Synthesis, formation mechanism, and intrinsic physical properties of several As/P-containing MAX phases

doi:10.1016/j.jmst.2022.06.016

Abstract

Abstract:

321 phases are an atypical series of MAX phases, in which A = As/P, with superior elastic properties, featuring in the MA-triangular-prism bilayers in the crystal structure. Until now, besides Nb₃As₂C, the pure phases of the other 321 compounds have not been realized, hampering the study of their intrinsic properties. Here, molten-salt sintering (MSS) and solid-state synthesis (SSS) were applied to synthesize As/P-containing 321 phases and 211 phases. Analyzing the phase composition of the end-product via multiple-phase Rietveld refinement, we found that MSS can effectively improve the purity of P-containing MAX phases, with the phase content up to 99% in Nb₃P₂C and 75.4(5)% in Nb₂PC. In contrast, MSS performed poorly on As-containing MAX phases, only 8.9(4)% for Nb₃As₂C and 64(2)% for Nb₂AsC, as opposed to the pure phases obtained by SSS. The experimental analyses combined with first-principles calculations reveal that the dominant formation route of Nb₃P₂C is through NbP + Nb + C → Nb₃P₂C. Moreover, we found that the benefits of MSS on P-containing MAX phases are on the facilitation of three considered chemical reaction routes, especially on Nb₂PC + NbP → Nb₃P₂C. Furthermore, the intrinsic physical properties and Fermi surface topology of two 321 phases consisting of electron, hole, and open orbits are revealed theoretically and experimentally, in which the electron carriers are dominant in electrical transport. The feasible synthesis methods and the formation mechanism are instructive to obtain high-purity As/P-containing MAX phases and explore new MAX phases. Meanwhile, the intrinsic physical properties will give great support for future applications on 321 phases.

Key words: MAX phase, Molten-salt synthesis, Chemical reaction route, Metallic ceramics, Formation mechanism, Quasi-harmonic approximation

Hongxiang Chen, Sheng Li, Jun Deng, Zhilong Zhang, Jianeng Huang, Fa Chang, Li Huang, Shixuan Du, Pinqiang Dai. Synthesis, formation mechanism, and intrinsic physical properties of several As/P-containing MAX phases[J]. J. Mater. Sci. Technol., 2023, 133: 23-31.

Figures/Tables 8

Fig. 1. Phase-composition and crystal-structure characterizations of Nb3P2C prepared by MSS. (a) XRD pattern and Rietveld refinement results of as-prepared Nb3P2C sintered at 1200 °C. The inset is the crystal structure of 321 phases viewed from the [110] direction. (b) XRD pattern of the sample sintered at 1150 °C. The ICDD PDF cards of NbP (PDF#17-0882) and Nb2PC (PDF#21-0600) are given below the XRD pattern. The red-heart symbol indicates the characteristic Bragg peak (105) of Nb3P2C. (c) HRTEM image of Nb3P2C, the green atoms can be regarded as a single layer of Nb/P atoms. (d) SAED pattern of Nb3P2C collected along the <001> zone axis.

Fig. 2. SEM and EDS mapping results of Nb3P2C. (a, b) Micro-morphology of as-prepared Nb3P2C powder by MSS. (c) EDS result of the particle in (b). EDS mapping analysis of (d) Nb and (e) P. (f) Morphology of the one prepared by SSS.

Fig. 3. Chemical reaction routes of Nb3P2C. XRD patterns of samples prepared via different chemical reaction routes by (a) SSS and (b) MSS. The cyan curves are the Rietveld refinement results. (c) Phase content of 321 phases prepared by SSS and MSS. (d) Calculated Gibbs free energy change of different chemical reaction routes to synthesize Nb3P2C and Nb3As2C.

Fig. 4. Phase content of As/P-containing MAX phases. (a) Phase content of target products prepared by SSS and MSS with optimal sintering process. (b) Phase content of Nb2PC and Nb3P2C in the end-product of “Nb2PC” using different Ts by MSS.

Fig. 5. Magneto-transport properties of Nb3As2C and Nb3P2C. (a) Temperature-dependent resistivity of Nb3As2C (0.3-700 K) and Nb3P2C (2-380 K). (b) Temperature-dependent carrier concentration and mobility of Nb3As2C. (c) Field-dependent magnetoresistance of Nb3As2C at 10 K, the navy line is the linear fit results.

Fig. 6. Electronic structure of Nb3As2C. (a) Band structures. (b) Partial density of states. (c) Fermi surface. The Fermi surface was visualized by the FermiSurfer package [53].

Fig. 7. Thermoelectric properties of Nb3As2C. (a) Temperature-dependent Seebeck coefficient and power factor. (b) Temperature dependence of total thermal conductivity (κtot), and the electronic contribution (κe) and lattice contribution (κlat) of it. (c) Temperature-dependent figure of merit, ZT.

Fig. 8. Magnetic properties of (a) Nb3As2C and (b) Nb3P2C. The inset of (a) is the M-H curve at 10 K.

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