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CN111164161B - 用于金属基材的室温固化锆酸酯-二氧化硅硅溶胶-凝胶预处理 - Google Patents

用于金属基材的室温固化锆酸酯-二氧化硅硅溶胶-凝胶预处理 Download PDF

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CN111164161B
CN111164161B CN201880061881.4A CN201880061881A CN111164161B CN 111164161 B CN111164161 B CN 111164161B CN 201880061881 A CN201880061881 A CN 201880061881A CN 111164161 B CN111164161 B CN 111164161B
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李蕾
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Abstract

一种用于金属基材的室温可固化的防腐溶胶‑凝胶涂料组合物，其包含羧酸或2,4‑戊二酮稳定的锆酸酯‑二氧化硅纳米颗粒的水基溶胶‑凝胶，在涂布到金属基材上之前所述溶胶‑凝胶与环氧丙氧基烷基‑烷氧基硅烷组合。涂层在金属基材上化学固化，形成防腐蚀层。

Description

用于金属基材的室温固化锆酸酯-二氧化硅硅溶胶-凝胶预 处理
发明背景
本申请要求于2017年9月25日提交的美国临时申请号62/562,720的权益，其全部内容通过引用合并于此。
本发明涉及用作金属腐蚀防护层的溶胶-凝胶涂料组合物，为金属表面提供溶胶-凝胶腐蚀防护层的方法，可通过这种方法获得的金属表面及其用途。
胶体，包括凝胶、溶胶和乳液，通常被定义为由一种物质的大分子或超细微颗粒通过第二种物质分散而组成的均匀的、非结晶的分散体系，其至少一个特征尺寸在约10-7至10-4厘米的范围内。该颗粒不会沉降，也无法像悬浮液中那样通过常规过滤或离心分离出来。更特别地，在溶胶-凝胶技术中，溶胶是任何固体在液体中的分散体。凝胶是例如普通的胶冻的体系，其中一种组分提供了足够的结构框架用于刚性而其他组分形成结构单元或空间之间的空间。在凝胶中，分散的组分和分散介质二者都连续地在整个体系中延伸。该体系具有平衡-弹性(随时间变化)变形，因此刚性剪切模量可使凝胶像固体一样发挥作用，即使在大多数其他物理方面它们的行为像液体一样。因此，可以从液体组分生产固体交联的材料。
如在常规分散体的情况下，溶胶，例如分散相，是相对自由移动的，而在凝胶中则不再如此，在凝胶中，颗粒以网状方式互连，因此很难相对于彼此移位。因此，溶胶-凝胶技术的本质是自由分散相和交联分散相之间的过渡。通常，材料从溶胶到凝胶的过渡是不可逆的，分散的固体成分以网状或蜂窝状方式分布在分散剂(通常是水)中，分散剂通过冷凝排出，从而得到固体交联的材料。
已知的基于溶胶-凝胶制剂的涂层体系的常见主要缺点是存在氯化物和高比例的有机的、通常为挥发性以及有毒的溶剂，它们是以硅烷水解的副产物而获得的或作为稀释剂添加。使用不足以使硅烷完全水解的水量，以及利用酸性水解催化剂，可以制备溶胶-凝胶体系，该体系在储存数月内稳定，但含有溶剂。还已知增加水的量导致烷氧基完全水解并因此导致体系的储存稳定性的急剧降低，和/或导致水解过程结束后凝胶的快速形成，更特别地是当此类体系旨在具有很高的固体含量时如此。
用于保护金属表面的基于溶胶-凝胶制剂的已知涂层体系的另一个缺点包括伴随着溶胶-凝胶涂层的复杂的镀液化学，以及为了具有足够的腐蚀防护能力经常需要施加多层体系。此外，需要用相对较高的温度(>150℃)进行后处理以提供具有令人满意的腐蚀防护性的致密层。另外，在溶胶-凝胶工艺中包括附加功能并保持足够的腐蚀防护是非常复杂的。
附图说明
图1示出了在用(A)市售基准溶胶-凝胶和(B)本发明的溶胶-凝胶组合物处理的铝合金A2022-T3覆层(clad)板上进行168小时的盐雾腐蚀(ASTM B117)；
图2示出了在(A)用市售基准溶胶-凝胶/底漆/面漆处理的和(B)用本发明的溶胶-凝胶/底漆/面漆处理的铝合金AA2024-T3裸板上进行3000小时的盐雾腐蚀(ASTM B117)；
图3示出了在(A)用市售基准溶胶-凝胶/底漆/面漆处理的和(B)用本发明的溶胶-凝胶/底漆/面漆处理的铝合金AA2024-T3裸板上进行1000小时、40℃、80％RH的丝状腐蚀；
图4：发明的溶胶凝胶的TEM图像示出了锆酸酯二氧化硅(zirconate silica)纳米颗粒。
发明内容
根据本发明的第一方面，提供了一种溶胶-凝胶组合物，其包含：
(a)第一部分，其包含至少一种具有通式为Zr(OC(O)R)4的锆化合物和粒径小于50nm的水合无机硅胶，
其中R代表1-6个碳原子的烷基；和
b)第二部分，其包含通式为SiXa(OR)4-a的有机硅烷化合物，其中R表示1-6个碳原子的烷基，X表示烷基环氧丙氧基(alkyl glycidoxy)并且a表示1-3的整数。
溶胶-凝胶是由至少一种有机前体和至少一种无机前体形成的有机-无机杂化溶胶，使得有机和无机组分在所得涂层结构中杂化。即，有机和无机组分化学键合在一起以产生完全杂化的有机-无机结构。通过添加2,4-戊二酮可以获得杂化溶胶-凝胶的进一步稳定性。
本发明的另一方面是金属基材，其包括化学键合到所述基材上的溶胶-凝胶组合物，其中所述溶胶-凝胶组合物包含：
(a)第一部分，其包含至少一种通式为Zr(OC(O)R)4的锆化合物和粒径小于50nm的水合无机硅胶，其中R代表1-6个碳原子的烷基；和
b)第二部分，其包含通式为SiXa(OR)4-a的有机硅烷化合物，其中R表示1-6个碳原子的烷基，X表示烷基环氧丙氧基，且a表示1-3的整数。
在一个实施方式中，该溶胶-凝胶涂料组合物具有至少50nm且至多1μm的干膜厚度。
根据本发明的另一个方面，存在两部分的涂料组合物，其包含：(a)如上所述的溶胶-凝胶组合物；(b)具有乙酰乙酸酯和丙烯酸酯官能团的树脂。
发明详述
已经发现，根据本发明，涂覆到金属表面(优选铝、铝合金或钢包括镀锌钢和不锈钢)的溶胶-凝胶涂料组合物可以通过如下更好地保护金属免受腐蚀：首先涂覆一种溶胶-凝胶涂层材料，该涂层材料包含：
(a)第一部分，其包含至少一种通式为Zr(OC(O)R)4的锆化合物和粒径小于50nm的水合无机硅胶，其中R代表1-6个碳原子的烷基；和
b)第二部分，其包含通式为SiXa(OR)4-a的有机硅烷化合物，其中R表示1-6个碳原子的烷基，X表示烷基环氧丙氧基，且a表示1-3的整数。
第一部分可以包括如下的化合物，至少一种锆化合物，例如在水中稳定的四价锆酸酯，特别是四乙酸锆，以及粒径小于50nm的水合无机硅胶(图4)。粒径小于50nm的水合无机硅胶对耐腐蚀性至关重要。在即将涂覆到基材上之前将第一部分和第二部分混合在一起并均质化。当将这两部分组合并涂覆到基材上时，锆化合物、无机硅胶和有机硅烷形成到表面的化学键并粘附在该表面上。初始溶胶-凝胶的pH值优选在3到6之间。
溶胶凝胶膜的厚度优选为50nm至1μm。通过使用氨基官能的硅烷作为锆酸酯、硅胶和环氧硅烷缩合形成致密网络的催化剂，可以实现改善的溶胶凝胶涂层的耐腐蚀性。然后可以在溶胶凝胶涂层上面涂一层或多层面漆，优选但不限于环氧/胺、乙酰乙酸丙烯酸类(acetoacetate acrylic)/丙烯酸酯、聚氨酯、丙烯酸类、聚酯、三聚氰胺或其混合物，作为水基或溶剂基液体体系或无溶剂粉末涂料体系。直接用环氧/胺涂料进行面涂时，可在室温下无需催化剂即可实现溶胶凝胶固化。基于上述有机树脂体系之一的面漆特别优选涂覆于溶胶-凝胶涂层。
结果，金属表面的本发明的薄的溶胶-凝胶涂层可以令人惊奇地实现表面涂层体系的腐蚀抑制作用的进一步明显改善。此外，通过溶胶-凝胶涂层明显改善了面漆体系对金属基材的粘附性。甚至单独的膜厚为100nm的溶胶-凝胶涂层也具有出色的防腐蚀作用，例如，当涂有底漆的金属基材在最终使用或最终涂层之前进行存储时，其可以用作一种形式的金属表面临时腐蚀控制。
金属基材包括任何金属和金属合金，特别是用于汽车、航空航天和航空工业的那些金属和金属合金。特别地，金属基材可以包括以下中的任何一种或组合：铝；铝合金；镁；镁合金；钢；不锈钢；锌或锌合金或钛或钛合金。该涂层也适用于涂覆暴露于风化腐蚀的其他基材。
实施例
实施例1
杂化溶胶凝胶的制备：
允许在IPA中用羧酸或2,4-戊二酮稳定烷氧基锆酸酯。然后通过加入过量的水将稳定的锆酸酯完全水解。然后将形成的锆溶胶-凝胶与作为无机硅胶原料的四烷基硅酸酯一起搅拌加入。硅酸酯完全水解并通过部分缩合形成纳米颗粒后，形成锆-二氧化硅杂化溶胶-凝胶。涂覆前，让环氧官能硅烷在溶胶-凝胶中水解。
湿磨铝合金AA2024-T3(覆层和/或裸露)板以进行脱氧。然后将板用干净的去离子水冲洗，并用丙酮擦干。然后用溶胶-凝胶预处理，环氧/胺底漆和/或乙酰乙酸丙烯酸类/丙烯酸酯底漆，和氨基甲酸酯面漆依次喷涂。室温干燥3小时后，可以用底漆涂布预处理。
为了比较，将一种可商购的预处理溶胶-凝胶涂层(3M的“Boegel”)和12种不同的溶胶-凝胶样品用于比较分析。
结果
为了测试目的，将板一式三份制备。体系由基准Boegel预处理、溶胶-凝胶(控制过程)预处理或基于Sol-Gel、环氧树脂/胺底漆和/或乙酰乙酸丙烯酸类/丙烯酸酯底漆和聚氨酯面漆的控制过程的12种预处理组成。在测试之前将板固化2周。测试板的3000小时盐雾暴露、1000小时丝状暴露和30天的耐Skydrol性。
Skydrol结果
胶粘板的边缘，并且在板上形成了1英寸的划线。将带有划线的板的一半浸入Skydrol溶液中30天。然后将板从Skydrol溶液中取出，并用IPA清洗以去除Skydrol油。然后检查板在划痕处及其周围是否有泡或缺陷。然后在划痕测试仪上测试板的硬度。沿板的涂层拉动针头时，使用1200克的重量。
所有板均通过Skydrol测试。划痕测试穿透了所有板上的面漆，但没有穿透底漆。
1000小时丝状结果
胶粘板的边缘和背面以用于丝状暴露。断裂的T划痕被蚀刻到板上穿透到基材中。然后使板在环境温度下朝下暴露于HCl蒸气中1小时。将板从酸蒸气暴露中移出并在露天中放置15分钟。然后将板以垂直位置方式在设定为40℃和82％相对湿度的热电瓶中放置1000小时。然后从热电瓶中除出板，并读取丝状读数。
与目前的市售基准相比，本发明的溶胶凝胶显示出更好的耐腐蚀性和更小的泡。
3000小时盐雾效果
利用AMS3095A认证测试确定了盐雾性能结果。胶粘板的边缘和背面以用于盐雾暴露。断裂的T划痕被蚀刻到板上穿透到基材中。然后将板暴露于3000小时的盐雾条件下。评定板在水平和垂直划线上的最大泡尺寸。没有泡的尺寸超过3毫米。所有板均符合AMS3095A规范。允许的最大泡尺寸为3毫米。所有板的读数均小于2毫米。与目前的市售基准相比，本发明的溶胶凝胶具有更好的耐腐蚀性和更短的蠕动(creepage)。

Claims (10)

1.一种稳定的锆-二氧化硅杂化溶胶-凝胶组合物，所述组合物包含：
（a）至少一种通式为Zr(OC(O)R)4的锆化合物：
其中R代表1-6个碳原子的烷基；和
（b）粒径小于50nm的水合无机硅胶，
所述溶胶-凝胶组合物还包含2,4-戊二酮。
2.两部分的溶胶-凝胶组合物，其包含：
（a）第一部分，其包含至少一种通式为Zr(OC(O)R)4的锆化合物和粒径小于50nm的水合硅胶，
其中R代表1-6个碳原子的烷基；和
b）第二部分，其包含通式为SiXa(OR)4-a的有机硅烷化合物，其中R表示1-6个碳原子的烷基，X表示烷基环氧丙氧基，a表示1-3的整数。
3.权利要求2所述的两部分溶胶-凝胶组合物，其中第一部分还包含2,4-戊二酮。
4.一种涂料组合物，其包含：
（a）权利要求2或3所述的溶胶-凝胶组合物；和
（b）至少一种具有以下通式的硅烷基化合物：
SiXa(OR)4-a
其中R表示1-6个碳原子的烷基，X表示烷基胺基，a表示1-3的整数。
5.权利要求4所述的涂料组合物，其中所述硅烷基化合物是氨基硅烷。
6.权利要求4所述的涂料组合物，其中所述硅烷基化合物是双硅烷基胺。
7.一种涂层体系，其包括：
（a）权利要求4所述的溶胶-凝胶组合物；和
（b）在所述溶胶-凝胶组合物上的具有环氧和胺官能团的底漆树脂层。
8.如权利要求7所述的涂层体系，还包括在所述底漆树脂层上的氨基甲酸酯面漆。
9.一种涂层体系，其包括：
（a）权利要求4所述的溶胶-凝胶组合物；和
（b）具有乙酰乙酸酯和丙烯酸酯官能团的底漆树脂层。
10.权利要求9所述的涂层体系，其还包含氨基甲酸酯面漆。
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