Structural changes in Sr9In(PO4)7 during antiferroelectric phase transition

Structural changes in Sr9In(PO4)7 during the antiferroelectric (AFE) phase transition are studied by X-ray powder diffraction, electron microscopy, second-harmonic-generation, and dielectric measurements. Sr9In(PO4)7 complements a group of Ca3(VO4)2-type ferroelectric (FE) phosphates and vanadates and is the first example of an AFE material in this family. Antiparallel shifts of Sr atoms from their average positions and ordering of the P1O4 tetrahedra form two contributions in the structural mechanism of the AFE phase transition a displacive contribution and an order-disorder constituent, respectively. The displacive and order-disorder type of structural changes may account for the obtained value of the Curie-Weiss constant (C ~ 104 K) which is in between the value usually observed for pure displacive (C ~ 105 K) and that for orderdisorder phase transitions (C ~ 103 K). The structural mechanism of the AFE phase transition in Sr9In(PO4)7 is very similar to that of the FE phase transition in Ca9R(PO4)7 and Ca9R(VO4)7. Both displacive and orderdisorder contributions are responsible for the physical properties of the Ca3(VO4)2-type materials. © 2016 Pleiades Publishing, Ltd

Structural changes in Sr9In(PO4)7 during antiferroelectric phase transition

International audienceStructural changes in Sr9In(PO4)7 during the antiferroelectric (AFE) phase transition are studied by X-ray powder diffraction, electron microscopy, second-harmonic-generation, and dielectric measurements. Sr9In(PO4)7 complements a group of Ca3(VO4)2-type ferroelectric (FE) phosphates and vanadates and is the first example of an AFE material in this family. Antiparallel shifts of Sr atoms from their average positions and ordering of the P1O4 tetrahedra form two contributions in the structural mechanism of the AFE phase transition a displacive contribution and an order-disorder constituent, respectively. The displacive and order-disorder type of structural changes may account for the obtained value of the Curie-Weiss constant (C ~ 104 K) which is in between the value usually observed for pure displacive (C ~ 105 K) and that for orderdisorder phase transitions (C ~ 103 K). The structural mechanism of the AFE phase transition in Sr9In(PO4)7 is very similar to that of the FE phase transition in Ca9R(PO4)7 and Ca9R(VO4)7. Both displacive and orderdisorder contributions are responsible for the physical properties of the Ca3(VO4)2-type materials. © 2016 Pleiades Publishing, Ltd

Enhanced nonlinear optical activity and Ca2+-conductivity in Са10.5-xPbx(VO4)7 ferroelectrics

Са3(VO4)2-based compositions are considered as promising multifunctional materials combining ferroelectric, optical nonlinear, and Ca2+-ion conductive properties. Their ferroelectric Curie points stretch from minimal for β-Ca3(PO4)2-type compounds temperatures of about 800 K to very high. Investigated in this paper lead substitution for calcium is as a factor controlling ferroelectricity, ionic-conductivity and non-linear optical activity in Ca3(VO4)2-based materials. Polar phase containing powders and ceramics in Ca10.5-xPbx(VO4)7 system are synthesized for 0 ≤ x ≤ 9.5 by the solid state method, and structurally characterized with X-ray powder diffraction and transmission electron microscopy. Dielectric properties, differential thermal analysis and second harmonic generation (SHG) evidence that Ca10.5-xPbx(VO4)7 solid solution (0 ≤ x ≤ 4.5) belongs to whitlockite-type ferroelectrics. SHG activity strongly increases with x up to its maximum at x = 4.5, where it has a record value among all studied before Ca3(XO4)2-related compounds (X = P,V). Ferroelectric Curie temperatures of Ca3(VO4)2 drops from its known value Tc = 1368 K (x = 0) to 770 K (x = 4.5). Crystal symmetry at Tc changes from R3c to R3¯c. After this, one more phase transition to the symmetry R3¯m takes place, its temperature bringing down from 1387 K (x = 0) to 804 K (x = 4.5). Ferroelectric and non-ferroelectric phase transitions in the Са10.5-xPbx(VO4)7 are separated by a broad interval ΔT = 20–50 K and both classified as first-order transformations going in the sequence: R3c↔R3¯c↔R3¯m. Structures of Са10.5-xPbx(VO4)7 compositions with x = 0.5–4 were refined by the Rietveld method and peculiarities of the Pb2+cations distribution in the M1 - M3 and M4 sites of β-Ca3(PO4)2-type structure are discussed regarding the optical nonlinear, ferroelectric and ion-conductive properties. Manifold increased Ca2+- ion conductivity of Са10.5-xPbx(VO4)7 in vicinity of 1000 K at x = 4–4.5 in combination with their ferroelectric and optical nonlinear properties extends applicability of ion-exchange technologies to new promising materials. © 2017 Elsevier B.V

Pure, lithium- or magnesium-doped ferroelectric single crystals of Ca9Y(VO4)7: Cation arrangements and phase transitions

Single crystals of Ca9Y(VO4)7 (1), Ca9Y(VO4)7:Li+ (2) and Ca9Y(VO4)7:Mg2+ (3) were grown by the Czochralski method. Their chemical composition was analyzed by ICP spectroscopy and their crystal structure was examined by single crystal X-ray analysis. The crystals are characterized by trigonal symmetry, space group R3c. Hexagonal unit-cell parameters are as follows: a=10.8552(1) Å, c=38.0373(2) Å, V=3881.65(1) Å3 for 1; a=10.8570(1) Å, c=38.0161(3) Å, V=3880.77(4) Å3 for 2; a=10.8465(1) Å, c=38.0366(2) Å, V=3875.36(3) Å3 for 3. All crystals are characterized by β-Ca3(PO4)2-type structure with statistical distribution of Ca2+ and Y3+ over M1, M2 and M5 sites in different ratios and with completely empty M4-cationsite. The impurity of Mg2+cations in structure 2 has been detected in octahedral M5 site. Ferroelectric phase transitions are evidenced by DSC and SHG. At about 1220 and 1300 K, they demonstrate phase transitions. Upon heating the symmetry of the crystal structure changes according to the scheme R3cm and is restored during consequent cooling. The first of them is of ferroelectric and the second of non-ferroelectric nature. Even a small amount of impurities in Ca9Y(VO4)7 structure is accompanied by a noticeable decrease in the temperature of the ferroelectric-paraelectric phase transition. © 2018 Walter de Gruyter GmbH, Berlin/Boston 2018

Pure, lithium- or magnesium-doped ferroelectric single crystals of Ca9Y(VO4)7: Cation arrangements and phase transitions

Single crystals of Ca9Y(VO4)7 (1), Ca9Y(VO4)7:Li+ (2) and Ca9Y(VO4)7:Mg2+ (3) were grown by the Czochralski method. Their chemical composition was analyzed by ICP spectroscopy and their crystal structure was examined by single crystal X-ray analysis. The crystals are characterized by trigonal symmetry, space group R3c. Hexagonal unit-cell parameters are as follows: a=10.8552(1) Å, c=38.0373(2) Å, V=3881.65(1) Å3 for 1; a=10.8570(1) Å, c=38.0161(3) Å, V=3880.77(4) Å3 for 2; a=10.8465(1) Å, c=38.0366(2) Å, V=3875.36(3) Å3 for 3. All crystals are characterized by β-Ca3(PO4)2-type structure with statistical distribution of Ca2+ and Y3+ over M1, M2 and M5 sites in different ratios and with completely empty M4-cationsite. The impurity of Mg2+cations in structure 2 has been detected in octahedral M5 site. Ferroelectric phase transitions are evidenced by DSC and SHG. At about 1220 and 1300 K, they demonstrate phase transitions. Upon heating the symmetry of the crystal structure changes according to the scheme R3cm and is restored during consequent cooling. The first of them is of ferroelectric and the second of non-ferroelectric nature. Even a small amount of impurities in Ca9Y(VO4)7 structure is accompanied by a noticeable decrease in the temperature of the ferroelectric-paraelectric phase transition. © 2018 Walter de Gruyter GmbH, Berlin/Boston 2018

Enhanced nonlinear optical activity and Ca2+-conductivity in Са10.5-xPbx(VO4)7 ferroelectrics

Са3(VO4)2-based compositions are considered as promising multifunctional materials combining ferroelectric, optical nonlinear, and Ca2+-ion conductive properties. Their ferroelectric Curie points stretch from minimal for β-Ca3(PO4)2-type compounds temperatures of about 800 K to very high. Investigated in this paper lead substitution for calcium is as a factor controlling ferroelectricity, ionic-conductivity and non-linear optical activity in Ca3(VO4)2-based materials. Polar phase containing powders and ceramics in Ca10.5-xPbx(VO4)7 system are synthesized for 0 ≤ x ≤ 9.5 by the solid state method, and structurally characterized with X-ray powder diffraction and transmission electron microscopy. Dielectric properties, differential thermal analysis and second harmonic generation (SHG) evidence that Ca10.5-xPbx(VO4)7 solid solution (0 ≤ x ≤ 4.5) belongs to whitlockite-type ferroelectrics. SHG activity strongly increases with x up to its maximum at x = 4.5, where it has a record value among all studied before Ca3(XO4)2-related compounds (X = P,V). Ferroelectric Curie temperatures of Ca3(VO4)2 drops from its known value Tc = 1368 K (x = 0) to 770 K (x = 4.5). Crystal symmetry at Tc changes from R3c to R3¯c. After this, one more phase transition to the symmetry R3¯m takes place, its temperature bringing down from 1387 K (x = 0) to 804 K (x = 4.5). Ferroelectric and non-ferroelectric phase transitions in the Са10.5-xPbx(VO4)7 are separated by a broad interval ΔT = 20–50 K and both classified as first-order transformations going in the sequence: R3c↔R3¯c↔R3¯m. Structures of Са10.5-xPbx(VO4)7 compositions with x = 0.5–4 were refined by the Rietveld method and peculiarities of the Pb2+cations distribution in the M1 - M3 and M4 sites of β-Ca3(PO4)2-type structure are discussed regarding the optical nonlinear, ferroelectric and ion-conductive properties. Manifold increased Ca2+- ion conductivity of Са10.5-xPbx(VO4)7 in vicinity of 1000 K at x = 4–4.5 in combination with their ferroelectric and optical nonlinear properties extends applicability of ion-exchange technologies to new promising materials. © 2017 Elsevier B.V

Autodetection of starting antiradiolocation missiles

В роботі сформульовані пропозиції до системи активного захисту радіолокаційних станцій від протирадіолокаційних ракет, запропонований алгоритм їх автоматичного виявлення, що заснований на визначенні ознак протирадіолокаційної ракети.В работе сформулированы предложения к системе активной защиты радиолокационных станций от противорадиолокационных ракет, предложен алгоритм их автоматического обнаружения, основанный на определении признаков противорадиолокационных ракет.Propositions to the system of active antiradiolocation missiles defense of radars are formulated in the article; the algorithm of their autodetection is based on detection of signs of antiradiolocation missiles is offered