• Korean Journal of Mineralogy and Petrology
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• v.35 no.4
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• pp.423-430
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• 2022

Pressure-dependent elastic behavior and chemical reaction of natural sepiolite (Mg₈Si₁₂O₃₀(OH)₄·12H₂O) was studied under two different pressure-transmitting medium (PTM) conditions using synchrotron X-ray powder diffraction. Under non pore-penetrating silicone oil PTM, we observed that the b-axis length increases up to ca. 3.6 GPa, marking an anisotropic compression region with negative linear compressibility of β^b= -0.0012 GPa^-1, which then decreases at 7.7 GPa. Under pore-penetrating water PTM, the anisotropic compression behavior is enhanced with doubled negative linear compressibility of β^b= -0.0025 GPa^-1 up to 3.2 GPa, where transformation into stevensite is observed upon ex-situ temperature treatment at 280 ℃ as confirmed via XRD and SEM. Derived bulk moduli (K₀) and linear compressibilities (β) were compared to other structurally and chemically related minerals.

• Korean Chemical Engineering Research
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• v.61 no.3
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• pp.394-400
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• 2023

In this study, the tuning phenomena, gas storage capacity, and thermal expansion behaviors of binary (cyclopentylamine + CH₄) and (cyclopropylamine + CH₄) clathrate hydrates were investigated for the potential applications of clathrate hydrates to gas storage. To understand the tuning behaviors of binary (cyclopentylamine + CH₄) and (cyclopropylamine + CH₄) clathrate hydrates, ¹³C solid-state NMR spectroscopy was used, and the results confirmed that maximum tuning factors for the binary (cyclopentylamine + CH₄) and (cyclopropylamine + CH₄) clathrate hydrates were achieved at 0.5 mol% and 1.0 mol% of guest concentration, respectively. The gas storage capacity of binary (cyclopentylamine + CH₄) and (cyclopropylamine + CH₄) clathrate hydrates were also checked, and the results showed the CH₄ capacity of our hydrate systems was superior to that of binary (tetrahydrofuran + CH₄) and (cyclopentane + CH₄) clathrate hydrates. The synchrotron diffraction patterns of these hydrates collected at 100, 150, 200, and 250 K confirmed the formation of a cubic Fd-3m hydrate. In addition, the lattice constant of clathrate hydrates with cyclopentylamine and methane were larger than that with cyclopropylamine and methane due to the effects of molecular size and shape.

• Proceedings of the Materials Research Society of Korea Conference
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• 2011.05a
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• pp.5-5
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• 2011

The research and development of hybrid electric vehicle (HEV), plug-in hybrid electric vehicle (PHEV) and electric vehicle (EV) are intensified due to the energy crisis and environmental concerns. In order to meet the challenging requirements of powering HEV, PHEV and EV, the current lithium battery technology needs to be significantly improved in terms of the cost, safety, power and energy density, as well as the calendar and cycle life. One new technology being developed is the utilization of composite cathode by mixing two different types of insertion compounds [e.g., spinel $LiMn_2O_4$ and layered $LiMO_2$ (M=Ni, Co, and Mn)]. Recently, some studies on mixing two different types of cathode materials to make a composite cathode have been reported, which were aimed at reducing cost and improving self-discharge. Numata et al. reported that when stored in a sealed can together with electrolyte at $80^{\circ}C$ for 10 days, the concentrations of both HF and $Mn^{2+}$ were lower in the can containing $LiMn_2O_4$ blended with $LiNi_{0.8}Co_{0.2}O_2$ than that containing $LiMn_2O_4$ only. That reports clearly showed that this blending technique can prevent the decline in capacity caused by cycling or storage at elevated temperatures. However, not much work has been reported on the charge-discharge characteristics and related structural phase transitions for these composite cathodes. In this presentation, we will report our in situ x-ray diffraction studies on this mixed composite cathode material during charge-discharge cycling. The mixed cathodes were incorporated into in situ XRD cells with a Li foil anode, a Celgard separator, and a 1M $LiPF_6$ electrolyte in a 1 : 1 EC : DMC solvent (LP 30 from EM Industries, Inc.). For in situ XRD cell, Mylar windows were used as has been described in detail elsewhere. All of these in situ XRD spectra were collected on beam line X18A at National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory using two different detectors. One is a conventional scintillation detector with data collection at 0.02 degree in two theta angle for each step. The other is a wide angle position sensitive detector (PSD). The wavelengths used were 1.1950 ${\AA}$ for the scintillation detector and 0.9999 A for the PSD. The newly installed PSD at beam line X18A of NSLS can collect XRD patterns as short as a few minutes covering $90^{\circ}$ of two theta angles simultaneously with good signal to noise ratio. It significantly reduced the data collection time for each scan, giving us a great advantage in studying the phase transition in real time. The two theta angles of all the XRD spectra presented in this paper have been recalculated and converted to corresponding angles for ${\lambda}=1.54\;{\AA}$, which is the wavelength of conventional x-ray tube source with Cu-$k{\alpha}$ radiation, for easy comparison with data in other literatures. The structural changes of the composite cathode made by mixing spinel $LiMn_2O_4$ and layered $Li-Ni_{1/3}Co_{1/3}Mn_{1/3}O_2$ in 1 : 1 wt% in both Li-half and Li-ion cells during charge/discharge are studied by in situ XRD. During the first charge up to ~5.2 V vs. $Li/Li^+$, the in situ XRD spectra for the composite cathode in the Li-half cell track the structural changes of each component. At the early stage of charge, the lithium extraction takes place in the $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component only. When the cell voltage reaches at ~4.0 V vs. $Li/Li^+$, lithium extraction from the spinel $LiMn_2O_4$ component starts and becomes the major contributor for the cell capacity due to the higher rate capability of $LiMn_2O_4$. When the voltage passed 4.3 V, the major structural changes are from the $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component, while the $LiMn_2O_4$ component is almost unchanged. In the Li-ion cell using a MCMB anode and a composite cathode cycled between 2.5 V and 4.2 V, the structural changes are dominated by the spinel $LiMn_2O_4$ component, with much less changes in the layered $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component, comparing with the Li-half cell results. These results give us valuable information about the structural changes relating to the contributions of each individual component to the cell capacity at certain charge/discharge state, which are helpful in designing and optimizing the composite cathode using spinel- and layered-type materials for Li-ion battery research. More detailed discussion will be presented at the meeting.

• Journal of the Korean Magnetics Society
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• v.26 no.4
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• pp.124-128
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• 2016

We have investigated the electronic structures of intermetallic multilayer (ML) films of [$Co(2{\AA})/Pd(x{\AA})$] (x: the thickness of the Pd sublayer; x = $1{\AA}$, $3{\AA}$, $5{\AA}$, $7{\AA}$, $9{\AA}$) by employing soft X-ray absorption spectroscopy (XAS) and soft X-ray magnetic circular dichroism (XMCD). Both Co 2p XAS and XMCD spectra are found to be similar to one another, as well as to those of Co metal, providing evidence for the metallic bonding of Co ions in [Co/Pd] ML films. By analyzing the measured Co 2p XMCD spectra, we have determined the orbital magnetic moments and the spin magnetic moments of Co ions in [$Co(2{\AA})/Pd(x{\AA})$] ML films. Based on this analysis, we have found that the orbital magnetic moments are enhanced greatly when x increases from $1{\AA}$ to $3{\AA}$, and then do not change much for $x{\geq}3{\AA}$. This finding suggests that the interface spin-orbit coupling plays an important role in determining the perpendicular magnetic anisotropy in [Co/Pd] ML films.

• Journal of the Mineralogical Society of Korea
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• v.30 no.2
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• pp.45-57
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• 2017

Two single crystals of fully dehydrated $Cd^{2+}$-exchanged zeolites Y were prepared by the exchange of ${\mid}Na_{75}{\mid}[Si_{117}Al_{75}O_{384}]-FAU$ ($Na_{75}-Y$, Si/Al = 1.56) with aqueous $0.05M\;Cd(NO_3)_2$ (pH = 3.65) at 294 K, followed by vacuum dehydration at 723 K (crystal 1) and a second crystal, similarly prepared, was exposed to zeolitically dried benzene for 72 hours at 294 K and evacuated (crystal 2). Their structures were determined crystallographically using synchrotron X-rays and were refined to the final error indices using $F_o$>$4{\sigma}(F_o)$ of $R_1/wR_2=0.040/0.121$ and 0.052/0.168, respectively. In crystal $1({\mid}Cd_{36}H_3{\mid}[Si_{117}Al_{75}O_{384}]-FAU)$, $Cd^{2+}$ ions primarily occupy sites I and II, with additional $Cd^{2+}$ ions at sites I', II', and a second site II. In crystal $2({\mid}Cd_{35}(C_6H_6)_{24}H_5{\mid}[Si_{117}Al_{75}O_{384}]-FAU)$, $Cd^{2+}$ ions occupy five crystallographic sites. The 24 benzene molecules are found at two distinct positions within the supercages. The 17 benzene molecules are found on the 3-fold axes in the supercages where each interacts facially with one of site IIa $Cd^{2+}$ ions. The remaining 7 benzene molecules lie on the planes of the 12-rings where each is stabilized by multiple weak electrostatic and van der Waals interactions with framework oxygens.

• Macromolecular Research
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• v.16 no.7
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• pp.575-585
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• 2008

There are two beamlines (BLs), 4C1 and 4C2, at the Pohang Accelerator Laboratory that are dedicated to small angle X-ray scattering (SAXS). The 4C1 BL was constructed in early 2000 and is open to public users, including both domestic and foreign researchers. In 2003, construction of the second SAXS BL, 4C2, was complete and commissioning and user support were started. The 4C2 BL uses the same bending magnet as its light source as the 4C1 BL. The 4C1 BL uses a synthetic double multilayer monochromator, whereas the 4C2 BL uses a Si(111) double crystal monochromator for both small angle and wide angle X-ray scattering. In the 4C2 BL, the collimating mirror is positioned behind the monochromator in order to enhance the beam flux and energy resolution. A toroidal focusing mirror is positioned in front of the monochromator to increase the beam flux and eliminate higher harmonics. The 4C2 BL also contains a digital cooled charge coupled detector, which has a wide dynamic range and good sensitivity to weak scattering, thereby making it suitable for a range of SAXS and wide angle X-ray scattering experiments. The general performance of the 4C2 BL was initially tested using standard samples and further confirmed by the experience of users during three years of operation. In addition, several grazing incidence X-ray scattering measurements were carried out at the 4C2 BL.

• Korean Journal of Mineralogy and Petrology
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• v.34 no.3
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• pp.169-176
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• 2021

This study aimed to fundamentally understand structural changes of zeolite under pressure and in the presence of different pressure-transmitting media (PTM) for application studies such as immobilization of heavy metal cation or CO₂ storage using pressure. High-pressure X-ray powder diffraction study was conducted on the zeolite-W (K_6.4Al_6.5Si_25.8O₆₄× 15.3H₂O, K-MER) to understand linear compressibility and the bulk moduli in different PTM conditions. Zeolite-w is a synthetic material having the same framework as natural zeolite merlinoite ((K, Ca_0.5, Ba_0.5, Na)₁₀ Al₁₀Si₂₂O₆₄× 22H₂O). The space group of the sample was identified as I4/mmm belonging to the tetragonal crystal system. Water, carbon dioxide, and silicone-oil were used as pressure-transmitting media. The mixture of sample and each PTM was mounted in a diamond anvil cell (DAC) and then pressurized up to 3 GPa with an increment of ca. 0.5 GPa. Pressure-induced changes of powder diffraction patterns were measured using a synchrotron X-ray light source. Lattice constants, and bulk moduli were calculated using the Le-Bail method and the Birch-Murnaghan equation. In all PTM conditions, linear compressibility of c-axis (𝛽^c) was 0.006(1) GPa^-1 or 0.007(1) GPa^-1. On the other hand, the linear compressibility of a(b)-axis (𝛽^a) was 0.013(1) GPa^-1 in silicone-oil run, which is twice more compressible than the a(b)-axis in water and carbon dioxide runs, 𝛽^a = 0.006(1) GPa^-1. The bulk moduli were measured as 50(3) GPa, 52(3) GPa, and 29(2) GPa in water, carbon dioxide, and silicone-oil run, respectively. The orthorhombicities of ac-plane in the water, and carbon dioxide runs were comparatively constant, near 0.350~0.353, whereas the value decreased abruptly in the silicone-oil run following formula, y = -0.005(1)x + 0.351(1) by non-penetrating pressure fluid condition.

• Journal of the Mineralogical Society of Korea
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• v.31 no.4
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• pp.235-248
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• 2018

The present work was performed in order to study the effect of competing cation of $Ca^{2+}$ ion on ion exchange of $Cs^+$ on zeolite Y (Si/Al = 1.56). Three single-crystals of fully dehydrated and partially $Cs^+$-exchanged zeolites Y (Si/Al = 1.56) were prepared by the flow method using mixed ion-exchange solutions. The $CsNO_3:Ca(NO_3)_2$ molar ratios of the ion exchange solution were 1 : 1 (crystal 1), 1 : 100 (crystal 2), and 1 : 250 (crystal 3) with a total concentration of 0.05 M. The single-crystals were then vacuum dehydrated at 723 K and $1{\times}10^{-4}Pa$ for 2 days. The structures of the crystals were determined by single-crystal synchrotron X-ray diffraction technique in the cubic space group $Fd{\bar{3}}m$, at 100(1) K. The unit-cell formulas of crystals 1, 2, and 3 were ${\mid}Cs_{21}Ca_{27}{\mid}[Si_{117}Al_{75}O_{384}]-FAU$, ${\mid}Cs_2Ca_{36.5}{\mid}[Si_{117}Al_{75}O_{384}]-FAU$, and ${\mid}Cs_1Ca_{37}{\mid}[Si_{117}Al_{75}O_{384}]-FAU$, respectively. In all three crystals, the $Ca^{2+}$ ions preferred to occupy site I in the D6Rs, with the remainder occupying sites I', II', and II. On the other hand, the significant differences in the fractional distribution of $Cs^+$ ions are observed depending on the intial $Cs^+$ concentrations in given ion exchange solution. In Crystal 1, $Cs^+$ ion are located at sites II', II, III, and III', and in crystal 2, at sites II, IIIa, and IIIb. In crystal 3, $Cs^+$ ions are only located at sites IIIa and IIIb. The degree of $Cs^+$ ion exchange decreased sharply from 28.0 to 2.7 to 1.3 % as the initial $Ca^{2+}$ concentration increases and the $Cs^+$ content decreases.

• Korean Journal of Mineralogy and Petrology
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• v.35 no.1
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• pp.41-50
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• 2022

To study the properties of Sr²⁺ exchange into zeolite A with increasing the molar concentration of Na⁺ in given exchange solution, four single crystals of fully dehydrated Sr²⁺- and Na⁺- exchanged zeolite A were prepared by the bath method using mixed ion-exchange solutions. The Sr(NO₃)₂:NaNO₃ molar rations of the ion exchange solution were 1:1(crystal 1), 1:100(crystal 2), 1:250(crystal 3), and 1:500 (crystal 4), respectively, with a total concentration of 0.05 M. The single-crystals were then vacuum dehydration at 623 K and 1×10^-4 Pa for 2 days. Their single-crystal structures were determined by single-crystal synchrotron X-ray diffraction techniques in the cubic space group Pm3-m, at 100(1) K, and were then refined to the final error indices of R₁/wR₂=0.047/0.146, 0.048/0.142, 0.036/0.128, and 0.040/0.156 for crystals 1, 2, 3, and 4, respectively. In crystals 1 and 2, the 6 Sr²⁺ ions are found at three different crystallographic sites. In crystal 3, 1 Sr²⁺ and 10 Na⁺ ions are found in large cavity and sodalite unit. In crystal 4, only 12 Na⁺ ions occupy three equipoints. The degree of Sr²⁺ ion-exchange decreased sharply from 100 to 16.7 to 0% as the initial Na⁺ concentration increase and the Sr²⁺ concentration decrease. In addition, the unit cell constant of the zeolite framework decreased with this lower level of Sr²⁺ exchange.

• Korean Journal of Mineralogy and Petrology
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• v.35 no.4
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• pp.447-455
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• 2022

Fully dehydrated Tl₁₂-LTA (|Tl₁₂|[Si₁₂Al₁₂O₄₈]-LTA,Tl₁₂-A) was treated with 6.0×10³ Pa of ZrI₄ (g) at 623 K for 72 hr under anhydrous conditions. The crystal structure of product, |Zr_0.25I_1.5Tl₁₂|[Si₁₂Al₁₂O₄₈]-LTA, was determined by single-crystal crystallography using synchrotron X-radiation in the cubic space group Pm3m (a = 12.337(2) Å). It was refined using all data to the final error index (for the 712 unique reflections for which F_o> 4σ(F_o) R₁/wR₂= 0.055/0.189. In this structure, octahedral ZrI₆^2- ions center about 25% of the large cavities (Zr-I = 2.91(4) Å). Each coordinates to eight Tl⁺ ions and they are further bridged by Tl⁺ ions in the planes of 8-rings to form a cubic three-dimensional ZrI₆Tl₁₁⁹⁺ cationic cluster. About 1.5 Tl⁺ ions per unit cell moved to deeper side of sodalite cavity after reaction with ZrI₄(g). The remaining Tl⁺ ions occupy well-established cation positions near 6- and 8-rings.