• Bulletin of the Korean Chemical Society
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• 제17권5호
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• pp.424-428
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• 1996

TlCl2(TCNQ)2.5 and Tl(TCNQ)3 were obtained from the reaction of LiTCNQ (TCNQ=tetracyanoquinodimethane) and TlX3 (X=Cl and NO3). These compounds were characterized by spectroscopic(IR, UV, EPR), electrochemical methods, and electrical conductivity measurements. Thermal analysis (TG, DSC) was also conducted. The room temperature electrical conductivities of these compounds are in the range of semiconductors. Spectroscopic studies indicate that Tl(TCNQ)3 has fully ionized TCNQ- ions in a form of simple salt, whereas TlCl2(TCNQ)2.5 is consisted of TCNQ- and TCNQ0 as a complex salt. EPR values of TCNQ- radical anion are 1.999 in both compounds and the signal attributable to metal ion is not observed, suggesting that any unpaired electrons are localized on TCNQ radicals, and metal atoms have diamagnetic state. Ligand decomposition and reduction process are simultaneously progressed in both compounds above at 200 ℃. The endothermic activation energy of TlCl2(TCNQ)2.5 is shown somewhat larger than that of Tl(TCNQ)3, it may be due to Tl-Cl bond strength. The mid-peak potentials of these compounds are very similar to those of TCNQ and the values of Epa and Epc are almost equal to 1. The wave of thallium ion is not detected in cyclic voltammogram, hence the redox processes of the complexes might be mainly localized to the TCNQ ligand rather than thallium ion.

• Bulletin of the Korean Chemical Society
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• 제15권6호
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• pp.432-436
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• 1994

Monomeric rhodium and iridium-diaryltetrazene complexes $Cp^*$M(RNN=NNR)($Cp^*$=1,2,3,4,5-pentamethylcyclope ntadienyl; M=Rh, Ir; R=Ph, 4-tolyl) have been synthesized from [$Cp^*MCl_2]_2$(M=Rh, Ir) and 2 equiv. of $[Li(THF)_x]_2(RN_4$R) in benzene. We have determined the crystal structure of (${\eta}^5$-pentamethylcyclopentadienyl)diphenyltetrazene iridium by using graphite-monochromated Mo-$K_a$ radiation. The compound was crystallized in the monoclinic space group $P2_{1/c}$ with a=13.781(3), b=9.035(l), c=17.699(3) ${\AA}$, and ${\beta}=111.93(l)^{\circ}$. An X-ray crystal structure of complex 1 showed a short N(2)-N(3) distance ($1.265 {\AA}$) consistent with the valence tautomer A with Ir(III) rather than Ir(I). All complexes are highly colored and decompose on irradiation at 254 nm. Electrochemical studies show that complex 1 displays a quasi-reversible reduction.

• Corrosion Science and Technology
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• 제20권5호
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• pp.315-323
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• 2021

In this study, we examined corrosion behaviors of two types of Pb alloys for a lead acid battery comparatively. One containing 6.6 wt% Sn, 36 mg/kg Bi, and 612.4 mg/kg Ca was prepared by twin-roll continuous casting. The other containing 5.2 wt% Sn, 30.5 mg/kg Ag, and 557 mg/kg Ca was made by twin-belt continuous casting. Potentiodynamic polarization tests were performed to evaluate corrosion resistance. Cyclic voltammetry was done to examine oxidation and reduction reactions occurring on the surface of each alloy in 4.8 M H₂SO₄ solution. Electrochemical test results implied that the Pb alloy prepared with the twin-belt casting method was less stable than that cast with the twin-roll method. Such results might be due to precipitations formed during the casting process. Rolling did not appear to affect the corrosion behavior of the twin-roll samples with Ag < 10 mg/kg, while it reduced the anodic reaction of Ag on the surface of the twin-belt sample with 30.5 mg/kg Ag.

• Corrosion Science and Technology
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• 제20권5호
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• pp.266-280
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• 2021

Since 2020, the International Maritime Organization (IMO) has updated regulations on the sulfur content to be less than 0.5% in exhaust gas emitted from ships. Accordingly, the exhaust gas post-treatment device for ships, which is SOx/NOx reduction technology, was introduced. However, the exhaust gas post-treatment device is suffering corrosion because of the harsh corrosive environment formed by sulfate and chlorine oxide through the desulfurization process. In this investigation, cyclic potentiodynamic polarization (CPDP) experiment for UNS S31603 and UNS N08367 was performed in a green death solution that simulates the environment of a desulfurization device. The corrosion rate of UNS S31603 at the highest temperature was about 3 times higher than that of UNS N83067. Also, electron microscope scan revealed corrosion type UNS N83067 presents intergranular corrosion tendency. On the other hand, UNS S31603 was observed as general corrosion. The α values of UNS N08367 at 30 ℃ and 60 ℃ were higher than those of UNS S31603, thus UNS N08367 is considered to have a higher local damage tendency. Whereas, since the α value of UNS S31603 at 90 ℃ is larger than that of UNS N08367, UNS S31603 is considered to have a higher local damage trend.

• 대한금속재료학회지
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• 제46권10호
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• pp.652-661
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• 2008

Reduction of NOx in emission gas, improvement of engine efficiency, and extension of warranty period has made demands for developing materials more corrosively resistant to the inner-muffler environments or predicting the lifetime of materials used in muffler more precisely. The corrosion inside muffler has been explained with condensate corrosion mainly though thermal oxidation experiences prior to condensate corrosion. Hence, the aim of this study is to describe how the thermal oxidation affects the corrosion of stainless steel exposed to the inner-muffler environments. Auger electron spectroscopy and electrochemical tests were employed to analyze oxide scale and to evaluate corrosion resistance, respectively. Thermal oxidation has different role of condensate corrosion depending on the temperature: inhibiting condensate corrosion below $380^{\circ}C$ and enhancing condensate corrosion above $380^{\circ}C$. The low temperature oxidation causes to form compact oxide layer functioning a barrier for penetrating condensate into a matrix. Although though thermal oxidation caused chromium-depleted layer between oxide layer and matrix, the enhancement of the condensate corrosion in high temperature oxidation resulted from corrosion-induced crevice formed by oxide scale rather than corrosion in chromium-depleted layer. It was proved by aids of anodic polarization tests and measurements of pitting corrosion potentials. By the study, the role of high temperature oxidation layer affecting the condensate corrosion of stainless steels used as muffler materials was well understood.

• 한국표면공학회지
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• 제53권6호
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• pp.312-321
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• 2020

Morphology of porous cobalt electro-deposits was systematically investigated as functions of cobalt precursors in the plating bath and applied cathodic current density with a special focus on cobalt nano-rod formation. It was proved that the concentration of cobalt precursor plays little effect on the morphology of cobalt electro-deposits at relatively low plating current density while it significantly affects the morphology with increasing plating current density. Such a dependence was discussed in terms of the kinetics of two competitive reactions of cobalt reduction and hydrogen evolution. Cobalt nano-rod structure was created at specific ranges of cobalt precursor content and applied cathodic current density, and its diameter and length varied with plating time without notable formation of side branches which is usually found during dendrite formation. Specifically, the nano-rod length was preferentially increased in relative short plating time (<15 s), resulting in higher aspect ratio of nano-rod with plating time. Whereas, both the nano-rod length and diameter were increased nearly at the same level in a prolonged plating time, making the aspect ratio unchanged. From the analysis of crystal structure, it was confirmed that the cobalt nano-rod preferentially grew in the form of single crystal on a dense poly-crystalline cobalt thin film initially formed on the substrate.

• 방사성폐기물학회지
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• 제21권1호
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• pp.9-22
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• 2023

Spin-off pyroprocessing technology and inert anode materials to replace the conventional carbon-based smelting process for critical materials were introduced. Efforts to select inert anode materials through numerical analysis and selected experimental results were devised for the high-throughput reduction of oxide feedstocks. The electrochemical properties of the inert anode material were evaluated, and stable electrolysis behavior and CaCu generation were observed during molten salt recycling. Thereafter, CuTi was prepared by reacting rutile (TiO₂) with CaCu in a Ti crucible. The formation of CuTi was confirmed when the concentration of CaO in the molten salt was controlled at 7.5mol%. A laboratory-scale electrorefining study was conducted using CuTi(Zr, Hf) alloys as the anodes, with a Ti electrodeposit conforming to the ASTM B299 standard recovered using a pilot-scale electrorefining device.

• 한국표면공학회지
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• 제56권5호
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• pp.320-327
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• 2023

In this study, the nickel hydroxide (Ni(OH)₂) electrode for supercapacitor was prepared via hydrothermal method. Based on the nickel (Ni) foam, the electrode does not require any additional binder material or post-processing. Nickel nitrate (Ni(NO₃)₂) and hexamethylenetetramine (C₆H₁₂N₄) were used for synthesis, and the synthesis condition was 12 hours at 80 ℃. X-ray diffraction (XRD) and field-emission scanning electron microscopy (FE-SEM) were used to analyze the structural characteristics of the electrode, and it shown that the nickel hydroxide was successfully prepared after only the one-step hydrothermal synthesis. The electrochemical properties were analyzed through the half-cell test. The prepared electrode shown a pair of oxidation/reduction peaks, indicating that the driving method included the redox reaction on the electrode surface. After the charge/discharge test, the specific capacitance was calculated as the value of 438 F/g at 3 A/g.

• 청정기술
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• 제24권1호
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• pp.77-84
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• 2018

리튬이온전지의 음극활물질로 사용되는 $Li_4Ti_5O_{12}$를 건식 볼밀법으로 합성하였고, $Li_4Ti_5O_{12}$의 전기화학적 특성을 향상시키기 위하여 탄소소재인 polyvinyl chloride (PVC)를 첨가하였다. PVC는 $Li_4Ti_5O_{12}$를 합성하고 난 후에 첨가하였을 때 스피넬 구조를 갖는 물질이 잘 합성되었음을 X-ray diffraction (XRD) 실험으로 확인하였다. 합성하기 전에 탄소재를 첨가하여 열처리를 한 경우에는 탄소재가 미량 첨가되더라도 다른 결정구조의 물질이 합성되는 것을 확인할 수 있었다. 탄소재를 첨가하지 않은 $Li_4Ti_5O_{12}$의 경우 전기전도도 값이 약 $10{\mu}S\;m^{-1}$으로 부도체에 가까운 매우 작은 값을 보였다. 탄소를 첨가함에 따라서 전기전도도가 크게 향상되었으며, 압력을 증가시킬 경우에 최대 10,000배 이상 증가되었다. Electrochemical impedance spectroscopy (EIS) 분석결과 탄소를 첨가할 경우 저항에 해당하는 반원의 크기가 감소하였으며, 이는 전극내의 저항이 감소하였음을 보여준다. Cyclic voltammetry (CV) 분석에 의하면 탄소를 첨가할 경우에 산화피크와 환원피크의 전위차가 줄어 들었으며, 이는 리튬이온의 삽입과 탈리의 속도가 증가하였음을 의미한다. PVC를 9.5 wt% 첨가한 물질의 경우, 0.2 C-rate에서 $180mA\;h\;g^{-1}$, 0.5 C-rate에서 $165mA\;h\;g^{-1}$, 5C-rate에서 $95.8mA\;h\;g^{-1}$의 용량을 나타냄으로써 우수한 출력 특성을 보여주었다.

• 마이크로전자및패키징학회지
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• 제31권2호
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• pp.54-62
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• 2024

SICM (scanning ion conductivity microscopy)은 nanopipette이 시료에 접근하게 되면서 tip에 인가되는 전류값의 변화가 발생하는데, 이를 이용하여 시료의 표면 형상을 측정하는 분석기술이다. 본 연구는 SICM mapping의 기본이 되는 tip과 시료 간의 거리에 의한 전류 반응곡선인 approach curve에 대해 연구한 결과를 담고 있다. Approach curve에 대해 우선 시뮬레이션 해석을 진행하였으며, 이를 기반으로 실험을 병행하여 이 둘 사이의 반응 곡선 차이를 분석하였다. 시뮬레이션 해석을 통해 tip과 시료와의 거리가 tip 내경의 절반 이하로 가까워지면서 current squeezing 효과를 확인할 수 있었다. 하지만, 시뮬레이션에 반영된 단순 이온 통로 감소에 의한 전류밀도 감소는 실제 실험을 통해 측정된 current squeezing 효과에 비해 훨씬 작은 것으로 측정되었다. 이는 나노 스케일의 매우 좁은 통로에서 이온전도도는 확산계수에 의한 단순 Nernst-Einstein 관계를 따르는 것이 아니라, tip과 시료가 만들어 내는 벽면에서의 유체역학적 유동 저항성을 고려하는 것이 추가로 필요할 것으로 보인다. 향후 이러한 SICM 측정은 전기화학 표면 반응성을 분석하는 SECM (scanning electrochemical microscopy) 측정기술과 통합되어 SECM 측정 한계를 보완될 수 있을 것으로 기대된다. 그렇게 되면, 반도체 배선 공정 및 패키징 공정에 사용되고 있는 다양한 패턴 형상에서 무전해 도금의 촉매 반응과 전기도금에서 유기첨가제 작용의 국부적 차이를 직접적으로 측정하는 것이 가능하게 될 것으로 기대된다.