CN101448975A - 在金属表面上的抗腐蚀涂料中使用的改进的含三价铬组合物 - Google Patents
在金属表面上的抗腐蚀涂料中使用的改进的含三价铬组合物 Download PDFInfo
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Abstract
提供低残余的三价铬基转化型涂布浴,通过在含三价铬离子和氟代金属酸根离子的水溶液内浸渍,接着任选地漂洗,它在铝和铝合金上形成抗腐蚀涂层。三价铬涂布的铝还充当油漆底漆的有效基质。
Description
发明领域
[0001]本发明涉及处理金属表面提高抗腐蚀性和油漆粘结特征的方法,和涉及在这一方法中使用的用于铝和铝合金的含三价铬涂料。更特别地,本发明涉及适合于用作可漂洗或原地干燥的用于金属的转化型涂料的含水组合物,它包括三价铬阳离子、氟代金属化物阴离子、它们的相应的抗衡离子和其他任选的组分,及其使用方法。
发明背景
[0002]通常已知用含六价铬的水溶液处理金属,例如锌、镉或铝等的表面,所述水溶液含有溶解金属表面并形成称为“铬酸盐转化型涂层”的不溶膜的化学品。这些含六价铬的涂料抗腐蚀且保护金属以防引起腐蚀的各种元素。另外,已知铬酸盐转化型涂料通常具有良好的油漆粘结特征,和因此提供用于油漆或其他罩面漆优良的基质。
[0003]尽管前述涂料提高抗腐蚀性和油漆粘结性能,但该涂料具有严重的缺点,即六价铬成分具有毒性。从两个角度考虑,这是严重的问题,一个角度是操作者处理该溶液,再一个是用过的溶液的处置。因此,高度期望下述涂料溶液和涂层,其具有基本上不含六价铬,但与此同时能赋予与常规的含六价铬的涂层相当的抗腐蚀性和油漆粘结性能。
[0004]特别感兴趣的是在飞行器铝合金上使用铬酸盐转化型涂层,这是因为它具有优良的抗腐蚀性且能充当油漆的有效基质。开发这些涂料所使用的常规浴含有六价铬,和正是在该涂层内的残留铬酸盐主要对高度腐蚀抑制负责。然而,这些相同的铬酸盐高度有毒,且它们在废水流出物中的存在受到严格限制。因此,希望使用可充当有毒六价铬酸盐涂层替代品的毒性相对小的化学品,提供用于铝及其合金和用于密封阳极化铝的涂层。在转化型涂层中除了使用和替代六价铬以外,还使用三价铬,以尝试生产含六价铬的涂料的替代品,但迄今为止,这些尝试仅仅有限地成功。
[0005]目前在工作溶液中以铬:锆之比为约0.4:1到约0.6:1的比例使用硫酸铬和氟代锆酸钾,施加三价铬腐蚀防护涂层。这一现有技术的方案的一个缺点是,工作浴不如所需的那样稳定。硫酸铬和氟代锆酸钾基组合物储存不稳定,因为当老化约1-2周时,甚至在未使用的组合物内,开始形成沉淀。在使用中,工作浴生成必须除去的显著大量的残渣,这导致生产线的昂贵的停工和处置问题。在浴中开始沉淀还对所形成的转化型涂层具有负面影响。现有技术的长期用浴得到的转化型涂层具有降低的抗腐蚀性。因此需要克服现有技术的这些和其他缺点的改进的三价铬腐蚀防护涂层。
发明内容
[0006]因此,本发明的目的是提供一种处理铝的新型不含六价铬的含铬溶液。
[0007]本发明另一目的是提供处理铝的组合物,它含有仅仅三价氧化态的铬。
[0008]本发明再一目的是提供含三价铬的溶液,其中所述铬具有很少或者不具有从溶液中沉淀的倾向。
[0009]本发明的目的是提供处理金属表面的组合物,它包括氟代金属化物阴离子;铬(III)阳离子的组分;和任选地,一种或更多种下述组分:游离的氟化物离子组分;表面活性剂分子组分;pH调节组分和粘度增加组分。
[0010]同样,本发明的目的是提供通过接触金属表面与本发明的组合物,然后漂洗形成的涂层,该涂层包括基本上仅仅三价形式的铬,且根据ASTM B-117,提供至少96、120、144、168、192、216、240、264、288、312、336、360、408、456、480、504小时的抗盐喷洒。
[0011]本发明尤其非常适合于在主要由铁、钛、铝、镁和/或锌及其合金组成的金属表面上形成涂层;它包括GalvalumeTM和GalvanealTM。本领域的技术人员要理解此处所使用的“主要”是指主要的元素是以合金的重量计,含最大量的元素。根据下述说明,本发明的其他目的对本领域技术人员将更明了。
[0012]除了在权利要求和操作例中以外,或者除非另外特意说明,在本说明书中的所有数值量,其中包括物质的用量或者反应和/或使用条件要理解为在描述本发明的最宽范围内用措辞“约”来修饰。通常优选在所述的数值极限内的实践。此外,在整个说明书中,除非特意另外说明,百分数,“份”和比例以重量计;术语“聚合物”包括“低聚物”、“共聚物”、“三元共聚物”和类似物;结合本发明,对于给定目的来说合适或优选的一组或一族材料的说明暗含任何两种或更多种该组或族中的成员的混合物同样是合适或优选的;用化学术语描述的各成分的说明是指在添加说明书中规定的或者通过说明书中规定的化学反应就地生成的任何结合物的时刻的各成分,且不必然排除在一旦混合时混合物中各成分其它的化学相互作用;离子形式的物质的规定另外暗含存在足量的抗衡离子,以产生组合物作为整体的电中性(按此明确地规定的任何抗衡离子在尽可能的程度上应当优选选自明确地以离子形式规定的成分;在其他情况下,这种抗衡离子可以自由地选择,除非避免对本发明目的起负面作用的抗衡离子);术语“油漆”包括可用更加专门的术语表示的所有可能的材料,例如底漆、挥发性漆、磁漆、清漆、紫胶、面漆和类似物;和术语“mol”及其变体可应用到通过所存在的原子数量和类型定义的元素、离子和任何其他化学物种以及应用到具有明确定义分子的化合物上。
具体实施方式
[0013]本发明的一个实施方案提供液体组合物,它包括下述,优选基本上由下述组成,或更优选由下述组成:水和
(A)氟代金属化物阴离子组分,其中所述阴离子中的每一种由下述组成:
(i)至少4个氟原子;和
(ii)选自钛、锆、铪、硅、铝和硼中的元素的至少一个原子;和任选地(iii)和(iv)中的一个或两个:
(iii)至少一个可离子化的氢原子;和
(iv)至少一个氧原子;
(B)铬(III)阳离子组分;
其中铬:锆之比的范围为10:1到25:1和
任选地,一种或更多种下述组分:
(C)游离氟化物离子组分,它不是前面所述的任何组分(A)-(B)中的一部分;
(D)表面活性剂分子组分,它不是前面所述的任何组分(A)-(C)中的一部分;
(E)pH调节组分,它不是前面所述的任何组分(A)-(D)中的一部分;和
(F)粘度增加组分,它不是前面所述的任何组分(A)-(E)中的一部分。
[0014]应当理解,所列的各组分不需要一定全部由单独的化学品来提供。
[0015]已发现,可通过下述步骤来实现在事先未处理的区域上的优良的涂层质量,尤其抗腐蚀性:
(I)使金属基底表面与以上所述的本发明的组合物接触,形成湿涂的金属基底表面;
(II)任选地,漂洗湿涂的金属基底表面;和
(III)干燥湿涂的金属基底表面。
[0016]开发了不含六价铬的本发明的组合物。尽管不优选,但可制备含六价铬的本发明的配方。本发明的组合物所需地含有小于0.04、0.02、0.01、0.001、0.0001、0.00001、0.000001wt%六价铬,最优选基本上不含六价铬。所需地最小化在本发明的组合物内存在的六价铬的用量,和优选仅仅痕量地存在,最优选不存在六价铬。
[0017]现有技术已知在涂层内一些三价铬将氧化形成六价铬,参见USP5304257。在本发明中,希望通过本发明的组合物形成的涂层很少或者不含有六价铬,尽管不优选,但该组合物可含有在前一段落中所述量的六价铬。本领域的技术人员要理解,本发明包括不含六价铬的涂层,但由于随后暴露于天候老化或其他处理条件下时,所述涂层可含有来自于氧化涂层内的三价铬得到的六价铬。
[0018]在本发明的优选实施方案中,组合物和所得涂层基本上不含,所需地根本不含六价铬。更优选以痕量或更少的量存在任何六价铬,和最优选组合物不含六价铬。
[0019]本发明的各种实施方案包括处理以上所述的表面的方法,任选地结合本身可能常规的其他工艺步骤,例如预清洁、漂洗等,和随后包括根据本发明形成的那些表面上的进一步的保护涂层;可用于处理以上所述的表面的组合物;和含根据本发明的方法处理的表面的制造制品。
[0020]与组分(A)的浓度无关,氟代金属化物阴离子优选是氟代硅酸根(即SiF6 -2)、氟代钛酸根(即TiF6 -2)或氟代锆酸根(即ZrF6 -2),更优选氟代钛酸根或氟代锆酸根,最优选氟代锆酸根。
[0021]在本发明的方法中使用的工作组合物优选具有至少下述的组分(A)浓度,其中以给定的顺序优先性增加:0.4、0.5、0.6、0.7、0.8、0.9、1.0、1.1、1.2、1.3、1.4、1.5、1.6、1.7、1.8、1.9、2.0、2.1、2.2、2.3、2.4、2.5、2.6、2.7、2.8、2.9、3.0、3.1、3.2、3.3、3.4、3.5、3.6、3.7、3.8、3.9、4.0、4.1、4.2、4.3、4.4、4.5、4.6、4.7、4.8、4.9、5.0、5.1、5.2、5.3、5.4、5.5、5.6、5.7、5.8、5.9、6.0、6.1、6.2、6.3、6.4、6.5、6.6、6.7、6.8、6.9、7.0、7.1、7.2、7.3、7.4、7.5、7.6、7.7、7.8、7.9、8.0、8.1、8.2、8.3、8.4、8.5、8.6、8.7、8.8、8.9、9.0、9.1、9.2、9.3、9.4、9.5、9.6、9.8、10.0g氟代金属化物阴离子,组分(A)/kg全部工作组合物。组分(A)的上限通常以溶解度和/或B:A之比为基础,和按增加的优先性顺序,优选不大于100、90、70、60g/kg。
[0022]所需地,用于氟代金属化物阴离子的阳离子选自第IA族元素的离子,或铵离子。优选地阳离子是K或H,最优选H。
[0023]以上定义的组分(B)要理解为包括一种或更多种下述三价铬阳离子源:铬(III)的硝酸盐、硫酸盐和氟化物。在优选的实施方案中,组分(B)包括三价氟化铬,优选基本上由三价氟化铬组成,最优选由三价氟化铬组成。在本发明的工作组合物内三价铬阳离子源的总浓度优选至少为下述,且以给定的顺序优先性增加:4、5、6、7、8、9、10、11、12、13、14、15、15.5、16、16.5、17、17.5、18、18.5、19、19.5、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35g/l,和独立地,主要由于经济和溶解度的原因,优选不大于,且以给定的顺序优先性增加:100、90、80、70、60、55、50、45、44、43、42、41、40、39、38、37、36g/l。三价铬源根据在工作浴内的溶解度而选择,所述溶解度常常是在浴内其他组分的性质与用量的函数。所需地,三价铬源的用量足以在本发明的工作组合物内提供至少下述的三价铬阳离子总浓度,且以给定的顺序优先性增加:1.0、1.5、2.0、2.5、3.0、3.5、4.0、4.5、5.0、5.5、6.0、6.5、7.0、7.5、8.0、8.5、9.0、9.5、10、11、12、13、14、15、15.5、16、16.5、17、17.5、18、18.5、19、19.5、20、21、22、23、24、25g/l。
[0024]与组分(A)和(B)的用量无关,希望三价铬阳离子对氟代金属化物阴离子内的金属,即钛、锆、铪、硅、铝和硼的重量比在0.725:1到39:1范围内。优选比值是至少下述,且以给定的顺序优先性增加:1:1、2:1、3:1、4:1、5:1、6:1、7:1、8:1、9:1和10:1,和优选不大于下述,且以给定的顺序优先性增加:30:1、29:1、27:1、25:1。根据ASTM B117的盐喷洒性能低于本发明组合物的这些范围以外的下限。
[0025]可任选地提供游离氟化物离子组分(C),它可以或可以不是前面所述的任何组分(A)-(B)的一部分。这一组分可由氢氟酸或具有充足水溶性的它的任何部分或完全中和的盐形式供应到组合物中。至少由于经济上的原因,组分(C)优选通过含水氢氟酸来提供,和独立地优选以至少下述浓度存在,且以给定的顺序优先性增加:每千份(ppt)0.10、0.30、0.50、0.60、0.70、0.80或0.90份HF的化学计量量。独立地,在本发明的方法中使用的工作组合物内,以HF的化学计量量形式测量的组分(C)的浓度优选不大于下述,且以给定的顺序优先性增加:每千份(ppt)10、8.0、6.0、4.0、3.0、2.0、1.5、1.3或1.1份。合适的游离氟化物离子来源是本领域的技术人员已知的。优选地(C)源是HF。
[0026]若使用的话,组分(D)选自阴离子表面活性剂,例如羧酸盐,烷基磺酸盐,烷基取代的苯基磺酸盐;非离子表面活性剂,例如烷基取代二苯基炔醇和壬基苯酚聚氧乙烯;和阳离子表面活性剂,例如烷基铵盐;所有这些可以且优选确实含有直接键合到其分子内的碳原子上的氟原子。所使用的表面活性剂的每一分子优选含有疏水部分,所述疏水部分(i)通过共价键的连续链和/或环键合;(ii)含有许多碳原子,所述碳原子数至少为下述,且以给定的顺序优先性增加:10、12、14或16,和独立地优选不大于下述,且以给定的顺序优先性增加:30、26、22或20;和(iii)不含除了氢、卤素和醚键合的氧原子以外的原子。组分(D)最优选是非离子的氟代表面活性剂,这种材料是本领域已知的且以商品名商购于E.I.du Pont de Nemours and Company。
[0027]本发明的工作组合物可含有至少下述,且以给定的顺序优先性增加:每千份(ppt)0.010、0.030、0.050、0.070、0.080、0.090或0.100份组分(D),和独立地主要由于经济原因,优选含有不大于下述,且以给定的顺序优先性增加:每千份5.0、2.5、1.30、0.80、0.60、0.40、0.30、0.20、0.18、0.15、0.13或0.11份组分(D)。
[0028]本发明的组合物为酸性。pH优选至少为下述,且以给定的顺序优先性增加:2.10、2.30、2.50、2.70、2.90、3.0、3.10、3.20、3.30、3.40、3.50、3.60、3.70、3.80、3.90或4.0,和独立地优选不大于下述,且以给定的顺序优先性增加:5.0、4.95、4.90、4.80、4.70、4.60、4.50、4.40、4.30或4.20。pH调节组分(E)可以或可以不是前面所述的任何组分(A)-(D)的一部分,视需要,可将其加入到组合物中,其用量足以提供在以上所述范围内的pH。pH调节组分可以是本领域已知的不干扰本发明目的的任何酸或碱。在一个实施方案中,pH调节剂是酸,所需地HF,HF还提供游离的氟化物离子(C)。在另一实施方案中,pH调节组分包括碱,和所需地为氢氧化铵。
[0029]可通过任何常规的方法,将本发明的工作组合物施加到金属工件上,漂洗并在其上干燥,数种常规方法对本领域的技术人员来说是显而易见的。例如,可通过在液体组合物的容器内浸渍表面,在表面上喷洒该组合物,使该表面在上部和下部辊之间穿过,涂布表面,其中下部辊浸渍在液体组合物的容器内,与用液体处理组合物和类似物饱和的刷子或毡子接触,或者这些方法的混合,从而实现用液体膜涂布金属。可通过任何常规的方法,例如漂洗、在重力影响下排放,在辊之间穿过,和类似方法,在干燥之前,除去否则在干燥之前可残留在表面上的过量的液体组合物。
[0030]在施加液体组合物过程中的温度可以是在组合物液体范围内的任何温度,但为了施加方便和经济原因,通常优选正常的室温,即20-27℃。
[0031]施加本发明的组合物将提供对随后施加的保护层,例如油漆、挥发性漆和其他树脂基涂层改进的粘合剂粘结。
[0032]在本发明的方法中施加的涂层的总质量增加(在干燥之后)为至少下述,且以给定的顺序优先性增加:20、21、22、23、24、25、26、27、28、29、30g/英尺2涂布的表面(下文常常缩写为“mg/ft2”)。独立地,即使净质量没有增加,则也通常实现至少相同的抗腐蚀性,和因此为了经济的原因,净质量增加优选不大于下述,且以给定的顺序优先性增加:120、115、110、100mg/ft2。
[0033]可通过测量在以上定义的组分(A)的阴离子内金属原子,或铬的净重量或质量增加,方便地监控并控制通过本发明方法形成的保护膜的净质量增加,除了在罕见的情况下,当起始的保护涂层和/或底层金属基底含有相同的金属元素例外。可通过本领域的技术人员已知的数种常规的分析技术中的任何一种,测量这些金属原子的含量。最可靠的测量通常牵涉从涂布基底的已知区域中溶解涂层,和测定在所得溶液内感兴趣的金属的含量。然后可根据在组分(A)内金属的含量和在干燥之后残留的总组合物的该部分的总质量之间的已知关系来计算总的总质量增加。然而,对于与本发明一起使用来说,这一方法常常是不实际的,因为补漆的区域并不总是精确地确定。通常通过小面积的X-射线光谱图来提供更加可操作的替代方案,其中在常规的校正之后,在几乎不存在所有干扰的情况下,该光谱图直接测量单位面积上在涂层内存在的单独的金属元素的含量,例外的是其他涂层内存在与底层金属表面本身的表面附近的薄层上或其内相同的元素。
[0034]本发明的处理方法的有效性似乎主要取决于在每一单位面积的处理表面上存在的活性成分的总量,和取决于活性成分的特性及其彼此的比例,而不是取决于所使用的酸性含水组合物的浓度,且没有观察到干燥速度对本发明具有任何技术上的影响,尽管由于经济原因,这可能是非常重要的。若在实践中,鉴于待处理的物体的尺寸和待处理的物体的面积大小,可通过在根据本发明的方法施加液体组合物到表面上之前或之后,在烘箱中放置待处理的表面,使用辐射或微波加热,或类似加热方式加速干燥。在实践中,与在处理之后加热相比,优选在处理之前加热表面,且可满意地使用直到至少65℃的预热温度。若在可接受的经济成本下获得充足时间,则根据本发明施加的液体膜常常可简单地允许在环境氛围下自发干燥,就涂层的保护质量来说,且同样获得良好的结果。每一情况下的合适的方法对本领域的技术人员来说是显而易见的。
[0035]优选地,首先清洁根据本发明待处理的表面上的任何污染物,尤其有机污染物和外来金属微粒和/或夹带物。可通过本领域已知的方法实现这种清洁,且这种清洁适合于待处理的基底的特定类型。例如,对于镀锌钢表面来说,最优选用常规的炽热碱清洁剂清洁基底,然后用热水漂洗并干燥。对于铝,最优选首先使待处理的表面与常规的热碱清洁剂接触,然后在热水内漂洗,然后任选地与中和酸漂洗剂接触和/或脱氧化,之后与以上所述的酸性含水组合物接触。
[0036]在预备清洁之后,可通过吸收清洁流体,蒸发,或本领域技术人员已知的任何合适的方法,干燥表面。当在预备清洁,或清洁和干燥,以及涂布表面之间存在延迟时,抗腐蚀性通常达不到最佳。清洁,或清洁和干燥,以及涂布表面之间的时间应当不大于下述,且优先性以下述顺序增加:48、24、12、6.0、5.0、4.0、3.0、2.0、1.0、0.50、0.25或0.1小时。
[0037]考虑到下述非限定性的工作例,可进一步理解本发明的实践。
实施例
对比例
根据现有技术,使用三价铬的硫酸盐水溶液(商购于McgeanSpecialty Chemicals公司,制造者显示具有12wt%Cr),制备对比例1-3。对比例2含有比对比例1多10wt%的硫酸盐。对比例3含有比对比例1多20wt%的硫酸盐。在Ridoline 4355(一种可商购于HenkelCorporation公司的碱性清洁剂)中清洁商购的2024 T3裸铝板10分钟,用水漂洗,与Deoxylyte 2310(商购于Henkel Corporation公司的脱氧剂)接触5分钟并漂洗。对于每一对比例,处理三块板,总计9块板。使该板与它们各自的工作浴在环境温度下接触10分钟。
表1
对比例1(g/l) | 对比例2+10%Cr2(SO4)3 | 对比例3+20%Cr2(SO4)3 | |
去离子水H2ZrF6(在水中40%)KOH(在水中40%)Cr2(SO4)3(12wt%Cr) | 986.455.483.624.45 | 986.455.483.624.90 | 986.455.483.625.35 |
Cr(g/l) | 0.53 | 0.59 | 0.64 |
Cr:Zr质量比 | 0.56 | 0.61 | 0.66 |
336小时盐喷洒结果:个斑点/面板 | 3个斑点/面板 | 15个斑点/面板 | 15个斑点/面板 |
在环境温度和湿度下固化面板3天。根据ASTM B117,将所有面板暴露于336小时盐喷洒测试下。增加三价铬硫酸盐的用量,同时保持其他组分的用量恒定导致盐喷洒性能下降,参见对比例2和3。
在老化1-2周之后,观察根据表1的对比例制备的浴。该浴形成以残余形式沉降到底部的微细沉淀。在未使用过的浴内,以及处理面板作的浴内出现残余的生成。通过面板涂布操作干扰所生成的残余,引起残余在浴内分散。涂布面板,同时残余分散在浴内导致在涂布的面板表面上非所需的粉状白色沉积物。
实施例1
根据表2制备三价铬转化型涂料组合物。在160℉下添加氟化铬(III)到水中,并混合,直到完全溶解。冷却该溶液到室温并添加氟代锆酸。使用氢氧化铵调节组合物的pH。
根据对比例的工序制备可商购的2024T3型3英寸×8英寸的裸铝板。然后,在环境温度下,使每一面板与表2的组合物之一接触指定的时间段。
表2
样品 | CrF3-4H2O | H2ZrF645%溶液 | 去离子水 | pH | 浸渍时间 | 腐蚀336小时盐喷洒 |
4.000 | 3.875 | 0.325 | 95.800 | 3.750 | 10.000 | 1.000 |
9.000 | 5.000 | 1.000 | 94.000 | 5.000 | 10.000 | 1.000 |
19.000 | 0.500 | 0.100 | 99.400 | 2.500 | 10.000 | 1.000 |
6.000 | 0.500 | 0.100 | 99.400 | 5.000 | 10.000 | 2.000 |
34.000 | 0.500 | 0.100 | 99.400 | 5.000 | 10.000 | 2.000 |
32.000 | 2.750 | 0.550 | 96.700 | 5.000 | 10.000 | 3.000 |
12.000 | 0.500 | 1.000 | 98.500 | 5.000 | 10.000 | 3.000 |
15.000 | 0.500 | 1.000 | 98.500 | 5.000 | 10.000 | 3.000 |
17.000 | 2.750 | 0.100 | 97.150 | 5.000 | 10.000 | 4.000 |
27.000 | 5.000 | 1.000 | 94.000 | 5.000 | 10.000 | 4.000 |
13.000 | 2.750 | 0.100 | 97.150 | 5.000 | 10.000 | 6.000 |
2.000 | 5.000 | 0.100 | 94.900 | 5.000 | 10.000 | 8.000 |
5.000 | 5.000 | 0.100 | 94.900 | 2.500 | 10.000 | 10.000 |
1.000 | 2.750 | 0.100 | 97.150 | 2.500 | 10.000 | 10.000 |
8.000 | 5.000 | 1.000 | 94.000 | 2.500 | 10.000 | 10.000 |
22.000 | 0.500 | 0.550 | 98.950 | 2.500 | 10.000 | 10.000 |
10.000 | 0.500 | 1.000 | 98.500 | 2.500 | 10.000 | 10.000 |
29.000 | 1.625 | 0.325 | 98.050 | 3.750 | 6.500 | 4.000 |
25.000 | 3.875 | 0.325 | 95.800 | 5.000 | 6.500 | 5.000 |
14.000 | 3.875 | 0.775 | 95.350 | 2.500 | 6.500 | 10.000 |
18.000 | 0.500 | 1.000 | 98.500 | 5.000 | 3.000 | 2.000 |
7.000 | 0.500 | 0.550 | 98.950 | 5.000 | 3.000 | 3.000 |
26.000 | 0.500 | 1.000 | 98.500 | 2.500 | 3.000 | 6.000 |
31.000 | 3.875 | 0.775 | 95.350 | 3.750 | 3.000 | 7.000 |
23.000 | 5.000 | 1.000 | 94.000 | 5.000 | 3.000 | 7.000 |
16.000 | 0.500 | 0.100 | 99.400 | 2.500 | 3.000 | 7.000 |
11.000 | 0.500 | 0.100 | 99.400 | 5.000 | 3.000 | 7.000 |
24.000 | 2.750 | 0.100 | 97.150 | 5.000 | 3.000 | 8.000 |
28.000 | 5.000 | 0.100 | 94.900 | 5.000 | 3.000 | 9.000 |
3.000 | 5.000 | 0.100 | 94.900 | 2.500 | 3.000 | 10.000 |
33.000 | 5.000 | 0.100 | 94.900 | 2.500 | 3.000 | 10.000 |
30.000 | 5.000 | 1.000 | 94.000 | 2.500 | 3.000 | 10.000 |
20.000 | 2.750 | 1.000 | 96.250 | 2.500 | 3.000 | 10.000 |
21.000 | 0.500 | 0.550 | 98.950 | 2.500 | 3.000 | 10.000 |
*组分用量以重量%计。
在环境温度和湿度下固化面板3天。根据ASTM B117,将所有面板暴露于336小时盐喷洒测试下并基于1-10级评定。1=没有腐蚀;2=沾污,但没有腐蚀;3=1-3个斑点/面板。等级3被视为充足的抗盐喷洒性的最差性能。
表3提供了在环境温度下,在10分钟的恒定接触时间下,具有充足盐喷洒性能的涂层的比较。
表3
样品 | CrF3-4H2O | CrIII | H2ZrF645%溶液 | Zr | Cr:Zr重量比 | 去离子水 | pH | 浸渍时间 | 腐蚀336小时盐喷洒 |
4 | 3.875 | 1.113 | 0.325 | 0.064 | 17.4 | 95.800 | 3.75 | 10.00 | 1 |
9 | 5.000 | 1.440 | 1.000 | 0.198 | 7.3 | 94.000 | 5.00 | 10.00 | 1 |
19 | 0.500 | 0.144 | 0.100 | 0.020 | 7.2 | 99.400 | 2.50 | 10.00 | 1 |
6 | 0.500 | 0.144 | 0.100 | 0.020 | 7.2 | 99.400 | 5.00 | 10.00 | 2 |
34 | 0.500 | 0.144 | 0.100 | 0.020 | 7.2 | 99.400 | 5.00 | 10.00 | 2 |
32 | 2.750 | 0.790 | 0.550 | 0.110 | 7.2 | 96.700 | 5.00 | 10.00 | 3 |
12 | 0.500 | 0.144 | 1.000 | 0.198 | 0.72 | 98.500 | 5.00 | 10.00 | 3 |
15 | 0.500 | 0.144 | 1.000 | 0.198 | 0.72 | 98.500 | 5.00 | 10.00 | 3 |
*组分用量以重量%计。
实施例2
根据表4制备三价铬的转化型涂料组合物。在160℉下添加氟化铬(III)到水中并混合,直到完全溶解。冷却该溶液到室温并添加氟代锆酸。
表4
通过添加氢氧化铵调节式A溶液的pH。根据对比例的工序,制备三块可商购的2024T3裸铝板。用蒸馏水稀释式A为75%的涂料组合物的工作浴。然后,在环境温度下,使每一面板与工作浴接触3分钟。在环境温度和湿度下固化面板3天。以29.6mg/ft2形式测量涂层重量。根据ASTM B1117,将所有面板暴露于336小时的盐喷洒测试下。在式A的工作浴内涂布的面板在336小时盐喷洒测试之后不具有斑点。
在老化1-2周之后观察根据表2制备的浴;在未使用过的浴内没有观察到残余。在环境温度下加工面板所使用的浴同样没有显示出形成残余。在长期浴内涂布的面板基本上与在本发明的新鲜浴内涂布的那些相同。
[0038]本发明提供含三价铬的转化型涂料组合物,它可在各种金属,其中包括铝和铝合金上的转化型涂料中使用。它可用于金属基底的转化型涂料中所使用的许多工艺变体上。尽管针对其具体实施方案描述了本发明,但要理解本领域的技术人员可容易地作出其他形式。因此,认为本发明的范围仅仅通过下述权利要求而限制。
Claims (19)
1.涂布金属表面的组合物,所述组合物包括水和:
(A)氟代金属化物阴离子组分,其中所述阴离子中的每一种由下述组成:
(i)至少4个氟原子;和
(ii)选自钛、锆、铪、硅、铝和硼中的元素的至少一个原子;和
任选地(iii)和(iv)中的一个或两个:
(iii)至少一个可离子化的氢原子;和
(iv)至少一个氧原子;
(B)水溶性氟化铬组分;
所述组合物基本上不含六价铬且在环境温度下稳定储存至少2周。
2.权利要求1的组合物,其中氟代金属化物阴离子选自氟代硅酸根、氟代钛酸根和氟代锆酸根阴离子。
3.权利要求1的组合物,其中氟代金属化物阴离子包括浓度范围为约0.4-100g/kg的氟代锆酸根阴离子;浓度范围为约4-100g/l的水溶性氟化铬,且所述液体组合物包括不大于0.06%的分散二氧化硅和硅酸盐。
4.权利要求1的组合物,其中三价铬和锆以三价铬与锆之比为0.725:1到39:1的范围存在。
5.权利要求1的组合物,其中在铝基底上原地干燥的所述组合物提供抗腐蚀性,使得当根据ASTMB-117,所述基底进行95℉的5%中性盐喷洒至少336小时时,形成小于约3个斑点/24英寸2。
6.权利要求1的组合物,其中:
氟代金属化物阴离子包括氟代锆酸根阴离子;
氟代锆酸根阴离子的浓度范围为约1-约10g/kg;
氟化铬的浓度范围为约4g/l-约100g/l;和三价铬与锆之比在7-17范围内。
7.通过一起混合水的第一物料和至少下述组分制备的储存稳定的组合物:
(A)在组合物内提供约1-约100g/kg氟代金属化物阴离子的氟代金属化物阴离子的水溶性源的第二物料;其中所述阴离子中的每一种由下述组成:
(i)至少4个氟原子;和
(ii)选自钛、锆、铪、硅、铝和硼中的元素的至少一个原子;和
任选地(iii)和(iv)中的一个或两个:
(iii)至少一个可离子化的氢原子;和
(iv)至少一个氧原子;
(B)用量为23g/l-约100g/l三价铬阳离子的水溶性源的第三物料;
(C)氟阴离子的水溶性源的任选的第四物料;
(D)表面活性剂和/或水溶性增稠剂组分的任选的第五物料;
所述组合物不含水溶性有机腐蚀抑制剂和水溶性有机稳定剂且在环境温度下储存稳定至少2周。
8.权利要求7的组合物,其中所述液体组合物包括不大于0.06%的分散二氧化硅和硅酸盐。
9.权利要求7的组合物,其中:
第二物料包括用量相当于在所述组合物内范围为约1-约8g/kg浓度的氟代锆酸根阴离子;并在所述组合物内混合用量相当于在所述组合物内范围为每千份约0.070-约0.13份浓度的氟化烷基酯表面活性剂分子的第五物料。
10.权利要求7的组合物,其中第五物料选自铬(III)的硝酸盐、硫酸盐和氟化物。
11.涂布或补漆或既涂布又补漆表面的方法,所述表面包括裸金属的至少一个区域,在底层金属基底上的涂层的至少一个区域,或者裸金属的至少一个区域和在底层金属基底上的涂层的至少一个区域二者,所述方法包括下述操作:
(I)用权利要求1的液体组合物层覆盖待涂布、补漆,或既涂布又补漆的表面;和
(II)干燥在操作(I)中形成的液体层,形成涂布的表面。
12.权利要求11的方法,其中表面包括裸金属的至少一个区域,和在底层金属基底上的涂层的至少一个区域;和在操作(I)中,在裸金属的至少一个区域上形成液体层。
13.权利要求11的方法,其中在操作(I)使用的所述液体组合物内,氟代金属化物阴离子选自氟代硅酸根、氟代钛酸根和氟代锆酸根。
14.权利要求11的方法,其中在操作(I)使用的所述液体组合物内,氟代金属化物阴离子包括氟代锆酸根阴离子;氟代锆酸根阴离子的浓度范围为约1-约10g/kg;铬(III)离子的浓度大于0且不大于100g/l。
15.权利要求14的方法,其中:
表面包括与在底层金属基底的涂层的至少一个区域相邻的裸金属的至少一个区域,
所述在底层金属基底的涂层的至少一个区域包括第一部分和第二部分,
在操作(I)中,在裸金属区域和在底层金属基底的涂层上的所述相邻区域的至少第一部分二者上形成液体层;和
在底层金属基底上的涂层选自磷酸盐转化型涂层、铬酸盐转化型涂层,和通过使主要由铁、钛、铝、镁和/或锌及其合金组成的表面与含氟代硅酸盐、氟代钛酸盐和氟代锆酸盐中至少一种的酸性处理溶液接触生产的转化型涂层。
16.权利要求13的方法,其中在操作(I)使用的所述液体组合物内,
氟代金属化物阴离子包括氟代锆酸根阴离子;
氟代锆酸根阴离子的浓度在约1-约8g/kg范围内;
氟化铬的浓度在约4g/l-约100g/l范围内;和
氢氟酸的存在浓度范围为每千份约0.70-约1.3份。
17.一种制造制品,它具有含权利要求11的涂布表面的至少一个部分。
18.权利要求17的制造制品,其中至少一个部分包括铝或铝合金。
19.权利要求17的制造制品,所述涂布表面基本上不含六价铬,且具有当根据ASTM B-117,进行95℉的5%中性盐喷洒至少336小时时,形成小于约3个斑点/24英寸2特征的抗腐蚀性。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103132067A (zh) * | 2013-02-17 | 2013-06-05 | 武汉风帆电镀技术股份有限公司 | 铝及铝合金表面用前处理剂 |
CN105051257A (zh) * | 2013-03-15 | 2015-11-11 | 汉高股份有限及两合公司 | 用于铝和铝合金的改进的含三价铬的组合物 |
CN113106434A (zh) * | 2021-04-12 | 2021-07-13 | 南昌大学 | 一种环保型铝合金化学氧化液及化学氧化方法 |
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Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2434972C2 (ru) | 2006-05-10 | 2011-11-27 | ХЕНКЕЛЬ АГ унд Ко. КГаА. | Улучшенная, содержащая трехвалентный хром композиция для применения в коррозионно-стойких покрытиях на металлических поверхностях |
DE102009036102B4 (de) | 2009-08-04 | 2011-09-01 | Airbus Operations Gmbh | Verfahren zur lokalen Applikation von chemischen Konversionsschichten und Verwendung eines Tuchs dazu |
JP5860582B2 (ja) * | 2010-01-29 | 2016-02-16 | 日本パーカライジング株式会社 | 金属表面処理剤及び金属表面処理方法 |
KR101444569B1 (ko) * | 2010-01-29 | 2014-09-24 | 니혼 파커라이징 가부시키가이샤 | 금속 표면 처리제 및 금속 표면 처리 방법 |
DE102012021241A1 (de) | 2012-10-29 | 2014-04-30 | Airbus Operations Gmbh | Zusammensetzung für die lokale Applikation von chemischen Konversionsschichten |
FR3025809B1 (fr) * | 2014-09-12 | 2016-09-30 | Herakles | Procede de controle d'une piece par colorimetrie |
US11008659B2 (en) * | 2014-12-26 | 2021-05-18 | Dipsol Chemicals Co., Ltd. | Trivalent chromium chemical conversion liquid for zinc or zinc alloy bases and chemical conversion coating film |
US10435806B2 (en) | 2015-10-12 | 2019-10-08 | Prc-Desoto International, Inc. | Methods for electrolytically depositing pretreatment compositions |
US10294570B2 (en) * | 2016-04-11 | 2019-05-21 | Hamilton Sundstrand Corporation | Method for making corrosion resistant coating |
US10400338B2 (en) | 2017-05-12 | 2019-09-03 | Chemeon Surface Technology, Llc | pH stable trivalent chromium coating solutions |
JP6443594B1 (ja) | 2017-10-20 | 2018-12-26 | Jfeスチール株式会社 | 高強度鋼板およびその製造方法 |
JP7118402B2 (ja) * | 2018-04-26 | 2022-08-16 | 奥野製薬工業株式会社 | アルミニウム合金の陽極酸化皮膜用封孔処理液、濃縮液及び封孔処理方法 |
DE102022105844A1 (de) * | 2022-03-14 | 2023-09-14 | Carl Freudenberg Kg | Passivierungsschicht für metallhaltige Substrate |
Family Cites Families (124)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3392008B2 (ja) | 1996-10-30 | 2003-03-31 | 日本表面化学株式会社 | 金属の保護皮膜形成処理剤と処理方法 |
US3932198A (en) * | 1974-05-24 | 1976-01-13 | Amchem Products, Inc. | Coating solution having trivalent chromium and manganese for coating metal surfaces |
ES452499A1 (es) | 1976-10-05 | 1978-04-01 | Brugarolas Sa | Procedimiento para colmatar peliculas obtenidas por oxida- cion anodica sobre el aluminio y sus aleaciones. |
DE2711431C2 (de) | 1977-03-16 | 1986-12-11 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur Oberflächenbehandlung von Metallen |
US4183772A (en) | 1978-01-30 | 1980-01-15 | Union Carbide Corporation | Composition and method for coating metal surfaces |
US4171231A (en) | 1978-04-27 | 1979-10-16 | R. O. Hull & Company, Inc. | Coating solutions of trivalent chromium for coating zinc surfaces |
US4266988A (en) | 1980-03-25 | 1981-05-12 | J. M. Eltzroth & Associates, Inc. | Composition and process for inhibiting corrosion of ferrous or non-ferrous metal surfaced articles and providing receptive surface for synthetic resin coating compositions |
GB2124241B (en) | 1982-05-31 | 1986-06-25 | Nippon Paint Co Ltd | Metal surface pretreating composition |
DE3247729A1 (de) | 1982-12-23 | 1984-07-05 | Gerhard Collardin GmbH, 5000 Köln | Verfahren zur behandlung von metalloberflaechen, insbesondere solchen von aluminium, aluminiumlegierungen und stahl, sowie hierfuer geeignete waessrige badloesungen |
JPS59197575A (ja) | 1983-04-19 | 1984-11-09 | Nippon Paint Co Ltd | 耐食性金属表面処理用組成物 |
US4647316A (en) | 1984-03-23 | 1987-03-03 | Parker Chemical Company | Metal base coating composition comprising chromium, silica and phosphate and process for coating metal therewith |
JPS61587A (ja) * | 1984-06-12 | 1986-01-06 | C Uyemura & Co Ltd | 化成処理液 |
GB8424159D0 (en) | 1984-09-25 | 1984-10-31 | Pyrene Chemical Services Ltd | Cromate coatings for metals |
SU1450400A1 (ru) | 1984-12-03 | 1990-11-07 | Институт Химии И Химической Технологии Ан Литсср | Раствор дл хроматировани цинковой поверхности |
GB8608508D0 (en) | 1986-04-08 | 1986-05-14 | Pyrene Chemical Services Ltd | Coating metal surfaces |
JPS62294184A (ja) | 1986-06-13 | 1987-12-21 | Nippon Parkerizing Co Ltd | クロメ−ト皮膜の溶出抑制方法 |
AU589541B2 (en) | 1986-07-14 | 1989-10-12 | Nihon Parkerizing Company Limited | Surface treatment for metal and composition therefor |
EP0264471B1 (en) | 1986-10-21 | 1991-07-24 | Procoat, S.A. | Coating applicable to hot metal surfaces |
US5859095A (en) | 1987-05-11 | 1999-01-12 | Morton International, Inc. | Epoxy corrosion-inhibiting coating composition |
FR2618164B1 (fr) | 1987-06-25 | 1994-02-04 | Roquette Freres | Solution et procede de phosphatation mixte. |
GB8802788D0 (en) | 1988-02-08 | 1988-03-09 | Brent Chemicals Int | Composition & process for treating metal surfaces |
JPH0730455B2 (ja) | 1988-09-27 | 1995-04-05 | 日本パーカライジング株式会社 | リン酸塩化成処理液 |
JP2879344B2 (ja) | 1989-04-07 | 1999-04-05 | 富山化学工業株式会社 | 3―ホルミルアミノ―7―メチルスルホニルアミノ―6―フェノキシ―4h―1―ベンゾピラン―4―オンまたはその塩を含有する抗炎症製剤 |
US4992116A (en) | 1989-04-21 | 1991-02-12 | Henkel Corporation | Method and composition for coating aluminum |
US5125989A (en) | 1989-04-21 | 1992-06-30 | Henkel Corporation | Method and composition for coating aluminum |
US5073196A (en) | 1989-05-18 | 1991-12-17 | Henkel Corporation | Non-accelerated iron phosphating |
US5082511A (en) | 1989-09-07 | 1992-01-21 | Henkel Corporation | Protective coating processes for zinc coated steel |
JPH07100873B2 (ja) | 1989-09-27 | 1995-11-01 | 日本パーカライジング株式会社 | 亜鉛系メッキ鋼板のクロメート塗布液 |
JPH03219086A (ja) | 1990-01-23 | 1991-09-26 | Nippon Parkerizing Co Ltd | 潤滑性に優れた金属表面処理組成物 |
US5318640A (en) | 1990-01-30 | 1994-06-07 | Henkel Corporation | Surface treatment method and composition for zinc coated steel sheet |
US5451271A (en) | 1990-02-21 | 1995-09-19 | Henkel Corporation | Conversion treatment method and composition for aluminum and aluminum alloys |
DE4012798C1 (zh) | 1990-04-21 | 1991-08-14 | Bayer Ag, 5090 Leverkusen, De | |
US5411606A (en) | 1990-05-17 | 1995-05-02 | The Boeing Company | Non-chromated oxide coating for aluminum substrates |
US5551994A (en) | 1990-05-17 | 1996-09-03 | The Boeing Company | Non-chromated oxide coating for aluminum substrates |
US5472524A (en) | 1990-05-17 | 1995-12-05 | The Boeing Company | Non-chromated cobalt conversion coating method and coated articles |
US5298092A (en) | 1990-05-17 | 1994-03-29 | The Boeing Company | Non-chromated oxide coating for aluminum substrates |
JP2839111B2 (ja) | 1990-08-28 | 1998-12-16 | 日本パーカライジング株式会社 | 亜鉛系メッキ鋼板のクロメート処理方法 |
JP2628782B2 (ja) | 1990-10-08 | 1997-07-09 | 日本パーカライジング株式会社 | 亜鉛系めっき鋼板のクロメート処理方法 |
US5089064A (en) | 1990-11-02 | 1992-02-18 | Henkel Corporation | Process for corrosion resisting treatments for aluminum surfaces |
JPH04193957A (ja) | 1990-11-28 | 1992-07-14 | Nippon Parkerizing Co Ltd | クリヤー塗装下地用クロメート処理液 |
JP2788131B2 (ja) | 1991-01-29 | 1998-08-20 | 日本パーカライジング株式会社 | アルミニウムまたはアルミニウム合金表面への複合皮膜形成方法 |
US5498759A (en) | 1991-06-26 | 1996-03-12 | Henkel Corporation | Surface treatment method for aluminum |
US5268042A (en) | 1991-06-28 | 1993-12-07 | Henkel Corporation | Composition and process for forming improved, non-cracking chromate conversion coatings |
JP2937274B2 (ja) | 1991-07-29 | 1999-08-23 | チッソ株式会社 | 反強誘電性液晶組成物 |
US5261973A (en) | 1991-07-29 | 1993-11-16 | Henkel Corporation | Zinc phosphate conversion coating and process |
MD960309A (ro) | 1991-08-30 | 1998-06-30 | Henkel Corporation | Procedeu de tratare a metalului cu o compoziţie acidă apoasă care nu conţine crom (VI) |
US5143562A (en) | 1991-11-01 | 1992-09-01 | Henkel Corporation | Broadly applicable phosphate conversion coating composition and process |
DE4141637A1 (de) | 1991-12-17 | 1993-06-24 | Metzeler Gimetall Ag | Aktives, elastisches lager |
US5242714A (en) | 1991-12-20 | 1993-09-07 | Henkel Corporation | Process for forming protective base coatings on metals |
US5454882A (en) | 1992-01-13 | 1995-10-03 | Henkel Corporation | Process for controlling a fluoride containing conversion coating forming composition during its use for conversion coating aluminum containing metal |
JP3219453B2 (ja) | 1992-03-17 | 2001-10-15 | 日本パーカライジング株式会社 | 耐黒変性に優れた亜鉛系めっき鋼板の製造方法 |
US5356490A (en) | 1992-04-01 | 1994-10-18 | Henkel Corporation | Composition and process for treating metal |
US5769967A (en) | 1992-04-01 | 1998-06-23 | Henkel Corporation | Composition and process for treating metal |
US5281282A (en) | 1992-04-01 | 1994-01-25 | Henkel Corporation | Composition and process for treating metal |
US5534082A (en) | 1992-04-01 | 1996-07-09 | Henkel Corporation | Composition and process for treating metal |
US5252363A (en) | 1992-06-29 | 1993-10-12 | Morton International, Inc. | Method to produce universally paintable passivated galvanized steel |
US5498300A (en) | 1992-12-09 | 1996-03-12 | Henkel Corporation | Composition and process for treating tinplate |
US5700334A (en) | 1993-04-28 | 1997-12-23 | Henkel Corporation | Composition and process for imparting a bright blue color to zinc/aluminum alloy |
CA2113968C (en) | 1993-07-29 | 2000-05-30 | Junichi Mano | Chromated metal sheet having high corrosion resistance with improved lubricity and electric conductivity |
US5449415A (en) | 1993-07-30 | 1995-09-12 | Henkel Corporation | Composition and process for treating metals |
US5427632A (en) | 1993-07-30 | 1995-06-27 | Henkel Corporation | Composition and process for treating metals |
US5415702A (en) | 1993-09-02 | 1995-05-16 | Mcgean-Rohco, Inc. | Black chromium-containing conversion coatings on zinc-nickel and zinc-iron alloys |
US5304257A (en) * | 1993-09-27 | 1994-04-19 | The United States Of America As Represented By The Secretary Of The Navy | Trivalent chromium conversion coatings for aluminum |
US5374347A (en) | 1993-09-27 | 1994-12-20 | The United States Of America As Represented By The Secretary Of The Navy | Trivalent chromium solutions for sealing anodized aluminum |
US5393354A (en) | 1993-10-07 | 1995-02-28 | Mcgean-Rohco, Inc. | Iridescent chromium coatings and method |
JP3278509B2 (ja) | 1993-10-21 | 2002-04-30 | 日本パーカライジング株式会社 | 亜鉛含有金属めっき鋼板の難溶性クロメート皮膜形成処理方法 |
JP3325366B2 (ja) | 1993-10-29 | 2002-09-17 | 日本パーカライジング株式会社 | マグネシウム含有金属用化成処理液組成物、化成処理方法、および化成処理された材料 |
US5391239A (en) | 1993-11-01 | 1995-02-21 | Henkel Corporation | Conversion coating of aluminum and its alloys and compositions and concentrates therefor |
JP3333611B2 (ja) * | 1993-11-09 | 2002-10-15 | 日本パーカライジング株式会社 | アルミニウム及びアルミニウム合金用6価クロムフリーの化成表面処理剤 |
US5378292A (en) | 1993-12-15 | 1995-01-03 | Henkel Corporation | Phosphate conversion coating and compositions and concentrates therefor with stable internal accelerator |
US5580279A (en) | 1994-10-31 | 1996-12-03 | Berg Technology, Inc. | Low cost filtered and shielded electronic connector and method of use |
US5507084A (en) | 1994-12-19 | 1996-04-16 | Walbro Corporation | Removal tool |
US5702759A (en) | 1994-12-23 | 1997-12-30 | Henkel Corporation | Applicator for flowable materials |
WO1996027034A1 (en) | 1995-02-28 | 1996-09-06 | Henkel Corporation | Reducing or avoiding surface irregularities in electrophoretic painting of phosphated metal surfaces |
US6149735A (en) | 1995-11-30 | 2000-11-21 | Henkel Corporation | Chromate treatment bath composition and process for application to metals |
US5683816A (en) | 1996-01-23 | 1997-11-04 | Henkel Corporation | Passivation composition and process for zinciferous and aluminiferous surfaces |
US5595611A (en) | 1996-02-14 | 1997-01-21 | Henkel Corporation | Moderate temperature manganese phosphate conversion coating composition and process |
WO1997041277A1 (en) | 1996-04-26 | 1997-11-06 | Henkel Corporation | Chromate passivating and storage stable concentrate solutions therefor |
US6099714A (en) | 1996-08-30 | 2000-08-08 | Sanchem, Inc. | Passification of tin surfaces |
US5958511A (en) | 1997-04-18 | 1999-09-28 | Henkel Corporation | Process for touching up pretreated metal surfaces |
WO1999008806A1 (en) * | 1997-08-21 | 1999-02-25 | Henkel Corporation | Process for coating and/or touching up coatings on metal surfaces |
EP0937757A1 (en) | 1998-02-19 | 1999-08-25 | Nihon Parkerizing Co., Ltd. | Composition and method for hydrophilic treatment of aluminium or aluminium alloy, and use of the composition |
JPH11343450A (ja) | 1998-02-19 | 1999-12-14 | Nippon Parkerizing Co Ltd | アルミニウムまたはアルミニウム合金の親水化処理用組成物および親水化処理方法 |
JP3983386B2 (ja) | 1998-04-03 | 2007-09-26 | 日本ペイント株式会社 | クロメート防錆処理剤 |
JP3987633B2 (ja) | 1998-05-21 | 2007-10-10 | 日本表面化学株式会社 | 金属の保護皮膜形成用処理剤と形成方法 |
US6723178B1 (en) | 1999-08-16 | 2004-04-20 | Henkel Corporation | Process for forming a phosphate conversion coating on metal |
JP4357059B2 (ja) | 1999-12-21 | 2009-11-04 | 日本パーカライジング株式会社 | 長期耐食性に優れたアルミニウム含有金属製熱交換器および製造方法 |
WO2002010476A1 (en) | 2000-08-01 | 2002-02-07 | Henkel Kommanditgesellschaft Auf Aktien | Phosphate conversion coating concentrate |
US6375726B1 (en) | 2000-10-31 | 2002-04-23 | The United States Of America As Represented By The Secretary Of The Navy | Corrosion resistant coatings for aluminum and aluminum alloys |
US6521029B1 (en) | 2000-10-31 | 2003-02-18 | The United States Of America As Represented By The Secretary Of The Navy | Pretreatment for aluminum and aluminum alloys |
US6511532B2 (en) | 2000-10-31 | 2003-01-28 | The United States Of America As Represented By The Secretary Of The Navy | Post-treatment for anodized aluminum |
US6527841B2 (en) | 2000-10-31 | 2003-03-04 | The United States Of America As Represented By The Secretary Of The Navy | Post-treatment for metal coated substrates |
US6669764B1 (en) | 2000-10-31 | 2003-12-30 | The United States Of America As Represented By The Secretary Of The Navy | Pretreatment for aluminum and aluminum alloys |
US6663700B1 (en) | 2000-10-31 | 2003-12-16 | The United States Of America As Represented By The Secretary Of The Navy | Post-treatment for metal coated substrates |
AU2002367628A1 (en) | 2001-01-29 | 2003-10-08 | The Board Of Regents For Oklahoma State University | Organic/inorganic multilayer coating system |
KR100371554B1 (ko) | 2001-02-08 | 2003-02-07 | 현대자동차주식회사 | 내식성이 우수한 다크로 피막 코팅용 피막조성물 |
JP5183837B2 (ja) * | 2001-05-07 | 2013-04-17 | 日本ペイント株式会社 | 化成処理剤及び処理方法 |
US7029541B2 (en) | 2002-01-24 | 2006-04-18 | Pavco, Inc. | Trivalent chromate conversion coating |
US20050109426A1 (en) * | 2002-03-14 | 2005-05-26 | Dipsol Chemicals Co., Ltd. | Processing solution for forming hexavalent chromium free, black conversion film on zinc or zinc alloy plating layers, and method for forming hexavalent chromium free, black conversion film on zinc or zinc alloy plating layers |
US7018486B2 (en) | 2002-05-13 | 2006-03-28 | United Technologies Corporation | Corrosion resistant trivalent chromium phosphated chemical conversion coatings |
US6648986B1 (en) | 2002-05-13 | 2003-11-18 | United Technologies Corporation | Stability additive for trivalent chrome conversion coating bath solutions |
US6887321B2 (en) | 2002-05-22 | 2005-05-03 | United Technologies Corporation | Corrosion resistant surface treatment for structural adhesive bonding to metal |
JP2004210873A (ja) | 2002-12-27 | 2004-07-29 | Teijin Ltd | ポリエステル樹脂組成物の製造方法とそれから得られるフィルム |
JP2004210872A (ja) | 2002-12-27 | 2004-07-29 | Teijin Ltd | ポリエステル樹脂組成物の製造方法とそれから得られるフィルム |
WO2004060805A1 (en) | 2003-01-03 | 2004-07-22 | Solvay Solexis S.P.A. | Aluminium fluoride |
JP4351926B2 (ja) | 2003-02-17 | 2009-10-28 | 日本ペイント株式会社 | 防錆処理剤及び防錆処理方法 |
JP2005155749A (ja) | 2003-11-25 | 2005-06-16 | Nifco Inc | パイプクランプ |
JP4446230B2 (ja) | 2003-12-09 | 2010-04-07 | ディップソール株式会社 | アルミニウム又はアルミニウム合金用3価クロメート液及びそれを用いたアルミニウム又はアルミニウム合金表面に耐食性皮膜を形成する方法 |
JP4628726B2 (ja) | 2004-03-02 | 2011-02-09 | 日本表面化学株式会社 | アルミニウム部材及びその製造方法と製造用薬剤 |
US20060180247A1 (en) | 2005-02-15 | 2006-08-17 | United States Of America As Represented By The Secretary Of The Navy | Process for preparing chromium conversion coatings for iron and iron alloys |
US20060240191A1 (en) | 2005-04-21 | 2006-10-26 | The U.S. Of America As Represented By The Secretary Of The Navy | Composition and process for preparing chromium-zirconium coatings on metal substrates |
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JP3784400B1 (ja) * | 2005-05-27 | 2006-06-07 | 日本パーカライジング株式会社 | 金属用化成処理液および処理方法 |
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WO2008029925A1 (fr) | 2006-09-08 | 2008-03-13 | Nippon Paint Co., Ltd. | Procédé de traitement de surface d'une base métallique, matériau métallique traité par ce procédé de traitement de surface et procédé de revêtement de ce matériau métallique |
DE102006052919A1 (de) | 2006-11-08 | 2008-05-15 | Henkel Kgaa | Zr-/Ti-haltige Phosphatierlösung zur Passivierung von Metallverbundoberflächen |
MX2009005041A (es) | 2006-11-15 | 2009-07-22 | Nippon Steel Corp | Material metalico tratado en la superficie y metodo para producir el mismo. |
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US9243333B2 (en) | 2012-09-27 | 2016-01-26 | The United States Of America, As Represented By The Secretary Of The Navy | Coated aluminum alloy pigments and corrosion-resistant coatings |
-
2007
- 2007-05-10 RU RU2008148610/02A patent/RU2434972C2/ru not_active IP Right Cessation
- 2007-05-10 EP EP07762078.9A patent/EP2044239B1/en not_active Not-in-force
- 2007-05-10 CN CN2007800167718A patent/CN101448975B/zh not_active Expired - Fee Related
- 2007-05-10 BR BRPI0711353-6A patent/BRPI0711353B1/pt not_active IP Right Cessation
- 2007-05-10 US US11/746,802 patent/US9487866B2/en active Active
- 2007-05-10 WO PCT/US2007/068640 patent/WO2007134152A1/en active Application Filing
- 2007-05-10 KR KR1020087028903A patent/KR20090018067A/ko not_active Application Discontinuation
- 2007-05-10 JP JP2009510172A patent/JP5690485B2/ja active Active
- 2007-05-10 CA CA2651393A patent/CA2651393C/en not_active Expired - Fee Related
-
2016
- 2016-09-26 US US15/276,093 patent/US20170009330A1/en not_active Abandoned
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CN103132067A (zh) * | 2013-02-17 | 2013-06-05 | 武汉风帆电镀技术股份有限公司 | 铝及铝合金表面用前处理剂 |
CN105051257A (zh) * | 2013-03-15 | 2015-11-11 | 汉高股份有限及两合公司 | 用于铝和铝合金的改进的含三价铬的组合物 |
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CN113106434A (zh) * | 2021-04-12 | 2021-07-13 | 南昌大学 | 一种环保型铝合金化学氧化液及化学氧化方法 |
CN113309933A (zh) * | 2021-05-06 | 2021-08-27 | 中电建宁夏工程有限公司 | 一种多功能地下水管道及其成型方法 |
Also Published As
Publication number | Publication date |
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KR20090018067A (ko) | 2009-02-19 |
US20170009330A1 (en) | 2017-01-12 |
EP2044239A4 (en) | 2011-08-24 |
BRPI0711353A2 (pt) | 2011-09-27 |
JP5690485B2 (ja) | 2015-03-25 |
US20100132843A1 (en) | 2010-06-03 |
BRPI0711353B1 (pt) | 2022-04-12 |
WO2007134152A1 (en) | 2007-11-22 |
JP2009536692A (ja) | 2009-10-15 |
CN101448975B (zh) | 2011-07-27 |
CA2651393C (en) | 2016-11-01 |
RU2434972C2 (ru) | 2011-11-27 |
CA2651393A1 (en) | 2007-11-22 |
US9487866B2 (en) | 2016-11-08 |
EP2044239A1 (en) | 2009-04-08 |
RU2008148610A (ru) | 2010-06-20 |
EP2044239B1 (en) | 2014-09-03 |
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