• Title/Summary/Keyword: Rietveld method.

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Crystal Structures, Electrical Conductivities and Electrochemical Properties of LiCo1-XMgxO2(x=0.03) for Secondary Lithium Ion Batteries (리튬 2차 전지용 LiCo1-XMgxO2(x=0.03)의 결정구조, 전기전도도 및 전기화학적 특성)

  • Kim, Ho-Jin;Chung, Uoo-Chang;Jeong, Yeon-Uk;Lee, Joon-Hyung;Kim, Jeong-Joo
    • Journal of the Korean Ceramic Society
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    • v.42 no.9 s.280
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    • pp.602-606
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    • 2005
  • [ $LiCoO_{2}$ ] is the most common cathode electrode materials in Lithium-ion batteries. $LiCo_{0.97}Mg_{0.03}O_2$ was synthesized by the solid-state reaction method. We investigated crystal structures, electrical conductivities and electrochemical properties. The crystal structure of $LiCo_{0.97}Mg_{0.03}O_2$ was analyzed by X-ray powder diffraction and Rietveld refinement. The material showed a single phase of a layered structure with the space group R-3m. The lattice parameter(a, c) of $LiCo_{0.97}Mg_{0.03}O_2$ was larger than that of $LiCoO_2$. The electrical conductivity of sintered samples was measured by the Van der Pauw method. The electrical conductivities of $LiCoO_2$ and $LiCo_{0.97}Mg_{0.03}O_2$ were $2.11{\times}10^{-4}\;S/cm$ and $2.41{\times}10^{-1}\;S/cm$ at room temperature, respectively. On the basis of the Hall effect analysis, the increase in electrical conductivities of $LiCo_{0.97}Mg_{0.03}O_2$ is believed due to the increased carrier concentrations, while the carrier mobility was almost invariant. The electrochemical performance was investigated by coin cell test. $LiCo_{0.97}Mg_{0.03}O_2$ showed improved cycling performance as compared with $LiCoO_2$.

USE OF NEAR INFRARED FOR THE QUANTITATIVE ANALYSES OF BAUXITE

  • Walker, Graham S.;Cirulis, Robyn;Fletcher, Benjimin;Chandrashekar, S.
    • Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
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    • 2001.06a
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    • pp.1171-1171
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    • 2001
  • Quantitative analysis is an important requirement in exploration, mining and processing of minerals. There is an increasing need for the use of quantitative mineralogical data to assist with bore hole logging, deposit delineation, grade control, feed to processing plants and monitoring of solid process residues. Quantitative analysis using X-Ray Powder Diffraction (XRD) requires fine grinding and the addition of a reference material, or the application of Rietveld analysis to XRD patterns to provide accurate analysis of the suite of minerals present. Whilst accurate quantitative data can be obtained in this manner, the method is time consuming and limited to the laboratory. Mid infrared when combined with multivariant analysis has also been used for quantitative analysis. However, factors such as the absorption coefficients and refractive index of the minerals requires special sample preparation and dilution in a dispersive medium, such as KBr to minimize distortion of spectral features. In contrast, the lower intensity of the overtones and combinations of the fundamental vibrations in the near infrared allow direct measurement of virtually any solid without special sample preparation or dilution. Thus Near Infrared Spectroscopy (NIR) has found application for quantitative on-line/in line analysis and control in a range of processing applications which include, moisture control in clay and textile processing, fermentation processes, wheat analysis, gasoline analysis and chemicals and polymers. It is developing rapidly in the mineral exploration industry and has been underpinned by the development of portable NIR spectrometers and spectral libraries of a wide range of minerals. For example, iron ores have been identified and characterized in terms of the individual mineral components using field spectrometers. Data acquisition time of NIR field instruments is of the order of seconds and sample preparation is minimal. Consequently these types of spectrometers have great potential for in-line or on-line application in the minerals industry. To demonstrate the applicability of NIR field spectroscopy for quantitative analysis of minerals, a specific example on the quantification of lateritic bauxites will be presented. It has been shown that the application of Partial Least Squares regression analysis (PLS) to the NIR spectra can be used to quantify chemistry and mineralogy in a range of lateritic bauxites. Important, issues such as sampling, precision, repeatability, and replication which influence the results will be discussed.

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Fine-scale Mineral Association and Crystal Structure Refinement of Spotted Cordierite from Northern Ogcheon Metamorphic Belt (북부 옥천변성대에서 산출되는 반점상 근청석의 미시적 공생관계 및 결정구조 해석)

  • 노진환;최진범;김건영
    • Journal of the Mineralogical Society of Korea
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    • v.12 no.2
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    • pp.55-65
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    • 1999
  • Spotted cordierite occurs as the result of intrusion of Wolaksan Granite of Cretaceous age in the northern part of the Ogcheon Metamorphic Belt, forming a contact metamorphic zoning in accordance with the distance from the granite body: a cordierite-muscovite-biotite-quartz assemblage and the higher-temperature cordierite-biotite-quartz-(cummingtonite). These quartz-ubiquitous mineral assemblages identified in the cordierite spot seem to reflect Al-deficient condition of the protolith. TEM observations of textural relations between the cordierite and mica within the cordierite spot clearly reflect that cordierite was formed at the expense of micaceous matrix. A structure refinement of the poikiloblastic cordierite was performed by the Rietveld refinement method. Unit cell of the cordierite was determined to be as follows : lower-temperature type: a=17.1480(9)${\AA}$, b=9.7743(6)${\AA}$, c=9.3184(5)${\AA}$, V=1561.9(4)${\AA}$3, higher-temperature type: a=17.136(2)${\AA}$, b=9.751(1)${\AA}$, c=9.322(1)${\AA}$, V=1557.7(4)${\AA}$3. They show a remarkable difference in the unit cell dimension. The refinement results indicate that structural sites of lower-temperature cordierite are wholly occupied by appropriating ions. Compared to this, tetrahedral sites of the higher-temperature type exhibit an order/disorder ranging about 5-8% as the result of substitution between Si4+ and Al3+, except for T26 site occupied wholly by Al3+. These structural differences seem to be related to the formation temperatures of both cordierite types.

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Crystal Structure of High Temperature Phase in ${Bi_2}{O_2}$-layered Perovskites ${ABi_2}{M_2}{O_9}$(A=Pb, Sr, M=Nb, Ta)

  • Kim, Jeong-Seog;Cheon, Chae-il;Lee, Chang-Hee;Choo, Woong-Gil
    • Journal of the Korean Ceramic Society
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    • v.38 no.11
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    • pp.962-966
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    • 2001
  • Crystal structure of PbBi$_2$Nb$_2$$O_{9}$ and $Sr_{1.2}$$Bi_{1.8}$Ta$_2$$O_{9}$ were determined by Rietveld method using neutron diffraction data in the temperature range of 300 K~1273K. Phase transition temperature were measured from the dielectric permittivitytemperature curve. The PbBi$_2$Nb$_2$$O_{9}$ showed a phase transition at about 810 K. In the Sr-excess compound $Sr_{1.2}$$Bi_{1.8}$Ta$_2$$O_{9}$ the phase transition was suppressed down to room temperature. Several structural models were tested by the Rietiveld refinement. Based on the \`R\` values and the structural parameters, the B2cb model is judged to be the most feasible one for the high temperature phase at above 810 K of the PbBi$_2$Nb$_2$$O_{9}$. The $Sr_{1.2}$$Bi_{1.8}$Ta$_2$$O_{9}$ sample was refined to show the most reliable results by the Am2m model.sults by the Am2m model.

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Structures and Electrochemical Properties of LiNi0.5-xCo2x}Mn0.5-xO2 as Cathode Materials for Lithium-ion Batteries

  • Choi, Hyun-Chul;Kim, Ho-Jin;Jeong, Yeon-Uk;Jeong, Soo-Hwan;Cheong, In-Woo;Jung, Uoo-Chang
    • Bulletin of the Korean Chemical Society
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    • v.30 no.11
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    • pp.2603-2607
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    • 2009
  • $LiNi_{0.5-x}Co_{2x}Mn_{0.5-x}O_{2}$ (x = 0, 0.1, 1/6, 1.2, 0.3) were synthesized by the solid-state reaction method. The crystal structure was analyzed by X-ray powder diffraction and Rietveld refinement. $LiNi_{0.5-x}Co_{2x}Mn_{0.5-x}O_{2}$ samples give single phases of hexagonal layered structures with a space group of R-3m for x = 0.1, 1/6, 0.2, and 0.3. The lattice constants of a and c-axis were decreased with the increase in Co contents in samples. The thickness of MO2 slab was decreased and inter-slab distance was increased with the increase in Co contents in $LiNi_{0.5-x}Co_{2x}Mn_{0.5-x}O_{2}$. According to XPS analysis, the valence states of Mn, Co, and Ni in the sample are mainly +4, +3, and +3, respectively. The discharge capacity of 202 mAh/g at 0.1C-rate in the potential range of 4.7 - 3.0 V was obtained in $LiNi_{0.3}Co_{0.4}Mn_{0.3}O_2$ sample, and $LiNi_{0.4}Co_{0.2}Mn_{0.4}O_2$ gives excellent cycle performance in the same potential range.

Manganese Doped LiFePO4 as a Cathode for High Energy Density Lithium Batteries (고에너지밀도 리튬전지를 위한 망간이 첨가된 LiFePO4 양극재료)

  • Kim, Dul-Sun;Kim, Jae-Kwang;Ahn, Jou-Hyeon
    • Journal of the Korean Electrochemical Society
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    • v.16 no.3
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    • pp.157-161
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    • 2013
  • Porous $LiMn_{0.6}Fe_{0.4}PO_4$ (LMFP) was synthesized by a sol-gel process. Uniform dispersion of the conductive carbon source throughout LMFP with uniform carbon coating was achieved by heating a stoichiometric mixture of raw materials at $600^{\circ}C$ for 10 h. The crystal structure of LMFP was investigated by Rietveld refinement. The surface structure and pore properties were investigated by SEM, TEM and BET. The LMFP so obtained has a high specific surface area with a uniform, porous, and web-like nano-sized carbon layer at the surface. The initial discharge capacity and energy density were 152 mAh/g and 570 Wh/kg, respectively, at 0.1 C current density, and showed stable cycle performance. The combined effect of high porosity and uniform carbon coating leads to fast lithium ion diffusion and enhanced electrochemical performance.

Crystallographic and Magnetic Properties of Brownmillerite Ca1-xSrxFeO2.5(x=0, 0.3, 0.5, 0.7, 1.0) (Brownmillerite Ca1-xSrxFeO2.5(x=0, 0.3, 0.5, 0.7, 1.0)의 결정학적 및 자기적 성질에 관한 연구)

  • Yoon, Sung-Hyun;Yang, Ju-Il;Kim, Chul-Sung
    • Journal of the Korean Magnetics Society
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    • v.14 no.2
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    • pp.76-82
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    • 2004
  • Crystallographic and magnetic properties for Brownmillerite-type oxides $Ca_{1-x}$Sr$_{x}$FeO$_{2.5}$ (x = 0, 0.3, 0.5, 0.7, 1.0) were investigated using x-ray diffraction (XRD) and Mossbauer spectroscopy. Polycrystalline samples were prepared by conventional solid-state reaction method. Information on exact crystalline structures, lattice parameters, bond lengths and bond angles were obtained by refining their XRD profiles using a Rietveld method. The crystal structures were found to be all orthorhombic with space group Icmm (x = 0, 0.3) and Icmm (x = 0.5, 0.7, 1.0) The lattice parameters increased monotonically with increasing Sr concentration. Both the tetrahedral and the octahedral sites were considerably distorted and elongated along b-axis. While bond lengths and bond angles O-Fe-O tend to increase minutely with the increase of Sr content, bond angles Fe-O-Fe decreased accordingly. The Mossbauer spectra showed two sets of sharp sextets originating from ferric ions occupying the tetrahedral and the octahedral sites under the magnetic transition temperature T$_{N}$. Regardless of the compositions x, the electric quadrupole splittings were -0.3 mm/s and 0.4 mm/s for the octahedral and the tetrahedral site, respectively. Above T$_{N}$, the Mossbauer spectra showed the paramagnetic doublets whose electric quadrupole splittings were about 1.6 mm/s, irrespective of compositions x. T$_{N}$ was found to decrease monotonically with the increase of Sr concentration. Ratios of absorption area for the two sites were almost 1:1 up to as high as 0.95 T$_{N}$ for all x. The result of the Debye temperature indicated that the inter-atomic binding force for the Fe atoms in the tetrahedral site was stronger than that for the octahedral site.hedral site.

Crystallographic and Magnetic Properties of KFeO2 (KFeO2 분말의 제조 및 뫼스바우어 분광학 연구)

  • Moon, Seung-Je;Shim, In-Bo;Kim, Chul-Sung
    • Journal of the Korean Magnetics Society
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    • v.17 no.1
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    • pp.38-42
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    • 2007
  • The crystallographic and magnetic properties of $KFeO_2$ powder prepared by ball-mill method, have been studied by x-ray diffraction(XRD), $M\"{o}ssbauer$ spectroscopy, and vibrating sample magnetometer(VSM) measurements. The crystal structure of $KFeO_2$ powder at room temperature is determined to be an orthorhombic structure of Pbca with its lattice constants $a_0=5.557{\AA},\;b_0=11.227{\AA},\;c_0=15.890{\AA}$ by Rietveld refinement. $M\"{o}ssbauer$ spectra of $KFeO_2$ were taken at various temperatures ranging from 4.2 to 818 K. The magnetic hyperfine field and isomer shift value at 4.2 K and RT were 519 kOe, 489 kOe and 0.19 mm/s, 0.05 mm/s respectively. The average hyperfine field $H_{hf}(T)$ of the $KFeO_2$ shows a temperature dependence of $[H_{hf}(T)-H_{hf}(0)]/H_{hf}(0)=-0.36(T/T_N)^{5/2}$ for $T/T_N$<0.7, indicative of spin-wave excitation.

Effect of Low-grade Limestone on Raw Mill Grinding and Cement Clinker Sintering (저품위 석회석이 원료밀의 분쇄성과 시멘트 클링커 소성성에 미치는 영향)

  • Yoo, Dong-Woo;Park, Tae-Gyun;Choi, Sang-Min;Lee, Chang-Hyun
    • Journal of the Korean Recycled Construction Resources Institute
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    • v.9 no.1
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    • pp.20-25
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    • 2021
  • The cement clinker, the main raw material of cement, is manufactured using limestone as the main material. Depending on the quality of limestone, the use of subsidiary materials changes, and has a great influence on the production of cement clinkers. In this study, the effect of CaO content of limestone, a cement clinker material, on Raw Mill grinding and sintering of cement clinker was investigated. The grinding time of the union materials changed in the content of limestone CaO was measured to identify the grinding properties. The raw material combination was cleaned within a range of 1,350-1,500℃. The sintering performance of cement clinker by Burnability index calculation was identified. The lower the grade of limestone, the lower the grinding quality of the raw material combination. The lower the CaO content of limestone, the greater the variation in F-CaO for sintering temperature. The lower the class of limestone, the higher B. I. value was calculated, indicating the lower cement clinker sintering. In addition, the mineral analysis results of cement clinker showed that if the F-CaO value was low due to the increase in sintering temperature, the Belite content decreased and the Alite content increased. In the case of Alite, the ratio of R-type decreased and that of M-type increased as the content of limestone CaO increased.

Applied-Mineralogical Characterization and Assessment of Some Domestic Bentonites (I): Mineral Composition and Characteristics, Cation Exchange Properties, and Their Relationships (국내산 벤토나이트에 대한 응용광물학적 특성 평가 (I): 광물 조성 및 특징과 양이온 교환특성과의 연계성)

  • 노진환
    • Journal of the Mineralogical Society of Korea
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    • v.15 no.4
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    • pp.329-344
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    • 2002
  • Mineralogical and chemical characterization of some domestic bentonites, such as quantitative XRD analysis, chemical leaching experiments, pH and CEC determinations, were done without any separation procedures to understand their relationships among mineral composition, characteristics, and cation exchange properties. XRD quantification results based on Rietveld method reveal that the bentonites contain totally more than 25 wt% of impurities, such as zeolites, opal-CT, and feldspars, in addition to montmorillonite ranging 30~75 wt%. Cation exchange properties of the zeolitic bentonites are deeply affected by the content of zeolites identified as clinoptilolite-heulandite series. Clinoptilolite is common in the silicic bentonites with lighter color. and occurs closely in association with opal-CT. Ca is mostly the dominant exchangeable cation, but some zeolitic bentonites have K as a major exchangeable cation, The values of cation exchange capacity (CEC) determined by Methylene Blue method are comparatively low and have roughly a linear relationship with the montmorillonite content of the bentonite, though the correlated data tend to be rather dispersed. Compared to this, the CEC determined by Ammonium Acetate method, i.e.‘Total CEC’, has much higher values (50~115 meq/100 g). The differences between those CEC values are much greater in zeolitic bentonites, which obviously indicates the CEC increase affected by zeolite. Other impurities such as opal-CT and feldspars seem to affect insignificantly on the CEC of bentonites. When dispersed in distilled water, the pH of bentonites roughly tends to increase up to 9.3 with increasing the alkali abundance, especially Na, in exchangeable cation composition. However, some bentonites exhibit lower pH (5~6) so as to regard as ‘acid clay’. This may be due to the presence of $H^{+}$ in part as an exchangeable cation in the layer site of montmorillonite. All the works of this study ultimately suggest that an assesment of domestic bentonites in grade and quality should be accomplished through the quantitative XRD analysis and the ‘Total CEC’measurement.