• Corrosion Science and Technology
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• 제22권3호
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• pp.137-152
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• 2023

Polarization behavior and corrosion inhibition of copper in acidic chloride solutions containing benzotriazole were studied. Pourbaix diagrams constructed for copper in NaCl solutions with different BTAH concentrations were used to understand the polarization behavior. Open circuit potential (OCP) depended not only on chloride concentration, but also on whether a CuBTA layer was formed on the copper surface. Only when the (pH, OCP) was located well in the CuBTA region of the Pourbaix diagram, a stable corrosion inhibiting CuBTA layer was formed, which was confirmed by X-ray Photoelectron Spectroscopy (XPS) and a long-term corrosion test. The OCP for the CuBTA layer decreased logarithmically with increasing [Cl^-] activity in the solution. A minimum BTAH concentration required to form a CuBTA layer for a given NaCl concentration and pH were determined from the Pourbaix diagram. It was found that 320 ppm BTAH solution could be used to form a corrosion-inhibiting CuBTA layer inside the corrosion pit in the sprinkler copper tube, successfully reducing water leakage rate of copper tubes. These experimental results could be used to estimate water chemistry inside a corrosion pit.

• 자원리싸이클링
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• 제21권6호
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• pp.74-81
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• 2012

온도에 따른 Pourbaix Diagram 을 열역학 계산에 의해 구성하여 수용액 상 은의 회수반응에 미치는 온도의 영향을 파악하였다. 온도의 상승에 따라 물의 안정성은 pH 변화에 대해 더 크게 영향을 받으며 ${Ag^+}_{(aq)}$의 안정영역은 감소하는 것으로 나타났다. 온도가 하강함에 따라 $Ag_{(aq)}$를 $Ag_{(s)}$ 및 $Ag_2O_{3(s)}$ 형태로 회수하고 온도 상승 시에는 $Ag_{(aq)}$를 $Ag_2O_{(s)}$ 및 $Ag_2O_{2(s)}$의 형태로 회수하는 것이 화학반응상 보다 유리할 것으로 고찰되었다. $pH{\leq}2$ 이하의 강산성 영역에서는 온도 상승에 따른 은 회수 효율성이 감소하고 pH가 2 이상인 조건에서는 온도 증가에 따라 은의 회수 효율성이 증대될 것으로 파악되었다. 또한, 은을 원소 상태로 회수하는 방안은 산화은 형태로 회수하는 방안에 비해 온도변화에 대해 더욱 민감하게 영향을 받는 것으로 고려되었다.

• 한국물환경학회지
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• 제29권2호
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• pp.176-183
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• 2013

The variation of the stable region of arsenic compounds in aqueous environment with temperature has been investigated by constructing the Pourbaix diagram of arsenic at different temperatures. The standard potential corresponding to the boundary between arsenic compounds with different charge valence was estimated to be decreased with temperature, which means the stability of arsenic compound with +5 charge valence increases. The distribution diagram of the most highly oxidized arsenic compound showed that arsenic acid is formed at higher pH and arsenate is generated at lower pH as temperature rises. The aquatic toxicity due to arsenic compounds was considered to be decreased with temperature in the neutral pH condition based on the $LD_T$ value defined in this study.

• 한국재료학회지
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• 제16권2호
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• pp.80-84
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• 2006

The removal efficiency of Cu and Fe contaminants on the silicon wafer surface was examined to investigate the effect of cleaning solutions on the behavior of metallic impurities. Silicon wafers were intentionally contaminated with Cu and Fe solutions by spin coating and cleaned in different types of cleaning solutions based on $NH_4OH/H_2O_2/H_2O\;(SC1),\;H_2O_2/HCl/H_2O$ (SC2), and/or HCl/$H_2O$ (m-SC2) mixtures. The concentration of metallic contaminants on the silicon wafer surface before and after cleaning was analyzed by vapor phase decomposition/inductively coupled plasma-mass spectrometry (VPD/ICP-MS). Cu ions were effectively removed both in alkali (SC1) and in acid (SC2) based solutions. When $H_2O_2$ was not added to SC2 solution like m-SC2, the removal efficiency of Cu impurities was decreased drastically. The efficiency of Cu ions in SC1 was not changed by increasing cleaning temperature. Fe ions were soluble only in acid solution like SC2 or m-SC2 solution. The removal efficiencies of Fe ions in acid solutions were enhanced by increasing cleaning temperature. It is found that the behavior of metallic contaminants as Cu and Fe from silicon surfaces in cleaning solutions could be explained in terms of Pourbaix diagram.

• 한국물환경학회지
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• 제30권2호
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• pp.175-183
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• 2014

The influence of temperature on the treatment efficiency of chlorinated organic substances contained in groundwater by permeable reactive barrier which is composed of $Fe^{\circ}$ has been investigated by constructing the Pourbaix diagrams for Fe-$H_2O$ system at different temperatures based on thermodynamic estimation. In aerobic condition, the equilibrium potentials for $Fe^{\circ}/Fe^{2+}$ and $Fe^{2+}/Fe^{3+}$ were observed to increase, therefore, the dechlorination reaction for organic pollutants by $Fe^{\circ}$ was considered to decline with temperature due to the diminished oxidation of reactive barrier. The result for the variations of the ionization fraction of $Fe^{2+}$ and $Fe^{3+}$ ion in the pH range of 0 ~ 2.5 obtained by employing Visual MINTEQ program showed that the ionization fraction of $Fe^{2+}$ increased with pH, however, that of $Fe^{3+}$ decreased symmetrically and the extent of the variation of ionization fraction for both ions was raised as temperature rises. The equilibrium pH for $Fe^{3+}/Fe(OH)_3$ was examined to decrease with temperature so that the treatment efficiency of chlorinated organic substance was expected to decrease with temperature due to the enhanced formation of passivating film in aerobic condition. The change of the reactivity of a specific chemical species with temperature was defined quantitatively based on the area of its stable region in Pourbaix diagram and depending on this the reactivity of $Fe^{3+}$ was shown to decrease with temperature, however, that of $Fe(OH)_3$ was decreased monotonously as temperature is raised for $Fe^{3+}/Fe(OH)_3$ equilibrium system. In anaerobic condition, the equilibrium potential for $Fe^{\circ}/Fe^{2+}$ was observed to rise and the equilibrium pH for $Fe^{2+}/Fe(OH)_2$ were examined to decrease as temperature increases, therefore, similar to that for aerobic condition the efficiency of the dechlorination reaction for organic substances was considered to be diminished when temperature rises because of the reduced oxidation of $Fe^{\circ}$ and increased formation of $Fe(OH)_2$ passivating film.

• Transactions on Electrical and Electronic Materials
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• 제7권3호
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• pp.108-111
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• 2006

The oxidizer-induced corrosion state and microstructure of surface passive metal-oxide layer greatly influenced on the removal rate of tungsten film according to the slurry chemical composition of different mixed oxidizers. In this paper, the actual polishing mechanism and pH-potential equilibrium diagram obtained from potentiodynamic polarization curve were electrochemically compared. An electrochemical corrosion effect implies that slurries with the highest removal rate (RR) have the high dissolution rate.

• 한국표면공학회지
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• 제35권2호
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• pp.93-100
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• 2002

To better understand the codeposition mechanism of phosphorous, surface pH and potential of cathode were measured during electrodeposition of Ni-P alloys. The pH of cathode surface was measured using a flat-bottom glass pH electrode and a 500 mesh gold gauze as cathode. The cathode surface pH was increased with increasing the current density and always higher than the pH in the bulk solution. As a result of overplotting the surface pH and cathode potential on the Pourbaix diagram, it was found that cathode surface shift to the domain of predominant of $H_2$$PO3$-or $H_2$$PO_2$-. Additionally, new deposition mechanism was suggested that $H_2$ $PO_2$- and $H_2$$PO_3$- play important roles in the deposition reaction of Ni-P alloys.

• 한국분말재료학회지
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• 제28권1호
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• pp.25-30
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• 2021

The surface of silicon dummy wafers is contaminated with metallic impurities owing to the reaction with and adhesion of chemicals during the oxidation process. These metallic impurities negatively affect the device performance, reliability, and yield. To solve this problem, a wafer-cleaning process that removes metallic impurities is essential. RCA (Radio Corporation of America) cleaning is commonly used, but there are problems such as increased surface roughness and formation of metal hydroxides. Herein, we attempt to use a chelating agent (EDTA) to reduce the surface roughness, improve the stability of cleaning solutions, and prevent the re-adsorption of impurities. The bonding between the cleaning solution and metal powder is analyzed by referring to the Pourbaix diagram. The changes in the ionic conductivity, H2O2 decomposition behavior, and degree of dissolution are checked with a conductivity meter, and the changes in the absorbance and particle size before and after the reaction are confirmed by ultraviolet-visible spectroscopy (UV-vis) and dynamic light scattering (DLS) analyses. Thus, the addition of a chelating agent prevents the decomposition of H2O2 and improves the life of the silicon wafer cleaning solution, allowing it to react smoothly with metallic impurities.

• 한국표면공학회지
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• 제50권1호
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• pp.46-54
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• 2017

Marcel Pourbaix에 의해 만들어진 Eh-pH 도표는 화학적으로 안정한 상을 pH와 전위 (Potential or Eh)의 관점으로 도시한 것으로서 수용액 내에서 일어나는 화학반응을 부식-방식의 관점에서 이해하데 유용하게 사용되어 왔다. pH (potential of hydrogen)는 수소이온의 농도의 함수이며, Eh는 표준수소전극 (SHE, standard hydrogen electrode) 에 대한 전위를 나타낸다. 수용액에서의 도금 반응은 부식반응의 역반응이라 할 수 있으므로 도금반응도 이 도표를 이용하면 반응에 대한 열역학적 예측이 가능하다. 국내외 전기화학 및 표면공학 관련 교재들을 보면 Eh-pH 도표로 대표되는 열역학이나 분극곡선으로 대표되는 속도론에 대한 설명은 주로 부식의 관점에서 설명이 되어있어 도금을 공부하는 학생들에게는 직접적인 이해가 쉽지 않은 것이 사실이다. 저자는 출연연구소에 근무하면서 새로 들어오는 학연생(대학원생)들의 Eh-pH 도표에 대한 이해도를 알아보면 이 도표를 이해하고 이용할 줄 아는 학생이 거의 없다는 점을 안타깝게 여겨왔다. 최근에는 단순한 금속 도금이 아니라 나노 분말 합성, 반도체 물질 합성 등 여러 가지 공정기술과 응용기술이 수용액에서의 산화-환원 반응을 이용하고 있기 때문에 Eh-pH 도표의 중요성은 더해가고 있음을 느끼고 있었다. 그러던 중, 일본의 표면 처리 학술지인 표면기술(表面技術) (2013년, 64권 2호)에 'Eh-pH 도표의 표면기술에의 응용'이라는 제하의 소특집이 발간되었다. 이 소특집은 6편의 논문으로 되어 있었다. 저자는 이 소특집을 읽는 순간 이 논문들을 번역하여 표면공학회지에 소개를 하면 도금이나 전기화학을 공부하는 학생들에게 큰 도움이 될 것이라는 생각을 하였다. 본 기술해설 논문은 저자가 이 소특집에 게재된 논문을 번역하고 일부 내용은 저자의 의견으로 가감하여 표면공학회 학생 회원 및 기업의 연구원들에게 소개하기 위하여 저역을 한 것이다. 이 논문은 매 호 한편씩 소개할 예정이며, 원문을 읽고 싶다면 표면기술(表面技術)을 참조하길 바란다.

• Nuclear Engineering and Technology
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• 제42권5호
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• pp.552-561
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• 2010

This study investigates the solubility of neptunium (Np) in the deep natural groundwater of the Korea Atomic Energy Research Institute Underground Research Tunnel (KURT). According to a Pourbaix diagram (pH-$E_h$ diagram) that was calculated using the geochemical modeling program PHREEQC 2.0, the redox potential and the carbonate ion concentration both control the solubility of neptunium. The carbonate effect becomes pronounced when the total carbonate concentration is higher than $1.5\;{\times}\;10^{-2}$ M at $E_h$ = -200 mV and the pH value is 10. Given the assumption that the solubility-limiting stable solid phase is $Np(OH)_4(am)$ under the reducing condition relevant to KURT, the soluble neptunium concentrations were in the range of $1\;{\times}\;10^{-9}$ M to $3\;{\times}\;10^{-9}$ M under natural groundwater conditions. However, the solubility of neptunium, which was calculated with the formation constants of neptunium complexes selected in an OECD-NEA TDB review, strongly deviates from the value measured in natural groundwater. Thus, it is highly recommended that a prediction of neptunium solubility is based on the formation constants of ternary Np(IV) hydroxo-carbonato complexes, even though the presence of those complexes is deficient in terms of the characterization of neptunium species. Based on a comparison of the measurements and calculations of geochemical modeling, the formation constants for the "upper limit" of the Np(IV) hydroxo-carbonato complexes, namely $Np(OH)_y(CO_3)_z^{4-y-2z}$, were appraised as follows: log $K^{\circ}_{122}\;=\;-3.0{\pm}0.5$ for $Np(OH)_2(CO_3)_2^{2-}$, log $K^{\circ}_{131}\;=\;-5.0{\pm}0.5$ for $Np(OH)_3(CO_3)^-$, and log $K^{\circ}_{141}\;=\;-6.0{\pm}0.5$ for $Np(OH)_4(CO_3)^{2-}$.