Фазовая диаграмма системы Ni-P

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Ni-P (Nickel-Phosphorus) K.J. Lee and P. Nash The Ni-P system is very complex and is not well established. The assessed Ni-P phase diagram is based on [08Kon], [58Koe], [65Lar], and [86Yup]. Above 40 at.% P, the diagram is not isobaric, because the vapor pressure of P over the alloys varies for different compositions and temperatures. From 0 to 75 at.% P, there are 11 intermediate phases. Among them, Ni12P5 (Ni7P3), Ni5P2 (Ni~2.5P, Ni~2.55P) and Ni5P4 (NiP~0.83, NiP0.8, Ni6P5) were designated differently by different investigators. [58Koe] found that the maximum solid solubility of P in (Ni) is 0.32 at.% P at the eutectic temperature (870 C). Metastable "Ni5P2" was observed by [78Vaf]; three additional metastable phases were observed by [80Vaf] at 25 at.% P. A remarkable metastable homogeneity range of "Ni5P2" was found, compared to that of stoichiometric equilibrium Ni5P2, [83Pit, 85Pit, 86Pit]. [85Kuo] and [87Zha] found a (metastable fcc phase), a1, a2, and a3 (metastable hexagonal phases) on heating electrodeposited and chemical-bath deposited amorphous Ni-P alloys. They argued that the three metastable phases found by [80Vaf] can be indexed to equilibrium Ni12P5. Amorphous or metastable Ni-P alloys can be obtained by electrodeposition, chemical deposition in acid bath or alkaline bath, vapor deposition, melt spinning, sputtering, and ion implantation up to 42 at.% P. [47Bre] and [50Bre] first observed amorphous Ni-P alloys prepared by electrodeposition and chemical bath deposition. Since then, many metastable and amorphous phases have been reported. However, contradictions have been found in terms of structure (interstitial or substitutional solid solution, microcrystalline or amorphous), crystallization and relaxation behavior, electronic structure ( rigid band or covalent model), and magnetic and electronic properties. It is considered that the extrinsic (preparation method, surface, and impurity effects) and intrinsic (magnetic and short-range order or medium-range order) inhomogeneities cause the controversial results. In early work on as-deposited Ni-P alloys, researchers were unable to determine whether the material was microcrystalline saturated solid solution or amorphous. Microcrystalline alloys with less than 3-nm grain size and amorphous alloys show a similar broadening effect in transmission electron microscopy (TEM) and by X-ray diffraction. However, crystallization of microcrystalline structures occurs by crystallite coarsening, whereas that of amorphous phases is the result of nucleation and grain growth [70Bag]. It is believed that the structure of as-deposited Ni-P materials is dependent on P content. Below about 12 at.% P, electrodeposited, chemical-bath deposited, or vapor-deposited Ni-P alloys are metastable solid solutions, and above 12 at.% P, they are amorphous. However, [87Din] argued that as-deposited Ni-P (16.7 at. % P) alloys are a mixture of amorphous and weakly bonded crystalline material. Using 100-kV TEM beam radiation, the crystalline phase can be converted to amorphous. For the supersaturated crystalline alloys, the material is more strained, and grain size decreases with increasing P content [70Mae, 74Tya, 78Vaf]. Ni is a ferromagnetic element with TC = 358 C, and sc is 58.5 emu/g. Ni3P (c = 0.4 x 10-6 emu/g) [80Ama] and Ni2P (c = 0.3 x 10-5 emu/g) [81Iwa] are temperature-independent, Pauli-paramagnetic compounds. More detailed study showed that crystalline Ni3P consists of a Pauli-paramagnetic matrix with ferromagnetic precipitates and Curie-Weiss type impurities. The amorphous Ni-P alloys have interesting magnetic properties. Below Xcr ( critical composition = 17 at.% P [74Pan], 18 at.% P [78Ber], 15 at.% P [86Son]) , amorphous Ni-P alloys are weak homogeneous ferromagnets, TC decreases rapidly with increasing P content, and sc decreases rapidly with increasing P content and temperature. Above Xcr, amorphous Ni-P alloys are weakly paramagnetic with magnetic inhomogeneity and c decreases rapidly with increasing P content. Magnetic inhomogeneity was studied based on the Arrott plot [s2 - (H/s)], which showed a deviation from linearity at low applied fields (H). It was suggested that there exist ferromagnetic precipitates, superparamagnetic clusters, or giant-moment paramagnetic clusters [85Bak, 86Son, 74Pan, 78Ber]. NiP2 was synthesized by [68Don] in a high-pressure anvil press at 65 kbar (64 x 103 atm) at 1100 to 1400 C and quenched. Electrical resistivity and magnetic susceptibility measurements suggested that it is metallic. 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Status Solidi (a), 93, 131-142 (1986) . 86Son: R. Sonnberger, E. Pfanner, and G. Dietz, Z. Phys. B, 63, 203-206 (1986). 86Yup L.M. Yupko, A.A. Svirid, and S.V. Muchnik, Sov. Powder Metall. Met. Ceram., 285(9), 768-773 (1986). 87Din: W. Ding, M.H. Wang, C.M. Hsiao, Y. Xu, and Z.Z. Tian, Scr. Metall., 21, 1685-1688 (1987). 87Zha: Z. Zhao, J. Yao, and B. Fu, Acta Metall. Sin. (China), 23(1), B44-46 ( 1987) in Chinese; from abstract. Published in Phase Diagrams of Binary Nickel Alloys, 1991. Complete evaluation contains 6 figures, 10 tables, and 100 references. Special Points of the Ni-P System