Maik Lang

Nanoscale Phase Transitions under Extreme Conditions within an Ion Track

The dynamics of track development due to the passage of relativistic heavy ions through solids is a long-standing issue relevant to nuclear materials, age dating of minerals, space exploration, and nanoscale fabrication of novel devices. We have integrated experimental and simulation approaches to investigate nanoscale phase transitions under the extreme conditions created within single tracks of relativistic ions in Gd2O3(TiO2)x and Gd2Zr2–x TixO7. Track size and internal structure depend on energy density deposition, irradiation temperature, and material composition. Based on the inelastic thermal spike model, molecular dynamics simulations follow the time evolution of individual tracks and reveal the phase transition pathways to the concentric track structures observed experimentally. Individual ion tracks have nanoscale core-shell structures that provide a unique record of the phase transition pathways under extreme conditions.

Probing disorder in isometric pyrochlore and related complex oxides

There has been an increased focus on understanding the energetics of structures with unconventional ordering (for example, correlated disorder that is heterogeneous across different length scales). In particular, compounds with the isometric pyrochlore structure, A2B2O7, can adopt a disordered, isometric fluorite-type structure, (A, B)4O7, under extreme conditions. Despite the importance of the disordering process there exists only a limited understanding of the role of local ordering on the energy landscape. We have used neutron total scattering to show that disordered fluorite (induced intrinsically by composition/stoichiometry or at far-from-equilibrium conditions produced by high-energy radiation) consists of a local orthorhombic structural unit that is repeated by a pseudo-translational symmetry, such that orthorhombic and isometric arrays coexist at different length scales. We also show that inversion in isometric spinel occurs by a similar process. This insight provides a new basis for understanding order-to-disorder transformations important for applications such as plutonium immobilization, fast ion conduction, and thermal barrier coatings.

Enhanced radiation resistance of nanocrystalline pyrochlore Gd2(Ti0.65Zr0.35)2O7

The radiation response of nanostructured materials is of great interest because of the potential of nanoscale materials design for mitigating radiation damage. We report a greatly enhanced resistance to radiation-induced amorphization in nanocrystalline Gd2(Ti0.65Zr0.35)2O7 at a particle size less than 20 nm while larger crystals with the size >100 nm are radiation sensitive. The grain size of pyrochlore, Gd2(Ti0.65Zr0.35)2O7, can be controlled by mechanical milling and subsequent thermal treatment (from 800 to 1500 °C), offering the possibility of designing pyrochlore materials at the nanoscale with enhanced performance for specific radiation environments.

Redox response of actinide materials to highly ionizing radiation

Energetic radiation can cause dramatic changes in the physical and chemical properties of actinide materials, degrading their performance in fission-based energy systems. As advanced nuclear fuels and wasteforms are developed, fundamental understanding of the processes controlling radiation damage accumulation is necessary. Here we report oxidation state reduction of actinide and analogue elements caused by high-energy, heavy ion irradiation and demonstrate coupling of this redox behaviour with structural modifications. ThO2, in which thorium is stable only in a tetravalent state, exhibits damage accumulation processes distinct from those of multivalent cation compounds CeO2 (Ce(3+) and Ce(4+)) and UO3 (U(4+), U(5+) and U(6+)). The radiation tolerance of these materials depends on the efficiency of this redox reaction, such that damage can be inhibited by altering grain size and cation valence variability. Thus, the redox behaviour of actinide materials is important for the design of nuclear fuels and the prediction of their performance.

High pressure synthesis of a hexagonal close-packed phase of the high-entropy alloy CrMnFeCoNi

High-entropy alloys, near-equiatomic solid solutions of five or more elements, represent a new strategy for the design of materials with properties superior to those of conventional alloys. However, their phase space remains constrained, with transition metal high-entropy alloys exhibiting only face- or body-centered cubic structures. Here, we report the high-pressure synthesis of a hexagonal close-packed phase of the prototypical high-entropy alloy CrMnFeCoNi. This martensitic transformation begins at 14 GPa and is attributed to suppression of the local magnetic moments, destabilizing the initial fcc structure. Similar to fcc-to-hcp transformations in Al and the noble gases, the transformation is sluggish, occurring over a range of >40 GPa. However, the behaviour of CrMnFeCoNi is unique in that the hcp phase is retained following decompression to ambient pressure, yielding metastable fcc-hcp mixtures. This demonstrates a means of tuning the structures and properties of high-entropy alloys in a manner not achievable by conventional processing techniques.

Zirconate pyrochlores under high pressure

Ab initio total-energy calculations and X-ray diffraction measurements have been combined to study the phase stability of zirconate pyrochlores (A(2)Zr(2)O(7); A = La, Nd and Sm) under pressures up to 50 GPa. Phase transformations to the defect-cotunnite structure are theoretically predicted at pressures of 22, 20 and 18 GPa, in excellent agreement with the experimentally determined values of 21, 22 and 18 GPa for La(2)Zr(2)O(7), Nd(2)Zr(2)O(7) and Sm(2)Zr(2)O(7), respectively. Analysis of the elastic properties indicates that elastic anisotropy may be one of the driving forces for the pressure-induced cubic-to-noncubic phase transformation.

Amorphization of nanocrystalline monoclinic ZrO2 by swift heavy ion irradiation

Bulk ZrO(2) polymorphs generally have an extremely high amorphization tolerance upon low energy ion and swift heavy ion irradiation in which ballistic interaction and ionization radiation dominate the ion-solid interaction, respectively. However, under very high-energy irradiation by 1.33 GeV U-238, nanocrystalline (40-50 nm) monoclinic ZrO(2) can be amorphized. A computational simulation based on a thermal spike model reveals that the strong ionizing radiation from swift heavy ions with a very high electronic energy loss of 52.2 keV nm(-1) can induce transient zones with temperatures well above the ZrO(2) melting point. The extreme electronic energy loss, coupled with the high energy state of the nanostructured materials and a high thermal confinement due to the less effective heat transport within the transient hot zone, may eventually be responsible for the ionizing radiation-induced amorphization without transforming to the tetragonal polymorph. The amorphization of nanocrystalline zirconia was also confirmed by 1.69 GeV Au ion irradiation with the electronic energy loss of 40 keV nm(-1). These results suggest that highly radiation tolerant materials in bulk forms, such as ZrO(2), may be radiation sensitive with the reduced length scale down to the nano-metered regime upon irradiation above a threshold value of electronic energy loss.

Liquid-like phase formation in Gd2Zr2O7 by extremely ionizing irradiation

Isometric Gd2Zr2O7 with the ordered, pyrochlore structure has an extremely high resistance to radiation-induced amorphization. Ion-beam irradiations at keV to GeV energies result in a disordered, defect-fluorite structure that remains crystalline to very large fluences. However, we report liquid-like phase formation of droplet-like surface hillocks and quenched molten tracks in Gd2Zr2O7. The extremely high energy density of 12-MeV C60 clusters creates tracks with substantial volumes of amorphous material, accompanied by the formation of nanocrystals of the disordered, defect-fluorite structure. This is the first evidence of irradiation-induced amorphization of Gd2Zr2O7. In contrast, irradiation of Gd2Zr2O7 pyrochlore with swift heavy ions of U resulted in an order-disorder transformation to defect-fluorite without any evidence of amorphization. Thermal-spike calculations highlight the dominance of the effect of deposited energy density, controlled by the projectile velocity, as compared with the energy loss.

High pressure phase transitions and compressibilities of Er2Zr2O7 and Ho2Zr2O7

Phase stability and compressibility of rare earth zirconates with the defect-fluorite structure were investigated by in situ synchrotron x-ray diffraction. A sluggish defect-fluorite to a cotunnitelike phase transformation occurred at pressures of ∼22 and ∼30GPa for Er2Zr2O7 and Ho2Zr2O7, respectively. Enhanced compressibility was found for the high pressure phase as a result of increasing cation coordination number and cation-anion bond length.

Structural Transitions and Electron Transfer in Coffinite, USiO4, at High Pressure

Abstract The compressibility, phase stability, and vibrational properties of coffinite (USiO4) were studied by in situ X-ray diffraction and infrared (IR) measurements at high pressures. An irreversible phase transition from the zircon-type to scheelite-type structure was found to occur at 14-17 GPa. Accompanying the structural transition, partial amorphization was also evident in the XRD analysis. The predicted transition pressure calculated by density functional theory is in good agreement with the experimental results. IR spectra also suggest that water is incorporated into the coffinite structure, and a pressure-induced electron transfer (U4+ → U5+) may also occur.