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1.
According to the compositions of the underground gasfield brines in the west of Sichuan Basin,the phase equilibria in the ternary systems KBr-K2B4O7-H2O and KCl-K2B4O7-H2O at 373 K were studied using the isothermal dissolution equilibrium method.The solubilities of salts and the densities of saturated solutions in these ternary systems were determined.Using the experimental data,phase diagrams and density-composition diagrams were constructed.The two phase diagrams were simple co-saturation type,each having an invariant point,two univariant curves and two crystallization regions.The equilibrium solid phases in the ternary system KBr-K2B4O7-H2O are potassium bromide （KBr） and potassium tetraborate tetrahydrate （K2B4O7·4H2O）,and those in the ternary system KCl-K2B4O7-H2O are potassium chloride （KCl） and potassium tetraborate tetrahydrate （K2B4O7·4H2O）.Comparisons of the phase diagrams of the two systems at different temperatures show that there is no change in the crystallization phases,but there are changes in the size of the crystallization regions.As temperature increases,the solubility of K2B4O7·4H2O increases rapidly,so the crystallization field of K2B4O7·4H2O becomes smaller. 相似文献
2.
David A. McKeown Charles C. Kim Michael I. Bell 《Physics and Chemistry of Minerals》1995,22(3):137-144
The normal modes of vibration and their frequencies are calculated for dioptase, a mineral whose crystal structure (space group R
or C
3i
2
) consists of puckered six-membered silicate rings (Si6O18) linked by Cu2+ ions and H2O groups. The calculation employs a valence force potential consisting of central interactions between nearest neighbors and bond-bending interactions centered at the Si4+ and Cu2+ ions. The force constants are determined by fitting the calculated frequencies to values obtained by measuring the single-crystal Raman spectra. The calculated frequencies are in reasonable agreement with experiment, permitting assignment of normal modes to the observed spectral frequencies. Considerable mixing of Cu and H2O motions with those of the ring is found for the Raman-active modes below 430 cm-1. The normal modes and frequencies of the hypothetical isolated ring with C
3i
symmetry are determined by neglecting all interactions between the rings and the surrounding Cu and H2O. The identification of normal modes characteristic of the puckered six-membered silicate rings and the effect of the environment on these modes may prove useful in the interpretation of the Raman spectra of amorphous silicates. 相似文献
3.
Andrea Orlando Yves Thibault Alan D. Edgar 《Contributions to Mineralogy and Petrology》2000,139(2):136-145
Experiments ranging from 2 to 3 GPa and 800 to 1300 °C and at 0.15 GPa and 770 °C were performed to investigate the stability
and mutual solubility of the K2ZrSi3O9 (wadeite) and K2TiSi3O9 cyclosilicates under upper mantle conditions. The K2ZrSi3O9–K2TiSi3O9 join exhibits complete miscibility in the P–T interval investigated. With increasing degree of melting the solid solution becomes progressively enriched in Zr, indicating
that K2ZrSi3O9 is the more refractory end member. At 2 GPa, in the more complex K2ZrSi3O9–K2TiSi3O9–K2Mg6Al2Si6O20(OH)4 system, the presence of phlogopite clearly limits the extent of solid solution of the cyclosilicate to more Zr-rich compositions
[Zr/(Zr + Ti) > 0.85], comparable to wadeite found in nature, with TiO2 partitioning strongly into the coexisting mica and/or liquid. However, at 1200 °C, with increasing pressure from 2 to 3 GPa,
the partitioning behaviour of TiO2 changes in favour of the cyclosilicate, with Zr/(Zr + Ti) of the K2(Zr,Ti)Si3O9 phase decreasing from ∼0.9 to ∼0.6. The variation in the Ti content of the coexisting phlogopite is related to its degree
of melting to forsterite and liquid, following the major substitution VITi+VI□=2VIMg.
Received: 26 January 1999 / Accepted: 10 January 2000 相似文献
4.
5.
6.
M. Wildner 《Mineralogy and Petrology》1993,48(2-4):215-225
Summary Crystals of K2[Co2(SeO3)3]-2H2O and K2[Ni2(SeO3)3]-2H2O were synthesized under low-hydrothermal conditions. Their structures were determined using single crystal X-ray data up to sin / = 0.7Å-1. [Space group P63/m; a = 9.091(3),9.016(2)Å; c = 7.562(2), 7.476(2)Å; Z = 2; RW = 1.6, 2.5%]. The investigations confirmed that K2[Co2(SeO3)3].2H2O and K2[Ni2(SeO3)3]-2H2O represent the first selenites belonging to the zemannite structure type, a framework structure with wide channels running parallel [0001]. In both compounds four maxima were clearly located in the channel by Fourier summations and attributed to two K atoms and two H2O molecules, each with an occupancy factor of 1/6; a possible ordering scheme (full occupancy) with local symmetry 1 and [6]-coordinated K atoms could be derived for the channel atoms.Zusammenfassung Kristalle von K2[Co2(SeO3)3]-2H2O und K2[Ni2(SeO3)3]-2H2O wurden unter niedrig-hydrothermalen Bedingungen synthetisiert. Die Strukturen wurden unter Verwendung von Einkristallröntgendaten bis sin /= 0.7Å-1 bestimmt. [Raumgruppe P63/m; a = 9.091(3), 9.016(2)Å; c = 7.562(2), 7.476(2)Å; Z = 2; RW = 1.6, 2.5%] Die Untersuchungen bestätigten, daß K2[Co2(SeO3)3] - 2H2O und K2 [Ni2(SeO3)3] - 2H2O als erste Selenite dem Strukturtyp des Zemannits angehören, einer Gerüststruktur mit weiten, parallel [0001] verlaufenden Kanälen. In beiden Verbindungen wurden im Kanal vier Maxima durch Fourier-Summationen eindeutig lokalisiert und zwei Kalium-atomen sowie zwei H2O Molekülen, jeweils mit einem Besetzungsfaktor von 1/6, zugeschrieben. Für die Kanalatome konnte ein möglicher Ordnungszustand (volle Besetzung) mit lokaler Symmetrie 1 und [6]-koordinierten Kaliumatomen abgeleitet werden.
Dedicated to Prof. Dr. Josef Zemann at the occasion of his 70th birthday
With 2 Figures 相似文献
Selenite des Zemannittyps: Kristallstrukturen von K2[Co2(SeO3)3] - 2H2O und K2[Ni2(SeO3)3]-2H2O
Dedicated to Prof. Dr. Josef Zemann at the occasion of his 70th birthday
With 2 Figures 相似文献
7.
Günther J. Redhammer Fernando Cámara Matteo Alvaro Fabrizio Nestola Gerold Tippelt Sebastian Prinz Jan Simons Georg Roth Georg Amthauer 《Physics and Chemistry of Minerals》2010,37(10):685-704
A synthetic clinopyroxene with composition LiFe3+Ge2O6, monoclinic s.g. P21/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) Å, β = 108.844(6)°, V = 442.75(16) Å3, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P21/c to C2/c at a transition temperature T tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T tr the thermal volume expansion is due to dilatation of the structure in the $(\bar{1}\,0\,1) A synthetic clinopyroxene with composition LiFe3+Ge2O6, monoclinic s.g. P21/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) ?, β = 108.844(6)°, V = 442.75(16) ?3, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters
and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P21/c to C2/c at a transition temperature T
tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds
to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T
tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T
tr the thermal volume expansion is due to dilatation of the structure in the ([`1] 0 1)(\bar{1}\,0\,1) plane, mostly along [0 1 0], and pure shear in the (0 1 0) plane due to the decrease of β. From comparison with silicate analogues, the germanate clinopyroxenes are more expansible, while the P21/c expands more than the C2/c phase. The evolution of Q
2 (calculated as the normalized intensity of b-type reflections) with T in the framework of the Landau theory has been done using a standard expression for a first order phase transition. We observe
a jump of Q
02 = 0.538(2) at T
tr, with T
c of 481(7) K, b/a = −2,290 K, and c/a = 3,192 K, and thus far from being tri-critical point. A closely related composition (LiFe3+Si2O6) shows an equivalent phase transition at 228 K, which is very close to the tri-critical point and 561 K cooler. This result
indicates that a change in the composition of tetrahedral sites can have dramatic effects on the P21/c ↔ C2/c displacive phase transition in clinopyroxenes. The major changes observed in the evolution of the crystal structure with
T are observed in the M2 polyhedron, with a volume decrease by ca. 13.3%, compared to ca. 1.3% observed in the M1 polyhedron.
The tetrahedra behave as rigid units with neither a significant change of volume at T > T
tr (<1‰), nor a change of tilting of the basal plane. No change in coordination is observed at T > T
tr in the M2 polyhedron, which remains sixfold coordinated although a strong deformation of this polyhedron is observed. This
deformation is related to a strong change by 51.4° at T
tr of the kinking angle (O3–O3–O3 angle) of the B-chain of tetrahedra, which switches from O-rotated to S-rotated [from 143.3(5)°
to 194.7(6)°]. The A-chain is S-rotated at T < T
tr [206.8(5)° at 703 K] and extends by 12° at the transition. 相似文献
8.
The existence of an incomplete solid solution series between loparite (NaLREETi2O6), a member of the perovskite mineral group, and thorutite (ThTi2O6) is established on the basis of experimental and mineralogical data. The products of low- and high-pressure synthesis in the system NaLaTi2O6– ThTi2O6 were studied by energy-dispersive spectrometry, X-ray diffractometry and Rietveld analysis. At atmospheric pressure, Th is incorporated in loparite as both ThTi2O6 and Na2ThTi3O9. In synthetic systems, the maximum determined ThTi2O6 content of loparite is 18 mol%, with a corresponding A-site cation deficiency of 9%. The structure of such loparite is tetragonal and presumably derived from the cubic aristotype by octahedral rotation [I4/mcm, a=5.4652(1) Å, c=7.7476(2) Å]. At a pressure of 6 GPa, no solubility between loparite and ThTi2O6 is observed, and Th is accommodated in the loparite structure entirely as Na2ThTi3O9 (up to 30 mol%). Naturally occurring loparite contains up to 29 mol% ThTi2O6, based on the conventional method of analysis recalculation, or 23.5 mol% ThTi2O6, assuming the presence of protons at the vacant A-sites. ThTi2O6 synthesized by the solid-state reaction, crystallizes with monoclinic symmetry [C2/m, a=9.8140(2) Å, b=3.8228(1) Å, c=7.0313(2) Å,β=118.82(1)°]. Atomic coordinates for ThTi2O6 obtained in this study from X-ray powder data, as well as structural parameters derived from the new data, are in a good agreement with those known from single-crystal refinement. ThTi2O6 does not crystallize at high pressure, and Th is accommodated in perovskite-type compounds and cubic ThO2 that provide a twelve- and eight-fold coordination site for Th, respectively. 相似文献
9.
V. G. Thomas S. Z. Smirnov O. A. Kozmenko V. A. Drebushchak V. S. Kamenetsky 《Petrology》2014,22(3):293-309
In order to determine the mechanisms of formation and properties of natural hydrosilicate liquids (HSLs), which are formed during the transition from magmatic to hydrothermal mineral formation in granitic pegmatites and rare-metal granites, the formation of HSLs was experimentally studied in the Na2O-SiO2-H2O, Na2O-Al2O3-SiO2-H2O, and Na2O-K2O-Li2O-Al2O3-SiO2-H2O systems at 600°C and 1.5 kbar. It was shown that the sequential extension of composition does not suppress HSL formation in the systems and expands the stability field of this phase. However, HSLs formed in extended chemical systems have different structure and properties: the addition of alumina induces some compression of the structure of the silicate framework of HSLs, which results in a decrease in water content in this phase and probably hinders the reversibility of its dehydration. It was demonstrated that HSL can be formed by the coagulation of silica present in a silica-oversaturated alkaline aqueous fluid. It was supposed that the HSL formed during this process has a finely dispersed structure. It was argued that anomalous enrichment in some elements in natural HSLs can be due to their sorption by the extensively developed surface of HSL at the moment of its formation. 相似文献
10.
The configurational heat capacity, shear modulus and shear viscosity of a series of Na2O–Fe2O3–Al2O3–SiO2 melts have been determined as a function of composition. A change in composition dependence of each of the physical properties
is observed as Na2O/(Na2O + Al2O3) is decreased, and the peralkaline melts become peraluminous and a new charge-balanced Al-structure appears in the melts.
Of special interest are the frequency dependent (1 mHz–1 Hz) measurements of the shear modulus. These forced oscillation measurements
determine the lifetimes of Si–O bonds and Na–O bonds in the melt. The lifetime of the Al–O bonds could not, however, be resolved
from the mechanical spectrum. Therefore, it appears that the lifetime of Al–O bonds in these melts is similar to that of Si–O
bonds with the Al–O relaxation peak being subsumed by the Si–O relaxation peak. The appearance of a new Al-structure in the
peraluminous melts also cannot be resolved from the mechanical spectra, although a change in elastic shear modulus is determined
as a function of composition. The structural shear-relaxation time of some of these melts is not that which is predicted by
the Maxwell equation, but up to 1.5 orders of magnitude faster. Although the configurational heat capacity, density and shear
modulus of the melts show a change in trend as a function of composition at the boundary between peralkaline and peraluminous,
the deviation in relaxation time from the Maxwell equation occurs in the peralkaline regime. The measured relaxation times
for both the very peralkaline melts and the peraluminous melts are identical with the calculated Maxwell relaxation time.
As the Maxwell equation was created to describe the timescale of flow of a mono-structure material, a deviation from the prediction
would indicate that the structure of the melt is too complex to be described by this simple flow equation. One possibility
is that Al-rich channels form and then disappear with decreasing Si/Al, and that the flow is dominated by the lifetime of
Si–O bonds in the Al-poor peralkaline melts, and by the lifetime of Al–O bonds in the relatively Si-poor peralkaline and peraluminous
melts with a complex flow mechanism occurring in the mid-compositions. This anomalous deviation from the calculated relaxation
time appears to be independent of the change in structure expected to occur at the peralkaline/peraluminous boundary due to
the lack of charge-balancing cations for the Al-tetrahedra. 相似文献
11.
12.
正1 Introduction The underground brine resources distributing widely in Sichuan Basin,China have drawn worldwide attention due to their unusual element abundance and excellent quality. 相似文献
13.
An in situ high-pressure (HP) X-ray diffraction investigation of synthetic diopside and of the Ca0.8Mg1.2Si2O6 clinopyroxene (Di80En20) was performed up to respectively P=40.8 and 15.1 GPa, using high brilliance synchrotron radiation. The compression of the cell parameters is markedly anisotropic,
with βb ⋙ βc > βa > βasinβ for any pressure range and for both diopside and Di80En20. The compressibility along the crystallographic axes decreases significantly with pressure and is higher in Di80En20 than in diopside. The β cell parameter decreases as well with pressure, at a higher rate in Di80En20. The cell volume decreases at almost the same rate for the two compositions, since in diopside a higher compression along
a* occurs. A change in the mechanism of deformation at P higher than about 5–10 GPa is suggested for both compositions from the analysis of the strain induced by compression. In
diopside at lower pressures, the deformation mainly occurs, at a similar rate, along the b axis and at a direction 145° from the c axis on the (0 1 0) plane. At higher pressures, instead, the deformation occurs mostly along the b axis. In Di80En20 the orientation of the strain axes is the same as in diopside. The substitution of Ca with Mg in the M2 site induces at a
given pressure a higher deformation on (0 1 0) with respect to diopside, but a similar change in the compressional behaviour
is found. Changes in the M2 polyhedron with pressure can explain the above compressional behaviour. A third-order Birch-Murnaghan
equation of state was fit to the retrieved volumes, with K=105.1(9) GPa, K′=6.8(1) for diopside and K=107.3(1.4) GPa, K′=5.7(3)
for Di80En20; the same equation can be applied for any pressure range. The elasticity of diopside is therefore not significantly affected
by Mg substitution into the M2 site, in contrast to the significant stiffening occurring for Ca substitution into Mg-rich
orthopyroxenes.
Received: 3 January 2000 / Accepted: 21 May 2000 相似文献
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16.
《Applied Geochemistry》2002,17(10):1305-1312
The effect of different drying conditions on the stability of NaNd(CO3)·6H2O and NaEu(CO3)·6H2O and the identity of the decomposition product have been investigated. The rate of decomposition and the nature of the altered phases are dependant on the drying conditions used. When the phases are oven dried at 120 °C, the decomposition is immediate and the phase completely alters to Nd2(CO3)3 or Eu2(CO3)3 respectively. Under less severe drying conditions, the Na rare earth carbonate phases alter to Nd2(CO3)3·8H2O and Eu2(CO3)3·8H2O over a period of 24–48 h, but they can be kept indefinitely in a water saturated environment. The implications for using Nd and Eu as actinide analogues are discussed. 相似文献
17.
为了精确测定分解反应过程中钾的挥发量,结合GB8574-2002,在样品高钾铝硅酸盐物料(钾长石、碳酸钾焙烧熟料,K2O含量大于15%)处理中采用聚环氧乙烷絮凝沉淀Si,新制Ca(OH)2溶液除去Mg2+、Fe2+、Fe3+、Mn2+等其他阳离子,加入碳酸铵稳定溶液pH值以除去Ca2+和Al3+.采用四苯硼钾重量法测定钾含量,测定结果与表样对照,相对误差在0.5%以内.实验表明:利用Ca(OH)2除杂,溶液pH值须控制在10～12;碳酸铵双水解反应后,溶液pH值须控制在7.35左右以除尽Ca2+和Al3+;低温(T＜473 K)蒸发溶液除去NH4+,消除了因生成四苯硼铵沉淀而带来的分析误差.结果表明该方法可以精确测定高钾铝硅酸盐物料的K2O含量,具有成本低、方便快捷、无需大型仪器之优点. 相似文献
18.
Mark I. Pownceby Michael J. Fisher-White 《Contributions to Mineralogy and Petrology》1999,135(2-3):198-211
Detailed phase relations have been determined within the systems Fe2O3-MgO-TiO2 and FeO-MgO-TiO2. Experiments were performed over the temperature interval 1173–1473 K by equilibrating pelletized, fine-grained oxide mixtures
in either inert calcia-stabilized zirconia pots (Fe2O3-MgO-TiO2 system) or evacuated silica tubes (FeO-MgO-TiO2 system). Equilibrium phase assemblages were determined by combined optical microscope, X-ray diffraction and EMP examination.
Phase relations in the Fe2O3-MgO-TiO2 ternary are dominated by the instability of the M2O3 solid solution relative to the phase assemblage M3O4 + M3O5. A miscibility gap along the M2O3 binary also gives rise to two, 3-phase fields (α-M2O3 + M3O5 + M3O4 and α′-M2O3 + M3O5 + M3O4) separated by the M3O4 + M3O5 phase field. Phase relations in the FeO-MgO-TiO2 ternary were divided into two sub-systems. For the FeTiO3-MgTiO3-TiO2 sub-ternary, there is complete solid solution along the M2O3 and M3O5 binary joins at high temperature. At low temperatures (T < 1373 K) the M3O5 pseudobrookite solid solution decomposes to M2O3 + TiO2. Increasing the concentration of MgO in M3O5 phase results in a decrease in the temperature at which M3O5 becomes unstable and compositional tie lines linking M2O3 and TiO2 fan out, before the appearance of a three-phase region where M2O3, M3O5, and TiO2 coexist. Within the expanded FeO-MgO-TiO2 system, at temperatures above ∼1273 K there is a continuous solid solution along the M3O4 binary. At low temperatures (T < 1273 K) the Mg2TiO4 end-member breaks down to MgO and MgTiO3. The M3O4 phase shows significant non-stoichiometry, down to at least 1173 K. Fe2+-Mg partitioning data were obtained for coexisting M2O3-M3O5 and M2O3-M3O4 pairs in the FeO-MgO-TiO2 ternary. Assuming a regular solution mixing model for all phases, the M2O3 and M3O4 solid solutions were both found to exhibit moderate positive deviations from ideality (∼2600 J/mol), whereas the data for
the M3O5 binary suggest close to ideal behaviour.
Received: 22 May 1998 / Accepted: 3 November 1998 相似文献
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20.
Fabrizio Nestola Tiziana Boffa Ballaran Christian Liebske Marco Bruno Mario Tribaudino 《Physics and Chemistry of Minerals》2006,33(6):417-425
The volume variation as a function of pressure along the jadeite–aegirine solid solution was determined at room temperature up to pressures between 6.5 and 9.7 GPa by single-crystal X-ray diffraction. The unit-cell volumes collected at room pressure for the different compositions indicate a slight deviation from linearity along the join. The pressure–volume data have been fitted using a third-order Birch-Murnaghan equation of state (BM3-EoS). The bulk modulus, K
T0, varies from 134.0(7) GPa for pure jadeite to 116.1(5) GPa for pure aegirine. Its evolution with composition along the join is not linear and can be described by the following second order polynomial:
The value of the first pressure derivative K′ is close to 4 for all the samples investigated and can be used in a BM3-EoS to determine the volume variations of these pyroxenes up to 7–10 GPa. Along the join the highest compressibility among the crystallographic directions is always observed along a, however, the compression along b is the most affected by compositional changes. The strain ellipsoid analysis indicates that the major compression occurs on the (0 1 0) plane along a direction at about 145° to the c axis (from c to a). The anisotropy of the compression increases with increasing the aegirine component, as confirmed by the analysis of both the axial compressibility and the strain tensor. 相似文献
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