The low O^(2-)diffusion rate in the electro-deoxidation of titanium containing compounds by either the OS process or the FFC process leads to a low reaction speed and a low current efficiency.In this study,Ca_(3)Ti_(2...The low O^(2-)diffusion rate in the electro-deoxidation of titanium containing compounds by either the OS process or the FFC process leads to a low reaction speed and a low current efficiency.In this study,Ca_(3)Ti_(2)O_(7) was used as a precursor to improve the reduction speed of titanium.Because of the greater number of"diffusion channels"created in cathode as Ca^(2+) liberates from Ca_(3)Ti_(2)O_(7) precursor in the electrodeoxidation process,the O^(2-)diffusion rate was improved significantly by using Ca_(3)Ti_(2)O_(7) instead of CaTiO3 as precursor.Parallel constant voltage electrolysis(3.2 V)confirms that Ca_(3)Ti_(2)O_(7) and CaTiO3 are reduced simultaneously because of their similar crystal structures.However,the reduction area of Ca_(3)Ti_(2)O_(7) spreads much faster than that of CaTiO3,indicating a difference in the O^(2-) diffusion rate.Constant voltage cyclic voltammetry(CV)and theoretical analysis of the crystal structure were also conducted to compare the differences between Ca_(3)Ti_(2)O_(7) and CaTiO3.The results indicate that using a precursor with a greater number of soluble cations,titanium reduction speed can be greatly improved in the electro-deoxidation process.Finally,a new electrolysis method for converting and recycling excess CaO from the Ca_(3)Ti_(2)O_(7) precursor was proposed.展开更多
A series of Sr_(2)MgSi_(2)O_(7):Tb^(3+)nanophosphors is prepared using a high-temperature solid-state reaction.The x-ray diffraction patterns show that the crystal structure of the sample is not significantly affected...A series of Sr_(2)MgSi_(2)O_(7):Tb^(3+)nanophosphors is prepared using a high-temperature solid-state reaction.The x-ray diffraction patterns show that the crystal structure of the sample is not significantly affected by Tb^(3+)ions.However,the images of the scanning electron microscope illustrate that the average size of nanoparticles becomes larger with the increase of Tb^(3+)concentration.Unlike earlier investigations on down-conversion emission of Tb^(3+)ion excited by deep ultraviolet light,in this work,the photoluminescence characteristics of Sr_(2)MgSi_(2)O_(7)nanophosphors doped with different Tb^(3+)concentrations are analyzed under 374-nm excitations.The intense green emission at 545 nm is observed at an optimal doping concentration of 1.6 mol%.The main reason for the concentration quenching is due to the electric dipole-electric dipole interaction among Tb^(3+)ions.展开更多
Three alkaline earth silicate phosphors: Sr2MgSi2O7∶Eu, Dy, Gd, Sr3MgSi2O8∶Eu, Dy, Gd and Sr2MgSi2O7∶Eu, Dy were prepared and their luminescent properties were investigated. The Photoluminescence (PL) measurements ...Three alkaline earth silicate phosphors: Sr2MgSi2O7∶Eu, Dy, Gd, Sr3MgSi2O8∶Eu, Dy, Gd and Sr2MgSi2O7∶Eu, Dy were prepared and their luminescent properties were investigated. The Photoluminescence (PL) measurements indicated that the phosphors gave a longer emitting phosphorescence phenomenon by comparing with those without Gd2O3 activator, in which a better afterglow characteristic was observed by adding Gd2O3 to the phosphors. While little influence on the structure of luminescent materials was observed via XRD spectra, and obvious emission wavelength shift was exhibited due to the differences in the structure parameters of the two hosts. The results revealed that the improvement was due to nonequivalent substitution to produce more e-traps, and energy transfer from Gd3+ to Dy3+, to boost the performance of Sr2MgSi2O7∶Eu, Dy phosphor. Role of Gd3+ co-doped into Sr2MgSi2O7∶Eu, Dy matrix and the possible long-lasting phosphorescence progress were discussed.展开更多
A red-emitting phosphor Ca_(2.91)Si_(2)O_(7):0.09Eu^(3+) with partial Al^(3+)/P^(5+) substitution on Si^(4+) was synthesized via a simple solid-state method,and the effects of the introduction of the M^(3+/5+)(M=Al,P)...A red-emitting phosphor Ca_(2.91)Si_(2)O_(7):0.09Eu^(3+) with partial Al^(3+)/P^(5+) substitution on Si^(4+) was synthesized via a simple solid-state method,and the effects of the introduction of the M^(3+/5+)(M=Al,P)ions on the crystal structure and photoluminescence performance of Ca_(2.91)Si_(2−x)M_(x)O_(7):0.09Eu^(3+) phosphors were investigated.The X-ray diffraction(XRD),energy-dispersive X-ray spectroscopy(EDS),and X-ray photoelectron spectroscopy(XPS)results revealed that the structure of Ca_(3)Si_(2)O_(7) remained the same after the introduction of Al^(3+) and P^(5+) ions.The characteristic emission of Eu^(3+)-doped Ca_(3)Si_(2−x)M_(x)O_(7) phosphors exhibited two main peaks at 617 nm(red)and 593 nm(orange)under excitation at 394 nm,which originated from the^(5)D_(0)→^(7)F_(2)and^(5)D_(0)→^(7)F_(1) electron transitions of Eu^(3+) ions.After the partial substitution of Al^(3+) and P^(5+),the red emission intensities of the Ca_(2.91)Si_(2)O_(7):0.09Eu^(3+) phosphors were significantly enhanced by 1.88-and 1.42-fold,respectively,which is attributed to the crystal-field effect around Eu^(3+).Meanwhile,the luminescence intensities of the Ca_(2.91)Si_(1.96)Al_(0.04)O_(7):0.09Eu^(3+) and Ca_(2.91)Si_(1.94)P_(0.06)O_(7):0.09Eu^(3+) phosphors at 210℃ were 79.36%and 77.53%of those at 30°C,respectively,indicating their excellent thermal stability.Moreover,the as-prepared Ca_(2.91)Si_(1.96)Al_(0.04)O_(7):0.09Eu^(3+)and Ca_(2.91)Si_(1.94)P_(0.06)O_(7):0.09Eu^(3+) red-emitting phosphors were combined with a near-ultraviolet chip of 395 nm to fabricate red-light-emitting diode(LED)and white(w)-LED devices with excellent chromaticity features.In summary,Al^(3+)/P^(5+)-substituted Ca_(2.91)Si_(2)O_(7):0.09Eu^(3+) can serve as red-emitting phosphors for applications in w-LEDs.展开更多
In order to improve the red luminescent properties,Sr_(2)MgSi_(2)O_(7):Eu^(2+),Dy^(3+)was selected as a blue persistent luminescent donor phosphor,while light conversion agent was utilized to tune the persistent lumin...In order to improve the red luminescent properties,Sr_(2)MgSi_(2)O_(7):Eu^(2+),Dy^(3+)was selected as a blue persistent luminescent donor phosphor,while light conversion agent was utilized to tune the persistent luminescent spectra from blue to red.Composite red luminescent material Sr_(2)MgSi_(2)O_(7):Eu^(2+),Dy^(3+)/light conversion agent(SMED/LCA)was fabricated with light conversion agent and Sr_(2)MgSi_(2)O_(7):Eu^(2+),Dy^(3+)at a certain mass ratio.SiO_(2)(Al2 O_(3) or MgF2)were coated on the surface of SMED/LCA through heterogeneous deposition method.The structural and optical characteristics of the resulting samples were launched in terms of X-ray diffraction and emission spectrum as well as afterglow brightness.The results demonstrate that the emission spectrum exhibits two emission bands,and the peaks are located at around 470 and 615 nm.SiO_(2),Al_(2)O_(3) and MgF_(2) are coated on the surface of SMED/LCA like a protective shell to maintain its stability and luminescent properties,the afterglow initial brightness is still up to 0.37 cd/m^(2) and the afterglow color purity calculated from CIE color coordinates is basically unchanged.展开更多
In this study, down-conversion fluorescent powder of Sr2ZnSi2O7：Eu-（2＋）,Dy-（3＋）, SrAl2O4：Eu-（2＋）,Dy-（3＋） and Y2O2S：Eu-（3＋）,Mg-（2＋）,Ti-（4＋）, which were the common three primary colors materials ...In this study, down-conversion fluorescent powder of Sr2ZnSi2O7：Eu-（2＋）,Dy-（3＋）, SrAl2O4：Eu-（2＋）,Dy-（3＋） and Y2O2S：Eu-（3＋）,Mg-（2＋）,Ti-（4＋）, which were the common three primary colors materials with long afterglow, were synthesized by high temperature solid state method. The blends of rare earth（RE） luminescent materials have been of interest to reinvest the luminescent characteristics of polyethylene terephtahalate（PET） luminous fiber. The scanning electron microscopy（SEM） and an inversion fluorescence microscope were used to characterize the surface morphology and the dispersion of inclusion. Through analysis of microcosmic morphology, three typical dispersions of luminescent particles were summarized. The X-ray diffraction indicated that the phase structure of fiber samples and crystal structure of luminescence materials kept complete after prilling and spinning. From the fluorescence spectra and CIE 1931 coordinates, it could be found that different combinations of luminous fibers were desired to obtain divers colors emission luminous fiber. And the fiber samples were a light sensation which could induct different excitation wavelengths and convert it down to different colors. The afterglow decay curve and its differential curve were summarized indicating the three decay stages. The decay curve and decay rate curve showed that the contents of Sr2ZnSi2O7：Eu-（2＋）,Dy-（3＋）, SrAl2O4：Eu-（2＋）,Dy-（3＋） and Y2O2S：Eu-（3＋）,Mg-（2＋）,Ti-（4＋） had obvious influence on the afterglow of fiber samples.展开更多
Ca_(3)Ti_(2)O_(7) with Ruddlesden-Popper structure exhibits the largest polarization among the known hybrid improper ferroelectrics.However,the high Curie temperature impedes the thorough study of phase transition thr...Ca_(3)Ti_(2)O_(7) with Ruddlesden-Popper structure exhibits the largest polarization among the known hybrid improper ferroelectrics.However,the high Curie temperature impedes the thorough study of phase transition through dielectric characterization.According to the previous theoretical design rule,the Curie temperature can be suppressed by increasing the tolerance factor.So,in the present work,high-quality Ca_(3-x)LaxTi_(2-x)Al_(x)O_(7)(x=0.0,0.1,0.2,0.3)ceramics with increased tolerance factors were successfully prepared.The amplitude of oxygen octahedral tilt mode indeed decreases with increasing tolerance factors,leading to a degeneration of ferroelectric polarization.However,the unexpected rigid rotation mode causes the composition-invariable coercive fields.The Curie temperatures decrease linearly with increasing x and tolerance factors.The variable-temperature dielectric constant confirms first-order improper ferroelectric transitions in Ca_(3)Ti_(2)O_(7)-based ceramics.The results of variable temperature Xray diffraction reveal the coexistence of two-phases below Curie temperature.The present work confidently confirms the first-order improper ferroelectric transition in Ca_(3)Ti_(2)O_(7)-based ceramics by combining results of variable-temperature dielectric response and in-situ X-ray powder diffraction.展开更多
基金the National Natural Science Foundation of China(Nos.51604255 and U1702251)。
文摘The low O^(2-)diffusion rate in the electro-deoxidation of titanium containing compounds by either the OS process or the FFC process leads to a low reaction speed and a low current efficiency.In this study,Ca_(3)Ti_(2)O_(7) was used as a precursor to improve the reduction speed of titanium.Because of the greater number of"diffusion channels"created in cathode as Ca^(2+) liberates from Ca_(3)Ti_(2)O_(7) precursor in the electrodeoxidation process,the O^(2-)diffusion rate was improved significantly by using Ca_(3)Ti_(2)O_(7) instead of CaTiO3 as precursor.Parallel constant voltage electrolysis(3.2 V)confirms that Ca_(3)Ti_(2)O_(7) and CaTiO3 are reduced simultaneously because of their similar crystal structures.However,the reduction area of Ca_(3)Ti_(2)O_(7) spreads much faster than that of CaTiO3,indicating a difference in the O^(2-) diffusion rate.Constant voltage cyclic voltammetry(CV)and theoretical analysis of the crystal structure were also conducted to compare the differences between Ca_(3)Ti_(2)O_(7) and CaTiO3.The results indicate that using a precursor with a greater number of soluble cations,titanium reduction speed can be greatly improved in the electro-deoxidation process.Finally,a new electrolysis method for converting and recycling excess CaO from the Ca_(3)Ti_(2)O_(7) precursor was proposed.
基金Project supported by the National Natural Science Foundation of China(Grant No.11004092)the Foundation of Science and Technology Department of Liaoning Province,China(Grant No.201602455)。
文摘A series of Sr_(2)MgSi_(2)O_(7):Tb^(3+)nanophosphors is prepared using a high-temperature solid-state reaction.The x-ray diffraction patterns show that the crystal structure of the sample is not significantly affected by Tb^(3+)ions.However,the images of the scanning electron microscope illustrate that the average size of nanoparticles becomes larger with the increase of Tb^(3+)concentration.Unlike earlier investigations on down-conversion emission of Tb^(3+)ion excited by deep ultraviolet light,in this work,the photoluminescence characteristics of Sr_(2)MgSi_(2)O_(7)nanophosphors doped with different Tb^(3+)concentrations are analyzed under 374-nm excitations.The intense green emission at 545 nm is observed at an optimal doping concentration of 1.6 mol%.The main reason for the concentration quenching is due to the electric dipole-electric dipole interaction among Tb^(3+)ions.
基金the National Natural Science Foundation (20376009)the Liaoning Natural Science Foundation(20032129) of China
文摘Three alkaline earth silicate phosphors: Sr2MgSi2O7∶Eu, Dy, Gd, Sr3MgSi2O8∶Eu, Dy, Gd and Sr2MgSi2O7∶Eu, Dy were prepared and their luminescent properties were investigated. The Photoluminescence (PL) measurements indicated that the phosphors gave a longer emitting phosphorescence phenomenon by comparing with those without Gd2O3 activator, in which a better afterglow characteristic was observed by adding Gd2O3 to the phosphors. While little influence on the structure of luminescent materials was observed via XRD spectra, and obvious emission wavelength shift was exhibited due to the differences in the structure parameters of the two hosts. The results revealed that the improvement was due to nonequivalent substitution to produce more e-traps, and energy transfer from Gd3+ to Dy3+, to boost the performance of Sr2MgSi2O7∶Eu, Dy phosphor. Role of Gd3+ co-doped into Sr2MgSi2O7∶Eu, Dy matrix and the possible long-lasting phosphorescence progress were discussed.
基金This work was financially supported by the Department of Science and Technology of Sichuan Province(No.2020YJ0157).
文摘A red-emitting phosphor Ca_(2.91)Si_(2)O_(7):0.09Eu^(3+) with partial Al^(3+)/P^(5+) substitution on Si^(4+) was synthesized via a simple solid-state method,and the effects of the introduction of the M^(3+/5+)(M=Al,P)ions on the crystal structure and photoluminescence performance of Ca_(2.91)Si_(2−x)M_(x)O_(7):0.09Eu^(3+) phosphors were investigated.The X-ray diffraction(XRD),energy-dispersive X-ray spectroscopy(EDS),and X-ray photoelectron spectroscopy(XPS)results revealed that the structure of Ca_(3)Si_(2)O_(7) remained the same after the introduction of Al^(3+) and P^(5+) ions.The characteristic emission of Eu^(3+)-doped Ca_(3)Si_(2−x)M_(x)O_(7) phosphors exhibited two main peaks at 617 nm(red)and 593 nm(orange)under excitation at 394 nm,which originated from the^(5)D_(0)→^(7)F_(2)and^(5)D_(0)→^(7)F_(1) electron transitions of Eu^(3+) ions.After the partial substitution of Al^(3+) and P^(5+),the red emission intensities of the Ca_(2.91)Si_(2)O_(7):0.09Eu^(3+) phosphors were significantly enhanced by 1.88-and 1.42-fold,respectively,which is attributed to the crystal-field effect around Eu^(3+).Meanwhile,the luminescence intensities of the Ca_(2.91)Si_(1.96)Al_(0.04)O_(7):0.09Eu^(3+) and Ca_(2.91)Si_(1.94)P_(0.06)O_(7):0.09Eu^(3+) phosphors at 210℃ were 79.36%and 77.53%of those at 30°C,respectively,indicating their excellent thermal stability.Moreover,the as-prepared Ca_(2.91)Si_(1.96)Al_(0.04)O_(7):0.09Eu^(3+)and Ca_(2.91)Si_(1.94)P_(0.06)O_(7):0.09Eu^(3+) red-emitting phosphors were combined with a near-ultraviolet chip of 395 nm to fabricate red-light-emitting diode(LED)and white(w)-LED devices with excellent chromaticity features.In summary,Al^(3+)/P^(5+)-substituted Ca_(2.91)Si_(2)O_(7):0.09Eu^(3+) can serve as red-emitting phosphors for applications in w-LEDs.
基金Project supported by Natural Science Foundation of Jiangsu Province(BK20171140,BK20180629)National Natural Science Foundation of China(51803076)。
文摘In order to improve the red luminescent properties,Sr_(2)MgSi_(2)O_(7):Eu^(2+),Dy^(3+)was selected as a blue persistent luminescent donor phosphor,while light conversion agent was utilized to tune the persistent luminescent spectra from blue to red.Composite red luminescent material Sr_(2)MgSi_(2)O_(7):Eu^(2+),Dy^(3+)/light conversion agent(SMED/LCA)was fabricated with light conversion agent and Sr_(2)MgSi_(2)O_(7):Eu^(2+),Dy^(3+)at a certain mass ratio.SiO_(2)(Al2 O_(3) or MgF2)were coated on the surface of SMED/LCA through heterogeneous deposition method.The structural and optical characteristics of the resulting samples were launched in terms of X-ray diffraction and emission spectrum as well as afterglow brightness.The results demonstrate that the emission spectrum exhibits two emission bands,and the peaks are located at around 470 and 615 nm.SiO_(2),Al_(2)O_(3) and MgF_(2) are coated on the surface of SMED/LCA like a protective shell to maintain its stability and luminescent properties,the afterglow initial brightness is still up to 0.37 cd/m^(2) and the afterglow color purity calculated from CIE color coordinates is basically unchanged.
基金Project supported by the National Natural Science Foundation of China(51503082)the Fundamental Research Funds for the Central Universities(JUSRP51505,JUSRP116020)Jiangsu Province Ordinary University Academic Degree Graduate Student Scientific Research Innovation Projects(KYLX16-0791)
文摘In this study, down-conversion fluorescent powder of Sr2ZnSi2O7：Eu-（2＋）,Dy-（3＋）, SrAl2O4：Eu-（2＋）,Dy-（3＋） and Y2O2S：Eu-（3＋）,Mg-（2＋）,Ti-（4＋）, which were the common three primary colors materials with long afterglow, were synthesized by high temperature solid state method. The blends of rare earth（RE） luminescent materials have been of interest to reinvest the luminescent characteristics of polyethylene terephtahalate（PET） luminous fiber. The scanning electron microscopy（SEM） and an inversion fluorescence microscope were used to characterize the surface morphology and the dispersion of inclusion. Through analysis of microcosmic morphology, three typical dispersions of luminescent particles were summarized. The X-ray diffraction indicated that the phase structure of fiber samples and crystal structure of luminescence materials kept complete after prilling and spinning. From the fluorescence spectra and CIE 1931 coordinates, it could be found that different combinations of luminous fibers were desired to obtain divers colors emission luminous fiber. And the fiber samples were a light sensation which could induct different excitation wavelengths and convert it down to different colors. The afterglow decay curve and its differential curve were summarized indicating the three decay stages. The decay curve and decay rate curve showed that the contents of Sr2ZnSi2O7：Eu-（2＋）,Dy-（3＋）, SrAl2O4：Eu-（2＋）,Dy-（3＋） and Y2O2S：Eu-（3＋）,Mg-（2＋）,Ti-（4＋） had obvious influence on the afterglow of fiber samples.
基金financially supported by the National Natural Science Foundation of China under Grant Nos.51772266 and 51790493the National Key R&D Program of China under Grant No.2016YFA0300101.
文摘Ca_(3)Ti_(2)O_(7) with Ruddlesden-Popper structure exhibits the largest polarization among the known hybrid improper ferroelectrics.However,the high Curie temperature impedes the thorough study of phase transition through dielectric characterization.According to the previous theoretical design rule,the Curie temperature can be suppressed by increasing the tolerance factor.So,in the present work,high-quality Ca_(3-x)LaxTi_(2-x)Al_(x)O_(7)(x=0.0,0.1,0.2,0.3)ceramics with increased tolerance factors were successfully prepared.The amplitude of oxygen octahedral tilt mode indeed decreases with increasing tolerance factors,leading to a degeneration of ferroelectric polarization.However,the unexpected rigid rotation mode causes the composition-invariable coercive fields.The Curie temperatures decrease linearly with increasing x and tolerance factors.The variable-temperature dielectric constant confirms first-order improper ferroelectric transitions in Ca_(3)Ti_(2)O_(7)-based ceramics.The results of variable temperature Xray diffraction reveal the coexistence of two-phases below Curie temperature.The present work confidently confirms the first-order improper ferroelectric transition in Ca_(3)Ti_(2)O_(7)-based ceramics by combining results of variable-temperature dielectric response and in-situ X-ray powder diffraction.
