On advanced casting methods for synthesis and improvement of microstructural and mechanical properties of graphene reinforced light metal matrix composites

Abstract

Graphene nanoplatelet (GNP)-reinforced metal matrix composites (MMCs) represent a groundbreaking group of lightweight structural materials, offering exceptional combinations of strength, toughness, and multifunctionality that are critical for next-generation applications. Graphene imparts exceptional properties that significantly enhance the performance of lightweight alloys such as aluminum and magnesium. The review first examines the ex situ incorporation of GNPs into metal matrices and their effects on alloy solidification and mechanical properties based on process parameters, volume fraction, and matrix material. It then highlights two emerging in situ strategies, including the Covetic process, which employs electrically assisted processing (EAP) to synthesize graphene within metallic melts, and CO₂ bubbling in magnesium alloys to form carbon–metal (C–M) bonds. Particular emphasis is placed on mechanisms of C–M bonding, dispersion challenges, and interfacial bonding between the metallic matrices and graphene. This review emphasizes the potential of graphene-reinforced MMCs across industries and identifies the persistent barriers to process upscaling.

Keywords

metal matrix composites / graphene nanoplatelets / liquid metallurgy / electrically assisted process / Covetic / CO₂ bubbling

References

[1] M.Y. Khalid, R. Umer, and K.A. Khan, Review of recent trends and developments in aluminium 7075 alloy and its metal matrix composites (MMCs) for aircraft applications, Results Eng., 20(2023), art. No. 101372.

[2] Rohatgi P, Weiss D, Srivatsan TS, Ghaderi O, Zare M. Solidification processing of aluminum alloy metal matrix composites for use in transportation applications. Metall. Mater. Trans. A, 2024, 55124867.

[3] Lv H, Tan J, Yuan Q, et al. Recent advancements in thermal conductivity of magnesium alloys. J. Magnes. Alloys, 2024, 1251687.

[4] Li SS, Yue X, Li QY, et al. Development and applications of aluminum alloys for aerospace industry. J. Mater. Res. Technol., 2023, 27: 944.

[5] P. Lava Kumar, A. Lombardi, G. Byczynski, S.V.S. Narayana Murty, B.S. Murty, and L. Bichler, Recent advances in aluminium matrix composites reinforced with graphene-based nanomaterial: A critical review, Prog. Mater. Sci., 128(2022), art. No. 100948.

[6] Liu BH, Liu S, Luo ZG, Shu RW. Construction of iron manganese metal–organic framework-derived manganese ferrite/carbon-modified graphene composites toward broadband and efficient electromagnetic dissipation. Int. J. Miner. Metall. Mater., 2025, 323546.

[7] Zhao J, Lai HR, Li M. Anchoring 1T-MoS2 petals on N-doped reduced graphene oxide for exceptional electromagnetic wave absorption. Int. J. Miner. Metall. Mater., 2025, 323619.

[8] Tian KH, Yang H, Zhang C, et al. Fabrication of flake-like NiCo₂O₄/reduced graphene oxide/melamine-derived carbon foam as an excellent microwave absorber. Int. J. Miner. Metall. Mater., 2025, 323556.

[9] Abazari S, Shamsipur A, Bakhsheshi-Rad HR, Soheilirad MS, Khorashadizade F, Mirhosseini SS. MgO-attached graphene nanosheet (MgO@GNS) reinforced magnesium matrix nanocomposite with superior mechanical, corrosion and biological performance. Int. J. Miner. Metall. Mater., 2024, 3192062.

[10] C. O’Brien. Graphene Market & 2D Materials Assessment 2024–2034: Technologies, Markets, Players, IDTechEx, [2024-09-07]. https://www.idtechex.com/en/research-report/graphene-market-and-2d-materials-assessment-2024-2034-technologies-markets-players/967.

[11] Hess P. Bonding, structure, and mechanical stability of 2D materials: The predictive power of the periodic table. Nanoscale Horiz., 2021, 611856.

[12] H. Liu, A. Deshmukh, N. Salowitz, J. Zhao, and K. Sobolev, Resistivity signature of graphene-based fiber-reinforced composite subjected to mechanical loading, Front. Mater., 9(2022), art. No. 818176.

[13] Lee JU, Yoon D, Cheong H. Estimation of Young’s modulus of graphene by Raman spectroscopy. Nano Lett., 2012, 1294444.

[14] Yoon D, Son YW, Cheong H. Negative thermal expansion coefficient of graphene measured by Raman spectroscopy. Nano Lett., 2011, 1183227.

[15] P. Cataldi, A. Athanassiou, and I.S. Bayer, Graphene nano-platelets-based advanced materials and recent progress in sustainable applications, Appl. Sci., 8(2018), No. 9, art. No. 1438.

[16] Prashantha Kumar HG, Xavior MA. Graphene reinforced metal matrix composite (GRMMC): A review. Procedia Eng., 2014, 97: 1033.

[17] Lucideon. Alumina–Aluminium Oxide–Al₂O₃–A Refractory Ceramic Oxide. AZoM, [2024-09-04]. https://www.azom.com/article.aspx?ArticleID=52

[18] Kuscer D, Bantan I, Hrovat M, Malič B. The microstructure, coefficient of thermal expansion and flexural strength of cordierite ceramics prepared from alumina with different particle sizes. J. Eur. Ceram. Soc., 2017, 372739.

[19] Parchovianský M, Galusek D, Švančárek P, Sedláček J, Šajgalík P. Thermal behavior, electrical conductivity and microstructure of hot pressed Al₂O₃/SiC nanocomposites. Ceram. Int., 2014, 40914421.

[20] Wang H, Li LH, Wei XZ, et al. Combining alumina particles with three-dimensional alumina foam for high thermally conductive epoxy composites. ACS Appl. Polym. Mater., 2021, 31216.

[21] Sekino T, Niihara K. Microstructural characteristics and mechanical properties for Al₂O₃/metal nanocomposities. Nanostruct. Mater., 1995, 65–8663.

[22] Imetra, Inc, Silicon Carbide Material Properties, Imetra, Inc, Rochester [2024-09-04]. https://www.imetra.com/silicon-carbide-material-properties/.

[23] Pensl G, Ciobanu F, Frank T, et al. SiC material properties. Int. J. Hi. Spe. Ele. Syst., 2005, 154705.

[24] Yajima S, Okamura K, Hayashi J, Omori M. Synthesis of continuous SiC fibers with high tensile strength. J. Am. Ceram. Soc., 1976, 597–8324.

[25] M. Cao, Y.Z. Luo, Y.Q. Xie, et al., The influence of interface structure on the electrical conductivity of graphene embedded in aluminum matrix, Adv. Mater. Interfaces, 6(2019), No. 13, art. No. 1900468.

[26] H. Döscher, Global Graphene Market will Continue to Grow, Researchers Find, Graphene Flagship, [2025-03-28]. https://graphene-flagship.eu/materials/news/global-graphene-market-will-continue-to-grow-researchers-find.

[27] Li XJ, Wang XJ, Hu XS, Xu C, Shao WZ, Wu K. Direct conversion of CO₂ to graphene via vapor–liquid reaction for magnesium matrix composites with structural and functional properties. J. Magnes. Alloys, 2023, 1141206.

[28] X.J. Li, H.L. Shi, X.J. Wang, X.S. Hu, C. Xu, and W.Z. Shao, Achieving high strength and ductility in GNSs/Mg nanocomposites fabricated by in-situ liquid metallurgy combined with hot extrusion, Composites Part A: Appl. Sci. Manuf., 161(2022), art. No. 107079.

[29] Kiciński W, Dyjak S. Transition metal impurities in carbon-based materials: Pitfalls, artifacts and deleterious effects. Carbon, 2020, 168: 748.

[30] Araujo PT, Terrones M, Dresselhaus MS. Defects and impurities in graphene-like materials. Mater. Today, 2012, 15398.

[31] Wang HT, Wang QX, Cheng YC, et al. Doping monolayer graphene with single atom substitutions. Nano Lett., 2012, 121141.

[32] O.V. Yazyev and S.G. Louie, Topological defects in graphene: Dislocations and grain boundaries, Phys. Rev. B, 81(2010), No. 19, art. No. 195420.

[33] Varnell JA, Bakir M, DiAscro AM, et al. Understanding the influence of carbon addition on the corrosion behavior and mechanical properties of Al alloy “Covetics”. J. Mater. Sci., 2019, 5432668.

[34] M. Yang, Y. Liu, T.X. Fan, and D. Zhang, Metal-graphene interfaces in epitaxial and bulk systems: A review, Prog. Mater. Sci., 110(2020), art. No. 100652.

[35] Li JC, Zhang XX, Geng L. Effect of heat treatment on interfacial bonding and strengthening efficiency of graphene in GNP/Al composites. Composites Part A: Appl. Sci. Manuf., 2019, 121: 487.

[36] S.E. Shin, H.J. Choi, J.Y. Hwang, and D.H. Bae, Strengthening behavior of carbon/metal nanocomposites, Sci. Rep., 5(2015), art. No. 16114.

[37] Salamanca-Riba LG, Isaacs RA, LeMieux MC, et al. Synthetic crystals of silver with carbon: 3D epitaxy of carbon nanostructures in the silver lattice. Adv. Funct. Mater., 2015, 25304768.

[38] X.Y. Sun, C.J. Li, X.B. Dai, et al., Microstructures and properties of graphene-nanoplatelet-reinforced magnesium-matrix composites fabricated by an in situ reaction process, J. Alloys Compd., 835(2020), art. No. 155125.

[39] Jiang T, Zhang XQ, Vishwanath S, et al. Covalent bonding modulated graphene–metal interfacial thermal transport. Nanoscale, 2016, 82110993.

[40] Jung J, Lim H, Oh J, Kim Y. Functionalization of graphene grown on metal substrate with atomic oxygen: Enolate vs epoxide. J. Am. Chem. Soc., 2014, 136248528.

[41] Kozlov SM, Viñes F, Görling A. Bonding mechanisms of graphene on metal surfaces. J. Phys. Chem. C, 2012, 116137360.

[42] Markevich AV, Baldoni M, Warner JH, Kirkland AI, Besley E. Dynamic behavior of single Fe atoms embedded in graphene. J. Phys. Chem. C, 2016, 1203821998.

[43] Liu Z, Zhang YL, Wang BY, Cheng H, Cheng XR, Huang ZC. DFT study on Al-doped defective graphene towards adsorption of elemental mercury. Appl. Surf. Sci., 2018, 427: 547.

[44] J.C. Dong, L.N. Zhang, and F. Ding, Kinetics of graphene and 2D materials growth, Adv. Mater., 31(2019), No. 9, art. No. 1801583.

[45] X. Zhang, Y.X. Xu, M.C. Wang, et al., A powder-metallurgy-based strategy toward three-dimensional graphene-like network for reinforcing copper matrix composites, Nat. Commun., 11(2020), No. 1, art. No. 2775.

[46] Du X, Du WB, Wang ZH, Liu K, Li SB. Ultra-high strengthening efficiency of graphene nanoplatelets reinforced magnesium matrix composites. Mater. Sci. Eng. A, 2018, 711: 633.

[47] Gobalakrishnan B, Rajaravi C, Udhayakumar G, Lakshminarayanan PR. A comparative study on ex-situ & in-situ formed metal matrix composites. Arch. Metall. Mater., 2023, 681171.

[48] Zuhailawati H, Yong TL. Consolidation of dispersion strengthened copper–niobium carbide composite prepared by in situ and ex situ methods. Mater. Sci. Eng. A, 2009, 5051–227.

[49] J. Liu, Y.Y. Zhang, Y.H. Zhang, S. Kitipornchai, and J. Yang, Machine learning assisted prediction of mechanical properties of graphene/aluminium nanocomposite based on molecular dynamics simulation, Mater. Des., 213(2022), art. No. 110334.

[50] Bisht A, Srivastava M, Kumar RM, Lahiri I, Lahiri D. Strengthening mechanism in graphene nanoplatelets reinforced aluminum composite fabricated through spark plasma sintering. Mater. Sci. Eng. A, 2017, 695: 20.

[51] Wang JY, Li ZQ, Fan GL, Pan HH, Chen ZX, Zhang D. Reinforcement with graphene nanosheets in aluminum matrix composites. Scripta Mater., 2012, 668594.

[52] Bartolucci SF, Paras J, Reif J, et al. Graphene-aluminum nanocomposites. Mater. Sci. Eng. A, 2011, 528277933.

[53] Wang J, Guo LN, Lin WM, et al. Effect of the graphene content on the microstructures and properties of graphene/aluminum composites. New Carbon Mater., 2019, 343275.

[54] Rashad M, Pan FS, Yu ZW, Asif M, Lin H, Pan RJ. Investigation on microstructural, mechanical and electrochemical properties of aluminum composites reinforced with graphene nanoplatelets. Prog. Nat. Sci. Mater. Int., 2015, 255460.

[55] Li M, Gao HY, Liang JM, et al. Microstructure evolution and properties of graphene nanoplatelets reinforced aluminum matrix composites. Mater. Charact., 2018, 140: 172.

[56] W.S. AbuShanab, E.B. Moustafa, E. Ghandourah, and M.A. Taha, Effect of graphene nanoparticles on the physical and mechanical properties of the Al2024-graphene nanocomposites fabricated by powder metallurgy, Results Phys., 19(2020), art. No. 103343.

[57] Li JL, Xiong YC, Wang XD, et al. Microstructure and tensile properties of bulk nanostructured aluminum/graphene composites prepared via cryomilling. Mater. Sci. Eng. A, 2015, 626: 400.

[58] Zhao LY, Lu HM, Gao ZJ. Microstructure and mechanical properties of Al/graphene composite produced by high-pressure torsion. Adv. Eng. Mater., 2015, 177976.

[59] Gao X, Yue HY, Guo EJ, et al. Preparation and tensile properties of homogeneously dispersed graphene reinforced aluminum matrix composites. Mater. Des., 2016, 94: 54.

[60] H. Yu, S.Q. Zhang, J.H. Xia, et al., Microstructural evolution, mechanical and physical properties of graphene reinforced aluminum composites fabricated via powder metallurgy, Mater. Sci. Eng. A, 802(2021), art. No. 140669.

[61] Su YS, Li Z, Yu Y, et al. Composite structural modeling and tensile mechanical behavior of graphene reinforced metal matrix composites. Sci. China Mater., 2018, 611112.

[62] Liu XH, Li JJ, Sha JW, et al. In-situ synthesis of graphene nanosheets coated copper for preparing reinforced aluminum matrix composites. Mater. Sci. Eng. A, 2018, 709: 65.

[63] J.C. Li, X.X. Zhang, M.F. Qian, Z.G. Jia, M. Imran, and L. Geng, Inhibiting GNPs breakage during ball milling for a balanced strength-ductility match in GNPs/Al composites, Composites Part A: Appl. Sci. Manuf., 166(2023), art. No. 107410.

[64] Z. Azizi, K. Rahmani, and F. Taheri-Behrooz, The influence of graphene nanoplatelets addition on the electrical and mechanical properties of pure aluminum used in high-capacity conductors, Metals, 12(2022), No. 11, art. No. 1883.

[65] Rashad M, Pan FS, Tang AT, Asif M. Effect of graphene nanoplatelets addition on mechanical properties of pure aluminum using a semi-powder method. Prog. Nat. Sci. Mater. Int., 2014, 242101.

[66] Prakash PB, Subbaiah KV, Dodda R, Murthy VSS, Vagesh SR. Influence of graphene nanoplatelets addition on microstructural and mechanical properties of pure aluminum through ultrasonic-assisted stir casting technique. SAE Int. J. Mater. Manuf., 2022, 1513.

[67] Srivastava AK, Sharma B, Saju BR, Shukla A, Saxena A, Maurya NK. Effect of Graphene nanoparticles on microstructural and mechanical properties of aluminum based nanocomposites fabricated by stir casting. World J. Eng., 2020, 176859.

[68] A. Shil, S. Roy, P.S. Balaji, J. Kumar Katiyar, S. Pramanik, and A. Kumar Sharma, Experimental analysis of mechanical properties of stir casted aluminium-graphene nanocomposites, [in] IOP Conference Series: Materials Science and Engineering, Bhubaneswar, 2019, No.1, art. No. 012021.

[69] Kotteda TK, Kumar M, Kumar P. Experimental insights and micrographical investigation on graphene nanoplatelet-reinforced aluminum cast composites. Int. J. Adv. Manuf. Technol., 2024, 13152707.

[70] Güler Ö, Bağcı N. A short review on mechanical properties of graphene reinforced metal matrix composites. J. Mater. Res. Technol., 2020, 936808.

[71] R. Maurya, V. Kumar, S. Gautam, S. Bharti, and S. Mallika, Investigation of microstructural and mechanical characteristics of Al–ZrO2 composites fabricated by stir casting, Interactions, 245(2024), No. 1, art. No. 301.

[72] Jayendra B, Sumanth D, Dinesh G, Rao MV. Mechanical characterization of stir cast Al-7075/B₄C/graphite reinforced hybrid metal matrix composites. Mater. Today Proc., 2020, 21: 1104.

[73] Singh NK, Balaguru S. Fabrication and mechanical characterization of Al–Zn–Cu alloy/SiC/TiB₂ hybrid reinforced metal matrix composite using top loaded bottom pouring stir casting method. Silicon, 2024, 16145.

[74] Mourad AI, Christy JV, Krishnan PK, Mozumder MS. Production of novel recycled hybrid metal matrix composites using optimized stir squeeze casting technique. J. Manuf. Process., 2023, 88: 45.

[75] Shao PZ, Chen GQ, Ju BY, et al. Effect of hot extrusion temperature on graphene nanoplatelets reinforced Al6061 composite fabricated by pressure infiltration method. Carbon, 2020, 162: 455.

[76] X.F. Li, D.H. Yi, B. Liu, et al., Graphene-strengthened inconel 625 alloy fabricated by selective laser melting, Mater. Sci. Eng. A, 798(2020), art. No. 140099.

[77] Kumar A, Singh RC, Chaudhary R. Investigation of microstructure and several quality characteristics of AA7075/Al2O3/coconut shell ash hybrid nano composite prepared through ultrasonic assisted stir-casting. J. Mater. Eng. Perform., 2023, 32209263.

[78] Venkatesan S, Xavior MA. Wear property evaluation of aluminum alloy (AA7050) metal matrix composite reinforced with graphene fabricated by stir and squeeze cast processes. Mater. Today Proc., 2020, 221–33330.

[79] Hu ZR, Wu ZK, Luo SC, et al. Large scale production of graphene aluminum composites by stir casting: Process, microstructure and properties. J. Mater. Res. Technol., 2023, 27: 681.

[80] V. Menda, S. Dora, S. Palli, et al., Mechanical and wear characteristics of aluminium-7075/graphene/TiB₂ prepared by stir casting, Eng. Res. Express, 6(2024), No. 2, art. No. 025571.

[81] Srivastava AK, Saxena A, Sharma B. Numerical study of tensile strength and hardness of the AA1100/graphene MMC produced by stir casting. Mater. Today Proc., 2021, 47: 3993.

[82] Dhananjaya Kumar LK, Sripad Kulkarni S, Deepu JN, Subramani N, Sivaprakash K. Investigation of mechanical & corrosion properties of graphene, R-glass fiber reinforced aluminium 2024 hybrid composites. Mater. Today Proc., 2021, 43: 1684.

[83] T.K. Kotteda, M. Kumar, P. Kumar, and A. Gupta, Development of forecast models on electrical discharge machined graphene nanoplatelets reinforced aluminum composite fabricated via stir casting route, Cogent Eng., 11(2024), No. 1, art. No. 2328821.

[84] B. Andilab, P. Emadi, and C. Ravindran, Casting and characterization of A319 aluminum alloy reinforced with graphene using hybrid semi-solid stirring and ultrasonic processing, Materials, 15(2022), No. 20, art. No. 7232.

[85] Andilab B, Emadi P, Sydorenko M, Ravindran C. Influence of GNP additions on the microstructure, mechanical properties, and electrical conductivity of cast A319 aluminum alloy. Int. J. Metalcast., 2024, 1843047.

[86] Li WT, Yang XD, Yang KM, et al. Simultaneously optimizing pore morphology and enhancing mechanical properties of Al–Si alloy composite foams by graphene nanosheets. J. Mater. Sci. Technol., 2022, 101: 60.

[87] A.A. Geetha, A.S. Nair, O. Ghaderi, J. Kalidoos, T.P.D. Rajan, and P.K. Rohatgi, Synthesis of graphene reinforced aluminum nanocomposites with enhanced mechanical and tribological properties by solidification processing, Diamond Relat. Mater., 152(2025), art. No. 111942.

[88] Han XQ, Yang LZ, Zhao NQ, He CN. Copper-coated graphene nanoplatelets-reinforced Al–Si alloy matrix composites fabricated by stir casting method. Acta Metall. Sin. (Engl. Lett.), 2021, 341111.

[89] Yang WS, Chen GQ, Qiao J, et al. Graphene nanoflakes reinforced Al–20Si matrix composites prepared by pressure infiltration method. Mater. Sci. Eng. A, 2017, 700: 351.

[90] Alipour M, Keshavamurthy R, Koppad PG, Shakiba A, Reddy NC. Investigation of microstructure and mechanical properties of cast Al–10Zn–3.5Mg–2.5Cu nanocomposite reinforced with graphene nano sheets produced by ultrasonic assisted stir casting. Int. J. Metalcast., 2023, 172935.

[91] Shao PZ, Yang WS, Zhang Q, et al. Microstructure and tensile properties of 5083 Al matrix composites reinforced with graphene oxide and graphene nanoplates prepared by pressure infiltration method. Composites Part A: Appl. Sci. Manuf., 2018, 109: 151.

[92] Kumar N, Lokesh KS, Kannantha V, Pai R, Hebbale AM. Development and experimental investigation of mechanical properties of graphene-based aluminum 6061 alloys. Mater. Today: Proc., 2021, 46: 2421

[93] Venkatesan S, Xavior MA. Mechanical behaviour of Aluminium metal matrix composite reinforced with graphene particulate by stir casting method. J. Chem. Pharm. Sci., 2017, 10155

[94] Venkatesan S, Xavior MA. Characterization on aluminum alloy 7050 metal matrix composite reinforced with graphene nanoparticles. Procedia Manuf., 2019, 30: 120.

[95] Alipour M, Eslami-Farsani R. Synthesis and characterization of graphene nanoplatelets reinforced AA7068 matrix nanocomposites produced by liquid metallurgy route. Mater. Sci. Eng. A, 2017, 706: 71.

[96] J.F. Leng, Y.F. Dong, B.H. Ren, R. Wang, and X.Y. Teng, Effects of graphene nanoplates on the mechanical behavior and strengthening mechanism of 7075Al alloy, Materials, 13(2020), No. 24, art. No. 5808.

[97] S. Patil, M. Haneef, L.H. Manjunath, and H.N. Reddappa, Investigation on mechanical properties of hybrid graphene and beryl reinforced aluminum 7075 composites, [in] IOP Conference Series: Materials Science and Engineering, Bengaluru, 2019, art. No. 012112.

[98] Lokesh KS. Assessment of axial cramp resistance of graphene based aluminium nano composites by stir casting technique. Int. J. Sci. Res. Mech. Mater. Eng., 2019, 321

[99] Ghazanlou SI, Eghbali B. Fabrication and characterization of GNPs and CNTs reinforced Al7075 matrix composites through the stir casting process. Int. J. Miner. Metall. Mater., 2021, 2871204.

[100] L. Natrayan, S. Yogeshwaran, L. Yuvaraj, and M.S. Kumar, Effect of graphene reinforcement on mechanical and microstructure behavior of AA8030/graphene composites fabricated by stir casting technique, AIP Conf. Proc., 2166(2019), art. No. 020012.

[101] A.N. Petrova, D.Y. Rasposienko, I.G. Brodova, et al., Structure and electrical properties of AlFe matrix composites with graphene, Appl. Sci., 13(2023), No. 18, art. No. 10501.

[102] J.C. Zhao, L.P. Bian, Z. Wang, et al., Effects of Graphene Content and Thermomechanical Processing on Mechanical Properties and Electrical Conductivity of Stir Cast Al–0.6Sc–0.2Zr/Gr Composites, Gr Composites, SSRN, [2026-08-21]. https://papers.ssrn.com/sol3/papers.cfm?abstract_id=5554973.

[103] Kumar D, Angra S, Singh S. Synthesis and characterization of DOE-based stir-cast hybrid aluminum composite reinforced with graphene nanoplatelets and cerium oxide. Aircr. Eng. Aerosp. Technol., 2023, 95101604

[104] S. Narayanan, G.G. Sozhamannan, K. Hemalatha, K. Velmurugan, and V.S.K. Venkatachalapathy, Corrosion and hardness behaviour of Al/GO nanocomposites processed by the ultrasonic gravitational stir casting method, Int. J. Corros., 2021(2021), No. 1, art. No. 6658186.

[105] E. Avcu, H.T. Cao, X. Zhang, et al., The effect of reduced graphene oxide content on the microstructural and mechanical properties of copper metal matrix composites, Mater. Sci. Eng. A, 856(2022), art. No. 143921.

[106] Yang YJ, Liu MB, Zhou SQ, Ren WJ, Zhou QH, Zhang W. Strengthening behaviour of continuous graphene network in metal matrix composites. Carbon, 2021, 182: 825.

[107] Chen WG, Yang T, Dong LL, et al. Advances in graphene reinforced metal matrix nanocomposites: Mechanisms, processing, modelling, properties and applications. Nanotechnol. Precis. Eng., 2020, 34189.

[108] Ali AM, Omar MZ, Hashim H, Salleh MS, Mohamed IF. Recent development in graphene-reinforced aluminium matrix composite: A review. Rev. Adv. Mater. Sci., 2021, 601801.

[109] Singh PK. Mechanical characterization of graphene-aluminum nanocomposites. Mater. Today Proc., 2021, 44: 2304.

[110] Guo EY, Shuai SS, Kazantsev D, et al. The influence of nanoparticles on dendritic grain growth in Mg alloys. Acta Mater., 2018, 152: 127.

[111] Chen HY, Kosiba K, Suryanarayana C, et al. Feedstock preparation, microstructures and mechanical properties for laser-based additive manufacturing of steel matrix composites. Int. Mater. Rev., 2023, 6881192.

[112] Y. Ruan, A. Mohajerani, and M. Dao, Microstructural and mechanical-property manipulation through rapid dendrite growth and undercooling in an Fe-based multinary alloy, Sci. Rep., 6(2016), art. No. 31684.

[113] Turhal M, Savaşkan T. Relationships between secondary dendrite arm spacing and mechanical properties of Zn–40Al–Cu alloys. J. Mater. Sci., 2003, 38: 2639.

[114] Y.W. Jia, D.F. Song, N. Zhou, K.H. Zheng, Y.N. Fu, and D. Shu, The growth restriction effect of TiCN nanoparticles on Al–Cu–Zr alloys via ultrasonic treatment, Ultrason. Sonochem., 80(2021), art. No. 105829.

[115] Jia YW, Wang SB, Huang HJ, et al. In situ observation of the Zr poisoning effect in Al alloys inoculated by Al–Ti–B. Metall. Mater. Trans. A, 2018, 49104771.

[116] Greer AL, Bunn AM, Tronche A, Evans PV, Bristow DJ. Modelling of inoculation of metallic melts: Application to grain refinement of aluminium by Al–Ti–B. Acta Mater., 2000, 48112823.

[117] Su XP, Yang S, Wang JH, et al. A new equation for temperature dependent solute impurity diffusivity in liquid metals. J. Phase Equilib. Diffus., 2010, 314333.

[118] Chen WM, Zhang LJ, Du Y, Huang BY. Viscosity and diffusivity in melts: From unary to multicomponent systems. Philos. Mag., 2014, 94141552.

[119] O. Ghaderi, M. Zare, B. Niroumand, B.C. Church, and P.K. Rohatgi, Selected challenges in solidification processing of graphene nanoplatelets (GNPs) reinforced aluminum alloys composites, Front. Mater., 11(2024), art. No. 1363270.

[120] G. Kaptay, A coherent set of model equations for various surface and interface energies in systems with liquid and solid metals and alloys, Adv. Colloid Interface Sci., 283(2020), art. No. 102212.

[121] Kaptay G. Interfacial criterion of spontaneous and forced engulfment of reinforcing particles by an advancing solid/liquid interface. Metall. Mater. Trans. A, 2001, 324993.

[122] Jiang YY, Tan ZQ, Fan GL, et al. Reaction-free interface promoting strength-ductility balance in graphene nanosheet/Al composites. Carbon, 2020, 158: 449.

[123] Su JL, Teng J. Recent progress in graphene-reinforced aluminum matrix composites. Front. Mater. Sci., 2021, 15179.

[124] Dahal A, Batzill M. Graphene-nickel interfaces: A review. Nanoscale, 2014, 652548.

[125] Wang K, Jiang HY, Wang QD, Ye B, Ding WJ. A novel method to achieve grain refinement in aluminum. Metall. Mater. Trans. A, 2016, 47104788.

[126] C.S. Xing, J. Sheng, L.D. Wang, and W.D. Fei, Research progress in molecular dynamics simulation of CNT and graphene reinforced metal matrix composites, Oxf. Open Mater. Sci., 1(2020), No. 1, art. No. itab008.

[127] Zhang E, Luo X. Reinforcement of aluminum metal matrix composites through graphene and graphene-like monolayers: A first-principles study. Mater. Adv., 2024, 5249596.

[128] D.F. Zhang, A.F. Fonseca, T. Liang, S.R. Phillpot, and S.B. Sinnott, Dynamics of graphene/Al interfaces using COMB3 potentials, Phys. Rev. Mater., 3(2019), No. 11, art. No. 114002.

[129] Voloshina E, Dedkov Y. Graphene on metallic surfaces: Problems and perspectives. Phys. Chem. Chem. Phys., 2012, 143913502.

[130] P.A. Khomyakov, G. Giovannetti, P.C. Rusu, G. Brocks, J. van den Brink, and P.J. Kelly, First-principles study of the interaction and charge transfer between graphene and metals, Phys. Rev. B, 79(2009), No. 19, art. No. 195425.

[131] J. Tesch, P. Leicht, F. Blumenschein, et al., Structural and electronic properties of graphene nanoflakes on Au (111) and Ag (111), Sci. Rep., 6(2016), art. No. 23439.

[132] Xiong T, Zhang DQ, Yeo JY, et al. Interfacial design towards stable zinc metal-free zinc-ion batteries with high energy density. J. Mater. Chem. A, 2024, 1295499.

[133] Mourdjeva Y, Karashanova D, Nihtianova D, Lazarova R. Microstructural characteristics of Al₄C₃ phase and the interfaces in Al/graphene nanoplatelet composites and their effect on the mechanical properties. J. Mater. Eng. Perform., 2024, 332111607.

[134] Bakshi SR, Keshri AK, Agarwal A. A comparison of mechanical and wear properties of plasma sprayed carbon nanotube reinforced aluminum composites at nano and macro scale. Mater. Sci. Eng. A, 2011, 52893375.

[135] Y.P. Zhang, Q. Wang, and C.S. Ramachandran, Synthesis of carbon nanotube reinforced aluminum composite powder (CNT-Al) by polymer pyrolysis chemical vapor deposition (PP-CVD) coupled high energy ball milling (HEBM) process, Diamond Relat. Mater., 104(2020), art. No. 107748.

[136] He CN, Zhao NQ, Shi CS, et al. An approach to obtaining homogeneously dispersed carbon nanotubes in Al powders for preparing reinforced Al-matrix composites. Adv. Mater., 2007, 1981128.

[137] Moghadam AD, Omrani E, Menezes PL, Rohatgi PK. Mechanical and tribological properties of self-lubricating metal matrix nanocomposites reinforced by carbon nanotubes (CNTs) and graphene–A review. Composites Part B: Eng., 2015, 77: 402.

[138] Ge X, Klingshirn C, Wuttig M, et al. Mechanism studies and fabrication for the incorporation of carbon into Al alloys by the electro-charging assisted process. Carbon, 2019, 149: 203.

[139] J.V. Shugart, R.C. Scherer, and R.L. Penn, Aluminum–carbon Compositions, United States Patent, No. US9273380B2, 2016.

[140] J.V. Shugart, and R.C. Scherer, Copper-carbon Composition, United States Patent, No. US8647534B2, 2014.

[141] Brown L, Joyce P, Forrest D, Salamanca-Riba L. Physical and mechanical characterization of a nanocarbon infused aluminum-matrix composite. Mater. Perform. Charact., 2014, 3165.

[142] Bakir M, Jasiuk I. Novel metal-carbon nanomaterials: A review on Covetics. Adv. Mater. Lett., 2017, 89884.

[143] Goettsch J, Gupta P, Aramanda S, et al. Edwards L, et al. Solidification processing by low-power electric current: Towards phase control in aluminum alloys. Light Metals 2025, 2025, Cham: Springer, 296.

[144] Vashchenko KI, Chernega DF, Vorobev SL, Lysenko NI, Yakovchuk YE. Effect of electric current on the solidification of cast iron. Met. Sci. Heat Treat., 1974, 163261.

[145] Nakada M, Shiohara Y, Flemings MC. Modification of solidification structures by pulse electric discharging. ISIJ Int., 1990, 30127.

[146] Barnak JP, Sprecher AF, Conrad H. Colony (grain) size reduction in eutectic Pb–Sn castings by electroplusing. Scripta Metall. Mater., 1995, 326879.

[147] H.X. Jiang, J. He, and J.Z. Zhao, Influence of electric current pulses on the solidification of Cu–Bi–Sn immiscible alloys, Sci. Rep., 5(2015), art. No. 12680.

[148] Y.H. Zhang, Y.Y. Xu, C.Y. Ye, et al., Relevance of electrical current distribution to the forced flow and grain refinement in solidified Al–Si hypoeutectic alloy, Sci. Rep., 8(2018), art. No. 3242.

[149] Jiang HX, Zhao JZ. Solidification of immiscible alloys under the effect of electric and magnetic fields. Acta Metall. Sin. (Engl. Lett.), 2018, 31121240.

[150] N. Li, L.M. Zhang, R. Zhang, et al., The role of electric current-associated free energy and forced convection on grain refinement in pure aluminum under electropulsing, Materials, 12(2019), No. 23, art. No. 3846.

[151] Q.H. Xiao, Y. Zhou, X.C. Miao, et al., Study on the as-cast microstructure and mechanical properties of 35CrMo steel based on electric field control, Mater. Res. Express, 11(2024), No. 4, art. No. 046512.

[152] Li YQ, Jiang HX, Sun H, Zhang LL, He J, Zhao JZ. Microstructure evolution of the Pb–Al alloy solidified under the effect of electric current pulses. Metall. Mater. Trans. B, 2023, 5452564.

[153] S.J. Choi, D. Kim, M. La, and M.J. Kim, Effect of cavity shape on microstructural evolution of pure aluminum in electrically-assisted solidification, Sci. Rep., 13(2023), No.1, art. No. 3382.

[154] X.F. Zhang and R.S. Qin, Exploring the particle reconfiguration in the metallic materials under the pulsed electric current, Steel Res. Int., 89(2018), No. 12, art. No. 1800062.

[155] R.S. Qin, Using electric current to surpass the microstructure breakup limit, Sci. Rep., 7(2017), art. No. 41451.

[156] Knych T, Kiesiewicz G, Kwaśniewski P, Mamala A, Kawecki A, Smyrak B. Fabrication and cold drawing of copper Covetic nanostructured carbon composites. Arch. Metall. Mater., 2014, 5941283.

[157] Jasiuk I, Nilufar S, Salamanca-Riba L, Isaacs R, Siddiqi S. Novel aluminum-carbon materials. Technical Proceedings of the 2013 NSTI Nanotechnology Conference and Expo, NSTI-Nanotech, 201327

[158] Rashad M, Pan FS, Asif M, Ullah A. Improved mechanical properties of magnesium-graphene composites with copper-graphene hybrids. Mater. Sci. Technol., 2015, 31121452.

[159] U. Balachandran, S.E. Dorris, B. Ma, T.H. Lee, D.R. Forrest, and C. Klingshirn, Electrodes for Making Nanocarbon-Infused Metals and Alloys, United States Patent, No. US2020 0176573A1, 2020.

[160] Ge X, Klingshirn C, Morales M, et al. Electrical and structural characterization of nano-carbon–aluminum composites fabricated by electro-charging-assisted process. Carbon, 2021, 173: 115.

[161] Oral EA. A study to define critical current limit for Covetic Al formation. Erzincan Üniversitesi Fen Bilimleri Enstitüsü Dergisi, 2020, 1331348.

[162] Kareem MQ, Jasim AH, Hamza NA. Fabrication of aluminium Covetic casts under different voltages and amperages of direct current. Open Eng., 2020, 1011.

[163] Jaim HMI, Isaacs RA, Rashkeev SN, et al. Sp² carbon embedded in Al-6061 and Al-7075 alloys in the form of crystalline graphene nanoribbons. Carbon, 2016, 107: 56.

[164] Zhou JJ, Shen JC, Yue WY, Liu Y, Chen ZM. Molecular dynamics simulation of reinforcement mechanism of graphene/aluminum composites and microstructure evolution. J. Mater. Res. Technol., 2023, 23: 2147.

[165] Rana D, Lachmayr K, Lustig SR. A review of Covetics–current understanding and future perspectives. Nanoscale Adv., 2023, 5111.

[166] Chu K, Wang XH, Wang F, et al. Largely enhanced thermal conductivity of graphene/copper composites with highly aligned graphene network. Carbon, 2018, 127: 102.

[167] Nan CW, Birringer R, Clarke DR, Gleiter H. Effective thermal conductivity of particulate composites with interfacial thermal resistance. J. Appl. Phys., 1997, 81106692.

[168] Forrest DR, Jasiuk I, Brown L, Joyce P, Mansour A, Salamanca-Riba L. Novel metal-matrix composites with integrally-bound nanoscale carbon. Technical Proceedings of the 2012 NSTI Nanotechnology Conference and Expo, 2012560

[169] Sarif Rana SM. Thermoelectrical Properties of Covetics, 2017, Dayton: Wright State University

[170] M. Cao, D.B. Xiong, L. Yang, et al., Ultrahigh electrical conductivity of graphene embedded in metals, Adv. Funct. Mater., 29(2019), No. 17, art. No. 1806792.

[171] Khan M, Din RU, Wadood A, Syed WH, Akhtar S, Aune RE. Effect of graphene nanoplatelets on the physical and mechanical properties of Al6061 in fabricated and T6 thermal conditions. J. Alloys Compd., 2019, 790: 1076.

[172] Bolotin KI, Sikes KJ, Jiang Z, et al. Ultrahigh electron mobility in suspended graphene. Solid State Commun., 2008, 1469–10351.

[173] Salamanca-Riba L, Isaacs R, Mansour AN, et al. A new type of carbon nanostructure formed within a metal-matrix. Technical Proceedings of the 2012 NSTI Nanotechnology Conference and Expo, 2012278

[174] Jaim HMI, Cole DP, Salamanca-Riba LG. Characterization of carbon nanostructures in Al and Ag covetic alloys. Carbon, 2017, 111: 309.

[175] Kinemuchi Y, Funakoshi H, Ishizaki K. Effects of coated carbon on Si₃N₄ powder for the surface reaction during pulsed electric current sintering. J. Ceram. Soc. Jpn., 1998, 1065535.

[176] D.R. Forrest, Navy Characterization of Covetic Aluminum, [2024-09-06]. https://ntrl.ntis.gov/NTRL/dashboard/searchResults/titleDetail/ADA552586.xhtml.

[177] Forrest DR, Brown CL, Salamanca-Riba LG, Wolk J, Joyce P, Zhang J. Nanoscale carbon in metals for energy applications. Materials Science & Technology 2011, 2011

[178] Salamanca-Riba L, Mansour A, Forrest DR, Hall AR, Lemieux M, Shugart JV. Investigation of the incorporation of nanostructured carbon in a metal-matrix. Microsc. Microanal., 2012, 18S21578.

[179] U. Balachandran, B.H. Ma, T.H. Lee, S.E. Dorris, and D.R. Forrest, Method for Making Metal-Nanostructured Carbon Composites, United States Patent, No. US10843261B2, 2020.

[180] H.J. Couch, M.A. Braydich, and L.A. Luedtke, Process Control to Develop a Continuous Flow Al Covetic Reactor Design, OSTI.GOV, [2024-09-09]. https://www.osti.gov/biblio/1838154.

[181] Morales MA. Understanding the Effect of Fabrication Conditions on the Structural, Electrical, and Mechanical Properties of Composite Materials Containing Carbon Fillers, 2022, College Park: University of Maryland

[182] L.G. Salamanca-Riba, Fabrication of Advanced Nanocarbonmetal Composites for Improved Energy Efficiency, OSTI. GOV, [2024-12-11]. https://www.osti.gov/biblio/1886284.

[183] M.W. Stowell, B. Lanning, P.T. Williams, and D. Cook, Apparatuses and Methods for Producing Covetic Materials Using Microwave Reactors, United State Patent, No. US1173 9409B2, 2023.

[184] D. Rana, E. Egli, L. Salamanca-Riba, and S.R. Lustig, Carbon chemical speciation and polymerization in liquid metals, Carbon Trends, 20(2025), art. No. 100540.

[185] J.V. Shugart and R.C. Scherer, Metal-carbon Compositions, United States Patent, No. US8541335B2, 2013.

[186] U. Balachandran, B.H. Ma, and S.E. Dorris, Method for Making Metal-carbon Composites and Compositions, United States Patent, No. US10662509B2, 2020.

[187] M.J. Koczak and K.S. Kumar, In Situ Process for Producing a Composite Containing Refractory Material, United States Patent, No. US4808372A, 1989.

[188] Gotman I, Koczak MJ, Shtessel E. Fabrication of Al matrix in situ composites via self-propagating synthesis. Mater. Sci. Eng. A, 1994, 1872189.

[189] Koczak MJ, Premkumar MK. Emerging technologies for the in-situ production of MMCs. JOM, 1993, 45144.

[190] Chakrabarti A, Lu J, Skrabutenas JC, et al. Conversion of carbon dioxide to few-layer graphene. J. Mater. Chem., 2011, 21269491.

[191] Shafirovich EY, Shiryaev AA, Goldshleger UI. Magnesium and carbon dioxide–A rocket propellant for Mars missions. J. Propuls. Power, 1993, 92197.

[192] Abbud-Madrid A, Modak A, Branch MC, Daily JW. Combustion of magnesium with carbon dioxide and carbon monoxide at low gravity. J. Propuls. Power, 2001, 174852.

[193] X.J. Li, H.L. Shi, X.J. Wang, X.S. Hu, C. Xu, and W.Z. Shao, Direct synthesis of graphene by blowing CO₂ bubble in Mg melt for the seawater/oil pollution, J. Alloys Compd., 921(2022), art. No. 165938.

[194] Strudwick AJ, Weber NE, Schwab MG, et al. Chemical vapor deposition of high quality graphene films from carbon dioxide atmospheres. ACS Nano, 2015, 9131.

[195] X.J. Li, H.L. Shi, X.J. Wang, et al., Achieving high strength and modulus in graphene reinforced Mg matrix composites via an in-situ process, Mater. Sci. Eng. A, 852(2022), art. No. 143713.

[196] S.H. Wei, H.L. Shi, X.J. Li, X.S. Hu, C. Xu, and X.J. Wang, A green and efficient method for preparing graphene using CO₂@Mg in-situ reaction and its application in high-performance lithium-ion batteries, J. Alloys Compd., 902(2022), art. No. 163700.

[197] Wei SH, Wang XJ, Li XJ, Shi HL, Hu XS, Xu C. Controlled preparation of a novel GNP@MgO particles and its refinement mechanism in Mg–9Al alloy. J. Magnes. Alloys, 2025, 1341536.

[198] Ferrari AC, Basko DM. Raman spectroscopy as a versatile tool for studying the properties of graphene. Nat. Nanotechnol., 2013, 84235.

[199] Li XJ, Shi HL, Wang XJ, Hu XS, Xu C, Shao WZ. Direct synthesis and modification of graphene in Mg melt by converting CO₂: A novel route to achieve high strength and stiffness in graphene/Mg composites. Carbon, 2022, 186: 632.

[200] Celebi K, Cole MT, Choi JW, et al. Evolutionary kinetics of graphene formation on copper. Nano Lett., 2013, 133967.

[201] Yuan QH, Zhou GH, Liao L, Liu Y, Luo L. Interfacial structure in AZ91 alloy composites reinforced by graphene nanosheets. Carbon, 2018, 127: 177.

[202] S.H. Wei, X.J. Wang, X.J. Li, et al., Microstructure refinement and mechanical properties enhancement of MgAl alloys via a novel of MgO nanoparticles modified graphene nanoplates refiner by in-situ synthesis, Mater. Charact., 210(2024), art. No. 113824.

[203] W.X. Fan, Y. Bai, G.L. Zuo, and H. Hao, The control of NbB2 particles in Al–NbB₂ master alloy and its effect on grain refinement of AZ91 magnesium alloy, Mater. Sci. Eng. A, 854(2022), art. No. 143808.

[204] Xing ZY, Wang B, Gao WY, et al. Reducing CO₂ to dense nanoporous graphene by Mg/Zn for high power electrochemical capacitors. Nano Energy, 2015, 11: 600.

[205] L. Wang, J.F. Jin, J.Y. Cao, P.J. Yang, and Q. Peng, Interaction of edge dislocations with graphene nanosheets in graphene/Fe composites, Crystals, 8(2018), No. 4, art. No. 160.

[206] Q.Y. Chen, J. Bergthorson, and M. Schiemann, A review of metal-carbon dioxide combustion, Renewable Sustainable Energy Rev., 203(2024), art. No. 114730.

[207] H. Fukuhara, Y. Suzuki, S. Tanaka, and T. Goto, Methane production via Al₄C₃ electrodeposition from CO₂ at an Al electrode/NaCl–CaCl₂ melt interface, J. Electrochem. Soc., 172(2025), No. 2, art. No. 022502.

[208] Yan M, Fan Z. Review Durability of materials in molten aluminum alloys. J. Mater. Sci., 2001, 362285.

[209] Novak B, Tschöpe K, Ratvik AP, Grande T. Suarez CE. Fundamentals of aluminium carbide formation. Light Metals 2012, 2012, Cham: Springer, 1343

[210] Etter T, Schulz P, Weber M, et al. Aluminium carbide formation in interpenetrating graphite/aluminium composites. Mater. Sci. Eng. A, 2007, 4481–21.

[211] Etter T, Kuebler J, Frey T, Schulz P, Löffler JF, Uggowitzer PJ. Strength and fracture toughness of interpenetrating graphite/aluminium composites produced by the indirect squeeze casting process. Mater. Sci. Eng. A, 2004, 3861–261.

[212] H.T. Zhang, X. Zhang, X.Z. Sun, and Y.W. Ma, Shape-controlled synthesis of nanocarbons through direct conversion of carbon dioxide, Sci. Rep., 3(2013), art. No. 3534.

[213] Tang YL, Peng P, Wang SY, Liu ZH, Zu XT, Yu QK. Continuous production of graphite nanosheets by bubbling chemical vapor deposition using molten copper. Chem. Mater., 2017, 29198404.

[214] H.Y. Dong, S.Q. Guo, and L.F. Zhao, Facile preparation of multilayered graphene with CO2 as a carbon source, Appl. Sci., 9(2019), No. 21, art. No. 4482.

[215] C. Luchetta, E.C.O. Munsignatti, and H.O. Pastore, CO₂ metallothermal reduction to graphene: The influence of Zn, Front. Chem. Eng., 3(2021), art. No. 707855.

[216] Zhao PT, Li XJ, Shi HL, et al. Fabrication, microstructure and mechanical properties of in situ GNPs reinforced magnesium matrix composites. Acta Metall. Sin. (Engl. Lett.), 2024, 373561.

[217] X.J. Li, X.J. Wang, H.L. Shi, et al., Bubble-mediated production of few-layer graphene via vapor–liquid reaction between carbon dioxide and magnesium melt, Materials, 17(2024), No. 4, art. No. 897.

[218] M.Y. Li, X.J. Li, H.L. Shi, et al., The effect of graphene nanoplatelets on the aging precipitation behavior and mechanical properties of magnesium matrix composite, J. Alloys Compd., 1010(2025), art. No. 177498.

[219] Li CM, Zhang A, Li YF, et al. Three-dimensional characteristics of shrinkage porosities in Mg–xAl–1Zn–0.2Mn alloys and their relationship with microstructures. J. Mater. Res. Technol., 2024, 33: 9372.

[220] Klocke F, Schwade M, Klink A, Kopp A. EDM machining capabilities of magnesium (Mg) alloy WE43 for medical applications. Procedia Eng., 2011, 19: 190.

[221] Kondori B, Mahmudi R. Effect of Ca additions on the microstructure, thermal stability and mechanical properties of a cast AM60 magnesium alloy. Mater. Sci. Eng. A, 2010, 5277–82014.

Rights & permissions

The Author(s)