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The phase relations in the (1-x)Nd2Fe14B-xSm2Fe14B system over the whole concentration range have been studied by means of X-ray powder diffraction (XRD), differential thermal analysis (DTA) and scanning electron microscopy with energy-dispersive X-ray spectroscopy. Crystal structure parameters for all studied compositions of (Nd1-xSmx)2Fe14B have been determined by full-profile Rietveld refinements. These results revealed that all intermediate alloys of (Nd1-xSmx)2Fe14B are similar to the end member of the investigated system, Nd2Fe14B, with a tetragonal structure (space group P42/mnm). The formation of continuous solid solutions has been found in this system. The normalized lattice parameters and unit-cell volumes of (Nd1-xSmx)2Fe14B solid solutions decrease linearly with increasing Sm content. The DTA measurements show that the melting temperature of (Nd1-xSmx)2Fe14B increases linearly with increasing Sm content and no metastable phases were detected. Based on the DTA data and XRD results, a tentative phase diagram for the pseudo-binary system Nd2Fe14B-Sm2Fe14B has been constructed.

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