CN105316673B - 在水溶液中均匀二氧化钛纳米晶涂层在铝片上的烧结辅助沉积 - Google Patents
在水溶液中均匀二氧化钛纳米晶涂层在铝片上的烧结辅助沉积 Download PDFInfo
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Abstract
本发明涉及在水溶液中均匀二氧化钛纳米晶涂层在铝片上的烧结辅助沉积。一种形成多层颜料的方法，其包括步骤：提供金属核材料；用酸处理该金属核材料，将钝化层沉积在该金属核材料上；将具有钝化层的金属核材料致密化，减小该钝化层的孔径；和将高折射率材料沉积到经烧结的材料上，其中高折射率层均匀且无裂纹。
Description
技术领域
本发明涉及形成颜料的方法以及由该方法形成的材料，该颜料具有金属核、钝化层和高折射率材料的均匀光滑层。
背景技术
通常，在本领域中已知光泽颜料用于各种应用，例如汽车面漆、涂层和其它颜料应用。
可通过在水体系中将二氧化钛沉积在高反射的片状的铝片上来形成这样的光泽颜料。铝片可包括SiO2的保护层。可在强酸条件下例如在小于2.0的pH下来将TiO2沉积于铝片，使得可实现对于TiO2的水解反应。然而，由于水溶液扩散穿过SiO2层，这样的方法导致不令人满意的涂层。
与上述沉积有关的问题包括Al核的刻蚀和对于TiO2沉积所不期望的在SiO2-Al表面附近的pH变化。在这样的低pH下，在典型的长沉积期间，水溶液中的质子仍能够扩散穿过SiO2层并且与Al核反应。质子与Al之间的该副反应以及所导致的在核表面的pH提高使得TiO2的沉积困难。质子扩散穿过SiO2层可引起与Al的反应，使得释放氢气，引起TiO2颗粒的弱粘附以及在SiO2和TiO2层中通道或裂纹的形成。另外，pH的提高可引起TiO2层的快速沉积和大的TiO2颗粒的形成，这会不利地影响颜料的性质。
进一步增加SiO2保护层的厚度也是不期望的，因为低折射率的 SiO2会降低颜料的整体色彩表现。因此，本领域存在对于改进的方法和颜料的需求，其解决上面发现的问题并制备具有无裂纹和均匀的 TiO2层的颜料。
发明内容
一方面，公开了一种形成多层颜料的方法，其包括如下步骤：提供金属核材料；用酸处理该金属核材料，将钝化层沉积在该金属核材料上；将该具有钝化层的金属核材料致密化，减小该钝化层的孔径；和将高折射率材料沉积到经烧结的材料上，其中高折射率层均匀且无裂纹。
另一方面，公开了一种包括金属核的多层颜料。将钝化层施加于并包围该金属核。该钝化层具有小于或等于100nm的厚度且该钝化层的90％具有2.3nm的孔径分布。将高折射率层施加于并包围该钝化层，其中该高折射率层均匀且无裂纹。
另一个方面，公开了一种包括金属核的多层颜料。将钝化层施加于并包围该金属核。该钝化层具有小于或等于100nm的厚度且该钝化层的90％具有2.3nm的孔径分布。将高折射率层施加于并包围该钝化层，其中该高折射率层均匀且无裂纹，并且具有50-200nm的厚度。
附图说明
图1是详细说明制备多层颜料的方法的操作pH范围的图。
图2是致密化前后的Al-SiO2材料的孔径分布的图。
图3是致密化前后的金属核和SiO2层的SEM图像。
图4a是包括在经致密化的SiO2-Al上涂覆的TiO2的颜料的SEM 图像。
图4b是图4 a的颜料的EDX图像，其详细说明了TiO2层在SiO2-Al 颗粒上的形成。
图4c是未致密化的涂覆有TiO2的SiO2-Al颗粒的SEM图像，其显示了粗糙表面。
具体实施方式
公开了一种形成多层颜料的方法，以及用于高色度和其它颜料体系的具有均匀表面涂层的多层颜料。该方法提供了一种低成本的溶胶- 凝胶方法，其使用含水体系以经济的方式制备颜料。该多层颜料包括高折射率材料的均匀涂层，该均匀涂层不包括裂纹或其他缺陷。
本发明的方法允许经济的工艺以在宽的pH范围内制备颜料并且消除现有技术应用中的副反应和加工问题。该方法解决了Al核的刻蚀以及对于TiO2沉积所不期望的在SiO2-Al表面附近的pH变化的问题。该方法限制了质子扩散穿过SiO2层，该扩散可能引起与Al的反应，使得释放氢气，引起TiO2颗粒的弱粘附和在SiO2和TiO2层中通道或裂纹的形成。
形成多层颜料的方法包括如下步骤：提供金属核材料；用酸处理该金属核材料，将钝化层沉积在该金属核材料上；将该具有钝化层的金属核材料致密化，减小该钝化层的孔径；和将高折射率材料沉积到该经致密化的材料上，其中高折射率层均匀且无裂纹。
在本发明中，金属核包括金属单质核和合金核。金属核材料可包括各种金属，包括Al、Cr、经涂覆的Al(例如需要另外厚度的用SiO2薄层涂覆的Al)。一方面，钝化层包括SiO2并且高折射率层包括TiO2。其它的钝化层材料可包括Al2O3。另外的高折射率材料可包括Fe2O3、ZrO2、Cr2O3和Fe3O4。一方面，该钝化层可具有小于或等于100nm 的厚度。该高折射率层可具有50-200nm的厚度。
处理金属核材料的步骤可包括将该金属核材料悬浮在磷酸与丙酮的溶液中并搅拌规定的时间。随后可洗涤和过滤所得到的颗粒。
将钝化层沉积在该金属核材料上的步骤可包括将经处理的金属核颗粒悬浮在乙醇中，加热添加有水和氨的悬浮液，以及在搅拌的同时加入四乙氧基硅烷的溶液。随后可洗涤和过滤所得到的颗粒。
在洗涤和过滤后，可将颗粒致密化使得该钝化层的90％具有 2.3nm的孔径分布。一方面，可在低于或等于400℃的温度下将颗粒致密化规定的时间。
将高折射率材料沉积到经致密化的材料上的步骤可包括将具有钝化层的经致密化的金属核材料悬浮在水中，以及在一边添加四氯化钛一边将悬浮液维持在1.8的pH的同时加热该悬浮液规定的时间，使得TiO2或其它高折射率材料均匀地沉积在经致密化的颗粒上而无裂纹或其它缺陷形成。经致密化的颗粒限制了在非常低的pH下水溶液的质子的扩散以避免与金属核材料反应。
另一方面，公开了一种包括金属核的多层颜料。将钝化层施加于并包围该金属核。该钝化层具有小于或等于100nm的厚度且该钝化层的90％具有2.3nm的孔径分布。将高折射率层施加于并包围该钝化层，其中该高折射率层均匀且无裂纹。
另一个方面，公开了一种包括金属核的多层颜料。将钝化层施加于并包围该金属核。该钝化层具有小于或等于100nm的厚度且该钝化层的90％具有2.3nm的孔径分布。将高折射率层施加于并包围该钝化层，其中该高折射率层均匀且无裂纹，并且具有50-200nm的厚度。
实施例
材料
由Silberline Manufacturing Co.提供涂覆有SiO2的铝片。从 Sigma-AldrichChemical Co.(St.Louis,MO)购买四乙氧基硅烷(TEOS)、乙醇(99％)、丙酮、磷酸(85％)、氨水溶液(28％) 和四氯化钛(IV)。
通过增加SiO2层的厚度来制备防腐的铝颜料：
防腐的铝颜料的制备如下：
a)利用磷酸化合物的处理：
将0.11g的磷酸(85％)添加至其中5g涂覆有SiO2的铝片(SiO2的厚度为约15nm)分散于55ml丙酮中的悬浮液中，并且在室温下搅拌30分钟。随后用丙酮过滤和洗涤该悬浮液两次。过滤固体部分并且得到用磷酸处理过的涂覆有SiO2的铝片。
b)氧化硅沉积：
在装备有回流冷凝器的圆底烧瓶中，将步骤a)中得到的用磷酸化合物处理过的铝片悬浮在85ml的乙醇中。在加入22g水和2.2g的 28％氨水溶液之后将该悬浮液加热至65℃。接着，在搅拌时，以小量加入用8ml的乙醇稀释的四乙氧基硅烷(6.5g)的溶液。将该反应混合物在65℃下搅拌18小时，随后从该液体过滤。
涂覆有SiO2的铝片的致密化
用水洗涤防腐的铝片并且随后在室温下干燥一整夜。随后在炉中加热该铝片。为了进一步的层沉积，将升温速率设为10℃/min并且将温度设为400℃，停留时间为1小时。
通过含水体系(水)在防腐的铝片上沉积TiO2：
将5g防腐的铝片悬浮在33ml水中并在搅拌下加热至75℃。在使用32wt％的氢氧化钠将pH保持在1.8的同时将3ml四氯化钛溶液 (40wt％)以0.01ml/min的流速滴入悬浮液。当反应完成时，过滤固体部分，用水洗涤，并随后在100℃下干燥。
在水中将高折射率或介电材料沉积在片或金属核上通常需要非常低的pH，例如pH1.8。在这样的低pH下，尽管已施加了～50-100nm 厚度的SiO2钝化层，但在长的沉积期间(例如4小时)，水溶液中的质子仍能够扩散穿过该SiO2层并与Al核反应。该现象通过如下显示出：在将TiO2沉积在具有SiO2层(其未被致密化)的金属核颗粒上时，在一小时后pH值从1.8提高至3.0。质子与Al之间的副反应以及在核表面所导致的pH提高使得利用现有工艺的TiO2沉积不令人满意。
制备多层颜料颗粒的方法在宽的pH范围内应当是稳定的并且制备均匀的无裂纹的颗粒。参照图1，示出了描述对于未致密化的Al核片(上部)、经致密化的Al核片(底部)和各种高折射率或介电层材料(上面)的操作pH范围的图。对于核和层材料两者，操作pH范围的重叠对在选定的核上成功沉积层是必要的。
为了降低水溶液在SiO2层中的扩散，期望更厚的保护性SiO2的层。然而，如果低折射率的SiO2层的厚度大于100nm，则颜料的色强度将会受到损害。
在TiO2沉积前将具有SiO2层的核金属颗粒致密化降低了材料的孔径并提供了限制质子扩散至Al核材料的窄的孔径分布。参照图2，示出了经致密化的和未处理的颗粒的孔径分布的曲线。从图中可以看出，未处理的颗粒中90％的颗粒具有10.1nm的孔径，而经致密化的颗粒中90％的颗粒具有2.3nm的孔径。图2中的结果清楚地证实了 SiO2的孔径分布被降低，因为存在从大的值向较小值的峰位移。另外的SiO2层均匀地沉积在金属核上并具有厚度约100nm的光滑表面。参照图3，示出了经致密化的和未处理的或原始的片或颗粒的SEM图像，证实了SiO2层的均匀沉积。
SiO2层中的窄的孔径分布导致在SiO2-Al表面上的均匀TiO2层的沉积而没有裂纹或缺陷。参照图4a-c，示出了经致密化的颗粒和未处理的颗粒两者的SEM图像。如图4a和4b所示的经致密化的颗粒具有光滑均匀的表面，而图4c的未处理的颗粒具有颗粒状的粗糙表面。
上面的实施例和实施方案仅用于说明性的目的，并且改变、修饰等对本领域技术人员而言是明显的并且仍落入本发明的范围。对其本身而言，本发明的范围通过权利要求定义。
Claims (18)
1.形成多层颜料的方法，包括步骤：
提供金属核材料；
用酸处理该金属核材料，
将钝化层沉积在该金属核材料上；
在低于或等于400℃的温度下将具有钝化层的金属核材料致密化，减小该钝化层的孔径；
将高折射率材料沉积到经烧结的材料上，其中高折射率层均匀且无裂纹。
2.权利要求1所述的形成多层颜料的方法，其中，该钝化层包含SiO2。
3.权利要求1所述的形成多层颜料的方法，其中，该高折射率层包含TiO2。
4.权利要求1所述的形成多层颜料的方法，其中，该钝化层的90％具有2.3nm的孔径分布。
5.权利要求1所述的形成多层颜料的方法，其中，该金属核选自由Al、Cr、涂覆的Al、Ag、Cu、黄铜、Mn组成的组。
6.权利要求1所述的形成多层颜料的方法，其中，该高折射率层具有50-200nm的厚度。
7.权利要求1所述的形成多层颜料的方法，其中，该钝化层具有小于或等于100nm的厚度。
8.权利要求1所述的形成多层颜料的方法，其中，该处理步骤包括将该金属核材料悬浮在磷酸与丙酮的溶液中并搅拌规定的时间。
9.权利要求8所述的形成多层颜料的方法，其中，该处理步骤进一步包括洗涤和过滤该金属核材料的步骤。
10.权利要求1所述的形成多层颜料的方法，其中，将钝化层沉积在该金属核材料上的步骤包括将经处理的金属核颗粒悬浮在乙醇中，加热添加有水和氨的悬浮液，以及在搅拌的同时添加四乙氧基硅烷的溶液。
11.权利要求10所述的形成多层颜料的方法，其中，将钝化层沉积在该金属核材料上的步骤进一步包括洗涤和过滤步骤。
12.权利要求1所述的形成多层颜料的方法，其中，将高折射率材料沉积到该经致密化的材料上的步骤包括将具有钝化层的经致密化的金属核材料悬浮在水中，并且一边将悬浮液维持在1.8的pH一边添加四氯化钛，同时加热该悬浮液。
13.多层颜料，其包括：
金属核；
施加于并包围该金属核的钝化层，该钝化层具有小于或等于100nm的厚度并且该钝化层的90％具有2.3nm的孔径分布；
施加于并包围该钝化层的高折射率层，其中该高折射率层均匀且无裂纹。
14.权利要求13所述的多层颜料，其中，该钝化层包含SiO2。
15.权利要求13所述的多层颜料，其中，该高折射率层包含TiO2。
16.权利要求13所述的多层颜料，其中，在施加该高折射率层之前将钝化层致密化。
17.权利要求13所述的多层颜料，其中，该金属核选自由Al、Cr、涂覆的Al、Ag、Cu、Mn、黄铜组成的组。
18.权利要求13所述的多层颜料，其中，该高折射率层具有50-200nm的厚度。
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| US9359504B2 (en) | 2016-06-07 |
| DE102015109299A8 (de) | 2016-03-10 |
| CN105316673A (zh) | 2016-02-10 |
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