了该目的,使用DIMATIX1024L打印头将M4墨水施加在它们上,设计分辨率为1200dpi,获得的施加墨水(每单位表面积)的重量约为55g/m2。
在1200℃的标准白瓷炻瓷单烧制周期烧制之后,发现瓷砖具有完整的金属化外观。为了使用多角度光泽仪计量金属外观,图3,在仅具有釉料(1)的区域中以及在用墨水(2)装饰的部分中,以不同的角度测量瓷砖的光泽度。正如可见于图3的图形的,由于金属效果的外观,在施加墨水的区域中在60°时光泽度显著增加。基于表格中的数据,根据方程3确定用墨水(2)装饰的区域的金属光泽度指数,给出值:
θM=61.7-35.2=26.5UB
该值指示由于金属效果引起光泽度增加了26.5光泽度单位,与此相反,在未装饰(仅上釉料)区域缺乏光泽度的增加,其金属光泽度指数值将为:
θM=33.4-36.1=-2.7UB
涉及包括表格的例子或者实施例的所有信息形成本发明的说明书的一部分。技术专家将易于理解的是,不同实施例的特性能够与其他可能实施例的特性结合,假设组合在技术上是可行的,诸如结合表格4的M3配方的组合,用来研磨颜料作为墨水,x=0.0且y=0.2,但是可用不同颜料,诸如表格2的P5(x=0.21和y=0.21),其可优化研磨的速度,或者甚至其他在颜料的通用配方(公式4)范围内的颜料,诸如能够通过使x=-0.1且y=0.3值获得的颜料,其允许Fe2O(1.10)的最大浓度在公式限定的范围内。
Claims (4)
1.一种用于陶瓷物品的装饰的陶瓷颜料,其特征在于,在其配方中作为基本氧化物包括:氧化磷和氧化铁,作为晶体的析晶的前体,用于获得金属光泽度;以及氧化锂,作为所述颜料的结构的改性剂以及作为其研磨的研磨助剂,其中,根据以下公式执行在磷酸铁中并入氧化锂,所述公式以摩尔数表示为:
(1-x)Fe 2O3·(1-y)P2O5·(x+y)Li2O
其中:
x在-0.10至0.30之间,
y在-0.10至0.30之间,以及
x和y的总和在0.20至0.60之间。
2.根据权利要求1所述的陶瓷颜料,其中,除了三个基本氧化物之外,其包含从由SiO2、SnO2、Al2O3、Na2O、K2O、MgO以及CaO形成的组中所选择的一种或者若干种少量的氧化物,所添加的氧化物的总和所表示的总含量小于0.10摩尔。
3.一种基于权利要求1或2所述的陶瓷颜料通过研磨制备的墨水,其中,其配方包括:按重量计算比例在25%至50%之间的固体部分,对应于P-Fe-Li颜料;按重量计算比例在1%至15%之间的分散剂;以及按重量计算比例在35%至74%之间的溶剂部分。
4.根据权利要求3所述的墨水,其中,所述溶剂选自以下组中:乙二醇、异链烷烃碳氢化合物以及羧酸酯。
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