Characterization of Corrosion Products Formed on Copper in Urban, Rural/Coastal, and Hot Spring Areas

Watanabe, Masamitsu; Tomita, Masato; Ichino, Toshihiro

doi:10.1149/1.1418377

Cited by 62 publications

(62 citation statements)

References 23 publications

(41 reference statements)

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“…The Cu 2p XPS spectra of copper exposed to an urban atmosphere in previous studies 21), 25) are completely different from those obtained in this study. For comparative purposes, the Cu 2p spectrum of copper exposed to an urban atmosphere is shown in Fig.…”

Section: ) 18)contrasting

confidence: 99%

“…While similar satellite peaks were previously observed for an as-cleaned copper surface, 21) in this study the copper surface was sputtered by Ar until carbon and oxygen were not observed in the spectra. Therefore, the initial surface conditions were different.…”

Section: ) 18)supporting

confidence: 82%

“…There is one peak centered at around 168.5 eV. 21), 25) Its broadness indicates that there is one more component on the lower binding energy side, but its contribution is negligibly small. The peak centered at 168.5 eV can be assigned to sulfate, which mainly originated from the hydrated basic copper sulfate (Cu 4 SO 4 (OH) 6 H 2 O) that had formed.…”

Section: ) 18)mentioning

confidence: 99%

“…The peak centered at 168.5 eV can be assigned to sulfate, which mainly originated from the hydrated basic copper sulfate (Cu 4 SO 4 (OH) 6 H 2 O) that had formed. 21), 25) In the urban atmosphere, both SO 2 and particulate sulfate adsorbed on and dissolved into the surface electrolyte on the copper surface. The former easily oxidized into stable sulfate ions due to the presence of oxidizing agents such as OH radicals (OH ) and hydrogen peroxide (H 2 O 2 ).…”

Section: ) 18)mentioning

confidence: 99%

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Comparative XPS Study of Silver and Copper Surfaces Exposed to Flowing Air Containing Low Concentration of Sulfur Dioxide

Watanabe

Andō²,

Handa

et al. 2007

ZAKAEP

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Sulfur dioxide (SO 2 ), a typical gaseous compound found in the atmosphere, corrodes metals, particularly outdoors. When SO 2 adsorbs on the surface electrolyte, it easily dissolves, resulting in the formation of protons (H ) and bisulfite ions (HSO 3 ). The former reduces the pH of the surface electrolyte, which promotes metal dissolution.Silver and copper are commonly used in the electronic components and devices typically found in telecommunication equipment. Since silver and copper are affected by SO 2 , it is important to know the effects of SO 2 on their corrosion behavior to predict the life expectancy of the equipment. Such knowledge would also be useful for coping with anomalous situations, such as volcanic eruptions, in which the SO 2 concentration can exceed several hundred ppb. A previous study showed that silver and copper plates exposed to the atmosphere were severely corroded following the volcanic eruption on Miyake Island in 2000. 1)Much effort has been expended on clarifying the effects of SO 2 on atmospheric silver and copper corrosion. A number of laboratory experiments have been reported regarding the effects of exposure to high SO 2 concentrations. 2) 15)Using infrared reflection absorption spectroscopy (IRAS), Persson and Leygraf showed that sulfite formed on the surface of copper during the initial stage when it was exposed to 0.21 ppm SO 2 in flowing air at 80 relative humidity (RH).16) In situ analysis using IRAS and a quartz crystal microbalance by Ito et al.17) 18) revealed that sulfite like CuSO 3 Cu 2 SO 3 2H 2 O (Chevreul's salt) and sulfate CuSO 4 5H 2 O formed as corrosion products on copper exposed to flowing air containing 10 ppm SO 2 at 80 RH. Moreover, the formation rate of sulfite was higher than that of sulfate in the very early stage. 17) 18) In contrast, the sulfidation rate by SO 2 for silver is much lower than that by reduced sulfur species, such as H 2 S and COS. 12) Since SO 2 is considered to be a weak corrosive agent for silver, the effect of SO 2 on atmospheric silver corrosion in the initial stage has received little attention.In this study, the chemical state of the sulfur was investigated when silver and copper plates were exposed for one hour to flowing air containing low concentrations of SO 2 . Since the electrochemical reactions occur at the metal/ electrolyte interface in the early stage of corrosion, X-ray photoelectron spectroscopy (XPS) was used. The SO 2 concentrations were 18 and 148 ppb ; the former is at least one order of magnitude lower than those in previous studies. 16) 18)The silver and copper plates were 99.99 pure and 5 5 0.1 mm in size. Their surfaces were sputtered with 3 kV Ar ions to clean them. The sputtering was conducted until both carbon and oxygen were not detected in the XPS spectra, as described elsewhere. Sulfur dioxide (SO 2 ) is a typical gas affecting the atmospheric corrosion of metals, particularly outdoors. Although many studies have investigated the effect of SO 2 on the atmospheric corrosion of silver and copper, little is ...

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Section: ) 18)contrasting

confidence: 99%

Section: ) 18)supporting

confidence: 82%

Section: ) 18)mentioning

confidence: 99%

Section: ) 18)mentioning

confidence: 99%

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Comparative XPS Study of Silver and Copper Surfaces Exposed to Flowing Air Containing Low Concentration of Sulfur Dioxide

Watanabe

Andō²,

Handa

et al. 2007

ZAKAEP

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“…Copper is widely used in a number of critical electrical applications, and the problem and study of copper corrosion is a major area of research [1][2][3][4][5][6][7][8]. Previous researchers have studied the sulfidation of copper using SO 2 and H 2 S gas and found that these reactants interact at the wateroxide interface, possibly at copper oxide grain boundaries [5,[9][10].…”

Section: Background On Copper Sulfidationmentioning

confidence: 99%

The effects of varying humidity on copper sulfide film formation.

Mayer¹,

Missert²,

Barbour³

et al. 2004

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Detailed experiments involving extensive high resolution transmission electron microscopy (TEM) revealed significant microstructural differences between Cu sulfides formed at low and high relative humidity (RH). It was known from prior experiments that the sulfide grows linearly with time at low RH up to a sulfide thickness approaching or exceeding one micron, while the sulfide initially grows linearly with time at high RH then becomes sub-linear at a sulfide thickness less than about 0.2 microns, with the sulfidation rate eventually approaching zero. TEM measurements of the Cu 2 S morphology revealed that the Cu 2 S formed at low RH has large sized grains (75 to greater than 150 nm) that are columnar in structure with sharp, abrupt grain boundaries. In contrast, the Cu 2 S formed at high RH has small equiaxed grains of 20 to 50 nm in size. Importantly, the small grains formed at high RH have highly disordered grain boundaries with a high concentration of nano-voids. Two-dimensional diffusion modeling was performed to determine whether the existence of localized source terms at the Cu/Cu 2 S interface could be responsible for the suppression of Cu sulfidation at long times at high RH. The models indicated that the existence of static localized source terms would not predict the complete suppression of growth that was observed. Instead, the models suggest that the diffusion of Cu through Cu 2 S becomes restricted during Cu 2 S formation at high RH. The leading speculation is that the extensive voiding that exists at grain boundaries in this material greatly reduces the flux of Cu between grains, leading to a reduction in the rate of sulfide film formation. These experiments provide an approach for adding microstructural information to Cu sulfidation rate computer models. In addition to the microstructural studies, new micro-patterned test structures -4 -were developed in this LDRD to offer insight into the point defect structure of Cu 2 S and to permit measurement of surface reaction rates during Cu sulfidation. The surface reaction rate was measured by creating micropatterned Cu lines of widths ranging from 5 microns to 100 microns. When sulfidized, the edges of the Cu lines show greater sulfidation than the center, an effect known as microloading. Measurement of the sulfidation profile enables an estimate of the ratio of the diffusivity of H 2 S in the gas phase to the surface reaction rate constant, k. Our measurements indicated that the gas phase diffusivity exceeds k by more than 10, but less than 100. This is consistent with computer simulations of the sulfidation process. Other electrical test structures were developed to measure the electrical conductivity of Cu 2 S that forms on Cu. This information can be used to determine relative vacancy concentrations in the Cu 2 S layer as a function of RH. The test structures involved micropatterned Cu disks and thin films, and the initial measurements showed that the electrical approach is feasible for point defect studies in Cu 2 S.

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Commentary: From Mindmeld to Mindset: Negotiating the Information Minefield in Developing Countries

Adamu

2002

Bul. Am. Soc. Info. Sci. Tech.

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Characterization of Corrosion Products Formed on Copper in Urban, Rural/Coastal, and Hot Spring Areas

Cited by 62 publications

References 23 publications

Comparative XPS Study of Silver and Copper Surfaces Exposed to Flowing Air Containing Low Concentration of Sulfur Dioxide

Comparative XPS Study of Silver and Copper Surfaces Exposed to Flowing Air Containing Low Concentration of Sulfur Dioxide

The effects of varying humidity on copper sulfide film formation.

Commentary: From Mindmeld to Mindset: Negotiating the Information Minefield in Developing Countries

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