• Title/Summary/Keyword: Tetrahedral

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Investigation of Electronic Structures of TCr2O4 (T = Fe, Co, Ni) Spinel Oxides by Employing Soft X ray Synchrotron Radiation Spectroscopy (연 X선 방사광 분광법을 이용한 TCr2O4(T = Fe, Co, Ni) 스피넬 산화물의 전자구조 연구)

  • Kim, Hyun Woo;Hwang, Jihoon;Kim, D.H.;Lee, Eunsook;Kang, J.S.
    • Journal of the Korean Magnetics Society
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    • v.23 no.5
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    • pp.149-153
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    • 2013
  • The electronic structures of $TCr_2O_4$ (T = Fe, Co, Ni) spinel oxides have been investigated by employing synchrotron radiation-based soft X ray absorption spectroscopy (XAS). The measured 2p XAS spectra of transition-metal ions reveal that Cr ions are trivalent ($Cr^{3+}$), and all the T (T = Fe, Co, Ni) ions are divalent ($Fe^{2+}$, $Co^{2+}$, $Ni^{2+}$). It is also found that most of T (T = Fe, Co, Ni) ions occupy the A sites under the tetrahedral symmetry, while Cr ions occupy mainly the B sites under the octahedral symmetry. These findings show that the structures of $TCr_2O_4$ (T = Fe, Co, Ni) are very close to the normal spinel structures. Based on these findings, it is expected that Jahn-Teller (JT) effects are important in $FeCr_2O_4$ and $NiCr_2O_4$. In contrast, $CoCr_2O_4$ maintains the cubic structure without having the JT distortion since both $Cr^{3+}$ and $Co^{2+}$ ions are non-JT ions. This work suggests that the antiferromagnetic interaction between $Cr^{3+}$ and $T^{2+}$ ions plays an important role in determining the magnetic properties of $TCr_2O_4$ (T = Fe, Co, Ni).

Electrochemical Properties of Kaolinite in Aqueous Suspension (수용액중(水溶液中)에서의 Kaolinite 입자(粒子)의 전기화학적(電氣化學的) 성질(性質))

  • Lim, Hyung-Sik;Baham, J.;Volk, V.V.
    • Korean Journal of Soil Science and Fertilizer
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    • v.16 no.4
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    • pp.318-324
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    • 1983
  • Electrochemical properties of Georgia kaolinite in aqueous suspension were studied by ion adsorption, potentiometric titration, and electrophoretic mobility measurements. Kaolinite in 0.001 M and 0.1 M NaCl solution showed qualitatively both pH independent and pH depender negative and positive charges through pH range 2.5-11.0 when dissolved aluminum ions from kaolinite were considered as well as $Na^+$ and $Cl^-$ as index ions. Electrophoretic mobilities (EM) of 0.02 wt. % kaolinite suspension in distilled water and 0.001 M NaCl solution were approximately constant against mobility measuring time consumed in the electrophoresis cell at different pH values, and isoelectric points(IEP) were around pH 4.7. EM values in 0.1 M NaCl solution were positive and constant against mobility measuring time below pH 4; but above pH 4, EM values were negative for the first 10 seconds followed by positive values which became approximately constant through stepped changes after 10 minutes. Hydrated cations may bind to the six- member oxygen ring sites having multiple partial negative charges on the exterior tetrahedral layer surface by both electrostatic and hydrogen bonding force while hydrated anions bind to the partially positively charged hydrogen atoms on the exterior octahedral layer surface. Parts of the aluminol groups on the exterior octahedral layer surface as well as edge faces may be involved in complex reactions and have both anion and cation exchange capacities in the electrolyte solution above pH 4.

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Formation and Color of the Spinel Solid Solution in CoO-ZnO-$Fe_2O_3$-$TiO_2$-$SnO_2$ System (CoO-ZnO-$Fe_2O_3$-$TiO_2$-$SnO_2$계 Spinel 고용체의 생성과 발색에 관한 연구)

  • 이응상;이진성
    • Journal of the Korean Ceramic Society
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    • v.28 no.11
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    • pp.897-907
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    • 1991
  • This study was conducted to research the formation and the color development of CoO-ZnO-Fe2O3-TiO2-SnO2 system for the purpose of synthesizing the spinel pigments which are stable at high temperature. After preparing CoO-ZnO-Fe2O3, in which CoO causes the color, as a basic composition, $\chi$CoO.(1-$\chi$)ZnO.Fe2O3 system, $\chi$CoO.(1-$\chi$)ZnO.TiO2 system and $\chi$CoO.(1-$\chi$)ZnO.SnO2 system were prepared with $\chi$=0, 0.2, 0.5, 0.7, 1.0 mole ratio respectively. The manufacturing was carried out at 128$0^{\circ}C$ for 90 minutes. These specimens were analyzed by the reflectance measurement and the X-ray diffraction analysis and the results were summarized as follows: 1. All of the specimens formed the spinel structure and were colored with stable yellow or blue. 2. As the content of CoO and Fe2O3 in the specimens being increased, the reflectance of each specimen was measured becoming lower and the colors were changed from yellow to greyish blue and from blue to dark blue. 3. As the substituting amount of Co2+ ion for Zn2+ ion in $\chi$CoO-ZnO-TiO2-SnO2 system being increased, the colors were changed from blue to greyish blue. The colors were changed from yellow to grayish green owing to the tetrahedral Co2+ ions being increased, the octahedral Co2+ ions being decreased with increasing the amount of Sn4+ ions. 4. CoO-ZnO-Fe2O3-TiO2-SnO2 system, in which Zn2+ was substituted with Co2+ and Fe3+ was substituted with Ti4+ and Sn4+, easily formed the spinel structure without regard to the amount of substitution or the ion owing to the selectivity of the coordination number: 4 of Zn2+, 4 of Co2+, 6 of Fe3+ or 6 of Ti4+ and Sn4+.

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Studies of Refractive Index and Hardness In Quarternary NaBAISi Glasses (4성분 NaBAISi 유리계의 굴절률과 경도 연구)

  • Moon, Seong-Jun;Hwang, In-Sun
    • Journal of Korean Ophthalmic Optics Society
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    • v.8 no.1
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    • pp.1-5
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    • 2003
  • Quarternary $Na_2O-B_2O_3-Al_2O_3-SiO_2$ glasses were fabricated by the function of $R({\equiv}Na_2O\;mole%/B_2O_3\;mole%)$ and $K({\equiv}(Al_2O_3\;mole%+SiO_2\;mole%)/B_2O_3mole%)$. The structures of these glasses were investigated through refractive index and vicker's hardness. The refractive index increased as the increase of the polarizability in the glass network. In the region of low $Na_2O$ content, the refractive index increased due to the increase of the polarizability in the glass network, but in the region of high $Na_2O$ content, the rate of increase of the refractive index decreased due to the increase of the molar volume caused by the formation of $BO_3{^-}$ units with relatively high molar volume. And, the refractive index decreased as the increase of $Al_2O_3+SiO_2$ content with the molar volume in the glass network. The increase and decrease of vicker's hardness values for those glasses depended on the fraction of tetrahedral $BO_4$ units and it of triangle $BO_3{^-}$ units with non-bridging oxygen, respectively.

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Burial Diagenesis of Smectite in the Tertiary Marine Basin, Japan (일본 제3기 해성 퇴적분지에서의 스멕타이트 매몰 속성작용)

  • Son, Byeong-Kook
    • Journal of the Mineralogical Society of Korea
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    • v.19 no.4 s.50
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    • pp.221-229
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    • 2006
  • Mineralogical and chemical examinations were performed on interstratified illite-smectite (I-S) minerals that occur in the mudstones from a petroleum exploration well in the Tertiary marine basin, Japan. X-ray diffraction analysis shows that component layers of illite in the interstratified I-S increase with increasing burial depth while those of smectie decrease. In addition, the randomly (R=0) interstratified illite-smectite is changed into Rp1 ordered I-S at a depth of about 4,000 m, which corresponds to the result of organic analysis and indicates a burial temperature of about $100^{\circ}C$. However, the present geothermal gradient shows that the conversion of the random I-S to R=0 ordered I-S is likely to occur at 3,000 m. This discrepancy may be interpreted by the reverse fault at 2,500 m which resulted in a deeper burial of sediments up to 1,000 m. Chemical analysis also shows the compositional variation in I-S with increasing depth: a decrease in Si and an increases in Al and K, indicating that the substitution of Al for Si in tetrahedral sheets is compensated by the addition of K to interlayers. K may be derived from K-feldspar and micas, which is present in the mudstones.

Surface Chemical Properties of Aqueous Kaolinite and Halloysite: Surface Complexation Modeling (수용액 내 캐올리나이트와 할로이사이트의 표면화학 특성: 표면복합반응 모델링)

  • 장세정;김수진
    • Journal of the Mineralogical Society of Korea
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    • v.17 no.2
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    • pp.157-168
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    • 2004
  • The surface chemical properties of aqueous kaolinite and halloysite were studied using a potentiometric titration experiment and a computer program FITEQL3.2. Among the surface complexation models a constant capacitance model was selected for this study. The 2 sites - 3 p $K_{a}$ s model, in which the surfaces were assumed to have tetrahedral and octahedral sites, was reasonable for the description of the experimental data. The surface charges of both minerals were negative above pH of 4. The higher the pH, the lower the proton surface charge densities of both minerals. The ≡ $SiO^{[-10]}$ site played an important role in cation adsorption in acid and neutral pH range; whereas the ≡ Al $O^{[-10]}$ site was in an alkaline pH range. The optimized intrinsic constants of kaolinite, p $K_{a2(Si)}$$^{int}$, p $K_{al(Al)}$$^{int}$ and p $K_{a2(Al)}$$^{int}$ were 4.436, 4.564, and 8.461 respectively, and those of halloysite were 7.852, 3.885, and 7.084, respectively. The total Si and Al surface sites concentrations of kaolinite were 0.215 and 0.148 mM, and those of halloysite were 0.357 and 0.246 mM. The ratio of Si and Al surface site densities ([≡SiOH]:[≡AlOH]) of both minerals was 1 : 0.69. The total surface site density of kaolinite, 3.774 sites/n $m^2$, was 1.6 times larger than that of halloysite, 2.292 sites/n $m^2$./TEX>.

$M\"{o}ssbauer$ Studies by a Heat Treatment in $CoFe_2O_4$ (열처리에 따른 $CoFe_2O_4$$M\"{o}ssbauer$ 분광학적 연구)

  • 이승화;김철성
    • Journal of the Korean Magnetics Society
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    • v.6 no.2
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    • pp.67-72
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    • 1996
  • The crystallographic and magnetic properties of the ferrimagnetic $CoFe_2O_4$ have been studied by X-ray and Mossbauer measurements. The crystal structure is found to be cubic spinel structure with the lattice constant $a_{0}=8.381{\pm}0.005{\AA}\;and\;a_{0}=8.391{\pm}0.005{\AA}$ for slow-cooled and quenched CoFeZ04' respectively. Mossbauer spectra of $CoFe_2O_4$ have been taken at various temperatures ranging from 13 to 780 K. The isorrer shifts indicate that the valence states of the Fe ions for tetrahedral(A) and octahedral(B) sites have ferric character. Debye temperatures for the A and B sites are found to be ${\theta}_A=734{\pm}5K\;and\;{\theta}_B=248{\pm}5K$ for slow-cooled and ${\theta}_A=531{\pm}5K\;and\;{\theta}_B=197{\pm}5K$ for quenched, respectively. Atomic migration from the A to the B sites starts near 400 K and 350 K for slow-cooled and quenched $CoFe_2O_4$, respectively, am increases rapidly with increasing temperature to such a degree that about 69 % for slow-cooled and 91 % for quenched of the ferric ions on the A sites have rmved over to the B sites at 700 K.

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Magnetic Properties of Mn-substituted Magnetite Thin Films (망간 치환된 마그네타이트 박막의 자기적 특성 연구)

  • Lee, Hee-Jung;Kim, Kwang-Joo
    • Journal of the Korean Vacuum Society
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    • v.16 no.4
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    • pp.262-266
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    • 2007
  • Polycrystalline $Mn_xFe_{3-x}O_4$ thin films were synthesized on Si(100) substrates using sol-gel method and the effects of Mn substitution on the structural, magnetic, and magnetotransport properties were analyzed. X-ray diffraction revealed that cubic structure is maintained up to x = 1.78 with increasing lattice constant for increasing x. Such increase of the lattice constant is attributable to the substitution of $Mn^{2+}$ (with larger ionic radius) ions into tetrahedral $Fe^{3+}$(with smaller ionic radius) sites. VSM measurements revealed that $M_s$ does not vary significantly with x, qualitatively explainable by comparing spin magnetic moments of Mn and Fe ions. On the other hand, $H_c$ was found to decrease with increasing x, attributable to the decrease of magnetic anisotropy due to the decrease of $Fe^{2+}$ density through $Mn^{2+}$ substitution. Magnetoresistance (MR) of the $Mn_xFe_{3-x}O_4$ films was found to decrease with increasing x. Analysis of the MR data in comparison with the VSM results gives an indication of the tunneling of spin-polarized carriers through the grain boundaries of the polycrystalline samples at low external field and spin-flip of the carriers at high external field.

Control of a- and c-plane Preferential Orientations of p-type CuCrO2 Thin Films

  • Kim, Se-Yun;Seong, Sang-Yun;Jo, Gwang-Min;Hong, Hyo-Gi;Kim, Jeong-Ju;Lee, Jun-Hyeong;Heo, Yeong-U
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.02a
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    • pp.119-120
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    • 2011
  • Kawazoe는 1997년 p-type TOS를 만들기 위해서는 3가지가 충족되어야 한다고 언급한바 있다. 첫 번째, 가시광영역에서 투명하기 위해서 cation의 d10s0이 가득 차야 한다. 가득 차지 않은 d10 shell은 광 흡수가 가능하여 투과도를 떨어뜨린다. N-type을 예로 들어 ZnO, TiO, In2O3가 각각 Zn2+, Ti4+, In3+가 되어 d shell을 가득 차게 만드는 것을 볼 수 있다. 두 번째, cation d10s0 shell은 산소의 2p shell과 overlap 되어야 한다. 이 valence band는 홀 전도를 더욱 좋게 한다. 예를 들어 Cu1+(3d), Ag1+(4d)가 해당한다. 세 번째로, 양이온과 산소간의 공유결합을 강하게 하기 위해서 결정학적 구조는 매우 중요하다. Delafossite 구조는 산소가 pseudo-tetrahedral 구조로서 공유결합에 유리하다. 이러한 환경은 O2- (2p6)을 형성하고 홀의 이동도를 증가시킨다. 예를 들어 Cu2O의 경우 앞의 2가지를 만족시키지만 광학적 특성에서 좋지 않다. 그 이유가 3번째 언급한 결정학적인 요인에 있다. 결정 계의 환경은 Cu2O를 따라가면서 3차원적인 연결을 2차원적으로 변형된 delafossite 구조에서는 quantum well이 형성되어 band gap이 커진다. 본 연구에서는 전기적 이방성을 가지고 있는 delafossite CuCrO2 상에서 우선배향을 일으키는 인자 중 기판을 변화시켜 실험을 진행하였다. 결과적으로 기판변화를 통해 우선배향조절이 가능하였으며 CuCrO2 박막을 시켰으며, 결정방향에 따른 전기적 물성의 이방성에 관한 연구는 계속 진행 중에 있다. c-plane sapphire 기판위에는 [00l]로 성장하는 반면, c-plane STO 기판 위에는 [015] 방향으로 성장하는 것을 확인하였다. 이러한 원인은 기판과 증착되는 박막간의 mismatch를 최소화 하여 strain을 줄이고, 계면에서의 Broken boning 수를 줄여 계면에너지를 낮추는 방법이기 때문일 것으로 예상된다. C-plane sapphire 기판위에 증착될 경우 증착온도가 증가함에 따라 c-축으로의 성장이 온전해지며 이에 따라 캐리어농도의 감소와 모빌리티의 증가가 급격하게 변하는 것을 확인할 수 있다. 반면 c-plane STO 기판에서는 증착온도에 따른 박막의 배향변화가 없으며 전기적 물성 변화 또한 비교적 작은 것을 간접적으로 확인하였다.

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Soft X-ray Synchrotron-Radiation Spectroscopy Study of Half-metallic Mn3Ga Heusler Alloy (반쪽 금속 호이슬러 화합물 Mn3Ga의 연 X선 방사광 분광 연구)

  • Seong, Seungho;Lee, Eunsook;Kim, Hyun Woo;Kim, D.H.;Kang, J.S.;Venkatesan, M.;Coey, J.M.D.
    • Journal of the Korean Magnetics Society
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    • v.26 no.6
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    • pp.185-189
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    • 2016
  • By employing photoemission spectroscopy (PES) and soft X-ray absorption spectroscopy (XAS), the electronic structure of the candidate half-metallic antiferromagnet of $Mn_3Ga$ Heusler compound has been investigated. We have studied two ball-milled $Mn_3Ga$ powder samples, one after annealing and the other without annealing, respectively. Based on the Mn 2p XAS study, we have found that Mn ions are nearly divalent in $Mn_3Ga$ and that the Mn ions having the locally octahedral symmetry and those having the locally tetrahedral symmetry are both present in $Mn_3Ga$. We have found relatively good agreement between the measured valence-band PES spectrum of $Mn_3Ga$ and the calculated density of states, which is in agreement with the half-metallic electronic structure of $Mn_3Ga$.