• Title/Summary/Keyword: X-Ray Diffraction

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Phase Transitions of $LiMn_2O_4$ on $CO_2$ Decomposition (($CO_2$ 분해시 $LiMn_2O_4$의 상변화)

  • Kwoen, Tae-Hwan;Yang, Chun-Mo;Park, Young-Goo;Cho, Young-Koo;Rim, Byung-O
    • Journal of the Korean Applied Science and Technology
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    • v.20 no.1
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    • pp.33-43
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    • 2003
  • $LiMn_2O_4$ catalyst for $CO_2$ decomposition was synthesized by oxidation method for 30 min at 600$^{\circ}C$ in an electric furnace under air condition using manganese(II) nitrate $(Mn(NO_3)_2{\cdot}6H_2O)$, Lithium nitrate ($LiNO_3$) and Urea $(CO(NH_2)_2)$. The synthesized catalyst was reduced by $H_2$ at various temperatures for 3 hr. The reduction degree of the reduced catalysts were measured using the TGA. And then $CO_2$ decomposition rate was measured using the reduced catalysts. Phase-transitions of the catalysts were observed after $CO_2$ decomposition reaction at an optimal decomposition temperature. As the result of X-ray powder diffraction analysis, the synthesized catalyst was confirmed that the catalyst has the spinel structure, and also confirmed that when it was reduced by $H_2$, the phase of $LiMn_2O_4$ catalyst was transformed into $Li_2MnO_3$ and $Li_{1-2{\delta}}Mn_{2-{\delta}}O_{4-3{\delta}-{\delta}'}$ of tetragonal spinel phase. After $CO_2$ decomposition reaction, it was confirmed that the peak of $LiMn_2O_4$ of spinel phase. The optimal reduction temperature of the catalyst with $H_2$ was confirmed to be 450$^{\circ}C$(maximum weight-increasing ratio 9.47%) in the case of $LiMn_2O_4$ through the TGA analysis. Decomposition rate(%) using the $LiMn_2O_4$ catalyst showed the 67%. The crystal structure of the synthesized $LiMn_2O_4$ observed with a scanning electron microscope(SEM) shows cubic form. After reduction, $LiMn_2O_4$ catalyst became condensed each other to form interface. It was confirmed that after $CO_2$ decomposition, crystal structure of $LiMn_2O_4$ catalyst showed that its particle grew up more than that of reduction. Phase-transition by reduction and $CO_2$ decomposition ; $Li_2MnO_3$ and $Li_{1-2{\delta}}Mn_{2-{\delta}}O_{4-3{\delta}-{\delta}'}$ of tetragonal spinel phase at the first time of $CO_2$ decomposition appear like the same as the above contents. Phase-transition at $2{\sim}5$ time ; $Li_2MnO_3$ and $Li_{1-2{\delta}}Mn_{2-{\delta}}O_{4-3{\delta}-{\delta}'}$ of tetragonal spinel phase by reduction and $LiMn_2O_4$ of spinel phase after $CO_2$ decomposition appear like the same as the first time case. The result of the TGA analysis by catalyst reduction ; The first time, weight of reduced catalyst increased by 9.47%, for 2${\sim}$5 times, weight of reduced catalyst increased by average 2.3% But, in any time, there is little difference in the decomposition ratio of $CO_2$. That is to say, at the first time, it showed 67% in $CO_2$ decomposition rate and after 5 times reaction of $CO_2$ decomposition, it showed 67% nearly the same as the first time.

Effect of starch extraction solutions on extraction and physicochemical property of Chinese yam (Dioscorea batatas) starch (마(Dioscorea batatas) 전분의 추출 및 물리화학적 특성에 대한 전분추출용액의 영향)

  • Lee, Hyunjeong;Seo, Dong-Ho;Kim, Hyun-Seok
    • Korean Journal of Food Science and Technology
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    • v.50 no.2
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    • pp.191-197
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    • 2018
  • This study investigated the influence of starch extraction (ST-EX) solutions on the extraction yield and characteristics of Chinese yam (CY) starches from domestic Dioscorea batatas. Ascorbic acid (VitC), $Na_2S_2O_3$, $NaHCO_3$, and $Na_2CO_3$ were used as ST-EX solutions (0.4%, w/v). The extracted CY starches were examined for ST-EX yield, chemical composition, size distribution, X-ray diffraction, solubility, swelling power, gelatinization, and pasting viscosity. The highest ST-EX yield was obtained from $NaHCO_3$, followed by VitC. Lower protein content, relative crystallinity, and gelatinization enthalpy were found in CY starches from alkaline ST-EX solutions ($NaHCO_3$ and $Na_2CO_3$). Size distribution and gelatinization temperature did not generally differ for CY starches from the different ST-EX solutions. Pasting viscosities increased in the order from $Na_2CO_3$ > $Na_2S_2O_3$ > $NaHCO_3$ > VitC ST-EX solutions. Thus, VitC may be most appropriate to extract CY starch from Dioscorea rhizomes, considering its ST-EX yield, total starch content, and variation in pasting viscosity.

Identification of Active Agents for Reductive Dechlorination in Cement/Fe(II) Systems (시멘트와 Fe(II)을 이용한 환원성 탈염소화반응의 유효반응성분 규명)

  • Kim, Hong-Seok;Lee, Yu-Jung;Kim, Ha-Yan;Hwang, In-Seong
    • Journal of Soil and Groundwater Environment
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    • v.11 no.6
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    • pp.35-42
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    • 2006
  • Experimental study was conducted to identify the active agent for reductive dechlorination of TCE in cement/Fe(II) systems. Several potential materials-hematite (${\alpha}-Fe_2O_3$), lepidocrocite (${\gamma}$-FeOOH), akaganeite (${\beta}$-FeOOH), ettringite ($Ca_6Al_2(SO_4)_3(OH)_{12}$)-that are cement components or parts of cement hydrates were tested if they could act as reducing agents by conducting TCE degradation experiments. From the initial degradation experiments, hematite was selected as a potential active agent. The pseudo-first-order degradation rate constant ($k\;=\;0.637\;day^{-1}$) for the system containing 200 mM Fe(II), hematite and CaO was close to that ($k\;=\;0.645\;day^{-1}$) obtained from the system containing cement and 200 mM Fe(II). CaO, which was originally added to simulate pH of the cement/Fe(II) system, was found to play an important role in degradation reactions. The reactivity of the hematite/CaO/Fe(II) system initially increased with increase of CaO dosage. However, the tendency declined in the higher CaO dosage region, implying a saturation type of behavior. The SEM analysis revealed that the hexagonal plane-shaped crystals were formed during the reaction with increasing degradation efficiency, which was brought about by increasing the CaO dosage. It was suspected that the crystals could be portlandite or green rust ($SO_4$) or Friedel's salt. The XRD analysis of the same sample identified the peaks of hematite, magnetite/maghemite, green rust ($SO_4$). Either instrumental analysis predicted the presence of the green rust ($SO_4$). Therefore, the green rust ($SO_4$) would potentially be a reactive agent for reductive dechlorination in cement/Fe(II) systems.

Mobility of Transition Metals by Change of Redox Condition in Dump Tailings from the Dukum Mine, Korea (덕음광산 광미의 산화${\cdot}$환원 조건에 따른 전이원소의 이동성)

  • 문용희;문희수;박영석;문지원;송윤구;이종천
    • Economic and Environmental Geology
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    • v.36 no.4
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    • pp.285-293
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    • 2003
  • Tailings of Dukum mine in the vadose and saturated zone were investigated to reveal the mobility of metal elements and the condition of mineralogical solubility according to redox environments throughout the geochemical analysis, thermodynamic modelling, and mineralogical study for solid-samples and water samples(vadose zone; distilled water: tailings=5 : 1 reacted, saturated zone; pore-water extracted). In the vadose zone, sulfide oxidation has generated low-pH(2.72∼6.91) condition and high concentration levels of S $O_4$$^{2-}$(561∼1430mg/L) and other metals(Zn : 0.12∼l57 mg/L, Pb : 0.06∼0.83 mg/L, Cd : 0.06∼l.35 mg/L). Jarosite$(KFe_3(SO_4)_2(OH)_6)$ and gypsum$(CaSO_4{\cdot}2H_2O$) were identified on XRD patterns and thermodynamics modelling. In the saturated zone, concentration of metal ions decreased because pH values were neutral(7.25∼8.10). But Fe and Mn susceptible to redox potential increased by low-pe values(7.40∼3.40) as the depth increased. Rhodochrosite$(MnCO_3)$ identified by XRD and thermodynamics modelling suggested that $Mn^{4+}$ or $Mn^{3+}$ was reduced to $Mn^{2+}$. Along pH conditions, concentrations of dissolved metal ions has been most abundant in vadose zone throughout borehole samples. It was observed that pH had more effect on metal solubilities than redox potential. How-ever, the release of co-precipitated heavy metals following the dissolution of Fe-Mn oxyhydroxides could be the mechanism by which reduced condition affected heavy metal solubility considering the decrease of pe as depth increased in tile saturated zone.

CO2 Sequestration and Utilization of Calcium-extracted Slag Using Air-cooled Blast Furnace Slag and Convert Slag (괴재 및 전로슬래그를 이용한 CO2 저감 및 칼슘 추출 후 슬래그 활용)

  • Yoo, Yeongsuk;Choi, Hongbeom;Bang, Jun-Hwan;Chae, Soochun;Kim, Ji-Whan;Kim, Jin-Man;Lee, Seung-Woo
    • Applied Chemistry for Engineering
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    • v.28 no.1
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    • pp.101-111
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    • 2017
  • Mineral carbonation is a technology in which carbonates are synthesized from minerals including serpentine and olivine, and industrial wastes such as slag and cement, of which all contain calcium or magnesium when reacted with carbon dioxide. This study aims to develop the mineral carbonation technology for commercialization, which can reduce environmental burden and process cost through the reduction of carbon dioxide using steel slag and the slag reuse after calcium extraction. Calcium extraction was conducted using NH4Cl solution for air-cooled slag and convert slag, and ${\geq}98%$ purity calcium carbonate was synthesized by reaction with calcium-extracted solution and carbon dioxide. And we conducted experimentally to minimize the quantity of by-product, the slag residue after calcium extraction, which has occupied large amount of weight ratio (about 80-90%) at the point of mineral carbonation process using slag. The slag residue was used to replace silica sand in the manufacture of cement panel, and physical properties including compressive strength and flexible strength of panel using the slag residue and normal cement panel, respectively, were analyzed. The calcium concentration in extraction solution was analyzed by inductively coupled plasma optical emission spectrometer (ICP-OES). Field-emission scanning electron microscope (FE-SEM) was also used to identify the surface morphology of calcium carbonate, and XRD was used to analyze the crystallinity and the quantitative analysis of calcium carbonate. In addition, the cement panel evaluation was carried out according to KS L ISO 679, and the compressive strength and flexural strength of the panels were measured.

Effects of Magnesium on Sulfate Resistance of Alkali-activated Materials (알칼리 활성화 결합재의 황산염 침식에 미치는 마그네슘의 영향)

  • Park, Kwang-Min;Cho, Young-Keun;Ra, Jung-Min;Kim, Hyung-Suk
    • Journal of the Korea institute for structural maintenance and inspection
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    • v.21 no.1
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    • pp.109-116
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    • 2017
  • This paper describes the investigation into the durability alkali-activated materials(AAM) mortar and paste samples manufactured using fly-ash(FA) and ground granulated blast furnace slag(GGBFS) exposed to a sulfate environment with different GGBFS replace ratios(30, 50 and 100%), sodium silicate modules($Ms[SiO_2/Na_2O]$ 1.0, 1.5 and 2.0). The tests involved immersions into 10% sodium sulfate solution($Na_2SO_4$), 10% magnesium sulfate solution($MgSO_4$), 10% magnesium nitrate solution($Mg(NO_3)_2$) and 5% magnesium nitrate($Mg(NO_3)_2$+5% sodium sulfate solution+$Na_2SO_4$). The evolution of compressive strength, weight, length expansion and microstructural observation such as x-ray diffraction were studied. As a results, in case of immersed in $Na_2SO_4$, $Mg(NO_3)_2$ and $Mg(NO_3)_2+Na_2SO_4$ shows increase in long-term strength. However, for samples immersed in $MgSO_4$, the general observation was that the compressive strength decreased after immersion. The most drastic reduction of compressive strength and expansion of weight and length occurred when GGBFS or Ms ratios were higher. Also, the XRD analysis of samples immersed in magnesium sulfate indicated that expansion of AAM caused by gypsum($CaSO_4{\cdot}2H_2O$) and brucite(MgOH). The results showed that, an additional condition $Mg^{2+}$ in which ${SO_4}^{2-}$ is the presence of a certain concentration, sulfate erosion has to be accelerated.

Pressure-load Calibration of Multi-anvil Press and the Thermal Gradient within the Sample Chamber (멀티 앤빌 프레스의 압력-부하 보정 작업과 시료 내의 온도구배 연구)

  • Kim, Eun Jeong;Lee, Sung Keun
    • Journal of the Mineralogical Society of Korea
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    • v.31 no.3
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    • pp.161-172
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    • 2018
  • Multi-anvil press (MAP) is one of the high pressure apparatuses and often generates the pressure-conditions ranging from 5 to 25 GPa and temperature-conditions up to $2,300^{\circ}C$. The MAP is, therefore, suitable to explore the pressure-induced structural changes in diverse earth materials from Earth's mantle and the bottom of the mantle transition zone (~660 km). In this study, we present the experimental results for pressure-load calibration of the 1,100-ton multi-anvil press equipped in the authors' laboratory. The pressure-load calibration experiments were performed for the 14/8 step, 14/8 G2, 14/8 HT, and 18/12 assembly sets. The high pressure experiments using ${\alpha}$-quartz, wollastonitestructure of $CaGeO_3$, and forsterite as starting materials were analyzed by powder X-ray diffraction spectroscopy. The phase transition of each mineral indicates the specific pressure that is loaded to a sample at $1,200^{\circ}C$: a transition of ${\alpha}$-quartz to coesite at 3.1 GPa, that of garnet-structure of $CaGeO_3$ to perovskite-structure at 5.9 GPa, that of coesite to stishovite at 9.2 GPa, and that of forsterite to wadsleyite at 13.6 GPa. While the estimated pressure-load calibration curve is generally consistent with those obtained in other laboratories, the deviation up to 50 tons is observed at high pressure above 10 GPa. This is partly because of the loss of oil pressure at high pressure resulting from the differences in a sample chamber, and the frictional force between pressure medium and second anvil. We also report the ${\sim}200^{\circ}C/mm$ of thermal gradient in the vertical direction of the sample chamber of 14/8 HT assembly. The pressure-load calibration curve and the observed thermal gradient within the sample chamber can be applied to explain the structural changes and the relevant macroscopic properties of diverse crystalline and amorphous earth materials in the mantle.

The Effect of Au Addition on the Hardening Mechanism in Ag-30wt%Pd-10wt%Cu Alloy (Ag-30wt% Pd-10wt% Cu 3원합금(元合金) 및 Au 첨가합금(添加合金)의 시효경화특성(時效硬化特性))

  • Lee, K.D.;Nam, S.Y.
    • Journal of Technologic Dentistry
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    • v.21 no.1
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    • pp.27-41
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    • 1999
  • The Ag-Pd-Cu alloys containing a small amount of Au is commonly used for dental purposes, because this alloy cheaper than Au-base alloys for clinical use. However, the most important characteristic of this alloy is age-hardenability, which is not exhibited by other Ag-base dental alloys. The specimens used were Ag-30Pd-10Cu ternary alloy and Au addition alloy. These alloys were melted and casted by induction electric furnace and centrifugal casting machine in Ar atmosphere. These specimens were solution treated for 2hr at $800^{\circ}C$ and were then quenched into iced water, and aged at 350-$550^{\circ}C$ Age-hardening characteristic of the small Au-containing Ag-Pd-Cu dental alloys were investigated by means of hardness testing, X-ray diffraction and electron microscope observations, electrical resistance, differential scanning calorimetric, energy dispersed spectra and electron probe microanalysis. Principal results are as follows ; Maximum hardening occured in two co-phases of ${\alpha}_2$ + PdCu In stage II, decomposition of the $\alpha$ solid solution to a PdCu ordered phase($L1_o$ type) and an Ag-rich ${\alpha}_2$ phase occurred and a discontinuous precipitation occurred at the grain boundary. From the electron microscope study, it was concluded that the cause of age-hardening in this alloy is the precipitation of the PdCu redered phase, which has AuCu I type face-centered tetragonal structure. Precipitation procedure was ${\alpha}{\to}{\alpha}_1+PdCu{\to}{\alpha}_2+PdCu$ at Pd/Cu = 3 Pd element of Ag-Pd-Cu alloy is more effective dental alloy on anti-corrosion and is suitable to isothermal ageing at $450^{\circ}C$.

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The Effect of Au Addition on the Hardening Mechanism in Ag-20wt% Pd-20wt% Cu (Ag-20wt% Pd-20wt% Cu 3원합금(元合金) 및 Au첨가합금(添加合金)의 시효경화특성(時效硬化特性))

  • Park, M.H.;Bae, B.J.;Lee, H.S.;Lee, K.D.
    • Journal of Technologic Dentistry
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    • v.19 no.1
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    • pp.21-35
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    • 1997
  • The Ag-Pd-Cu alloys containing a small amount of Au is commonly used for dental purposes, because this alloy is cheaper than Au-base alloys for clinical use. However, the most important characteristic of this alloy is age-hardenability, which is not exhibited by other Ag-base dental alloys. The specimens used were Ag-20Pd-20Cu ternary alloy and Au addition alloy. These alloys were melted and casted by induction electic furace and centrifugal casting machine in Ar atmoshpere. These specimens were solution treated for 2hr at $800^{\circ}C$ and were then quenched into iced water, and aged at $350{\sim}550^{\circ}C$ Age-hardening characteristics of the small Au-containing Ag-pPd-Cu dental alloys were investigated by means of hardness testing, X-ray diffraction and electron microscope observations, electrical resistance, differential scanning calorimetric, emergy dispersed spectra and electron probe microanalysis. Principal results are as follows : Hardening occured in two stages, I. e., stage I in low temperature and stage II in high temperature regions, during continuous aging. The case of hardening in stage I was due to the formation of the Llo type face centered tetragonal PdCu-ordered phase in the grain interior and hardening in stage I was affedted by the Cu concentration. In stage II, decomposition of the $\alpha$ solid solution to a PdCu ordered phase(L1o type) and an Agrich ${\alpha}2$ phase occurred and a discontiunous precipitation occurred at the grain boundary. Form the electron microscope study, it was concluded that the cause of age-hardening in this alloy is the precipitation of the PdCu ordered phase, which has AuCu I type face-centered tetragonal structure. Precipitation procedure was ${\alpha}\to{\alpha}+{\alpha}2+PdCu\to{\alpha}1+{\alpha}2+PdCu$ at Pd/Cu = 1 Ag-Pd-Cu alloy is more effective dental alloy as ageing treatment and is suitable to isothermal ageing at $450^{\circ}C$.

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Synthesis of Fully Dehydrated Partially Cs+-exchanged Zeolite Y (FAU, Si/Al = 1.56), |Cs45Na30|[Si117Al75O384]-FAU and Its Single-crystal Structure

  • Seo, Sung-Man;Kim, Ghyung-Hwa;Lee, Seok-Hee;Bae, Jun-Seok;Lim, Woo-Taik
    • Bulletin of the Korean Chemical Society
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    • v.30 no.6
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    • pp.1285-1292
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    • 2009
  • Large single crystals of zeolite, |$Na_{75}$|[$Si_{117}Al_{75}O_{384}$]-FAU (Na-Y, Si/Al = 1.56), were synthesized from gels with composition of 3.58Si$O_2$ : 2.08NaAl$O_2$ : 7.59NaOH : 455$H_2$O : 5.06TEA : 2.23TCl. One of these, a colorless single-crystal was ion exchanged by allowing aqueous 0.02 M CsOH to flow past the crystal at 293 K for 3 days, followed by dehydration at 673 K and 1 ${\times}\;10^{-6}$ Torr for 2 days. The crystal structure of fully dehydrated partially $Cs^+$-exchanged zeolite Y, |$Cs_{45}Na_{30}$|[$Si_{117}Al_{75}O_{384}$]-FAU per unit cell (a = 24.9080(10) $\AA$) was determined by single-crystal X-ray diffraction technique in the cubic space group Fd $\overline{3}$ m at 294(1) K. The structure was refined using all intensities to the final error indices (using only the 877 reflections with $F_o\;>\;4{\sigma}(F_o))\;R_1$ = 0.0966 (Based on F) and $R_2\;=\;0.2641\;(Based\;on\;F^2$). About forty-five $Cs^+$ ions per unit cell are found at six different crystallographic sites. The 2 $Cs^+$ ions occupied at site I, at the centers of double 6-ring (D6Rs, Cs-O = 2.774(10) $\AA$ and O-Cs-O = 88.9(3) and 91.1(3)$^o$). Two $Cs^+$ ions are found at site I’ in the sodalite cavity; the $Cs^+$ ions were recessed 2.05 $\AA$ into the sodalite cavity from their 3-oxygen plane (Cs-O = 3.05(3) $\AA$ and O-Cs-O = 77.4(13)$^o$). Site-II’ positions (opposite single 6-rings in the sodalite cage) are occupied by 7 $Cs^+$ ions, each of which extends 2.04 $\AA$ into the sodalite cage from its 3-oxygen plane (Cs-O = 3.067(11) $\AA$ and O-Cs-O = 80.1(3)$^o$). The 26 $Cs^+$ ions are nearly three-quarters filled at site II in the supercage, being recessed 2.34 $\AA$ into the supercage (Cs-O = 3.273(8) $\AA$ and O-Cs-O = 74.3(3)$^o$). The 4 $Cs^+$ ions are found at site III deep in the supercage (Cs-O = 3.321(19) and 3.08(3) $\AA$), and 4 $Cs^+$ ions at another site III’ (Cs-O = 2.87(4) and 3.38(4) $\AA$). About 30 $Na^+$ ions per unit cell are found at one crystallographic site; The $Na^+$ ions are located at site I’ in the sodalite cavity opposite double 6-rings (Na-O = 2.578(11) $\AA$ and O-Na-O = 97.8(4)$^o$).