• Title/Summary/Keyword: cation substitution

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Fabrication and dielectric properties of $LaAlO_3-BaZrO_3$ perovskites ($LaAlO_3-BaZrO_3$계 perovskites의 제조 및 유전특성)

  • Lee, So-Hee;Kim, Shin;Shin, Hyun-Ho
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2007.06a
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    • pp.325-325
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    • 2007
  • The perovskites in the $LaAlO_3-BaZrO_3$ system (i.e., $(1-x)LaAlO_3-xBaZrO_3$ were fabricated by a solid state reaction and their dielectric properties were investigated. For the compositions of x=0.1~0.9, the mixture of $LaAlO_3$ with a rhombohedral structure and $BaZrO_3$ with a cubic was observed when the sintering was conducted at $1500^{\circ}C$, indicating that the solubility of constituent elements was very low and a narrow solid solution region might exist. The large difference of ionic radii between $La^{3+}$ ion (0.136nm, C.N.=12) and $Ba^{2+}$ ion (0.161nm) or $Al^{3+}$ ion (0.0535nm, C.N.=6) and $Zr^{4+}$ ion (0.072nm) might hinder the mutual substitution. Within the compositions of x=0~0.7, the dielectric constant of the mixture increased with the amount of $BaZrO_3$, i.e., x value, which was in good agreement with the logarithmic mixing rule (In $_{r,i}={\Sigma}v_iln\;_{r,i}$). The increase in $BaZrO_3$ doping decreased $Q{\times}f$ value significantly due to the low $Q{\times}f$ value of $BaZrO_3$ itself, a poor microstructure of the mixture with an increased grain boundary area per volume, and defects in the cation and oxygen sub-lattices which were respectively caused by the evaporation of barium during the sintering process and the substitution of Ba on La-site or Al on Zr-site.

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Synthesis of O-Diethylaminoethyl Chitosan for Chromatography; I. Separation of Protein (크로마토그래피용 O-Diethylaminoethyl Chitosan의 합성; I. 단백질의 분리)

  • Park, Chang-Gu;Lee, Young-Moo;Kim, Jin-Hong;Jeong, Chang-Nam
    • Applied Chemistry for Engineering
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    • v.4 no.3
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    • pp.583-590
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    • 1993
  • O-Diethylaminoethyl chitosan containing weak cation exchange group had been synthesized. It was used to separate albumin and lysozyme as stationary phase in liquid chromatography column. The separation of acidic and basic dyes were preliminarily conducted to investigate the effect of polarity parameter of solvents. Based on this result, we investigated various factors on the separation efficiency of chromatography in column. In the case of using water-methanol as cosolvent, the resolution factor depended on the polarity parameter. The best resolution factor was 1.42 for DEAE-chitosan with the degree of substitution of 0.23.

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Mass Spectrometric Identification of Thiohydantoins Derived from Amino Acids (II) (Amino acid Thiohydantoin 유도체(誘導體)의 질량분석(質量分析) (제II보)(第II報))

  • Song, Kyung-Duck
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.3 no.1
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    • pp.69-76
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    • 1974
  • The method of amino acid sequence determination from the C-terminal amino acid is proposed and mass spectrometric identification of thiohydantoins described previously. In this paper was discussed the fragmentation of thiohydantoin-ring by deutero substitution and model tripeptide have been degraded through three stages each, with interpretable results. The conditions employed in this method are mild enough for biological materials. The main features of the method are the following. 1. Thiohydantoins were formed in a non-aqueous medium a mixture of acetic anhydride, acetic acid and ammonium thiocyanate. 2. Mass sepectra of thiohydantoins derived from 20 amino acids were obtained with a mass spectrometer, JEOL model JMS-06H. 3. Cleavage of peptidyl thiohydantoin was made with an acidic from of a cation-exchange resin. (Amberlite IR-120) 4. Separation of the cleaved thiohydantoin and the parent peptide less one amino acid moiety was made by chromatography on a Sephadex G-10 column. 5. The peptide fraction was concentrated by freezedrying. 6. Thiohydantoin derivative of carboxyl terminal amino acid residue was introduced with a direct inlet probe in methanol solution.

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Solid-Solution Mechanism of Aluminum and Hydrogen in Stishovite (스티쇼바이트에 고용하는 알루미늄과 수소와의 관계)

  • 정정인;김희수
    • Journal of the Mineralogical Society of Korea
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    • v.16 no.3
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    • pp.245-254
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    • 2003
  • Stishovite was synthesized from hydrous basaltic starting materials at 10∼15 ㎬ and $1000∼1400^{\circ}C$. Water content of synthetic stishovite has been determined, and solid solution mechanism of $H_2$ and Al in stishovite was investigated. The maximum water content obtained from stishovite single crystal was up to $844\pm$44 ppm $H_2$O. The concentration of hydrogen increased with increasing substitution of trivalent cation, mainly Al. The temperature effect on the hydrogen content in stishovite is more sensitive than that on any other impurities. Among the nominally anhydrous mantle-minerals, stishovite could be an important water-containing phase and contribute to the transportation of $H_2$O to lower mantle.

Structure and Properties of $LiTaO_3$ Type Solid Solutions in $Li_2O-Al_2O_3-Ta_2O_5$ Ternary System ($Li_2O-Al_2O_3-Ta_2O_5$ 삼성분계에 있어 $LiTaO_3$ 고용체의 구조 및 특성에 관한 연구)

  • 김정돈;흥국선;주기태
    • Journal of the Korean Ceramic Society
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    • v.33 no.4
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    • pp.405-410
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    • 1996
  • The partial substitution of LiTaO3 with Al2O3 caused the variation of dielectric properties and a lower melting temperature yielding an easier growth of single crystal. The lattice constants and Raman band broadening were measured for the LiTaO3 solid solution in which the cations of Li+ and Ta5+ were partially substituted by Al3+ cation. The LiTaO3 type limit phases were obtained. ; Li1.15Al0.45Ta0.7O3 for cationic excess Li1.15Al0.45Ta0.7O3 for stoichiometry Li0.85Al0.05TaO3 for cationic deficit. The second phase was formed beyond the solubility limit. The limit phase (Li0.85Al0.05TaO3) in the region of cationic deficit showed the lowest Cuire temperature of 61$0^{\circ}C$ and melting point of 152$0^{\circ}C$ compared to the solid solutions in other regions (TMp=1$650^{\circ}C$, Tc=69$0^{\circ}C$ for LiTaO3)

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Comparison of Photocyclization Reactions of Fluoro- vs Nonfluoro-Substituted Polymethyleneoxy Donor Linked Phthalimides

  • Park, Hea Jung;Ryu, Young Ju;Kim, Kyung Mok;Yoon, Ung Chan;Kim, Eunae;Sohn, Youngku;Cho, Dae Won;Mariano, Patrick S.
    • Bulletin of the Korean Chemical Society
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    • v.34 no.4
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    • pp.1108-1114
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    • 2013
  • Photochemical reactions of fluoro- vs. nonfluoro-substituted polymethylenoxy chain linked phthalimide were carried out to explore how electronegative fluorine atoms inside the donor chain influence photocyclization reaction efficiencies and to briefly determine the alkali metal binding properties of the photoproducts. The results of this study show that the fluorine-substituted donor chain linked phthalimide undergoes inefficient photocyclization via single electron transfer (SET)-induced excited state pathways to generate 14-membered cyclic amidol compared to nonfluoro-analog due to low electron donor ability of the terminal oxygen donor site. These results show that photoinduced intramolecular SET processes arising from ${\alpha}$-silyl ether electron donors to phthalimides are largely dependent on the kinds of substituents inside donor chain. Finally, a preliminary study with the cyclic amidols generated in this effort showed that they have weak alkali metal cation binding properties regardless of absence/presence of fluoro-substituents.

Nucleophilic Substitution at a Carbonyl Carbon Atom. Part II. CNDO/2 Studies on Conformation and Reactivity of the Thio-Analogues of the Thio-Analogues of Methyl Chloroformate (카보닐 탄소원자 친핵 치환반응. 제2보. Methyl chloroformate의 티오 치환제들의 구조와 반응성에 관한 CNDO/2 계산)

  • Lee Ikchoon
    • Journal of the Korean Chemical Society
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    • v.16 no.6
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    • pp.334-340
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    • 1972
  • CNDO/2 calculations have been carried out on methyl chloro-thiol-, methyl chloro-thiono-, and methyl chloro-dithio-formates. Results show that the trans is the stable configuration for these compounds. It was found that sulfur atom has much less tendency to use its lone pair electrons for ${\pi}$ bond formation compared with oxygen, and that thiolformates are stabilized by hyperconjugation of methyl hydrogens. The order of solvolytic reactivity was found to follow the order of cation stability, which is consistent with the $S_N1$ mechanism proposed for these compounds.

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Crystallographic Effects of Larger Indium Ion Substitution in NiFe2-xInxO4 (x = 0, 0.2, 0.5, and 1.0) System

  • Yoon, Sung-Hyun;Yoon, Chang-Sun;Kim, Byung-Ho
    • Journal of Magnetics
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    • v.10 no.1
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    • pp.23-27
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    • 2005
  • The crystallographic and magnetic properties of a series of substitutions in nickel ferrite where the Fe3+ is replaced with In3+ have been investigated using X-ray diffraction (XRD) and Mössbauer spectroscopy. Information on the exact crystalline structure, lattice parameters, bond lengths and bond angles were obtained by refining their XRD profiles by a Rietveld method. All the crystal structures were found to be cubic with the space group Fd/3m. The lattice constants increased with In3+ concentration. The expansion of the tetrahedron was outstanding, indicative of the tetrahedral (A) site preference of larger indium ion. The Mossbauer spectra showed two sets of sextuplet originating from ferric ions occupying the tetrahedral sites and the octahedral (B) sites under the Neel temperature TN. Regardless of the composition x, the electric quadrupole splitting was zero within the experimental error. At x = 0.2, the magnetic hyperfine fields increased slightly, which meant that the nonmagnetic indium ions occupied preferentially the A-site. At the same time, the intensity of the B-site sub-spectra decreased markedly at the elevated temperature, indicating that the occupation of the A site by indium induced a considerable perturbation on the B site.

Effects of Fe Substitution on Lithium Incorporation into Muscovite (백운모 내 리튬 함유에 대한 Fe 치환의 영향)

  • Chae, Jin-Ung;Kwon, Kideok D.
    • Journal of the Mineralogical Society of Korea
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    • v.28 no.2
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    • pp.127-133
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    • 2015
  • Li-bearing muscovite is commonly found along with trioctahedral lepidolite in granitic pegmatites. Structurally, $Li^+$ ions can replace $K^+$ ions in the interlayer (Int) of muscovite or incorporate into vacancies of the dioctahedral sheet (Sub). However, detailed mechanism of the lithium incorporation into muscovite is challenging to investigate using experimental techniques alone. In the current study, density functional theory (DFT) has been applied to examine the crystal structure and energy variation when $Li^+$ resides in the interlayer or the octahedral sheet. Depending on the position of $Li^+$ (i.e., Int vs. Sub), DFT showed significant differences in the mica's structures such as lattice parameters, sheet thickness, interlayer separation, and OH angles with respect to the ab plane. DFT further showed that, in pure muscovite, $Li^+$ has a lower energy when it is located in Int than Sub. By contrast, in the case of $Fe^{2+}$ substitution into the octahedral sheet, $Li^+$ has a lower energy in Sub than in Int. These results imply that $Li^+$ incorporates into the Al octahedral sheets only when the octahedral sheets possess structural charges, suggesting cation substitution in the octahedral sheets plays an important role in the Li incorporation mechanism into muscovite. They can also explain the experimental observation about the positive relationship between $Fe^{2+}$ and $Li^+$ amounts in Li-bearing muscovite.

CEMS Study of Ferrite Films M0.2Fe2.8O4 (M =Mn, Ni, Cu) (페라이트 박막 M0.2Fe2.8O4(M=Mn, Ni, Cu)의 Mössbauer 분광학적 연구)

  • Park, Jae Yun;Kim, Kwang Joo
    • Journal of the Korean Magnetics Society
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    • v.24 no.2
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    • pp.46-50
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    • 2014
  • The crystallographic properties and cationic distribution of $M_{0.2}Fe_{2.8}O_4$ (M =Mn, Ni, Cu) and $Fe_3O_4$ thin films prepared by sol-gel method have been investigated by X-ray diffraction (XRD) and conversion electron M$\ddot{o}$ssbauer spectroscopy (CEMS). The ionic valence, preferred site, and hyperfine field of Fe ions of the ferrites could be obtained by analyzing the CEMS spectra. The $M_{0.2}Fe_{2.8}O_4$ films were found to maintain cubic spinel structure as in $Fe_3O_4$ with the lattice constant slightly decreased for Ni substitution and increased for Mn and Cu substitution from that of $Fe_3O_4$. Analyses on the CEMS data indicate that $Mn^{2+}$ and $Ni^{2+}$ ions substitute octahedral $Fe^{2+}$ sites mostly, while $Cu^{2+}$ ions substitute both the octahedral and tetrahedral sites. The observed intensity ratio $A_B/A_A$ of the CEMS subspectra of the samples exhibited difference from the theoretical value. It is interpreted as due to the effect of the M substitution for A and B on the Debye temperature of the site. The relative line-broadening of the B-site CEMS subspectra can be explained by the dispersion of magnetic hyperfine fields due to random distribution of M cations in the B sites.