CN101203628A - 阴极保护化合物在经处理的金属制品上的应用 - Google Patents
阴极保护化合物在经处理的金属制品上的应用 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
- C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
- C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C09D5/08—Anti-corrosive paints
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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Abstract
揭示了一种阴极保护涂层，尽管在金属基材和阴极保护化合物之间存在含磷酸盐的转化涂层，该涂层仍然可以出乎意料地保护经过处理的金属基材。阴极保护涂层包括牺牲金属颗粒，该金属比要保护的金属基材的金属活泼。涂层还包括固有导电性聚合物。
Description
优先权声明
本申请要求于2004年10月1日提交的美国临时专利申请第60/615278号(代理人卷宗号12004011)的优先权。
发明领域
本发明涉及用于保护经处理的金属制品的阴极保护化合物。
发明背景
过去的五十年间，现代社会已从金属时代转向聚合物时代，部分原因是因为聚合物不会在环境中氧化。例如，金属因腐蚀破坏了其有价值的性能。当金属暴露于会发生这种腐蚀的环境条件时，腐蚀是金属形成金属氧化物的必然反应。由于这种腐蚀，每年需要耗资数十亿美金来修复或更换金属结构。
含铁制品腐蚀的自然过程通常被称为“生锈”，人们已花费相当大的努力来寻找能防止或减少生锈的有效而经济的方式。最初，试图采用对含铁制品表面进行涂布即上漆的方法来保护制品，以避免制品接触到开始自然生锈反应所需的元素。
含铁制品形成了建立城市以及城市之间商业联系的结构。用于各种用途例如多层建筑物、吊桥、山体或河道下面的隧道、公用事业的高压输电线、燃料储罐、自由女神像、艾菲尔铁塔以及各种类型混凝土结构的增强钢筋的铁制品都需要这种防腐蚀保护。
通常，作为制造工艺的一部分，对许多类型的金属进行处理。“处理”是指非裸金属的金属表面的处理，优选是之前通过常规的转化涂层法进行过处理。这类转化涂层是众所周知的，例如，已经在美国金属学会(AmericanSociety for Metals)的《金属手册(Metal Handbook)》，第II卷，第8版，第529-547页和《金属表面处理指南和目录(Metal Finishing Guidebook andDirectory)》第590-603页(1972)中进行了描述。美国专利第4376000号(Lindert)描述了转化涂层法，包括：
1.清洁；
2.水洗涤；
3.通过与合适的磷酸盐、铬酸盐或类似的常规浴接触形成转化涂料；
4.水洗涤；
5.施涂处理溶液；
6.任选地，干燥表面。
合适的常规涂料包括，但不限于，磷酸铁、磷酸锰、磷酸锌、用钙、镍或锰离子改性的磷酸锌。由于环境原因，铬酸盐涂料不是优选的。
适合用转化涂料处理的金属表面的例子包括锌，铁，铝，经过冷轧、抛光、浸渍和热轧的钢材以及镀锌钢的表面。
通常，现代钢处理包括在制造时用含磷酸盐的材料进行涂布，在钢材表面形成磷酸铁涂层。该处理通常整合在钢材制造方法中。用磷酸盐材料处理钢领域的例子是美国专利第4,132,572号(Parant等)，该专利揭示了在磷酸处理之前或之后，在上漆之前，用氟磷酸盐水溶液处理钢、铝和铝合金、锌和锌合金，使金属表面钝化，从而提高耐腐蚀性。美国专利第3,333,988、3,297,494、3,425,876、3,520,737、3,101,286、2,987,428和3,129,123号中描述了常用的磷酸锌和磷酸铁涂布方法和组合物的其它例子。
其它抗腐蚀机理是利用电势序(Galvanic Series)，从而在铁原本会生锈的环境中牺牲一种比铁活泼的金属。这种金属的“阴极保护”发展成为致力于保存金属性质免受环境破坏的庞大工业。
阴极保护利用了原电池回路的物理特性，该回路受到电力供应时成为有源回路，使被保护的金属不发生腐蚀作用，而该回路得不到电力供应时是无源的。无源原电池回路的例子，有美国专利第5,650,060号(Huang等)中揭示的基于电极的系统，以及美国专利第5,976,419号(Hawkins等)中揭示的基于涂层的系统。这两种系统都依赖于在电势序中阳极性更强的金属如锌，用以保护该结构中更有价值的铁。在Huang等的电极中，用离子导电性粘合剂将锌板粘着到一结构上。在Hawkins等的涂层中，锌以颗粒形式分散在粘合剂和固有导电性聚合物中。这两种情况下，锌是原电池回路中的阳极。牺牲阳极锌来保存阴极铁。
固有导电性聚合物与牺牲金属颗粒的组合成为阴极保护涂层用以保护金属基材，其中金属颗粒比基材的金属更活泼。美国专利第6,627,117号(Geer等)揭示了这种阴极保护涂层，该专利文献的内容通过参考结合于此。这类阴极保护涂层在市场上由PolyOne Corporation以商标
涂料出售。
之前已经意识到，如Hawkin等和Geer等所述的阴极保护涂层需要直接施加在未处理钢的表面。这种想法引起了阴极保护涂层使用者的关心，因为通常希望这类涂层在具体金属在钢厂中制造后即施涂到该金属制品上。阴极保护涂层必须在钢厂中进行施涂，替代磷酸盐处理步骤，或者钢在没有进行磷酸盐处理的情况下被转移到客户手中。前一种情况中断了组织良好的钢制造过程；后一种情况使钢在其运输和储存期间暴露于生锈环境。无论哪一种安排都无法令钢和其它易受腐蚀金属的使用者满意。
发明内容
本领域需要的是可用于经过磷酸盐处理的钢和其它类似受到保护的金属的阴极保护化合物。
出乎意料并且背离常规的认识和技术，已经发现，即使在如以上专利和技术参考文献所述的磷酸盐处理转化涂层上，Hawkin等和Geer等描述的阴极保护涂层也能够有效地进行使用。
换言之，阴极保护涂层能够与虽然在该涂层存在时还是用含磷酸盐的转化涂层处理过的钢和其它金属形成原电池回路。阴极保护涂层中的锌或铝金属颗粒是牺牲性的，即使这些颗粒在涂层中与它们选择要保护的金属不相邻也是如此。
本发明的一个方面是使用阴极保护化合物保护金属基材的方法，该方法包括以下步骤：将阴极保护化合物的涂料施涂到已经用含磷酸盐的转化涂层处理过的金属基材的表面上，其中所述阴极保护涂料包括：(a)电有效量的固有导电性聚合物；(b)电有效量的金属颗粒，其中所述金属比金属基材的金属更活泼；和(c)粘合剂。
“电有效量”指维持足够的导电性以保持用于阴极保护的原电池回路所需的固有导电性聚合物和金属颗粒的最小浓度，该原电池回路中金属基材中的金属是阴极，涂层中的金属颗粒是牺牲阳极。
粘合剂以及所述化合物最好是可流动材料的形式。“可流动材料”可以是：
(a)成膜液体，诸如油漆或其它涂料，将被喷涂或刷涂到需要阴极保护的含金属制品上；
(b)无定形固体，诸如聚合物粘合剂或其它聚合物，将在含金属制品上形成层；
(c)进行施涂从而在含金属制品上形成涂层的粉末；或
(d)蒸汽，诸如过热气体，它们将在含金属制品上凝聚。
较佳地，可流动材料是能够在需要阴极保护的含金属制品上快速且廉价地形成膜或其它涂层的聚合物粘合剂。如果可流动材料的选择能够降低花费，可流动材料本身可以不必是导电性的。
更佳地，可流动材料能够按照与任何油漆或其它涂料相同的方式形成阻挡层，从而对需要阴极保护的含金属制品提供物理方面的保护。
本发明的另一个方面是用本发明的阴极保护化合物进行了阴极保护的金属基材。
本发明的优点是在储存期间容易被腐蚀的钢和其它大规模生产的金属可以按照常规方式制造，但是由它们制备的某些制品仍然可以通过阴极保护涂层予以保护，该阴极保护涂层通过含磷酸盐材料的处理涂层提供对金属的无源的电化学(passively and galvanically)保护。
下文中将结合所述附图对本发明的这些和其它出乎意料的优点进行详细描述。
附图说明
图1是对比例A样品的数字图像。
图2是对比例B样品的数字图像。
图3是对比例C样品的数字图像。
图4是实施例1样品的数字图像。
实施方式
金属颗粒
如果要用金属颗粒保护与阴极保护膜或涂层电连接的某些其它金属，则根据电势序，选择的金属的阳极性必须大于被保护的金属的阳极性(前者的惰性(noble)小于后者的惰性)。美国专利第5,976,419号(Hawkins等)中揭示了这种理念，该专利通过参考结合于此。
平均粒径范围约为0.2-25微米，较好约为2-10微米，最好约为2微米。
金属颗粒的形状也是一个参数。颗粒形状可以是球形到片形范围。通常，优选单位体积有较大表面积的形状。然而，本领域技术人员必须还考虑纵横比较大的片状颗粒比纵横比较小的球形颗粒更难处理。
虽然并不优选，但是金属颗粒可以在聚合物内聚结或聚集，这一点不偏离本发明的范围。
牺牲阳极金属颗粒存在于可流动材料中，优选与可流动材料密切混合或共连续，所述可流动材料可以容易地靠近处理转化涂层，而被保护的阴极金属位于该转化涂层下方。
选择牺牲阳极取决于被保护的阴极金属，并受到成本、可用性、易加工性、对环境的作用影响以及其它因素的影响。发现可根据电势序来决定其可用的金属，电势序建立了金属性能的连续集。只要阳极金属在电势序内的位置高于阴极金属的位置，即阳极金属的阳极性较大，则是候选金属。
电势序为电化学工作者熟知，可以无需过多的试验就可以使用，选择用于牺牲阳极用途的合适候选金属。可用来检查候选金属的选择的一个网址是www.corrosionsource.com。另一个基于军用规格(MilitarySpecifications)的网址是www.eaa1000.av.org/technicl/corrosion/galvanic. htm，它可用来在腐蚀控制-原电池表中确定金属合金以及纯金属。
相对于要保护的阴极金属的常用牺牲阳极的非限制性例子可见表1。
表1
| 要保护的阴极金属 | 牺牲阳极金属 |
| 铁 | 锌、铝、锡 |
| 铜 | 铁+保护铁的那些金属 |
| 镍 | 铜+保护铜的那些金属 |
| 钛 | 镍+保护镍的那些金属 |
| 银 | 钛+保护钛的那些金属 |
各种可能用的金属中优选过渡金属，因为这类金属具有低电离能，正氧化态，高熔点，高沸点，高电导率，延展性和其它需要的性质。
化合物内阳极金属的量约为0.1-95％，优选约为0.2-40％。所有百分数都是相对于全部化合物中总固体重量的重量百分数。考虑到作为牺牲阳极的金属的消耗速度，阳极金属在化合物内的量应超过原电池保护预期的持续时间。本领域技术人员能够计算确定在可流动材料中阳极金属的较佳加入量。
金属颗粒可以是惰性小于要保护的金属的任何金属。较好地，金属颗粒是锌，因为锌的成本低于其它金属，而且锌的惰性小于铁(铁是时常需要用阴极保护系统进行保护的金属)。或者，可以在使用锌会有问题的环境中使用铝。如军用规格的原电池表所示，有许多适用于腐蚀控制的、由铝和另一种金属组成的合金。
锌颗粒可以从诸如Purity Zinc Metals LLC of Clarksville，TN；HumelCroton，Inc.和Trident Alloys，Ltd的来源获得。铝颗粒可从Eckart，Inc.获得。
可流动材料
可流动材料可以是电活性或惰性的。含有至少电有效量的本发明的固有导电性聚合物时，使用电惰性的可流动材料成本较低。但是，在某些实施方式中，要求使可流动材料也是电活性的，从而帮助导电介质促进原电池回路中的电子转移，该原电池回路中要保护的金属基材是阴极，与可流动材料中的导电介质混合的金属颗粒是牺牲阳极。
电惰性的可流动材料的非限制性例子是能形成膜或涂层或模塑或挤出产品的任何聚合物，例如来自烯烃、丙烯酸类、环氧化物、氨基甲酸酯、醇酸类、可UV固化或电子束固化的丙烯酸酯类、聚氯乙烯、聚酯、聚乙烯醇、乙烯乙酸乙酯的聚合物，乙烯丙烯酸离聚物，含氟聚合物，硅酮的聚合物，酚醛树脂，三聚氰胺，聚酰胺，天然和合成橡胶，苯乙烯嵌段共聚物，聚丙烯酰胺，聚乙烯基噁唑啉和聚乙烯亚胺。
“聚合物”是指天然存在的聚合物、合成制备的聚合物、天然存在的聚合物与合成制备的聚合物通过物理或化学相互作用的组合，或上述各聚合物的组合。
聚合物的所有主要物理形式都能被本发明接受使用，它们是热塑性塑料、热塑性弹性体、热固性塑料、热固性弹性体、以及这四种聚合物物理形式之间的混合物。优选热塑性材料，因为它容易配制和应用，但是由于其性能效果优选热固性塑料。可接受的聚合物化学组成的非限制性例子可在www.PolyOne.com.上找到。
聚合物可以是粘性或非粘性的。其粘性可以是天然固有的或通过增塑剂或增粘剂来产生。可接受的粘合剂的非限制性例子可在www.3M.com.上找到。
可商购的热塑性聚合物和热固性聚合物包括可商购的漆和其它成膜混合物，包括但不限于：牌的漆和涂料(来自Valspar of Minneapolis，MN USA)；Sherwin-Williams of Cleveland，Ohio USA的产品以及牌的漆和涂料(来自RPM Industries of Medina，Ohio USA)。
电活性的可流动材料作为任选的电活性、电镀惰性材料(例如碳纤维、碳颗粒和碳纳米管)组分也适合于本发明，该组分的量应能够有效地提高导电性，而不会干扰用于阴极保护金属基材的原电池回路。
以可流动材料的总固体重量为基准计，任选的碳纤维、碳颗粒或碳纳米管的含量可以约是0-10重量％。
可能的候选材料中，优选碳纤维和碳纳米管，原因是尽管它们的长度很短，但纵横比较大。例如，碳纤维的纵横比大于10∶1(L/W)，纳米管的直径尽管与碳纤维的直径为同一数量级或更小，却仍可达到同样的纵横比。
如果选用纳米管，相对于多壁纳米管来说优选单壁纳米管。
单壁碳纳米管是一种优选的新兴技术，如美国专利公报20030075682(Colbert等)中揭示的那些，该文献的内容通过参考结合于此。
碳纤维和碳纳米管的商业来源目前包括
碳纤维产品系列(Zoltek Corporation of St.Louis，Missouri)、Pyrograf-ITM多壁碳纳米管产品系列(Nano Graphite Materials，Inc.of Cedarville，Ohio)和Buckytube单壁碳纳米管产品系列(Carbon Nanotechnologies，Inc.of Houston，Texas)。
固有导电性聚合物
适用于本发明的固有导电性聚合物包括具有苯胺、噻吩、吡咯、苯基硫醇等重复单体单元的聚合物。其它例子包括选自下组的导电聚合物：取代和未取代的聚对亚苯基亚乙烯基、取代和未取代的聚苯胺、取代和未取代的聚吖嗪、取代和未取代的聚噻吩、取代和未取代的聚对亚苯基、取代和未取代的聚对亚苯基硫醚、取代和未取代的聚呋喃、取代和未取代的聚吡咯、取代和未取代的聚硒吩、取代和未取代的多炔、它们的混合物、它们的共聚物。许多专利中揭示了这些导电聚合物，包括美国专利5,069,820(Jen等)；5,160,457(Elsenbaumer)；5,185,100(Han等)；5,281,363(Shacklette等)；5,378,403(Shacklette)；5,422,423(Shacklette等)；5,456,862(Kwan-Yue等)；5,567,355(Wessling等)；5,700,398(Angelopoulos等)和5,911,918(Shacklette等)。如这些专利中所描述的，固有导电性聚合物通常掺杂有如盐酸或对甲苯磺酸之类的酸，
优选的是如美国专利5,968,417(Visawanathan)中所揭示的取代的聚苯胺，更优选的是市场上由PolyOne Corporation以TeslartTM出售的那些固有导电性聚合物。该取代的聚苯胺是木质素磺酸接枝的聚苯胺。
虽然本领域技术人员由于考虑成本的因素不太可能希望使用不止一种的固有导电性聚合物，但是可以将聚苯胺接枝的木质素磺酸与上述其它固有导电性聚合物混合。
方法
本发明化合物的制备并不复杂，特别是当制备是通过将可涂布材料混合来完成时更是如此。在磨碎机中混合，足以使固有导电性聚合物和金属颗粒的预混物得到充分混合，然后使用混漆器将该预混物混合到载体/粘合剂(通常是一种漆)中。混合速度为600-1000rpm，混合温度可以是室温。
本发明的有用性
本发明的阴极保护化合物可保护金属基材，诸如铁、铝和其它金属基材，基材金属的惰性大于涂层的金属颗粒的惰性。
对作为可流动材料以制备本发明涂层的涂料粘合剂/载体的选择应该考虑涂层对金属基材的良好粘着性。已经成功与固有导电性聚合物和金属颗粒组合使用的涂料体系的一些例子是丙烯酸、氨基甲酸酯、环氧化物和醇酸。此外，水基、溶剂基以及100％固体涂料能够提供对金属基材的阴极保护。
以下实施例说明了本发明的其它特点。
实施例
表2表示了用在涂料中的各组分和它们的商品来源。表3具有两部分：对比例A-C和实施例1的汇总，以及当根据ASTM Test B117测试时得到的性质结果。
根据ASTM测试通过视觉观察得到的盐雾数据结果得到了涂布的金属基材的数字影像的支持，对各涂布的金属基材的未擦伤(野外)表面和擦伤的区域进行视觉比较。
图1-4分别显示了本发明的对比例A-C和实施例1的明显且出乎意料的有效性。
使用混漆器在环境条件下制备对比例A-C和实施例1的涂料混合物。用商用喷漆器在环境条件下喷涂所有测试板，先喷涂底漆，然后喷涂面漆。
当综合考虑野外腐蚀级别和划线腐蚀级别时，实施例1优于对比例A-C中的任何一个。2850小时相当于188天，几乎连续暴露于盐雾中4个月。
实施例1显示出比对比例B出乎意料优越的性能，即使有磷酸盐处理层处于阴极保护层和要保护的金属基材之间也是如此。
实施例1显示出比对比例C明显优越的性能，特别是在野外腐蚀级别中，表明常规的仅使用锌金属进行腐蚀保护可以保护阻挡层中断处(划线表面)的位置，但是不能保护未受伤的表面。因此，当检查金属基材时，腐蚀的潜藏程度更高。
在野外腐蚀级别中，对比例C的性能比对比例A差，或许表明磷酸盐处理的钢与锌粉组合比锌粉位于金属基材的相邻层中得到的效果差。
最后，使用电有效量的固有导电性聚合物在锌金属颗粒量极少情况下能够提高性能，因为原电池回路使用了在常规高装载锌底漆中不存在的固有导电性聚合物。本发明涂层的重量也得到明显减低。
本发明不限于上述实施方式。
Claims (12)
1.一种使用阴极保护化合物来保护金属基材的方法，其包括以下步骤：将阴极保护化合物的涂料施涂到已经用含磷酸盐的转化涂层处理过的金属基材的表面上，
其中所述阴极保护涂料包含(a)电有效量的固有导电性聚合物；(b)电有效量的金属颗粒，其中所述金属的惰性小于金属基材的金属的惰性；和(c)粘合剂。
2.一种用如权利要求1所述的方法保护的经过处理的金属基材。
3.如权利要求2所述的基材，其特征在于，所述粘合剂包括可流动材料，所述可流动材料包括成膜液体、无定形固体、粉末或蒸汽。
4.如权利要求2所述的基材，其特征在于，所述金属颗粒的平均粒度约为0.2-25微米，颗粒形状从球形至片形。
5.如权利要求2所述的基材，其特征在于，所述基材包括铁和选自下组的金属颗粒：锌、铝、锡和它们的组合。
6.如权利要求3所述的基材，其特征在于，所述可流动材料是电惰性的，并且是由烯烃、丙烯酸类、环氧化物、氨基甲酸酯、醇酸、可紫外固化或可电子束固化的丙烯酸酯类、聚氯乙烯、聚酯、聚乙烯醇、乙烯乙酸乙烯酯中的一种或多种制成的聚合物、乙烯丙烯酸离聚物、含氟聚合物、硅酮的聚合物、酚醛树脂、三聚氰胺、聚酰胺、天然和合成橡胶、苯乙烯嵌段共聚物，聚丙烯酰胺，聚乙烯基噁唑啉和聚乙烯亚胺。
7.如权利要求6所述的基材，其特征在于，所述聚合物是粘性的。
8.如权利要求3所述的基材，其特征在于，所述可流动材料是电活性的，包括碳纤维、碳颗粒、碳纳米管和它们的组合。
9.如权利要求3所述的基材，其特征在于，所述可流动材料是电活性的，包括固有导电性聚合物。
10.如权利要求9所述的基材，其特征在于，所述固有导电性聚合物包括具有以下重复单体单元的聚合物：苯胺、噻吩、吡咯、苯基硫醇和它们的组合。
11.如权利要求9所述的基材，其特征在于，所述固有导电性聚合物选自下组：取代和未取代的聚对亚苯基亚乙烯基、取代和未取代的聚苯胺、取代和未取代的聚吖嗪、取代和未取代的聚噻吩、取代和未取代的聚对亚苯基、取代和未取代的聚对亚苯基硫醚、取代和未取代的聚呋喃、取代和未取代的聚吡咯、取代和未取代的聚硒吩、取代和未取代的多炔、它们的混合物、它们的共聚物。
12.如权利要求9所述的基材，其特征在于，所述固有导电性聚合物是取代或未取代的聚苯胺。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101855276B (zh) * | 2007-09-13 | 2013-11-06 | 斯蒂茨丁荷兰聚合物学会 | 用于制备导电性聚合物组合物的方法 |
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| CN110893065A (zh) * | 2018-09-12 | 2020-03-20 | 武汉苏泊尔炊具有限公司 | 锅体、锅体的加工方法及烹饪器具 |
| CN110893065B (zh) * | 2018-09-12 | 2023-04-25 | 武汉苏泊尔炊具有限公司 | 锅体、锅体的加工方法及烹饪器具 |
| CN111979550A (zh) * | 2020-08-11 | 2020-11-24 | 神华神东煤炭集团有限责任公司 | 一种牺牲阳极复合物及其制备方法 |
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| WO2006039179A3 (en) | 2007-11-01 |
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