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HNO3-Induced Atmospheric Corrosion of Copper, Zinc and Carbon Steel
KTH, School of Chemical Science and Engineering (CHE), Chemistry.
2006 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

The role of nitric acid (HNO3) on the atmospheric corrosion of metals has so far received little or no attention. However, the last decades of decreasing sulphur dioxide (SO2) levels and unchanged HNO3 levels in many industrialized countries have resulted in an increased interest in possible HNO3-induced atmospheric corrosion effects. In this study a new method was developed for studying the corrosion effects of HNO3 on metals at well-defined laboratory exposure conditions. The method has enabled studies to be performed on the influence of individual exposure parameters, namely HNO3-concentration, air velocity, temperature and relative humidity, as well as comparisons with newly generated field exposure data.

The corrosion rate and deposition rate of HNO3 on copper was shown to follow a linear increase with HNO3 concentration. The deposition velocity (Vd) of HNO3 increased up to an air velocity of 11.8 cm s-1. Only at a higher air velocity (35.4 cm s-1) the Vd on copper was lower than the Vd on an ideal absorbent, implying the Vd of HNO3 at lower air velocities to be mass-transport limited.

Within the investigated temperature range of 15 to 35 ºC only a minor decrease in the HNO3-induced copper corrosion rate could be observed. The effect of relative humidity (RH) was more evident. Already at 20 % RH a significant corrosion rate could be measured and at 65 % RH the Vd of HNO3 on copper, zinc and carbon steel reached maximum and nearly ideal absorption conditions.

During identical exposure conditions in HNO3-containing atmosphere, the corrosion rate of carbon steel was nearly three times higher than that of copper and zinc. The HNO3-induced corrosion effect of copper, zinc and steel turned out to be significantly higher than that induced by SO2 alone or in combination with either NO2 or O3. This is mainly attributed to the much higher water solubility and reactivity of HNO3 compared to SO2, NO2 and O3. Relative to SO2, zinc exhibits the highest sensitivity to HNO3, followed by copper, and carbon steel with the lowest sensitivity.

Extrapolation of laboratory data to an assumed average outdoor wind velocity of 3.6 m s-1 enabled a good comparison with field data. Despite the fact that ambient SO2 levels are still much higher than HNO3 levels, the results show that HNO3 plays a significant role for the atmospheric corrosion of copper and zinc, but not for carbon steel. The results generated within this doctoral study emphasize the importance of further research on the influence of HNO3 on degradation of other materials, e.g. stone and glass, as well as of other metals.

Place, publisher, year, edition, pages
Stockholm: Kemi , 2006.
Keyword [en]
Nitric acid, deposition velocity, mass transport, air velocity, relative humidity
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-4194ISBN: 91-7178-483-7 (print)OAI: oai:DiVA.org:kth-4194DiVA: diva2:11161
Public defence
2006-12-08, Sal F3, KTH, Lindstedtsvägen 26, Stockholm, 10:00
Opponent
Supervisors
Available from: 2006-11-29 Created: 2006-11-29 Last updated: 2016-12-21
List of papers
1. Atmospheric corrosion effects of HNO3—method development and results on laboratory-exposed copper
Open this publication in new window or tab >>Atmospheric corrosion effects of HNO3—method development and results on laboratory-exposed copper
2005 (English)In: Atmospheric Environment, ISSN 1352-2310, Vol. 39, no 38, 7362-7373 p.Article in journal (Refereed) Published
Abstract [en]

The effects of the atmospheric pollutant nitric acid (HNO3) on materials compared to other corrosive gases, e.g. sulphur dioxide (SO2), nitrogen dioxide (NO2) or ozone (O-3), have so far received little or no attention. The high sticking coefficient of HNO3 makes this gas one of the most difficult gases to work with. A new apparatus has now successfully been developed for studying the atmospheric corrosion effects of HNO3 Oil materials. HNO3 concentration measurements up to 1080 mu g m(-3) (420 ppb) were performed by dissolving the gas in water and analysing the nitrate concentration with ion chromatography (IC). Small changes in relative humidity (RH) largely affect the concentration of this pollutant in the exposure chamber and the high sticking coefficient of this gas on copper and quartz glass has been shown. The quartz glass surface, however, became saturated after a certain time of exposure and at 82% RH, the number of monolayers on the surface was estimated to be 10-13. Initial results of copper samples exposed to HNO3 show that at 63% RH and 25 degrees C, the deposition of HNO3 on copper is slightly lower than on a perfect absorber. The loss of HNO3 during exposure of the samples showed good agreement with the amount of nitrates dissolved from surfaces of the samples after exposure. FT-I R, XRD and IC analyses of copper exposed to HNO3 and mass loss and mass gain analyses confirmed cuprite (Cu2O) and the basic copper nitrate, gerhardtite, as the main corrosion products. Deposition, as well as the corrosion effect, of HNO3 on copper appeared to be greater than that of any of the other above-mentioned pollutants.

Keyword
nitric acid, relative humidity, gerhardtite deposition, material degradation
National Category
Engineering and Technology
Identifiers
urn:nbn:se:kth:diva-6441 (URN)10.1016/j.atmosenv.2005.09.022 (DOI)000233671700015 ()2-s2.0-27544481257 (Scopus ID)
Note
QC 20100831Available from: 2006-11-29 Created: 2006-11-29 Last updated: 2010-08-31Bibliographically approved
2. Atmospheric corrosion effects of HNO3—Influence of concentration and air velocity on laboratory-exposed copper
Open this publication in new window or tab >>Atmospheric corrosion effects of HNO3—Influence of concentration and air velocity on laboratory-exposed copper
2006 (English)In: Atmospheric Environment, ISSN 1352-2310, Vol. 40, no 20, 3631-3639 p.Article in journal (Refereed) Published
Abstract [en]

 `A recently developed experimental set-up has been used to explore the atmospheric corrosion effects of nitric acid (HNO3) on copper, in particular the influence of concentration and air velocity. Characterization and quantification of the corrosion products on exposed samples were performed with Fourier transform infrared (FT-IR) microspectrocscopy, ion chromatography, X-ray diffraction (XRD), micro-balance and microscopy. At low air velocity (0.03 cm s(-1)) HNO3 deposition and weight gain of copper increased linearly with concentration Lip to 400 mu g m(-3) or 156 ppb. The influence of air velocity on corrosion of copper was tested within the range of 0.03-35.4 cm s(-1). Although the air velocity in this study was significantly lower than typical outdoor wind values, a high HNO3 concentration of the air velocity of 35.4 cm s(-1) resulted in a relatively high deposition velocity (V-d) of 0.9 cm s(-1) on the metal surface and 1.2 cm s(-1) on an ideal absorbent, which would imply a limiting deposition velocity on the copper surface (V-d,V-surf) of 3.6 cm s(-1). Results obtained in this study emphasize the importance for future research on the corrosion effects of HNO3 on materials as very little has so far been done in this field.

Keyword
nitric acid, deposition rate, mass transport, materials degradation, gerhardtite
National Category
Engineering and Technology
Identifiers
urn:nbn:se:kth:diva-6442 (URN)10.1016/j.atmosenv.2006.03.026 (DOI)000238588600001 ()2-s2.0-33646826683 (Scopus ID)
Note
QC 20100831Available from: 2006-11-29 Created: 2006-11-29 Last updated: 2010-08-31Bibliographically approved
3. Atomospheric corrosion effects on HNO3 - influence of temperature and relative humidity on laboratory exposed copper
Open this publication in new window or tab >>Atomospheric corrosion effects on HNO3 - influence of temperature and relative humidity on laboratory exposed copper
2007 (English)In: Atmospheric Environment, ISSN 1352-2310, Vol. 41, no 1, 1374-1382 p.Article in journal (Refereed) Published
Abstract [en]

The effect of HNO3 on the atmospheric corrosion of copper has been investigated at varied temperature (15-35 degrees C) and relative humidity (0-85% RH). Fourier transform infrared (FT-IR) spectroscopy and X-ray diffraction (XRD) confirmed the existence of cuprite and gerhardtite as the two main corrosion products on the exposed copper surface. For determination of the corrosion rate and for estimation of the deposition velocity (V-d) of HNO3 on copper, gravimetry and ion chromatography has been employed. Temperature had a low effect on the corrosion of copper. A minor decrease in the mass gain was observed as the temperature was increased to 35 degrees C, possibly as an effect of lower amount of cuprite due to a thinner adlayer on the metal surface at 35 degrees C. The V-d of HNO3 on copper, however, was unaffected by temperature. The corrosion rate and V-d of HNO3 on copper was the lowest at 0% RH, i. e. dry condition, and increased considerably when changing to 40% RH. A maximum was reached at 65% RH and the mass gain remained constant when the RH was increased to 85% RH. The V-d of HNO3 on copper at >= 65% RH, 25 degrees C and 0.03 cm s(-1) air velocity was as high as 0.15 +/- 0.03 cm s(-1) to be compared with the value obtained for an ideal absorbent, 0.19 +/- 0.02 cm s(-1). At sub-ppm levels of HN03, the corrosion rate of copper decreased after 14 d and the growth of the oxide levelled off after 7 d of exposure.

Keyword
nitric acid, material degradation, deposition velocity, gerhardtite, cuprite
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-6443 (URN)10.1016/j.atmosenv.2006.10.018 (DOI)000244410400003 ()2-s2.0-33846414367 (Scopus ID)
Note
Uppdaterad från accepted till published: 20100917 QC 20100917Available from: 2006-11-29 Created: 2006-11-29 Last updated: 2010-09-17Bibliographically approved
4. Atomospheric corrosion effects on HNO3 - comparison of laboratory exposed copper, cinc and carbon steel
Open this publication in new window or tab >>Atomospheric corrosion effects on HNO3 - comparison of laboratory exposed copper, cinc and carbon steel
2007 (English)In: Atmospheric Environment, ISSN 1352-2310, Vol. 41, no 23, 4888-4896 p.Article in journal (Refereed) Published
Abstract [en]

The effect of HNO3 on the atmospheric corrosion of copper has been investigated at varied temperature (15-35 degrees C) and relative humidity (0-85% RH). Fourier transform infrared (FT-IR) spectroscopy and X-ray diffraction (XRD) confirmed the existence of cuprite and gerhardtite as the two main corrosion products on the exposed copper surface. For determination of the corrosion rate and for estimation of the deposition velocity (V-d) of HNO3 on copper, gravimetry and ion chromatography has been employed. Temperature had a low effect on the corrosion of copper. A minor decrease in the mass gain was observed as the temperature was increased to 35 degrees C, possibly as an effect of lower amount of cuprite due to a thinner adlayer on the metal surface at 35 degrees C. The V-d of HNO3 on copper, however, was unaffected by temperature. The corrosion rate and V-d of HNO3 on copper was the lowest at 0% RH, i. e. dry condition, and increased considerably when changing to 40% RH. A maximum was reached at 65% RH and the mass gain remained constant when the RH was increased to 85% RH. The V-d of HNO3 on copper at >= 65% RH, 25 degrees C and 0.03 cm s(-1) air velocity was as high as 0.15 +/- 0.03 cm s(-1) to be compared with the value obtained for an ideal absorbent, 0.19 +/- 0.02 cm s(-1). At sub-ppm levels of HN03, the corrosion rate of copper decreased after 14 d and the growth of the oxide levelled off after 7 d of exposure

Keyword
nitric acid, materials degradation, deposition velocity, iron, gerhardtite, cuprite, nitrate
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-6444 (URN)10.1016/j.atmosenv.2007.02.007 (DOI)000247868300010 ()2-s2.0-34249702872 (Scopus ID)
Note
Uppdaterad från submitted till published: 20100917 QC 20100917Available from: 2006-11-29 Created: 2006-11-29 Last updated: 2010-09-17Bibliographically approved
5. Atomospheric corrosion effects on HNO3 - a comparison of laboratory and field exposed copper, zinc and carbon steel
Open this publication in new window or tab >>Atomospheric corrosion effects on HNO3 - a comparison of laboratory and field exposed copper, zinc and carbon steel
2007 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, Vol. 154, no 5, C249-C254 p.Article in journal (Refereed) Published
Abstract [en]

The present trends with decreasing ambient SO2 levels and unchanged HNO3 levels has resulted in an increased interest in HNO3 as a corrosive pollutant. Despite the fact that ambient SO2 levels are still in general much higher than HNO3 levels, this study shows that HNO3 plays a significant role for the atmospheric corrosion of copper and zinc but not for carbon steel. A comparison of laboratory and field corrosion effects of HNO3 on copper, zinc, and carbon steel is presented. The quantitative agreement between extrapolated laboratory results and field results are good for both copper and zinc and the total corrosion effect can be represented by the sum of two contributions; one from HNO3 and one from remaining corrosion stimulators, including SO2. However, an extrapolation of laboratory results of HNO3-induced corrosion of carbon steel resulted in corrosion effects much lower than the total effect observed in the field. The field data used for comparison are from the international projects model for multipollutant impact and assessment of threshold levels for cultural heritage, with 29 sites in Europe, and Regional Air Pollution in Developing Countries with 12 sites in Asia and 4 in Africa.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-6445 (URN)10.1149/1.2712817 (DOI)000245371700027 ()2-s2.0-34047179977 (Scopus ID)
Note
Uppdaterad från submitted till published: 20100917 QC 20100917Available from: 2006-11-29 Created: 2006-11-29 Last updated: 2010-09-17Bibliographically approved

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