Microstructures and micromechanical behaviors of high -entropy alloys investigated by synchrotron X-ray and neutron diffraction techniques: A review

High-entropy alloys(HEAs)possess outstanding features such as corrosion resistance,irradiation resistance,and good mechan-ical properties.A few HEAs have found applications in the fields of aerospace and defense.Extensive studies on the deformation mech-anisms of HEAs can guide microstructure control and toughness design,which is vital for understanding and studying state-of-the-art structural materials.Synchrotron X-ray and neutron diffraction are necessary techniques for materials science research,especially for in situ coupling of physical/chemical fields and for resolving macro/microcrystallographic information on materials.Recently,several re-searchers have applied synchrotron X-ray and neutron diffraction methods to study the deformation mechanisms,phase transformations,stress behaviors,and in situ processes of HEAs,such as variable-temperature,high-pressure,and hydrogenation processes.In this review,the principles and development of synchrotron X-ray and neutron diffraction are presented,and their applications in the deformation mechanisms of HEAs are discussed.The factors that influence the deformation mechanisms of HEAs are also outlined.This review fo-cuses on the microstructures and micromechanical behaviors during tension/compression or creep/fatigue deformation and the application of synchrotron X-ray and neutron diffraction methods to the characterization of dislocations,stacking faults,twins,phases,and intergrain/interphase stress changes.Perspectives on future developments of synchrotron X-ray and neutron diffraction and on research directions on the deformation mechanisms of novel metals are discussed.

Exploring battery material failure mechanisms through synchrotron X-ray characterization techniques

Rechargeable battery cycling performance and related safety have been persistent concerns.It is crucial to decipher the capacity fading induced by electrode material failure via a range of techniques.Among these,synchrotron-based X-ray techniques with high flux and brightness play a key role in understanding degradation mechanisms.In this comprehensive review,we summarize recent advancements in degra-dation modes and mechanisms that were revealed by synchrotron X-ray methodologies.Subsequently,an overview of X-ray absorption spectroscopy and X-ray scattering techniques is introduced for charac-terizing failure phenomena at local coordination atomic environment and long-range order crystal struc-ture scale,respectively.At last,we envision the future of exploring material failure mechanism.

A Novel High Temperature Apparatus for in situ Synchrotron X-ray Diffraction Studies of Molten Salt

This study demonstrates the design and application of a novel high temperature rotatory apparatus for insitu synchrotron X-ray diffraction studies of molten salts,facilitating investigation into the interaction between various structural materials and molten salts.The apparatus enables accurate detection of every phase change during hightemperature experiments,including strong reaction processes like corrosion.Molten salts,such as chlorides or fluo⁃rides,together with the structure materials,are inserted into either quartz or boron nitride capillaries,where X-ray diffraction pattern can be continuously collected,as the samples are heated to high temperature.The replacement re⁃action,when molten ZnCl2 are etching Ti3AlC2,can be clearly observed through changes in diffraction peak intensity as well as expansion in c-axis lattice parameter of the hexagonal matrix,due to the larger atomic number and ionic ra⁃dius of Zn2+.Furthermore,we investigated the high-temperature corrosion process when GH3535 alloy is in FLiNaK molten salt,and can help to optimize its stability for potential applications in molten salt reactor.Additionally,this high temperature apparatus is fully compatible with the combined usage of X-ray diffraction and Raman technique,providing both bulk and surface structural information.This high temperature apparatus has been open to users and is extensively used at BL14B1 beamline of the Shanghai Synchrotron Radiation Facility.

The application of synchrotron X-ray techniques to the study ofrechargeable batteries

The increased use of rechargeable batteries in portable electronic devices and the continuous develop-ment of novel applications （e.g. transportation and large scale energy storage）, have raised a strong de-mand for high performance batteries with increased energy density, cycle and calendar life, safety andlower costs. This triggers significant efforts to reveal the fundamental mechanism determining batteryperformance with the use of advanced analytical techniques. However, the inherently complex character-istics of battery systems make the mechanism analysis sophisticated and difficult. Synchrotron radiationis an advanced collimated light source with high intensity and tunable energies. It has particular ad-vantages in electronic structure and geometric structure （both the short-range and long-range structure）analysis of materials on different length and time scales. In the past decades, synchrotron X-ray tech-niques have been widely used to understand the fundamental mechanism and guide the technologicaloptimization of batteries. In particular, in situ and operando techniques with high spatial and temporalresolution, enable the nondestructive, real time dynamic investigation of the electrochemical reaction,and lead to significant deep insights into the battery operation mechanism. This review gives a brief introduction of the application of synchrotron X-ray techniques to the inves-tigation of battery systems. The five widely implicated techniques, including X-ray diffraction （XRD）, PairDistribution Function （PDF）, Hard and Soft X-ray absorption spectroscopy （XAS） and X-ray photoelectronspectroscopy （XPS） will be reviewed, with the emphasis on their in situ studies of battery systems during cycling.

Three-dimensional morphology of the Sinocyclocheilus hyalinus(Cypriniformes: Cyprinidae) horn based on synchrotron X-ray microtomography

Sinocyclocheilus is a cave-dwelling cyprinid genus endemic to southwest China. Several species possess a conspicuous horn on their head, which has been suggested as a constructive troglomorphic trait but lacks substantial evidence. We used non- invasive, high spatial resolution synchrotron X-ray microtomography to investigate the three-dimensional （3D） morphology of the horn of Sinocyclocheilus hyalinus, one of eight such troglobiotic species. 3D renderings demonstrated the osteological components, which were comprised of a rear wall comprised of the supraoccipital bone, a remaining frontal wall with numerous fenestrae, and the bottom continuous with the parietal and epiotic. A horn cavity occurred within the horn. The fenestrae in the frontal wall were continuous in the horn cavity and showed elaborate channeling, and were, connected to the cranial cavity by soft tissue. We tentatively called this configuration the ＂otocornual connection＂ due to its anatomic and putative functional similarity to the otolateralic connection in clupeids and loricariids, which provide an indirect pathway to enhance perception of underwater sound signals. This study provides a functional morphology context for further histological and physiological investigations of such horn structures in Sinocyclocheilus cavefish, and we suggest that the horn might enhance acoustic perception to compensate for visual loss in subterranean life, which warrants future physiological examination as lab-reared S. hyalinus become available.

In situ characterizations of solid-solid interfaces in solid-state batteries using synchrotron X-ray techniques

The solid-solid electrode-electrolyte interface represents an important component in solid-state batteries(SSBs),as ionic diffusion,reaction,transformation,and restructuring could all take place.As these processes strongly influence the battery performance,studying the evolution of the solid-solid interfaces,particularly in situ during battery operation,can provide insights to establish the structure-property relationship for SSBs.Synchrotron X-ray techniques,owing to their unique penetration power and diverse approaches,are suitable to investigate the buried interfaces and examine structural,compositional,and morphological changes.In this review,we will discuss various surface-sensitive synchrotron-based scattering,spectroscopy,and imaging methods for the in situ characterization of solid-solid interfaces and how this information can be correlated to the electrochemical properties of SSBs.The goal is to overview the advantages and disadvantages of each technique by highlighting representative examples,so that similar strategies can be applied by battery researchers and beyond to study similar solid-solid interface systems.

Synchrotron X-Ray Diffraction Studies on the New Generation Ferromagnetic Semiconductor Li(Zn,Mn)As under High Pressure

The pressure effect on the crystalline structure of the I-II- V semiconductor Li（Zn,Mn）As ferromagnet is studied using in situ high-pressure x-ray diffraction and diamond anvil cell techniques. A phase transition starting at -11.6GPa is found. The space group of the high-pressure new phase is proposed as Pmca. Fitting with the Birch-Murnaghan equation of state, the bulk modulus B0 and its pressure derivative B0 of the ambient pressure structure with space group of F43m are B0 = 75.4 GPa and B0 = 4.3, respectively.

Fast synchrotron X-ray tomography study of the packing structures of rods with different aspect ratios

We present a fast synchrotron X-ray tomography study of the packing structures of rods with different aspect ratios. Utilizing the high flux of the X-rays generated from the third-generation synchrotron source, we can complete a high- resolution tomography scan within a short period of time, after which the three-dimensional （3D） packing structure can be obtained for the subsequent structural analysis. The image phase-retrieval procedure has been implemented to enhance the image contrast. We systematically investigated the effects of particle shape and aspect ratio on the structural properties including packing density and contact number. It turns out that large aspect ratio rod packings will have wider distributions of free volume fraction and larger mean contact numbers.

Understanding Pseudocapacitance Mechanisms by Synchrotron X-ray Analytical Techniques

Pseudocapacitive materials that store charges via reversible surface or near-surface faradaic reactions are capable of overcoming the capacity limitations of electrical double-layer capacitors.Revealing the structure–activity relationship between the microstructural features of pseudocapacitive materials and their electrochemical performance on the atomic scale is the key to build high-performance capacitor-type devices containing ideal pseudocapacitance effect.Currently,the high brightness(flux),and spectral and coherent nature of synchrotron X-ray analytical techniques make it a powerful tool for probing the structure–property relationship of pseudocapacitive materials.Herein,we report a comprehensive and systematic review of four typical characterization techniques(synchrotron X-ray diffraction,pair distribution function[PDF]analysis,soft X-ray absorption spectroscopy,and hard X-ray absorption spectroscopy)for the study of pseudocapacitance mechanisms.In addition,we offered significant insights for understanding and identifying pseudocapacitance mechanisms(surface redox pseudocapacitance,intercalation pseudocapacitance,and the extrinsic pseudocapacitance phenomenon in battery materials)by combining in situ hard XAS and electrochemical analyses.Finally,a perspective for further depth of understanding into the pseudocapacitance mechanism using synchrotron X-ray analytical techniques is proposed.

Three-dimensional morphology of the Sinocyclocheilus hyalinus(Cypriniformes:Cyprinidae)horn based on synchrotron X-ray microtomography

Sinocyclocheilus is a cave-dwelling cyprinid genus endemic to southwest China.Several species possess a conspicuous horn on their head,which has been suggested as a constructive troglomorphic trait but lacks substantial evidence.We used non-invasive,high spatial resolution synchrotron X-ray microtomography to investigate the three-dimensional(3D)morphology of the horn of Sinocyclocheilus hyalinus,one of eight such troglobiotic species.3D renderings demonstrated the osteological components,which were comprised of a rear wall comprised of the supraoccipital bone,a remaining frontal wall with numerous fenestrae,and the bottom continuous with the parietal and epiotic.A horn cavity occurred within the horn.The fenestrae in the frontal wall were continuous in the horn cavity and showed elaborate channeling,and were,connected to the cranial cavity by soft tissue.We tentatively called this configuration the“otocornual connection”due to its anatomic and putative functional similarity to the otolateralic connection in clupeids and loricariids,which provide an indirect pathway to enhance perception of underwater sound signals.This study provides a functional morphology context for further histological and physiological investigations of such horn structures in Sinocyclocheilus cavefish,and we suggest that the horn might enhance acoustic perception to compensate for visual loss in subterranean life,which warrants future physiological examination as lab-reared S.hyalinus become available.

Thermal expansivity of geikielite and ilmenite utilizing in-situ synchrotron X-ray diffraction at high temperature

The unit-cell parameters and volumes of geikielite(MgTiO_(3))and ilmenite(FeTiO_(3))were investigated at high temperatures up to 700 K and ambient pressure,using in-situ angle-dispersive synchrotron X-ray diffraction.No phase transition was detected over the experimental temperature range.Using(Berman in J Petrol29:445-522,1988.10.1093/petrology/29.2.445)equations to fit the temperature-volume data,the volumetric thermal expansion coefficients at ambient conditions(α_(V0))of MgTiO_(3) and FeTiO_(3) were obtained as follows:2.55(6)×10^(-5)K^(-1)and 2.82(10)×10^(-5)K^(-1),respectively.We infer that the larger effective ionic radius of Fe^(2+)(Ⅵ)(0.78 A)than that of Mg^(2+)(Ⅵ)(0.72?)renders FeTiO_(3)has a larger volumetric thermal expansivity than MgTiO_(3).Simultaneously,the refined axial thermal expansion coefficients under ambient conditions areα_(a0)=0.74(3)×10^(-5)K^(-1)andα_(c0)=1.08(5)×10^(-5)K^(-1)for the aaxis and c-axis of MgTiO_(3),respectively,andα_(a0)=0.95(5)×10^(-5)K^(-1)andα_(c0)=0.92(12)×10^(-5)K^(-1)for the aaxis and c-axis of FeTiO_(3),respectively.The axial thermal expansivity of MgTiO_(3) is anisotropic,but that of FeTiO_(3) is nearly isotropic.We infer that the main reason for the different axial thermal expansivity between MgTiO_(3) and FeTiO_(3) is that the thermal expansion mode of the Mg-O bond in MgTiO_(3) is different from that of the Fe-O bonds in FeTiO_(3).

Ultrasmall CoS nanoparticles embedded in heteroatom-doped carbon for sodium-ion batteries and mechanism explorations via synchrotron X-ray techniques

Transition metal sulfides have been regarded as promising anode materials for sodium-ion batteries(SIB).However,they face the challenges of poor electronic conductivity and large volume change,which result in capacity fade and low rate capability.In this work,a composite containing ultrasmall CoS(~7 nm)nanoparticles embedded in heteroatom(N,S,and O)-doped carbon was synthesized by an efficient one-step sulfidation process using a Co(Salen)precursor.The ultrasmall CoS nanoparticles are beneficial for mechanical stability and shortening Na-ions diffusion pathways.Furthermore,the N,S,and O-doped defect-rich carbon provides a robust and highly conductive framework enriched with active sites for sodium storage as well as mitigates volume expansion and polysulfide shuttle.As anode for SIB,CoS@HDC exhibits a high initial capacity of 906 mA h g^(-1)at 100 mA g^(-1)and a stable long-term cycling life with over 1000 cycles at 500 mA g^(-1),showing a reversible capacity of 330 mA h g^(-1).Meanwhile,the CoS@HDC anode is proven to maintain its structural integrity and compositional reversibility during cycling.Furthermore,Na-ion full batteries based on the CoS@HDC anode and Na_(3)V_(2)(PO_(4))_(3)cathode demonstrate a stable cycling behavior with a reversible specific capacity of~200 m A h g^(-1)at least for 100 cycles.Moreover,advanced synchrotron operando X-ray diffraction,ex-situ X-ray absorption spectroscopy,and comprehensive electrochemical tests reveal the structural transformation and the Co coordination chemistry evolution of the CoS@HDC during cycling,providing fundamental insights into the sodium storage mechanism.

Neutron powder diffraction and high-pressure synchrotron x-ray diffraction study of tantalum nitrides

Tantalum nitride （TAN） compact with a Vickers hardness of 26 GPa is prepared by a high-pressure and high- temperature （HPHT） method. The crystal structure and atom occupations of WC-type TaN have been investigated by neutron powder diffraction, and the compressibility of WC-type TaN has been investigated by using in-situ high-pressure synchrotron x-ray diffraction. The third-order Birch-Murnaghan equation of state fitted to the x-ray diffraction pressure- volume （P-V） sets of data, collected up to 41 GPa, yields ambient pressure isothermal bulk moduli of B0 = 369（2） GPa with pressure derivatives of B~ = 4 for the WC-type TaN. The bulk modulus of WC-type TaN is not in good agreement with the previous result （Bo = 351 GPa）, which is close to the recent theoretical calculation result （Bo = 378 GPa）. An analysis of the experiment results shows that crystal structure of WC-type TaN can be viewed as alternate stacking of Ta and N layers along the c direction, and the covalent Ta-N bonds between Ta and N layers along the c axis in the crystal structure play an important role in the incompressibility and hardness of WC-type TaN.

In Situ Synchrotron X-ray Diffraction Studies of Single-walled Carbon Nanotubes for Electric Double-layer Capacitors

In situ synchrotron X-ray diffraction experiments of SWCNT （single-walled carbon nanotube） electrode in alkali halide aqueous electrolyte at several applied potentials were performed, and the change in the diffraction pattern of SWCNTs was observed. It was found that the position of the 100 diffraction peak does not change with applied potential while the peak intensity decreases with anion adsorption. It was concluded that the space inside the tube would be the important ion adsorption site for the well-gown SWCNT bundles.

Research progress on solidification structure of alloys by synchrotron X-ray radiography: A review

The synchrotron radiation technology has recently emerged as a powerful tool to characterize the real-time microstructure evolution during solidification of alloys.Compared with other methods,the synchrotron radiation technology,along with its unique advantages of strong brightness,high energy,excellent resolution,and good monochromaticity,allows for capturing the dendrite evolution behavior of alloys in real time and can be dynamically coordinated with high-resolution CCD(Charge-coupled Device)imaging systems.This paper briefly reviews the recent advances in developing synchrotron radiation for solidification of alloys with low,medium,and high melting points,and under the external electric,magnetic,and ultrasonic fields.Furthermore,a series of microstructural features and behaviors such as dendrite morphology,growth orientation,dendrite fracture,and rotation are described in detail.Finally,the development trends and application prospects of synchrotron radiation technology in alloy solidification are forecasted.

High-Pressure Phase Transitions of Cubic Y_2O_3 under High Pressures by In-situ Synchrotron X-Ray Diffraction

High-pressure phase transitions of cubic Y_2O_3 are investigated using in situ synchrotron x-ray diffraction in a diamond anvil cell up to 36.3 GPa. The pressure-induced phase transitions of cubic Y_2O_3, which display apparent inconsistencies in previous studies, are verified to be from a cubic phase to a monoclinic phase and further to a hexagonal phase at 11.7 and 21.6 GPa, respectively. The hexagonal Y_2O_3 displays noticeable anisotropic compressibility due to its layered structure and it is stable up to the highest pressure in the present study. A third-order Birch–Murnaghan fit based on the observed pressure-volume data yields zero pressure bulk moduli of180(3), 196(7) and 177(7) GPa for cubic, monoclinic and hexagonal phases, respectively.

Tracking the phase transformation and microstructural evolution of Sn anode using operando synchrotron X-ray energy-dispersive diffraction and X-ray tomography

Tin(Sn)holds great promise as an anode material for next-generation lithium(Li)ion batteries but suffers from massive volume change and poor cycling performance.To clarify the dynamic chemical and microstructural evolution of Sn anode during lithiation and delithiation,synchrotron X-ray energydispersive diffraction and X-ray tomography are simultaneously employed during Li/Sn cell operation.The intermediate Li-Sn alloy phases during de/lithiation are identified,and their dynamic phase transformation is unraveled which is further correlated with the volume variation of the Sn at particle-and electrode-level.Moreover,we find that the Sn particle expansion/shrinkage induced particle displacement is anisotropic:the displacement perpendicular to the electrode surface(z-axis)is more pronounced compared to the directions(x-and y-axis)along the electrode surface.This anisotropic particle displacement leads to an anisotropic volume variation at the electrode level and eventually generates a net electrode expansion towards the separator after cycling,which could be one of the root causes of mechanical detachment and delamination of electrodes during long-term operation.The unraveled chemical evolution of Li-Sn and deep insights into the microstructural evolution of Sn anode provided here could guide future design and engineering of Sn and other alloy anodes for high energy density Li-and Na-ion batteries.

Preliminary determination of calcium,phosphorus,and the calcium/phosphorus ratio in cortical bone of Chinstrap penguin using synchrotron X-ray fluorescence analysis

Synchrotron radiation X-ray fluorescence （SR-XRF） approach was applied to analyzing of Chinstrap penguin （ Pygoscelis Antarctica） cortical bone. The method enabled the in situ determination of Ca and P concentrations and the Ca/P ratio in cortical bone. The preliminary results show that ： （ 1 ） there is the bone site-related difference for Ca and P concentrations. The mean values for the investigated parameters （ on a dry-weight basis） are： 30.7% （Ca） and 14.9% （P） for the femoral cortical bone, 21.4% （Ca） and 11.5% （P） for wing cortical bone. （2） The variation for the Ca/P ratio in cortical bone is lower than those for Ca and P separately. This is in agreement with the previous report that the specificity of the Ca/P ratio is better than that of Ca and P concentrations and is more reliable for the diagnosis of bone disorders. The authors suggest that further studies be conducted to establish norreal values of Ca, P and Ca/P ratio for polar animals and provide a basis for the diagnosis of bone disorders.

Direct Evidence of Coal Swelling and Shrinkage with Injecting CO_(2) and N_(2) Using in-situ Synchrotron X-ray Microtomography

Deep coal seams are one of the world’s most widespread deposits for carbon dioxide(C02)disposal and are generally located near large point sources of CO_(2)emissions.The injection of CO_(2)into coal seams has great potential to sequester CO_(2)while simultaneously enhancing coalbed methane(CO_(2)-ECBM)recovery.Pilot tests of CO_(2)-ECBM have been conducted in coal seams worldwide with favorable early results.However,one of the main technical barriers in coal seams needs to be resolved:Injecting CO_(2)reduces coal permeability and well injectivity.Here,using in situ synchrotron X-ray microtomography,we provide the first observational evidence that injecting nitrogen(N_(2))can reverse much of this lost permeability by reopening fractures that have closed due to coal swelling induced by CO_(2)adsorption.Our findings support the notion that injecting minimally treated flue gas-a mixture of mainly N_(2) and CO_(2)-is an attractive alternative for ECBM recovery instead of pure CO_(2)injection in deep coal seams.Firstly,flue gas produced by power plants could be directly injected after particulate removal,thus avoiding high CO_(2)-separation costs.Secondly,the presence of N_(2)makes it possible to maintain a sufficiently high level of coal permeability.These results suggest that flue-gas ECBM for deep coal seams may provide a promising path toward net-zero emissions from coal mines.

Synchrotron X-ray diagnostics of cutoff shape of nonthermal electron spectrum at young supernova remnants

Synchrotron X-rays can be a useful tool to investigate electron accelera- tion at young supemova remnants （SNRs）. At present, since the magnetic field con- figuration around the shocks of SNRs is uncertain, it is not clear whether electron acceleration is limited by SNR age, synchrotron cooling, or even escape from the ac- celeration region. We study whether the acceleration mechanism can be constrained by the cutoff shape of the electron spectrum around the maximum energy. We derive analytical formulae of the cutoff shape in each case where the maximum electron en- ergy is determined by SNR age, synchrotron cooling and escape from the shock. They are related to the energy dependence of the electron diffusion coefficient. Next, we discuss whether information on the cutoff shape can be provided by observations in the near future which will simply give the photon indices and the flux ratios in the soft and hard X-ray bands. We find that if the power-law index of the electron spectrum is independently determined by other observations, then we can constrain the cutoff shape by comparing theoretical predictions of the photon indices and/or the flux ratios with observed data which will be measured by NuSTAR and/or ASTRO-H. Such study is helpful in understanding the acceleration mechanism. In particular, it will supply another independent constraint on the magnetic field strength around the shocks of SNRs.