Energy and environmental issues have become critical factors shaping contemporary economic and social development. In response to the International Maritime Organization (IMO)'s strategy for reducing greenhouse gas emissions from shipping and China's national goals of carbon neutrality, the development of low-carbon and zero-carbon energy sources has become essential for the future maritime industry. Compared with conventional fossil fuels such as diesel, ammonia fuel demonstrates a distinct advantage as a carbon-neutral energy carrier due to its inherent carbon-free molecular structure. When subject to complete combustion processes, the resultant products are exclusively dihydrogen monoxide and nitrogen gas (N2), thereby achieving zero emission of carbon-containing pollutants. This combustion characteristic positions ammonia as a particularly promising alternative fuel for maritime applications, aligning with stringent environmental regulations and sustainable development objectives.
The paper addresses the corrosion risks associated with ammonia fuel, a promising zero-carbon alternative for the shipping industry, which can accelerate the degradation of critical engine components. To mitigate this issue, the paper focuses on developing ammonia-resistant surface treatment technologies to enhance the corrosion resistance of materials used in key components of marine engines. Environment simulation experiments of engine piston components under service conditions in ammonia fuel combustion products are conducted using a high-temperature and high-pressure autoclave. Surface nitriding treatments are studied for tempered 16CrMo steel used in pistons to improve its resistance to ammonia corrosion. Gas nitriding and composite salt bath nitriding with QPQ (Quench-Polish-Quench) treatment techniques are applied to investigate the nitrided layer structures and their corrosion behavior in an ammonia fuel combustion environment.
Both gas nitriding and composite salt bath nitriding with QPQ treatment produced compound layers with comparable hardness and diffusion layer thickness. The nitriding layer formed by gas nitriding consists exclusively of iron nitrides (e-Fe2-3N and g′-Fe4N), achieving a corrosion rate of 0.0220 mm/a in the ammonia fuel combustion environment, which represents a 13.39% improvement in corrosion resistance compared with the alloy substrate. In contrast, the composite nitriding layer formed by composite salt bath nitriding with QPQ treatment, comprising iron nitrides, carbides, and Fe3O4, demonstrates a significantly lower corrosion rate of 0.014 65 mm/a, corresponding to a 42.32% enhancement in corrosion resistance. These findings indicate that the composite salt bath nitriding with QPQ treatment provides superior corrosion resistance, making it a more effective surface treatment method for improving the performance and durability of 16CrMo steel under ammonia fuel combustion conditions.
In conclusion, both gas nitriding and composite salt bath nitriding with QPQ treatment rely primarily on the diffusion of nitrogen atoms into the substrate and their combination with iron. However, the latter achieves a synergistic enhancement of surface hardness and corrosion resistance through a "nitriding-carbonitriding + oxidation" process. Notably, under harsh conditions involving high temperature, high pressure, and corrosive environments, the multilayer composite structure formed by QPQ treatment significantly inhibits the penetration of oxidative media, thereby demonstrating superior corrosion resistance and economic efficiency. This process holds substantial engineering value for the application of 16CrMo alloy steel in future high-temperature combustion or corrosive environments and offers a feasible direction for further optimization of salt bath compositions and process parameters.
Key words
16CrMo alloy steel /
ammonia fuel /
gas nitriding /
composite salt bath nitriding with QPQ treatment /
high- temperature and high-pressure corrosion
{{custom_sec.title}}
{{custom_sec.title}}
{{custom_sec.content}}
References
[1] TADROS M, VENTURA M, SOARES C G.Review of Current Regulations, Available Technologies, and Future Trends in the Green Shipping Industry[J]. Ocean Engineering, 2023, 280: 114670.
[2] ZINCIR B.Environmental and Economic Evaluation of Ammonia as a Fuel for Short-Sea Shipping: A Case Study[J]. International Journal of Hydrogen Energy, 2022, 47(41): 18148-18168.
[3] ZAMFIRESCU C, DINCER I.Using Ammonia as a Sustainable Fuel[J]. Journal of Power Sources, 2008, 185(1): 459-465.
[4] ZINCIR B.Ammonia for Decarbonized Maritime Transportation[M]//Clean Fuels for Mobility. Singapore: Springer Singapore, 2022: 171-199.
[5] ZAMFIRESCU C, DINCER I.Ammonia as a Green Fuel and Hydrogen Source for Vehicular Applications[J]. Fuel Processing Technology, 2009, 90(5): 729-737.
[6] GU Z W, LUO H, ZHANG H D, et al.The Experimental Research on Explosively High Magnetic Field Generator[C]//2012 14th International Conference on Megagauss Magnetic Field Generation and Related Topics (MEGAGAUSS). Maui, HI, USA. IEEE, 2014: 1-4.
[7] WANG Y, CAO Q, LIU L, et al.A Review of Low and Zero Carbon Fuel Technologies: Achieving Ship Carbon Reduction Targets[J]. Sustainable Energy Technologies and Assessments, 2022, 54: 102762.
[8] SUN L, XIONG Z, QIU J, et al.Corrosion Behavior of Carbon Steel in Dilute Ammonia Solution[J]. Electrochimica Acta, 2020, 364: 137295.
[9] BORGIOLI F.Formation of Expanded Phases in Ferritic Stainless Steel Nitrided at Low Temperatures[J]. Surface and Coatings Technology, 2024, 477: 130309.
[10] HE Z, JIA W J, LIU X L, et al.The Effect of Aluminum Addition on Plasma Nitriding for 42CrMo Steel[J]. Materials Letters, 2024, 377: 137440.
[11] ANIL KUMAR REDDY C, SRINIVASAN T, VENKATESH B. Effect of Plasma Nitriding on M50 NiL Steel-a Review[J]. Materials Today: Proceedings, 2022, 52: 1073-1077.
[12] PSYLLAKI P, KEFALONIKAS G, PANTAZOPOULOS G, et al.Microstructure and Tribological Behaviour of Liquid Nitrocarburised Tool Steels[J]. Surface and Coatings Technology, 2003, 162(1): 67-78.
[13] 黄周锋. 金属材料先进化学热处理技术及应用[J]. 科技视界, 2012(13): 114-115.
HUANG Z F.Advanced Chemical Heat Treatment Technology of Metal Materials and Its Application[J]. Science&Technology Vision, 2012(13): 114-115.
[14] KORKMAZ E E, BAYRAM A, ERTAN R, et al.Effect of Plasma Nitriding Parameters on the Wear Behaviour of AISI D6 Tool Steel[J]. Materials Testing, 2013, 55(6): 455-461.
[15] KOCHMAŃSKI P, NOWACKI J. Activated Gas Nitriding of 17-4 pHStainless Steel[J]. Surface and Coatings Technology, 2006, 200(22/23): 6558-6562.
[16] WANG J, LIN Y H, YAN J, et al.Influence of Time on the Microstructure of AISI 321 Austenitic Stainless Steel in Salt Bath Nitriding[J]. Surface and Coatings Technology, 2012, 206(15): 3399-3404.
[17] TANG L N, YAN M F.Effects of Rare Earths Addition on the Microstructure, Wear and Corrosion Resistances of Plasma Nitrided 30CrMnSiA Steel[J]. Surface and Coatings Technology, 2012, 206(8/9): 2363-2370.
[18] 姚玲珍, 邓益中. 复合盐浴渗氮QPQ处理新技术的发展与应用[J]. 内燃机与配件, 2012(5): 36-40.
YAO L Z, DENG Y Z.Composite Aitrided QPQ Treatment New Technology Development and Application[J]. Internal Combustion Engine & Parts, 2012(5): 36-40.
[19] WANG K, LUO D F, ZHANG L.Research on Fast Nitriding by Direct Current Field Base on the Deep-Layer QPQ Technology[J]. Physics Procedia, 2013, 50: 113-119.
[20] LI S, ZHANG C S, CHEN D Z, et al.Catalytic Gas Nitriding of M50NiL Steel by LaFeO3 Pervoskite Oxide under Low-Pressure Conditions[J]. Surfaces and Interfaces, 2023, 40: 103098.
[21] 陈海, 崔鼎. 42CrMo钢稀土微合金化对气体渗氮性能的影响[J]. 金属热处理, 2023, 48(9): 180-182.
CHEN H, CUI D.Effect of Rare Earth Microalloying on Gas Nitriding Properties of 42CrMo Steel[J]. Heat Treatment of Metals, 2023, 48(9): 180-182.
[22] CAI W, MENG F N, GAO X Y, et al.Effect of QPQ Nitriding Time on Wear and Corrosion Behavior of 45 Carbon Steel[J]. Applied Surface Science, 2012, 261: 411-414.
[23] 叶宏, 雷临苹, 季涵涛, 等. H13钢QPQ处理工艺及耐磨性[J]. 表面技术, 2017, 46(4): 84-88.
YE H, LEI L P, JI H T, et al.Process and Wear Resistance of QPQ Treatment on Steel H13[J]. Surface Technology, 2017, 46(4): 84-88.
[25] CHEN F S, CHANG C N.Effect of CH4 Addition on Plasma Nitrocarburizing of Austenitic Stainless Steel[J]. Surface and Coatings Technology, 2003, 173(1): 9-18.
[26] CAI Y, WANG Z M, TANG Y H, et al.Corrosion Fatigue Behavior of Cast Iron in Simulated Combustion Product Solutions of Ammonia and Methanol Fuels[J]. International Journal of Fatigue, 2025, 191: 108715.
Funding
A High-Tech Ship Research Program of the Ministry of Industry and Information Technology of China, MIIT
PDF(11771 KB)
