TiNb_(2)O_(7)represents an up-and-coming anode material for fast-charging lithium-ion batteries,but its practicalities are severely impeded by slow transfer rates of ionic and electronic especially at the low-temperat...TiNb_(2)O_(7)represents an up-and-coming anode material for fast-charging lithium-ion batteries,but its practicalities are severely impeded by slow transfer rates of ionic and electronic especially at the low-temperature conditions.Herein,we introduce crystallographic engineering to enhance structure stability and promote Li+diffusion kinetics of TiNb_(2)O_(7)(TNO).The density functional theory computation reveals that Ti^(4+)is replaced by Sb^(5+)and Nb^(5+)in crystal lattices,which can reduce the Li+diffusion impediment and improve electronic conductivity.Synchrotron radiation X-ray 3D nano-computed tomography and in situ X-ray diffraction measurement confirm the introduction of Sb/Nb alleviates volume expansion during lithiation and delithiation processes,contributing to enhancing structure stability.Extended X-ray absorption fine structure spectra results verify that crystallographic engineering also increases short Nb-O bond length in TNO-Sb/Nb.Accordingly,the TNO-Sb/Nb anode delivers an outstanding capacity retention rate of 89.8%at 10 C after 700 cycles and excellent rate performance(140.4 mAh g^(−1) at 20 C).Even at−30℃,TNO-Sb/Nb anode delivers a capacity of 102.6 mAh g^(−1) with little capacity degeneration for 500 cycles.This work provides guidance for the design of fast-charging batteries at low-temperature condition.展开更多
NASICON-type vanadium fluorophosphate is a promising cathode for sodium-ion batteries.Yet,the thermally-driven loss of undercoordinated dangling fluorine anions weakens its structural stability,which triggers severe f...NASICON-type vanadium fluorophosphate is a promising cathode for sodium-ion batteries.Yet,the thermally-driven loss of undercoordinated dangling fluorine anions weakens its structural stability,which triggers severe framework distortion from interconnected double-octahedral to isolated local octahedral units,as well as a degeneracy of t_(2g) electronic configuration of vanadium(V)3d orbit.In this work,it is clarified that such a degenerate state undergoes spontaneous lattice evolution to reduce the system energy,which causes a low crystalline symmetry and a parasitic V^(4+)/V^(3+)redox reaction in the low-voltage region.Herein,an anion-coordination regulation strategy is developed to suppress this degeneration by anchoring fluorine anions in the double-octahedral[V_(2)O_(8)F_(3)]framework.Density functional theory calculations and in-situ techniques track the F-anion-driven structural evolution and charge compensation mechanisms,revealing that this strategy mitigates detrimental phase segregation during the initial desodiation stage and enhances the Na^(+)diffusion kinetic rate over a factor of 100.Concurrently,this strategy releases the V^(4+)/V^(3+)redox kinetics by eliminating the parasitic low-voltage plateau.The full-cell assembled with the optimized fluorophosphate cathode delivers an increase of 50%in discharge capacity and stable two-voltage-plateau behavior,enabled by its double-octahedral[V_(2)O_(8)F_(3)]polyanionic structure that facilitates unimpeded three-dimensional(3D)Na^(+)transport.By correlating anion-coordination stability with orbital-level charge compensation,this work establishes a universal paradigm for highperformance polyanionic cathodes,positioning it as a competitive candidate for battery applications.展开更多
Shearing behavior and failure mechanism of bolt-grout interface are of great significance for load transfer capacity and design of rock bolting system.In this paper,direct shear tests on bolt-grout interfaces under co...Shearing behavior and failure mechanism of bolt-grout interface are of great significance for load transfer capacity and design of rock bolting system.In this paper,direct shear tests on bolt-grout interfaces under constant normal load(CNL) conditions were conducted to investigate the effects of bolt profile(i.e.rib spacing and rib height) and grout mixture on the bolt-grout interface in terms of mechanical behaviors and failure modes.Test results showed that the peak shear strength and the deformation capacity of the bolt-grout interface are highly dependent on the bolt profile and grout mixture,suggesting that bolt performances can be optimized,which were unfortunately ignored in the previous studies.A new interface failure mode,i.e.'sheared-crush' mode,was proposed,which was characterized by progressive crush failure of the grout asperities between steel ribs during shearing.It was shown that the interface failure mode mainly depends on the normal stress level and rib spacing,compared with the rib height and grout mixture for the range of tested parameters in this study.展开更多
Sodium-ion batteries stand a chance of enabling fast charging ability and long lifespan while operating at low temperature(low-T).However,sluggish kinetics and aggravated dendrites present two major challenges for ano...Sodium-ion batteries stand a chance of enabling fast charging ability and long lifespan while operating at low temperature(low-T).However,sluggish kinetics and aggravated dendrites present two major challenges for anodes to achieve the goal at low-T.Herein,we propose an interlayer confined strategy for tailoring nitrogen terminals on Ti_(3)C_(2) MXene(Ti_(3)C_(2)-N_(funct)) to address these issues.The introduction of nitrogen terminals endows Ti_(3)C_(2)-N_(funct) with large interlayer space and charge redistribution,improved conductivity and sufficient adsorption sites for Na^(+),which improves the possibility of Ti_(3)C_(2) for accommodating more Na atoms,further enhancing the Na^(+) storage capability of Ti_(3)C_(2).As revealed,Ti_(3)C_(2)-N_(funct) not only possesses a lower Na-ion diffusion energy barrier and charge trans-fer activation energy,but also exhibits Na^(+)-solvent co-intercalation behavior to circumvent a high de-solvation energy barrier at low-T.Besides,the solid electrolyte interface dominated by inorganic com-pounds is more beneficial for the Na^(+)transfer at the electrode/electrolyte interface.Compared with of the unmodified sample,Ti_(3)C_(2)-Nfunct exhibits a twofold capacity(201 mAh g^(-1)),fast-charging ability(18 min at 80% capacity retention),and great superiority in cycle life(80.9%@5000 cycles)at -25℃.When coupling with Na_(3)V_(2)(PO_(4))_(2)F_(3) cathode,the Ti_(3)C_(2)-N_(funct)//NVPF exhibits high energy density and cycle stability at -25℃.展开更多
Rock bolts have been widely used for stabilizing rock mass in geotechnical engineering.It is acknowledged that the bolt profiles have a sound influence on the support effect of the rock bolting system.Previous studies...Rock bolts have been widely used for stabilizing rock mass in geotechnical engineering.It is acknowledged that the bolt profiles have a sound influence on the support effect of the rock bolting system.Previous studies have proposed some optimal rib parameters(e.g.rib spacing);unfortunately,the interface shear behaviors are generally ignored.Therefore,determination of radial stress and radial displacement on the bolt-grout interface using traditional pull-out tests is not possible.The load-bearing capacity and deformation capacity vary as bolt profiles differ,suggesting that the support effect of the bolting system can be enhanced by optimizing bolt profiles.The aim of this study is to investigate the effects of bolt profiles(with/without ribs,rib spacing,and rib height)on the shear behaviors between the rock bolt and grout material using direct shear tests.Thereby,systematic interfacial shear tests with different bolt profiles were performed under both constant normal load(CNL)and constant normal stiffness(CNS)boundary conditions.The results suggested that rib spacing has a more marked influence on the interface shear behavior than rib height does,in particular at the post-yield stage.The results could facilitate our understanding of bolt-grout interface shear behavior under CNS conditions,and optimize selection of rock bolts under in situ rock conditions.展开更多
Objective:To observe the chitooligosaccharides(COS) effect on the proliferation inhibition and radiosensitivity of three types of human gastric cancer cell line.Mothods:CCK-8 assay was employed to obtain the inhibitio...Objective:To observe the chitooligosaccharides(COS) effect on the proliferation inhibition and radiosensitivity of three types of human gastric cancer cell line.Mothods:CCK-8 assay was employed to obtain the inhibition ratio of COS on BGC823 cells,MKN45 cells and SGC7901 cells at 48 h after treatment and the proliferation-inhibition curve was drawn with the inhibition ratio of COS on three types of cells.The clonogenic assay was used to detect the cell viability of 0,1,2,4,6 and 8 Gy(6 dose grades) in RAY group and RAY+COS group after X-ray,and the cell survival curve was used to analyze the sensitization enhancement ratio of COS.Flow cytometry was employed to detect cell cycle and apoptosis rate in control group,RAY group and RAY+COS group after 48 h treatment.Results:COS inhibited the proliferation of three types of cells.The inhibition rate was positively correlated with the concentration of COS,and the susceptibility of MKN45 cells,SGC7901 cells and BGC823 cells to COS decreased in turn.The cell viability decreased gradually with the increasing radiation dose in RAY group and RAY+COS group(P<0.01).The cell viabilities of RAY+COS group were lower than those of RAY group at all the dose grades under X-ray exposure(P<0.01),and the sensitization enhancement ratios of COS on BGC823 cells,MKN45 cells and SGC7901 cells were 1.06,1.28 and 1.15 respectively.In controlled trials,apoptosis rate and percentage in the G_2/M phase of three types of cells in RAY+COS group were higher than those in control group and RAY group,and percentage in the S phase and the G_0/G_1 phase in RAY+COS group were lower than those in the other two groups(P<0.01).Conclusions:COS can inhibit the proliferation of three types of human gastric cancer cells and enhance the radiosensitivity by inducing apoptosis and G_2/M phase arrest.展开更多
Monolithic bulk metallic glass and glass matrix composites with a relative density above 98%were produced by processing Cu_(46)Zr_(46)Al_(8)(at.%)via selective laser melting(SLM).Their microstructures and mechanical p...Monolithic bulk metallic glass and glass matrix composites with a relative density above 98%were produced by processing Cu_(46)Zr_(46)Al_(8)(at.%)via selective laser melting(SLM).Their microstructures and mechanical properties were systematically examined.B2 CuZr nanocrystals(30-100 nm in diameter)are uniformly dispersed in the glassy matrix when SLM is conducted at an intermediate energy input.These B2 CuZr nanocrystals nucleate the oxygen-stabilized big cube phase during a remelting step.The presence of these nanocrystals increases the structural heterogeneity as indirectly revealed by mircrohardness and nanoindentation measurements.The corresponding maps in combination with calorimetric data indicate that the glassy phase is altered by the processing conditions.Despite the formation of crystals and a high overall free volume content,all additively manufactured samples fail at lower stress than the as-cast glass and without any plastic strain.The inherent brittleness is attributed to the presence of relatively large pores and the increased oxygen content after selective laser melting.展开更多
Steel matrix composites(SMCs),reinforced by ceramic particles,have received a consistent attention in recent years.Using conventional methods to prepare SMCs is generally challenging,and the mechanical properties of c...Steel matrix composites(SMCs),reinforced by ceramic particles,have received a consistent attention in recent years.Using conventional methods to prepare SMCs is generally challenging,and the mechanical properties of conventionally fabricated SMCs are limited.In this study,we successfully fabricated highperformance SMCs by laser powder bed fusion(LPBF)of a composite powder consisting of Fe-based alloy powder and submicron-sized WC particles.The effect of laser energy density on the phase formation,microstructural evolution,overall density and resulting mechanical properties of LPBF-fabricated composites was investigated.The present results show that a novel Fe_(2)W_(4)C carbidic network precipitates in the solidified microstructure entailing segregations along the boundaries of cellular sub-grains.The presence of this carbidic network hampers the growth of sub-grains even at elevated temperatures,and hence,stabilizes the grain size though prepared at a broad range of different energy densities.The exact distribution of the Fe_(2)W_(4)C carbides depends on the employed laser energy densities,as for instance they are more uniformly distributed at higher energy input.The density of LPBF samples reaches the maximum value of 99.4%at 150 J/mm^(3).In this parameter set,high microhardness of~753 HV,compression strength of~3350 MPa and fracture strain of~24.4%are obtained.The enhanced mechanical properties are ascribed to less metallurgical defects,higher volume fraction of the martensitic phase and increasing pile-up dislocations resulting from the pinning effect by Fe_(2)W_(4)C carbide.展开更多
The effect of spiral magnetic field （SMF） on the solidification process of Sn-20 wt.%Pb hypoeutectic alloy was studied in this work. The temperature distribution and the macrosegregation together with the eutectic l...The effect of spiral magnetic field （SMF） on the solidification process of Sn-20 wt.%Pb hypoeutectic alloy was studied in this work. The temperature distribution and the macrosegregation together with the eutectic lamellar spacing during solidification were measured under different magnetic fields. The results indicate that the compositions in the top and bottom portions of the sample are nearly the same and the segregation phenomenon is basically eliminated by SMF at an exciting current of 125 A. The morphology of the primary phase transforms from coarse dendrite to rosette or ellipsoidal equiaxed crystal and the spacing of the eutectic lamellar increases from 1.6 to 3.9 μm when the exciting current increases from 0 to 125 A. Moreover, if the exciting current is high enough, the forced fluid flow caused by SMF will enhance the process of transition from lamellar eutectic structure to anomalous rod-like one.展开更多
Silyl cobalt species are putative intermediates in cobalt-catalyzed transformations of hydrosilanes.However,their reactivity has remained poorly understood.Reported here is the investigation on four-coordinate disilyl...Silyl cobalt species are putative intermediates in cobalt-catalyzed transformations of hydrosilanes.However,their reactivity has remained poorly understood.Reported here is the investigation on four-coordinate disilyl Co(Ⅱ)complexes with N-hetereocyclic carbene ligation.The reactions of[(ICy)_(2)Co(vtms)](ICy=1,3-dicyclohexylimidazol-2-ylidene,vtms=vinyltrimethylsilane)with primary and secondary hydrosilanes(3 equiv.)furnish the four-coordinate disilyl complexes[trans-(ICy)_(2)Co(SiHRR')_(2)](SiHRR'=SiH_(2)Mes,1;SiH_(2)Ph,2;SiH_(2)Cy,3;SiHPh_(2),4;SiHEt_(2),5)in moderate to good yields.The structures of 1,2 and 4 were established by single-crystal X-ray diffraction.Solution magnetic susceptibility measurement and EPR spectroscopy indicate their low-spin nature(S=1/2).Reactivity studies on 4 led to the establishment of the conversions of 4 to the disilyl dihydride Co(Ⅲ)complex[K(THF)][(ICy)_(2)Co(H)_(2)(SiHPh_(2))_(2)]_n(6)and the fluorosilyl Co(Ⅱ)complex[(ICy)_(2)Co(THF)(SiFPh_(2))][BF_(4)](7)when 4 was treated with excess amount of K and AgBF_(4),respectively,in THF.These conversions hint at the high activity of low-valent and high-valent disilyl cobalt species[trans-(ICy)_(2)Co(SiHPh_(2))_(2)]^(1-)and[trans-(ICy)_(2)Co(SiHPh_(2))_(2)]^(2+).Complex 4 is reactive toward terminal alkynes,but inert toward alkenes and internal alkynes.The reactions of 4 with terminal alkynes CyC≡CH and Me_(3)SiC≡CH(3 equiv.)yield the Co(Ⅱ)complexes[(ICy)_(2)Co(C≡CCy)_(2)](8)and[(ICy)_(2)Co(C≡CSiMe_(3))((SiMe_(3))C=CH_(2))](9),respectively,along with H_(2)SiPh_(2)and alkynylsilanes RC≡CSiHPh_(2)(R=Cy,SiMe_(3)),whereas the reaction with 4-CF_(3)C_(6)H_(4)C≡CH(3 equiv.)produce[(ICy)_(2)Co(C≡CAr)((Ar)C=CH(SiHPh_(2))C=CHAr)](Ar=4-CF_(3)C_(6)H_(4))(10)and H_(2)SiPh_(2).These reactions are proposed to involveσ-bond metathesis reactions between alkyne C(sp)-H bonds and Co-Si bonds in 4.Complexes 6–10 have been characterized by NMR spectroscopy,X-ray diffraction study,and elemental analysis.展开更多
The key to managing fracture is to achieve stable internal fixation,and currently,biologically and mechanically appropriate internal fixation devices are urgently needed.With excellent biocompatibility and corrosion r...The key to managing fracture is to achieve stable internal fixation,and currently,biologically and mechanically appropriate internal fixation devices are urgently needed.With excellent biocompatibility and corrosion resistance,titanium–niobium alloys have the potential to become a new generation of internal fixation materials for fractures.However,the role and mechanism of titanium–niobium alloys on promoting fracture healing are still undefined.Therefore,in this study,we systematically evaluated the bone-enabling properties of Ti45Nb via in vivo and in vitro experiments.In vitro,we found that Ti45Nb has an excellent ability to promote MC3T3-E1 cell adhesion and proliferation without obvious cytotoxicity.Alkaline phosphatase(ALP)activity and alizarin red staining and semiquantitative analysis showed that Ti45Nb enhanced the osteogenic differentiation of MC3T3-E1 cells compared to the Ti6Al4V control.In the polymerase chain reaction experiment,the expression of osteogenic genes in the Ti45Nb group,such as ALP,osteopontin(OPN),osteocalcin(OCN),type 1 collagen(Col-1)and runt-related transcription factor-2(Runx2),was significantly higher than that in the control group.Meanwhile,in the western blot experiment,the expression of osteogenic-related proteins in the Ti45Nb group was significantly increased,and the expression of PI3K–Akt-related proteins was also higher,which indicated that Ti45Nb might promote fracture healing by activating the PI3K–Akt signaling pathway.In vivo,we found that Ti45Nb implants accelerated fracture healing compared to Ti6Al4V,and the biosafety of Ti45Nb was confirmed by histological evaluation.Furthermore,immunohistochemical staining confirmed that Ti45Nb may promote osteogenesis by upregulating the PI3K/Akt signaling pathway.Our study demonstrated that Ti45Nb exerts an excellent ability to promote fracture healing as well as enhance osteoblast differentiation by activating the PI3K/Akt signaling pathway,and its good biosafety has been confirmed,which indicates its clinical translation potential.展开更多
Li4Ti5O12（LTO）/carbon nanotubes（CNTs） composite material is synthesized based on a solid-state method by sand-milling, spray-drying and calcining at 850 8C under N2 flow. The LTO/CNTs samples with1 wt% and 3 wt% w...Li4Ti5O12（LTO）/carbon nanotubes（CNTs） composite material is synthesized based on a solid-state method by sand-milling, spray-drying and calcining at 850 8C under N2 flow. The LTO/CNTs samples with1 wt% and 3 wt% weight ratio of CNTs addition and the pristine LTO sample are prepared. The rate performance and the thermal stability of these samples are investigated based on Li Mn2O4（LMO）/LTO full-cell. The results show that the weight ratio of CNTs addition has distinct effect on LTO performances.The composite materials of LTO composited CNTs have better performance at high-rate due to the intercalation enhancement by conductive network of CNTs. At second, the overcharging temperature response of the cell＇s surface with 1 wt% CNTs addition is the lowest. The particle size distribution is measured and the most uniform particles are obtained with 1 wt% CNTs addition. This trend could explain that the medium quantity of CNTs is optimal to improve the heat and mass transfer and prevent the problems of crystallite growing interference and aggregation during the calcination process.展开更多
In situ NMR measurements of the diffusion coefficients,including an estimate of signal strength,of lithium ion conductor using diffusion-weighting pulse sequence are performed in this study.A cascade bilinear model is...In situ NMR measurements of the diffusion coefficients,including an estimate of signal strength,of lithium ion conductor using diffusion-weighting pulse sequence are performed in this study.A cascade bilinear model is proposed to estimate the diffusion sensitivity factors of pulsed-field gradient using prior information of the electrochemical performance and Arrhenius constraint.The model postulates that the active lithium nuclei participating electrochemical reaction are relevant to the NMR signal intensity,when discharge rate or temperature condition is varying.The electrochemical data and the NMR signal strength show a highly fit with the proposed model according our simulation and experiments.Furthermore,the diffusion time is constrained by temperature based on Arrhenius equation of reaction rates dependence.An experimental calculation of Li_4Ti_5O_（12）（LTO）/carbon nanotubes（CNTs） with the electrolyte evaluating at 20 ℃ is presented,which the b factor is estimated by the discharge rate.展开更多
The limited knowledge on low-coordinate zero-valent transition-metal species has intrigued great synthetic efforts in developing ligand sets for their stabilization.While the combined ligand set of Nheterocyclic carbe...The limited knowledge on low-coordinate zero-valent transition-metal species has intrigued great synthetic efforts in developing ligand sets for their stabilization.While the combined ligand set of Nheterocyclic carbene(NHC)with vinylsilanes was the only known ligand system amenable to the stabilization of three-coordinate formal zero-valent cobalt,iron,and manganese complexes,the exploration on other ligands has proved that the ligand set of NHCs with styrene is equally effective in stabilizing three-coo rdinate formal zero-valent metal complexes in the form of(NHC)M(η2-CH2CHPh)2(NHC=IPr,IMes;M=Co,Fe,Mn).These styrene complexes can be prepared by the one-pot reactions of MCl2 with styrene,NHC and KC8,and have been characterized by various spectroscopic methods.Preliminary reactivity study indicated that the interaction of[(IMes)Fe(η2-CH2 CHPh)2]with DippN3 produces the iron(IV)bisimido complex[(IMes)Fe(NDipp)2]and styrene,which hints at the utility of these zero-valent metal styene complexes as synthons of the mono-coordinate species(NHC)M(O).展开更多
基金supported by the National Natural Science Foundation of China(22279026,2247090373)the Natural Science Foundation of Chongqing(CSTB2022NSCQ-MSX1401)+2 种基金the China Postdoctoral Science Foundation(2024M764198)the National Natural Science Foundation of China(22509044)the Fundamental Research Funds for the Central Universities(grant no.HIT.OCEF.2022017).
文摘TiNb_(2)O_(7)represents an up-and-coming anode material for fast-charging lithium-ion batteries,but its practicalities are severely impeded by slow transfer rates of ionic and electronic especially at the low-temperature conditions.Herein,we introduce crystallographic engineering to enhance structure stability and promote Li+diffusion kinetics of TiNb_(2)O_(7)(TNO).The density functional theory computation reveals that Ti^(4+)is replaced by Sb^(5+)and Nb^(5+)in crystal lattices,which can reduce the Li+diffusion impediment and improve electronic conductivity.Synchrotron radiation X-ray 3D nano-computed tomography and in situ X-ray diffraction measurement confirm the introduction of Sb/Nb alleviates volume expansion during lithiation and delithiation processes,contributing to enhancing structure stability.Extended X-ray absorption fine structure spectra results verify that crystallographic engineering also increases short Nb-O bond length in TNO-Sb/Nb.Accordingly,the TNO-Sb/Nb anode delivers an outstanding capacity retention rate of 89.8%at 10 C after 700 cycles and excellent rate performance(140.4 mAh g^(−1) at 20 C).Even at−30℃,TNO-Sb/Nb anode delivers a capacity of 102.6 mAh g^(−1) with little capacity degeneration for 500 cycles.This work provides guidance for the design of fast-charging batteries at low-temperature condition.
基金supported by the National Key Research and Development Program of China(2023YFB2406100)the National Natural Science Foundation of China(Grant No.22075062 and U23A20573)+6 种基金the Heilongjiang Touyan Team(Grant No.HITTY20190033)the Heilongjiang Postdoctoral Financial Assistance(Grant No.LBH-Z23137)the Postdoctoral Fellowship Program of CPSF(Grant No.GZC20233448)the China Postdoctoral Science Foundation(Grant No.2024M754198)the Shenzhen Science and Technology Program(KCXST20221021111216037)the Fundamental Research Funds for the Central Universities(Grant No.FRFCU5710051922)the program of “Open bidding for selecting the best candidates”(Grant No.2023JCA06)from Jiangxi Fuzhou Municipal Government。
文摘NASICON-type vanadium fluorophosphate is a promising cathode for sodium-ion batteries.Yet,the thermally-driven loss of undercoordinated dangling fluorine anions weakens its structural stability,which triggers severe framework distortion from interconnected double-octahedral to isolated local octahedral units,as well as a degeneracy of t_(2g) electronic configuration of vanadium(V)3d orbit.In this work,it is clarified that such a degenerate state undergoes spontaneous lattice evolution to reduce the system energy,which causes a low crystalline symmetry and a parasitic V^(4+)/V^(3+)redox reaction in the low-voltage region.Herein,an anion-coordination regulation strategy is developed to suppress this degeneration by anchoring fluorine anions in the double-octahedral[V_(2)O_(8)F_(3)]framework.Density functional theory calculations and in-situ techniques track the F-anion-driven structural evolution and charge compensation mechanisms,revealing that this strategy mitigates detrimental phase segregation during the initial desodiation stage and enhances the Na^(+)diffusion kinetic rate over a factor of 100.Concurrently,this strategy releases the V^(4+)/V^(3+)redox kinetics by eliminating the parasitic low-voltage plateau.The full-cell assembled with the optimized fluorophosphate cathode delivers an increase of 50%in discharge capacity and stable two-voltage-plateau behavior,enabled by its double-octahedral[V_(2)O_(8)F_(3)]polyanionic structure that facilitates unimpeded three-dimensional(3D)Na^(+)transport.By correlating anion-coordination stability with orbital-level charge compensation,this work establishes a universal paradigm for highperformance polyanionic cathodes,positioning it as a competitive candidate for battery applications.
基金supported by the Key Projects of the Yalong River Joint Fund of the National Natural Science Foundation of China(Grant No.U1865203)the National Natural Science Foundation of China(Grant No.51279201)+1 种基金Special project of the National Natural Science Foundation of China(Grant No.41941018)The partial support from the Youth Innovation Promotion Association,Chinese Academy of Sciences。
文摘Shearing behavior and failure mechanism of bolt-grout interface are of great significance for load transfer capacity and design of rock bolting system.In this paper,direct shear tests on bolt-grout interfaces under constant normal load(CNL) conditions were conducted to investigate the effects of bolt profile(i.e.rib spacing and rib height) and grout mixture on the bolt-grout interface in terms of mechanical behaviors and failure modes.Test results showed that the peak shear strength and the deformation capacity of the bolt-grout interface are highly dependent on the bolt profile and grout mixture,suggesting that bolt performances can be optimized,which were unfortunately ignored in the previous studies.A new interface failure mode,i.e.'sheared-crush' mode,was proposed,which was characterized by progressive crush failure of the grout asperities between steel ribs during shearing.It was shown that the interface failure mode mainly depends on the normal stress level and rib spacing,compared with the rib height and grout mixture for the range of tested parameters in this study.
基金the National Natural Sci-ence Foundation of China(Grant Nos.21673064,51902072 and 22109033)Heilongjiang Touyan Team(Grant No.HITTY-20190033)+1 种基金Fundamental Research Funds for the Central Universities(Grant Nos.HIT.NSRIF.2019040 and 2019041)State Key Laboratory of Urban Water Resource and Environment(Harbin Institute of Technology)(Grant No.2020 DX11).
文摘Sodium-ion batteries stand a chance of enabling fast charging ability and long lifespan while operating at low temperature(low-T).However,sluggish kinetics and aggravated dendrites present two major challenges for anodes to achieve the goal at low-T.Herein,we propose an interlayer confined strategy for tailoring nitrogen terminals on Ti_(3)C_(2) MXene(Ti_(3)C_(2)-N_(funct)) to address these issues.The introduction of nitrogen terminals endows Ti_(3)C_(2)-N_(funct) with large interlayer space and charge redistribution,improved conductivity and sufficient adsorption sites for Na^(+),which improves the possibility of Ti_(3)C_(2) for accommodating more Na atoms,further enhancing the Na^(+) storage capability of Ti_(3)C_(2).As revealed,Ti_(3)C_(2)-N_(funct) not only possesses a lower Na-ion diffusion energy barrier and charge trans-fer activation energy,but also exhibits Na^(+)-solvent co-intercalation behavior to circumvent a high de-solvation energy barrier at low-T.Besides,the solid electrolyte interface dominated by inorganic com-pounds is more beneficial for the Na^(+)transfer at the electrode/electrolyte interface.Compared with of the unmodified sample,Ti_(3)C_(2)-Nfunct exhibits a twofold capacity(201 mAh g^(-1)),fast-charging ability(18 min at 80% capacity retention),and great superiority in cycle life(80.9%@5000 cycles)at -25℃.When coupling with Na_(3)V_(2)(PO_(4))_(2)F_(3) cathode,the Ti_(3)C_(2)-N_(funct)//NVPF exhibits high energy density and cycle stability at -25℃.
基金This study is supported by the key projects of the Yalong River Joint Fund of the National Natural Science Foundation of China(Grant No.U1865203)the National Key Research and Development Program of China(Grant Nos.2019YFC0605103,2019YFC0605100)the National Natural Science Foundation of China(Grant No.51279201).The partial support from the Youth Innovation Promotion Association CAS is gratefully acknowledged。
文摘Rock bolts have been widely used for stabilizing rock mass in geotechnical engineering.It is acknowledged that the bolt profiles have a sound influence on the support effect of the rock bolting system.Previous studies have proposed some optimal rib parameters(e.g.rib spacing);unfortunately,the interface shear behaviors are generally ignored.Therefore,determination of radial stress and radial displacement on the bolt-grout interface using traditional pull-out tests is not possible.The load-bearing capacity and deformation capacity vary as bolt profiles differ,suggesting that the support effect of the bolting system can be enhanced by optimizing bolt profiles.The aim of this study is to investigate the effects of bolt profiles(with/without ribs,rib spacing,and rib height)on the shear behaviors between the rock bolt and grout material using direct shear tests.Thereby,systematic interfacial shear tests with different bolt profiles were performed under both constant normal load(CNL)and constant normal stiffness(CNS)boundary conditions.The results suggested that rib spacing has a more marked influence on the interface shear behavior than rib height does,in particular at the post-yield stage.The results could facilitate our understanding of bolt-grout interface shear behavior under CNS conditions,and optimize selection of rock bolts under in situ rock conditions.
基金supported by Youth Science Fund Project(No.81400612)
文摘Objective:To observe the chitooligosaccharides(COS) effect on the proliferation inhibition and radiosensitivity of three types of human gastric cancer cell line.Mothods:CCK-8 assay was employed to obtain the inhibition ratio of COS on BGC823 cells,MKN45 cells and SGC7901 cells at 48 h after treatment and the proliferation-inhibition curve was drawn with the inhibition ratio of COS on three types of cells.The clonogenic assay was used to detect the cell viability of 0,1,2,4,6 and 8 Gy(6 dose grades) in RAY group and RAY+COS group after X-ray,and the cell survival curve was used to analyze the sensitization enhancement ratio of COS.Flow cytometry was employed to detect cell cycle and apoptosis rate in control group,RAY group and RAY+COS group after 48 h treatment.Results:COS inhibited the proliferation of three types of cells.The inhibition rate was positively correlated with the concentration of COS,and the susceptibility of MKN45 cells,SGC7901 cells and BGC823 cells to COS decreased in turn.The cell viability decreased gradually with the increasing radiation dose in RAY group and RAY+COS group(P<0.01).The cell viabilities of RAY+COS group were lower than those of RAY group at all the dose grades under X-ray exposure(P<0.01),and the sensitization enhancement ratios of COS on BGC823 cells,MKN45 cells and SGC7901 cells were 1.06,1.28 and 1.15 respectively.In controlled trials,apoptosis rate and percentage in the G_2/M phase of three types of cells in RAY+COS group were higher than those in control group and RAY group,and percentage in the S phase and the G_0/G_1 phase in RAY+COS group were lower than those in the other two groups(P<0.01).Conclusions:COS can inhibit the proliferation of three types of human gastric cancer cells and enhance the radiosensitivity by inducing apoptosis and G_2/M phase arrest.
基金L.Deng acknowledges financial support by the Chinese Scholarship Council(CSC)support by German Research Foundation(DFG)(Nos.PA 2275/4-1,PA2275/6-1 and KO5771/1-1)+1 种基金support by the National Natural Science Foundation of China(Nos.51701213 and 51790484)the National key research and development program(2018YFB0703402)。
文摘Monolithic bulk metallic glass and glass matrix composites with a relative density above 98%were produced by processing Cu_(46)Zr_(46)Al_(8)(at.%)via selective laser melting(SLM).Their microstructures and mechanical properties were systematically examined.B2 CuZr nanocrystals(30-100 nm in diameter)are uniformly dispersed in the glassy matrix when SLM is conducted at an intermediate energy input.These B2 CuZr nanocrystals nucleate the oxygen-stabilized big cube phase during a remelting step.The presence of these nanocrystals increases the structural heterogeneity as indirectly revealed by mircrohardness and nanoindentation measurements.The corresponding maps in combination with calorimetric data indicate that the glassy phase is altered by the processing conditions.Despite the formation of crystals and a high overall free volume content,all additively manufactured samples fail at lower stress than the as-cast glass and without any plastic strain.The inherent brittleness is attributed to the presence of relatively large pores and the increased oxygen content after selective laser melting.
基金the financial support from the National Natural Science Foundation of China(No.51735005)Basic Strengthening Program of Science and Technology(No.2019-JCJQJJ-331)+3 种基金the 5th Jiangsu Province 333 High Level Talents Training Project(BRA2019048)The 15th Batch of“Six Talents Peaks”Innovative Talents Team Program“Laser Precise Additive Manufacturing of Structure-Performance Integrated Lightweight Alloy Components”(No.TD-GDZB-001)2017 Excellent Scientific and Technological Innovation Teams of Universities in Jiangsu“Laser Additive Manufacturing Technologies for Metallic Components”funded by Jiangsu Provincial Department of Education of China(No.51921003)the support from DFG under grant no.KO 5771/1-1。
文摘Steel matrix composites(SMCs),reinforced by ceramic particles,have received a consistent attention in recent years.Using conventional methods to prepare SMCs is generally challenging,and the mechanical properties of conventionally fabricated SMCs are limited.In this study,we successfully fabricated highperformance SMCs by laser powder bed fusion(LPBF)of a composite powder consisting of Fe-based alloy powder and submicron-sized WC particles.The effect of laser energy density on the phase formation,microstructural evolution,overall density and resulting mechanical properties of LPBF-fabricated composites was investigated.The present results show that a novel Fe_(2)W_(4)C carbidic network precipitates in the solidified microstructure entailing segregations along the boundaries of cellular sub-grains.The presence of this carbidic network hampers the growth of sub-grains even at elevated temperatures,and hence,stabilizes the grain size though prepared at a broad range of different energy densities.The exact distribution of the Fe_(2)W_(4)C carbides depends on the employed laser energy densities,as for instance they are more uniformly distributed at higher energy input.The density of LPBF samples reaches the maximum value of 99.4%at 150 J/mm^(3).In this parameter set,high microhardness of~753 HV,compression strength of~3350 MPa and fracture strain of~24.4%are obtained.The enhanced mechanical properties are ascribed to less metallurgical defects,higher volume fraction of the martensitic phase and increasing pile-up dislocations resulting from the pinning effect by Fe_(2)W_(4)C carbide.
基金supported by the National Natural Science Foundation of China (No.50875031)High-Tech Project of Bao Steel (No.10K029ECES)
文摘The effect of spiral magnetic field （SMF） on the solidification process of Sn-20 wt.%Pb hypoeutectic alloy was studied in this work. The temperature distribution and the macrosegregation together with the eutectic lamellar spacing during solidification were measured under different magnetic fields. The results indicate that the compositions in the top and bottom portions of the sample are nearly the same and the segregation phenomenon is basically eliminated by SMF at an exciting current of 125 A. The morphology of the primary phase transforms from coarse dendrite to rosette or ellipsoidal equiaxed crystal and the spacing of the eutectic lamellar increases from 1.6 to 3.9 μm when the exciting current increases from 0 to 125 A. Moreover, if the exciting current is high enough, the forced fluid flow caused by SMF will enhance the process of transition from lamellar eutectic structure to anomalous rod-like one.
基金supported by the National Key Research and Development Program of the Ministry of Science and Technology of China(No.2021YFA1500203)Natural Science Foundation of China(Nos.22231010,22061160464,21821002,and 22201290)Shanghai Sailing Program(No.22YF1458200)。
文摘Silyl cobalt species are putative intermediates in cobalt-catalyzed transformations of hydrosilanes.However,their reactivity has remained poorly understood.Reported here is the investigation on four-coordinate disilyl Co(Ⅱ)complexes with N-hetereocyclic carbene ligation.The reactions of[(ICy)_(2)Co(vtms)](ICy=1,3-dicyclohexylimidazol-2-ylidene,vtms=vinyltrimethylsilane)with primary and secondary hydrosilanes(3 equiv.)furnish the four-coordinate disilyl complexes[trans-(ICy)_(2)Co(SiHRR')_(2)](SiHRR'=SiH_(2)Mes,1;SiH_(2)Ph,2;SiH_(2)Cy,3;SiHPh_(2),4;SiHEt_(2),5)in moderate to good yields.The structures of 1,2 and 4 were established by single-crystal X-ray diffraction.Solution magnetic susceptibility measurement and EPR spectroscopy indicate their low-spin nature(S=1/2).Reactivity studies on 4 led to the establishment of the conversions of 4 to the disilyl dihydride Co(Ⅲ)complex[K(THF)][(ICy)_(2)Co(H)_(2)(SiHPh_(2))_(2)]_n(6)and the fluorosilyl Co(Ⅱ)complex[(ICy)_(2)Co(THF)(SiFPh_(2))][BF_(4)](7)when 4 was treated with excess amount of K and AgBF_(4),respectively,in THF.These conversions hint at the high activity of low-valent and high-valent disilyl cobalt species[trans-(ICy)_(2)Co(SiHPh_(2))_(2)]^(1-)and[trans-(ICy)_(2)Co(SiHPh_(2))_(2)]^(2+).Complex 4 is reactive toward terminal alkynes,but inert toward alkenes and internal alkynes.The reactions of 4 with terminal alkynes CyC≡CH and Me_(3)SiC≡CH(3 equiv.)yield the Co(Ⅱ)complexes[(ICy)_(2)Co(C≡CCy)_(2)](8)and[(ICy)_(2)Co(C≡CSiMe_(3))((SiMe_(3))C=CH_(2))](9),respectively,along with H_(2)SiPh_(2)and alkynylsilanes RC≡CSiHPh_(2)(R=Cy,SiMe_(3)),whereas the reaction with 4-CF_(3)C_(6)H_(4)C≡CH(3 equiv.)produce[(ICy)_(2)Co(C≡CAr)((Ar)C=CH(SiHPh_(2))C=CHAr)](Ar=4-CF_(3)C_(6)H_(4))(10)and H_(2)SiPh_(2).These reactions are proposed to involveσ-bond metathesis reactions between alkyne C(sp)-H bonds and Co-Si bonds in 4.Complexes 6–10 have been characterized by NMR spectroscopy,X-ray diffraction study,and elemental analysis.
基金This work was supported by the National Natural Science Foundation of China(Nos.81972058,81902194 and 82202680)the Science and Technology Commission of Shanghai Municipality(No.22YF1422900)+3 种基金the Shanghai Municipal Key Clinical Specialty,China(No.shslczdzk06701)the National Facility for Translational Medicine(Shanghai),China(No.TMSZ-2020-207)the Shanghai Engineering Research Center of Orthopedic Innovative Instruments and Personalized Medicine Instruments and Personalized Medicine(No.19DZ2250200)the Key R&D Program of Ningxia,China(Nos.2020BCH01001 and 2021BEG02037).
文摘The key to managing fracture is to achieve stable internal fixation,and currently,biologically and mechanically appropriate internal fixation devices are urgently needed.With excellent biocompatibility and corrosion resistance,titanium–niobium alloys have the potential to become a new generation of internal fixation materials for fractures.However,the role and mechanism of titanium–niobium alloys on promoting fracture healing are still undefined.Therefore,in this study,we systematically evaluated the bone-enabling properties of Ti45Nb via in vivo and in vitro experiments.In vitro,we found that Ti45Nb has an excellent ability to promote MC3T3-E1 cell adhesion and proliferation without obvious cytotoxicity.Alkaline phosphatase(ALP)activity and alizarin red staining and semiquantitative analysis showed that Ti45Nb enhanced the osteogenic differentiation of MC3T3-E1 cells compared to the Ti6Al4V control.In the polymerase chain reaction experiment,the expression of osteogenic genes in the Ti45Nb group,such as ALP,osteopontin(OPN),osteocalcin(OCN),type 1 collagen(Col-1)and runt-related transcription factor-2(Runx2),was significantly higher than that in the control group.Meanwhile,in the western blot experiment,the expression of osteogenic-related proteins in the Ti45Nb group was significantly increased,and the expression of PI3K–Akt-related proteins was also higher,which indicated that Ti45Nb might promote fracture healing by activating the PI3K–Akt signaling pathway.In vivo,we found that Ti45Nb implants accelerated fracture healing compared to Ti6Al4V,and the biosafety of Ti45Nb was confirmed by histological evaluation.Furthermore,immunohistochemical staining confirmed that Ti45Nb may promote osteogenesis by upregulating the PI3K/Akt signaling pathway.Our study demonstrated that Ti45Nb exerts an excellent ability to promote fracture healing as well as enhance osteoblast differentiation by activating the PI3K/Akt signaling pathway,and its good biosafety has been confirmed,which indicates its clinical translation potential.
基金supported by the National Major Scientific Equipment R&D Project(No.ZDYZ2010-2)the National Natural Science Foundation of China(No.51307165)
文摘Li4Ti5O12（LTO）/carbon nanotubes（CNTs） composite material is synthesized based on a solid-state method by sand-milling, spray-drying and calcining at 850 8C under N2 flow. The LTO/CNTs samples with1 wt% and 3 wt% weight ratio of CNTs addition and the pristine LTO sample are prepared. The rate performance and the thermal stability of these samples are investigated based on Li Mn2O4（LMO）/LTO full-cell. The results show that the weight ratio of CNTs addition has distinct effect on LTO performances.The composite materials of LTO composited CNTs have better performance at high-rate due to the intercalation enhancement by conductive network of CNTs. At second, the overcharging temperature response of the cell＇s surface with 1 wt% CNTs addition is the lowest. The particle size distribution is measured and the most uniform particles are obtained with 1 wt% CNTs addition. This trend could explain that the medium quantity of CNTs is optimal to improve the heat and mass transfer and prevent the problems of crystallite growing interference and aggregation during the calcination process.
基金supported by the National Major Scientific Equipment R&D Project (No. ZDYZ2010-2)the National Natural Science Foundation of China (No. 51307165)
文摘In situ NMR measurements of the diffusion coefficients,including an estimate of signal strength,of lithium ion conductor using diffusion-weighting pulse sequence are performed in this study.A cascade bilinear model is proposed to estimate the diffusion sensitivity factors of pulsed-field gradient using prior information of the electrochemical performance and Arrhenius constraint.The model postulates that the active lithium nuclei participating electrochemical reaction are relevant to the NMR signal intensity,when discharge rate or temperature condition is varying.The electrochemical data and the NMR signal strength show a highly fit with the proposed model according our simulation and experiments.Furthermore,the diffusion time is constrained by temperature based on Arrhenius equation of reaction rates dependence.An experimental calculation of Li_4Ti_5O_（12）（LTO）/carbon nanotubes（CNTs） with the electrolyte evaluating at 20 ℃ is presented,which the b factor is estimated by the discharge rate.
基金financial support from the National Natural Science Foundation of China(Nos.21725104,21690062,21432001,and 21821002)the National Key Research and Development Program(No.2016YFA0202900)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB20000000)the Program of Shanghai Academic Research Leader(No.19XD1424800)。
文摘The limited knowledge on low-coordinate zero-valent transition-metal species has intrigued great synthetic efforts in developing ligand sets for their stabilization.While the combined ligand set of Nheterocyclic carbene(NHC)with vinylsilanes was the only known ligand system amenable to the stabilization of three-coordinate formal zero-valent cobalt,iron,and manganese complexes,the exploration on other ligands has proved that the ligand set of NHCs with styrene is equally effective in stabilizing three-coo rdinate formal zero-valent metal complexes in the form of(NHC)M(η2-CH2CHPh)2(NHC=IPr,IMes;M=Co,Fe,Mn).These styrene complexes can be prepared by the one-pot reactions of MCl2 with styrene,NHC and KC8,and have been characterized by various spectroscopic methods.Preliminary reactivity study indicated that the interaction of[(IMes)Fe(η2-CH2 CHPh)2]with DippN3 produces the iron(IV)bisimido complex[(IMes)Fe(NDipp)2]and styrene,which hints at the utility of these zero-valent metal styene complexes as synthons of the mono-coordinate species(NHC)M(O).
