• 대한화학회지
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• 제61권1호
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• pp.29-33
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• 2017

Formation of Au particles in nonstoichiometric $Cu_{2-x}{^I}Cu{_2}^{II}O_{3-{\delta}}$ ($x{\approx}0.20$; ${\delta}{\approx}0.10$) oxide from aniline + hydrochloric acid mixtures and chloroauric acid in the ratios 30 : 1; 60 : 1; 90 : 1 (S1-S3) by volume and 0.01 mol of copper acetate, $Cu(OCOCH_3)_2.H_2O$, in each case is performed by sol-gel growth. Powder x-ray diffraction (XRD) results show Au particles are dispersed in tetragonal nonstoichiometric dicopper (I) dicopper (II) oxides, $Cu_{2-x}{^I}Cu{_2}^{II}O_{3-{\delta}}$ ($x{\approx}0.20$; ${\delta}{\approx}0.10$). Average crystallite sizes of Au particles determined using Scherrer equation are found to be in the approximate ranges ${\sim}85-140{\AA}$, ${\sim}85-150{\AA}$ and ${\sim}80-150{\AA}$ in S1-S3, respectively which indicate the formation of Au nano-micro size particles in $Cu_{2-x}{^I}Cu{_2}^{II}O_{3-{\delta}}$ ($x{\approx}0.20$; ${\delta}{\approx}0.10$) oxides. Hysteresis behaviour at 300 K having low loop areas and magnetic susceptibility values ${\sim}5.835{\times}10^{-6}-9.889{\times}10^{-6}emu/gG$ in S1-S3 show weakly ferromagnetic nature of the samples. Broad and isotropic electron paramagnetic resonance (EPR) lineshapes of S1-S4 at 300, 77 and 8 K having $g_{iso}$-values ${\sim}2.053{\pm}0.008-2.304{\pm}0.008$ show rapid spin-lattice relaxation process in magnetic $Cu^{2+}$ ($3d^9$) sites as well as delocalized electrons in Au ($6s^1$) nano-micro size particles in the $Cu_{2-x}{^I}Cu{_2}^{II}O_{3-{\delta}}$ ($x{\approx}0.20$; ${\delta}{\approx}0.10$) oxides. Broad and weak UV-Vis diffuse reflectance optical absorption band ~725 nm is assigned to $^2B_{1g}{\rightarrow}^2A_{1g}$ transitions, and the weak band ~470 nm is due to $^2B_{1g}{\rightarrow}^2E_g$ transitions from the ground state $^2B_{1g}$(${\mid}d_{x^2-y^2}$>) of $Cu^{2+}$ ($3d^9$) ions in octahedral coordination having tetragonal distortion.

• 대한화학회지
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• 제56권1호
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• pp.62-67
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• 2012

A series of homo binuclear complexs of the type $[M_2(L/L^')(NO_3)n].mH_2O$, [where $M=U{O_2}^{2+},\;Th^{4+},\;ZrO^{2+}$] and $[(VO)_2(L/L^')(SO_4)_2]{\cdot}2H_2O$, L=1,5,6,9,12,15,16,20 octaaza-7,813,14-tetraphenyl-2,4,17,19-tetramethyl-1,4,6,8,12,14,16,19-docosaoctene (OTTDO) or L'=10:11;21:22-dibenzo-1,5,6,9,12,15,16,20-octaaza-7,813,14-tetraphenyl-2,4,17,19-tetramethyl-1,4,6,8,12,14,16,19-docosaoctene (DOTTOT), n=4 for $U{O_2}^{2+}$, $ZrO^{2+}$ n=8 for $Th^{4+}$ m=1,2,3 respectively, have been synthesized in template method from ethylenediamine/orthophenylene diamine, benzil monohydrazone and acetyl acetone and characterized on the basis of elemental analysis, thermal analysis, molar conductivity, magnetic moment, electronic, infrared, $^1H$-NMR studies. The results indicate that the VO(IV) ion is penta co-ordinated yielding paramagnetic complexes; $UO_2(VI)$, ZrO(IV) ions are hexa co-ordinated where as Th(IV) ion is octa co-ordinated yielding diamagnetic complexes of above composition. The fungi toxicity of the ZrO(IV) and VO(IV) complexes against some fungal pathogen has been studied.

• 한국자기학회지
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• 제10권2호
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• pp.81-85
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• 2000

Orthoferrite LaFeO$_3$ 화합물에서 Fe 이온의 미량을 Mn 이온으로 치환시킨 시료인 LaFe$_{1-x}$Mn$_{x}$ O$_3$(0.0$\leq$x$\leq$0.4)을 제조하여 Mn 이온의 치환에 따른 결정학적 및 자기적 특성의 변화를 밝히기 위하여 x-선 회절기, M ssbauer 분광기, 진동자력계와 초전도 양자간섭계 등을 이용한 연구를 하였다. 제조한 시료는 모든 조성비 범위에서 단일상의 orthorhombic distorted perovskite 구조를 보였다. M ssbauer 스펙트럼은 상온에서 한 개의 육중선(x=0.0)에서 두 개의 육중선 세트(x=0.1, 0.2, 0.4)로 변했다. 특히 x=0.4에서는 상자성의 이중선과 육중선이 중첩된 모양을 보였다. 본 시료에서 Fe는 모두 Fe$^{3+}$ 상태로 팔면체자리에 위치함을 알았다. 또 LaFe$_{1-x}$Mn$_{x}$ O$_3$에서 Mn의 양이 증가함에 따라 포화자화 값은 증가하지만 보자력은 감소함을 알아냈다.

• Korean Chemical Engineering Research
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• 제44권4호
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• pp.369-374
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• 2006

$V_2O_5$와 AlMCM-48을 고체상에서 반응시킨 후 소성하면 메조포러스 물질 내에서 V(V) 화학종이 아주 약하게 나타난다. 그러나 환원 과정을 거치면 EPR로 조사할 수 있는 바나딜 $VO^{2+}$ 화학종이 생성된다. $VO^{2+}-AlMCM-48$에 들어있는 바나듐의 화학적 환경을 XRD, EDX, UV-Vis, EPR, $^{29}Si$ and $^{27}Al$ and $^{51}V$ NMR로 조사하였다. 탈수하거나 CO 로 환원하면 바나듐은 MCM-48에 유사 사면체형 $VO^{2+}$ 바나딜 이온 상태로 존재하며 물이 배위되면 찌그러진 팔면체구조로 바뀐다.

• 한국자기학회지
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• 제15권2호
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• pp.106-108
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• 2005

The rutile polycrystal $Ti_{0.99}\;^{57}Fe_{0.01}O_2$ prepared with $^{57}Fe$ enriched iron have been studied by $M\ddot{o}ssbauer$ spectroscopy, X-ray diffraction and VSM. The $M\ddot{o}ssbauer$ spectrum of $Ti_{0.99}\;^{57}Fe_{0.01}O_2$ consists of a ferromagnetic and a paramagnetic phase over all temperature ranging from 4 to 300 K. Isomer shifts indicate $Fe^{2+}$ for the ferromagnetic phase, but $Fe^{3+}$ for the paramagneic phase of $Ti_{0.99}\;^{57}Fe_{0.01}O_2$ sample. It is noted that the magnetic hyperfine field of ferromagnetic phase had the value about 1.48 times as large as that of $\alpha$-Fe. The XRD data for $Ti_{0.99}\;^{57}Fe_{0.01}O_2$ showed a pure rutile phase with tetragonal structures without any segregation of Fe into particulates within the instrumental resolution limit The magnetic hysteresis (M-H) curve at room temperature showed an obvious ferromagnetic behavior and the magnetic moment per Fe atom under the applied field of 1 T was estimated to be about $0.71{\mu}_B$, suggesting a low spin configuration of Fe ions.

• 한국자기학회지
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• 제20권6호
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• pp.216-221
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• 2010

본 연구에서는 dimethylacetamide(DMAc)와 toluen을 용매로 사용하여 만들어진 양친매성 urethan acrylate nonionomer(UAN) 선구고리를 기초로 하는 양친매성 고분자 망상구조 복합체에 철산화물을 주입시킨 나노복합체의 구조와 자기적성질 그리고 나노복합체에 존재하는 Fe 이온의 원자가 상태를 알아보기 위하여 전계방출주사전자현미경(FESEM)과 X-ray diffraction 그리고 Mossbauer spectrum을 측정하였다. 결과로부터 나노복합체 시료 내에 존재하는 모든 Fe이온은 $Fe^{3+}$의 상태로 존재하고 $Fe_2O_3$의 결정구조를 갖고 있음을 알 수 있으며, 시료 내에 철산화물 나노복합체가 형성되어 있음을 알 수 있었다. 그리고 urethan acrylate nonionomer(UAN) 선구 고리를 기초로 하는 양친매성 고분자 망상구조 복합체를 형성시키는 경우 용매로 DMAc를 이용하는 경우가 toluen을 이용한 경우 보다 더 미세한 나노구조를 형성함을 알 수 있으며, 시료들의 자기적 성질이 상온에서 상자성을 나타내는 것은 나노크기의 단일자구형성에 따른 초상자성효과에 의한 것임을 알 수 있었다.

• 한국자기학회지
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• 제16권1호
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• pp.11-13
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• 2006

[ $M\"{o}ssbauer$ ] spectra of $Ti_{1-x-y}Co_xFe_yO_2(0.01{\leq}x,\;y{\leq}0.05)$ prepared with $^{57}Fe$ enriched iron have been taken at various temperatures ranging from 80 to 300K. The Mossbauer spectrum of $Ti0.94Co_{0.03}Fe_{0.03}O_2$ consists of a ferromagnetic (six-Lorentzian), a paramagnetic phase (doublet) and armorphous phase over all temperature ranges. Isomer shifts indicate $Fe^{3+}$ for the ferromagnetic phase and the paramagneic phase of $Ti_{1-x-y}Co_xFe_yO_2$ samples. It is noted that the magnetic hyperfine field of ferromagnetic phase had the value about 1.5 times as large as that of u-fe. The XRB data for $Ti_{1-x-y}Co_xFe_yO_2$ showed mainly rutile phase with tetragonal structures without any segregation of Co and Fe into particulates within the instrumental resolution limit. The magnetic moment per (Co+Fe) atom in $Ti0.94Co_{0.03}Fe_{0.03}O_2$, under the applied field of 1T was estimated to be about $0.332{\mu}_B$ which is ten times as large as that of $Ti0.97Co_{0.03}Fe_{0.03}O_2,\;0.024{\mu}_B$ per Co atom, suggesting a high spin configuration of Co and fe ions.

• Journal of Magnetics
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• 제10권1호
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• pp.5-9
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• 2005

Nanoparticles $Ni_{0.9}Zn_{0.1}Fe_2O_4$ is fabricated by a sol-gel method. The magnetic and structural properties of powders were investigated with XRD, SEM, Mossbauer spectroscopy, and VSM. $Ni_{0.9}Zn_{0.1}Fe_2O_4$ powders annealed at $300{^{\circ}C}$ have a spinel structure and behaved superparamagnetically. The estimated size of $Ni_{0.9}Zn_{0.1}Fe_2O_4$ nanoparticle is about 10 nm. The hyperfine fields at 13 K for the A and B patterns are found to be 533 and 507 kOe, respectively. The ZFC curves are rounded at the blocking temperature ($T_B$)and show a paramagnetic-like behavior above $T_B$. $T_B$ of $Ni_{0.9}Zn_{0.1}Fe_2O_4$ nanoparticle is about 250 K. Nanoparticles $Ni_{0.9}Zn_{0.1}Fe_2O_4$ annealed at 400 and $500{^{\circ}C}$ have a typical spinel structure and is ferrimagnetic in nature. The isomer shifts indicate that the iron ions were ferric at the tetrahedral (A) and the octahedral (B). The saturation magnetization of nanoparticles $Ni_{0.9}Zn_{0.1}Fe_2O_4$ annealed at 400 and $500{^{\circ}C}$ are 40 and 43 emu/g, respectively. The magnetic anisotropy constant of $Ni_{0.9}Zn_{0.1}Fe_2O_4$ annealed at $300{^{\circ}C}$ were calculated to be 1.6 ${\times}$ $10^6$ ergs/$cm^3$.

• Journal of Magnetics
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• 제18권1호
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• pp.21-25
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• 2013

Nickel substituted manganese ferrites, $Mn_{1-x}Ni_xFe_2O_4$ ($0.0{\leq}x{\leq}0.6$), were fabricated by sol-gel method. The effects of sintering and substitution on their crystallographic and magnetic properties were studied. X-ray diffractometry of $Mn_{0.6}Ni_{0.4}Fe_2O_4$ ferrite sintered above 523 K indicated a spinel structure; particles increased in size with hotter sintering. The M$\ddot{o}$ssbauer spectrum of this ferrite sintered at 523 K could be fitted as a single quadrupole doublet, indicative of a superparamagnetic phase. Sintering at 573 K led to spectrum fitted as the superposition of two Zeeman sextets and a single quadrupole doublet, indicating both ferrimagnetic and paramagnetic phase. Sintering at 673 K and at 773 K led to spectra fitted as two Zeeman sextets due to a ferrimagnetic phase. The saturation magnetization and the coercivity of $Mn_{0.6}Ni_{0.4}Fe_2O_4$ ferrite sintered at 773 K were 53.05 emu/g and 142.08 Oe. In $Mn_{1-x}Ni_xFe_2O_4$ ($0.0{\leq}x{\leq}0.6$) ferrites, sintering of any composition at 773 K led to a single spinel structure. Increased Ni substitution decreased the ferrites' lattice constants and increased their particle sizes. The M$\ddot{o}$ssbauer spectra could be fitted as the superposition of two Zeeman sextets due to the tetrahedral and the octahedral sites of the $Fe^{3+}$ ions. The variations of saturation magnetization and coercivity with changing Ni content could be explained using the changes of particle size.

• Journal of Magnetics
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• 제21권3호
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• pp.308-314
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• 2016

Cobalt-, zinc-, and nickel-zinc-substituted nano-size manganese ferrite powders, $MnFe_2O_4$, $Mn_{0.8}Co_{0.2}Fe_2O_4$, $Mn_{0.8}Zn_{0.2}Fe_2O_4$ and $Mn_{0.8}Ni_{0.1}Zn_{0.1}Fe_2O_4$, were fabricated using a sol-gel method, and their crystallographic and magnetic properties were subsequently studied. The $MnFe_2O_4$ ferrite powder annealed at temperatures above 523 K exhibited a spinel structure, and the particle size increased as the annealing temperature increased. All ferrites annealed at 773 K showed a single spinel structure, and the lattice constants and particle size decreased with the substitution of Co, Zn, and Ni-Zn. The $M{\ddot{o}}ssbauer$ spectrum of the $MnFe_2O_4$ ferrite powder annealed at 523 K only showed a doublet due to its superparamagnetic phase, and the $M{\ddot{o}}ssbauer$ spectra of the $MnFe_2O_4$, $Mn_{0.8}Co_{0.2}Fe_2O_4$, and $Mn_{0.8}Zn_{0.2}Fe_2O_4$ ferrite powders annealed at 773 K could be fitted as the superposition of two Zeeman sextets due to the tetrahedral and octahedral sites of the $Fe^{3+}$ ions. However, the $M{\ddot{o}}ssbauer$ spectrum of the $Mn_{0.8}Ni_{0.1}Zn_{0.1}Fe_2O_4$ ferrite powder annealed at 773 K consisted of two Zeeman sextets and one quadrupole doublet due to its ferrimagnetic and paramagnetic behavior. The area ratio of the $M{\ddot{o}}ssbauer$ spectra could be used to determine the cation distribution equation, and we also explained the variation in the $M{\ddot{o}}ssbauer$ parameters by using this cation distribution equation, the superexchange interaction and the particle size. Relative to pure $MnFe_2O_4$, the saturation magnetizations and coercivities were larger in $Mn_{0.8}Co_{0.2}Fe_2O_4$ and smaller in $Mn_{0.8}Zn_{0.2}Fe_2O_4$, and $Mn_{0.8}Ni_{0.1}Zn_{0.1}Fe_2O_4$. These variations could be explained using the site distribution equations, particle sizes and magnetic moments of the substituted ions.