Polyaniline-silane-nano-ceramics composite surface treatment agent

A composite surface treatment, nano-ceramic technology, applied in coatings, anti-corrosion coatings, etc., can solve the problems of weak physical bonding ability, high dependence and environmental hazards of film corrosion resistance, and achieve good compactness and strong rigidity. , the effect of reducing metal corrosion

Active Publication Date: 2019-01-11
NANJING KERUN LUBRICANTS
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  • Claims
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Problems solved by technology

However, this treatment method contains harmful heavy metal ions such as zinc and nickel and chemical components such as phosphorus, and produces a large amount of phosphating slag during production, causing potential harm to the environment.
As a technology that can replace the traditional phosphating treatment, there are known zirconium salt treatment methods and silane-zirconium salt composite treatment methods. This treatment method uses silane and zirconium fluoride composite treatment methods for surface treatment. However, this The film layer formed on the metal surface by such products is thinner than the traditional phosphating film layer, so the corrosion resistance of the film layer and the physical bonding ability with subsequent coatings are relatively weak
High dependence on metal surface pretreatment state and supporting electrophoretic paint

Method used

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  • Polyaniline-silane-nano-ceramics composite surface treatment agent

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] 配制聚苯胺-硅烷-纳米陶瓷复合表面处理剂:将质量浓度为500mg / L的磺酸基改性聚苯胺(数均分子量为20000)、200mg / L甲氧基改性聚苯胺(数均分子量为10000)、400mg / L分散性聚苯胺纳米颗粒(为气相合成的纳米级聚苯胺,粒径为15nm,PDI=0.1,数均分子量为20000)、300mg / L氟锆酸(以锆计)、100mg / L硝酸氧锆(以锆计)、10mg / Lγ-氨丙基三甲氧基硅烷、10mg / L烷基糖苷以及去离子水余量混合均匀搅拌至溶液澄清透明,即得到聚苯胺-纳米陶瓷复合表面处理剂。

[0023] 使用硝酸水溶液调节复合表面处理剂pH值至3.00±0.01,使用此复合表面处理剂浸泡处理脱脂预处理并水洗后的金属样板3分钟;

[0024] 准备板材:采用市售SPCC冷轧标准板(上海宝钢生产),规格为(150mm×70mm×0.8mm)来作为实施的金属样板。

[0025] 脱脂处理:采用市售某加热冷轧板脱脂剂,在50℃条件下浸泡冷轧板材5分钟。

[0026] 脱脂预处理后的水洗处理:在室温下自来水中摆洗1分钟。

[0027] 聚苯胺-硅烷-纳米陶瓷复合表面处理剂处理:将脱脂预处理并水洗后的金属样板在pH值至3.00±0.01的复合表面处理剂中浸泡3分钟。

[0028] 表面处理剂处理后的水洗处理:在自来水中浸泡处理复合表面处理剂处理后的金属样板30秒钟,然后使用去离子水冲洗30秒钟。此时可以取出并晾干或以冷风吹干后,以美国Filmetrics F20膜厚仪测试其膜厚(见表1中的金属表面裸膜厚度)。

[0029] 电泳涂装:

[0030] 使用关西公司生产的HT8000C水性阴极电泳涂料对表面湿润的经复合表面处理剂处理后的金属样板进行电泳,所得金属样板表面漆膜厚度为20±1μm范围内即得到试验样板。处理后的样板使用去离子水冲洗30秒钟。将水洗后的电泳后样板在180℃条件下干燥20分钟,取出后在室温下晾干。

[0031] 漆膜的性能见表1所述。

[0032] 磺酸基改性聚苯胺的分子结构:

[0033]

[0034] 在金属基材上的磺酸基改性聚苯胺与其它物质的反应机理:

[0035]

[0036] 磺酸基改性聚苯胺分子聚合形成聚苯胺膜;

[0037]...

Embodiment 2

[0042] 配制聚苯胺-硅烷-纳米陶瓷复合表面处理剂:将质量浓度为40mg / L的分散性聚苯胺纳米颗粒(为气相合成的纳米级聚苯胺,粒径为15nm,PDI=0.1,数均分子量为20000)、10mg / L乙氧基改性聚苯胺(数均分子量为8000)、100mg / L胺基改性聚苯胺(数均分子量12000)、5mg / Lγ-氨丙基甲基二乙氧基硅烷、100mg / L氟锆酸钾(以锆计)、5mg / L十二烷基硫酸钠以及去离子水余量混合均匀搅拌至溶液澄清透明,即得到聚苯胺-纳米陶瓷复合表面处理剂。

[0043]The prepared polyaniline-silane-nanometer ceramic composite surface treatment agent is adjusted to pH 4.20±0.01 with ammonia solution. Use this treatment solution to soak the metal sample after degreasing pretreatment and washing with water for 3 minutes.

[0044] All the other processes are the same as in Example 1.

[0045] Molecular structure of ethoxylated polyaniline:

[0046]

[0047] Table 1

[0048]

[0049] It can be seen from Table 1 that the thickness of the film formed on the surface of the metal substrate after being treated with the surface treatment agent of the present invention is far greater than the thickness of the film formed on the surface of the metal substrate after the treatment with the existing phosph...

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Abstract

The invention discloses a polyaniline-silane-nano-ceramics composite surface treatment agent. Each liter of the composite surface treatment agent is composed of the following components: 100-1000 mg of water-soluble polyaniline, 100-1000 mg of dispersed polyaniline nano-particles, 10-50 mg of a silane coupling agent, a zirconium compound, 5 mg-10 mg of a surfactant, and the balance water, whereinthe zirconium has a mass concentration of 100 mg to 500 mg / L in terms of zirconium. By the use of the composite surface treatment agent, a film formed on the metal surface is thick, and the film has good compactness. Thereby, the corrosion resistance of the treated metal substrate can be improved, and the adhesiveness between the film formed in the subsequent coating process and the metal substrate can be good.

Description

technical field [0001] 本发明涉及一种聚苯胺-硅烷-纳米陶瓷复合表面处理剂,属于金属材料表面处理技术领域。 Background technique [0002] 导电高分子聚苯胺由于原料易得,制备简易,且具有特殊的电化学性质和导电特性而被广泛的研究。而由于聚苯胺本身具有较大刚性导致溶解性较差,仅在部分有机溶剂中可溶。为扩大其应用,通过在苯环或氮原子上引入磺酸基、乙酸基、氟原子、氯原子、甲氧基等基团,通过降低大分子链之间大π键的相互作用,在牺牲一部分导电性的基础上大大提升了其在水中的溶解度。同时,这些官能团与涂料中的环氧树脂、聚氨脂、丙烯酸树脂等具有非常良好的相容性。利用机械加工将聚苯胺粒度降低到10~50nm的级别可以得到聚苯胺液体,该液体为聚苯胺的纳米颗粒,相当于几个到十几个聚苯胺分子团聚,在水中稳定存在,具有pH稳定性和储存稳定性。这些方式使得聚苯胺的应用面得到了广泛的延伸。 [0003] 金属材料进行涂装前通常需要进行表面处理以增强金属与涂料间的附着性能,目前,涂装前的金属表面处理多采用磷化处理工艺。但是,该处理方法由于含锌、镍等有害重金属离子以及磷等化学成分,且生产中产生大量的磷化渣,对环境造成潜在的危害。作为可以替代传统磷化处理方式的技术,已知的有锆盐处理方式和硅烷-锆盐复合处理方式,此种处理方式是采用硅烷以及氟化锆复合的处理方式进行表面处理,不过,该类产品在金属表面形成的膜层较传统的磷化膜层薄,因此其膜层耐蚀性以及与后续涂料的物理结合能力相对较弱。对于金属表面预处理后状态和配套电泳漆的依赖性较高。因此一种不含磷、但能达到含磷表面处理剂处理效果的聚苯胺-硅烷-纳米陶瓷复合表面处理剂的开发很有必要。 Contents of the invention [0004] 发明目的:为解决现有技术中的问题,本发明提供一种聚苯胺-硅烷-纳米陶瓷复合表面处理剂,该复合表面处理剂在金属表面形成的膜层厚,且膜层还具有良好的致密度,不仅能够使处理后的金属基材耐蚀性提高,而且还能使金属基材与后续涂饰工序所形成的漆膜的附着性能得到有效提高。 [0005] The technical scheme adopted in the present invention is: [0006] 一种聚苯胺-硅烷-纳米陶...

Claims

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Application Information

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IPC IPC(8): C09D179/02C09D183/08C09D5/08C09D7/61
CPCC08L2205/025C08L2205/035C09D5/08C09D179/02C09D7/61C08L79/02C08L83/08C08K3/24
Inventor 叶磊付海罗黄海威徐旭王娟聂晓霖
Owner NANJING KERUN LUBRICANTS
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