目的 基于431不锈钢零件在海水环境中的耐腐蚀性有限,探究薄膜组织结构对431不锈钢耐腐蚀性能的改善作用。方法 利用磁控溅射物理气相沉积技术制备了不同调制比结构的DLC复合薄膜;采用SEM、Raman、XRD、XPS及电化学工作站对薄膜的形貌、结构和性能进行测试。结果 调制比为1∶4时,薄膜表面粗糙度最小、致密度最高,薄膜中CrC和CrN的原子百分比含量分别达到峰值。此外,薄膜中出现了CrN(100)和CrN(110)的强衍射峰以及较弱的Cr2N(110)衍射峰,且能够观察到C(111)衍射峰。电化学实验表明,调制比为1∶4时,薄膜在人工海水溶液中具有最低的致钝电流密度、维钝电流密度、最高的电荷转移电阻和最低的点蚀因子。结论 改变薄膜调制比参数能够改变DLC复合薄膜的组织结构从而改善薄膜的耐腐蚀性能。调制比<1∶4时,中间层在沉积过程中极易生长为粗大柱状晶,表界面缺陷增加,致密度降低,无法有效抵抗腐蚀介质的渗透;调制比为1∶4的过渡层结构能促进Cr与C 2种元素互扩散,形成元素过渡界面,降低界面应力,提升薄膜致密度,在腐蚀过程中易于形成致密的钝化膜,有效抑制点蚀发展进程,提升薄膜的耐腐蚀性能;继续增加调制比,过渡层厚度进一步降低,薄膜均匀性下降,点蚀发展迅速,耐腐蚀性能下降。
Abstract
The use of 431 stainless steel parts in marine operations has become increasingly widespread, imposing higher demands on their corrosion resistance. To meet the stringent requirements for critical components in seawater environments, this study investigates the effect of different modulation ratios in transition layers on the corrosion resistance of DLC composite films.
Cr/CrN/CrCN/DLC films with modulation ratios of 1∶1, 1∶2, 1∶4, 1∶5, and 1∶10 are deposited on 431 stainless steel substrates by magnetron sputtering physical vapor deposition (PVD). The film structure and corrosion performance are characterized by scanning electron microscopy, while the structural and functional properties are analyzed by Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and electrochemical workstation.
As the modulation ratio increases, the surface roughness of the film shows an initial decrease followed by an increase, reaching a minimum value of 0.012 μm at a modulation ratio of 1∶4. The film density exhibits an initial rise followed by a decline, achieving a peak value of 2.20 g/cm³ at a ratio of 1∶4. Strong diffraction peaks corresponding to CrN(100), CrN(110), and C(111) appear in the film, along with a weaker Cr2N(110) peak. Structurally, the atomic percentages of both CrC and CrN increase initially and then decrease with the increase of the modulation ratio, peaking at 21.44% and 26.86% respectively at 1∶4. Conversely, the atomic percentage of Cr2N demonstrates the opposite trend, reaching its lowest value of 20.68% at 1∶4. Electrochemical tests reveal that films with a modulation ratio of 1∶4 display; Conversely, the atomic percentage of Cr2N demonstrates the opposite trend, reaching its lowest value of 20.68% at a modulation ratio of 1:4. Electrochemical tests reveal that at this ratio (1∶4), the film in artificial seawater exhibits the highest corrosion potential (-0.183 V), the lowest corrosion current density (9.107×10-8 A/cm2), the minimal passivation current density (7.943×10-8 A/cm2) and reduced passive current density, elevated breakdown voltage (-0.083 V). And the maximum charge transfer resistance, the lowest pitting factor. It shows excellent corrosion resistance.
Adjusting the modulation ratio of films modifies the microstructure of DLC composite films, thereby enhancing their corrosion resistance. At a modulation ratio of 1∶1, the interlayer readily develops coarse columnar grains during deposition. This leads to an increase in surface and interfacial defects, reduced density, and consequently compromises its ability to effectively resist the penetration of corrosive agents. At a modulation ratio of 1∶2, although a weak interdiffusion effect occurs within the coating, it is insufficient to facilitate effective interlayer bonding. The coating exhibits low density and a porous internal structure, which fails to impede the ingress of corrosive agents, resulting in poor corrosion resistance. At the optimal ratio of 1∶4, the transition layer structure promotes interdiffusion of Cr and C elements, forming a compositionally graded interface that reduces interfacial stress and enhances film density. Concurrently, this facilitates the formation of a dense passivation film during corrosion, effectively inhibiting pitting propagation and significantly improving corrosion resistance. Further increasing the ratio to 1∶5 and 1∶10, the thickness of the interlayer is progressively reduced. This leads to the penetration of high-energy ions through the interlayer during the deposition process, resulting in an increase in surface and interface defects within the film. Consequently, film uniformity deteriorates, the capability to act as a barrier against corrosive media is diminished, pit propagation accelerates, and the overall corrosion resistance is significantly degraded.
Therefore, rational design of the interlayer thickness and controlled interfacial organization create effective barriers against corrosive medium ingress, ultimately optimizing the corrosion resistance of DLC composite films.
关键词
DLC复合薄膜 /
调制比 /
组织结构 /
耐腐蚀性能 /
点蚀 /
腐蚀防护
Key words
DLC composite film /
modulation ratio /
microstructure /
corrosion resistance /
pitting corrosion /
corrosion protection
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基金
国家自然科学基金（51861031）; 青岛市关键技术攻关及产业化示范类项目（25-1-1-gigg-45-hy）; 山东省先进发动机活塞组件重点实验室开放课题（BH202509）
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