• Journal of the Korean Chemical Society
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• v.43 no.4
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• pp.384-385
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• 1999

Two anhydrous crystal structures of fully dehydrated, $Ca^{2+}$- and $Tl^+$-exchanged zeolite X, TEX>$Ca_{18}Tl_{56}Si_{100}Al_{92}O_{384}($Ca_{18}Tl_{56}$-X;\alpha=24.883(4)\AA)$ and TEX>$Ca_{32}Tl_{28}Si_{100}Al_{92}O_{384}($Ca_{32}Tl_{28}$-X;\alpha=24.973(4)\AA)$ per unit cell, have been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd3 at $21(1)^{\circ}C.$ $Ca_{18}Tl_{56}-X$ was prepared by ion exchange in a flowing stream of 0.045 M aqueous $Ca(NO_3)_2$ and 0.005 M $TlNO_3$. $Ca_{32}Tl_{28}-X$ was prepared similarly using a mixed solution of 0.0495 M $Ca(NO_3)_2$ and 0.0005M $TlNO_3$. Each crystal was then dehydrated at 360 $^{\circ}C$ and $2{\times}10^{-6}$ Torr for 2 days. Their structures were refined to the final error indices, $R_1=0.039\;and\;R_2=0.036$ with 382 reflections for $Ca_{18}Tl_{56}-X$ , and $R_1=0.046\;and\;R_2=0.045$ with 472 reflections for $Ca_{32}Tl_{28}$-X for which $/>3\sigma(I).$ In the structures of dehydrated $Ca_{18}Tl_{56^-}X\;and\;Ca_{32}Tl_{28}$-X, $Ca^{2+}\;and\;Tl^+$ ions are located at six crystallographic sites. Sixteen $Ca^{2+}$ ions fill the octahedral sites I at the centers of double six rings ($Ca_{18}Tl_{56}$-X:Ca-O=2.42(1) and O-Ca-O=93.06(4)$^{\circ}$; $Ca_{32}Tl_{28}$-X Ca-O=2.40(1) $\AA$ and O-Ca-O=93.08(3)$^{\circ}$). In the structure of $Ca_{18}Tl_{56}$-X, another two $Ca^{2+}$ ions occupy site II (Ca-O=2.35(2) $\AA$ and O-Ca-O=111.69(2)$^{\circ}$) and twenty six $Tl^+$ ions occupy site II opposite single six-rings in the supercage; each is 1.493 $\AA$ from the plane of three oxygens $(Tl-O=2.70(8)\AA$ and O-Tl-O=92.33(4)$^{\circ}$). About four $Tl^+$ ions are found at site II',1.695 $\AA$ into sodalite cavity from their three oxygen plane (Tl-O=2.81 (1) and O-Tl-O=87.48(3)). The remaining twenty six $Tl^+$ ions are distributed over site III'(Tl-O=2.82 (1) $\AA$ and Tl-O=2.88(3)$^{\circ}$). In the structure of $Ca_{32}Tl_{28}$-X, sixteen $Ca^{2+}$ ions and fifteen $Tl^+$ ions occupy site III' (Ca-O=2.26(1) $\AA$ and O-Ca-O=119.14(4)$^{\circ}$; Tl-O=2.70(1) $\AA$ and O-Tl-O=92.38$^{\circ}$) and one $Tl^+$ ion occupies site II'. The remaining twelve $Tl^+$ ions are distributed over site III'. It appears that $Ca^{2+}$ ions prefer sites I and II in that order and $Tl^+$ ions occupy the remaining sites.

• Journal of Korea Foundry Society
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• v.34 no.6
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• pp.194-199
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• 2014

The effect of $Al_2Ca$ on the oxidation resistance and tensile property of Al-5Mg alloys was investigated. According to the TGA (Thermogravimetric analysis) result at $550^{\circ}C$ after 24hrs, the Al-5Mg alloy showed parabolic behavior with weight gain. On the other hand, there was almost no difference in the weight changes of the $Al_2Ca$ added Al-5Mg alloys during the oxidation. It was thought that the improvement of oxidation resistance in $Al_2Ca$ added Al-5Mg alloys might be due to the formation of a protective oxide layer with CaO and MgO on the surface. The microstructures of the alloys showed grain refinement with an increasing $Al_2Ca$ content. From the tensile test, the yield strength of the alloys were improved with an increasing $Al_2Ca$ content. The 0.07 mass%$Al_2Ca$ added Al-5Mg alloy showed similar elongation and increased strength, simultaneously. It was considered that the addition of $Al_2Ca$, which was superior in the oxidation resistance of Al, reduced the formation of Mg oxides and inclusions during the alloying. This, partly led to the improvement of tensile properties.

• 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.

• Journal of the Korea institute for structural maintenance and inspection
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• v.24 no.4
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• pp.1-9
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• 2020

This study conducted to understand effects of CA (CaAl₂O₄) and CA₂ (CaAl₄O₇) ratio on chloride binding ability and compressive strength and pore structure of cement mortar incorporating mixture of CA and CA₂. The Portland cement based specimens were mixed with the clinkers CA and CA₂, and these calcium aluminate clinker mixture were replaced 0, 5, 10% by weight of cement. After all the test specimens were cured for 28 days under water curing, they were immersed in the distilled water and NaCl solution. As a result, 28 days compressive strength of all specimens was similar, and As the replacement ratio of calcium aluminate clinker in the specimen increased, Friedel's salt production tended to increase. However, it was dependent on the amount of Al₂O₃ in the level of 5% replacement and CA ratio in the level of 10% replacement. Through equilibrium isotherm result, it was also indicated that as replacement ratio of calcium aluminate clinker in cement matrix increased, chloride binding capacity was improved, and chloride penetration was suppressed. In this study, the specimen replaced with 10% of the calcium aluminate clinker mixture (CA 39%, CA₂ 60%) was remarkable to control chloride attack. We figured out necessity to understand optimal CA/CA₂ ratio to effectively apply CA₂ as a sustainable building material by improving the chloride binding ability in Portland cement based system.

• Journal of the Korean Chemical Society
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• v.40 no.6
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• pp.427-435
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• 1996

The structures of fully dehydrated $Ca^{2+}$- and $Cs^+$-exchanged zeolite X, $Ca_{35}Cs_{22}Si_{100}Al_{92}O_{384}$($Ca_{35}Cs_{22}$-X; a=25.071(1) $\AA)$ and $Ca_{29}Cs_{34}Si_{100}Al_{92}O_{384}$($Ca_{29}Cs_{34}$-X; a=24.949(1) $\AA)$, have been determined by single-crystal X-ray diffraction methods in the cubic space group Fd3 at $21(1)^{\circ}C.$ Their structures were refined to the final error indices $R_1$=0.051 and $R_2$=0.044 with 322 reflections for $Ca_{35}Cs_{22}$-X, and $R_1$=0.058 and $R_2$=0.055 with 260 reflections for $Ca_{29}Cs_{34}$-X; $I>3\sigma(I).$ In both structures, $Ca^{2+}$ and $Cs^+$ ions are located at five different crystallographic sites. In dehydrated $Ca_{35}Cs_{22}$-X, sixteen $Ca^{2+}$ ions fill site I, at the centers of the double 6-rings(Ca-O=2.41(1) $\AA$ and $O-Ca-O=93.4(3)^{\circ}).$ Another nineteen $Ca^{2+}$ ions occupy site II (Ca-O=2.29(1) $\AA$, O-Ca-O=118.7(4)') and ten $Cs^+$ ions occupy site II opposite single six-rings in the supercage; each is $1.95\AA$ from the plane of three oxygens (Cs-O=2.99(1) and $O-Cs-O=82.3(3)^{\circ}).$ About three $Cs^+$ ions are found at site II', 2.27 $\AA$ into sodalite cavity from their three-oxygen plane (Cs-O=3.23(1) $\AA$ and $O-Cs-O=75.2(3)^{\circ}).$ The remaining nine $Cs^+$ ions are statistically distributed over site Ⅲ, a 48-fold equipoint in the supercages on twofold axes (Cs-O=3.25(1) $\AA$ and Cs-O=3.49(1) $\AA).$ In dehydrated $Ca_{29}Cs_{34}$-X, sixteen $Ca^{2+}$ ions fill site I(Ca-O=2.38(1) $\AA$ and $O-Ca-O=94.1(4)^{\circ})$ and thirteen $Ca^{2+}$ ions occupy site II (Ca-O=2.32(2) $\AA$, $O-Ca-O=119.7(6)^{\circ}).$ Another twelve $Cs^+$ ions occupy site II; each is $1.93\AA$ from the plane of three oxygens (Cs-O=3.02(1) and $O-Cs-O=83.1(4)^{\circ})$ and seven $Cs^+$ ions occupy site II'; each is $2.22\AA$ into sodalite cavity from their three-oxygen plane (Cs-O=3.21(2) and $O-Cs-O=77.2(4)^{\circ}).$ The remaining sixteen $Cs^+$ ions are found at III site in the supercage (Cs-O=3.11(1) $\AA$ and Cs-O=3.46(2) $\AA).$ It appears that $Ca^{2+}$ ions prefer sites I and II in that order, and that $Cs^+$ ions occupy the remaining sites, except that they are too large to be stable at site I.

• Journal of the Korean Ceramic Society
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• v.47 no.4
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• pp.325-328
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• 2010

Varying quantities of a high-thermal-expansion glass, 50CaO-20ZnO-$20B_2O_3-10SiO_2$ (CZBS), were added to alumina and sintered at $875^{\circ}C$ for 2 h for low temperature co-firing ceramic (LTCC) applications. As the amount of glass addition increased from 40 wt% to 70 wt%, the apparent density of the sintered product increased from 88.8% to 91.5%, which was also qualitatively confirmed by microstructural observation. When the glass addition was very high, e.g., 70 wt%, an apparent formation of secondary phases such as $CaZn_2AlZnSiAlO_7$, $Ca_2Al(AlSi)O_7$, $Ca_2Al_2SiO_7$, $Ca_2ZnSi_2O_7$ and ZnO, was observed. Both the dielectric constant and the coefficient of thermal expansion increased with the glass addition, which was qualitatively consistent with the analytical models, while the experimental values were lower than the predicted ones due to the presence of pores and secondary phases.

• Journal of the Korean Ceramic Society
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• v.31 no.4
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• pp.389-398
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• 1994

Calcium aluminate glasses transmit light at relatively long wavelengths up to 6 ㎛ and exhibit also low Rayleigh scattering values. However they have a tendency to get devitrified easily, which limits their use as routine optical materials. Here, the ternary system CaO-Al2O3-SiO2 glasses with low-silica (<30 mol%) were prepared to prevent the devitrification of CaO-Al2O3 glasses and the properties were investigated as functions of composition. The addition of SiO2 to calcium aluminate glasses promoted their stability, which was due to the decrease of non-bridging oxygens and the reconnection of network. As SiO2 was added, density, refractive index, molar volume of oxygens and thermal expansion coefficient decreased continuously. But the glass transition temperatures with increasing SiO2 contents were raised and then lowered. It was postulated that the anomaly was related to the changes of the middle range order as well as the short range order. As the amount of SiO2 in the glass was increased, the IR cut-off values moved to shorter wavelength owing to 'Si-O' antisymetric stretching vibration. The IR cut-off wavelength of the glasses with 5 and 30 mol% SiO2 was 4.90, 4.55 ㎛, respectively.

• Korean Journal of Crystallography
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• v.11 no.4
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• pp.195-199
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• 2000

Ceramics based on CaTiO₃-NdAlO₃ solid solutions were synthesized in order to study their dielectric microwave properties. Microstructural analysis was performed with scanning electron microscopy (SEM) and transmission electron microscopy (TEM) using different analytical methods such as energy-dispersive X-ray spectroscopy (EDXS). It was observed that the heating conditions during sintering and cooling strongly affect the microstructural development of CaTiO₃-NdAlO₃-based ceramics. Various types and concentrations of structural defects were identified, for example, dislocations, twins and/or antiphase boundaries. all such defects resulted in a degradation of the dielectric microwave properties, in particular the quality factor Q. Dielectric properties of CaTiO₃-NdAlO₃-based ceramics can be improved by an appropriate thermal treatment of ceramics which results in a decrease in the concentrations of the identified microstructural defects.

• Journal of the Korean Ceramic Society
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• v.17 no.2
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• pp.96-100
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• 1980

The castable refractory, CaO.$2Al_2O_3$ is a useful alumina cement for iron, steel and cement for iron, steel and cement industries, however it is difficult to produce CaO.$2Al_2O_3$because of its high melting point(180$0^{\circ}C$) and narrow firing range. In this study, the coprecipitation method was used to produce CaO.$2Al_2O_3$ for lower temperature firing . This method involved the titration of mixed solution of calicum and aluminate which extracted from domestic kaolin with $NH4_OH$ solution under blowing $CO_2$ gas into the solution. The coprecipitate and its clacined products were analyzed by X-ray diffraction and DTA. The calcined products fired between 400 and 90$0^{\circ}C$ were amorphous, but at 100$0^{\circ}C$ the coprecipitate was converted into one compound, CaO$2Al_2O_3$. From those experimental results, it was found that we could synthesizze CaO.$2Al_2O_3$ at about 100$0^{\circ}C$ which is lower than conventional firing temperature by around 80$0^{\circ}C$. The refractoriness of this alumina cement was SK 34 and the compressive strength ( 1 day) was about 250kg/$\textrm{cm}^2$.

• Proceedings of the Ginseng society Conference
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• 2008.05a
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• pp.74-75
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• 2008

This study is for geochemical relationships between ginsengs and soils from three representative soil types from Keumsan, shale, phyllite and granite. For these study, ginsengs, with the field and weathered soils were collected from the three regions, and are analysed for the major and trace elements. In the weathered soils(avg.), the granite and phyllite areas are high in the most of elements while the shale area is low. In the correlation coefficients, negative correlations are shown in the $Al_2O_3$-MgO pair while positive correlations, are shown in the Ba-Sr, Zr, Sr-Zr and Cs-Ge pairs. In the field soils(avg.), the granite and phyllite areas are, generally, high in the most of elements while the shale area is low. In the shale area, the major elements are high in the 4 year soils, but low in the 2 year soils. The LFS(Ba, Sr, Cs) and transitional elements are high in the 2 year soils, but low in the 4 year soils. The HFS(Y, Zr) is high in the 4 year soils. In the correlation coefficients, most of the elements from the 4 year show positive relationships. Positive correlations are shown in the $Al_2O_3$-CaO, MnO-MgO, V-Tl, and Ba-Sr pairs in all localities. In the ginseng contents, clear chemical differences with the ages are shown in the shale and granite ares, but not clear in the phyllite area. In the shale area Mn, Mg, Ba, Sr, and Y contents, increase with ages but decrease in Al, Cs, Be and Cd. In the correlation coefficients, degrees of the correlations for the major elements become low with the ages. Positive correlations are shown in the Al-Mn, Ti, Mn-Ti, Mg-Ca, Ca-K, Ba-Cs, Y and Cs-Y pairs. Comparisons with ginsengs of the same ages from the different areas suggest that generally, the 2 years in the shale and 3 and 4 years in the granite area are distinctive. Relative ratios(granite/ shale area) of the ginsengs are below 1 in the major elements except Mn in the 2 year ginsengs and above 1 in the other elements except Mg and Na in the 4 year. Relative ratios(granite/ phyllite area) of the ginsengs are high in the 3 year from the phyllite area. In the relative ratios(weathered/field soils) of the soils, numbers of the elements showing the ratios of above 1 increase from the shale, to phyllite and granite in the case of the major elements, but decrease in the case of the trace elements. These results suggest that major elements are high in the granite while trace elements are high in the shale area. In the relative ratios between field soils and ginsengs(field soils/ginseng), the shale area, regardless of the ages, show differences of several hundred times in the $Al_2O_3$, $TiO_2$, Y and Tl, of several ten times in the MnO, MgO and Ba and of several times in the CaO contents. These results suggest that ginseng contents are significantly different from the field soils in the $Al_2O_3$, $TiO_2$, Y and Tl, but similar in the CaO contents. The phyllite area, regardless of the ages, show differences of several hundred times in the $Al_2O_3$, $TiO_2$, Y, Tl and Be, of several ten times in the MnO, MgO, $Na_2O$ and Ba, and of several times to ten times in the CaO, $K_2O$ and Sr contents. These results suggest that ginseng contents are significantly different from those of the field soils in the $Al_2O_3$, $TiO_2$, Y, Tl and Be, but similar in the CaO, $K_2O$ and Sr contents. The granite area, regardless of the ages, show differences of several hundred times in the $Al_2O_3$, $TiO_2$, Tl and Be, of several ten times in the Ba, and of several times to ten times in the MgO and CaO contents. Of the other elements, differences of several times to ten times are shown in the MnO, $K_2O$ and Sr contents. These results suggest that ginseng contents are significantly different from those of the field soils in the $Al_2O_3$, $TiO_2$, Tl and Be, but similar in the $K_2O$ and Sr contents. Comparisons among the different ages from the same area suggest that, in the case of shale area, differences of several hundred times in the $Al_2O_3$ and $TiO_2$, of the several ten times in the MnO, MgO and Ba and several times in the CaO and $K_2O$ are shown in the 2 year ginsengs. Differences of several hundred times in the $Al_2O_3$, $TiO_2$, Cs, Y, Tl and Be, of above several ten times in the MnO, MgO, $K_2O$ and Ba, and of several times in the CaO and Sr are shown in the 3 year ginsengs. Differences of several hundred to thousand times in the $Al_2O_3$, of above several hundred times in the $TiO_2$, Cs and Y, and of several ten times in the MnO, MgO, $K_2O$ and Ba, and of several times in the $Na_2O$ are shown in the 4 year ginsengs. These relationships suggest that, regardless of the localities in the shale area, $Al_2O_3$ contents of the soils show big differences from those of the ginsengs. Regardless of the ages of ginsengs, comparisons with the overall average contents of each area show differences of several hundred times in the $Al_2O_3$, $TiO_2$, Cs and Tl and of several ten times in the MnO. These overall relationships suggest that the $Al_2O_3$, $TiO_2$, Cs and Tl contents of the soils are higher than those of the ginsengs, show big differences between two and low different contents are found in the MnO. In detail, differences of several hundred times in the Y, and ten times in the MgO and Sr, and of several times in the CaO, $Na_2O$, $K_2O$ in the case of shale area, are shown. These results suggest that the soils are higher than the ginsengs in the Y and significantly differences in Y, and moderately differences in the MgO and Sr, and low differences in the CaO, $Na_2O$ and $K_2O$ are shown between soils and ginsengs.