The Early Stage of Atmospheric Corrosion of Copper by Sulfur Dioxide

Chawla, S. K.; Payer, Joe H.

doi:10.1149/1.2086439

Cited by 35 publications

(21 citation statements)

References 11 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Later the typical greenish color of the copper patina appears. The primary corrosion product present at that time is posnjakite, Cu 4 (SO 4 )(OH) 6 •H 2 O, which later converts to brochantite, Cu 4 (SO 4 )(OH) 6 . Additionally smaller amounts of antlerite, Cu 3 (SO 4 )(OH) 4 , atacamite, Cu 2 Cl(OH) 3 , and organic components were found.…”

mentioning

confidence: 99%

Mechanism of Atmospheric Corrosion of Copper in the Presence of Ammonium Sulfate Particles

Lobnig¹,

Sinclair²,

Unger³

et al. 2003

J. Electrochem. Soc.

View full text Add to dashboard Cite

The effect of the surface concentration of submicrometer ammonium sulfate (NH 4 ) 2 SO 4 dust particles on the mechanism of atmospheric corrosion of copper has been investigated at 298 K and 93% relative humidity ͑RH͒. For surface concentrations from 1 g/cm 2 to 10 mg/cm 2 , the same corrosion products are formed at relative humidities well above the critical relative humidity of (NH 4 ) 2 SO 4 . Initially, a Cu(NH 3 ) 2ϩ complex is formed. The basic copper sulfate posnjakite precipitates when its solubility product is exceeded while NH 3 evaporates. Posnjakite may be converted to antlerite or brochantite if higher amounts of (NH 4 )SO 4 particles were deposited. The basic copper sulfates then decompose at the inner interface to form Cu 2 O. With low amounts of (NH 4 ) 2 SO 4 particles, the conversion is 100%. With high amounts of particle deposits, residual copper sulfate remains on top of a Cu 2 O-layer. With increasing amounts of deposited (NH 4 ) 2 SO 4 particles on copper, the sequence of corrosion products that are formed takes more time. The mechanism proposed in earlier work for the corrosion of copper with (NH 4 ) 2 SO 4 particles in humid air is improved to explain the new experimental findings.Before 1995, essentially all laboratory studies on the atmospheric corrosion of metals were conducted using corrosive gases in concentrations that were excessively high relative to those found in the troposphere. The corrosion product films that were produced were frequently unrealistic. For example, for copper it was not possible to produce a surface layer similar to the naturally formed patina using gaseous pollutantes like SO 2 and NO 2 . [1][2][3][4][5][6][7][8][9] However, the 1930s, Vernon demonstrated that dust particles, especially dust particles consisting of ammonium sulfate, significantly influence the corrosion of copper and lead to higher corrosion rates. [10][11][12][13][14][15][16] The factors that determine the amount of ionic surface contamination relevant for atmospheric corrosion on metal surfaces was later studied by Sinclair et al. [17][18][19][20][21][22][23] The extent of ionic deposition on indoor surfaces is influenced by the concentration of dust particles in the outdoor air, the air exchange rate between indoors and outdoors, efficiency of air filtration systems, the velocity of the air, the surface area to volume ratio, the temperature of the surface, the distance between surfaces and source of particles, and the orientation of the surface. It was shown that most of the sulfur acquired by zinc and aluminum surfaces is supplied as dry deposition, and not, as previously assumed, in gaseous form from the reaction with SO 2 . It was also shown that fine particles ͑Ͻ1 m͒, produced from corrosive gases through chemical and physical processes that occur in the atmosphere, play the decisive role in the atmospheric corrosion of metals because of their higher concentration indoors ͑due to low filtration efficiencies for fine particles͒ and because of their greater content of soluble ions compare...

show abstract

mentioning

confidence: 99%

Mechanism of Atmospheric Corrosion of Copper in the Presence of Ammonium Sulfate Particles

Lobnig¹,

Sinclair²,

Unger³

et al. 2003

J. Electrochem. Soc.

View full text Add to dashboard Cite

show abstract

“…For copper, the bisulfite seen in the S 2p XPS spectra originated from SO 2 adsorption on the surface electrolyte, as shown in equation (1). Although Chawla and Payer reported the formation of copper sulfide (Cu 2 S) in the early stage of copper corrosion with 0.5 SO 2 , 28) we did not detect any sulfide component (Fig. 9(b)).…”

Section: )mentioning

confidence: 68%

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

View full text Add to dashboard Cite

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 ...

show abstract

“…Chawla et al reported that they found cuprite in the ED pattern of an unexposed copper surface. 20 The oxide thickness is several nanometers and its existence can be confirmed by XPS. The O 1s XPS spectra of as-cleaned copper included the lattice oxygen component ͑O 2Ϫ in Cu 2 O͒.…”

Section: Resultsmentioning

confidence: 86%

“…Figure 3 shows a ternary Cu-S-O compositional triangle. 20 The compositions of the crystallized and noncrystallized phases are plotted as an open circle A and a closed circle B, respectively. The composition of the crystallized phase was very close to the theoretical composition of antlerite also shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

Microstructural Analysis of Artificially Formed Patinas on Copper

Watanabe

Higashi

Tomita

et al. 2002

Electrochem. Solid-State Lett.

View full text Add to dashboard Cite

We analyzed artificially formed copper patinas to obtain microstructural information by means of transmission electron microscopy, energy dispersed X-ray spectroscopy, electron diffraction ͑ED͒, and X-ray diffraction ͑XRD͒. We found that there were two different phases in the patinas. One was a well-crystallized phase composed of copper, sulfur, and oxygen, and whose ED pattern exhibited many spots. The ED and XRD patterns revealed that this crystalline phase was antlerite Cu 3 SO 4 (OH) 4 . The other phase was a noncrystalline phase with no spots but with a diffused pattern. This phase also contained copper, sulfur, and oxygen; however, the sulfur X-ray intensity was much stronger than that from the crystallized phase. We believe this phase to be composed of cuprite Cu 2 O and sulfate.

show abstract

The Early Stage of Atmospheric Corrosion of Copper by Sulfur Dioxide

Cited by 35 publications

References 11 publications

Mechanism of Atmospheric Corrosion of Copper in the Presence of Ammonium Sulfate Particles

Mechanism of Atmospheric Corrosion of Copper in the Presence of Ammonium Sulfate Particles

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

Microstructural Analysis of Artificially Formed Patinas on Copper

Contact Info

Product

Resources

About