Effect of Modulation Ratio on Structure and Corrosion Resistance of DLC Composite Films

YANG Xiangdong; ZHANG Shuling; JIANG Di; MA Xinghua; LIU Yi; CAO Guoshuai; GUO Feng

doi:10.16490/j.cnki.issn.1001-3660.2025.22.003

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Surface Technology ›› 2025, Vol. 54 ›› Issue (22) : 31-43. DOI: 10.16490/j.cnki.issn.1001-3660.2025.22.003

Corrosion and Protection

Effect of Modulation Ratio on Structure and Corrosion Resistance of DLC Composite Films

YANG Xiangdong¹, ZHANG Shuling^1*, JIANG Di¹, MA Xinghua¹, LIU Yi²,CAO Guoshuai³, GUO Feng¹

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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.

Key words

DLC composite film / modulation ratio / microstructure / corrosion resistance / pitting corrosion / corrosion protection

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YANG Xiangdong, ZHANG Shuling, JIANG Di, MA Xinghua, LIU Yi, CAO Guoshuai, GUO Feng. Effect of Modulation Ratio on Structure and Corrosion Resistance of DLC Composite Films[J]. Surface Technology. 2025, 54(22): 31-43 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.22.003

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Funding

National Natural Science Foundation of China (51861031); Key Technology Research and Industrialization Demonstration Projects in Qingdao (25-1-1-gigg-45-hy); Open Funding of Shandong Key Laboratory of Advanced Engine Piston Assembly (BH202509)