Temperature-dependent resistivity,upper critical field H_(c2)and its anisotropy in overdoped superconducting Ba_(1-x)K_x Fe_2As_2(x=0.6-1)single crystals have been measured in steady magnetic fields up to 44 T and low...Temperature-dependent resistivity,upper critical field H_(c2)and its anisotropy in overdoped superconducting Ba_(1-x)K_x Fe_2As_2(x=0.6-1)single crystals have been measured in steady magnetic fields up to 44 T and low temperatures down to 0.4 K.Analysis using both the quadratic term and power-law fitting demonstrates that the in-plane resistivityρ_(ab)(T)progressively approaches the Fermi-liquid T~2behavior with increasing K doping and reaches a saturation plateau at x≈0.8.The temperature dependence of both H_(c2)^(ab)and H^(c)_(c2)follows the Werthamer-Helfand-Hohenberg model,incorporating orbital and spin paramagnetic effects.For x≤0.8,the orbital effect dominates for H ab,while the Pauli paramagnetic effect prevails for H c.For x>0.8,the Pauli paramagnetic effect becomes dominant in both crystallographic directions.The anisotropy of H_(c2)(0)exhibits a discontinuity in its dependence on K doping concentration with a significant enhancement at x=0.8 and a maximum at x=0.9.These experimental results indicate that the electron correlation effect is enhanced in the heavily overdoped Ba_(1-x)K_(x)Fe_(2)As_(2)system where the underlying symmetries are broken due to the Fermi surface reconstruction before x=0.9.展开更多
Multi-component transition group metal borides(MMB_(2))have become a research hotspot due to their new composition design concepts and superior properties compared with conventional ceramics.Most of the current method...Multi-component transition group metal borides(MMB_(2))have become a research hotspot due to their new composition design concepts and superior properties compared with conventional ceramics.Most of the current methods,however,are complicated and time-consuming,the mass production remains a chal-lenge.Herein,we proposed a new high-efficiency strategy for synthesis of MMB_(2)using molten aluminum as the medium for the first time.The prepared Al-containing multi-component borides(TiZrHfNbTa)B_(2)microcrystals had a homogeneous composition with a hexagonal AlB_(2)structure and ultra-high hardness value of∼35.3 GPa,which was much higher than data reported in the literature and the rule of mix-ture estimations.Furthermore,combined with the First-principles calculation results,we found that the Poisson’s ratio(v)values exhibit a clearly ascending trend from 0.17 at VEC=3.5 to 0.18 at VEC=3.4,then to 0.201 at VEC=3.2 with the increasing of Al content.This indicates that the intrinsic toughness of multi-component boride microcrystals is obviously enhanced by the trace-doped Al elements.Besides,the fabricated Al-containing multi-component boride microcrystals have superior oxidation activation en-ergy and structural stability.The enhanced oxidation resistance is mainly attributed to the formation of a protective Al2 O3 oxide layer and the lattice distortion,both of which lead to sluggish diffusion of O_(2).These findings propose a new unexplored avenue for the fabrication of MMB_(2)materials with supe-rior comprehensive performance including ultra-hardness and intrinsically improved thermo-mechanical properties.展开更多
The unique structure and exceptional properties of two-dimensional(2D)materials offer significant potential for transformative advancements in semiconductor industry.Similar to the reliance on wafer-scale single-cryst...The unique structure and exceptional properties of two-dimensional(2D)materials offer significant potential for transformative advancements in semiconductor industry.Similar to the reliance on wafer-scale single-crystal ingots for silicon-based chips,practical applications of 2D materials at the chip level need large-scale,high-quality production of 2D single crystals.Over the past two decades,the size of 2D single-crystals has been improved to wafer or meter scale,where the nucleation control during the growth process is particularly important.Therefore,it is essential to conduct a comprehensive review of nucleation control to gain fundamental insights into the growth of 2D single-crystal materials.This review mainly focuses on two aspects:controlling nucleation density to enable the growth from a single nucleus,and controlling nucleation position to achieve the unidirectionally aligned islands and subsequent seamless stitching.Finally,we provide an overview and forecast of the strategic pathways for emerging 2D materials.展开更多
Based on the relationship between deformation microstructures and grain orientations,three characteristic Cu single crystals were used to investigate the opposite effects of ultrasonic superimposed high-strain-rate on...Based on the relationship between deformation microstructures and grain orientations,three characteristic Cu single crystals were used to investigate the opposite effects of ultrasonic superimposed high-strain-rate on the dislocation motion during ultrasonic welding(UW).The results revealed that equiaxed dislocation cells and discontinuous dynamic recrystallization(DRX)grains dominated in the joint microstructures.Three Cu single crystal joints exhibited an isotropic trend in grain orientation,welding quality,and microscopic mechanical properties.The preferred dislocation behaviors and DRX modes were further analyzed by modelling the stored energy difference,indicating that high mobility of intra-granular dislocations and homogeneous dislocation motion induced by the ultrasonic excitation were the intrinsic factors contributing to the formation of isotropic microstructures and welding quality.展开更多
Transition-metal monosilicide RhGe has been reported to exhibit weak itinerant ferromagnetism,superconductivity,and topological properties.In this study,we report the high-pressure growth of high-quality RhGe single c...Transition-metal monosilicide RhGe has been reported to exhibit weak itinerant ferromagnetism,superconductivity,and topological properties.In this study,we report the high-pressure growth of high-quality RhGe single crystals up to millimeter size using a flux method.Transport measurements reveal metallic behavior in RhGe from 2 K to 300 K with Fermi liquid behavior at low temperatures.However,no superconductivity was observed with variations in the Ge composition.Magnetic characterizations indicate that RhGe exhibits paramagnetic behavior between 2 K and 300 K.The high-quality and large-size RhGe single crystals pave the way for further investigation of their topological properties using spectroscopic techniques.展开更多
Polysynthetic twinned(PST)TiAl single crystal specifically refers to a fully lamellar TiAl single crystal with parallel phase interfaces and twin interfaces grown by directional solidification.In this paper,PST single...Polysynthetic twinned(PST)TiAl single crystal specifically refers to a fully lamellar TiAl single crystal with parallel phase interfaces and twin interfaces grown by directional solidification.In this paper,PST single crystals with different phase ratios are obtained by annealing at specific temperatures and holding times.The results show that the diffusion rates of Ti and Al elements at various temperatures directly trigger and propel the surface recrystallization and variation in the internal phase ratio.When the temperature is lower than 1448 K,the diffusion rate of Ti is obviously higher than that of Al,which causes one denseα_(2)recrystallized layer to form on the surface of TiAl single crystals.Meanwhile,as more Ti elements migrate to the surface,theα_(2)phase ratio inside the TiAl single crystal thereby decreases.When the temperature exceeds 1448 K,the diffusion rate of Al gradually reverses to exceed that of Ti,which forms the surface sandwiched recrystallization dominated byγphase and simultaneously increasesα_(2)phase ratio inside the TiAl single crystal.The variation in the two-phase ratio directly induces a significant change in the lamellae thickness,which exhibits different tensile behaviors of PST-TiAl single crystal.When theα_(2)phase content is less than 20%,widerγlamellae make it easier for dislocations to be activated within its lamellae and continuously move across theγ/α_(2)interfaces,thereby obtaining better tensile plasticity.As theα_(2)phase content exceeds 30%,finerγlamellae inhibit the dislocation initiation,resulting in the fracture occurrence of TiAl single crystal before yielding.No matter how the phase ratio changes,the crack preferentially initiates withinα_(2)lamellae.However,the crack propagation follows different paths based on variousγlamella thicknesses.The fracture mode of PST-TiAl single crystal also changes from shear fracture along slip bands within theγlamella to brittle fracture along the{1¯100}planes withinα_(2)lamella.展开更多
To enhance boron doping efficiency and reduce metal impurities in diamonds,selecting an appropriate metal solvent is essential for producing p-type diamonds using the high-pressure high-temperature(HPHT)method.This pa...To enhance boron doping efficiency and reduce metal impurities in diamonds,selecting an appropriate metal solvent is essential for producing p-type diamonds using the high-pressure high-temperature(HPHT)method.This paper presents a detailed study of the properties and characteristics of boron-doped diamond(BDD)single crystals grown using FeNi and FeCo solvents through the HPHT method.The results indicate that,with the same TiB_(2)addition ratio,BDD crystals grown using FeCo solvent have a higher concentration of uncompensated boron ions,resulting in improved boron doping efficiency.Additionally,by growing BDD in the same synthesis environment(FeCo-3 wt%TiB_(2))using(111)and(100)seed crystals as growth surfaces,it was found that the boron content in the crystal grown from the(100)seed crystal was higher than that in the crystal grown from the(111)seed crystal.Additionally,the crystals grown with the FeCo solvent contained fewer metal elements(Fe and Co)compared to those produced with the FeNi solvent(Fe and Ni),which supported the growth of high-quality BDD single crystals.This indicated that the choice of growth planes significantly influences the incorporation of boron in diamonds.Our findings hold significant research value for the development of high-quality p-type diamond semiconductors using the HPHT method.展开更多
Although three-dimensional metal halide perovskites are promising candidates for direct X-ray detection,the ion migration of perovskites seriously affects the detector stability.Herein,face-/edge-shared 3D heterometal...Although three-dimensional metal halide perovskites are promising candidates for direct X-ray detection,the ion migration of perovskites seriously affects the detector stability.Herein,face-/edge-shared 3D heterometallic glycinate hybrid perovskitoid Pb_(2)CuGly_(2)X_(4)(Gly=-O_(2)C-CH_(2)-NH_(2);X=Cl,Br)single crystals(SCs),in which the adjacent lead halide layers are linked by large-sized Cu(Gly)_(2)pillars,are synthesized in water.The Cu(Gly)_(2)pillars in combination with face-/edge-shared inorganic skeleton are found able to synergistically suppress the ion migration,delivering a high ion migration activation energy(Ea)of 1.06 eV.The Pb_(2)CuGly_(2)Cl_(4)SC X-ray detector displays extremely low dark current drift of 1.20×10^(-9)nA mm^(-1)s^(-1)V^(-1)under high electric field(120 V mm^(-1))and continuous X-ray irradiation(2.86 Gy),and a high sensitivity of 9,250μC Gy^(-1)cm^(-2)is also achieved.More excitingly,the Pb_(2)CuGly_(2)Cl_(4)nanocrystal can be easily dispersed in water and directly blade-coated on thin-film transistor(TFT)array substrate,and the obtained Pb_(2)CuGly_(2)Cl_(4)-based TFT array detector offers an X-ray imaging capability with spatial resolution of 2.2 lp mm^(-1).展开更多
Uranium extraction from seawater(UES)is crucial for reducing nuclear fuel supply pressure and promoting the comprehensive utilization of marine resources.The successful implementations of UES engineering critically re...Uranium extraction from seawater(UES)is crucial for reducing nuclear fuel supply pressure and promoting the comprehensive utilization of marine resources.The successful implementations of UES engineering critically rely on the highly efficient sorbent materials with exceptional performance in binding uranyl ions.Herein,a universal and facile“organic ion building blocks self-assembly”strategy is established to realize a first class of carboxyl functionalized ionic single crystals,named BPTC-BPY-R(R=1–6,the R corresponds to alkyl chain length modifier,e.g.,R=1 corresponds to iodomethane derivatives,R=2 corresponds to bromoethane derivatives,etc.),derived from rationally designed viologen-derivatives with different alkyl chain lengths and polycarboxylic acid.This strategy effectively exploits the organic ion building block properties to achieve U(VI)adsorption based on the synergistic effects of anions(ligand interaction)and cations(electrostatic interaction).Notably,attributed to the special crystal stacking mode and higher specific surface area,the resulting BPTC-BPY-3 not only achieves ultrahigh selectivity for U(VI)adsorption with a partition coefficient of 3.998×10^(6) mL/g,but also possesses an ultrafast U(VI)adsorption kinetics and an uptake capacity of 686.8 mg/g within 2 min.More importantly,it realizes a U(VI)uptake capacity of 7.41 mg/g from natural seawater in 20 days.The designed material with ultra-selectivity,high capacity,ultrafast kinetics,and good recyclability exhibits a great promise for efficient U(VI)extraction from seawater.展开更多
SnSe_(2) single crystals,as novel n-type plastic thermoelectric materials,present advantages such as envi-ronmental sustainability and cost-effectiveness.Single crystals of SnSe_(2)+x%PbBr_(2)(x=0,0.5,1,2,and 3)with l...SnSe_(2) single crystals,as novel n-type plastic thermoelectric materials,present advantages such as envi-ronmental sustainability and cost-effectiveness.Single crystals of SnSe_(2)+x%PbBr_(2)(x=0,0.5,1,2,and 3)with large size and high quality were successfully synthesized via the Bridgman method.The significant enhancement in power factor and effective suppression of lattice thermal conductivity can be achieved through PbBr_(2) doping,verifying a synergistic optimization of electrical and thermal transport properties.Specifically,Br atoms are effectively incorporated into the Se sites to manipulate the carrier concentra-tion and optimize the power factor,while simultaneously inducing a strong phonon softening effect by introducing Pb atoms at the Sn sites,which leads to a reduced phonon group velocity and a suppres-sion of lattice thermal conductivity.Consequently,SnSe_(2)+2%PbBr_(2) single-crystal sample achieves a peak figure of merit zT of~0.76 and an average zT of~0.51,giving rise to corresponding improvements of~533% and~538%,respectively,compared to the pristine SnSe_(2) sample,thereby outperforming most of the previously reported SnSe_(2)-based materials.This work provides a viable approach for promoting the thermoelectric performance of SnSe^(2)-based single crystals across a broad temperature range and supports the advancement of plastic thermoelectric materials.展开更多
Chiral topological semimetals hosting multifold fermions and exotic surface states represent a frontier in topological materials research. Among them, noncentrosymmetric cubic B20 compounds—notably transitionmetal si...Chiral topological semimetals hosting multifold fermions and exotic surface states represent a frontier in topological materials research. Among them, noncentrosymmetric cubic B20 compounds—notably transitionmetal silicides and germanides—offer a unique platform for realizing symmetry-protected topological phases and unconventional optoelectronic responses. Here, we report the physical properties of Rh Ge and Co Ge single crystals with B20 structure in detail. Transport measurements revea metallic behavior with characteristic Fermi-liquid scaling at low temperatures, while magnetization results confirm paramagnetism in both compounds. In addition,both materials exhibit low carrier concentrations with small electronic specific heat coefficients, indicating their semimetal feature with weak electronic correlations. Such high-quality Co Ge and Rh Ge single crystals provide a material platform to explore the evolution of multifold fermions and the instability of helicoid-arc surface states with spin–orbit coupling and surface environment in B20 material systems.展开更多
The(010)-oriented substrates of β-Ga_(2)O_(3) are endowed with the maximum thermal conductivity and fastest homoepi-taxial rate,which is the preferred substrate direction for high-power devices.However,the size of(01...The(010)-oriented substrates of β-Ga_(2)O_(3) are endowed with the maximum thermal conductivity and fastest homoepi-taxial rate,which is the preferred substrate direction for high-power devices.However,the size of(010)plane wafer is critically limited by die in the commercial edge-defined film-fed growth(EFG)method.It is difficult to grow the β-Ga_(2)O_(3) crystal with(010)principal face due to the(100)and(001)are cleavage planes.Here,the 2-inch diameter(010)principal-face β-Ga_(2)O_(3) sin-gle crystal is successfully designed and grown by improved EFG method.Unlike previous reported techniques,the single crys-tals are pulled with[001]direction,and in this way the(010)wafers can be obtained from the principal face.In our experi-ments,tree-like defects(TLDs)in(010)principal-face bulk crystals are easy to generate.The relationship between stability of growth interface and origin of TLDs are thoroughly discussed.The TLDs are successfully eliminated by optimizing growth condi-tions.The high crystalline quality of(010)-oriented substrates are comprehensive demonstrated by full width at half maximum(FWHM)with 50.4 arcsec,consistent orientation arrangement of(010)plane,respectively.This work shows that the(010)-ori-ented substrates can be obtained by EFG method,predicting the commercial prospects of large-scale(010)-oriented β-Ga_(2)O_(3) substrates.展开更多
The high-cycle fatigue fracture characteristics and damage mechanism of nickel-based single crystal superalloys at 850℃ was investigated.The results indicate that high-cycle fatigue cracks in single crystal superallo...The high-cycle fatigue fracture characteristics and damage mechanism of nickel-based single crystal superalloys at 850℃ was investigated.The results indicate that high-cycle fatigue cracks in single crystal superalloys generally originate from defect locations on the subsurface or interior of the specimen at 850℃.Under the condition of stress ratio R=0.05,as the fatigue load decreases,the high-cycle fatigue life gradually increases.The high-cycle fatigue fracture is mainly characterized by octahedral slip mechanism.At high stress and low lifespan,the fracture exhibits single or multiple slip surface features.Some fractures originate along a vertical small plane and then propagate along the{111}slip surface.At low stress and high lifespan,the fracture surface tend to alternate and expand along multiple slip planes after originating from subsurface or internal sources,exhibiting characteristics of multiple slip planes.Through electron backscatter diffraction and transmission electron microscope analysis,there is obvious oxidation behavior on the surface of the high-cycle fatigue fracture,and the fracture section is composed of oxidation layer,distortion layer,and matrix layer from the outside to the inside.Among them,the main components of the oxidation layer are oxides of Ni and Co.The distortion layer is mainly distributed in the form of elongated or short rod-shaped oxides of Al,Ta,and W.The matrix layer is a single crystal layer.Crack initiation and propagation mechanism were obtained by systematical analysis of a large number of highcycle fatigue fractures.In addition,the stress ratio of 0.05 is closer to the vibration mode of turbine blades during actual service,providing effective guidance for the study of failure and fracture mechanisms of turbine blades.展开更多
In contrast to research on active sites in nanomaterials,lithium tantalate single crystals,known for their exceptional optical properties and long-range ordered lattice structure,present a promising avenue for in-dept...In contrast to research on active sites in nanomaterials,lithium tantalate single crystals,known for their exceptional optical properties and long-range ordered lattice structure,present a promising avenue for in-depth exploration of photocatalytic reaction systems with fewer constraints imposed by surface chemistry.Typically,the isotropy of a specific facet provides a perfect support for studying heteroatom doping.Herein,this work delves into the intrinsic catalytic sites for photocatalytic nitrogen fixation in iron-doped lithium tantalate single crystals.The presence of iron not only modifies the electronic structure of lithium tantalate,improving its light absorption capacity,but also functions as an active site for the nitrogen adsorption and activation.The photocatalytic ammonia production rate of the iron-doped lithium tantalate in pure water is maximum 26.95μg cm^(−2)h^(−1),which is three times higher than that of undoped lithium tantalate.The combination of first-principles simulations with in situ characterizations confirms that iron doping promotes the rate-determining step and changes the pathway of hydrogenation to associative alternating.This study provides a new perspective on in-depth investigation of intrinsic catalytic active sites in photocatalysis and other catalytic processes.展开更多
Downconversion (DC) with emission of two near-infrared photons about 1000 nm for each blue photon absorbed was obtained in thulium (Tm3+) and ytterbium (Yb3+) codoped yt- trium lithium fluoride (LiYF4) singl...Downconversion (DC) with emission of two near-infrared photons about 1000 nm for each blue photon absorbed was obtained in thulium (Tm3+) and ytterbium (Yb3+) codoped yt- trium lithium fluoride (LiYF4) single crystals grown by an improved Bridgman method. The luminescent properties of the crystals were measured through photoluminescence excitation, emission spectra and decay curves. Luminescence between 960 and 1050 nm from yb3+: 2Fs/2--+2FT/2 transition, which was originated from the DC from Tm3+ ions to Yb3+ ions, was observed under the excitation of blue photon at 465 nm. Moreover, the energy transfer processes were studied based on the Inokuti-Hirayama model, and the results indicated that the energy transfer from Tm3+ to Yb3+ was an electric dipole-dipole interaction. The max- imum quantum cutting efficiency approached with 0.49mo1% Tm3+ and 5.99mo1% Yb3+. increasing the energy efficiency of crystalline energy part of the solar spectrum. up to 167.5% in LiYF4 single crystal codoped Application of this crystal has prospects for Si solar cells by photon doubling of the high展开更多
Arising from the increasing demand for electric vehicles(EVs),Ni-rich LiNi_(x)Co_(y)Mn_(z)O_(2)(NCM,x+y+z=1,x≥0.8)cathode with greatly increased energy density are being researched and commercialized for lithium-ion ...Arising from the increasing demand for electric vehicles(EVs),Ni-rich LiNi_(x)Co_(y)Mn_(z)O_(2)(NCM,x+y+z=1,x≥0.8)cathode with greatly increased energy density are being researched and commercialized for lithium-ion batteries(LIBs).However,parasitic crack formation during the discharge–charge cycling process remains as a major degradation mechanism.Cracking leads to increase in the specific surface area,loss of electrical contact between the primary particles,and facilitates liquid electrolyte infiltration into the cathode active material,accelerating capacity fading and decrease in lifetime.In contrast,Ni-rich NCM when used as a single crystal exhibits superior cycling performances due to its rigid mechanical property that resists cracking during long charge–discharge process even under harsh conditions.In this paper,we present comparative investigation between single crystal Ni-rich LiNi_(0.92)Co_(0.04)Mn_(0.04)O_(2)(SC)and polycrystalline Ni-rich LiNi_(0.92)Co_(0.04)Mn_(0.04)O_(2)(PC).The relatively improved cycling performances of SC are attributed to smaller anisotropic volume change,higher reversibility of phase transition,and resistance to crack formation.The superior properties of SC are demonstrated by in situ characterization and battery tests.Consequently,it is inferred from the results obtained that optimization of preparation conditions can be regarded as a key approach to obtain well crystallized and superior electrochemical performances.展开更多
Sulfide-based all-solid-state lithium batteries suffer from electrochemo-mechanical damage to Ni-rich oxide-based cathode active materials(CAMs),primarily caused by severe volume changes,results in significant stress ...Sulfide-based all-solid-state lithium batteries suffer from electrochemo-mechanical damage to Ni-rich oxide-based cathode active materials(CAMs),primarily caused by severe volume changes,results in significant stress and strain,causes micro-cracks and interfacial contact loss at potentials>4.3 V(vs.Li/Li^(+)).Quantifying micro-cracks and voids in CAMs can reveal the degradation mechanisms of Ni-rich oxidebased cathodes during electrochemical cycling.Nonetheless,the origin of electrochemical-mechanical damage remains unclear.Herein,We have developed a multifunctional PEG-based soft buffer layer(SBL)on the surface of carbon black(CB).This layer functions as a percolation network in the single crystal LiNi_(0.83)Co_(0.07)Mn_(0.1)O_(2)and Li_(6)PS_(5)Cl composite cathode layer,ensuring superior ionic conductivity,reducing void formation and particle cracking,and promoting uniform utilization of the cathode active material in all-solid-state lithium batteries(ASSLBs).High-angle annular dark-field STEM combined with nanoscale X-ray holo-tomography and plasma-focused ion beam scanning electron microscopy confirmed that the PEG-based SBL mitigated strain induced by reaction heterogeneity in the cathode.This strain produces lattice stretches,distortions,and curved transition metal oxide layers near the surface,contributing to structural degradation at elevated voltages.Consequently,ASSLBs with a LiNi_(0.83)Co_(0.07)Mn_(0.1)O_(2)cathode containing LCCB-10(CB/PEG mass ratio:100/10)demonstrate a high areal capacity(2.53 mAh g^(-1)/0.32 mA g^(-1))and remarkable rate capability(0.58 mAh g^(-1)at 1.4 mA g^(-1)),with88%capacity retention over 1000 cycles.展开更多
The deformation and fracture of a third-generation single crystal superalloy during in-situ tension at room temperature were investigated at multiple scales by scanning electron microscope,electron back-scattered diff...The deformation and fracture of a third-generation single crystal superalloy during in-situ tension at room temperature were investigated at multiple scales by scanning electron microscope,electron back-scattered diffractometer,and transmission electron microscope to reveal the deformation and fracture mechanism during tension.The proportion of low angle boundaries(LABs)with angles from 2.5°to 5.5°increases during tension.The change in LABs is particularly pronounced after elongation over 7%.The initiation of microcracks is caused by{111}<110>slip systems.After initiation,the crack size along the stress direction increases whereas the size extension along slip systems is suppressed.The fracture mode of the alloy is quasi-cleavage fracture and the slip lines near the fracture are implicit at room temperature.展开更多
Interrupted and ruptured creep tests were conducted on single crystal superalloy DD9 at 980℃/250 MPa and 1100℃/137 MPa conditions.Microstructure evolution during creep was analyzed through scanning electron microsco...Interrupted and ruptured creep tests were conducted on single crystal superalloy DD9 at 980℃/250 MPa and 1100℃/137 MPa conditions.Microstructure evolution during creep was analyzed through scanning electron microscope and transmission electron microscope.Results show that the microstructure evolutions are similar under the creep conditions of 980℃/250 MPa and 1100℃/137 MPa.Cubicalγ′phase,which is dispersedly distributed in theγmatrix,gradually evolves into a layered structure perpendicular to the stress direction.The width of theγmatrix channel along the direction parallel to the stress increases.The relationship between the increase in width of theγmatrix channel and the strain satisfies linear relationship in logarithmic form,indicating that the width of theγmatrix can be deduced via the strain under creep state.This may provide an approach to investigate the width ofγmatrix in single crystal superalloys during creep under high temperature and low stress conditions.In the early creep stage,dislocations formed in theγphase generate mutually perpendicular networks through cross-slip at theγ/γ′interface.Then,stable hexagonal dislocation networks form as a result of the coupling effects of external stress and mismatch stress at high temperatures.In the later period of creep,dislocations shear theγ′phase,ultimately causing the fracture.展开更多
The microstructure of single crystal superalloy is relatively simple,consisting primarily ofγdendrites andγ/γ′eutectics.During the directional solidification process of Ni-based single crystal superalloys,withdraw...The microstructure of single crystal superalloy is relatively simple,consisting primarily ofγdendrites andγ/γ′eutectics.During the directional solidification process of Ni-based single crystal superalloys,withdrawal rate is a critical parameter affecting the spatial distribution ofγ/γ′eutectic along gravity direction.The results show that theγ/γ′eutectic fraction of the upper platform surface is always higher than that of the lower one,regardless of withdrawal rate.As the withdrawal rate decreases,there is a significant increase inγ/γ′eutectic fraction on the upper surface,while it decreases on the lower surface.The upward accumulation ofγ/γ′eutectic becomes more severe as the withdrawal rate decreases.It is also found that the percentage of Al+Ta is positively correlated with theγ/γ′eutectic fraction.Thermo-solute convection of Al and Ta solutes in the solidification front is the prime reason for the non-uniform distribution of eutectic.The non-uniform distribution ofγ/γ′eutectic cannot be eliminated even after subsequent solution heat treatment,resulting in excess eutectic on the upper surface and thus leading to the scrapping of the blade.展开更多
基金supported by the National Key Research and Development Program of China(Grant Nos.2024YFA1611100,2023YFA1406100,and 2018YFA0704201)the Systematic Fundamental Research Program Leveraging Major Scientific and Technological Infrastructure,Chinese Academy of Sciences(Grant No.JZHKYPT-2021-08)+1 种基金the National Natural Science Foundation of China(Grant Nos.11704385,11874359,and 12274444)the Strategic Priority Research Program(B)of the Chinese Academy of Sciences(Grant No.XDB25000000)。
文摘Temperature-dependent resistivity,upper critical field H_(c2)and its anisotropy in overdoped superconducting Ba_(1-x)K_x Fe_2As_2(x=0.6-1)single crystals have been measured in steady magnetic fields up to 44 T and low temperatures down to 0.4 K.Analysis using both the quadratic term and power-law fitting demonstrates that the in-plane resistivityρ_(ab)(T)progressively approaches the Fermi-liquid T~2behavior with increasing K doping and reaches a saturation plateau at x≈0.8.The temperature dependence of both H_(c2)^(ab)and H^(c)_(c2)follows the Werthamer-Helfand-Hohenberg model,incorporating orbital and spin paramagnetic effects.For x≤0.8,the orbital effect dominates for H ab,while the Pauli paramagnetic effect prevails for H c.For x>0.8,the Pauli paramagnetic effect becomes dominant in both crystallographic directions.The anisotropy of H_(c2)(0)exhibits a discontinuity in its dependence on K doping concentration with a significant enhancement at x=0.8 and a maximum at x=0.9.These experimental results indicate that the electron correlation effect is enhanced in the heavily overdoped Ba_(1-x)K_(x)Fe_(2)As_(2)system where the underlying symmetries are broken due to the Fermi surface reconstruction before x=0.9.
基金financially supported by the National Natural Science Foundation of China(Nos.52271033 and 52071179)the Key program of National Natural Science Foundation of China(No.51931003)+2 种基金Natural Science Foundation of Jiangsu Province,China(No.BK20221493)Jiangsu Province Leading Edge Technology Basic Research Major Project(No.BK20222014)Foundation of“Qinglan Project”for Colleges and Universities in Jiangsu Province.
文摘Multi-component transition group metal borides(MMB_(2))have become a research hotspot due to their new composition design concepts and superior properties compared with conventional ceramics.Most of the current methods,however,are complicated and time-consuming,the mass production remains a chal-lenge.Herein,we proposed a new high-efficiency strategy for synthesis of MMB_(2)using molten aluminum as the medium for the first time.The prepared Al-containing multi-component borides(TiZrHfNbTa)B_(2)microcrystals had a homogeneous composition with a hexagonal AlB_(2)structure and ultra-high hardness value of∼35.3 GPa,which was much higher than data reported in the literature and the rule of mix-ture estimations.Furthermore,combined with the First-principles calculation results,we found that the Poisson’s ratio(v)values exhibit a clearly ascending trend from 0.17 at VEC=3.5 to 0.18 at VEC=3.4,then to 0.201 at VEC=3.2 with the increasing of Al content.This indicates that the intrinsic toughness of multi-component boride microcrystals is obviously enhanced by the trace-doped Al elements.Besides,the fabricated Al-containing multi-component boride microcrystals have superior oxidation activation en-ergy and structural stability.The enhanced oxidation resistance is mainly attributed to the formation of a protective Al2 O3 oxide layer and the lattice distortion,both of which lead to sluggish diffusion of O_(2).These findings propose a new unexplored avenue for the fabrication of MMB_(2)materials with supe-rior comprehensive performance including ultra-hardness and intrinsically improved thermo-mechanical properties.
基金supported by the National Natural Science Foundation of China(12322406,12404208)the National Key R&D Program of China(2022YFA1403503)+2 种基金China Postdoctoral Science Foundation(2024M750970)the Science and Technology Program of Guangzhou(SL2024A04J00033)the Scientific Research lnnovation Project of Graduate School of South China Normal University.
文摘The unique structure and exceptional properties of two-dimensional(2D)materials offer significant potential for transformative advancements in semiconductor industry.Similar to the reliance on wafer-scale single-crystal ingots for silicon-based chips,practical applications of 2D materials at the chip level need large-scale,high-quality production of 2D single crystals.Over the past two decades,the size of 2D single-crystals has been improved to wafer or meter scale,where the nucleation control during the growth process is particularly important.Therefore,it is essential to conduct a comprehensive review of nucleation control to gain fundamental insights into the growth of 2D single-crystal materials.This review mainly focuses on two aspects:controlling nucleation density to enable the growth from a single nucleus,and controlling nucleation position to achieve the unidirectionally aligned islands and subsequent seamless stitching.Finally,we provide an overview and forecast of the strategic pathways for emerging 2D materials.
基金supported by the National Natural Science Foundation of China(Nos.52175310,52232004)the Launch Research Program of Fuzhou University,China(No.XRC-23083)+1 种基金the Education&Research Project of Fujian Province,China(No.JAT231003)the Open Test Fund for Valuable Instruments and Equipment of Fuzhou University,China(No.2024T036).
文摘Based on the relationship between deformation microstructures and grain orientations,three characteristic Cu single crystals were used to investigate the opposite effects of ultrasonic superimposed high-strain-rate on the dislocation motion during ultrasonic welding(UW).The results revealed that equiaxed dislocation cells and discontinuous dynamic recrystallization(DRX)grains dominated in the joint microstructures.Three Cu single crystal joints exhibited an isotropic trend in grain orientation,welding quality,and microscopic mechanical properties.The preferred dislocation behaviors and DRX modes were further analyzed by modelling the stored energy difference,indicating that high mobility of intra-granular dislocations and homogeneous dislocation motion induced by the ultrasonic excitation were the intrinsic factors contributing to the formation of isotropic microstructures and welding quality.
基金supported by the National Key Research&Development Program of China(Grant Nos.2023YFA1406000,2022YFA1403800,2021YFA1400300,and 2023YFA1406500)the National Natural Science Foundation of China(Grant Nos.12474002,22171283,12425403,12261131499,12304268,and 12274459)the China Postdoctoral Science Foundation(Grant Nos.2023M730011 and 2023M743741).
文摘Transition-metal monosilicide RhGe has been reported to exhibit weak itinerant ferromagnetism,superconductivity,and topological properties.In this study,we report the high-pressure growth of high-quality RhGe single crystals up to millimeter size using a flux method.Transport measurements reveal metallic behavior in RhGe from 2 K to 300 K with Fermi liquid behavior at low temperatures.However,no superconductivity was observed with variations in the Ge composition.Magnetic characterizations indicate that RhGe exhibits paramagnetic behavior between 2 K and 300 K.The high-quality and large-size RhGe single crystals pave the way for further investigation of their topological properties using spectroscopic techniques.
基金supported by the National Natural Science Foundation of China(NSFC)under Grant Nos.52288102,52322101,92163215,52174364,52101143,U23A20542the Fundamental Research Funds for the Central Universities under Grant No.30922010202+1 种基金the 100 Talents Plan of Hebei Province under Grant No.E2020100005the Natural Science Foundation of Hebei Province under Grant No.E2022203109.
文摘Polysynthetic twinned(PST)TiAl single crystal specifically refers to a fully lamellar TiAl single crystal with parallel phase interfaces and twin interfaces grown by directional solidification.In this paper,PST single crystals with different phase ratios are obtained by annealing at specific temperatures and holding times.The results show that the diffusion rates of Ti and Al elements at various temperatures directly trigger and propel the surface recrystallization and variation in the internal phase ratio.When the temperature is lower than 1448 K,the diffusion rate of Ti is obviously higher than that of Al,which causes one denseα_(2)recrystallized layer to form on the surface of TiAl single crystals.Meanwhile,as more Ti elements migrate to the surface,theα_(2)phase ratio inside the TiAl single crystal thereby decreases.When the temperature exceeds 1448 K,the diffusion rate of Al gradually reverses to exceed that of Ti,which forms the surface sandwiched recrystallization dominated byγphase and simultaneously increasesα_(2)phase ratio inside the TiAl single crystal.The variation in the two-phase ratio directly induces a significant change in the lamellae thickness,which exhibits different tensile behaviors of PST-TiAl single crystal.When theα_(2)phase content is less than 20%,widerγlamellae make it easier for dislocations to be activated within its lamellae and continuously move across theγ/α_(2)interfaces,thereby obtaining better tensile plasticity.As theα_(2)phase content exceeds 30%,finerγlamellae inhibit the dislocation initiation,resulting in the fracture occurrence of TiAl single crystal before yielding.No matter how the phase ratio changes,the crack preferentially initiates withinα_(2)lamellae.However,the crack propagation follows different paths based on variousγlamella thicknesses.The fracture mode of PST-TiAl single crystal also changes from shear fracture along slip bands within theγlamella to brittle fracture along the{1¯100}planes withinα_(2)lamella.
基金supported by the National Natural Science Foundation of China(Grant Nos.12274373 and 12274372)the Natural Science Foundation of Henan Province(Grant Nos.242300421155 and 252300421475)+2 种基金the Key Research Projects of Higher Education Institutions in Henan Province(Grant No.25A140008)the Natural Science Foundation of Chongqing,China(Grant Nos.CSTB2023NSCQ-LZX0100 and CSTB2023NSCQ-MSX0362)Central Plains Science and Technology Innovation Youth Top Notch Talents,and Independent Innovation Project for Graduate Students of Zhengzhou University(Grant No.20250450).
文摘To enhance boron doping efficiency and reduce metal impurities in diamonds,selecting an appropriate metal solvent is essential for producing p-type diamonds using the high-pressure high-temperature(HPHT)method.This paper presents a detailed study of the properties and characteristics of boron-doped diamond(BDD)single crystals grown using FeNi and FeCo solvents through the HPHT method.The results indicate that,with the same TiB_(2)addition ratio,BDD crystals grown using FeCo solvent have a higher concentration of uncompensated boron ions,resulting in improved boron doping efficiency.Additionally,by growing BDD in the same synthesis environment(FeCo-3 wt%TiB_(2))using(111)and(100)seed crystals as growth surfaces,it was found that the boron content in the crystal grown from the(100)seed crystal was higher than that in the crystal grown from the(111)seed crystal.Additionally,the crystals grown with the FeCo solvent contained fewer metal elements(Fe and Co)compared to those produced with the FeNi solvent(Fe and Ni),which supported the growth of high-quality BDD single crystals.This indicated that the choice of growth planes significantly influences the incorporation of boron in diamonds.Our findings hold significant research value for the development of high-quality p-type diamond semiconductors using the HPHT method.
基金financially supported by the National Natural Science Foundation of China (62004089,62374053, 62474187 and 12235006)the Special Zone Support Program for Outstanding Talents of Henan University+4 种基金the Shenzhen Basic Research Program (JCYJ20220818101612027)the Guangdong Basic and Applied Basic Research Foundation (2024A1515012494)the Henan Province Postdoctoral Science Foundation (J23029Y)the Natural Science Foundation of Henan Province (232300420412)the Science and Technology Tackling Project of Henan Province (242102210160)
文摘Although three-dimensional metal halide perovskites are promising candidates for direct X-ray detection,the ion migration of perovskites seriously affects the detector stability.Herein,face-/edge-shared 3D heterometallic glycinate hybrid perovskitoid Pb_(2)CuGly_(2)X_(4)(Gly=-O_(2)C-CH_(2)-NH_(2);X=Cl,Br)single crystals(SCs),in which the adjacent lead halide layers are linked by large-sized Cu(Gly)_(2)pillars,are synthesized in water.The Cu(Gly)_(2)pillars in combination with face-/edge-shared inorganic skeleton are found able to synergistically suppress the ion migration,delivering a high ion migration activation energy(Ea)of 1.06 eV.The Pb_(2)CuGly_(2)Cl_(4)SC X-ray detector displays extremely low dark current drift of 1.20×10^(-9)nA mm^(-1)s^(-1)V^(-1)under high electric field(120 V mm^(-1))and continuous X-ray irradiation(2.86 Gy),and a high sensitivity of 9,250μC Gy^(-1)cm^(-2)is also achieved.More excitingly,the Pb_(2)CuGly_(2)Cl_(4)nanocrystal can be easily dispersed in water and directly blade-coated on thin-film transistor(TFT)array substrate,and the obtained Pb_(2)CuGly_(2)Cl_(4)-based TFT array detector offers an X-ray imaging capability with spatial resolution of 2.2 lp mm^(-1).
基金supported by the National Natural Science Foundation of China(No.22374159)the Youth Innovation Promotion Association CAS(No.2021420).
文摘Uranium extraction from seawater(UES)is crucial for reducing nuclear fuel supply pressure and promoting the comprehensive utilization of marine resources.The successful implementations of UES engineering critically rely on the highly efficient sorbent materials with exceptional performance in binding uranyl ions.Herein,a universal and facile“organic ion building blocks self-assembly”strategy is established to realize a first class of carboxyl functionalized ionic single crystals,named BPTC-BPY-R(R=1–6,the R corresponds to alkyl chain length modifier,e.g.,R=1 corresponds to iodomethane derivatives,R=2 corresponds to bromoethane derivatives,etc.),derived from rationally designed viologen-derivatives with different alkyl chain lengths and polycarboxylic acid.This strategy effectively exploits the organic ion building block properties to achieve U(VI)adsorption based on the synergistic effects of anions(ligand interaction)and cations(electrostatic interaction).Notably,attributed to the special crystal stacking mode and higher specific surface area,the resulting BPTC-BPY-3 not only achieves ultrahigh selectivity for U(VI)adsorption with a partition coefficient of 3.998×10^(6) mL/g,but also possesses an ultrafast U(VI)adsorption kinetics and an uptake capacity of 686.8 mg/g within 2 min.More importantly,it realizes a U(VI)uptake capacity of 7.41 mg/g from natural seawater in 20 days.The designed material with ultra-selectivity,high capacity,ultrafast kinetics,and good recyclability exhibits a great promise for efficient U(VI)extraction from seawater.
基金financially supported by the National Natural Science Foundation of China(Nos.52125103,52371212,52071041,12204080,12374002)the Scientific and Technological Research Program of Chongqing Municipal Education Commission(Nos.KJQN202400604,KJQN202200623,KJZD-K202100602)+1 种基金the Fundamental Research Funds for the Central Universities(Nos.2024IAIS-ZX002,2023CDJKYJH006)the Natural Science Foundation of Chongqing(No.CSTB2022NSCQ-MSX0382).
文摘SnSe_(2) single crystals,as novel n-type plastic thermoelectric materials,present advantages such as envi-ronmental sustainability and cost-effectiveness.Single crystals of SnSe_(2)+x%PbBr_(2)(x=0,0.5,1,2,and 3)with large size and high quality were successfully synthesized via the Bridgman method.The significant enhancement in power factor and effective suppression of lattice thermal conductivity can be achieved through PbBr_(2) doping,verifying a synergistic optimization of electrical and thermal transport properties.Specifically,Br atoms are effectively incorporated into the Se sites to manipulate the carrier concentra-tion and optimize the power factor,while simultaneously inducing a strong phonon softening effect by introducing Pb atoms at the Sn sites,which leads to a reduced phonon group velocity and a suppres-sion of lattice thermal conductivity.Consequently,SnSe_(2)+2%PbBr_(2) single-crystal sample achieves a peak figure of merit zT of~0.76 and an average zT of~0.51,giving rise to corresponding improvements of~533% and~538%,respectively,compared to the pristine SnSe_(2) sample,thereby outperforming most of the previously reported SnSe_(2)-based materials.This work provides a viable approach for promoting the thermoelectric performance of SnSe^(2)-based single crystals across a broad temperature range and supports the advancement of plastic thermoelectric materials.
基金supported by National Key R&D Program of China (Grant Nos.2022-YFA1403800,2023YFA1406000,and 2023YFA1406500)the National Natural Science Foundation of China (Grant Nos.12274459,12474002,22171283,and 52130103)+1 种基金China Postdoctoral Science Foundation (Grant No.2023M730011)supported by the Synergetic Extreme Condition User Facility (SECUF,https://cstr.cn/31123.02.SECUF)。
文摘Chiral topological semimetals hosting multifold fermions and exotic surface states represent a frontier in topological materials research. Among them, noncentrosymmetric cubic B20 compounds—notably transitionmetal silicides and germanides—offer a unique platform for realizing symmetry-protected topological phases and unconventional optoelectronic responses. Here, we report the physical properties of Rh Ge and Co Ge single crystals with B20 structure in detail. Transport measurements revea metallic behavior with characteristic Fermi-liquid scaling at low temperatures, while magnetization results confirm paramagnetism in both compounds. In addition,both materials exhibit low carrier concentrations with small electronic specific heat coefficients, indicating their semimetal feature with weak electronic correlations. Such high-quality Co Ge and Rh Ge single crystals provide a material platform to explore the evolution of multifold fermions and the instability of helicoid-arc surface states with spin–orbit coupling and surface environment in B20 material systems.
基金support by the fund of the National Natural Science Foundation of China(NSFC)(Grant No.U23A20358,51932004)Key-Area Research and Development Program of Guangdong Province(Grant No.2020B010174002)+3 种基金Natural Science Foundation of Shandong Province(Grant No.ZR2023ZD05,2022TSGC2120)the Shenzhen Fundamental Research Program(Grant No.GJHZ20220913142605011)the 111 Project 2.0(Grant No.BP2018013)Laboratory Construction and Management Research Project of Shandong University(Grant No.sy20233203)。
文摘The(010)-oriented substrates of β-Ga_(2)O_(3) are endowed with the maximum thermal conductivity and fastest homoepi-taxial rate,which is the preferred substrate direction for high-power devices.However,the size of(010)plane wafer is critically limited by die in the commercial edge-defined film-fed growth(EFG)method.It is difficult to grow the β-Ga_(2)O_(3) crystal with(010)principal face due to the(100)and(001)are cleavage planes.Here,the 2-inch diameter(010)principal-face β-Ga_(2)O_(3) sin-gle crystal is successfully designed and grown by improved EFG method.Unlike previous reported techniques,the single crys-tals are pulled with[001]direction,and in this way the(010)wafers can be obtained from the principal face.In our experi-ments,tree-like defects(TLDs)in(010)principal-face bulk crystals are easy to generate.The relationship between stability of growth interface and origin of TLDs are thoroughly discussed.The TLDs are successfully eliminated by optimizing growth condi-tions.The high crystalline quality of(010)-oriented substrates are comprehensive demonstrated by full width at half maximum(FWHM)with 50.4 arcsec,consistent orientation arrangement of(010)plane,respectively.This work shows that the(010)-ori-ented substrates can be obtained by EFG method,predicting the commercial prospects of large-scale(010)-oriented β-Ga_(2)O_(3) substrates.
基金National Science and Technology Major Project(J2019-VI-0022-0138)。
文摘The high-cycle fatigue fracture characteristics and damage mechanism of nickel-based single crystal superalloys at 850℃ was investigated.The results indicate that high-cycle fatigue cracks in single crystal superalloys generally originate from defect locations on the subsurface or interior of the specimen at 850℃.Under the condition of stress ratio R=0.05,as the fatigue load decreases,the high-cycle fatigue life gradually increases.The high-cycle fatigue fracture is mainly characterized by octahedral slip mechanism.At high stress and low lifespan,the fracture exhibits single or multiple slip surface features.Some fractures originate along a vertical small plane and then propagate along the{111}slip surface.At low stress and high lifespan,the fracture surface tend to alternate and expand along multiple slip planes after originating from subsurface or internal sources,exhibiting characteristics of multiple slip planes.Through electron backscatter diffraction and transmission electron microscope analysis,there is obvious oxidation behavior on the surface of the high-cycle fatigue fracture,and the fracture section is composed of oxidation layer,distortion layer,and matrix layer from the outside to the inside.Among them,the main components of the oxidation layer are oxides of Ni and Co.The distortion layer is mainly distributed in the form of elongated or short rod-shaped oxides of Al,Ta,and W.The matrix layer is a single crystal layer.Crack initiation and propagation mechanism were obtained by systematical analysis of a large number of highcycle fatigue fractures.In addition,the stress ratio of 0.05 is closer to the vibration mode of turbine blades during actual service,providing effective guidance for the study of failure and fracture mechanisms of turbine blades.
基金supported by Natural Science Foundation of Shandong Province(Nos.ZR2022YQ42,ZR2021JQ15,ZR2021QE011,ZR2021ZD20,2022GJJLJRC-01)Innovative Team Project of Jinan(No.2021GXRC019)the National Natural Science Foundation of China(Nos.52022037,52202366).
文摘In contrast to research on active sites in nanomaterials,lithium tantalate single crystals,known for their exceptional optical properties and long-range ordered lattice structure,present a promising avenue for in-depth exploration of photocatalytic reaction systems with fewer constraints imposed by surface chemistry.Typically,the isotropy of a specific facet provides a perfect support for studying heteroatom doping.Herein,this work delves into the intrinsic catalytic sites for photocatalytic nitrogen fixation in iron-doped lithium tantalate single crystals.The presence of iron not only modifies the electronic structure of lithium tantalate,improving its light absorption capacity,but also functions as an active site for the nitrogen adsorption and activation.The photocatalytic ammonia production rate of the iron-doped lithium tantalate in pure water is maximum 26.95μg cm^(−2)h^(−1),which is three times higher than that of undoped lithium tantalate.The combination of first-principles simulations with in situ characterizations confirms that iron doping promotes the rate-determining step and changes the pathway of hydrogenation to associative alternating.This study provides a new perspective on in-depth investigation of intrinsic catalytic active sites in photocatalysis and other catalytic processes.
文摘Downconversion (DC) with emission of two near-infrared photons about 1000 nm for each blue photon absorbed was obtained in thulium (Tm3+) and ytterbium (Yb3+) codoped yt- trium lithium fluoride (LiYF4) single crystals grown by an improved Bridgman method. The luminescent properties of the crystals were measured through photoluminescence excitation, emission spectra and decay curves. Luminescence between 960 and 1050 nm from yb3+: 2Fs/2--+2FT/2 transition, which was originated from the DC from Tm3+ ions to Yb3+ ions, was observed under the excitation of blue photon at 465 nm. Moreover, the energy transfer processes were studied based on the Inokuti-Hirayama model, and the results indicated that the energy transfer from Tm3+ to Yb3+ was an electric dipole-dipole interaction. The max- imum quantum cutting efficiency approached with 0.49mo1% Tm3+ and 5.99mo1% Yb3+. increasing the energy efficiency of crystalline energy part of the solar spectrum. up to 167.5% in LiYF4 single crystal codoped Application of this crystal has prospects for Si solar cells by photon doubling of the high
基金supported by the Technology Innovation Program(RS-2023-00256202Development of MLCB design and manufacturing process technology for board mounting)funded By the Ministry of Trade,Industry&Energy(MOTIE,Korea)+2 种基金supported by the Technology Innovation Program(or Industrial Strategic Technology Development Program-Public-private joint investment semiconductor R&D program(K-CHIPS)to foster high-quality human resources)(RS-2023-00237003,High selectivity etching technology using cryoetch)funded By the Ministry of Trade,Industry&Energy(MOTIE,Korea)supported by 2022 Research Grant from Kangwon National University(No.202203080001)supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(RS-2023-00280367).
文摘Arising from the increasing demand for electric vehicles(EVs),Ni-rich LiNi_(x)Co_(y)Mn_(z)O_(2)(NCM,x+y+z=1,x≥0.8)cathode with greatly increased energy density are being researched and commercialized for lithium-ion batteries(LIBs).However,parasitic crack formation during the discharge–charge cycling process remains as a major degradation mechanism.Cracking leads to increase in the specific surface area,loss of electrical contact between the primary particles,and facilitates liquid electrolyte infiltration into the cathode active material,accelerating capacity fading and decrease in lifetime.In contrast,Ni-rich NCM when used as a single crystal exhibits superior cycling performances due to its rigid mechanical property that resists cracking during long charge–discharge process even under harsh conditions.In this paper,we present comparative investigation between single crystal Ni-rich LiNi_(0.92)Co_(0.04)Mn_(0.04)O_(2)(SC)and polycrystalline Ni-rich LiNi_(0.92)Co_(0.04)Mn_(0.04)O_(2)(PC).The relatively improved cycling performances of SC are attributed to smaller anisotropic volume change,higher reversibility of phase transition,and resistance to crack formation.The superior properties of SC are demonstrated by in situ characterization and battery tests.Consequently,it is inferred from the results obtained that optimization of preparation conditions can be regarded as a key approach to obtain well crystallized and superior electrochemical performances.
基金supported by the Hainan Province Science and Technology Special Fund(ZDYF2021SHFZ232,ZDYF2023GXJS022)the Hainan Province Postdoctoral Science Foundation(300333)the National Natural Science Foundation of China(21203008,21975025,12274025,22372008)。
文摘Sulfide-based all-solid-state lithium batteries suffer from electrochemo-mechanical damage to Ni-rich oxide-based cathode active materials(CAMs),primarily caused by severe volume changes,results in significant stress and strain,causes micro-cracks and interfacial contact loss at potentials>4.3 V(vs.Li/Li^(+)).Quantifying micro-cracks and voids in CAMs can reveal the degradation mechanisms of Ni-rich oxidebased cathodes during electrochemical cycling.Nonetheless,the origin of electrochemical-mechanical damage remains unclear.Herein,We have developed a multifunctional PEG-based soft buffer layer(SBL)on the surface of carbon black(CB).This layer functions as a percolation network in the single crystal LiNi_(0.83)Co_(0.07)Mn_(0.1)O_(2)and Li_(6)PS_(5)Cl composite cathode layer,ensuring superior ionic conductivity,reducing void formation and particle cracking,and promoting uniform utilization of the cathode active material in all-solid-state lithium batteries(ASSLBs).High-angle annular dark-field STEM combined with nanoscale X-ray holo-tomography and plasma-focused ion beam scanning electron microscopy confirmed that the PEG-based SBL mitigated strain induced by reaction heterogeneity in the cathode.This strain produces lattice stretches,distortions,and curved transition metal oxide layers near the surface,contributing to structural degradation at elevated voltages.Consequently,ASSLBs with a LiNi_(0.83)Co_(0.07)Mn_(0.1)O_(2)cathode containing LCCB-10(CB/PEG mass ratio:100/10)demonstrate a high areal capacity(2.53 mAh g^(-1)/0.32 mA g^(-1))and remarkable rate capability(0.58 mAh g^(-1)at 1.4 mA g^(-1)),with88%capacity retention over 1000 cycles.
文摘The deformation and fracture of a third-generation single crystal superalloy during in-situ tension at room temperature were investigated at multiple scales by scanning electron microscope,electron back-scattered diffractometer,and transmission electron microscope to reveal the deformation and fracture mechanism during tension.The proportion of low angle boundaries(LABs)with angles from 2.5°to 5.5°increases during tension.The change in LABs is particularly pronounced after elongation over 7%.The initiation of microcracks is caused by{111}<110>slip systems.After initiation,the crack size along the stress direction increases whereas the size extension along slip systems is suppressed.The fracture mode of the alloy is quasi-cleavage fracture and the slip lines near the fracture are implicit at room temperature.
文摘Interrupted and ruptured creep tests were conducted on single crystal superalloy DD9 at 980℃/250 MPa and 1100℃/137 MPa conditions.Microstructure evolution during creep was analyzed through scanning electron microscope and transmission electron microscope.Results show that the microstructure evolutions are similar under the creep conditions of 980℃/250 MPa and 1100℃/137 MPa.Cubicalγ′phase,which is dispersedly distributed in theγmatrix,gradually evolves into a layered structure perpendicular to the stress direction.The width of theγmatrix channel along the direction parallel to the stress increases.The relationship between the increase in width of theγmatrix channel and the strain satisfies linear relationship in logarithmic form,indicating that the width of theγmatrix can be deduced via the strain under creep state.This may provide an approach to investigate the width ofγmatrix in single crystal superalloys during creep under high temperature and low stress conditions.In the early creep stage,dislocations formed in theγphase generate mutually perpendicular networks through cross-slip at theγ/γ′interface.Then,stable hexagonal dislocation networks form as a result of the coupling effects of external stress and mismatch stress at high temperatures.In the later period of creep,dislocations shear theγ′phase,ultimately causing the fracture.
基金Shenzhen Science and Technology Program(JSGG20220831092800001)。
文摘The microstructure of single crystal superalloy is relatively simple,consisting primarily ofγdendrites andγ/γ′eutectics.During the directional solidification process of Ni-based single crystal superalloys,withdrawal rate is a critical parameter affecting the spatial distribution ofγ/γ′eutectic along gravity direction.The results show that theγ/γ′eutectic fraction of the upper platform surface is always higher than that of the lower one,regardless of withdrawal rate.As the withdrawal rate decreases,there is a significant increase inγ/γ′eutectic fraction on the upper surface,while it decreases on the lower surface.The upward accumulation ofγ/γ′eutectic becomes more severe as the withdrawal rate decreases.It is also found that the percentage of Al+Ta is positively correlated with theγ/γ′eutectic fraction.Thermo-solute convection of Al and Ta solutes in the solidification front is the prime reason for the non-uniform distribution of eutectic.The non-uniform distribution ofγ/γ′eutectic cannot be eliminated even after subsequent solution heat treatment,resulting in excess eutectic on the upper surface and thus leading to the scrapping of the blade.