Pressure-induced phase transformations (PTs) in Si, the most important electronic material, have been broadly studied. However, strain-induced PTs in Si were never studied in situ. Here, we revealed in situ various important plastic strain-induced PT phenomena. A correlation between the particle size's direct and inverse Hall-Petch effect on yield strength and pressure for strain-induced PT is found. For 100 nm particles, strain-induced PT Si-IĀ³Si-II initiates at 0.3 GPa versus 16.2 GPa under hydrostatic conditions; Si-IĀ³Si-III PT starts at 0.6 GPa and does not occur under hydrostatic pressure. Pressure in small Si-II and Si-III regions is ~5-7 GPa higher than in Si-I. Retaining Si-II and single-phase Si-III at ambient pressure and obtaining reverse Si-IIĀ³Si-I PT demonstrates the possibilities of manipulating different synthetic paths. The obtained results corroborate the elaborated dislocation pileup-based mechanism and have numerous applications for developing economic defect-induced synthesis of nanostructured materials, surface treatment (polishing, turning, etc.), and friction.
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Structural Behavior of C2/m Tremolite to 40 GPa: A High-Pressure Single-Crystal X-ray Diffraction Study
The high-pressure structure and stability of the calcic amphibole tremolite (Ca2Mg5Si8O22(OH)2) was investigated to ~40 GPa at 300 K by single-crystal X-ray diffraction using synchrotron radiation. C2/m symmetry tremolite displays a broader metastability range than previously studied clinoamphiboles, exhibiting no first-order phase transition up to 40 GPa. Axial parameter ratios a/b and a/c, in conjunction with finite strain versus normalized pressure trends, indicate that changes in compressional behavior occur at pressures of ~5 and ~20 GPa. An analysis of the finite strain trends, using third-order Birch-Murnaghan equations of state, resulted in bulk moduli (š¾) of 72(7), 77(2), and 61(1) GPa for the compressional regimes from 0-5 GPa (regime I), 5-20 GPa (II), and above 20 GPa (III), respectively, and accompanying pressure-derivatives of the bulk moduli (š¾ā²) of 8.6(42), 6.0(3), and 10.0(2). The results are consistent with first-principle theoretical calculations of tremolite elasticity. The axial compressibility ratios of tremolite, determined as š½a : š½b : š½c = 2.22:1.0:0.78 (regime I), 2.12:1.0:0.96 (II), and 1.03:1.0:0.75 (III), demonstrate a substantial reduction of the compressional anisotropy of tremolite at high pressures, which is a notable contrast with the increasingly anisotropic compressibility observed in the high-pressure polymorphs of the clinoamphibole grunerite. The shift in compression-regime at 5 GPa (I-II) transition is ascribed to stiffening along the crystallographic a-axis corresponding to closure of the vacant A-site in the structure, and a shift in the topology of the a-oriented surfaces of the structural I-beam from concave to convex. The II-III regime shift at 20 GPa corresponds to an increasing rate of compaction of the Ca-polyhedra and increased distortion of the Mg-octahedral sites, processes which dictate compaction in both high-pressure compression-regimes. Bond-valence analyses of the tremolite structure under pressure show dramatic overbonding of the Ca-cations (75% at 30 GPa), with significant Mg-cation overbonding as well (40%). These imply that tremoliteās notable metastability range hinges on the calcium cationās bonding environment. The 8-fold coordinated Ca-polyhedron accommodates significant compaction under pressure, while the geometry of the Ca-O polyhedron becomes increasingly regular and inhibits the reorientation of the tetrahedral chains that generate phase transitions observed in other clinoamphiboles. Peak/background ratio of diffraction data collected above 40 GPa and our equation of state determination of bulk moduli and compressibilities of tremolite in regime III, in concert with the results of our previous Raman study, suggest that C2/m tremolite may be approaching the limit of its metastability above 40 GPa. Our results have relevance for both the metastable compaction of tremolite during impact events, and for possible metastable persistence of tremolite within cold subduction zones within the Earth.
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- Award ID(s):
- 2017294
- PAR ID:
- 10332084
- Date Published:
- Journal Name:
- American Mineralogist
- ISSN:
- 0003-004X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract The perovskite (BA)4[CuII(CuIInIII)0.5]Cl8(
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.2138/am-2022-8278
