• Bulletin of the Korean Chemical Society
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• v.30 no.6
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• pp.1274-1284
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• 2009

Single crystals of fully dehydrated and fully $Ca^{2+}$-exchanged zeolites A (|$Ca_6$|[$Si_{12}Al_{12}O_{48}$]-LTA) and X (|$Ca_{46}$| [$Si_{100}Al_{92}O_{384}$]-FAU) were brought into contact with Te in fine pyrex capillaries at 623 K and 673 K, respectively, for 5 days. Crystal structures of Te-sorbed $Ca^{2+}$-exchanged zeolites A and X have been determined by single-crystal X-ray diffraction techniques at 294 K in the cubic space group Pm$\overline{3}$ m (a = 12.288(2) $\AA$) and Fd $\overline{3}$ (a = 25.012(1) $\AA$), respectively. The crystal structures of pale red-brown |$Ca_6Te_3$|[$Si_{12}Al_{12}O_{48}$]-LTA and black coloured |$Ca_{46}Te_8$| [$Si_{100}Al_{92}O_{384}$]-FAU have been refined to the final error indices of $R_1/wR_2\;=\;0.1096/0.2768\;and\;R_1/wR_2$ = 0.1054/ 0.2979 with 204 and 282 reflections for which $F_o\;>\;4{\sigma}(F_o)$, respectively. In the structure of |Ca6Te3|[$Si_{12}Al_{12}O_{48}$]- LTA, 6 $Ca^{2+}$ ions per unit cell were found at one crystallographic positions, on 3-fold axes equipoints of opposite 6-rings. In |$Ca_{46}Te_8$|[$Si_{100}Al_{92}O_{384}$]-FAU, 46 $Ca^{2+}$ ions per unit cell were found at four crystallographically distinct positions: 3 $Ca^{2+}$ ions at Ca(1) fill the 16 equivalent positions of site I, 21 $Ca^{2+}$ ions at Ca(2) fill the 32 equivalent positions of site I’, 10 and 12 $Ca^{2+}$ ions at Ca(3) and Ca(4), respectively, fill the 32 equivalent positions of site II. The Te clusters are stabilized by interaction with cations and framework oxygen. In sodalite units, Te-Te distances of 2.86(10) and 2.69(4) $\AA$ in zeolites A and X, respectively exhibited strong covalent properties due to their interaction with $Ca^{2+}$ ions. On the other hand, in large cavity and supercage, those of 2.99(3) and 2.76(11) $\AA$ in zeolites A and X, respectively, showed ionic properties because alternative ionic interaction was formed through framework oxygen at one end and $Ca^{2+}$ cations at the other end.

• Resources Recycling
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• v.27 no.2
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• pp.38-47
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• 2018

Integrated gasification combined cycle (IGCC) is a next generation energy production technology that converts coal into syngas with enhanced power generation efficiency and environmental performance. IGCC produces almost coal gasification slag as the solid by-product. IGCC slag is generated about 140,000 tons for a year although recycling of it is still in the early stages. We evaluated the potential of IGCC slag which is generated from a pilot plant in South Korea as an alkali-activated cement. Samples which were activated with the combined activator of sodium silicate solution and caustic soda had an average compressive strength of 4.5 MPa, showing expansion. Expansion of the alkali-activated slag was presumed to be caused by free CaO in the slag, although it was not detected by the ethylene glycol method. Samples that were activated with the combined activator of sodium aluminate and caustic soda had an average compressive strength of 10 MPa. Hydroxy sodalite and $C_3AH_6$ were found to be the new crystalline phases. IGCC slag can be used as an alkali-activated material, but the strength performance should be improved with proper mix design approach to calculate optimum proportions which can alleviate the expansion issue at the same time.

• Bulletin of the Korean Chemical Society
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• v.30 no.3
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• pp.543-550
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• 2009

The single-crystal structure of largely ammonium-exchanged zeolite Y dehydrated at room temperature (293 K) and 1 ${\times}\;10^{-6}$ Torr. has been determined using synchrotron X-radiation in the cubic space group $Fd\overline{3}m\;(a=24.9639(2)\AA)$ at 294 K. The structure was refined to the final error index $R_1$ = 0.0429 with 926 reflections where $F_o>4\sigma(F_o)$; the composition (best integers) was identified as |$(NH_4)_{60}Na_{11}$|[$Si_{121}Al_{71}O_{384}$]-FAU. The 11 $Na^{+}$ ions per unit cell were found at three different crystallographic sites and 60 ${NH_4}^{+}$ ions were distributed over three sites. The 3 $Na^{+}$ ions were located at site I, the center of the hexagonal prism ($Na-O\;=\;2.842(5)\;\AA\;and\;O-Na-O\;=\;85.98(12)^{\circ}$). The 4 $Na^{+}$ and 22 ${NH_4}^{+}$ ions were found at site I' in the sodalite cavity opposite the double 6-rings, respectively ($Na-O\;=\;2.53(13)\;\AA,\;O-Na-O\;=\;99.9(7)^{\circ},\;N-O\;=\;2.762(11)\;\AA,\;and\;O-N-O =\;89.1(5)^{\circ}$). About 4 $Na^{+}$ ions occupied site II ($(Na-O\;=\;2.40(4)\;\AA\;and\;O-Na-O\;=\;108.9(3)^{\circ}$) and 29 ${NH_4}^{+}$ ions occupy site II ($N-O\;=\;2.824(9)\;\AA\;and\;O-N-O\;=\;87.3(3)^{\circ}$) opposite to the single 6-rings in the supercage. The remaining 9 ${NH_4}^{+}$ ions were distributed over site III' ($N-O\;=\;2.55(3),\;2.725(13)\;\AA\;and\;O-N-O\;=\;94.1(13),\;62.16(15),\;155.7(14)^{\circ}$).

• Journal of the Korean Chemical Society
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• v.38 no.9
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• pp.621-627
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• 1994

Two crystal structures of dehydrated, $Ag^{+}$ and $Ca^{2+}$-exchanged zeolite A treated at $250^{\circ}C$ with 0.15 torr of Cs vapor have been determined by single-crystal X-ray diffraction technique in the cubic space group $Pm{\bar\3m$ at $21(1)^{\circ}C$ (a = 12.344(2) $\AA$ and 12.304(2) $\AA$). Their structures were refined to the final error indices, R (weighted), of 0.091 with 180 reflections, and 0.093 with 179 reflections, respectively, for which I > $3\sigma(I).$ In each structure, Cs species are found at four different crystallographic sites: 3 $Cs^{+}$ ions per unit cell are located at 8-ring centers, ca. 6.81∼7.14 $Cs^{+}$ ions are found on opposite 6-rings on threefold axes in the large cavity, ca. 1.93∼2.03 $Cs^{+}$ ions are found on threefold axes in the sodalite unit, and 0.53∼0.66 $Cs^{+}$ ions lie on opposite 4-rings. Also, ca. 4.12∼4.27 Ag atoms are located near the center of the large cavity. In these structures, excess cesium atoms in a unit cell are associated with other $Cs^{+}$ ions on a single threefold axis to form the linear cationic cluster $(Cs_4)^{3+}$. By blocking 8-rings, the $Cs^{+}$ ions may have prevented silver atoms from migrating out of the structure. The Ag atoms are likely to have formed hexasilver clusters at the centers of the large cavities. Each hexasilver cluster is stabilized by coordination to 14 $Cs^{+}$ ions.

• Bulletin of the Korean Chemical Society
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• v.22 no.1
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• pp.30-36
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• 2001

The crystal structures of fully dehydrated $Pd^{2+}$ - and $TI^{+}$ -exchanged zeolite X, $Pd_{18}TI_{56}Si_{100}Al_{92}O_{384}(Pd_{18}TI_{50-}X$, a = $24.935(4)\AA$ and $Pd_{21}TI_{50}Si_{100}Al_{92}O_{384}(Pd_{21}TI_{50-}X$ a = $24.914(4)\AA)$, have been determined by single-crystal X-ray diffraction methods in the cubic space group Fd3 at $21(1)^{\circ}C.$ The crystals were prepared using an exchange solution that had a $Pd(NH_3)_4Cl_2\;:TINO_3$ mole ratio of 50 : 1 and 200 : 1, respectively, with a total concentration of 0.05M for 4 days. After dehydration at $360^{\circ}C$ and 2 ${\times}$$10^{-6}$ Torr in flowing oxygen for 2 days, the crystals were evacuated at $21(1)^{\circ}C$ for 2 hours. They were refined to the final error indices $R_1$ = 0.045 and $R_2$ = 0.038 with 344 reflections for $Pd_{18}Tl_{56-}X$, and $R_1$ = 0.043 and $R_2$ = 0.045 with 280 reflections for $Pd_{21}Tl_{50-}X$; I > $3\sigma(I).$ In the structure of dehydrated $Pd_{18}Tl_{56-}X$, eighteen $Pd^{2+}$ ions and fourteen $TI^{+}$ ions are located at site I'. About twenty-seven $TI^{+}$ ions occupy site II recessed $1.74\AA$ into a supercage from the plane of three oxygens. The remaining fifteen $TI^{+}$ ions are distributed over two non-equivalent III' sites, with occupancies of 11 and 4, respectively. In the structure of $Pd_{21}Tl_{50-}X$, twenty $Pd^{2+}$ and ten $TI^{+}$ ions occupy site I', and one $Pd^{2+}$ ion is at site I. About twenty-three $TI^{+}$ ions occupy site II, and the remaining seventeen $TI^{+}$ ions are distributed over two different III' sites. $Pd^{2+}$ ions show a limit of exchange (ca. 39% and 46%), though their concentration of exchange was much higher than that of $TI^{+}$ ions. $Pd^{2+}$ ions tend to occupy site I', where they fit the double six-ring plane as nearly ideal trigonal planar. $TI^{+}$ ions fill the remaining I' sites, then occupy site II and two different III' sites. The two crystal structures show that approximately two and one-half I' sites per sodalite cage may be occupied by $Pd^{2+}$ ions. The remaining I' sites are occupied by $TI^{+}$ ions with Tl-O bond distance that is shorter than the sum of their ionic radii. The electrostatic repulsion between two large $TI^{+}$ ions and between $TI^{+}$ and $Pd^{2+}$ ions in the same $\beta-cage$ pushes each other to the charged six-ring planes. It causes the Tl-O bond to have some covalent character. However, $TI^{+}$ ions at site II form ionic bonds with three oxygens because the super-cage has the available space to obtain the reliable ionic bonds.

• Bulletin of the Korean Chemical Society
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• v.10 no.3
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• pp.243-247
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• 1989

Two crystal structures of dehydrated $Ag^+\;and\;Ca^{2+}$ exchanged zeolite A, $Ag_2Ca_$5-A, reacting with 0.01 Torr of Cs vapor at $200^{\circ}C$ for 2 hours and 0.1 Torr of Cs vapor at $250^{\circ}C$ for 48 hours, respectively, have been determined by single crystal X-ray diffraction techniques. Their structures were solved and refined in the cubic space group Pm3m at $21(1)^{\circ}C$. The stoichiometry of first crystal was $Ag_2Ca_5$-A (a = 12.294(1)${\AA}$), indicating that Cs vapor did not react with cations in zeolite A and that of second crystal was $Ag_2Cs_{10}$-A (a = 12.166(1)${\AA}$), indicating that all $Ca^{2+}$ ions were reduced by Cs vapor and replaced by $Cs^+$ ions. Full-matrix least-squares refinements of $Ag_2Ca_5-A\;and\;Ag_2Cs_{10}$-A has converged to the final error indices, $R_1\;=\;0.041\;and\;R_2$ = 0.048 with 227 reflections, and $R_1\;=\;0.117\;an\;n\;fdd\;R_2$ = 0.120 with 167 reflections, respectively, for which I > $3{\sigma}$(I). In the structure of $Ag_2Ca_5$-A, both $Ag^+$ ions and $Ca^{2+}$ ions lie on two crystal symmetrically independent threefold axis sites on the 6-rings; $2\;Ag^+$ ions are recessed 0.33 ${\;AA}$ from the (111) planes of three O(3) oxygens and 5 $Ca^{2+}$ ions lie on the nearly center of each 6-oxygen planes. In the structure of $Ag_2Cs_{10}-A,\;Cs^+$ ions lie on the 5 different crystallographic sites. 3 $Cs^+$ ions lie at the centers of the 8-rings at sites of D4h symmetry. 6 $Cs^+$ ions lie on the threefold axes of unit cell: $4\;Cs^+$ ions are found deep in the large cavity and 2 $Cs^+$ ions are found in the sodalite cavity. One $Cs^+$ ion is found in the large cavity near a 4-ring.

• Economic and Environmental Geology
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• v.43 no.3
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• pp.269-278
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• 2010

We investigated characteristics of the coloring material of Dancheong pigments and hope that this study contributes the revival of traditional Dancheong pigments color. For this purpose, we collected Dancheong fragment samples that fell off naturally from old wooden buildings in Gwangju and Jeonnam and analyzed the natural coloring material by XRD and EDS-SEM analysis method. In white pigments of Dancheong fragments, it is confirmed that gypsum$(CaSO_{4}{\cdot}2H_{2}O)$, quartz$(SiO_{2})$, white lead$(PbCO_{3})$ and calcite$(CaCO_{3})$ which have been used for white pigments since ancient times and $TiO_{2}$ which is common used in modern times. In red pigments of Dancheong fragments, it is confirmed that hematite$(Fe_{2}O_{3})$ and red lead$(Pb_{3}O_{4})$, which have been used for red pigments since ancient times and C.I. pigment orange $13(C_{32}H_{24}C_{12}N_{8}O_{2})$ but there is no cinnabar(HgS) which has been used since B.C. 3000 in China. In yellow pigments of Dancheong fragments, it is confirmed that crocoite$(PbCrO_{4})$ and massicot(PbO). In blue pigments of Dancheong fragments, it is confirmed that sodalite$(Na_{4}BeAlSi_{4}O_{12}Cl)$ and nosean $(Na_{8}Al_{6}Si_{6}O_{24}SO_{4})$ as coloring material of blue pigment and C.I. pigments blue $29(Na_{7}Al_{6}Si_{6}O_{24}S_{3})$ which is used in modern times. In green pigments of Dancheong fragments, it is confirmed that calumetite$(Cu(OHCI)_{2}{\cdot}2H_{2}O)$, escolaite(Cr2O3), dichromium trioxide$(Cr_{2}O_{3})$, emerald green$(C_{2}H_{3}As_{3}Cu_{2}O_{8})$, and C.I. pigments green$(C_{32}H_{16}-XCl_{x}Cu_{8})$ which is used in modern time. In black pigments of Dancheong fragments, Chiness ink(carbon black) is confirmed.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.10 no.1
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• pp.27-36
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• 2012

Metal chloride waste is generated as a main waste streams in a series of electrolytic processes of a pyrochemical process. Different from carbonate or nitrate salt, metal chloride is not decomposed into oxide and chlorine but it is just vaporized. Also, it has low compatibility with conventional silicate glasses. Our research group adapted the dechlorination approach for the immobilization of waste salt. In this study, the composition of SAP ($SiO_2-Al_2O_3-P_2O_5$) was adjusted to enhance the reactivity and to simplify the solidification process as a subsequent research. The addition of $Fe_2O_3$ into the basic SAP decreased the SAP/Salt ratio in weight from 3 for SAP 1071 to 2.25 for M-SAP( Fe=0.1). The experimental results indicated that the addition of $Fe_2O_3$ increased the reactivity of M-SAP with LiCl-KCl but the reactivity gradually decreased above Fe=0.1. Also, introducing $B_2O_3$ into M-SAP requires no glass binder for the consolidation of reaction products. U-SAP ($SiO_2-Al_2O_3-Fe_2O_3-P_2O_5-B_2O_3$) could effectively dechlorinate the LiCl-KCl waste and its reaction product could be consolidated as a monolithic form without a glass binder. The leaching test result indicated that U-SAP 1071 was more durable than other SAPs wasteform. By using U-SAP, 1 g of waste salt could generated 3~4 g of wasteform for final disposal. The final volume would be about 3~4 times lower than the glass-bonded sodalite. From these results, it could be concluded that the dechlorination approach using U-SAP would be one of prospective methods to manage the volatile waste salt.

• Journal of the Korean Chemical Society
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• v.38 no.3
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• pp.186-196
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• 1994

Three fully dehydrated partially $Ag^+$-exchanged zeolite A(Ag_4Na_8-A, Ag_6Na_6-A, and Ag_8Na_4-A) were treated at $250^{\circ}C$ with 0.1 torr Rb vapor at 4 h. Their structures were determined by singlecrystal X-ray diffraction methods in the cubic space group $Pm{\bar3}m$ (a = 12.264(4) $\AA$, a = 12.269(1) $\AA$, and a= 12.332(3) $\AA$, respectively) at $22(1)^{\circ}C$, and were refined to the final error indices, R(weighed), of 0.056 with 131 reflections, 0.068 with 108 reflections, and 0.070 with 94 reflections, respectively, for which I > $3\sigma(I).$ In these structures, Rb species are found at three different crystallographic sites; three $Rb^+$ ions per unit cell are located at 8-ring centers, ca. 6.0∼6.8 $Rb^+$ ions are found opposite 6-rings on threefold axes in the large cavity, and ca. 2.5 $Rb^+$ ions are found on three fold axes in the sodalite unit. Also, Ag species are found at two different crystallographic sites; ca. 0.6∼1.0 $Ag^+$ ion lies opposite 4-rings and about 1.8∼4.2 Ag atoms are located near the center of the large cavity. In these structures, the numbers of Ag atoms per unit cell are 1.8, 3.0, and 4.2, respectively, and these are likely to form hexasilver clusters at the centers of the large cavities. The $Rb^+$ ions, by blocking 8-rings, may have prevented silver atoms from migrating out of the structure. Each hexasilver cluster is stabilized by coordination to 6-ring, 8-ring $Rb^+$ ions, and also by coordination to a 4-ring $Ag^+$ ion.

• Journal of the Korean Chemical Society
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• v.39 no.1
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• pp.7-13
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• 1995

The crystal sructures of $X(Ca_{46}Al_{92}Si_{100}O_{384})$ and $Ca_{32}K_{28}-X(Ca_{32}K_{28}Al_{92}Si_{100}O_{384})$ dehydrated at $360^{\circ}C$ and $2{\times}10^{-6}$ Torr have been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd3 at $21(1)^{\circ}C.$ Their structures were refined to the final error indices, R_1=0.096,\;and\;R_2=0.068$ with 166 reflections, and R_1=0.078\;and\;R_2=0.056$ with 130 reflections, respectively, for which I > $3\sigma(I).$ In dehydrated $Ca_{48}-X,\;Ca^{2+}$ ions are located at two different sites opf high occupancies. Sixteen $Ca^{2+}$ ions are located at site I, the centers of the double six rings $(Ca(1)-O(3)=2.51(2)\AA$ and thirty $Ca^{2+}$ ions are located at site II, the six-membered ring faces of sodalite units in the supercage. Latter $Ca^{2+}$ ions are recessed $0.44\AA$ into the supercage from the three O(2) oxygen plane (Ca(2)-O(2)= $2.24(2)\AA$ and $O(2)-Ca(2)-O(2)=119(l)^{\circ}).$ In the structure of $Ca_{32}K_{28}-X$, all $Ca^{2+}$ ions and $K^+$ ions are located at the four different crystallographic sites: 16 $Ca^{2+}$ ions are located in the centers of the double six rings, another sixteen $Ca^{2+}$ ions and sixteen $K^+$ ions are located at the site II in the supercage. These $Ca^{2+}$ ions adn $K^+$ ions are recessed $0.56\AA$ and $1.54\AA$, respectively, into the supercage from their three O(2) oxygen planes $(Ca(2)-O(2)=2.29(2)\AA$, $O(2)-Ca(2)-O(2)=119(1)^{\circ}$, $K(1)-O(2)=2.59(2)\AA$, and $O(2)-K(1)-O(2)=99.2(8)^{\circ}).$ Twelve $K^+$ ions lie at the site III, twofold axis of edge of the four-membered ring ladders inside the supercage $(K(2)-O(4)=3.11(6)\AA$ and $O(1)-K(2)-O(1)=128(2)^{\circ}).$