The electrochemical property, chemical composition and crystal structure of electroless Co-Ni-B-Ce alloy plated in general state as well as in magnetic field were studied using potentiometer, plasma emission spectrome...The electrochemical property, chemical composition and crystal structure of electroless Co-Ni-B-Ce alloy plated in general state as well as in magnetic field were studied using potentiometer, plasma emission spectrometer, X-ray diffractometer, transmission electron microscope. The results show that the static potential and polarizability of electroless Co-Ni-B alloy are remarkably improved as the plating is carried out in magnetic field in the presence of a little amount of cerium in plating bath. Because of the action of magnetic field and rare earth element cerium, the boron content in alloy decreases, while cobalt and nickel contents increase. As a result, the amorphous Co-Ni-B alloy transforms to the microcrystalline Co-Ni-B-Ce alloy when the plating is in general state, and the Co-Ni-B alloy makes a crystalline transformation because of the action of magnetic field and rare earth element cerium.展开更多
The effectsof melt overheating degree on the undercooling degree and resultant solidification structures of Nd9Fe85-xTi4C2Bx(x=10, 12) glass-forming alloyswerestudied by differential thermal analysis combining with ...The effectsof melt overheating degree on the undercooling degree and resultant solidification structures of Nd9Fe85-xTi4C2Bx(x=10, 12) glass-forming alloyswerestudied by differential thermal analysis combining with solidification structure analysis. The results indicate that the undercooling degree of Nd9Fe85-xTi4C2Bx(x=10, 12) alloys significantly increaseswith the rise of melt overheating degree, and two overheating degree thresholds corresponding to the drastic increase of the mean undercooling degree are found for each of the alloys. The existence of two turning points of the mean undercooling degreescan be linked to the structure transitions inside the overheated melts, which result in the evident increase of volume fraction of amorphous phasein the solidified structures.展开更多
Microstructure and phase transformation of disodium guanosine 5′-monophosphate(5′-GMPNa_2) are extremely important for controlling the process and understanding the mechanism of crystallization. In this work, the th...Microstructure and phase transformation of disodium guanosine 5′-monophosphate(5′-GMPNa_2) are extremely important for controlling the process and understanding the mechanism of crystallization. In this work, the thermodynamic properties of polymorphous 5′-GMPNa_2 especially the solubility were studied, the solubility results show that 5′-GMPNa_2 is more soluble in ethanol–water(E–W) than in isopropanol–water(I–W). The amorphous form of 5′-GMPNa_2 is more soluble than the crystalline form at the same mole fraction and temperature. Meanwhile, the crystalline forms and morphologies of the residual solids were characterized by PXRD and SEM. The results indicate that solid forms of 5′-GMPNa_2 transformed spontaneously from amorphous to crystalline when the ethanol proportion is ≥20%. In addition, increasing the pH facilitates the dissolution of 5′-GMPNa_2 and helps to maintain the crystalline form. The associated Gibbs free energy values were calculated to verify the trend of transformation from amorphous to crystalline 5′-GMPNa_2. These results should help to guide the industrial crystallization process and to obtain the crystalline form of 5′-GMPNa_2.展开更多
The wear behavior and mild−severe(M−S)wear transition of Mg−10Gd−1.5Y−0.4Zr alloy were investigated within a temperature range of 20−200℃.The morphologies and compositions of worn surfaces were examined to identify t...The wear behavior and mild−severe(M−S)wear transition of Mg−10Gd−1.5Y−0.4Zr alloy were investigated within a temperature range of 20−200℃.The morphologies and compositions of worn surfaces were examined to identify the wear mechanisms using scanning electron microscope and energy dispersive X-ray spectrometer.The microstructure and hardness in the subsurfaces were analyzed to reveal the M−S wear transition mechanism.Under a constant loads of 20,35 and 40 N,each wear rate−test temperature curve presented a turning point which corresponded to the M−S wear transition.In mild wear,the surface material was plastically deformed and hence was strainhardened,whereas in severe wear,the surface material was dynamically recrystallized and consequently was softened.It has been found that the critical temperature for M−S wear transition decreases with increasing the normal load,and the normal load exhibits an almost linear relationship with critical temperature for M−S wear transition.This work reveals that the M−S wear transition of the studied alloy conforms to the surface DRX temperature criterion.展开更多
The influence of free-end torsion on compressive behavior of an extruded AZ31 rod at various temperatures was studied.Pre-torsion generates a high density of dislocations and a large number of{1012}twins in the matrix...The influence of free-end torsion on compressive behavior of an extruded AZ31 rod at various temperatures was studied.Pre-torsion generates a high density of dislocations and a large number of{1012}twins in the matrix,which can largely enhance the compressive yield strength at RT and 100℃.However,with increasing temperature,hardening effect via pre-torsion gradually decreases.When the compressive temperature reaches 300℃,pre-torsion reduces the compressive yield strength.Moreover,initial dislocations and twins via torsion help to refine the sub-structure and accelerate the continuous dynamic recrystallization during compression at 200℃.Thus,twisted sample exhibits more rapid flow softening behavior than the as-extruded sample at 200℃.When compressed at 300℃,the twins and dislocations via torsion were largely eliminated during the holding time,and the discontinuous dynamic recrystallization was enhanced.It is found that the compression curves of twisted sample and as-extruded sample tended to be coincident at 300℃.Related mechanisms were discussed in detail.展开更多
The aim of this research was to examine the influence of vanadium on the structure, hardness and tensile strength of X I60CrMo 12-1 self-hardened steels. It is known that vanadium affects the process of solidification...The aim of this research was to examine the influence of vanadium on the structure, hardness and tensile strength of X I60CrMo 12-1 self-hardened steels. It is known that vanadium affects the process of solidification of this alloy in a way that narrows temperature interval of crystallization. Vanadium, as an alloying element, moves liquidus and solidus lines toward higher temperatures, approximately for 25 to 30 ~C. In addition, vanadium forms V6C5 carbides, which, are partly distributed between present phases in the steel; carbide (Cr,Fe)7C3 and austenite. The presence of vanadium enables the formation of (Cr, Fe)23C6 carbide and its precipitation into austenite during the cooling process. In local areas around fine carbide particles, austenite is transformed into martensite, i.e., vanadium reduces remained austenite and improves steel air-hardening. Vanadium concentration over 2.5% significantly improves the impact toughness. The basic problem in the application of high alloyed Cr-Mo steels is to increase their impact toughness and thereby sustain a relatively high value of hardness. Recent studies, concerning to the chemical composition and heat treatment regime, show that it is possible to get a martensitic structure with a very small amount of retained austenite. Investigations are directed toward the testing of the influence of alloying elements such as molybdenum, manganese and especially vanadium. Vanadium has great influence to the crystallization process. With increasing of its content, the eutectic point moves toward lower carbon concentrations and the temperature interval of solidification is narrowing.展开更多
In this study, we used the crystal structure search method and first-principles calculations to systematically explore the highpressure phase diagrams of the TaAs family (NbP, NbAs, TaP, and TaAs). Our calculation r...In this study, we used the crystal structure search method and first-principles calculations to systematically explore the highpressure phase diagrams of the TaAs family (NbP, NbAs, TaP, and TaAs). Our calculation results show that NbAs and TaAs have similar phase diagrams, the same structural phase transition sequence I41md→Pδm2→}P21/c→Pm3m, and slightly different transition pressures. The phase transition sequence of NbP and TaP differs somewhat from that of NbAs and TaAs, in which new structures emerge, such as the Cmcm structure in NbP and the Pmmn structure in TaP. Interestingly, we found that in the electronic structure of the high-pressure phase Pδm2-NbAs, there are coexisting Weyl points and triple degenerate points, similar to those found in high-pressure Pδm2-TaAs.展开更多
Structural and thermal sensitivity of Cu(60-x)Zr(30+x) Ti 10 (x=0,5,and 10 at%) amorphous alloys to the application of tension was investigated. The structural sensitivity to tension decreases with increasing Cu conte...Structural and thermal sensitivity of Cu(60-x)Zr(30+x) Ti 10 (x=0,5,and 10 at%) amorphous alloys to the application of tension was investigated. The structural sensitivity to tension decreases with increasing Cu content. The crystallization enthalpy increases with increasing excess free volume. The characteristic temperatures of the tensile samples can surpass those of the as-cast ones under a critical heating rate which differs in the Cu content. The increase of the excess free volume significantly influences the glass transition and crystallization procedures.展开更多
The bilayer compounds[n-CnH2n+1N(CH3)3]2Zn Cl4(n=16,18)experience solid-solid phase transition within the temperature range of 310 to 340 K.The low-temperature crystal structures of the pure compounds are characterist...The bilayer compounds[n-CnH2n+1N(CH3)3]2Zn Cl4(n=16,18)experience solid-solid phase transition within the temperature range of 310 to 340 K.The low-temperature crystal structures of the pure compounds are characteristic of the piling effect in which a 2D macro-anion Zn Cl42- is sandwiched between two alkylammonium layers.These layers become conformationally disordered in the high-temperature phases.The structures can alternatively be viewed as a double layer of alkylammonium ions between Zn Cl42- sheets and can be considered as crystalline models of lipid bilayers.The experimental subsolidus binary phase diagram of[n-C16H33N(CH3)3]2Zn Cl4-[n-C18H37N(CH3)3]2Zn Cl4 has also been established over the whole composition range by differential scanning calorimetry(DSC)and X-ray diffraction.In the phase diagram,one intermediate compound[n-C16H33N(CH3)3][n-C18H37N(CH3)3]Zn Cl4 at WC16C3Zn%47.50 and two eutectoid invariants points at WC16C3Zn%35.10 and75.70 were observed;the respective temperatures of the two eutectoids are 320±1 and 315±1 K.In addition,there are three noticeable solid solution ranges in the phase diagram:α-phase at the left,β-phase at the right,andγ-phase in the middle.展开更多
Ultrafast quasiparticle dynamics of single crystalline LaOFeAs were investigated by pump-probe measurement.The compound experiences structural and spin-density-wave(SDW)phase transitions at 150 K(TS1)and 130 K(TS2),re...Ultrafast quasiparticle dynamics of single crystalline LaOFeAs were investigated by pump-probe measurement.The compound experiences structural and spin-density-wave(SDW)phase transitions at 150 K(TS1)and 130 K(TS2),respectively.The relaxation time of quasiparticles was somewhat temperature independent at high temperature but exhibited a sharp upturn at TS1and reached the maximum at approximately TS2.The remarkable slowing down of quasiparticle relaxation time is caused by the formation of energy gap.By employing the Rothwarf-Taylor model analysis,we found that there should be already energy gaps opening just below the structural transition.The magnitude of SDW gap was identified to be 72 meV.展开更多
Eight chiral vinylterphenyl monomers, (+)-2,5-bis{4'-[(S)-1"-methylpropyloxy]phenyl}styrene (Ia), (+)-2,5-bis{4'-[(S)-2"- methylbutyloxy]phenyl}styrene (Ib), (+)-2,5-bis{4'-[(S)-3"-methylpenty...Eight chiral vinylterphenyl monomers, (+)-2,5-bis{4'-[(S)-1"-methylpropyloxy]phenyl}styrene (Ia), (+)-2,5-bis{4'-[(S)-2"- methylbutyloxy]phenyl}styrene (Ib), (+)-2,5-bis{4'-[(S)-3"-methylpentyloxy]phenyl}styrene (Ic), (+)-2,5-bis{4'-[(S)-4"- methylhexyloxy]phenyl}styrene (Id), (-)-2,5-bis{4'-[(R)-1"-methylpropyloxy]phenyl}styrene (le), (+)-2-/4'-[(S)-l"-methyl- propyloxy]phenyl}-5-{4'-[(R)-1"-methylpropyloxy]phenyl}styrene (Ⅱa), (-)-2-{4'-[(R)-1"-methylpropyloxy]phenyl}-5-{4'- [(S)- 1 "-methylpropyloxy]phenyl } styrene (lib), and (+)-2- { 4'-[(S)-2"-methylbutyloxy]phenyl }-5- { 4'-[(S)- 1"-methylpropyl- oxy]phenyl}styrene (Ⅲ), were synthesized and radically polymerized. These molecules were designed to further understand long-range chirality transfer in radical polymerization and to possibly tune the chiroptical properties of the polymers by varying the spatial configuration, position, and various combination of the stereogenic centers at the ends ofp-terphenyl pendants. The resultant polymers adopted helical conformations with a predominant screw sense. When the stereogenic centers ran away from the terphenyl group as in Ⅰb-d, the corresponding polymers changed the direction of optical rotation in an alternative way and showed no obvious stereomutation upon annealing in tetrahydrofuran. The two stereogenic centers of Ⅱa, Ⅱb, and Ⅲ acted concertedly in chiral induction, whereas those of la and Ie played a counteractive role. The five polymers derived from Ⅰa, Ⅰe, Ⅱa, Ⅱb, and Ⅲ underwent stereomutation when annealed in tetrahydrofuran. The polymers PIa-e had good thermal stability and high glass transition temperatures (Tgs). They generated liquid crystalline phases at above Tgs that could be kept upon cooling, with the exception of Pie. This result was consistent with the extended helical structures.展开更多
Two-dimensional(2D)superconductors have intriguing physical properties and abundant potential applications.Recently,2D superconductingα-Mo2C and facecentered cubic Mo2C have been controllably prepared and they bring ...Two-dimensional(2D)superconductors have intriguing physical properties and abundant potential applications.Recently,2D superconductingα-Mo2C and facecentered cubic Mo2C have been controllably prepared and they bring new viewpoints to carbon-based superconductivity.Although molybdenum carbides(Mo-Cs)have multiple crystalline stacking orders,there are still few structures reported for the lack of higher energy supply during growth.In this study,we report a two-step vapor deposition method to grow superconducting η-Mo3C2 films with different thicknesses,with the assistance of controllable plasma power.The grownη-Mo3C2 films show polycrystalline characteristics,but they still present superior superconductivity.The 3.0-nm-thick film has the superconducting transition temperature of 5.38 K,and its electrical performances follow truly 2D superconducting transitions.This study will not only exhibit a robust superconductingη-Mo3C2 ultrathin film,but also provides a convenient growth way to realize more carbide-based heterostructures for future device applications.展开更多
基金Project(50371023) supported by the National Natural Science Foundation of China
文摘The electrochemical property, chemical composition and crystal structure of electroless Co-Ni-B-Ce alloy plated in general state as well as in magnetic field were studied using potentiometer, plasma emission spectrometer, X-ray diffractometer, transmission electron microscope. The results show that the static potential and polarizability of electroless Co-Ni-B alloy are remarkably improved as the plating is carried out in magnetic field in the presence of a little amount of cerium in plating bath. Because of the action of magnetic field and rare earth element cerium, the boron content in alloy decreases, while cobalt and nickel contents increase. As a result, the amorphous Co-Ni-B alloy transforms to the microcrystalline Co-Ni-B-Ce alloy when the plating is in general state, and the Co-Ni-B alloy makes a crystalline transformation because of the action of magnetic field and rare earth element cerium.
基金Projects(51174121,51274125)supported by the National Natural Science Foundation of ChinaProject(2010R50016-30)supported by Zhejiang Province Science and Technology Innovation Team of Key Projects,ChinaProject supported by the K.C.Wong Magna Fund of Ningbo University,China
文摘The effectsof melt overheating degree on the undercooling degree and resultant solidification structures of Nd9Fe85-xTi4C2Bx(x=10, 12) glass-forming alloyswerestudied by differential thermal analysis combining with solidification structure analysis. The results indicate that the undercooling degree of Nd9Fe85-xTi4C2Bx(x=10, 12) alloys significantly increaseswith the rise of melt overheating degree, and two overheating degree thresholds corresponding to the drastic increase of the mean undercooling degree are found for each of the alloys. The existence of two turning points of the mean undercooling degreescan be linked to the structure transitions inside the overheated melts, which result in the evident increase of volume fraction of amorphous phasein the solidified structures.
基金Supported by the Program for Changjiang Scholars and Innovative Research Team in University(IRT_14R28)the National Basic Research Program of China(2013CB733602)+4 种基金the Major Research Plan of the National Natural Science Foundation of China(21390204)the National Natural Science Foundation of China(21636003,21506090)Open Fund by Jiangsu Key Lab of Biomass-based Green Fuels and Chemicals(JSBGFC14005)Jiangsu National Synergetic Innovation Center for Advanced Materials(SICAM)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)
文摘Microstructure and phase transformation of disodium guanosine 5′-monophosphate(5′-GMPNa_2) are extremely important for controlling the process and understanding the mechanism of crystallization. In this work, the thermodynamic properties of polymorphous 5′-GMPNa_2 especially the solubility were studied, the solubility results show that 5′-GMPNa_2 is more soluble in ethanol–water(E–W) than in isopropanol–water(I–W). The amorphous form of 5′-GMPNa_2 is more soluble than the crystalline form at the same mole fraction and temperature. Meanwhile, the crystalline forms and morphologies of the residual solids were characterized by PXRD and SEM. The results indicate that solid forms of 5′-GMPNa_2 transformed spontaneously from amorphous to crystalline when the ethanol proportion is ≥20%. In addition, increasing the pH facilitates the dissolution of 5′-GMPNa_2 and helps to maintain the crystalline form. The associated Gibbs free energy values were calculated to verify the trend of transformation from amorphous to crystalline 5′-GMPNa_2. These results should help to guide the industrial crystallization process and to obtain the crystalline form of 5′-GMPNa_2.
基金financial support from the National Natural Science Foundation of China (No.51775226)。
文摘The wear behavior and mild−severe(M−S)wear transition of Mg−10Gd−1.5Y−0.4Zr alloy were investigated within a temperature range of 20−200℃.The morphologies and compositions of worn surfaces were examined to identify the wear mechanisms using scanning electron microscope and energy dispersive X-ray spectrometer.The microstructure and hardness in the subsurfaces were analyzed to reveal the M−S wear transition mechanism.Under a constant loads of 20,35 and 40 N,each wear rate−test temperature curve presented a turning point which corresponded to the M−S wear transition.In mild wear,the surface material was plastically deformed and hence was strainhardened,whereas in severe wear,the surface material was dynamically recrystallized and consequently was softened.It has been found that the critical temperature for M−S wear transition decreases with increasing the normal load,and the normal load exhibits an almost linear relationship with critical temperature for M−S wear transition.This work reveals that the M−S wear transition of the studied alloy conforms to the surface DRX temperature criterion.
基金the National Natural Science Foundation of China(No.51601154)Southwest University Undergraduate Innovation Project(No.zsm2021026).
文摘The influence of free-end torsion on compressive behavior of an extruded AZ31 rod at various temperatures was studied.Pre-torsion generates a high density of dislocations and a large number of{1012}twins in the matrix,which can largely enhance the compressive yield strength at RT and 100℃.However,with increasing temperature,hardening effect via pre-torsion gradually decreases.When the compressive temperature reaches 300℃,pre-torsion reduces the compressive yield strength.Moreover,initial dislocations and twins via torsion help to refine the sub-structure and accelerate the continuous dynamic recrystallization during compression at 200℃.Thus,twisted sample exhibits more rapid flow softening behavior than the as-extruded sample at 200℃.When compressed at 300℃,the twins and dislocations via torsion were largely eliminated during the holding time,and the discontinuous dynamic recrystallization was enhanced.It is found that the compression curves of twisted sample and as-extruded sample tended to be coincident at 300℃.Related mechanisms were discussed in detail.
文摘The aim of this research was to examine the influence of vanadium on the structure, hardness and tensile strength of X I60CrMo 12-1 self-hardened steels. It is known that vanadium affects the process of solidification of this alloy in a way that narrows temperature interval of crystallization. Vanadium, as an alloying element, moves liquidus and solidus lines toward higher temperatures, approximately for 25 to 30 ~C. In addition, vanadium forms V6C5 carbides, which, are partly distributed between present phases in the steel; carbide (Cr,Fe)7C3 and austenite. The presence of vanadium enables the formation of (Cr, Fe)23C6 carbide and its precipitation into austenite during the cooling process. In local areas around fine carbide particles, austenite is transformed into martensite, i.e., vanadium reduces remained austenite and improves steel air-hardening. Vanadium concentration over 2.5% significantly improves the impact toughness. The basic problem in the application of high alloyed Cr-Mo steels is to increase their impact toughness and thereby sustain a relatively high value of hardness. Recent studies, concerning to the chemical composition and heat treatment regime, show that it is possible to get a martensitic structure with a very small amount of retained austenite. Investigations are directed toward the testing of the influence of alloying elements such as molybdenum, manganese and especially vanadium. Vanadium has great influence to the crystallization process. With increasing of its content, the eutectic point moves toward lower carbon concentrations and the temperature interval of solidification is narrowing.
基金supported by the National Key R&D Program of China(Grant No.2016YFA0300404)the National Key Projects for Basic Research in China(Grant No.2015CB921202)+4 种基金the National Natural Science Foundation of China(Grant Nos.11574133,and 51372112)the Natural Science Foundation Jiangsu Province(Grant No.BK20150012)the Science Challenge Project(Grant No.TZ2016001)the Fundamental Research Funds for the Central UniversitiesSpecial Program for Applied Research on Super Computation of the National Natural Science FoundationGuangdong Joint Fund
文摘In this study, we used the crystal structure search method and first-principles calculations to systematically explore the highpressure phase diagrams of the TaAs family (NbP, NbAs, TaP, and TaAs). Our calculation results show that NbAs and TaAs have similar phase diagrams, the same structural phase transition sequence I41md→Pδm2→}P21/c→Pm3m, and slightly different transition pressures. The phase transition sequence of NbP and TaP differs somewhat from that of NbAs and TaAs, in which new structures emerge, such as the Cmcm structure in NbP and the Pmmn structure in TaP. Interestingly, we found that in the electronic structure of the high-pressure phase Pδm2-NbAs, there are coexisting Weyl points and triple degenerate points, similar to those found in high-pressure Pδm2-TaAs.
基金the National Natural Science Foundation (Grant No. 50874045)the Scientific Research Fund of the Hunan Provincial Education Department (Grant No. 10A044)
文摘Structural and thermal sensitivity of Cu(60-x)Zr(30+x) Ti 10 (x=0,5,and 10 at%) amorphous alloys to the application of tension was investigated. The structural sensitivity to tension decreases with increasing Cu content. The crystallization enthalpy increases with increasing excess free volume. The characteristic temperatures of the tensile samples can surpass those of the as-cast ones under a critical heating rate which differs in the Cu content. The increase of the excess free volume significantly influences the glass transition and crystallization procedures.
基金financially supported by the National Natural Science Foundation of China(21473048,21246006)the Natural Science Foundation of Hebei Province(B2012205034)the Science Foundation of Hebei Normal University(L2011K04,L2013B07)
文摘The bilayer compounds[n-CnH2n+1N(CH3)3]2Zn Cl4(n=16,18)experience solid-solid phase transition within the temperature range of 310 to 340 K.The low-temperature crystal structures of the pure compounds are characteristic of the piling effect in which a 2D macro-anion Zn Cl42- is sandwiched between two alkylammonium layers.These layers become conformationally disordered in the high-temperature phases.The structures can alternatively be viewed as a double layer of alkylammonium ions between Zn Cl42- sheets and can be considered as crystalline models of lipid bilayers.The experimental subsolidus binary phase diagram of[n-C16H33N(CH3)3]2Zn Cl4-[n-C18H37N(CH3)3]2Zn Cl4 has also been established over the whole composition range by differential scanning calorimetry(DSC)and X-ray diffraction.In the phase diagram,one intermediate compound[n-C16H33N(CH3)3][n-C18H37N(CH3)3]Zn Cl4 at WC16C3Zn%47.50 and two eutectoid invariants points at WC16C3Zn%35.10 and75.70 were observed;the respective temperatures of the two eutectoids are 320±1 and 315±1 K.In addition,there are three noticeable solid solution ranges in the phase diagram:α-phase at the left,β-phase at the right,andγ-phase in the middle.
基金supported by the National Science Foundation of China(Grant No.2011CB921701)the National Basic Research Program of China(Grant No.2012CB821403)
文摘Ultrafast quasiparticle dynamics of single crystalline LaOFeAs were investigated by pump-probe measurement.The compound experiences structural and spin-density-wave(SDW)phase transitions at 150 K(TS1)and 130 K(TS2),respectively.The relaxation time of quasiparticles was somewhat temperature independent at high temperature but exhibited a sharp upturn at TS1and reached the maximum at approximately TS2.The remarkable slowing down of quasiparticle relaxation time is caused by the formation of energy gap.By employing the Rothwarf-Taylor model analysis,we found that there should be already energy gaps opening just below the structural transition.The magnitude of SDW gap was identified to be 72 meV.
基金supported by the National Natural Science Foundation of China(21274003)the Research Fund for Doctoral Program of Higher Education of Ministry of Education(20110001110084)
文摘Eight chiral vinylterphenyl monomers, (+)-2,5-bis{4'-[(S)-1"-methylpropyloxy]phenyl}styrene (Ia), (+)-2,5-bis{4'-[(S)-2"- methylbutyloxy]phenyl}styrene (Ib), (+)-2,5-bis{4'-[(S)-3"-methylpentyloxy]phenyl}styrene (Ic), (+)-2,5-bis{4'-[(S)-4"- methylhexyloxy]phenyl}styrene (Id), (-)-2,5-bis{4'-[(R)-1"-methylpropyloxy]phenyl}styrene (le), (+)-2-/4'-[(S)-l"-methyl- propyloxy]phenyl}-5-{4'-[(R)-1"-methylpropyloxy]phenyl}styrene (Ⅱa), (-)-2-{4'-[(R)-1"-methylpropyloxy]phenyl}-5-{4'- [(S)- 1 "-methylpropyloxy]phenyl } styrene (lib), and (+)-2- { 4'-[(S)-2"-methylbutyloxy]phenyl }-5- { 4'-[(S)- 1"-methylpropyl- oxy]phenyl}styrene (Ⅲ), were synthesized and radically polymerized. These molecules were designed to further understand long-range chirality transfer in radical polymerization and to possibly tune the chiroptical properties of the polymers by varying the spatial configuration, position, and various combination of the stereogenic centers at the ends ofp-terphenyl pendants. The resultant polymers adopted helical conformations with a predominant screw sense. When the stereogenic centers ran away from the terphenyl group as in Ⅰb-d, the corresponding polymers changed the direction of optical rotation in an alternative way and showed no obvious stereomutation upon annealing in tetrahydrofuran. The two stereogenic centers of Ⅱa, Ⅱb, and Ⅲ acted concertedly in chiral induction, whereas those of la and Ie played a counteractive role. The five polymers derived from Ⅰa, Ⅰe, Ⅱa, Ⅱb, and Ⅲ underwent stereomutation when annealed in tetrahydrofuran. The polymers PIa-e had good thermal stability and high glass transition temperatures (Tgs). They generated liquid crystalline phases at above Tgs that could be kept upon cooling, with the exception of Pie. This result was consistent with the extended helical structures.
基金the National Key R&D Program of China(2018YFA0305800)the Fundamental Research Funds for the Central Universities(020414380145 and 020414380153)+2 种基金the National Natural Science Foundation of China(11674154,11761131010,51972163,11904163,61974021 and 11525415)the Natural Science Foundation of Jiangsu Province(BK20190010)the Fok Ying-Tong Education Foundation of China(171038)。
文摘Two-dimensional(2D)superconductors have intriguing physical properties and abundant potential applications.Recently,2D superconductingα-Mo2C and facecentered cubic Mo2C have been controllably prepared and they bring new viewpoints to carbon-based superconductivity.Although molybdenum carbides(Mo-Cs)have multiple crystalline stacking orders,there are still few structures reported for the lack of higher energy supply during growth.In this study,we report a two-step vapor deposition method to grow superconducting η-Mo3C2 films with different thicknesses,with the assistance of controllable plasma power.The grownη-Mo3C2 films show polycrystalline characteristics,but they still present superior superconductivity.The 3.0-nm-thick film has the superconducting transition temperature of 5.38 K,and its electrical performances follow truly 2D superconducting transitions.This study will not only exhibit a robust superconductingη-Mo3C2 ultrathin film,but also provides a convenient growth way to realize more carbide-based heterostructures for future device applications.