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In the present paper, Natural Metal-Matrix Composites (NMMC) based on multicomponent hypereutectic Al-Ca-(Mn)-(Ni) alloys were studied in as-cast, annealed and rolled conditions. Thermo-Calc software and microstructural observations were utilised for analysing the equilibrium and actual phase composition of the alloys including correction of the Al-Ca-Mn system liquidus projection and the solid phase distribution in the Al-Ca-Mn-Ni system. A previously unknown Al10CaMn2 was discovered by both electron microprobe analysis and X-ray studies. The Al-6Ca-3Mn, Al-8Ca-2Mn, Al-8Ca-2Mn-1Ni alloys with representative NMMC structure included ultrafine Сa-rich eutectic and various small-sized primary crystals were found to have excellent feasibility of rolling as compared to its hypereutectic Al-Si counterpart. What is more, Al-Ca alloys showed comparable Coefficient of Thermal Expansion values due to enormous volume fraction of Al-based eutectic and primary intermetallics. Analysis of tensile samples’ fracture surfaces revealed that primary intermetallics may act either as stress raisers or malleable particles depending on their stiffness under deformation. It is shown that a compact morphology can be achieved by conventional casting without using any refining agents. Novel hypereutectic Al-Ca NMMC materials solidifying with the formation of Al10Mn2Ca primary compound have the best ductility and strength. We reasonably propose these materials for high-load pistons.

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