Time-resolved X-ray Diffraction Techniques Research Articles

Time-Resolved X-ray Observation of Intracellular Crystallized Protein in Living Animal

Understanding the cellular environment as molecular crowding that supports the structure-specific functional expression of biomolecules has recently attracted much attention. Time-resolved X-ray observations have the remarkable capability to capture the structural dynamics of biomolecules with subnanometre precision. Nevertheless, the measurement of the intracellular dynamics within live organisms remains a challenge. Here, we explore the potential of utilizing crystallized proteins that spontaneously form intracellular crystals to investigate their intracellular dynamics via time-resolved X-ray observations. We generated transgenic Caenorhabditis elegans specifically expressing the crystallized protein in cells and observed the formation of the protein aggregates within the animal cells. From the toxic-effect observations, the aggregates had minimal toxic effects on living animals. Fluorescence observations showed a significant suppression of the translational diffusion movements in molecules constituting the aggregates. Moreover, X-ray diffraction measurements provided diffraction signals originating from these molecules. We also observed the blinking behaviour of the diffraction spots, indicating the rotational motion of these crystals within the animal cells. A diffracted X-ray blinking (DXB) analysis estimated the rotational motion of the protein crystals on the subnanometre scale. Our results provide a time-resolved X-ray diffraction technique for the monitoring of intracellular dynamics.

In situ observation of the phase transformation kinetics of bismuth during shock release

A time-resolved x-ray diffraction technique is employed to monitor the structural transformation of laser-shocked bismuth. Results reveal a retarded transformation from the shock-induced Bi-V phase to a metastable Bi-IV phase during the shock release, instead of the thermodynamically stable Bi-III phase. The emergence of the metastable Bi-IV phase is understood by the competitive interplay between two transformation pathways towards the Bi-IV and Bi-III, respectively. The former is more rapid than the latter because the Bi-V to B-IV transformation is driven by interaction between the closest atoms while the Bi-V to B-III transformation requires interaction between the second-closest atoms. The nucleation time for the Bi-V to Bi-IV transformation is determined to be 5.1±0.9 ns according to a classical nucleation model. This observation demonstrates the importance of the formation of the transient metastable phases, which can change the phase transformation pathway in a dynamic process.

Direct Monitoring of Conical Intersection Passage via Electronic Coherences in Twisted X-Ray Diffraction.

Quantum coherences in electronic motions play a critical role in determining the pathways and outcomes of virtually all photophysical and photochemical molecular processes. However, the direct observation of electronic coherences in the vicinity of conical intersections remains a formidable challenge. We propose a novel time-resolved twisted x-ray diffraction technique that can directly monitor the electronic coherences created as the molecule passes through a conical intersection. We show that the contribution of electronic populations to this signal is canceled out when using twisted x-ray beams that carry a light orbital angular momentum, providing a direct measurement of transient electronic coherences in gas-phase molecules.

Visualizing Light-Induced Microstrain and Phase Transition in Lead-Free Perovskites Using Time-Resolved X-Ray Diffraction.

Metal halide perovskites have emerged as promising materials for optoelectronic applications in the last decade. A large amount of effort has been made to investigate the interplay between the crystalline lattice and photoexcited charge carriers as it is vital to their optoelectronic performance. Among them, ultrafast laser spectroscopy has been intensively utilized to explore the charge carrier dynamics of perovskites, from which the local structural information can only be extracted indirectly. Here, we have applied a time-resolved X-ray diffraction technique to investigate the structural dynamics of prototypical two-dimensional lead-free halide perovskite Cs3Bi2Br9 nanoparticles across temporal scales from 80 ps to microseconds. We observed a quick recoverable (a few ns) photoinduced microstrain up to 0.15% and a long existing lattice expansion (∼a few hundred nanoseconds) at mild laser fluence. Once the laser flux exceeds 1.4 mJ/cm2, the microstrain saturates and the crystalline phase partially transfers into a disordered phase. This photoinduced transient structural change can recover within the nanosecond time scale. These results indicate that photoexcitation of charge carriers couples with lattice distortion, which fundamentally affects the dielectric environment and charge carrier transport.

RT-XAMF and TR-XRD studies of solid-state synthesis and thermal stability of NaNiO2 as cathode material for sodium-ion batteries

Room-temperature sodium storage technology has been attracting considerable attention, and its potential as a alternative technology to lithium-ion batteries for electrical energy storage has been studied owing to the abundance of sodium resources and its inexpensiveness. In situ X-ray diffraction (XRD) techniques, such as real-time X-ray analytical micro-furnace (RT-XAMF) and time-resolved X-ray diffraction (TR-XRD), are utilized to identify the synthesis process and thermal stability of the NaNiO2 cathode material for Na-ion batteries. Using the RT-XAMF technique, the solid-state reaction of Na2O2 and NiO was investigated in real-time to verify the phase transition from rhombohedral NaNiO2 at temperatures above 243 °C to monoclinic NaNiO2 at temperatures below 243 °C during heat treatment. In addition, the structural instability of the monoclinic NaNiO2 phase changes to the Na-deficient Na0.91NiO2 phase. The TR-XRD technique was used to investigate the thermal stability of the desodiated Na1−xNiO2 (x = 0.09, 0.5) cathodes in the presence of an electrolyte. It was confirmed that the structural changes of desodiated Na1−xNiO2 were relatively simple compared to those of the Ni-based cathode material in Li-ion batteries. First, the layered structure of Na1−xNiO2 at room temperature turns into an MO-type rock salt phase (NiO) and subsequently into a metallic phase (Ni) without the appearance of spinel-type (Li1−xM2O4 and M3O4) intermediates, which are typically observed in lithium nickel-based oxides. In addition, it was concluded that desodiated Na1−xNiO2 materials have higher thermal stability than delithiated Li1−xNiO2 (x = 0.5, below ∼200 °C) based on its high decomposition temperature (∼300 °C for Na0.91NiO2 and ∼280 °C for Na0.5NiO2). From these results, we believe that our in-situ XRD findings on the real-time solid-state synthesis process and thermal stability can be used as a fundamental guide for the development of Ni-based NaMO2 (M = Ni, Co, Mn, etc.) oxides for next-generation advanced Na-ion batteries.

High-Pressure Nonequilibrium Dynamics on Second-to-Microsecond Time Scales: Application of Time-Resolved X-ray Diffraction and Dynamic Compression in Ice.

The study of nonequilibrium transition dynamics on structural transformation from the second to microsecond regime, a time scale between static and shock compression, is an emerging field of high-pressure research. There are ample opportunities to uncover novel physical phenomena within this time regime. Herein, we briefly review the development and application of a dynamic compression technique based on a diamond anvil cell (DAC) and time-resolved X-ray diffraction (TRXRD) for the study of time-, pressure-, and temperature-dependent structural dynamics. Applications of the techniques are illustrated with our recent investigations on the mechanisms of the interconversions between different high-pressure ice polymorphs. These examples demonstrate that a combination of dynamic compression and TRXRD is a versatile approach capable of providing information on the kinetics and thermodynamic nature associated with structural transformations. Future improvement of rapid compression and TRXRD techniques and potentially interesting research topics in this area are suggested.

Bulk piezo-photovoltaic effect in LiNbO3

The deformations arising in iron-doped lithium niobate crystals (LiNbO3:Fe) under laser illumination were registered by changes in the parameters of X-ray diffraction rocking curves. The piezoelectric deformation as a result of the bulk photovoltaic effect was separated from heating according to the different kinetics of these processes using a set of time-resolved X-ray diffraction techniques. The dependence of the peak shift on the diffraction order confirmed the manifestation of the bulk piezo-photovoltaic effect. Additionally, the measurements of an external electric field influence on the diffraction peaks parameters were carried out as well as the measurements of the electrophysical and bulk photovoltaic characteristics of the crystal.

Diagnostic Studies on Ni-Rich NMC Layered Cathode Materials By Using Synchrotron-Based X-Ray Techniques

Layered Ni-rich LiNixMnyCozO2 (NMC, x ≥ 0.6, x+y+z=1) cathode have attracted significant interest as the cathode materials for rechargeable lithium batteries (LIBs) owing to their high capacity, excellent rate capability and low cost. However, some drawbacks such as capacity fade during cycling and low thermal-abuse tolerance at elevated temperature, prohibiting their use in practical batteries. In addition, when in highly charged states, the reduction of Ni ions during thermal heating releases oxygen from the crystal structure, which can lead thermal runaway and violent reactions with the flammable electrolyte. To overcome performance degradation and improve battery safety, several strategies including lattice doping, surface treatment/modification, tuning the material compositions has been proposed and demonstrated. As one of promising approaches, concentration gradient LiNixMnyCozO2 (CG-NMC) cathode material, in which the Ni concentration decreases and the Mn concentration increases linearly toward the particle surface, has received considerable attention due to its high capacity and improved structural stability. [1-3] The concept of CG-NMC opens many new possibilities for developing high Ni content NMC cathode with high capacity and improved safety characteristic for practical LIB applications. It is well-accepted that the material design of Ni-rich core and Mn-rich surface leads to the high capacity and better thermal stability, compared with normal NMC cathode materials. However, more detailed working mechanisms of CG-NMC cathode have not been fully understood yet. In this study, the structural and chemical changes of normal NMC and CG-NMC cathode materials with various testing conditions including cycling numbers, different cut-off voltages, thermal heating, will be investigated by using synchrotron based time-resolved X-ray diffraction (TR-XRD), hard and soft X-ray absorption spectroscopy (XAS) techniques. Due to its structural and chemical inhomogeneity of CG-NMC cathode materials, the combined use of various types of characterization techniques is essential. Combinations of TR-XRD, hard and soft XAS techniques allow us to distinguish the electronic and crystal structure differences between the bulk and surface of cathode materials in various conditions. The result will provide valuable information for the development and optimize Ni-rich NMC cathode materials with increased capacity and better thermal stability. Acknowledgement The work at Brookhaven National Lab. was supported by the U.S. Department of Energy, the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies (BMR and VTO Battery500 projects) under Contract Number DE-AC02-98CH10886. The work was collaborated with UChicago Argonne, LLC, Operator of Argonne National Laboratory (“Argonne”). Argonne, a U.S. Department of Energy Office of Science Laboratory, is operated under Contract No. DE-AC02-06CH11357.

In Situ Observation of Thermal Proton Transport through Graphene Layers.

Protons can penetrate through single-layer graphene, but thicker graphene layers (more than 2 layers), which possess more compact electron density, are thought to be unfavorable for penetration by protons at room temperature and elevated temperatures. In this work, we developed an in situ subsecond time-resolved grazing-incidence X-ray diffraction technique, which fully realizes the real-time observation of the thermal proton interaction with the graphene layers at high temperature. By following the evolution of interlayer structure during the protonation process, we demonstrated that thermal protons can transport through multilayer graphene (more than 8 layers) on nickel foil at 900 °C. In comparison, under the same conditions, the multilayer graphenes are impermeable to argon, nitrogen, helium, and their derived ions. Complementary in situ transport measurements simultaneously verify the penetration phenomenon at high temperature. Moreover, the direct transport of protons through graphene is regarded as the dominant contribution to the penetration phenomenon. The thermal activation, weak interlayer interaction between layers, and the affinity of the nickel catalyst may all contribute to the proton transport. We believe that this method could become one of the established approaches for the characterization of the ions intercalated with 2D materials in situ and in real-time.

Electronic structural studies on the improved thermal stability of Li(Ni0.8Co0.15Al0.05)O2 by ZrO2 coating for lithium ion batteries

The electronic structures of bare and ZrO2-coated Li(Ni0.8Co0.15Al0.05)O2 electrode systems were investigated using a combination of time-resolved X-ray diffraction and soft X-ray absorption spectroscopy (XAS) techniques. The ZrO2 coating on the surface of Li(Ni0.8Co0.15Al0.05)O2 was effective in elevating the onset temperature of the dissociation of charged Li0.33(Ni0.8Co0.15Al0.05)O2, which will enhance the safety of Li-ion cells. Soft XAS spectra of the Ni LII,III-edge in the partial electron yield mode were obtained, which showed that the enhanced electrochemical properties and thermal stability of the cathode materials by ZrO2 coating can be attributed to the suppression of unwanted Ni oxidation state changes at the surface. The electronic structural effects of a ZrO2 coating on Li(Ni0.8Co0.15Al0.05)O2 were examined by soft X-ray absorption spectroscopy. The coating stabilized the Ni oxidation state at the electrode surface against decomposition

(Invited) Investigation of the Reaction & Degradation Mechanism of Iron Based Cathodes for Sodium-Ion Batteries Using X-Ray Absorption and Time-Resolved X-Ray Diffraction Techniques

Because of the growing level of energy consumption, numerous efforts have been made to develop high performance rechargeable batteries to use for large scale applications such as electrical energy storage systems (ESS). Lithium ion batteries have been the most popular and widely used batteries in portable devices like cell phones, laptops, etc. However, it has some constraints to be used for large scale applications as the cost for the raw materials for lithium is expensive. There have been ongoing studies searching for alternative shuttle ions and sodium can be one of the possible substitutes since it is more abundant and cheaper. The development of high performance cathode materials is required for the realization of sodium-ion batteries (SIBs) as the reduction potential of sodium is lower and its ionic radius is larger compare to lithium. Because of larger ionic radius, the de/intercalation of sodium causes to large volume contraction/expansion of the host materials which could affect the rate capability and long cycle life. The structural analysis during electrochemical reaction can provide better insight to understand the material’s behavior. Furthermore, thermal analysis is one of the critical issues for the electrodes and causes to the failure of the battery system. Here, we report the synthesis, electrochemical properties and investigate the reaction mechanism of iron fluoride hydrate and iron phosphate cathodes for SIBs. The crystal structure of iron fluoride hydrate is refined and the results show pyrochlore structure (with space group of Fd3m) with hydrate contents residing in zigzag positions. Thermal stability of the as prepared iron fluoride hydrate is determined using thermogravimetric analysis coupled with temperature-dependent TR-XRD. A nanocomposite of iron fluoride hydrate encapsulated within reduced graphene oxide sheets is prepared as cathode for the high performance SIBs. The nanocomposite delivers a high discharge capacity of ~260 mAh/g at current density of 0.05 C (1C=220 mAh/g) and it retains a discharge capacity of 230 mAh/g over 100 cycles, demonstrating a good cycle stability. The ex situ TEM and XANES have employed to determine the reaction mechanism. The surface of the olivine iron phosphate is modified with a polymer (thiophene) to improve the electrochemical performance. The coating with thiophene not only increases the electrical conductivity but also prevent the degradation of the material. The coated electrode exhibits high electrochemical performance and delivers a discharge capacity of 142 mAh g-1 with capacity retention of 94% after 100 cycles. The reaction mechanism of the coated electrode has been investigated using x-ray absorption spectroscopy. Thermal analysis of the cycled electrode is conducted using temperature-dependent TR-XRD.

Simultaneous resonant x-ray diffraction measurement of polarization inversion and lattice strain in polycrystalline ferroelectrics.

Structure-property relationships in ferroelectrics extend over several length scales from the individual unit cell to the macroscopic device, and with dynamics spanning a broad temporal domain. Characterizing the multi-scale structural origin of electric field-induced polarization reversal and strain in ferroelectrics is an ongoing challenge that so far has obscured its fundamental behaviour. By utilizing small intensity differences between Friedel pairs due to resonant scattering, we demonstrate a time-resolved X-ray diffraction technique for directly and simultaneously measuring both lattice strain and, for the first time, polarization reversal during in-situ electrical perturbation. This technique is demonstrated for BaTiO3-BiZn0.5Ti0.5O3 (BT-BZT) polycrystalline ferroelectrics, a prototypical lead-free piezoelectric with an ambiguous switching mechanism. This combines the benefits of spectroscopic and diffraction-based measurements into a single and robust technique with time resolution down to the ns scale, opening a new door to in-situ structure-property characterization that probes the full extent of the ferroelectric behaviour.

Strong lattice correlation of non-equilibrium quasiparticles in a pseudospin-1/2 Mott insulator Sr2IrO4.

In correlated oxides the coupling of quasiparticles to other degrees of freedom such as spin and lattice plays critical roles in the emergence of symmetry-breaking quantum ordered states such as high temperature superconductivity. We report a strong lattice coupling of photon-induced quasiparticles in spin-orbital coupling Mott insulator Sr2IrO4 probed via optical excitation. Combining time-resolved x-ray diffraction and optical spectroscopy techniques, we reconstruct a spatiotemporal map of the diffusion of these quasiparticles. Due to the unique electronic configuration of the quasiparticles, the strong lattice correlation is unexpected but extends the similarity between Sr2IrO4 and cuprates to a new dimension of electron-phonon coupling which persists under highly non-equilibrium conditions.

Spherulitic morphologies of the triblock Poly(GL)-b-poly(GL-co-TMC-co-CL)-b-poly(GL) copolymer: Isothermal and non-isothermal crystallization studies

Crystallization of a biodegradable segmented copolymer constituted by polyglycolide hard segments and a middle soft segment constituted by a random disposition of glycolyl, ε-caproyl and trimethylene carbonyl units has been studied by means of optical microscopy, atomic force microscopy and time resolved X-ray diffraction techniques. This Poly(GL)-b-poly(GL-co-TMC-co-CL)-b-poly(GL) copolymer is widely employed as surgical suture and has similar characteristics than previously studied copolymers having a middle soft segment constituted by only two monomers (i.e. glycolide and trimethylene carbonate).FTIR and NMR spectroscopies demonstrated that the middle segment had an amorphous character and a random microstructure as consequence of transesterification reactions that took place during synthesis. Nevertheless, polyglycolide segments were able to crystallize giving rise to peculiar positive birefringent spherulites with a morphology, which depends on crystallization temperature (i.e. flat-on and edge-on crystals) as verified by AFM and electron diffraction patterns.Complete bell shaped curves that defined the temperature dependence of the crystal growth rate could be experimentally obtained from both, isothermal and non-isothermal crystallizations. Data from both analyses were in close agreement and pointed out a secondary nucleation constant (2.42–2.88×105K2) which was clearly higher than that determined for the related system with two components. Lamellar morphologic parameters were similar for samples crystallized from the melt state and after the reordering process that took place on heating. Comparing to the bicomponent system, significant differences were again observed highlighting the influence of the soft segment on the crystallization behavior.

Structural changes and thermal stability of charged LiNixMnyCozO₂ cathode materials studied by combined in situ time-resolved XRD and mass spectroscopy.

Thermal stability of charged LiNixMnyCozO2 (NMC, with x + y + z = 1, x:y:z = 4:3:3 (NMC433), 5:3:2 (NMC532), 6:2:2 (NMC622), and 8:1:1 (NMC811)) cathode materials is systematically studied using combined in situ time-resolved X-ray diffraction and mass spectroscopy (TR-XRD/MS) techniques upon heating up to 600 °C. The TR-XRD/MS results indicate that the content of Ni, Co, and Mn significantly affects both the structural changes and the oxygen release features during heating: the more Ni and less Co and Mn, the lower the onset temperature of the phase transition (i.e., thermal decomposition) and the larger amount of oxygen release. Interestingly, the NMC532 seems to be the optimized composition to maintain a reasonably good thermal stability, comparable to the low-nickel-content materials (e.g., NMC333 and NMC433), while having a high capacity close to the high-nickel-content materials (e.g., NMC811 and NMC622). The origin of the thermal decomposition of NMC cathode materials was elucidated by the changes in the oxidation states of each transition metal (TM) cations (i.e., Ni, Co, and Mn) and their site preferences during thermal decomposition. It is revealed that Mn ions mainly occupy the 3a octahedral sites of a layered structure (R3̅m) but Co ions prefer to migrate to the 8a tetrahedral sites of a spinel structure (Fd3̅m) during the thermal decomposition. Such element-dependent cation migration plays a very important role in the thermal stability of NMC cathode materials. The reasonably good thermal stability and high capacity characteristics of the NMC532 composition is originated from the well-balanced ratio of nickel content to manganese and cobalt contents. This systematic study provides insight into the rational design of NMC-based cathode materials with a desired balance between thermal stability and high energy density.

Ultrafast chemical kinetics: Elementary chemical act

Predictions of the classical theory of chemical reaction rates are compared with experimental results obtained by ultrafast time-resolved X-ray diffraction techniques. Our analysis is illustrated with the reaction I+I=I2 in solution at times immediately preceding recombination. Main features of experimentally detected dynamics are discussed and are compared with what is expected according to Eyring and Kramers. It is emphasized that atomic dynamics are unexpectedly complex at very earliest times.

Time-resolved x-ray diffraction techniques for bulk polycrystalline materials under dynamic loading.

We have developed two techniques for time-resolved x-ray diffraction from bulk polycrystalline materials during dynamic loading. In the first technique, we synchronize a fast detector with loading of samples at strain rates of ~10(3)-10(4) s(-1) in a compression Kolsky bar (split Hopkinson pressure bar) apparatus to obtain in situ diffraction patterns with exposures as short as 70 ns. This approach employs moderate x-ray energies (10-20 keV) and is well suited to weakly absorbing materials such as magnesium alloys. The second technique is useful for more strongly absorbing materials, and uses high-energy x-rays (86 keV) and a fast shutter synchronized with the Kolsky bar to produce short (~40 μs) pulses timed with the arrival of the strain pulse at the specimen, recording the diffraction pattern on a large-format amorphous silicon detector. For both techniques we present sample data demonstrating the ability of these techniques to characterize elastic strains and polycrystalline texture as a function of time during high-rate deformation.

Selective time-dependent changes of Cu(DPPE)(DMP)·PF6on photoexcitation

Thanks to their potential applications as light-emitting devices, chemical sensors and dye-sensitized solar cells, heteroleptic copper (I) complexes have been extensively studied. Cu(DPPE)(DMP)·PF6(dppe= 1,2-bis(diphenylphosphino)ethane; dmp = 2,9-dimethyl-1,10-phenanthroline) crystallizes in the monoclinic system, P21/c, with two independent molecules in the asymmetric unit. Previous studies on this system [1,2] show strong temperature-dependent emission. The complex was studied at 90K under 355nm laser excitation. At this temperature, the luminescence decay for Cu(DPPE)(DMP)·PF6is biexponential with lifetimes of ~3μs and ~28μs. Two time-resolved X-ray diffraction techniques were applied for studies: (1) a Laue technique at BioCARS ID-14 beamline at the Advanced Photon Source, and (2) monochromatic diffraction at a newly constructed in-house pump-probe monochromatic facility at the University at Buffalo. Structural changes determined with the two methods are in qualitative agreement; discrepancies in position of the Cu and P atoms were observed. The molecular distortions were smaller than those determined at 16K in the earlier synchrotron study by Vorontsov et al. [2]. Photodeformation maps (see Figure below), in which the increase in temperature on photoexcitation has been eliminated, clearly illustrate the photoinduced atomic shifts for both data sets. Results will be compared with those obtained for other studied heteroleptic copper (I) complexes, for instance Cu[(1,10-phenanthroline-N,N′) bis(triphenylphosphine)]·BF4[3]. The in-house pump-probe facility is discussed by Radoslaw Kaminski at this meeting. Research funded by the National Science Foundation (CHE1213223). BioCARS Sector 14 at APS is supported by NIH (RR007707). The Advanced Photon Source is funded by the Office of Basic Energy Sciences, U.S. Department of Energy, (W-31-109-ENG-38). KNJ is supported by the Polish Ministry of Science and Higher Education through the "Mobility Plus" program.

Structural and electronic recovery pathways of a photoexcited ultrathin VO2film

The structural and electronic recovery pathways of a photoexcited ultrathin VO2 film at nanosecond time scales have been studied using time-resolved x-ray diffraction and transient optical absorption techniques. The recovery pathways from the tetragonal metallic phase to the monoclinic insulating phase are highly dependent on the optical pump fluence. At pump fluences higher than the saturation fluence of 14.7 mJ/cm2, we observed a transient structural state with lattice parameter larger than that of the tetragonal phase, which is decoupled from the metal-to-insulator phase transition. Subsequently, the photoexcited VO2 film recovered to the ground state at characteristic times dependent upon the pump fluence, as a result of heat transport from the film to the substrate. We present a procedure to measure the time-resolved film temperature by correlating photoexcited and temperature-dependent x-ray diffraction measurements. A thermal transport model that incorporates changes of the thermal parameters across the phase transition reproduces the observed recovery dynamics. The optical excitation and fast recovery of ultrathin VO2 films provides a practical method to reversibly switch between the monoclinic insulating and tetragonal metallic state at nanosecond time scales.

Complex structural dynamics of bismuth under laser-driven compression

With the aid of nanosecond time-resolved X-ray diffraction techniques, we have explored the complex structural dynamics of bismuth under laser-driven compression. The results demonstrate that shocked bismuth undergoes a series of structural transformations involving four solid structures: the Bi-I, Bi-II, Bi-III, and Bi-V phases. The transformation from the Bi-I phase to the Bi-V phase occurs within 4 ns under shock compression at ∼11 GPa, showing no transient phases with the available experimental conditions. Successive phase transitions (Bi-V → Bi-III → Bi-II → Bi-I) during the shock release within 30 ns have also been resolved, which were inaccessible using other dynamic techniques.