CN1204294C - 应用双官能聚硫硅烷的金属的腐蚀防护 - Google Patents

应用双官能聚硫硅烷的金属的腐蚀防护 Download PDF

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CN1204294C
CN1204294C CNB998077275A CN99807727A CN1204294C CN 1204294 C CN1204294 C CN 1204294C CN B998077275 A CNB998077275 A CN B998077275A CN 99807727 A CN99807727 A CN 99807727A CN 1204294 C CN1204294 C CN 1204294C
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W·J·范奥伊捷
V·苏布拉马尼安
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Abstract

一种应用双官能聚硫硅烷防止金属腐蚀的方法。该方法包括：提供一个金属表面，以及将处理溶液涂到所述金属表面上。所述处理溶液包含至少一种式(I)水解的双官能聚硫硅烷；其中，每个R是烷基或乙酰基，Z或者是-SX或者是-Q-SX-Q-，其中，每个Q是脂族基或芳基，x则是2～9的整数。还提供了一种处理溶液和具有改善的耐腐蚀性的金属表面。

Description

应用双官能聚硫硅烷的金属的腐蚀防护
本发明涉及一种防止金属表面腐蚀的方法。更具体地说，本发明提供了一种防止金属表面腐蚀的方法，它包括将包含一种或多种双官能聚硫硅烷的溶液涂到金属表面上。本方法特别适合处理锌、铜、铝和上述金属的合金(例如黄铜和青铜)的表面。
大多数金属易受不同程度和类别的腐蚀，腐蚀将大为影响这类金属的质量，还影响从这类金属生产的产品的质量。虽然有时可避免很多腐蚀形式，但这样的处理步骤费用大，而且还可能减小终产品的效用。此外，当聚合物涂料(例如油漆)、粘合剂或橡胶被涂到金属上后，基体金属材料的腐蚀可能引起聚合物涂料和基体金属之间粘合作用的丧失。
关于改善金属(尤其是金属板)的耐腐蚀性的现有技术方法包括，通过重铬酸盐处理钝化表面。然而，这样的处理方法是不合乎需要的，因为铬酸盐离子毒性大、致癌和污染环境。还已知应用磷酸盐转化型涂料与铬酸盐淋洗相结合而改善油漆附着力和提供腐蚀防护。人们认为，铬酸盐淋洗覆盖磷酸盐涂层中的孔，于是改善耐腐蚀性和粘附特性。然而，又一次地，极其需要完全消除铬酸盐的应用。遗憾的是，如果没有铬酸盐淋洗，磷酸盐转化型涂料通常是无效的。
最近，提出了关于省去铬酸盐的应用的各种方法。这些方法包括：用无机硅酸盐涂布金属，接着用有机官能硅烷处理硅酸盐涂层(美国专利No.5,108,793)。美国专利No.5,292,549启示了用含有机官能硅烷和交联剂的溶液淋洗金属板以便提供暂时的腐蚀防护。交联剂交联有机官能硅烷而形成更致密的硅氧烷膜。然而，所述专利方法的一个显著缺点是有机官能硅烷将不与金属表面良好地粘合，所以，美国专利No.5,292,549的涂料可被容易地淋洗掉。还提出了关于防止金属板腐蚀的各种其它方法。然而，这些提出的方法有很多效率低或者要求费时、能量效率低、多步骤操作。
进一步使防止金属腐蚀的工作复杂化的这一事实(即，腐蚀可通过若干不同的机制发生)在很大程度上取决于所涉及的具体金属。黄铜例如对在水性环境中的腐蚀(特别是均匀的腐蚀)、脱锌腐蚀(尤其在含酸一氯化物的溶液中)和应力腐蚀裂开(特别是在氨和胺的存在下)很敏感。铜和铜合金(包括黄铜)将容易在空气中和在含硫环境中失去光泽。另一方面，锌和锌合金在潮湿条件下特别易于形成“白锈”。遗憾的是，很多关于防腐蚀的现有技术处理方法对锌、锌合金、铜和铜合金(尤其黄铜和青铜)的效果较小，或者只对某些类型的腐蚀有效。
因此，需要一种简单、低成本的方法来防止金属表面[特别是锌、锌合金、铝、铝合金、铜和铜合金(尤其黄铜和青铜)]的腐蚀。
本发明的一个目的是提供一种防止金属表面腐蚀的改良方法。
本发明的另一目的是提供一种防止金属表面腐蚀的处理溶液。
本发明的又一目的是提供一种防止金属表面(特别是锌、铜、铝和上述金属的合金)腐蚀的方法。
上述目的可这样达到：按本发明的一方面，通过提供一种处理金属表面而改善耐腐蚀性的方法，该方法包括如下步骤：
(a)提供一个金属表面；以及
(b)将处理溶液涂到金属表面上，该处理溶液包含至少一种已被至少部分地水解了的双官能聚硫硅烷，该硅烷包括：
其中，(在水解前)每个R是烷基或乙酰基，Z或者是-Sx或者是-Q-Sx-Q-，其中，每个Q是脂族基或芳基，x则是2～9的整数(优选是4)。
每个R可以独自选自如下基：乙基、甲基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基和乙酰基。然而，应懂得，硅烷的水解导致R基(至少它们的一部分，优选它们的几乎全部)被一个氢原子替代。每个Q可以独自选自如下基：C1～C6烷基(线型或支化的)、C2～C6烯基(线型或支化的)、被一个或多个氨基取代的C1～C6烷基、被一个或多个氨基取代的C2～C6烯基、苄基和被C1～C6烷基取代的苄基。一组优选的硅烷是具有2～9个硫原子的双(三乙氧基甲硅烷基丙基)硫化物，特别是双(三乙氧基甲硅烷基丙基)四硫化物。
本发明的处理方法特别适合选自下组的金属：锌、锌合金、铜、铜合金、铝和铝合金。这类金属表面的实例有：黄铜、青铜和甚至热浸镀锌的钢。
所述处理溶液还优选包含水和溶剂，例如一种或多种醇(例如，乙醇、甲醇、丙醇和异丙醇)。所述处理溶液中双官能聚硫硅烷的总浓度在约0.1vol％～约25vol％之间，更优选在约1vol％～约5vol％之间。一个优选的实施方案包括：每份水约3～约20份甲醇(作为溶剂)。
本发明还提供了一种防止金属底材腐蚀的处理溶液，它包含至少一种已被至少部分地水解了的双官能聚硫硅烷，即下式的硅烷：
其中，每个R(在水解前)是烷基或乙酰基，Z或者是-Sx或者是-Q-Sx-Q-，其中，每个Q是脂族基或芳基，x则是2～9的整数。
还提供了一种具有改善的耐腐蚀性的金属表面，它包括：
(a)一个金属表面；以及
(b)附着在该金属表面的一种硅烷涂层，该硅烷包含至少一种已被至少部分地水解了的双官能聚硫硅烷，该双官能聚硫硅烷包括：
Figure C9980772700071
其中，每个R是烷基或乙酰基，Z或者是-Sx或者是-Q-Sx-Q-，其中，
每个Q是脂族基或芳基，x则是2～9的整数。
美国专利Nos.US 3,842,111、US 3,873,489、US 3,978,103和US5,405,985都指出，含硫的有机硅化合物适用作活性偶合剂和助粘剂(尤其适用于橡胶和金属)。所以，预计本发明的方法和处理溶液可被用于促进橡胶或其它聚合物涂料(例如油漆)或粘合剂与金属底材的粘合。因此，涂布的表面将表现改善的耐腐蚀性，同时赋予在硫硅烷涂布的金属底材上面设置的其它涂料的增粘作用。
本申请人发现了，金属表面(特别是锌、锌合金、铝、铝合金、铜和铜合金的表面)的腐蚀可通过涂布一种处理溶液来预防，该溶液包含一种或多种双官能聚硫硅烷，其中，该硅烷已至少被部分地水解了。可被用于制备所述处理溶液的双官能聚硫硅烷包括：
Figure C9980772700072
其中，每个R是烷基或乙酰基，Z或者是-Sx或者是-Q-Sx-Q-。每个Q是脂族基(饱和的或不饱和的)或芳基，x则是2～9的整数(优选是4)。
所述含硫硅烷中的每个R可以相同或不同，所以，所述硅烷既可包括烷氧基部分，又可包括乙酸基部分。不过，如下文进一步概述的那样，所述硅烷在处理溶液中被水解，于是，几乎全部(或者至少一部分)R基被氢原子替代了。在一个优选的实施方案中，每个R可以独自选自：乙基、甲基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基和乙酰基。同样，所述双官能聚硫硅烷中的Q可以相同或不同。在一个优选的实施方案中，每个Q独自选自如下基：C1～C6烷基(线型或支化的)、C2～C6烯基(线型或支化的)、被一个或多个氨基取代的C1～C6烷基、被一个或多个氨基取代的C2～C6烯基、苄基和被C1～C6烷基取代的苄基。
特别优选的双官能聚硫硅烷包括具有2～9个硫原子的双(三乙氧基甲硅烷基丙基)硫化物。这样的化合物具有下式：
其中，x是2～9的整数。一种特别优选的化合物是双(三乙氧基甲硅烷基丙基)四硫化物[也称为双(三乙氧基甲硅烷基丙基)硫烷]，其中，x是4。
本发明人发现了，上述双官能聚硫硅烷对锌、锌合金、铝、铝合金、铜和铜合金(特别是黄铜和青铜)的表面提供意外优良的防腐作用。此外，这些含硫硅烷保护以抗多种腐蚀，包括：均匀腐蚀、脱锌和应力腐蚀裂开。本发明方法提供的防腐还比基于铬酸盐的常规处理优越，避免了铬处理问题。
应用于本发明的双官能聚硫硅烷必须被水解，以便所述硅烷将与金属表面结合。在水解过程中，烷基或乙酰基(即“R”部分)被氢原子替代。虽然所述硅烷应该被至少部分地水解，但制备本发明的处理溶液的方法通常将导致硅烷几乎完全水解。本文应用的术语“部分地水解”仅仅表示硅烷上只有一部分R基被氢原子替代了。优选地，所述双官能聚硫硅烷应当被水解至这样的程度，即，每个分子上至少两个(更优选几乎全部)烷基或乙酰基被氢原子替代了。
所述双官能聚硫硅烷的水解可这样实现：仅仅将所述硅烷加到醇/水混合物中，于是形成本发明的处理溶液。通常，将硅烷与醇/水混合物混合将导致硅烷的充分水解(几乎全部R基被氢原子替代了)。水真正水解硅烷，但需要醇来保证适当的硅烷溶解性和溶液稳定性。当将所述处理溶液涂到金属表面上时，醇还改善润湿性，并且减少干燥所需的时间。当然，也可应用其它合适的溶剂来代替醇。现在优选的醇是甲醇和乙醇，不过，可同样应用其它醇(例如丙醇或异丙醇)。应懂得，可应用一种以上的醇。
为了制备本发明的处理溶液，醇和水应当首先彼此混合，优选在约3～约99份醇/1份水的比率(体积比)、更优选在约3～约20份醇/1份水的比率下混合。充分混合后，将硅烷加到醇/水混合物中并充分混合以保证适当水解。应将处理溶液混合至少30分钟，至多24小时，以便保证完全水解(几乎全部R基被氢原子替代了)，于是，形成本发明的处理溶液。
本发明的处理溶液稳定性可这样增强(例如，抑制了硫沉淀)，即，通过在小于室温(25℃)、更优选约0～约20℃之间的温度下制备和贮存所述处理溶液。但是，应注意，本申请人已阐述了，即使在室温下混合和贮存该处理溶液，也获得良好的防腐蚀结果。此外，应当尽可能地限制将所述处理溶液暴露于光中，因为我们认为，光将降低溶液稳定性。本发明的处理溶液的pH通常不需修改，只要所述处理溶液的正常pH[就双(三乙氧基甲硅烷基丙基)四硫化物来说，在约4和约4.5之间]允许完全水解即可。当然，可根据需要调节pH以便保证完全水解，例如通过添加乙酸或甲酸调节。
基于前面的描述，应懂得，本发明的处理溶液可以仅仅包含一种或多种水解的(至少部分水解的)双官能聚硫硅烷(如上所述)优选在醇/水溶液中的溶液。实际上，本发明的处理溶液一个优选的实施方案基本上包括水解的双官能聚硫硅烷的溶液。
所述处理溶液中双官能聚硫硅烷的浓度应当在约0.1vol％～约25vol％之间，更优选在约1％～约5％之间。比这些优选的范围更高的浓度不是成本低的，因为对耐腐蚀性没有显著改善，反而可能导致溶液不稳定性。应注意，本文讨论和主张的硅烷浓度都是根据未水解的、用于制备处理溶液的双官能聚硫硅烷(即，水解前)的体积和处理溶液组分(即，硅烷、水和醇)的总体积之间的比率测定的。此外，这些浓度表示用于制备所述处理溶液的未水解双官能聚硫硅烷的总量，因为，在所述处理溶液中可任选应用多种硅烷。
一旦按上述方法制备了处理溶液，应当在应用上述处理溶液之前，用溶剂和/或碱(通过现有技术中熟知的方法)清洗需要处理的金属底材，再用去离子水漂洗，然后让它干燥。所述处理溶液就可被直接通过下列方法涂到清洁的金属(即，在金属和本发明的处理组合物之间没有其它层)上：或者将金属浸入所述溶液(也称为“漂洗”)，将溶液喷到金属表面上，或者甚至将处理溶液抹或刷到金属底材上。当采用浸渍这种优选的应用方法时，浸渍时间不是关键的，因为它一般不会影响形成的膜厚度或特性。尽管如此，优选的是浸渍时间在约1秒～约30分钟之间，更优选在约5秒～约2分钟之间，以便保证完全覆盖金属。与其它硅烷处理方法不同，可在室温下干燥这样涂布的金属，因为不必加热或固化硅烷涂料。通常，在室温下干燥将需要两三分钟，部分地取决于处理溶液中供给的水量多少(干燥时间随着醇与水比率的减小而延长)。虽然可涂布多层，但涂布一层通常就足够了。
已证实上述处理方法提供意外优越的防腐蚀效果，尤其对锌、铜、铝和上述金属的合金。本文应用的术语“铜合金”指铜在其中是主要的金属的任何合金(即，不存在比铜的量更大的其它金属)。锌合金和铝合金的定义也类似。本发明的处理方法对于黄铜(含锌的铜合金)和青铜(铜合金，它一般含锡)的防腐蚀特别有效。例如，黄铜对腐蚀(尤其在水性环境中的均匀腐蚀)、脱锌(尤其在含酸-氯化物的溶液中)和应力腐蚀裂开(尤其在氨和胺的存在下)极其敏感。迄今，本申请人知道的、关于黄铜的唯一有效的防腐蚀方法是涂漆，或者在炼制合金过程中将另外的金属掺入黄铜(例如在海军黄铜中)。然而，涂漆并不总是可能的或所希望的(例如，当黄铜被用于艺术雕塑时)，而其它合金元素的添加又昂贵。不过，本申请人发现了，本发明的处理方法在黄铜(和青铜)的防腐蚀中很有效，不需外层油漆。因此，本发明的方法在黄铜和青铜雕塑的防腐蚀中特别适用而且有效。
如下实施例阐述了通过应用本发明的方法和处理溶液获得的优越的和意外的结果。在所有情况下，首先采用标准的、非侵蚀性碱清洗剂(AC1055，可得自Brent America，Inc.)对金属底材样品进行碱洗。将8％所述清洗剂的水溶液加热到70～80℃，再将金属底材浸入该热溶液达2～3分钟。然后，在去离子水中漂洗所述底材直至实现无水膜残迹表面。再用压缩空气吹干漂洗后的样品。
                        实施例1
为了比较本发明的方法与其它处理技术提供的防腐效果，用1，2-双(三乙氧基甲硅烷基)乙烷(“BTSE”)溶液、乙烯基三甲氧基硅烷溶液和双(三乙氧基甲硅烷基丙基)胺溶液以及本发明的处理溶液涂布了相同的黄铜样品(碱洗过、冷轧的70/30黄铜板)。
本发明的处理溶液是这样制备的：将25ml水和450ml甲醇充分混合(每份水18份甲醇，体积比)。接着，在搅拌下将25ml双(三乙氧基甲硅烷基丙基)四硫化物缓慢地加到甲醇/水混合物中，于是形成硅烷浓度约为5vol％的溶液。将该处理溶液混合至少1小时以确保硅烷的充分水解。为了防止硫沉淀，再冷藏所述溶液，使温度降到约5℃。冷藏还使所述处理溶液避光。然后，就可通过浸渍将该处理溶液涂到冷轧的、70/30黄铜板上。溶液温度约为5～10℃，将样品浸渍约100秒。涂布后，在室温下的空气中干燥样品。
按类似方式配制了1，2-双(三乙氧基甲硅烷基)乙烷(“BTSE”)、乙烯基三甲氧基硅烷、双(三乙氧基甲硅烷基丙基)胺的对比处理溶液。在所有情况下，硅烷浓度约为5％，并且应用醇/水混合物。此外，根据需要调节每种溶液的pH，从而保证最大程度的水解。BTSE溶液和乙烯基三甲氧基硅烷溶液的pH为约4～约6，而双(三乙氧基甲硅烷基丙基)胺溶液的pH则为约10～约11。应用乙酸和氢氧化钠对pH进行任何所需的调节。按上述相同的方式用这些溶液涂布碱洗过的、冷轧的70/30黄铜板。
为了模拟海水的腐蚀环境，将涂布的样品和未涂布的对比样品部分地浸入3％NaCl溶液达1000小时。然后取出样品，目视检查任何可见的腐蚀痕迹(包括水线的侵蚀和变色)。结果如下表所示。
样品 在3％NaCl溶液中1000小时后
未涂布的(只碱洗过) 严重变色，水线侵蚀(存在铜沉积物)
BTSE 严重变色，水线侵蚀(存在大量的铜沉积物)
乙烯基硅烷 稍微变色，水线沉积极少的铜
双(三乙氧基甲硅烷基丙基)胺 在整个浸渍部位存在蓝色铜沉积物，严重的水线侵蚀
双(三乙氧基甲硅烷基丙基)四硫化物 原来的外观未变
                      实施例2
按上述实施例1中描述的方法制备了黄铜样品。然后，将涂布的样品和未涂布的对比样品浸入0.2N HCl溶液达5天以便检验本发明的处理溶液防止脱锌的能力。获得了下列结果：
样品 在0.2N HCl溶液中5天后
未涂布的(只碱洗过) 在整个浸渍部位观察到脱锌
BTSE 在整个浸渍部位观察到严重脱锌
乙烯基硅烷 在整个浸渍部位观察到脱锌
双(三乙氧基甲硅烷基丙基)四硫化物 原来的外观未变(即，未脱锌)
                        实施例3
将三个黄铜样品碱洗过，并且按实施例1的方法制备了本发明的处理溶液。一个黄铜样品未被涂布，所以用作对比物。将未涂布的样品弯成对折(180度)以便在样品上构成模拟应力腐蚀裂开的高应力区。第二个样品用本发明的处理溶液按实施例1中描述的那样涂布，再弯成对折。第三个样品首先被弯成对折，再用本发明的处理溶液按实施例1中描述的那样涂布。然后，将所有样品暴露于浓氨蒸汽中达18小时。暴露后，目视检查腐蚀的情况，随后掰开(即，“未弯曲”)。下表给出的结果又一次阐明了本发明的处理方法防腐的能力，还显示了这样构成的涂层是可变形的：
    样品 暴露于氨蒸汽中18小时后 弯折掰开的结果
    未涂布的对比物 整个表面严重发黑 弯折处断裂
    涂布，然后弯曲 边缘极少的发黑 在弯折的一端引起开裂
    弯曲，然后涂布 边缘极少的发黑 未引起开裂
                      实施例4
按上述方式将三个Al 2024样品碱洗。一个样品用作对比物，碱洗后未按任何方式涂布。按本领域技术人员熟知的方法对第二块板条进行标准的铬酸盐处理。用实施例1中描述的双(三乙氧基甲硅烷基丙基)四硫化物溶液按本文所述方式涂布第三块板条。
为了检测涂层的可成形性以及成形对腐蚀特性的任何负效果，在杯形拉制机(cup drawing machine)中将所有三个样品深拉成约8mm的深度以便制作标准的杯用于Olsen测试。因为拉制过程需要在杯的内表面涂布润滑剂，所以在拉制后进行了溶剂清洗(应用甲醇和己烷)以便除去任何油污染物。然后，将拉制的样品完全浸入3％NaCl溶液达一周的时间，再目视观察(内表面和外表面)腐蚀的痕迹：
样品 处于3％NaCl溶液中1周后
对比物(只碱洗) 整个表面变色，拉制区更严重；在样品的多处存在白色沉积物麻点；边缘腐蚀
铬酸盐处理过 样品稍微变色，拉制区更严重；整个样品存在稠密的白色沉积物麻点；
双(三乙氧基甲硅烷基丙基)四硫化物 整个样品(包括拉制区)如原来的外观；没有麻点；边缘未腐蚀
上述结果阐明了应用于本发明方法和处理溶液中的含硫硅烷对铝和铝合金也有效。
                        实施例5
为了检测本发明的方法在锌和锌合金(例如包括热浸镀锌的钢)表面防腐中的效果，按上述方式将标准钛锌板条(主要是锌，含少于1％的钛；可得自Nedzinc)碱洗。一块板条未涂布，而另一块则用实施例1的处理溶液按本文所述的方式涂布。然后，将这些板进行Butler水平水浸渍试验(Butler Horizontal Water Immersion Test)(由the ButlerManufacturing Company of Grandview，Missouri开发的)。未涂布的板条只一天后就在其表面的80％出现了白色锈斑，而按本发明处理的板条在暴露6周后仅显示5％的白色锈斑。
前文对优选的实施方案的描述决不是穷举本发明中可能的变化，给出这些实施方案仅仅是为了阐释和描述本发明。本领域技术人员根据前述启示会明白明显的修饰和变化不会偏离本发明的范围。所以，预期本发明的范围由附后的权利要求书限定。

Claims (13)

1.一种处理金属表面而改善耐腐蚀性的方法，它包括如下步骤：
(a)提供一个金属表面；以及
(b)将处理溶液涂到所述金属表面上，所述处理溶液包含水、醇和至少一种已被至少部分水解从而使其烷基或乙酰基被氢原子替代的双官能聚硫硅烷，所述硅烷包括：
其中，每个R是烷基或乙酰基，Z是-SX或-Q-SX-Q-，其中，每个Q是脂族基或芳基，x则是2～9的整数，并且所述处理溶液中所述双官能聚硫硅烷的总浓度在约0.1vol％～约25vol％之间。
2.权利要求1的方法，其中，每个R独自选自下列基：乙基、甲基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基和乙酰基。
3.权利要求1或2的方法，其中，每个Q独自选自如下基：线型或支化的C1～C6烷基、线型或支化的C2～C6烯基、被一个或多个氨基取代的C1～C6烷基、被一个或多个氨基取代的C2～C6烯基、苄基和被C1～C6烷基取代的苄基。
4.权利要求1或2的方法，其中，所述双官能聚硫硅烷包括具有2～9个硫原子的双-(三乙氧基甲硅烷基丙基)硫化物。
5.权利要求4的方法，其中所述双-(三乙氧基甲硅烷基丙基)硫化物具有4个硫原子。
6.权利要求1或2的方法，其中，所述双官能聚硫硅烷包括双-(三乙氧基甲硅烷基丙基)四硫化物。
7.权利要求1或2的方法，其中，所述金属选自：锌、锌合金、铜、铜合金、铝和铝合金。
8.权利要求1或2的方法，其中，所述金属包括黄铜或青铜。
9.权利要求1或2的方法，其中，所述醇选自：乙醇、甲醇、丙醇和异丙醇。
10.权利要求1或2的方法，其中，所述处理溶液中所述双官能聚硫硅烷的总浓度在约1vol％～约5vol％之间。
11.权利要求9的方法，其中，所述醇是甲醇，并且所述处理溶液具有约3～约20份甲醇/1份水。
12.权利要求1～6任一项中所定义的包含水醇和至少一种双官能聚硫硅烷的处理溶液在改善耐腐蚀性的方法中用于金属底材防腐方面的应用，所述方法包括如下步骤：
(a)提供一个金属表面；以及
(b)将处理溶液涂到所述金属表面上。
13.权利要求12的方法，其中，在水解前每个R独自选自：乙基、甲基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基和乙酰基。
CNB998077275A 1998-06-24 1999-06-24 应用双官能聚硫硅烷的金属的腐蚀防护 Expired - Fee Related CN1204294C (zh)

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Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6416869B1 (en) * 1999-07-19 2002-07-09 University Of Cincinnati Silane coatings for bonding rubber to metals
ATE506465T1 (de) * 1998-12-30 2011-05-15 Univ Cincinnati Silanbeschichtungen für metalle
AU4556200A (en) * 1999-04-14 2000-11-02 University Of Cincinnati, The Silane coatings for adhesion promotion
DE10084461T1 (de) * 1999-04-14 2002-03-21 Univ Cincinnati Cincinnati Silanbehandlungen für Korrosionsbeständigkeit und Haftvermittlung
US6827981B2 (en) 1999-07-19 2004-12-07 The University Of Cincinnati Silane coatings for metal
JP2001240977A (ja) * 2000-02-29 2001-09-04 Nippon Paint Co Ltd 金属表面処理方法
DE60236006D1 (de) * 2001-06-28 2010-05-27 Alonim Holding Agricultural Co Verfahren zum anodisieren von magnesium und magnesiumlegierungen und zur herstellung von leitfähigen schichten auf einer anodisierten oberfläche
US7959826B2 (en) * 2004-08-16 2011-06-14 Honeywell International Inc. Methods of preventing frost formation and facilitating the removal of winter precipitation relative to a windshield and compositions for use therein
TW200626358A (en) 2004-11-30 2006-08-01 Nippon Steel Chemical Co Copper-clad laminate
RU2415881C2 (ru) 2005-03-24 2011-04-10 Бриджстоун Корпорейшн Составление резиновой смеси, армированной диоксидом кремния, с низким уровнем выделения летучих органических соединений (лос)
US10041176B2 (en) 2005-04-07 2018-08-07 Momentive Performance Materials Inc. No-rinse pretreatment methods and compositions
DE102005045034A1 (de) * 2005-09-21 2007-03-29 Rasselstein Gmbh Verfahren zur Passivierung der Oberfläche von beschichteten Metallbändern und Vorrichtung für das Aufbringen der Passivschicht auf ein metallisch beschichtetes Stahlband
DE102006054761A1 (de) * 2006-11-14 2008-05-15 Hansgrohe Ag Bereitstellung von wasserführenden Bauteilen aus Messinglegierungen mit verringerter Metallionenfreisetzung
FR2914631B1 (fr) 2007-04-06 2009-07-03 Eads Europ Aeronautic Defence Materiau nanostructure particulier, comme revetement protecteur de surfaces metalliques.
US8501895B2 (en) 2007-05-23 2013-08-06 Bridgestone Corporation Method for making alkoxy-modified silsesquioxanes and amino alkoxy-modified silsesquioxanes
US7915368B2 (en) 2007-05-23 2011-03-29 Bridgestone Corporation Method for making alkoxy-modified silsesquioxanes
US8962746B2 (en) 2007-12-27 2015-02-24 Bridgestone Corporation Methods of making blocked-mercapto alkoxy-modified silsesquioxane compounds
US8513371B2 (en) 2007-12-31 2013-08-20 Bridgestone Corporation Amino alkoxy-modified silsesquioxanes and method of preparation
US8794282B2 (en) * 2007-12-31 2014-08-05 Bridgestone Corporation Amino alkoxy-modified silsesquioxane adhesives for improved metal adhesion and metal adhesion retention to cured rubber
WO2010025567A1 (en) * 2008-09-05 2010-03-11 National Research Council Of Canada Corrosion inhibitor for mg and mg-alloys
US8642691B2 (en) 2009-12-28 2014-02-04 Bridgestone Corporation Amino alkoxy-modified silsesquioxane adhesives for improved metal adhesion and metal adhesion retention to cured rubber
US20120267011A1 (en) * 2011-04-25 2012-10-25 Lawrence Benjamin L Sulfur treatment for copper zinc alloys
US9829122B2 (en) 2011-11-07 2017-11-28 Nibco Inc. Leach-resistant leaded copper alloys
JP2013221210A (ja) 2012-04-19 2013-10-28 Hitachi Ltd 防食処理アルミニウム材及びその製造方法
US8970034B2 (en) * 2012-05-09 2015-03-03 Micron Technology, Inc. Semiconductor assemblies and structures
DE102013202286B3 (de) * 2013-02-13 2014-01-30 Chemetall Gmbh Verwendung eines Silan-, Silanol- oder/und Siloxan-Zusatzes zur Vermeidung von Stippen auf Zink-haltigen Metalloberflächen und Verwendung der beschichteten Metallsubstrate
CN104497871B (zh) * 2014-12-22 2017-07-28 江苏兴达钢帘线股份有限公司 一种用于胎圈钢丝镀后处理的水基底涂液
EP3241221A4 (en) 2014-12-31 2018-08-08 Bridgestone Corporation Amino alkoxy-modified silsesquioxane adhesives for adhering steel alloy to rubber

Family Cites Families (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR435781A (fr) * 1911-10-28 1912-03-09 Jules Rene Prochasson Cable à self-induction réglable pour télégraphie rapide et téléphonie
US3392182A (en) * 1963-02-28 1968-07-09 Goldschmidt Ag Th Novel organosilicon compounds and process for their preparation
US3978103A (en) * 1971-08-17 1976-08-31 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Sulfur containing organosilicon compounds
US4015044A (en) * 1975-03-27 1977-03-29 Union Carbide Corporation Process of bonding polyurethane-sealants and caulks
US4000347A (en) * 1975-03-27 1976-12-28 Union Carbide Corporation Process of bonding polysulfide sealant and caulk compositions
JPS51139831A (en) * 1975-05-29 1976-12-02 Shin Etsu Chem Co Ltd Primer composition
DE2658368C2 (de) * 1976-12-23 1982-09-23 Degussa Ag, 6000 Frankfurt Schwefel und Phosphor enthaltende Organosiliciumverbindungen, Verfahren zu ihrer Herstellung und ihre Verwendung
US4243718A (en) * 1978-11-24 1981-01-06 Toshiba Silicone Co. Ltd. Primer compositions for Si-H-olefin platinum catalyzed silicone compositions
US4315970A (en) * 1980-02-11 1982-02-16 Dow Corning Corporation Adhesion of metals to solid substrates
JPS5765758A (en) * 1980-10-09 1982-04-21 Toray Silicone Co Ltd Primer composition for bonding
JPS57159865A (en) * 1981-03-27 1982-10-02 Toray Silicone Co Ltd Primer composition for bonding
DE3119151A1 (de) * 1981-05-14 1982-12-02 Bayer Ag, 5090 Leverkusen Verfahren zur splittersicheren beschichtung von glasoberflaechen
US4364509A (en) * 1981-06-25 1982-12-21 The Mead Corporation Article carrier with dispensing feature
US4457970A (en) * 1982-06-21 1984-07-03 Ppg Industries, Inc. Glass fiber reinforced thermoplastics
JPS6081256A (ja) * 1983-10-12 1985-05-09 Shin Etsu Chem Co Ltd 被覆用組成物
US4618688A (en) * 1985-04-12 1986-10-21 Scm Corporation Silane compositions
JPS61237636A (ja) * 1985-04-15 1986-10-22 大同鋼板株式会社 塗装鋼板
JPS61278582A (ja) * 1985-06-03 1986-12-09 Toray Silicone Co Ltd 接着用プライマ−組成物
US4689085A (en) * 1986-06-30 1987-08-25 Dow Corning Corporation Coupling agent compositions
JPS6397266A (ja) * 1986-10-09 1988-04-27 Kawasaki Steel Corp 加工性、加工部耐食性に優れたプレコ−ト鋼板
US5200275A (en) * 1990-12-24 1993-04-06 Armco Steel Company, L.P. Steel sheet with enhanced corrosion resistance having a silane treated silicate coating
US5108793A (en) * 1990-12-24 1992-04-28 Armco Steel Company, L.P. Steel sheet with enhanced corrosion resistance having a silane treated silicate coating
US5221371A (en) * 1991-09-03 1993-06-22 Lockheed Corporation Non-toxic corrosion resistant conversion coating for aluminum and aluminum alloys and the process for making the same
US5217751A (en) * 1991-11-27 1993-06-08 Mcgean-Rohco, Inc. Stabilized spray displacement plating process
US5455080A (en) * 1992-08-26 1995-10-03 Armco Inc. Metal substrate with enhanced corrosion resistance and improved paint adhesion
US5292549A (en) * 1992-10-23 1994-03-08 Armco Inc. Metallic coated steel having a siloxane film providing temporary corrosion protection and method therefor
US5326594A (en) * 1992-12-02 1994-07-05 Armco Inc. Metal pretreated with an inorganic/organic composite coating with enhanced paint adhesion
US5322713A (en) * 1993-03-24 1994-06-21 Armco Inc. Metal sheet with enhanced corrosion resistance having a silane treated aluminate coating
US5393353A (en) * 1993-09-16 1995-02-28 Mcgean-Rohco, Inc. Chromium-free black zinc-nickel alloy surfaces
US5389405A (en) * 1993-11-16 1995-02-14 Betz Laboratories, Inc. Composition and process for treating metal surfaces
IL111497A (en) * 1993-12-08 2001-01-28 Rohco Inc Mcgean Seelan preparations are useful as adhesives
US5433976A (en) * 1994-03-07 1995-07-18 Armco, Inc. Metal pretreated with an aqueous solution containing a dissolved inorganic silicate or aluminate, an organofuctional silane and a non-functional silane for enhanced corrosion resistance
US5405985A (en) * 1994-07-08 1995-04-11 The Goodyear Tire & Rubber Company Preparation of sulfur-containing organosilicon compounds
US5468893A (en) * 1994-07-08 1995-11-21 The Goodyear Tire & Rubber Company Preparation of sulfur-containing organosilicon compounds
US5466848A (en) * 1994-09-28 1995-11-14 Osi Specialties, Inc. Process for the preparation of silane polysulfides
FR2732364A1 (fr) * 1995-03-29 1996-10-04 Michelin & Cie Procede pour traiter un corps en acier inoxydable de facon a favoriser son adhesion a une composition de caoutchouc
US5700523A (en) * 1996-06-03 1997-12-23 Bulk Chemicals, Inc. Method for treating metal surfaces using a silicate solution and a silane solution
US5750197A (en) * 1997-01-09 1998-05-12 The University Of Cincinnati Method of preventing corrosion of metals using silanes

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