CN109154086B - 溶胶-凝胶防腐蚀处理的开发 - Google Patents

溶胶-凝胶防腐蚀处理的开发 Download PDF

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CN109154086B
CN109154086B CN201780012907.1A CN201780012907A CN109154086B CN 109154086 B CN109154086 B CN 109154086B CN 201780012907 A CN201780012907 A CN 201780012907A CN 109154086 B CN109154086 B CN 109154086B
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让-巴蒂斯特·康邦
朱利安·埃斯特班
罗兰·罗德里格·马福阿纳
让-菲利普·吕特施
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Safran SA
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Abstract

本发明涉及一种用于处理金属合金部件的方法,其特征在于,所述方法包括以下步骤:通过以等摩尔份的硅混合经水解的环氧硅烷的醇溶液和经水解的氨基硅烷的醇溶液来制备母液制剂;将所述母液制剂与悬浮液混合以获得稀释制剂,所述悬浮液含有基于所述母液制剂总重量,0.1wt%~10wt%的导电纳米线;以及,将所述稀释制剂沉积至所述部件上以获得涂层。

Description

溶胶-凝胶防腐蚀处理的开发
技术领域
本发明涉及金属如铝、钢或镁及其金属合金的抗腐蚀处理的开发。
背景技术
金属及其合金广泛用于工业中,并且,制造商根据所寻求的性质(机械、热、化学传导等)来选择所使用的金属(或合金)类型。
例如,铝由于既具有低密度又具有良好的机械和防腐性能而常常用于航空领域。然而,为了进一步提高铝的机械强度,该金属通常与其他化学元素,诸如铜(Cu)、铁(Fe)、锌(Zn)、硅(Si)等形成合金,从而形成硬化沉淀物并显著降低铝的抗腐蚀性的作用。
为了克服这个问题,特别是在飞机制造业中已知的是,对铝合金部件的表面进行保护性表面处理。实例包括化学转化方法,其是适于在铝合金部件的表面上形成厚度非常薄(通常小于1微米)的复合氧化物层(通常基于铬酸盐和锆酸盐)的化学处理。例如,基于六价铬的化学转化工艺的Alodine 1200,使得能够获得保护铝合金免受腐蚀、使铝合金具有良好的耐久性和良好的导电性(对于确保飞机在高放电情况下的电气连接是至关重要)以及对油漆的良好附着力(精加工处理)的涂层。
通常,通过浸泡待处理部件(完全处理的部件)或通过修整待处理部件(局部处理)来进行化学转化方法。
在航空领域中,铝合金部件的预期性能特征如下:
良好的耐腐蚀性(即,根据标准ASTM B 117或ISO 9227,在浸泡处理的情况下暴露于盐雾中168小时后,以及在修整处理的情况下暴露于盐雾中72小时后,每平方分米中凹陷不超过2.5个);
良好的导电性(即,导电性符合或超过标准MIL-DTL-81706的要求);
油漆对所得涂层的附着力(0/1级干燥,浸入流体后最多1/2级);
耐流体性(水、液压油、燃料、除冰剂、溶剂等);
所获得的涂层是有色的或至少肉眼可见的(未施加颜色)。
基于六价铬的化学转化方法,诸如Alodine 1200使得能够在铝合金部件上形成具有非常好的耐腐蚀性和优异的油漆附着力的涂层。由此获得的涂层还是自修复的(局部修整)并且具有杀菌作用以及易于被操作者察觉的黄色/金色。
因此,这些化学转化工艺确实使得铝合金部件具有航空领域中所期望的性能特征。
然而,含六价铬的废水的处理非常昂贵且毒性很高。此外,这种处理不符合环境标准的要求(诸如1907/2006号法规),并且很可能在2017年之后不再使用。
因此,已经提出采用清洁(décapage)、阳极氧化、密封(colmatage)或化学转化替代性处理,以通过其他方式在金属部件上获得可能具有尤其是航空领域中预期性能特征的涂层。
然而,结果证明,所设想的替代性处理中没有一种是通用的,即能够应用于大量金属合金(包括铝合金在内)。
同样地,结果证明,在所考虑的替代性处理中,只有基于三价铬的化学转化处理
Figure BDA0001774653360000021
650V和Lanthane 613.3,能够生产有色涂层,其它获得的涂层几乎无色(或仅是略带闪亮蓝色)。然而,这种着色的存在是优选的,以便操作者能够验证在整个处理过的金属部件上已经获得了涂层。此外,
Figure BDA0001774653360000022
650V和Lanthane 613.3化学转化处理为5000系列和6000系列铝合金提供了令人满意的结果。然而,这些方法不是通用的,并因此不能令人满意地应用于所有系列的铝合金或其它金属合金,诸如基于镁或铁的合金。
最后,通过化学转化处理获得的涂层尚不足够坚固以满足上述2000系列和7000系列高性能铝合金的耐盐雾性标准。
发明内容
因此,本发明的目的是提出一种处理由金属合金制成的部件的方法,该方法可以应用于大量合金,特别是所有系列的铝合金、铁合金和镁合金,从而使得其具有良好的耐腐蚀性、良好的导电性、良好的油漆附着力、良好的耐流体性,并且易于操作者通过肉眼可见。
优选地,该方法应该能够应用于由条或片或锻制件(1000系列至8000系列)、铸造件(合金AS7G0.6等)制成的部件,以及直接由铝合金制成的部件。
为此,本发明提出一种处理金属合金部件的方法,其特征在于,所述方法包括以下步骤:
通过以等摩尔份的硅混合经水解的环氧硅烷的醇溶液和经水解的氨基硅烷的醇溶液来制备母液制剂;
将所述母液制剂与悬浮液混合以获得稀释制剂,所述悬浮液含有基于所述母液制剂总重量,0.1wt%~10wt%的导电纳米线;以及
将所述稀释制剂沉积至所述部件上以获得涂层。
因此,该方法能够获得溶胶-凝胶涂层,从而为金属合金(特别是基于铝、钢或镁的金属合金)提供抗腐蚀性能,其中掺入导电纳米线(基于银),以赋予涂层导电性。该涂层还符合基于六价铬的当前化学转化处理的规格。具体应用包括对整个部件的处理或者在发生碰撞或局部剥离时对阳极氧化表面的局部修整。
如下示出了如上所述方法的某些优选但非限制性的特征,这些特征可单独或组合使用:
所述导电纳米线包括银纳米线、碳纳米线和/或铜纳米线;
所述导电纳米线包括银纳米线,所述银纳米线的悬浮液通过以2000转/分钟至6000转/分钟的速度离心纳米线和银颗粒的悬浮液而制备;
所述银纳米线的悬浮液根据以下子步骤获得:将聚乙烯吡咯烷酮溶解在乙二醇中以获得溶液,将由此获得的溶液加热至100℃至160℃的温度,以及待温度稳定后,加入氯化钠和乙酰丙酮铁(II)的溶液,然后加入硝酸银的乙二醇溶液;
所述氨基硅烷的醇溶液包含异丙醇;
所述经水解的环氧硅烷的醇溶液的浓度和所述经水解的氨基硅烷的醇溶液的浓度约为0.1mol/L;
所述母液制剂进一步包含氟硅烷,所述氟硅烷基于源自环氧硅烷和源自氨基硅烷的硅和/或源自纳米二氧化硅的硅,摩尔浓度为0.5%~5%,基于源自环氧硅烷和氨基硅烷的,摩尔浓度为1%~5%;
所述母液制剂进一步包含:基于所述母液制剂干重,重量浓度为0.5%至5%的染料;
所述方法进一步包括:在沉积所述涂层之前,对所述部件进行清洁的步骤和/或用促粘剂对所述部件进行预处理的步骤;
所述方法进一步包括:在沉积所述涂层的步骤之后,在80℃至150℃、优选80℃至120℃的温度下,使该部件聚合的步骤;
在所述母液制剂中,所述导电纳米线具有1至100的纵横比;和/或
通过将所述稀释制剂喷雾到所述部件上,通过在所述稀释制剂中浸涂所述部件或通过机械方法进行沉积。
根据第二方面,本发明还提出了一种金属合金部件,所述金属合金部件包括根据如上所述的处理方法获得的具有0.5微米至5微米的涂层厚度的涂层。
以下示出了如上所述部件的某些优选但非限制性的特征,这些特征可单独或组合使用:
所述部件的构成材料包括铝合金、铁合金或镁合金,和/或
所述涂层包含银纳米线。
附图说明
通过阅读以下详细描述并参考以非限制性实例给出的单一附图,本发明的其他特征、目的和优点将更加明显,其中,上述单一附图是示出根据本发明的处理部件的方法的步骤的流程图。
具体实施方式
本发明提出了一种用于金属合金部件的处理方法S,以便用具有良好耐腐蚀性、良好导电性、良好油漆附着力和良好耐流体性的涂层涂覆该金属合金部件。如有必要,涂层还必须具有颜色,以便操作者可以看到。
例如,在铝合金部件的情况下,涂层必须赋予部件以下特性:
根据标准ASTM B 117或ISO 9227,在浸泡处理的情况下暴露于盐雾168小时后,以及在修整处理的情况下暴露于盐雾中72小时后,每平方分米中凹陷不超过2.5个;
导热性符合或超过标准MIL-DTL-81706的要求;
油漆对所述涂层的附着力,0/1级干燥,且浸入流体后最多1/2级;和
耐流体性(水、液压油、燃料、除冰剂、溶剂等)。
为此,用于金属合金部件的处理方法S包括以下步骤:
通过以等摩尔份的硅混合经水解的环氧硅烷的醇溶液和经水解的氨基硅烷的醇溶液来制备(步骤S1)母液制剂;
将所述母液制剂与悬浮液混合(步骤S2)以获得稀释制剂,所述悬浮液含有基于所述母液制剂干重,0.1wt%~10wt%的导电纳米线;以及
将所述稀释制剂沉积(步骤S3)至所述部件上以获得涂层。
更确切地说,在第一步骤S1期间,通过以等摩尔份的硅混合经水解的环氧硅烷的醇溶液和经水解的氨基硅烷的醇溶液来获得母液制剂。
在一实施方案中,经水解的氨基硅烷的醇溶液可包含异丙醇。
在一示例性实施方案中,可制备已测量加入物的量的两种溶液来获得母液制剂。为此,可通过称量24.622g的2-(3,4-环氧环己基)乙基三甲氧基硅烷(摩尔质量为246.22g.mol-1)来制备在异丙醇(IP)中的0.1mol环氧硅烷的第一溶液。然后,加入769.778g的异丙醇(IP)和0.3摩尔的水(即5.4g)来水解环氧硅烷的三个烷氧基官能团。然后将第一溶液置于封闭瓶中,于50℃烘箱中放置12小时。然后用氨基硅烷进行相同的步骤,例如称重3-N,N-二甲基氨基丙基)三甲氧基硅烷。由此获得含有相等体积的相同量的硅的两种溶液。
根据金属合金部件所需的抗腐蚀性和/或导电纳米线的量可调节环氧硅烷的醇溶液和氨基硅烷的醇溶液的水解度。例如,如果涂层沉积于其上的表面(诸如经清洁的铝表面)是疏水的,则优选已经历一次或两次水解的溶液。
使用处理方法S获得的涂层的厚度取决于母液制剂的粘度。例如,可通过改变氨基硅烷的醇溶液的溶剂稀释度来调节母液制剂的粘度。
母液制剂的两部分中的每一部分的浓度可以是,例如约0.1mol/L。然后将两种溶液以等摩尔份的硅混合,得到母液制剂。
可选地,可将氟硅烷以0.5%至5%的摩尔浓度(基于源自环氧硅烷和氨基硅烷的硅的摩尔浓度)添加至母液制剂中,以增加利用方法S所获得的涂层的疏水性。
同样可选地,可将纳米二氧化硅以1%至5%的摩尔浓度(基于源自环氧硅烷和氨基硅烷的硅)加入到母液制剂中,以改善涂层的硬度。如本文所用,“纳米二氧化硅”是指平均粒径为7纳米至40纳米的二氧化硅。这种二氧化硅例如以商品名
Figure BDA0001774653360000061
出售。
为了获得操作者肉眼可见的涂层,可将合成染料,诸如以商品名
Figure BDA0001774653360000062
销售的溶剂合成染料以0.5%和5%的重量浓度(基于母液制剂的总干重)加入到制剂中。
在第二步骤S2中,将悬浮液引入由此获得的母液制剂中以获得稀释制剂,其中,所述悬浮液包含0.1wt%~10wt%(基于母液制剂的总干重)的导电纳米线。
根据在金属合金部件上待获得的涂层所需的导电性可调节悬浮液中导电纳米线以重量计的量。
此外,悬浮液优选基于醇。
导电纳米线可包括银纳米线、碳纳米线、铜纳米线或这些纳米线的混合物。
优选地,导电纳米线具有1~100的纵横比,以便在沉积步骤S3之前在稀释制剂中形成稳定的悬浮状态。
导电纳米线可以以常规方式合成。
银纳米线合成的实例可参见以下出版物:Highly Flexible Transparent FilmHeaters Based on Random Networks of Silver Nanowires,Caroline Celle,CélineMayousse,Eléonore Moreau,Henda Basti,Alexandre Carella,and Jean–PierreSimonato,Nano Res.2012,5(6):427–433;Fabrication of Silver NanowireTransparent Electrodes at Room Temperature,Takehiro Tokuno,Masaya Nogi(),Makoto Karakawa,Jinting Jiu,Thi Thi Nge,Yoshio Aso,and Katsuaki Suganuma,NanoRes.2011,4(12):1215–1222;Scalable Coating and Properties of Transparent,Flexible,Silver Nanowire Electrodes,Liangbing Hu,Han Sun Kim,Jung–Yong Lee,Peter Peumans,and Yi Cui,ACSnano VOL.4·NO.5·2955–2963·2010;Silvernanowire–based transparent,flexible,and conductive thin film,Cai–Hong Liu,XunYu,Nanoscale Research Letters 2011,6:75;Ag–nanowire films coated with ZnOnanoparticles as a transparent electrode for solar cells,FrederikS.F.Morgenstern,Dinesh Kabra,Sylvain Massip,Thomas J.K.Brenner,Philip E.Lyonset al.,Appl.Phys.Lett.99,183307(2011);doi:10.1063/1.3656973。
如果需要,可以调整这些银纳米线合成方法以获得透明涂层(其中,仅可选地,加入染料以使涂层具有有色的外观)。
示例性银纳米线合成方法可如下进行:
(i)将约0.2g的聚乙烯吡咯烷酮(PVP)溶解在20g至30g乙二醇中,然后在该乙二醇溶液中加入200至600mg硝酸银。优选地,只有在将溶液加热至合成温度并稳定在所述温度之后,才加入硝酸银。可选地,可以加入乙酰丙酮铁以获得具有更大长度(10μm)并因此具有更高纵横比的银纳米线。
(ii)将由此获得的溶液加热至100℃至160℃的温度,持续10分钟至60分钟的时间。由此获得银纳米线的悬浮液。
(iii)使悬浮液冷却。
(iv)以2000rpm(209.4rad/s)至6000rpm(628.3rad/s)的速度离心悬浮液。作为最大质量元素的银纳米线在离心装置的底部形成离心球状物,同时纳米颗粒保持悬浮状态。然后,充分除去上清液并用醇洗涤球状物数次以收集银纳米线。
应当注意,本文描述的示例性合成方法易于适用于更大的规模。
在第三步骤S3中,将由此获得的稀释制剂沉积在金属合金部件上以形成涂层。该沉积可以通过喷涂(有时称为热喷涂)稀释制剂、通过在稀释制剂中浸涂部件,或通过使用机械通过喷雾来进行。
沉积技术的选择尤其取决于待涂覆的金属合金部件的形状和待生产的部件的数量。例如,对于简单形状的部件,可以考虑浸涂和喷涂。另一方面,对于复杂几何形状(存在通孔,锐角等)的部件,可优选使用机械进行喷雾以使稀释制剂能够通过部件相对于涂覆机械的旋转和/或平移而有效地流动。
可选地,在沉积步骤S3之前,可以清洁和/或用促粘剂如羧酸铁或高稀释度的氨基硅烷预处理待涂覆的铝部件表面。
在第四步骤S4中,使由此在金属合金部件上形成的涂层在80℃~150℃的温度下聚合。优选地,当金属合金是铝基合金时,使聚合温度保持低于120℃,以便不会改变铝合金的机械性能,特别是当硬化或轧制处理过的部件时。通过导电纳米线与金属部件表面之间的渗透获得构成金属部件的金属合金与涂层之间的传导。
因此,处理方法S使得能够用具有良好机械、防腐和导电性能、良好的油漆附着力和良好的耐流体性的涂层来涂覆金属合金部件。依据所述稀释制剂所选的稀释度,涂有这种涂层的部件的表面积可以在每升含导电纳米线的稀释制剂1.7m2至5m2/变化。当母液制剂包含染料时,在该部件上形成的涂层还是肉眼可见的。
应该注意的是,通过在液体中形成金属-氧-金属键来产生凝胶化,称为溶胶,其被转化为假固体,称为凝胶。在更具体的情况下,在溶剂蒸发以及为这些键的形成提供能量的温度的作用下,产生Si-O-Si键。
最后,调节母液制剂(特别是氨基硅烷的醇溶液)的稀释度使得能够形成厚度在0.5微米和5微米之间的涂层。
实施例
例如,可如下获得用于航空领域的铝合金部件的涂层。在本文中,铝合金是基准牌号为2024-T351-215的2000系列合金。
在第一步骤S1中,通过将4.5g的经水解的环氧硅烷的醇溶液(水解度在1.5和3之间)与3.59g的经水解的氨基硅烷的醇溶液(水解度在1.5和3之间)混合来获得母液制剂,上述醇溶液的浓度为0.1mol/L。将下述物质添加到该制剂:
0.1g至0.6g的氟硅烷,
1.44g的具有氨基硅烷的纳米二氧化硅(10重量%SiO2)(例如纳米二氧化硅
Figure BDA0001774653360000091
200)和
0.100g的
Figure BDA0001774653360000092
染料(例如
Figure BDA0001774653360000093
蓝色BL)
3.98g的异丙醇以调节制剂的粘度。
在第二步骤S2中,将悬浮液引入由此获得的母液制剂中,其中,该悬浮液包含30mg至150mg的纵横比为5至60(例如平均约30)的银纳米线。在本文中,通过将约0.2g的摩尔质量为55000g.mol-1(该参数影响纳米线长度和直径)的聚乙烯吡咯烷酮(PVP)连续溶解在23g的乙二醇中,然后加热至130℃来获得银纳米线。在温度稳定后,加入124μL的氯化钠(NaCl)溶液(100mM)和833μL的乙酰丙酮铁(II)(2.2mM)。在此,使氯化钠和乙酰丙酮铁在乙二醇中形成溶液。10分钟后,加入硝酸银(AgNO3)溶液(包含溶解在4.2mL乙二醇中的0.83g的AgNO3),并使其反应60分钟至180分钟。冷却后,以2000rad/s至6000rad/s的速度离心悬浮液,以收集银纳米线。
在第三步骤S3中,对待涂覆的铝部件表面进行清洁,然后通过喷涂将由此获得的稀释制剂沉积在金属合金部件上以形成涂层。
在第四步骤S4中,使由此在金属合金部件上形成的涂层在120℃的温度下聚合1小时。
由此获得的涂层具有以下性质:
拉脱附着力:大于7MPa;
横切附着力:ISO标准下为0;
铅笔测试>6H;
硬度测试:8N;
粗糙度(Ra):0.4μm至0.7μm;
对于约1微米至5微米的涂层厚度,覆盖1平方米表面所需的含银纳米线的稀释制剂的体积为1L至5L。

Claims (15)

1.一种用于金属合金部件的处理方法(S),其特征在于,所述处理方法包括以下步骤:
通过以等摩尔份的硅混合(S1)经水解的环氧硅烷的醇溶液和经水解的氨基硅烷的醇溶液来制备母液制剂;
将所述母液制剂与悬浮液混合(S2)以获得稀释制剂,所述悬浮液含有基于所述母液制剂总重量,0.1wt%~10wt%的导电纳米线;以及
将所述稀释制剂沉积(S3)至所述部件上以获得涂层;
所述导电纳米线包括银纳米线、碳纳米线和/或铜纳米线。
2.根据权利要求1所述的处理方法(S),其中,所述导电纳米线包括银纳米线,所述银纳米线的悬浮液通过以2000转/分钟至6000转/分钟的速度离心纳米线和银颗粒的悬浮液而制备。
3.根据权利要求2所述的处理方法(S),其中,所述银纳米线的悬浮液根据以下子步骤获得:
将聚乙烯吡咯烷酮溶解在乙二醇中以得到溶液;
将由此获得的溶液加热至100℃至160℃的温度;以及
待温度稳定后,加入氯化钠和乙酰丙酮铁(II)的溶液,然后加入硝酸银的乙二醇溶液。
4.根据权利要求1~3中任一项所述的处理方法(S),其中,所述氨基硅烷的醇溶液包含异丙醇。
5.根据权利要求1~3中任一项所述的处理方法(S),其中,所述经水解的环氧硅烷的醇溶液的浓度和所述经水解的氨基硅烷的醇溶液的浓度约为0.1mol/L。
6.根据权利要求1~3中任一项所述的处理方法(S),其中,所述母液制剂进一步包含:氟硅烷,所述氟硅烷基于源自环氧硅烷和源自氨基硅烷的硅,摩尔浓度为0.5%~5%;和/或,纳米二氧化硅,所述纳米二氧化硅基于源自环氧硅烷和氨基硅烷的硅,摩尔浓度为1%~5%。
7.根据权利要求1~3中任一项所述的处理方法(S),其中,所述母液制剂进一步包含:基于所述母液制剂的干重,重量浓度为0.5%至5%的染料。
8.根据权利要求1~3中任一项所述的处理方法(S),所述处理方法进一步包括:在沉积所述涂层之前,对所述部件进行清洁的步骤和/或用促粘剂对所述部件进行预处理的步骤。
9.根据权利要求1~3中任一项所述的处理方法(S),所述处理方法进一步包括:在沉积(S3)所述涂层的步骤之后,在80℃至150℃的温度下,使所述部件聚合的步骤(S4)。
10.根据权利要求1~3中任一项所述的处理方法(S),所述处理方法进一步包括:在沉积(S3)所述涂层的步骤之后,在80℃至120℃的温度下,使所述部件聚合的步骤(S4)。
11.根据权利要求1~3中任一项所述的处理方法(S),其中,在所述母液制剂中,所述导电纳米线具有1至100的纵横比。
12.根据权利要求1~3中任一项所述的处理方法(S),其中,通过将所述稀释制剂喷雾到所述部件上、通过在所述稀释制剂中浸涂所述部件或通过机械方法进行沉积。
13.一种金属合金部件,其特征在于,所述金属合金部件包括根据权利要求1~12中任一项所述的处理方法(S)获得的涂层厚度为0.5微米至5微米的涂层。
14.根据权利要求13所述的部件,其中,所述部件的构成材料包括铝合金、铁合金或镁合金。
15.根据权利要求13或14所述的部件,其中,所述涂层包含银纳米线。
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