水性环氧涂层/碳钢体系腐蚀电化学行为研究
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摘要
水性涂料替代传统溶剂型涂料是涂料工业的发展趋势,其具有低污染和低成本的优点,在金属防护领域得到了广泛应用,但目前水性防护涂层的性能还远远达不到溶剂型涂层的水平。机械零部件在安装、拆卸和使用过程中承受着不同程度的磨损,导致涂层防护寿命降低,因此,具有优异防腐性能同时兼具耐磨、润滑等功能性是机械零部件防护涂层发展的新要求。本文以用于海洋工程的紧固件腐蚀防护涂层为工程研究背景,以水性环氧清漆为涂层基料,通过加入不同的颜料,制备了具有防腐性能同时兼具润滑性能的紧固件水性防护涂层。采用电化学阻抗谱(EIS)、扫描电镜(SEM)和拉曼(Raman)光谱等测试技术研究了涂层中水的传输及浸泡过程中涂层/碳钢体系的腐蚀电化学行为,研究了颜料种类、含量、颜料与水性环氧树脂相容性对涂层抗渗透能力的影响。并将扫描振动电极技术(SVET)和EIS相结合,研究了带有人造缺陷的不同涂层/碳钢体系的腐蚀电化学行为,深化了对涂层阴极剥离行为的认识。
首先,研究了水性环氧清漆中水的传输行为,结果表明,水性环氧清漆的抗渗透能力低于传统溶剂型环氧涂层。进一步的研究发现造成该现象的主要原因是清漆中存在大量纳米级微观缺陷。并且发现涂层的剥离机理是阴极剥离,缺陷处暴露的碳钢为阳极,剥离前缘处是阴极。
进而,向水性环氧清漆中分别加入聚四氟乙烯(PTFE)、鳞片铝粉和纳米铝粉来提高涂层的防腐性能。结果表明,PTFE复合涂层可实现自分层结构,而且PTFE在涂层表面富集,赋予涂层润滑功能,但PTFE与水性环氧树脂的界面存在缝隙,导致PTFE复合涂层防腐性能下降。
进行了利用鳞片状铝粉来提高水性环氧涂层防腐性能的研究。发现随着颜料体积浓度(PVC)增大,鳞片铝粉改性涂层的抗渗透能力下降。高PVC涂层浸泡过程中出现微弱的阴极保护作用,腐蚀产物堵塞涂层缺陷,短期内使涂层变得致密,但长期浸泡,由于涂层孔隙率较大,铝粉不能有效改善涂层防腐能力。
还进行了向水性环氧树脂中加入纳米铝粉以提高涂层致密性的研究,发现当颜料含量为1%时,涂层的抗腐蚀介质渗透能力最好。并且纳米铝粉还具有阴极保护作用,有效抑制了涂层的阴极剥离,降低了涂层剥离速度。
最后,进行了将纳米铝粉和PTFE复合来改性水性环氧清漆的研究,结果表明,纳米铝粉与PTFE发挥了协同效应,显著提高了涂层的抗渗透能力和防腐性能。
Substituting waterborne paint for traditional solvent paint is one of the development trends in coating industry. Waterborne coating is widely used to protecting metals due to its advantages such as low pollution and low cost, however, its anti-corrosion performance is farther inferior to solvent coating. Machinery components often undergo wear during installing, dismantling and using, which may lead to lifetime reducing. Therefore, it is needful that the protective coating for machinery components should have the performance of both anticorrosion and lubricantion. In this thesis, some research work has been done taking the fastener protection coating as engineering background. The fastener coating with anticorrosion performance and lubricantion was prepared by adding different kinds of pigments into the waterborne epoxy resin. Water transport in the coating and the corrosion electrochemical behavior of the coating/steel systems were investigated using EIS and various physical testing techniques such as SEM and Raman spectroscopy. The kind, the dosage of pigments and the compatibility between the pigment and the waterborne epoxy binder were studied. In this paper, the corrosion electrochemical behavior of various coating system with artificial defect on steel was also analysed using SVET connecting with EIS, which deepened the understanding of the behavior of coating cathodic delamination. The main results are listed as follows:
Firstly, water transport behavior in waterborne epoxy coating without pigment was investigated. The result showed that the penetrability-resistance of the waterborne epoxy coating without pigment is not as good as solvent one due to a mass of nano size micro-defect in the waterborne coating. The delamination behavior of the water-borne epoxy coating with an artificial defect on carbon steel was investigated. The result showed that the delamination mechanism of the waterborne epoxy coating is the cathodic delamination, with the exposed steel in the defect as the anode and the delamination front as the cathode.
Farther, it was experimented to enhance the film anticorrosive performance by adding PTFE、aluminum flakes and nano Al powder into the matrixes, respectively. The result showed that the stratified structure with PTFE enriched on the surface of the coating can be obtained by control the cure process, which can provid lubricantion. The flaw due to the poor compatibility between PTFE and the waterborne epoxy resin is the main reason resulting in the poor anticorrosion performance.
Moreover, the anticorrosive performance of the waterborne epoxy resin modified by lamellar aluminum was investigated. The results showed that protective properties of aluminum flakes modified coating decreased with PVC increasing. The aluminum flakes had feeble cathodic protection effect in high PVC coating, and the corrosion product of aluminum powder repaired holes in short time. However, after enough time, the barrier effect of the lamellar aluminum-rich coating was less notable. The aluminum flakes can not increase the anticorrosion performance of the coating due to the high porosity of the coating.
The addition of nano Al powder can enhance the compactness of the waterborne epoxy resin. The best permeability-resistance of the coating was obtained when the pigment concentration is 1%. The corrosion electrochemical behavior of the nano Al composite coating/steel system with artificial defect was investigated and the results showed that nano Al powder can provide cathodic protection effect, which decreased the coating delamination rate.
Finally, Nano Al and PTFE composite pigment was experimented to modify the waterborne epoxy resin. The result showed that Nano Al and PTFE particles had synergetic effect, thus the permeability-resistant of the composite coating was increased. Moreover, the coating delamination rate decreased comparing with the waterborne epoxy varnish.
首先,研究了水性环氧清漆中水的传输行为,结果表明,水性环氧清漆的抗渗透能力低于传统溶剂型环氧涂层。进一步的研究发现造成该现象的主要原因是清漆中存在大量纳米级微观缺陷。并且发现涂层的剥离机理是阴极剥离,缺陷处暴露的碳钢为阳极,剥离前缘处是阴极。
进而,向水性环氧清漆中分别加入聚四氟乙烯(PTFE)、鳞片铝粉和纳米铝粉来提高涂层的防腐性能。结果表明,PTFE复合涂层可实现自分层结构,而且PTFE在涂层表面富集,赋予涂层润滑功能,但PTFE与水性环氧树脂的界面存在缝隙,导致PTFE复合涂层防腐性能下降。
进行了利用鳞片状铝粉来提高水性环氧涂层防腐性能的研究。发现随着颜料体积浓度(PVC)增大,鳞片铝粉改性涂层的抗渗透能力下降。高PVC涂层浸泡过程中出现微弱的阴极保护作用,腐蚀产物堵塞涂层缺陷,短期内使涂层变得致密,但长期浸泡,由于涂层孔隙率较大,铝粉不能有效改善涂层防腐能力。
还进行了向水性环氧树脂中加入纳米铝粉以提高涂层致密性的研究,发现当颜料含量为1%时,涂层的抗腐蚀介质渗透能力最好。并且纳米铝粉还具有阴极保护作用,有效抑制了涂层的阴极剥离,降低了涂层剥离速度。
最后,进行了将纳米铝粉和PTFE复合来改性水性环氧清漆的研究,结果表明,纳米铝粉与PTFE发挥了协同效应,显著提高了涂层的抗渗透能力和防腐性能。
Substituting waterborne paint for traditional solvent paint is one of the development trends in coating industry. Waterborne coating is widely used to protecting metals due to its advantages such as low pollution and low cost, however, its anti-corrosion performance is farther inferior to solvent coating. Machinery components often undergo wear during installing, dismantling and using, which may lead to lifetime reducing. Therefore, it is needful that the protective coating for machinery components should have the performance of both anticorrosion and lubricantion. In this thesis, some research work has been done taking the fastener protection coating as engineering background. The fastener coating with anticorrosion performance and lubricantion was prepared by adding different kinds of pigments into the waterborne epoxy resin. Water transport in the coating and the corrosion electrochemical behavior of the coating/steel systems were investigated using EIS and various physical testing techniques such as SEM and Raman spectroscopy. The kind, the dosage of pigments and the compatibility between the pigment and the waterborne epoxy binder were studied. In this paper, the corrosion electrochemical behavior of various coating system with artificial defect on steel was also analysed using SVET connecting with EIS, which deepened the understanding of the behavior of coating cathodic delamination. The main results are listed as follows:
Firstly, water transport behavior in waterborne epoxy coating without pigment was investigated. The result showed that the penetrability-resistance of the waterborne epoxy coating without pigment is not as good as solvent one due to a mass of nano size micro-defect in the waterborne coating. The delamination behavior of the water-borne epoxy coating with an artificial defect on carbon steel was investigated. The result showed that the delamination mechanism of the waterborne epoxy coating is the cathodic delamination, with the exposed steel in the defect as the anode and the delamination front as the cathode.
Farther, it was experimented to enhance the film anticorrosive performance by adding PTFE、aluminum flakes and nano Al powder into the matrixes, respectively. The result showed that the stratified structure with PTFE enriched on the surface of the coating can be obtained by control the cure process, which can provid lubricantion. The flaw due to the poor compatibility between PTFE and the waterborne epoxy resin is the main reason resulting in the poor anticorrosion performance.
Moreover, the anticorrosive performance of the waterborne epoxy resin modified by lamellar aluminum was investigated. The results showed that protective properties of aluminum flakes modified coating decreased with PVC increasing. The aluminum flakes had feeble cathodic protection effect in high PVC coating, and the corrosion product of aluminum powder repaired holes in short time. However, after enough time, the barrier effect of the lamellar aluminum-rich coating was less notable. The aluminum flakes can not increase the anticorrosion performance of the coating due to the high porosity of the coating.
The addition of nano Al powder can enhance the compactness of the waterborne epoxy resin. The best permeability-resistance of the coating was obtained when the pigment concentration is 1%. The corrosion electrochemical behavior of the nano Al composite coating/steel system with artificial defect was investigated and the results showed that nano Al powder can provide cathodic protection effect, which decreased the coating delamination rate.
Finally, Nano Al and PTFE composite pigment was experimented to modify the waterborne epoxy resin. The result showed that Nano Al and PTFE particles had synergetic effect, thus the permeability-resistant of the composite coating was increased. Moreover, the coating delamination rate decreased comparing with the waterborne epoxy varnish.
引文
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