• 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.

• Journal of the Korean Ceramic Society
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• v.46 no.2
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• pp.181-188
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• 2009

The electrical property and microstructure in $BaTiO_3$ ceramics doped rare-earth ions with intermediate ionic size ($Dy^{3+},Ho^{3+},Y^{3+}$) were investigated. Microstructures have been characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). Incorporation of rare-earth ions to $BaTiO_3$ ceramics depended on their ionic radius sensitively. Compared to Ho and Y ions, Dy ions provide $BaTiO_3$ ceramics with the high rate of densification and well-developed shell formation, due to their high solubility in the $BaTiO_3$ lattice, but the microstructure of Dy doped $BaTiO_3$ ceramics is unstable at high temperature, because Dy ions could not play a role of grain growth inhibition, leading to diffuse into $BaTiO_3$ lattice continuously after completion of densification during sintering. Comparing electrical property and microstructure, it is shown that the reliability of capacitor improved by high shell ratio.

• Journal of the Korean Ceramic Society
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• v.14 no.3
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• pp.187-192
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• 1977

For the purpose researching to the influence of tetrahedral and octahedral preference of cations of $Ni^{2+}$, $Ti^{4+}$ upon the formation and the color development of the $ZnO-SnO_2$ spinel containing $Ni^{2+}$ and $Ti^{4+}$ ions, the gradual substitution of $Ni^{2+}$ ions for $Zn^{2+}$ ions and of $Ti^{4+}$ ions for $Sn^{4+}$ ions of the spinel in NiO-ZnO-$SnO_2$-$TiO_2$ system was carried out. On samples prepared by calcining the oxide and basic cabonate mixtures at $1300^{\circ}C$ for 2 hours, the X-ray analysis, measurement of reflectance and the test of their stabilaity as a glaze pigment were also carried out. The results are summarized as follows 1) Single spinel was formed completely to x=1 in the $xNiO\cdot(2-x)ZnO\cdot{SnO}_2$system, and gave brilliant lightgreen hue. Moreover, $NiO\cdot{ZnO}\cdot{SnO}_2$ formed easily spinel than $NiO\cdot{MgO}\cdot{SnO}_2$ because Zn^{2+}$ ions had more strong tetrahedral preference than $Mg^{2+}$ ions. 2) As the gradual substitution of $Ti^{4+}$ ions for $Sn^{4+}$ ions in $NiO\cdot{MgO}\cdot{SnO}_2$ system, the spinels formed well and was nearly not changed in the hue. 3) The results of glaze test. (1) As the gradual substitution of $Ni^{2+}$ ions for $Zn^{2+}$ ions, the color changed from dull white to graish broun gradually in calcium-zinc glaze and calcium glaze, and from white to beige in tile glaze. (2) As the gradual substitution of $Ti^{4+}$ ions for $Sn^{4+}$ ions in $NiO-ZnO-SnO_2-TiO_2$ system, the color was become dull generally and was not change in tile glaze.

• Transactions of Materials Processing
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• v.8 no.3
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• pp.319-319
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• 1999

From isothermal and cyclic oxidation tests on thermomechanically treated Ti-5%Al, Ti47%Al-4%Cr, and Ti-48%Al-2%Cr-2%Nb alloys at 800, 900, 1000℃ in air, it was found that Ti-48%Al-2%Cr-2%Nb and Ti-47%Al-4%Cr had the best and the worst oxidation resistance, respectively. The oxide scales consisted primarily of TiO₂and Al₂O₃, with and without a small amount of dissolved Cr and 7b ions, depending on the alloy composition. These ions were slightly enriched inside the inner oxide layer, and strongly enriched around the scale-matrix interface. The outer TiO₂-rich layer was formed by the outward diffusion of Ti ions, while the inner (TiO₂+A1₂O₃,) mixed layer was formed by the inward transport of oxygen. The outward movement of Al ions farmed the intermediate Al₂O₃-rich Iayer, above talc prepared alloys.

• Journal of the Korean Ceramic Society
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• v.28 no.5
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• pp.359-364
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• 1991

The effects of Pb5Ge3O11 on the sinterbility and lattice variation of the semiconducting 0.15 mol% Y2O3 doped BaTiO3 have been investigated as functions of additive contents (from 0.25 mol% to 2.5 mol%) and sintering temperatures (from 110$0^{\circ}C$ to 130$0^{\circ}C$). As the amount of Pb5Ge3O11 increases, the sinterbility of BaTiO3 increases abruptly at around 115$0^{\circ}C$. During the sintering, the most of Pb+2 ions in additives penetrate into BaTiO3 lattices and Ge+4 ions present at grain boundaries. Therefore the c lattice of the BaTiO3 increases largely and then the tetragonality increases due to the diffusion of the Pb+2 ions.

• Bulletin of the Korean Chemical Society
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• v.24 no.2
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• pp.197-204
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• 2003

The intracluster ion-molecule reactions of $Ti^+(H_2O)_n,\;Ti^+(CH_3OCH_3)_n,\;and\;Ti^+(CH_3OD)_n$ complexes produced by the mixing of the laser-vaporized plasma and the pulsed supersonic beam were studied using a reflectron time-of-flight mass spectrometer. The reactions of $Ti^+$ with water clusters were dominated by the dehydrogenation reaction, which produces $TiO^+(H_2O)_n$ clusters. The mass spectra resulting from the reactions of $Ti^+\;with\;CH_3OCH_3$ clusters exhibit a major sequence of $Ti^+(OCH_3)_m(CH_3OCH_3)_n$ cluster ions, which is attributed to the insertion of $Ti^+$ ion into C-O bond of $CH_3OCH_3$ followed by $CH_3$ elimination. The prevalence of $Ti^+(OCH_3)_m(CH_3OD)_n$ ions in the reaction of $Ti^+\;with\;CH_3OD$ clusters suggests that D elimination via O-D bond insertion is the preferred decomposition pathway. In addition, the results indicate that consecutive insertion reactions by the $Ti^+$ ion occur for up to three precursor molecules. Thus, examination of $Ti^+$ insertion into three different molecules establishes the reactivity order: O-H > C-O > C-H. The experiments additionally show that the chemical reactivity of heterocluster ions is greatly influenced by cluster size and argon stagnation pressure. The reaction energetics and formation mechanisms of the observed heterocluster ions are also discussed.

• Journal of the Korean Ceramic Society
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• v.13 no.2
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• pp.24-30
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• 1976

To observe the influence of tetrahedral and octahedral preference of cations of Ni2+, Ti4+ upon the formation and the color development of the MgO-SnO2 spinel containing Ni2+ and Ti4+ ions, the gradual substitution of Ni2+ ions for Mg2+ ions and of Ti4+ ions for Sn4+ ions of the spinel in NiO-MgO-SnO2-TiO2 system was carried out. On samples prepared by calcining the oxide and basic carbonate mixtures at 130$0^{\circ}C$ for 1.5 hour, the X-ray analysis, measurement of reflectance and the test of their stability as a glaze pigment were also carried out. On samples prepared by calcining the oxide and basic carbonate mixtures at 130$0^{\circ}C$ for 1.5 hour, the X-ray analysis, measurement of reflectance and the test of their stabiality as a glaze pigment were also carried out. The results are summarized as follows. 1) As increasing the amounts of Ni2+ ions in the xNiO.(2-x)MgO.SnO2 system, spinel was not formed easily, and the mixed-spinel was formed in NiO.MgO.SnO2 of x=1 but the spinels was not formed completely in the range of x>1.5 2) The spinels was not more formed in NiO-MgO-TiO2 system than NiO-MgO-SnO2 system. Therefore, Ti4+ ions have strong octahedral preference than Sn4+ ions. The color changed the yellow region little. The mixed-spinel or non-spinel was formed easily NiO.TiO2, MgO.TiO2 of illmenite type as the gradual substitution of Ti4+ ions for Sn4+ ions. 3) The results of glaze test. The color changed from white through graish brown to brown as the gradual substitution of Ni2+ ions for Mg2+ ions in calcium-zinc glaze and calcium glaze, and from white through light yellowish beige to dull beige in tile glaze. Also, the color did not change generally as the gradual substitution of Ti4+ ions for Sn4+ ions in NiO-MgO-SnO2-TiO2 system.

• Bulletin of the Korean Chemical Society
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• v.21 no.10
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• pp.1047-1048
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• 2000

Dye-sensitized nanocrystalline rutile $TiO_2$ solar cells were prepared, and the influence of Li+ and 1,2-dimethyl-3-hexyl imidazolium ions in the electrolyte on the photovoltaic properties was compared. The electrolyte con-taining Li+ ions produced a lower open-circuit photovoltage than the electrolyte with 1,2-dimethyl-3-hexyl im-idazolium ions, suggesting that the adsorption of Li+ ions to the rutile $TiO_2$ surface causes a shift in the band edges toward more positive potentials. At the same time, both the short-circuit photocurrent and the maximum value of the incident-photon-current conversion efficiency (IPCE) of the electrolyte containing Li+ ions were relatively higher. Data analysis suggests that presence of adsorbed Li+ ions improves via the phenomenon of band-edge movement the charge-injection efficiency by altering both the energy and number of excited state levels of the dye that participate in electron injection.

• Korean Journal of Materials Research
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• v.14 no.4
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• pp.293-299
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• 2004

Transition metal ions doped $TiO_2$ nanostructured powders were prepared with simply heating aqueous $TiOCl_2$ solutions, contained various metal ions (Ni, Al, Fe, Zr, and Nb) of 1.47 mol% added as metal-chlorides, at $100^{\circ}C$ for 4 hrs by homogeneous precipitation process under suppressing conditions of water vaporization. The characterizations for prepared $TiO_2$ powders were carried out to observe doping of metal ions, their concentrations and microstructures using XRD, UV-VIS (DRS), XPS, SEM, TEM and ICP. Also, photo-oxidative abilities were evaluated by decomposition of 4-chlorophenol (4CP) under ultraviolet light irradiations. No secondary oxide phases were formed in all the $VTiO_2$ powders, showing doping with various transition metal ions. When adding ions ($Ni^{2+}$ or$ Al^{3+ }$ and $Zr^{4+}$ ) having valance states or ionic radii greatly different from those of $Ti^{4+}$ , the $TiO_2$ powders of mixed anatase and rutile phases were formed, whereas in the case of additions of $^Fe{3+ }$ and $Nb^{ 5+}$ as well as no addition of metal ion the powders with pure rutile phase alone were formed. Among the prepared $TiO_2$ powders, Ni$^{2+}$ doped $TiO_2$ powders, containing a small amount of anatase phase, showed excellent photo-oxidative ability in 4CP decomposition because of relative decreases in electron-hole recombination and poisoning of $TiO_2$ surface during the photoreaction.n.

• Korean Journal of Materials Research
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• v.18 no.8
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• pp.432-437
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• 2008

Titanium oxide films and powders are attached onto carbon cloths via RF reactive sputtering and an epoxy resin mixture, respectively. $TiO_2$/carbon composite materials were used to investigate the photoelectrochemical degradation of perchlorate ions in water. The energy band gaps of the RF-sputtered $TiO_2$ thin films ranged from 3.35-3.44 eV. A photocurrent of the powdered $TiO_2$ as illuminated by ultra-violet light for 30 min. was $2.79\;mA/cm^2$. Perchlorate ions in water were shown to be degradable by a UV-illuminated $TiO_2$ powder/carbon/Nafion/carbon composite.