• Journal of the Korean Chemical Society
• /
• v.40 no.6
• /
• pp.427-435
• /
• 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 Microelectronics and Packaging Society
• /
• v.3 no.2
• /
• pp.39-50
• /
• 1996

본 연구에선 주어진 조성의 알루미나 green sheet에 대하여 텅스텐의 입경 및 산화 물의 조성을 변화시키므로써 수축률을 제어하여 camber를최소화하여 결합강도를 최대로 하 는 텅스텐 페스트조성을 찾아내는 것을 목적으로 하였다. 본 실험에서 사용한 텅스텐 분말 의 입경은 0.35$\mu$m, 0.6$\mu$m, 0.72$\mu$m, $1.5\mu$m, 1.9$\mu$m, 3.2$\mu$m이며 frit는 Al2O3, MgO, SiO2 와 Al2O3, CaO, SiO2를 사용하여 각각의 조성에 따라 함량을 변화시키며 실험하였다. 소성 은 154$0^{\circ}C$로 습윤 수소분위기에서 시행하였으며 사용된 알루미나 green sheet의 알루미나 중심 입경은 2.8$\mu$m이었다. 분석은 주사전자 현미경으로 미세구조를 관찰하였고 EPMA Line Profile로 원소 분석을 하였으며 잔류응력을 측정하기 위하여 XRD분석을 하였다. Frit 을 함유하지 않은 경우 텅스텐 분말의 입경이 1.9$\mu$mdlfEo 최대 접합 강도를 나타내었다. Frit을 함유한 경우 Mgo계 frit조성에서는 MgO/Al2O3/SiO3=1/1/1일 때 CaO계 frot 조성에 서는 CaO/Al2O3/SiO2=1/2/1일 때 최대 접합 강도를 나타내었다. Frit 함량을 변화시킨 경우 MgO계는 10wt%함유하였을 때 CaO 계는 5wt%함유하였을 때 최대 접합강도를 나타내었 다. Frit 함량을 변화시킨 경우 MgO계는 10wt%함유하였을 때, CaOr계는 5wt%함유하였을 때 최대 접합강도를 나타내었다.

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

• Transactions of Materials Processing
• /
• v.15 no.8 s.89
• /
• pp.615-620
• /
• 2006

The reduction behavior of $TiO_{2}$ in Al and Al/CaSi containing self-reducing $TiO_{2}$ briquettes(SRTB) was investigated. The maximum yield of Ti was expected with the slag composition of 45-55%CaO in the $CaO-Al_{2}O_{3}$ system. When $CaCO_{3}$ was used as a flux, the oxidation loss of reducing agent by $CO_{2}$ should be compensated, and therefore it leads to excessive requirement of the reducing agent. By using Al and CaSi mixture as a reducing agent of $TiO_{2}$, the reaction products both oxide and metal could be liquefied, and separated effectively with each other. As a result, the yield of Ti increases remarkably. The optimum mixing ratio of CaSi to Al is 78%CaSi-22%Al.

• Journal of the Korean Ceramic Society
• /
• v.47 no.5
• /
• pp.467-473
• /
• 2010

The objective of this study is to prepare lead-free thick film resistor (TFR) paste compatible with AlN substrate for hybrid microelectronics. For this purpose, CaO-ZnO-$B_2O_3-Al_2O_3-SiO_2$ glass system was chosen as a sintering aid of $RuO_2$. The effects of the weight ratio of CaO to ZnO in glass composition, the glass content and the sintering temperature on the electrical properties of TFR were investigated. $RuO_2$ as a conductive and glass powder were dispersed in an organic binder to obtain printable paste and then thick-film was formed by screen printing, followed by sintering at the range between $750^{\circ}C$ and $900^{\circ}C$ for 10 min with a heating rate of $50^{\circ}C$/min in an ambient atmosphere. The addition of ZnO to glass composition and sintering at higher temperature resulted in increasing sheet resistance and decreasing temperature coefficient of resistance. Using $RuO_2$-based resistor paste containing 40 wt%glass of CaO-20.5%ZnO-25%$B_2O_3$-7%$Al_2O_3$-15%$SiO_2$ composition, it is possible to produce thick film resistor on AlN substrate with sheet resistance of $10.6\Omega/\spuare$ and the temperature coefficient of resistance of 702ppm/$^{\circ}C$ after sintering at $850^{\circ}C$.

• Journal of the Korean Ceramic Society
• /
• v.23 no.5
• /
• pp.25-34
• /
• 1986

This study was to refined the crystal structure of solid solution to determine the position and amount of Al in diopside and to relate crystal structure changes and properties of solid solution. Single crystals of the solid solution in the system CaO.MgO.$2 SiO_2-Al_2O_3$ were made from the melt with slow cooling and used to refine the structure. The following were obtained. 1. Tetrahedra rotated around axis parallel to the direction which the angle 03-03-03 became small. 2. Tetrahedron became large and regular. Average T-O bond distance increased 0.53 percent. 3. M1 octahedron became small and average M1-O bond distance decreased 1.1 percent. 4, M2 polyhedron became small and average M2-O bond distance decreased 0.37 percent Polythedron was affected not so much compared with any cation site. 5. Distance between metal ions distances between T and oxygens which were coordinated with M2 and meighboring tetrahedron distances between M2 and oxygens which coordinated with M1 and M2 were not changed almost. 6. $Al^{3+}$ substituted 4Mg^{2+}$ and $Si^{4+}$

• Bulletin of the Korean Chemical Society
• /
• v.17 no.7
• /
• pp.631-637
• /
• 1996

The structures of fully dehydrated Ca2+- and Rb+-exchanged zeolite X, Ca31Rb30Si100Al92O384(Ca31Rb30-X; a=25.009(1) Å) and Ca28Rb36Si100Al92O384(Ca28Rb36-X; a=24.977(1) Å), have been determined by single-crystal X-ray diffraction methods in the cubic space group Fd&bar{3} at 21(1) ℃. Their structures were refined to the final error indices R1=0.048 and R2=0.041 with 236 reflections for Ca31Rb30-X, and R1=0.052 and R2=0.043 with 313 reflections for Ca28Rb36-X; I>3σ(I). In both structures, Ca2+ and Rb+ ions are located at six different crystallographic sites. In dehydrated Ca31Rb30-X, sixteen Ca2+ ions fill site I, at the centers of the double 6-rings (Ca-O=2.43(1) Å and O-Ca-O=93.3(3)°). Another fifteen Ca2+ ions occupy site II (Ca-O=2.29(1) Å, O-Ca-O=119.5(5)°) and fifteen Rb+ ions occupy site II opposite single six-rings in the supercage; each is 1.60 Å from the plane of three oxygens (Rb-O=2.77(1) Å and O-Rb-O=91.1(4)°). About two Rb+ ions are found at site II', 1.99 Å into sodalite cavity from their three-oxygen plane (Rb-O=2.99(1) Å and O-Rb-O=82.8(4)°). The remaining thirteen Rb+ ions are statistically distributed over site III, a 48-fold equipoint in the supercages on twofold axes (Rb-O=3.05(1) Å and Rb-O=3.38(1) Å). In dehydrated Ca28Rb36-X, sixteen Ca2+ ions fill site I (Ca-O=2.41(1) Å and O-Ca-O=93.6(3)°) and twelve Ca2+ ions occupy site II (Ca-O=2.31(1) Å, O-Ca-O=119.7(4)°). Sixteen Rb+ ions occupy site II; each is 1.60 Å from the plane of three oxygens (Rb-O=2.81(1) Å and O-Rb-O=90.6(3)°) and four Rb+ ions occupy site II'; each is 1.88 Å into sodalite cavity from their three-oxygen plane (Rb-O=2.99(1) Å and O-Rb-O=83.8(2)°). The remaining sixteen Rb+ ions are found at III site in the supercage (Rb-O=2.97(1) Å and Rb-O=3.39(1) Å). It appears that Ca2+ ions prefer sites I and II in that order, and that Rb+ ions occupy the remaining sites. Rb+ ions are too large to be stable at site I, when they are competing with other smaller cations like Ca2+ ions.

• Journal of the Korean Ceramic Society
• /
• v.46 no.3
• /
• pp.323-329
• /
• 2009

Influences of ceramic filler types and dose on the sintering, phase evolution, and dielectric properties of ceramic/CaO-$Al_2O_3-SiO_2$ glass composites were investigated. All of the specimens were sintered at $900^{\circ}C$ for 2 h, which conditions are required by the lowtemperature co-firing ceramic (LTCC) technology. Ceramic fillers of $Al_2O_3,\;SiO_2$, kaolin, and wollastonite were used. The addition of $Al_2O_3$ filler yielded the crystalline phases of alumina and wollastonite, and the densification over 95% of the relative density was achieved up to 50 wt% addition of the filler. For the cases of the fillers of $SiO_2$, kaolin, and wollastonite, crystalline phases of quartz, mullite, and wollastonite formed, while the densification decreased monotonically with the filler addition. In overall, all the investigated fillers with 10 wt% addition resulted in a reasonable sintering (over 95 %) and low dielectric constants (less than 6), demonstrating the feasibility of the investigated composites for application to a LTCC substrate material with a low dielectric constant.

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

• The Journal of the Petrological Society of Korea
• /
• v.1 no.1
• /
• pp.42-48
• /
• 1992

The equilibrium pressure-temperature curve of the reaction: 6 Ca$_2$Al$_3$(OH)Si$_3$O$_{12}$=6 CaAl$_2$Si$_2$O$_{8}$+2 Ca$_3$Al$_2$Si$_3$O$_{12}$+Al$_2$O$_3$+3 H$_2$O zoisite anorthite grossularite corundum was experimentally determined using both externally and internally heated pressure vessels in the pressure range of 2-4 kbar. Synthetic zoisite, anorthite, grossularite and corundum were used as starting materials. Starting materials were synthesized at 13-16 kbar using the piston-cylinder apparatus. The dehydration temperature of zoisite at 2 kbar is 550${\pm}$12$^{\circ}C$ and at 4 kbar is 575${\pm}$20$^{\circ}C$. Low thermal stability of synthetic zoisite relative to natural zoisite at 4 kbar is attributed to the structural disorder of synthetic anorthite.