Atmospheric corrosion and runoff processes on copper and zinc as roofing materials

Sammanfattning: An extensive investigation with parallel field andlaboratory exposures has been conducted to elucidateatmospheric corrosion and metal runoff processes on copper andzinc used for roofing applications. Detailed studies have beenperformed to disclose the effect of various parameters on therunoff rate including: surface inclination and orientation,natural patination (age), patina composition, rain duration andvolume, rain pH, and length of dry periods inbetween rainevents. Annual and average corrosion rates and runoff rateshave been determined consecutively during urban field exposuresin Stockholm on naturally patinated copper and zinc of varyingage and patina composition. The corrosion rate was found todecrease with time, amounting to 6.7 g Cu/(m2.y) and 5.0 gZn/(m2.y) after 48 weeks of exposure, whereas the runoff ratewas relatively constant with time on a yearly basis, being 1.3g/(m2.y) and 3.1 g/(m2.y) for copper and zinc, respectively.The annual runoff rate was found to be significantly lower thanthe corresponding corrosion rate for both copper and zinc.Somewhat higher runoff rates of copper were determined fromnaturally green-patinated copper (>40 years old, 2.0g/(m2.y)) compared to brown-patinated copper (1 year old). Themain reasons are specific environmental conditions combinedwith characteristics of the patina layer, which increase themagnitude of dissolved species flushed from the surface duringthe first flush volume of a rain event. No intrinsic effect ofpanel age on the runoff rate was seen for naturally patinatedzinc. However, differences in prevailing environmentalconditions during the initial exposure period and, hence,differences in formation rate and surface coverage of thecorrosion patina, resulted in variations in runoff rate. Thisinitial difference remained also during prolonged exposureperiods and was referred to as a memory effect.Model roof investigations and laboratory studies showedsurface orientation and inclination to have a detrimentaleffect on the runoff rate with high runoff rates from surfacesof low inclination from horizon and surfaces exposed towardsthe wind direction.Based on fieldexposures and literature data, a correlationwas established between the runoff rate and the prevailingSO2-concentration. The runoff rate increases with increasingSO2 level for exposure sites of similar annual precipitationquantities (500-1000 mm/y). A rain device, using artificialrain, was shown to successfully simulate outdoor rain events ofvarying intensity and pH and result in realistic runoff ratesof both copper and zinc. The device was used to monitor changesin metal concentration and quantity of runoff water duringindividual rain events. High metal concentrations are found inthe initial rain volume flushing the surface (first flush),which decreased to rather constant metal concentrations duringthe subsequent rain volume (steady-state). The magnitude offirst flush depends primarily on environmental conditions priorto a rain event and the characteristics of the corrosionpatina. The metal concentration in runoff water increases withrain acidity, decreases with rain intensity and increases withlength of the dry period preceding a rain event.A comparison between instantaneous corrosion rates,monitored by electrochemical impedance spectroscopy using a2-electrode set-up, and runoff rates during a continuous rainevent was performed for naturally patinated copper panels.Corrosion rates were found to be approximately 10 (brownishpatina) and 25 times (greenish patina) lower than correspondinginstantaneous runoff rates.A schematic description of the first flush and steady-stateregion of the runoff process was established. The magnitude ofthe concentration during first flush is primarily affected byprevailing environmental conditions prior to a rain event,while rain pH and intensity primarily affect the concentrationduring steady-state.Key words:atmospheric corrosion, corrosion rate, runoffrate, copper, zinc, field study, laboratory study, roof, firstflush, rain quantity, rain intensity, rain pH, dry and wetdeposition, corrosion and runoff process.