• Bulletin of the Korean Chemical Society
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• v.23 no.8
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• pp.1121-1126
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• 2002

Two anhydrous crystal structures of fully dehydrated Cd2+ - and Cs+ -exchanged zeolite X, Cd32Cs28Si100Al92O384 (Cd32Cs28-X: a = 24.828(11) $\AA)$ and fully dehydrated Cd,sup>2+ - and Rb+ -exchanged zeolite X, Cd28Rb36Si100Al92O384 (Cd28Rb36-X: a = 24.794(2) $\AA$), have been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd3 at $21(1)^{\circ}C.$ The structures were refined to the final error indices, R1 = 0.058 and R2 = 0.065 with 637 reflections for Cd32Cs28-X and R1 = 0.086 and R2 = 0.113 with 521 reflections for Cd28Rb36-X for which I > $3\sigma(I)$. In the structure of Cd,sub>32Cs28-X, 16 Cd2+ ions fill the octahedral sites I at the centers of the double six rings (Cd-O = $2.358(8)\AA$ and O-Cd-O = $90.8(3)^{\circ}$ ). The remaining 16 Cd2+ ions occupy site II (Cd-O = $2.194(8)\AA$ and O-Cd-O = $119.7(4)^{\circ})$ and six Cs+ ions occupy site II opposite to the single six-rings in the supercage; each is $2.322\AA$ from the plane of three oxygens (Cs-O = 3.193(13) and O-Cs-O = $73.0(2)^{\circ}).$ Aboutten Cs+ ions are found at site II', $1.974\AA$ into the sodalite cavity from their three oxygen plane (Cs-O = $2.947(8)\AA$ and O-Cs-O = $80.2(3)^{\circ}).$ The remaining 12 Cs+ ions are distributed over site III' (Cs-O = 3.143(9) and O-Cs-O= $59.1(2)^{\circ})$. In the structure of Cd28Rb36-X, 16 Cd2+ ions fill the octahedral sites I at the center of the double-sixrings (Cd-O = 2.349(15) and O-Cd-O = $91.3(5)^{\circ}$ ). Another 12 Cd2+ ions occupy two different II sites (Cd-O = $2.171(18)/2.269(17)\AA$ and O-Cd-O = $119.7(7)/113.2(7)^{\circ}).$ Fifteen Rb+ ions occupy site II (Rb-O = $2.707(17)\AA$ and O-Rb-O = $87.8(5)^{\circ}).$ The remaining 21 Rb+ ions are distributed over site III' (Rb-O = $3.001(16)\AA$ and O-Rb-O = $60.7(4)^{\circ})$. It appears that the smaller and more highly charged Cd2+ ions prefer sites I and Ⅱ in that order, and the larger Rb+ and Cs+ ions, which are less able to balance the anionic charge of the zeolite framework, occupy sites II and II' with the remainder going to the least suitable site in the structure, site III'.The maximum Cs+ and Rb+ ion exchanges were 30% and 39%, respectively. Because these cations are too largeto enter the small cavities and their charge distributions may be unfavorable, cation-sieve effects might appear.

• KSCE Journal of Civil and Environmental Engineering Research
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• v.10 no.3
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• pp.107-113
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• 1990

A series of cubical triaxial tests with independent control of the three principal stresses were performed on a compressible sand. All specimens which were formed by depositing the fine sand loosely, were used. It was found that slope of the stress-strain curve increased with increased b value, and the major principal strain at failure first remains approximetely constant for b values smaller than about 0.3 for drained condition and 0.6 for undrained condition respectively, and thereafter decreases with increasing value of b. The test results showed that the direction of the strain increments at failure form acute angles with the failure surfaces for both the drained and undrained condition. The results are thus not in agreement with the normality criterion from classic plasticity theory. However, it was found that the projections of the plastic strain increment vectors on the octahedral plane are perpendicular to the faiure surface in that plane.

• Journal of the Korean earth science society
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• v.25 no.1
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• pp.22-31
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• 2004

Laboratory experiments were conducted in order to find effects of the intermediate principal stress of ${\sigma}_{2}$ on rock fractures and faults. Polyaxial tests were carried out under the most generalized compressive stress conditions, in which different magnitudes of the least and intermediate principal stresses ${\sigma}_{3}$ and ${\sigma}_{2}$ were maintained constant, and the maximum stress ${\sigma}_{1}$, was increased to failure. Two crystalline rocks (Westerly granite and KTB amphibolite) exhibited similar mechanical behavior, much of which is neglected in conventional triaxial compression tests in which ${\sigma}_{2}$ = ${\sigma}_{3}$. Compressive rock failure took the form of a main shear fracture, or fault, steeply dipping in ${\sigma}_{3}$ direction with its strike aligned with ${\sigma}_{2}$ direction. Rock strength rose significantly with the magnitude of ${\sigma}_{2}$, suggesting that the commonly used Mohr-type failure criteria, which ignore the ${\sigma}_{2}$ effect, predict only the lower limit of rock strength for a given ${\sigma}_{3}$ level. The true triaxial failure criterion for each of the crystalline rocks can be expressed as the octahedral shear stress at failure as a function of the mean normal stress acting on the fault plane. It is found that the onset of dilatancy increases considerably for higher ${\sigma}_{2}$. Thus, ${\sigma}_{2}$ extends the elastic range for a given ${\sigma}_{3}$ and, hence, retards the onset of the failure process. SEM inspection of the micromechanics leading to specimen failure showed a multitude of stress-induced microcracks localized on both sides of the through-going fault. Microcracks gradually align themselves with the ${\sigma}_{1}$-${\sigma}_{2}$ plane as the magnitude of ${\sigma}_{2}$ is raised.

• Bulletin of the Korean Chemical Society
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• v.16 no.7
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• pp.634-641
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• 1995

The metal-carbon σ-bond cluster complexes 1-Mn(CO)5-2-R-1,2-C2B10H10 (R=CH3 Ia, C6H5 Ib) have been prepared in good yields from readily available carboranyl lithium complexes, 1-Li+-2-R-1,2-C2B10H10- (R=CH3, C6H5), by direct reaction with (CO)5MnBr. These manganese metal complexes are rapidly converted to the corresponding manganese metal carbene complexes, 1-[(CO)4Mn=C(OCH3)(CH3)]-2-R-1,2-C2B10H10 (R=CH3 IIIa, C6H5 IIIb), via alkylation with methyllithium followed by O-methylation with CF3SO3CH3. The crystal structure of IIIb was determined by X-ray diffraction. Thus, complex IIIb crystallizes in the orthorhombic space group P212121 with cell parameters a=15.5537(5), b=19.0697(5), c=7.4286(3) Å, V=2203.4(1) Å3, and Z=4. Of the reflections measured a total of 3805 unique reflections with F2>3σ(F2) was used during subsequent structure refinement. Refinement converged to R1=0.053 and R2=0.091. Structural studies showed that the manganese atom had a slightly distorted pseudo-octahedral configuration about the metal center with the carbene and ortho-carborane occupying the equatorial plane cis-orientation to each other.

• Journal of the Mineralogical Society of Korea
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• v.27 no.4
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• pp.271-281
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• 2014

The physicochemical properties of clay minerals have been investigated at the atomistic to nano scale. The microscopic studies are often challenging to perform by using experimental approaches alone. In particular, hydroxyl groups of octahedral sheets in 2:1 clay minerals have been hypothesized to impact the sorption process of metal cations; however, X-ray based techniques alone, a common tool for mineral structure examination, cannot properly test the hypothesis. The current study has examined whether computational mineralogy techniques can be applied to examine the hydroxyl structures of clay minerals. Based on quantum-mechanics and molecular-mechanics computational methods, geometry optimizations were carried out for representative dioctahedral and trioctahedral phyllosilicate minerals. Both methods well reproduced the experimental lattice parameters; however, for structural distortion occurring in the tetrahedral or octahedral sheets, molecular mechanics showed significant deviations from experimental data. The orientation angle of the hydroxyl with respect to (001) basal plane is determined by the balance of repulsion between the hydroxyl proton and Si cations of tetrahedral sites; the quantum-mechanics method predicted $25-26^{\circ}$ for the angle, whereas the angle predicted by the molecular-mechanics method was much higher by $10^{\circ}$ (i.e., $35^{\circ}$). These results demonstrate that computational mineralogy techniques are a reliable tool for clay mineral studies and can be used to further elucidate the roles of hydroxyls in metal sorption process.

• KSCE Journal of Civil and Environmental Engineering Research
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• v.13 no.1
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• pp.161-171
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• 1993

The aim of this study is to provide the stress-strain behavior of hardening geological materials such as rock or concrete on three dimensional spaces by using Desai model based on plastic theory. To validate proposed model, truly triaxial tests with high pressure under variety of stress paths in which three principal stresses were controlled independently using concrete materials were performed. The main results are summerized as follows: 1. Various stress paths for hardening materials used are satisfactorily explained by performing the truly triaxial test with high pressure. This is very important to investigate constitutive equations for materials like rock or concrete. 2. Since the proposed yield function is continuous, it avoids the singularity point at the intersection of two function in the previous models, thus, reducing the difficulties for computer implementation. 3. Analytic predictions for yielding behavior on $J_1-{\sqrt{J_{2D}}}$ octahedral and triaxial plane, as well as volumetric strain and stress-strain behavior agree well with experimental results.

• Korean Journal of Materials Research
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• v.10 no.9
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• pp.648-655
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• 2000

Synthesis of the crystalline film was investigated under the diamond growth condition with altering the addition of the nitrogen from 0% to 95%. With increasing the nitrogen concentration, surface morphology of the film was changed from the diamond film with {100} growth plane to the non-faceted diamond film with nano-scale grains. It also showed that the deposition of the diamond film could be synthesized using only methane and nitrogen gases without hydrogen gas. Separated particles with diamond structure showed an octahedral shaped I the nitrogen ranges between 30% and 80%, and newly formed hexagonal crystals are observed when substrate temperature with diamond structure, however, also identify that the hexagonal crystal was SiCN composite composed of Si, C and N atoms.

• Korean Journal of Materials Research
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• v.8 no.11
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• pp.1067-1073
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• 1998

High quality diamond films of the silicon on diamond (SOD) structure are deposited using CO and $H_2$ gas mixture in microwave plasma chemical vapor deposition (CVD), a SOD structure is fabricated using low pressure CVD polysilicon on diamond/ Si(100) substrate. The crystalline structure of the diamond films which composed of { 111} and {100} planes. were changed from octahedral one to cubo-octahedron one as the CO/$H_2$ ratios are increased. The high quality diamond films without amorphous carbon and non-diamond elements were deposited at the CO/$H_2$ flow rate of 0.18. and the main phase of the diamond films shows (111) plane. The diamond/Si(lOO) structure shows that the interface is flat without voids. The measured dielectric constant. leakage current and breakdown field were $5.31\times10^{-9}A/cm^2$ and $9\times{10^7}{\Omega}cm$ respectively.

• Geotechnical Engineering
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• v.6 no.3
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• pp.65-76
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• 1990

A series of consolidated drained and untrained cubical triaxial tests were performed to investigate three dimensional strength characteristics of compressible sand. All specimens, which are formed by deposisting a fine sand loosely, were used. Failure strength in terms of effective stress analysis was greatly influenced by the variation of intermediate principal stress and so was failure criterion The adjusted effective frictional angles obtained by the stress state projected on the same octahedral plane showed almost same value, while the measured effective frictional angles showed considerable difference depending on the drainage conditions. Results of total stress analysis in undrained test turned out to fit Tresca's failure criterion well, but results of effective stress analysis turned out to fit Lade's failure criterion well.

• Korean Journal of Materials Research
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• v.20 no.2
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• pp.55-59
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• 2010

$Na^+$ ion conductivity can be improved by the substitution of an Mg atom for an Al atom to form a nonstoichiometric $Na^+$ $\beta$-alumina. We performed a first principles study to investigate the most stable substitution site of an Mg atom and the resulting structural change of the nonstoichiometric $Na^+$ $\beta$-alumina. Al atoms were classified as four different layers in the spinel block that are separated by conduction planes in the nonstoichiometric $Na^+$ $\beta$-alumina. The substitution of an Mg atom for an Al atom at a tetragonal site was more favorable than that at an octahedral site. The substitution in the spinel block was more favorable than that close to the conduction plane. This result was well explained by the volume changes of the polyhedrons, by the standard deviation of the Mg-O distance, and by the comparison with bulk MgO structure. Our result indicates that the most preferable site for the Mg atom was the tetrahedral site at the spinel block in the nonstoichiometric $Na^+$ $\beta$-alumina.