The minerals of chevkinite group were commonly considered to be anhydrous minerals. The infrared absorption spectrum of natural nonmetamict chevkinite-（Ce） from the aegirine-alkali granite, Miannlng, Sichuan Provinc...The minerals of chevkinite group were commonly considered to be anhydrous minerals. The infrared absorption spectrum of natural nonmetamict chevkinite-（Ce） from the aegirine-alkali granite, Miannlng, Sichuan Province, China, exhibited two broad peaks in the 3600-2800 cm^-1 region owing to the OH stretching. The corresponding H20 content required for the charge balance in formula was 1.27%. The O-H. … O bond lengths maight cover from 0.2658 to 0.2794 nm by the correlated OH stretching energies. An electrostatic charge balance for chevkinite-（Ce） based on the assigned site-population from chemical data was calculated without the hydrogen contribution. The resulting empirical bond-valence sum on 06, 08, 02, 03, 05, and 04 ranged from 1.73 to 1.95 vu. The partial substitution of O by OH may occur in four atom sites： 06, 02, 04, and 05. The small differences in the bond-valence sums between the supposed donors and acceptors may mean a mixed donor/acceptor role of the involved oxygen atoms. The IR spectral features between 3394 and 3035 cm-1 consisted of various hydrous species at different structural sites and orientations. The OH groups in the chevkinlte-（Ce） appeared to be involved in local charge imbalance in the structure and to be present when the mineral crystallized hydrothermally.展开更多
The crystal structure of ludwigite from Vranovac ore deposit （Boranja Mt., Serbia） was refined using the X-ray powder diffraction （XRPD） Rietveld method in the space group Pbam to a final RB=7.45% and RF=5.26%. It...The crystal structure of ludwigite from Vranovac ore deposit （Boranja Mt., Serbia） was refined using the X-ray powder diffraction （XRPD） Rietveld method in the space group Pbam to a final RB=7.45% and RF=5.26%. It has the unit cell dimensions of： a=9.2515（2） A; b=12.3109（2） A; c=3.03712 （7） A; and V=345.91（1） A3. The calculated distances and angles are mostly in good agreement with the Mg2＋-Fe2＋ substitutions across the M（1） and M（3） sites, as well as with the Fe3＋-AI3＋ replacement in the M（4） site. However, the mean observed M（2）-O distance is considerably shorter than prescribed, due to a slight increase of the Fe3＋ content in the M（2） site. Such replacement was compensated by slight increase of the Fe2＋ content in the M（4） site, resulting in the （Mg1.4sFe2＋o.46Fe3＋o.osMno.o2）2.o1 （Fe3＋o.94Fe2＋0.04Al0.02）1.00B1.00Os composition. The formation temperature was estimated to be about 500- 600C. The influences of the various chemical compositions to the crystallographic parameters, M-O distances, M（3） and M（4） sites shift, distortion parameters and estimated valences, were also studied and compared with other reference samples.展开更多
The constitution of the binary system Ir-B has been established between 10 and 70 at.% boron for temperatures above 700°C based on differential scanning calorimetry, electron probe microanalysis, and isothermal l...The constitution of the binary system Ir-B has been established between 10 and 70 at.% boron for temperatures above 700°C based on differential scanning calorimetry, electron probe microanalysis, and isothermal low temperature annealing experiments(≤1000°C). Four binary phases have been found, namely Ir4B5+x, Ir5B4+x and the high and low temperature modification of Ir4B3-x. X-ray structure analyses were performed on single crystals of Ir4B5+x(x = 0, Ir4B5 type; space group C2/m; a = 1.05200(2), b = 0.289564(6) and c = 0.60958(1) nm, β = 91.156(2)°), Ir5B4+x(x=0, Ir5B4 type; space group I41/a; a = 0.62777(1) and b = 1.02599(2) nm) and on the low temperature modification of Ir4B3-x(x=0, Ir B0.9 type; space group Cmc21; a = 0.27728(1), b = 0.75742(2) and c = 0.73152(2) nm). The high temperature modification of Ir4B3-x(WC type; space group P6-m2; a = 0.28137(5) and c = 0.2828(1) nm) has been confirmed by X-ray powder diffraction. By means of the first-principle calculations, in combination with the evolutionary structural search algorithm, the compositions, structures and enthalpies of the Ir-B system have been investigated theoretically. Confirming the experimental observations on Ir4B5, Ir5B4 and Ir4B3, we have investigated several metastable phases at other stoichiometries, such as Ir B, Ir B2 and Ir3B2. We also proposed three thermodynamically and dynamically stable new structures of o F28-Ir4B3, o C8-Ir B and m C10-Ir3B2, which may be synthesized under certain conditions.展开更多
The Pt（IV） complex cis,cis,trans-[Pt（PMSA）2Cl2（OH）2]·2H2O（1）, where PMSA = N-3-pyridinylmethanesulfonamide, has been synthesized and characterized by elemental analysis, molar electric conductivity and IR...The Pt（IV） complex cis,cis,trans-[Pt（PMSA）2Cl2（OH）2]·2H2O（1）, where PMSA = N-3-pyridinylmethanesulfonamide, has been synthesized and characterized by elemental analysis, molar electric conductivity and IR spectrum. X-ray crystallography revealed that the title compound crystallizes in the monoclinic C2/c space group with unit cell dimensions a = 16.5424（7）, b = 8.6973（3）, c = 16.6079（6） A, β = 117.185（5）° and Z = 4. Pt（IV） has an octahedral coordination geometry and the PMSA ligands are coordinated via the pyridine N atom. They are in a transoid orientation between each other and are inclined in the same direction with respect to the Pt-C1-Cli-N-Ni plane at an angle of 64.6（1）° （symmetry operation： （i） 1- x, y, 3/2-z）. The structure is stabilized by a system of hydrogen bonds involving the complex and water molecules.展开更多
The ideal formula for chevkinite can be expressed as A4BC2D2Si4O22. It is important to determine the valence state and site occupation proportions for Fe among the B, C, and D octahedral sites as it may help to identi...The ideal formula for chevkinite can be expressed as A4BC2D2Si4O22. It is important to determine the valence state and site occupation proportions for Fe among the B, C, and D octahedral sites as it may help to identify different species in the chevkinite group. Non-metamict chevkinite-（Ce） from Mianxi alkali feldspar-granite, Sichuan Province, China, was investigated using Moessbauer spectroscopy. The Fe^3＋/∑Fe ratio was 39.2%. A significant increase of Fe^3＋ occured during metamictization and annealing for chevkinite-group minerals. In metamict samples Fe tended to lower coordination, According to the correlation between bond length and isomer shift （IS）, the quadrupole doublets with IS = 1.10 and 0.94 mm·s^-1 can be assigned to Fe^2＋ in the B and C octahedral sites, respectively. Based on the correlation between octahedral distortion and quadrupole splitting （QS）, the quadrupole doublets with QS = 0.86 and 0.77 mm·s^-1 can be assigned to Fe^3＋ in the C and D sites, respectively. The simplified formula can be revised as： Ce4Fe^2＋ （Ti, Fe^2＋, Fe^3＋ ）2（Ti, Fe^3＋ ）2Si4（O,OH）22. It indicated that the non-metamict chevkinite-（Ce） belonged to Fe^2＋ end member of the chevkinite group because Fe^2＋ was the predominant component in the B site.展开更多
Complex crystal aggregates from fluorspar vapor phase were grown at specific low-pressure/high-temperature conditions. The quasi-equilibrium of initiated crystal-chemical reactions at the proceeding vapour-crystal pha...Complex crystal aggregates from fluorspar vapor phase were grown at specific low-pressure/high-temperature conditions. The quasi-equilibrium of initiated crystal-chemical reactions at the proceeding vapour-crystal phase transformation was strongly dependent on the mass-transport inside an originally designed multicameral crucible, loaded by several portions of natural fluorite. By changing the temperature pressure over the already molten fluorspar portions as well as the gas-permeability of the channels connecting different sections in crucible interior to vacuum ambient, one may control the rate of gaseous-vapour diffusion and the degree of supper-saturation inside the peripheral crucible compartment wherein nucleation and crystal growing occurred. In this way, grown aggregates revealed a complicated habit formed during three-stage growing process provided by relevant thermodynamic and phase. Residual stresses were not observed in the aggregates whereas those in simultaneously grown boules from the non-vaporized melts in crucible cameras were clearly distinguished. The optical transmittance spectra of the boules were obtained considerably better, especially in the UV, comparing to those for crystal aggregates, both showing several peaks of specific light-absorption due to enhanced presence of rare-earth (RE) impurities. The aggregates manifest nearly full reflectivity from Vis to near IR region. The vapor phase growth mechanisms, when natural fluorite with some RE contents has been used, were explained on thermodynamic grounds that shown the manner of reliable control on the phenomenon. The results were anticipated to help for developing new perspective techniques for growth from vapor of several fluoride compounds with complex structure and composition and wide application. It was speculated that similar growth mechanisms of CaF2?crystals were possible on the moon in its very early period of formation.展开更多
To make inorganic structure data more useful for further studies a five-point list of simple procedures to be followed by authors of crystal structure papers is proposed. 1. A crystal structure should be described wit...To make inorganic structure data more useful for further studies a five-point list of simple procedures to be followed by authors of crystal structure papers is proposed. 1. A crystal structure should be described with the space group corresponding to its true symmetry. 2. A new structure proposal should be tested, if it is realistic in principle. 3. A structure should be described with a space group in a setting given in the International Tables. 4. For a comparison with other structures the structure data should be standardized with the program STRUCTURE TIDY. 5. 揘ew?structure data should be checked in the databases, Chemical Abstracts or on-line internet resources, if they are really new. The list is supplemented with many explanations, commentaries, examples and references.展开更多
基金the National Natural Science Foundation of China (40572029)
文摘The minerals of chevkinite group were commonly considered to be anhydrous minerals. The infrared absorption spectrum of natural nonmetamict chevkinite-（Ce） from the aegirine-alkali granite, Miannlng, Sichuan Province, China, exhibited two broad peaks in the 3600-2800 cm^-1 region owing to the OH stretching. The corresponding H20 content required for the charge balance in formula was 1.27%. The O-H. … O bond lengths maight cover from 0.2658 to 0.2794 nm by the correlated OH stretching energies. An electrostatic charge balance for chevkinite-（Ce） based on the assigned site-population from chemical data was calculated without the hydrogen contribution. The resulting empirical bond-valence sum on 06, 08, 02, 03, 05, and 04 ranged from 1.73 to 1.95 vu. The partial substitution of O by OH may occur in four atom sites： 06, 02, 04, and 05. The small differences in the bond-valence sums between the supposed donors and acceptors may mean a mixed donor/acceptor role of the involved oxygen atoms. The IR spectral features between 3394 and 3035 cm-1 consisted of various hydrous species at different structural sites and orientations. The OH groups in the chevkinlte-（Ce） appeared to be involved in local charge imbalance in the structure and to be present when the mineral crystallized hydrothermally.
文摘The crystal structure of ludwigite from Vranovac ore deposit （Boranja Mt., Serbia） was refined using the X-ray powder diffraction （XRPD） Rietveld method in the space group Pbam to a final RB=7.45% and RF=5.26%. It has the unit cell dimensions of： a=9.2515（2） A; b=12.3109（2） A; c=3.03712 （7） A; and V=345.91（1） A3. The calculated distances and angles are mostly in good agreement with the Mg2＋-Fe2＋ substitutions across the M（1） and M（3） sites, as well as with the Fe3＋-AI3＋ replacement in the M（4） site. However, the mean observed M（2）-O distance is considerably shorter than prescribed, due to a slight increase of the Fe3＋ content in the M（2） site. Such replacement was compensated by slight increase of the Fe2＋ content in the M（4） site, resulting in the （Mg1.4sFe2＋o.46Fe3＋o.osMno.o2）2.o1 （Fe3＋o.94Fe2＋0.04Al0.02）1.00B1.00Os composition. The formation temperature was estimated to be about 500- 600C. The influences of the various chemical compositions to the crystallographic parameters, M-O distances, M（3） and M（4） sites shift, distortion parameters and estimated valences, were also studied and compared with other reference samples.
基金supported by Austrian Science Fund FWF under P22295partially supported by the ‘Hundred Talents Project’ of Chinese Academy of Sciences+1 种基金the Key Research Program of Chinese Academy of Sciences (KGZD-EW-T06)the National Natural Science Foundation of China (NSFC) (51074188 and 51474202)
文摘The constitution of the binary system Ir-B has been established between 10 and 70 at.% boron for temperatures above 700°C based on differential scanning calorimetry, electron probe microanalysis, and isothermal low temperature annealing experiments(≤1000°C). Four binary phases have been found, namely Ir4B5+x, Ir5B4+x and the high and low temperature modification of Ir4B3-x. X-ray structure analyses were performed on single crystals of Ir4B5+x(x = 0, Ir4B5 type; space group C2/m; a = 1.05200(2), b = 0.289564(6) and c = 0.60958(1) nm, β = 91.156(2)°), Ir5B4+x(x=0, Ir5B4 type; space group I41/a; a = 0.62777(1) and b = 1.02599(2) nm) and on the low temperature modification of Ir4B3-x(x=0, Ir B0.9 type; space group Cmc21; a = 0.27728(1), b = 0.75742(2) and c = 0.73152(2) nm). The high temperature modification of Ir4B3-x(WC type; space group P6-m2; a = 0.28137(5) and c = 0.2828(1) nm) has been confirmed by X-ray powder diffraction. By means of the first-principle calculations, in combination with the evolutionary structural search algorithm, the compositions, structures and enthalpies of the Ir-B system have been investigated theoretically. Confirming the experimental observations on Ir4B5, Ir5B4 and Ir4B3, we have investigated several metastable phases at other stoichiometries, such as Ir B, Ir B2 and Ir3B2. We also proposed three thermodynamically and dynamically stable new structures of o F28-Ir4B3, o C8-Ir B and m C10-Ir3B2, which may be synthesized under certain conditions.
基金support of the Bulgarian National Science Fund under contract DRNF 02/1
文摘The Pt（IV） complex cis,cis,trans-[Pt（PMSA）2Cl2（OH）2]·2H2O（1）, where PMSA = N-3-pyridinylmethanesulfonamide, has been synthesized and characterized by elemental analysis, molar electric conductivity and IR spectrum. X-ray crystallography revealed that the title compound crystallizes in the monoclinic C2/c space group with unit cell dimensions a = 16.5424（7）, b = 8.6973（3）, c = 16.6079（6） A, β = 117.185（5）° and Z = 4. Pt（IV） has an octahedral coordination geometry and the PMSA ligands are coordinated via the pyridine N atom. They are in a transoid orientation between each other and are inclined in the same direction with respect to the Pt-C1-Cli-N-Ni plane at an angle of 64.6（1）° （symmetry operation： （i） 1- x, y, 3/2-z）. The structure is stabilized by a system of hydrogen bonds involving the complex and water molecules.
基金Project supported by the National Natural Science Foundation of China (40572029)
文摘The ideal formula for chevkinite can be expressed as A4BC2D2Si4O22. It is important to determine the valence state and site occupation proportions for Fe among the B, C, and D octahedral sites as it may help to identify different species in the chevkinite group. Non-metamict chevkinite-（Ce） from Mianxi alkali feldspar-granite, Sichuan Province, China, was investigated using Moessbauer spectroscopy. The Fe^3＋/∑Fe ratio was 39.2%. A significant increase of Fe^3＋ occured during metamictization and annealing for chevkinite-group minerals. In metamict samples Fe tended to lower coordination, According to the correlation between bond length and isomer shift （IS）, the quadrupole doublets with IS = 1.10 and 0.94 mm·s^-1 can be assigned to Fe^2＋ in the B and C octahedral sites, respectively. Based on the correlation between octahedral distortion and quadrupole splitting （QS）, the quadrupole doublets with QS = 0.86 and 0.77 mm·s^-1 can be assigned to Fe^3＋ in the C and D sites, respectively. The simplified formula can be revised as： Ce4Fe^2＋ （Ti, Fe^2＋, Fe^3＋ ）2（Ti, Fe^3＋ ）2Si4（O,OH）22. It indicated that the non-metamict chevkinite-（Ce） belonged to Fe^2＋ end member of the chevkinite group because Fe^2＋ was the predominant component in the B site.
文摘Complex crystal aggregates from fluorspar vapor phase were grown at specific low-pressure/high-temperature conditions. The quasi-equilibrium of initiated crystal-chemical reactions at the proceeding vapour-crystal phase transformation was strongly dependent on the mass-transport inside an originally designed multicameral crucible, loaded by several portions of natural fluorite. By changing the temperature pressure over the already molten fluorspar portions as well as the gas-permeability of the channels connecting different sections in crucible interior to vacuum ambient, one may control the rate of gaseous-vapour diffusion and the degree of supper-saturation inside the peripheral crucible compartment wherein nucleation and crystal growing occurred. In this way, grown aggregates revealed a complicated habit formed during three-stage growing process provided by relevant thermodynamic and phase. Residual stresses were not observed in the aggregates whereas those in simultaneously grown boules from the non-vaporized melts in crucible cameras were clearly distinguished. The optical transmittance spectra of the boules were obtained considerably better, especially in the UV, comparing to those for crystal aggregates, both showing several peaks of specific light-absorption due to enhanced presence of rare-earth (RE) impurities. The aggregates manifest nearly full reflectivity from Vis to near IR region. The vapor phase growth mechanisms, when natural fluorite with some RE contents has been used, were explained on thermodynamic grounds that shown the manner of reliable control on the phenomenon. The results were anticipated to help for developing new perspective techniques for growth from vapor of several fluoride compounds with complex structure and composition and wide application. It was speculated that similar growth mechanisms of CaF2?crystals were possible on the moon in its very early period of formation.
文摘To make inorganic structure data more useful for further studies a five-point list of simple procedures to be followed by authors of crystal structure papers is proposed. 1. A crystal structure should be described with the space group corresponding to its true symmetry. 2. A new structure proposal should be tested, if it is realistic in principle. 3. A structure should be described with a space group in a setting given in the International Tables. 4. For a comparison with other structures the structure data should be standardized with the program STRUCTURE TIDY. 5. 揘ew?structure data should be checked in the databases, Chemical Abstracts or on-line internet resources, if they are really new. The list is supplemented with many explanations, commentaries, examples and references.
