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1.
Single crystals of akermanite (Ca1–x
Sr
x
)2Co-Si2O7 solid solution were grown in nitrogen by the floating zone method using a lamp-image furnace. The grown crystals were 6 mm in diameter by 50 mm in length. Microprobe analyses indicate uniform strontium content x except in the initially crystallized part. Synthetic crystals with x from 0.0 to 0.3 give, at room temperature, satellite reflections and circular diffuse scatterings in the electron diffraction pattern, which are related to an incommensurate phase and microdomains, respectively. With increasing Sr content the wavelength of a modulation increases and the intensity of satellites decreases, but the intensity of circular diffuse scattering increases up to x=0.15 and then decreases until eventually the satellites and the circular diffuse scatterings disappear at x = 0.3. The circular diffuse scattering is explained by the cluster model for the transition state, proposed by De Ridder et al. (1976). 相似文献
2.
K. Kusaka K. Hagiya M. Ohmasa Y. Okano M. Mukai K. Iishi N. Haga 《Physics and Chemistry of Minerals》2001,28(3):150-166
The structures of Ca2CoSi2O7, Ca2MgSi2O7, and Ca2(Mg0.55Fe0.45)Si2O7 have been determined in the temperature range between 297 and 773 K with arbitrary intervals. The structures of the incommensurate
phase of the three compounds are characterized by the presence of the six-, seven-, and eight-coordinated Ca–O polyhedra and
of the bundles along the c-axes consisting of four arrays of the six-coordinated Ca–O polyhedra and an array of T1O4 (T1: Co, Mg, or Mg–Fe) tetrahedra in the structures. The number of bundles in each material decreases at elevated temperatures.
The incommensurate phase undergoes a phase transition into the normal phase at 493 K in Ca2CoSi2O7, at 360 K in Ca2MgSi2O7, and at 510 K in Ca2(Mg0.55Fe0.45)Si2O7. The features of the structures of the normal phase are almost the same as those found in the basic structures (the averaged
structures of the incommensurate structures), and this fact implies that the characteristics of the structures, such as the
six-coordinated Ca–O polyhedra or fragments of the bundles, should be partially preserved at higher temperatures both in the
incommensurate structures and also in the structures of the normal phase. Analyses of anisotropic displacement parameters
clarified that disorder of the modulation waves is developed in the structures at higher temperatures. The evolution of a
disorder in the structures was ascertained by observation of the circular diffuse streaks in the vicinity of the transition
temperature between the incommensurate and normal phases.
Received: 3 July 2000 / Accepted: 26 October 2000 相似文献
3.
Polarised Raman and infrared spectra of (ir) andalusite (Al2SiO5) single crystals have been measured and interpreted on the basis of a rigid-ion model calculation. The Al-O bond strength is found to be about 70% ionic in character whereas the mainly covalently bound SiO4 tetrahedra show ca. 40% ionicity. The interatomic short range forces are strongest between silicon and oxygen and rather weak around the fivefold coordinated aluminium. Thermal soft modes appear above 200°C and are correlated with a weakening of the Al-O bonds. 相似文献
4.
Kazuaki Iishi 《Physics and Chemistry of Minerals》1978,3(1):1-10
The short-range force constants and the contribution of the potential energy to the elastic constants have been calculated from explicit expressions for the elastic constants and for the optical frequencies. The large elastic constants of corundum are attributable to the contribution of the large short-range stretching forces. The frequencies of the phonon spectrum and the contribution of the potential energy to the frequencies have also been calculated based on a rigid-ion and polarizable-ion model. The effective charge of an oxygen ion is found to be ?0.955e. The electronic polarizability of an aluminium and oxygen ion is found to be 0.05 and 1.36 Å3, respectively. 相似文献
5.
Iron-rich olivines (Fa100∼Fa70Fo30) experimentally altered in alkaline and acidic aqueous oxidizing environment were examined in transmission electron microscope
to determine the precipitate phases and their crystallographic relationships to the host. The planar zones consist of precipitates
of laihunite and hematite in alkaline aqueous oxidizing environment while hematite and amorphous silica in acidic aqueous
oxidizing environment. The directions of planar zones produced in alkaline aqueous oxidizing environment are parallel to (100)∼(001)
of olivine dependent on the composition of the host olivines, while those produced in acidic aqueous oxidizing environment
are always parallel to (001) of olivine independent from the composition of the host olivine. These differences are interpreted
by the dissolution kinetics of olivine.
The present experimental results explain why the planar zones found in oxidized iron-rich olivines in carbonaceous chondrite
are parallel to (100) of olivine while those in terrestrial olivines are parallel to (001) of olivine. That is, the difference
is attributed to the pH of the alteration environment.
Received: August 19, 1996 / Revised, accepted: February 14, 1997 相似文献
6.
The heat capacity of åkermanite solid solutions was measured by a small scale adiabatic calorimeter near the incommensurate-normal (I-N) transition. The heat capacity anomalies caused by the I-N transition show the type characteristic behavior implying the presence of dynamical fluctuations. The heat capacity anomalies were observed over the whole range of the åkermanite solid solutions Ca2Mg1-xCoxSi2O7 and Ca2Mg1-x-ZnxSi2O2. With increase of Co or Zn atoms, the transition temperature, Ti, rises linearly from ca. 83° C to 220° C and to 130° C, respectively. In the system Ca2CoSi2O7-Ca2FeSi2O7 and Ca2MgSi2O7-Ca2-FeSi2O7 electronic microscopy revealed that the temperature of the heat capacity anomaly decreases with increasing Fe content, whereas the Ti rises. This unusual behavior is ascribed to the microdomains observed in high resolution lattice images. 相似文献
7.
Kazuaki Iishi Mitiko Miura Yuji Shiro Hiromu Murata 《Physics and Chemistry of Minerals》1983,9(2):61-66
On the basis of the polarizable-ion model (PIM) the effect of the width of the atomic electron distribution on the lattice dynamics of α-quartz was taken into account using the Birman method. The frequencies of optical mode, elastic constants and piezoelectric constants were reproduced using the parameters of this model (an effective charge z, a width parameter w, an electronic polarizability α, and force constants). The width parameter of oxygen atom was found to be about 0.59 Å, and the effective charge of the silicon atom 1.42 electron charges. 相似文献
8.
Takuo Tamura Akira Yoshiasa Kazuaki Iishi Setsuo Takeno Hironobu Maeda Shuichi Emura Kichiro Koto 《Physics and Chemistry of Minerals》1996,23(2):81-88
The local structure around Co, Zn and Sr atoms in incommensurately modulated, melilite-type X2T1 T 2 2 O7 (X=Ca and Sr, T1=Mg, Co and Zn, T2=Si) solid-solutions has been investigated by EXAFS analyses. The modulated structure was confirmed in Ca2-xSrxCoSi2O7 solid-solutions with X=0.0 to 0.6 and for both Ca2Mg1-YCoYSi2O7 and Ca2Mg1-YZnYSi2O7 solid-solutions over the whole compositional range at room temperature. The actual bond-distances determined by the EXAFS method for the T1 site (Co-, Zn-O) in the modulated structure are longer than the mean bond-distances obtained from the X-ray diffraction method. This is attributable to the libration of the T1 tetrahedra. In the Ca1-XSrXCoSi2O7 solid-solution both the Sr-O and Co-O distances by the EXAFS method for the X-site increase from Ca end-member to Sr end-member. These increases are respectively 0.8% and 0.6%. This means the local expansions of the tetrahedral sheets and of the XO polyhedra are well matched. In the modulated Ca2Co1-YMgYSi2O7 and Ca2Zn1-YMgYSi2O7 solid-solutions, the actual Co-O and Zn-O distances for the T1-sites are nearly constant in the whole compositional range. The compositional variations of the local structure around the cations in the solid-solution are different for the X and T1 sites. It is concluded that the local geometric restriction for the size of substituted cation in X site is larger than that in T1 site. The dimension of the tetrahedral sheet puts restriction on the size of the cations situated at the interlayer X sites. In other words, the different behavior of the local geometric restriction between the X and T1 sites is an important feature of the melilite structure and is also related to the modulated structure. 相似文献
9.
Kazuaki Iishi 《Physics and Chemistry of Minerals》1979,4(4):341-359
Detailed experimental and theoretical studies of the k=0 vibrational spectra of anhydrite and gypsum are reported. The dielectric constants and the infrared reflection and Raman spectra of the single crystal have been measured. The frequencies of the phonon spectrum, the contribution of potential terms to potential energy and detailed mode assignments have been determined based on a polarizable-ion model. The relative experimental intensity of the spectra, the observed crystal field effects, the rotatory lattice modes of the H2O molecule and the mixed character of translatory and rotatory modes of the Ca, SO4, and H2O groups are discussed based on the theoretical vibrational modes and the potential energy distribution. The principal moments of inertia of the water molecule and the Lennard-Jones potential constants for nonbonded oxygen-oxygen interactions are presented. 相似文献
10.
Circular diffuse scattering appears when the incommensurate phase of akermanite transforms partly to either the normal phase or the commensurate phase by exchanging Ca atoms for larger alkali-earth atoms such as Sr or by exchanging Mg atoms for larger atoms such as Fe and/or by increasing the temperature. The scattering effect has been investigated by using an optical diffraction method. To induce the appearance of circular satellite reflections around the Bragg reflections, the modulation waves must repeat with a phase difference in one direction, x or y, together with a wavelength change. If the modulation waves repeat with phase differences in both x and y directions, circular satellite reflection will be induced without varying the modulation wavelength. Experimental reproduction of circular diffuse scattering shows that this phenomenon is ascribed to modulation waves repeating with a layer-to-layer phase difference and with a constant phase difference within each layer of the akermanite structure. 相似文献