CN114774904A - 一种含有荧光剂的铝合金无铬钝化药剂及其制备方法和使用方法 - Google Patents
一种含有荧光剂的铝合金无铬钝化药剂及其制备方法和使用方法 Download PDFInfo
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Abstract
本发明公开了一种含有荧光剂的铝合金无铬钝化药剂及其制备方法和使用方法,属于金属表面处理领域。一种含有荧光剂的铝合金无铬钝化药剂,包括如下组成成分及重量百分比为:去离子水30%‑90%、无机酸1%‑10%、成膜主剂1%‑10%、荧光剂1%‑10%、促进剂1%‑10%、络合剂1%‑10%以及缓蚀剂1%‑10%。
Description
技术领域
本发明涉及金属表面处理领域,具体涉及一种含有荧光剂的铝合金无铬钝化药剂及其制备方法和使用方法。
背景技术
铝合金作为轻金属材料之一,以其较低的密度,较高的强度,良好的耐蚀性、力学性能和加工性能,在航空航天、交通运输、建筑、金属包装以及3C电子等领域中有着广泛的应用。钝化处理是一种有效的提高铝合金防腐性能的化学处理方法,其可以在铝材表面形成一层致密的转化膜保护层,大大延缓铝合金的电化学腐蚀速率,同时还能为铝合金与后道涂层提供优异的附着力。传统的铝合金钝化工艺有六价铬钝化处理和三价铬钝化处理,但因六价铬和三价铬处理均含有不同程度的致癌物,对人体及环境有着严重危害,因此开发无毒环保、高效、低耗的无铬钝化技术成为了现今铝合金钝化处理的发展方向之一。
目前,市场上及相关专利公开的铝合金无铬钝化药剂所形成的无铬转化膜颜色多为无色(接近铝合金本色)。无色转化膜在现场应用过程中不易在线识别,且难以通过肉眼观察来判断无铬转化膜的上膜是否完整,是否存在上膜不良区域,即使有一些识别手段也属于非常局部性的判别,且还会对铝制品造成破坏(如裁剪取样后高温煅烧或是点滴酸性胂(Ⅲ)显色剂)。而黄色转化膜虽然在线便于识别,但对于一些涉及涂装的场景,尤其是使用透明淸漆、透明粉或浅色系涂料的铝制品,则可能会引起外观色差,从而无法满足客户要求。
发明内容
针对现有技术的不足,本发明提出了一种含有荧光剂的铝合金无铬钝化药剂及其制备方法和使用方法。
本发明的目的可以通过以下技术方案实现:
一种含有荧光剂的铝合金无铬钝化药剂,包括如下组成成分及重量百分比为:
可选地,所述去离子水的电阻率大于4MΩ·cm。
可选地,所述无机酸为硫酸、硝酸、磷酸、氢氟酸、柠檬酸、草酸、乳酸、水杨酸中的一种或多种。
可选地,所述成膜主剂为硝酸锆、碳酸锆、氢氧化锆、二氧化锆、氟锆酸、锆酸钾、碳酸锆铵、碱式碳酸锆、氟钛酸、硫酸氧钛、二氧化钛、钙钛矿、钛铁矿中的一种或多种。
可选地,所述荧光剂为六苯基噻咯、二苯乙烯联苯二磺酸钠(CBS)、4,4'-双(2-磺酸钠苯乙烯基)联苯(CBS-X)、1-邻氰苯乙烯基-4-对氰苯乙烯基苯(ER-II)、2.2'-(4,4'-二苯乙烯基-)双苯并恶唑(OB-1)、双三嗓氨基二苯乙烯类(BC、VBU)、7-二乙氨基-4-甲基香豆素(荧光增白剂52)、2-(乙硫甲基)苯基N-甲基氨基甲酸酯(荧光增白剂33)、3-(4-氯苯基)-1-(4-氨基磺酰苯基)-2-吡唑啉(荧光增白剂121)、C34H28N10Na2O8S2(荧光增白剂134)、C40H38N12Na2O8S2(荧光增白剂71)、1,4-二(4-氰苯乙烯)苯(荧光增白剂199)、C40H42N12O10S2.2Na(荧光增白剂113)、荧光增白剂353、荧光增白剂357、荧光增白剂4BK、荧光增白剂5BM、荧光增白剂BAC、荧光增白剂31#、荧光增白剂DMS-X、荧光增白剂AMS、荧光增白剂CBW、荧光增白剂APC、荧光增白剂CXT、荧光增白剂VBL、荧光增白剂BBU、荧光增白剂BA-L、荧光增白剂HL-A、荧光增白剂184、荧光增白剂185、荧光增白剂KCB、荧光增白剂PF、荧光增白剂127、荧光增白剂KSN、荧光增白剂KH-BX、荧光增白剂OB、荧光增白剂FP-127、荧光增白剂LR-B1、1,1,2,2-(4-溴甲苯基)三苯乙烯、四苯基乙烯(TPE)及其衍生物、9,10-二苯乙烯基蒽(DSA)及其衍生物、水溶性聚集诱导发射(AIE)材料中的一种或多种。
可选地,所述促进剂为氟硅酸、氟化氢铵、水性丙烯酸树脂、水性聚氨酯、环氧基硅烷偶联剂、钼酸钠、钨酸钠、硝酸铜、溴酸钠中的一种或多种。
可选地,所述络合剂为乙二胺四乙酸、乙二胺四乙酸二钠、乙二胺四乙酸四钠、柠檬酸、柠檬酸钠、草酸、草酸钠、葡萄糖酸钠、羟基乙叉二膦酸、植酸、单宁酸、氨基三亚甲基膦酸、环氧琥珀酸、环氧琥珀酸钠、聚天冬氨酸、聚天冬氨酸钠中的一种或两种。
可选地,所述缓蚀剂为单乙醇胺、二乙醇胺、三乙醇胺、二异丙醇胺、三异丙醇胺、五水偏硅酸钠中的一种或多种。
一种所述无铬钝化药剂的制备方法,包括以下步骤:先将无机酸溶于去离子水中形成酸基液,然后依次加入成膜主剂、荧光剂、促进剂、络合剂和缓蚀剂,搅拌使所有组份完全溶解,得到所述无铬钝化药剂。
所述的药剂的使用方法,包括以下步骤:
(1)将铝合金材质的工件经除油,除氧化层后用自来水清洗干净;
(2)利用本发明所述的无铬钝化药剂经配制成钝化槽液后对步骤(1)处理后的铝合金材质工件进行钝化处理;
(3)钝化完成后取出烘干。
本发明的有益效果:
1.通过荧光剂成分的引入,本发明的无铬钝化药剂处理得到的化学转化膜常规状态下为无色,能够匹配各种颜色的涂料,不用担心造成色差影响。但在365nm波长的紫外灯光源照射下该化学转化膜即可呈现出特定的荧光颜色,从而能够在不对铝制品造成破坏的前提下,简单便捷地在现场进行在线识别和对转化膜上膜情况的判定;
2.本发明的无铬钝化药剂安全环保,不仅可以提高铝材本身的耐腐蚀性,还能增强铝材与涂层的附着力;
3.本发明的无铬钝化药剂对生产设备和生产工艺要求简单,使用方法简单,稳定性好,能够很好的满足生产、使用、运输和储存的要求,具有很好的经济性。
附图说明
下面结合附图对本发明作进一步的说明。
图1为本申请的使用方法流程图;
图2为本申请实施例中获得产品在紫外灯照射前后对比的视图;
图3为本申请对比例中获得产品在紫外灯照射前后对比的视图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1:
一种含有荧光剂的铝合金无铬钝化药剂含有如下各组分:
脱漆剂成分 | 重量百分比 |
去离子水 | 74% |
氢氟酸 | 5% |
碱式碳酸锆 | 2% |
荧光增白剂BBU | 5% |
水性丙烯酸树脂 | 10% |
葡萄糖酸钠 | 3% |
三乙醇胺 | 1% |
上述实施例1无铬钝化药剂的制备方法包括如下步骤:
先将氢氟酸溶于去离子水中形成酸基液,然后依次加入碱式碳酸锆、荧光增白剂BBU、水性丙烯酸树脂、葡萄糖酸钠和三乙醇胺,搅拌使所有组份完全溶解,得到所述无铬钝化药剂。
上述实施例1无铬钝化药剂的使用方法,包括以下步骤:
(1)将铝合金材质的工件经除油,除氧化层后用自来水清洗干净;
(2)利用实施例1所述的无铬钝化药剂经配制成钝化槽液后对步骤(1)处理后的铝合金材质工件进行钝化处理;
(3)钝化完成后取出烘干。
优选地,步骤(2)中所述无铬钝化药剂配制成钝化槽液的配制方法为:将所述无铬钝化药剂用去离子水进行稀释,并调整稀释液pH值和温度后即为所述钝化槽液,稀释浓度为10g/L,钝化槽液pH值调整至3.0,钝化槽液的温度调至25℃;
优选地,步骤(2)中所述钝化处理的时间为1min,钝化处理的方式为浸渍。
根据实施例1配方所得无铬钝化药剂,配制所述钝化槽液并按其使用方法处理铝合金样板,所形成的化学转化膜在常规状态为无色,即呈现基材本色,而在紫外灯光源照射下则呈现蓝色,见图2。
对比例1:一种铝合金无铬钝化药剂含有如下各组分:
脱漆剂成分 | 重量百分比 |
去离子水 | 79% |
氢氟酸 | 5% |
碱式碳酸锆 | 2% |
水性丙烯酸树脂 | 10% |
葡萄糖酸钠 | 3% |
三乙醇胺 | 1% |
上述对比例1无铬钝化药剂的制备方法包括如下步骤:
先将氢氟酸溶于去离子水中形成酸基液,然后依次加入碱式碳酸锆、水性丙烯酸树脂、葡萄糖酸钠和三乙醇胺,搅拌使所有组份完全溶解,得到所述无铬钝化药剂。
上述对比例1无铬钝化药剂的使用方法,包括以下步骤:
(1)将铝合金材质的工件经除油,除氧化层后用自来水清洗干净;
(2)利用对比例1所述的无铬钝化药剂经配制成钝化槽液后对步骤(1)处理后的铝合金材质工件进行钝化处理;
(3)钝化完成后取出烘干。
优选地,步骤(2)中所述无铬钝化药剂配制成钝化槽液的配制方法为:将所述无铬钝化药剂用去离子水进行稀释,并调整稀释液pH值和温度后即为所述钝化槽液,稀释浓度为10g/L,钝化槽液pH值调整至3.0,钝化槽液的温度调至25℃;
优选地,步骤(2)中所述钝化处理的时间为1min,钝化处理的方式为浸渍。
根据对比例1配方所得无铬钝化药剂,配制所述钝化槽液并按其使用方法处理铝合金样板,所形成的化学转化膜在常规状态和紫外灯光源照射下均为无色,即呈现基材本色,见图3。
本发明通过上述实施例来说明本发明的详细技术方案和工艺流程,但本发明并不局限于上述详细技术方案和工艺流程,即不意味着本发明必须依赖上述详细技术方案和工艺流程才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
在本说明书的描述中,参考术语“一个实施例”、“示例”、“具体示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不一定指的是相同的实施例或示例。而且,描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。
Claims (10)
2.根据权利要求1所述的铝合金无铬钝化药剂及其制备方法,其特征在于,所述去离子水的电阻率大于4MΩ·cm。
3.根据权利要求1所述的铝合金无铬钝化药剂及其制备方法,其特征在于,所述无机酸为硫酸、硝酸、磷酸、氢氟酸、柠檬酸、草酸、乳酸、水杨酸中的一种或多种。
4.根据权利要求1所述的铝合金无铬钝化药剂及其制备方法,其特征在于,所述成膜主剂为硝酸锆、碳酸锆、氢氧化锆、二氧化锆、氟锆酸、锆酸钾、碳酸锆铵、碱式碳酸锆、氟钛酸、硫酸氧钛、二氧化钛、钙钛矿、钛铁矿中的一种或多种。
5.根据权利要求1所述的铝合金无铬钝化药剂及其制备方法,其特征在于,所述荧光剂为六苯基噻咯、二苯乙烯联苯二磺酸钠(CBS)、4,4'-双(2-磺酸钠苯乙烯基)联苯(CBS-X)、1-邻氰苯乙烯基-4-对氰苯乙烯基苯(ER-II)、2.2'-(4,4'-二苯乙烯基-)双苯并恶唑(OB-1)、双三嗓氨基二苯乙烯类(BC、VBU)、7-二乙氨基-4-甲基香豆素(荧光增白剂52)、2-(乙硫甲基)苯基N-甲基氨基甲酸酯(荧光增白剂33)、3-(4-氯苯基)-1-(4-氨基磺酰苯基)-2-吡唑啉(荧光增白剂121)、C34H28N10Na2O8S2(荧光增白剂134)、C40H38N12Na2O8S2(荧光增白剂71)、1,4-二(4-氰苯乙烯)苯(荧光增白剂199)、C40H42N12O10S2.2Na(荧光增白剂113)、荧光增白剂353、荧光增白剂357、荧光增白剂4BK、荧光增白剂5BM、荧光增白剂BAC、荧光增白剂31#、荧光增白剂DMS-X、荧光增白剂AMS、荧光增白剂CBW、荧光增白剂APC、荧光增白剂CXT、荧光增白剂VBL、荧光增白剂BBU、荧光增白剂BA-L、荧光增白剂HL-A、荧光增白剂184、荧光增白剂185、荧光增白剂KCB、荧光增白剂PF、荧光增白剂127、荧光增白剂KSN、荧光增白剂KH-BX、荧光增白剂OB、荧光增白剂FP-127、荧光增白剂LR-B1、1,1,2,2-(4-溴甲苯基)三苯乙烯、四苯基乙烯(TPE)及其衍生物、9,10-二苯乙烯基蒽(DSA)及其衍生物、水溶性聚集诱导发射(AIE)材料中的一种或多种。
6.根据权利要求1所述的铝合金无铬钝化药剂及其制备方法,其特征在于,所述促进剂为氟硅酸、氟化氢铵、水性丙烯酸树脂、水性聚氨酯、环氧基硅烷偶联剂、钼酸钠、钨酸钠、硝酸铜、溴酸钠中的一种或多种。
7.根据权利要求1所述的铝合金无铬钝化药剂及其制备方法,其特征在于,所述络合剂为乙二胺四乙酸、乙二胺四乙酸二钠、乙二胺四乙酸四钠、柠檬酸、柠檬酸钠、草酸、草酸钠、葡萄糖酸钠、羟基乙叉二膦酸、植酸、单宁酸、氨基三亚甲基膦酸、环氧琥珀酸、环氧琥珀酸钠、聚天冬氨酸、聚天冬氨酸钠中的一种或两种。
8.根据权利要求1所述的铝合金无铬钝化药剂及其制备方法,其特征在于,所述缓蚀剂为单乙醇胺、二乙醇胺、三乙醇胺、二异丙醇胺、三异丙醇胺、五水偏硅酸钠中的一种或多种。
9.一种所述无铬钝化药剂的制备方法,包括以下步骤:先将无机酸溶于去离子水中形成酸基液,然后依次加入成膜主剂、荧光剂、促进剂、络合剂和缓蚀剂,搅拌使所有组份完全溶解,得到所述无铬钝化药剂。
10.权利要求1~8任一所述的药剂的使用方法,包括以下步骤:
(1)将铝合金材质的工件经除油,除氧化层后用自来水清洗干净;
(2)利用本发明所述的无铬钝化药剂经配制成钝化槽液后对步骤(1)处理后的铝合金材质工件进行钝化处理;
(3)钝化完成后取出烘干。
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