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    Daño del ácido carbónico en el acero inoxidable

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    De Waard_Carbonic Acid Corrosion Steel

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    Daño del ácido carbónico en el acero inoxidable

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
    Flag for inappropriate content
    8 views5 pages

    De Waard - Carbonic Acid Corrosion Steel

    Uploaded by

    tinovelazquez
    Daño del ácido carbónico en el acero inoxidable

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
    Flag for inappropriate content
    of 5
    higher Tafel constants, ¢., Dg" 60 mV and be = 120 mV, almost any reasonable estimate of bg’ (43 FeOH +e Ga 7 RD FoQH = FeOH’ +6” oo) FoOH™ >Re + 08” ea With this mechanism, the anodic dissoludon rate at sny constant Potential is inversely proportional to the H" concentration, which Jeads to a less marked dependence of corrosion rate on pH, A being about 0.5. Another mechanism, proposed by Heuser," leads to 0. ‘The aim of che present work is ta investigate the value of A for jsomosion by carbonic acd, and to explain this value in terms of the snodicand cathodic reaction mechanisms, Experimental Ina first series of experiments, corrosion rates were determined £05 polished cylindrical specimens (2 4 mm,d'= 6 mm) machined from X-S2 carbon steal bur. Fora single rn, shree such epecimens were polished with grade 600 emery paper, brushed with a mildly abrasive detergent, rinsed with dlsilled water, and degreased with acetone efter mounting on 2 threeslectrode probe by means of Shreaded connections, thus providing measuting, reference and auiilisry electrodes. The test medium conristad of a 0.1% NaCl solution through which an adjustable migture of COz and specially purified oxygenttee Nz was bubbled, Tests were carried out in bout I iter of this solution, which was thermostatted at the desired temperature ad stired vigorously in such away that flow speed of liguid around the electrodes of about 1 m/s was achieved, ‘The corrosion rate was monitored by means of the linear polar tion technique, The instruments used were: (1) the Pewolte Corzosion Rate Meter, automatic mode! M-ID0U and (2)a Wenking potentosiat driven by a Philips (PMS168) square wave oseillator (10 mY amplitude) with an adjustable de-bias. This bint was used to correct for the open voluge between reference and measuring slectzodes, All the readings obtained were corrected for iRdrop in the lectrolyie; the associated resistance (R) was determined at regular intervals by impressing 2 2 kHz alteinating current of knows amplitude between measuring and ausiiry electrodes and noting the resulting voltage drop between measuring and reference elec luodes. This was done vith the aid of a Hewlett-Packard 43284 milliohm-meter, which gives a dizect readout of the eesstnce (R) ‘The corrected readings were converted to corrosion rates bY means of a calibration factor which was obtained by comparing time integrated readings with the weight lostes of the electrodes Measurements of the effect of CO pressure at a given temperature ‘were made by beginning at a low partial CO pressure, and after ‘reaching the steady-state corrosion rte after about 24 hours, aiing "he partial pressure and allowing this system to reach is new steudy state, which then only required about 3 hours. Ths procedure was ‘repeated with further inereatesn presure In & second series of experiments the specimens were grit- Diasted before exposure. In this case, weight losses were determined cover longer periods, e., 7 days, while the corrosion rate was also monitored. In these cess, Hotled mixtures of oxygemree Np and C02 were used to ensure constant gas composition, and the tests ‘were carried out in an autoclave Potentiodynamic polarization curves were recorded with abora+ tory-built potentostats with 2 builtin electronic potential sweep tnd a logarithmic readout, Scans were made going fram exthodie to anodic potentials with a speed of 1 mVjs. The measuring electrode sas embedded! in bakelite, and mechanically polished in successive steps down to 0.25 41 just before use. In these tests, a Ii NaCl solution was used as supporting electrolyte. A capillary connection between reference electrode Isuturated cilomel) and a point close to the measuring electrode was filled with the sume solution, The auxiliary electrode consisted of platinum gaute, pH measurements ‘were carried out with spot lectrode Results Influence of Surface Preparation For the polished specimens of the first experimental series the 178 4 © s0%e, pause + 25%c, paused of cog Parvin. bess’ aot FIGURE 1 Influence of COs prossure and temperature on of carbon ste corrosion rate, ys measured with the polarization technique, ‘ncreaved with time nia virtually constant level was ceacied. This level isthe corrosion rate given for two test series (25 and 60)C) in Figure 1. The corosion rate oF grit-blasted steel however, decreased er initially high value, ad the Tia level reached was 30% higher than that for polished sizel, An exception to this were ests at $C, where polished specimens often filed to become active, and cortoslon rates remained ubout ten times lower thin those ‘or wivblasied specimens. Those results were not further taken io secount, For the gri-blasted specimens (15 C) the werage corrosion rte over the whole time of exposure i indicated. J both eases, the calibvation factor for the polirization resistance measurements, which equils the ratio of earosion current {from weight los) and polarization admittance (Grom polation measurements), varied from cun to run, The value of thie factor was 9522 mv. Influence of CO, Partial Pressure The slope A in Equation (2) can also be dotermined from a plot ‘of log corrosion rate against log CO pressure, us presented in Figure 1. From the definition of the disseeistion constant (K) of earbonie acid (neglecting the second dissociation step) it follows that WY? =k MH,COy) o Since the concentration of earboni sedis proportional to tke CO arta pressure (PCO), aceording to Heary's lw: pil = 4 log co, + const o where the constant incorporates Henry's constant and K, both at campnsian sioe TABLE 1— Comparison of Experimental and Calculated Corrosion Rates of Grit-Blasted Samples ‘Under Various Conditions Caleuiated ] Experimental Paria COz | Corvasion | Corrosion Pressure Rate Rate oar | tmmive) | Imeived 55 1 0.80 oa 2 1 058 06 6 1 oss 07 02 043, oa 037 0.38 03 o2t 024 02 2 2 16 1 9 20 1 13 40 92 7 50 oss 23 60 ozo 394 39 70 09 502 43 80 053, 5.73 57 the temperature concerned. With the ald of this expresion, which ‘was experimentally obeyed within 0.1 pH uni, Equation (2) can be tos Atos co, +B" o ‘The straight lines drawn in Figure 1 correspond to A» 1.3, which ve the best it forall data obtained, Effect of Temperature Corrosion rates for grit-blasted stel at various temperatures up to 80 C aze given in Table 1. The CO partial pressures in this table have been corrected for the vapor pressure of water. Especially at temperatures above 60 C, some of the electrodes became covered with a black layer, while the corrosion rate dropped to low value, Ine stagnant envisonment, this effect was observed even at 40.C. In these cases the results were rejected, and the tests were repeuted until suficient data were obtained from electrodes in the active ate, Abowe 80 Call specimens became pasive ina matter of hours In otder to be able to account for changes in CO solubility and iswociation constant, the pH as measured asa function of temperature for PCO; * { Dat (corrected for water vapor pressure, Figure 2 shows that in the ange of temperatures studied, 2 linear relation between pH and temperature (¢(C)] is obtained: Peco, =p TAIT N17 E371 o Polarization Curves In Figure 3, 4 typical polatization cumve is represented, which leasly shows anodic Tafel behavior. The Tafel slopes (bg) ftom a umber of cures varied between 30 and 60 mV, but 2 slope of 40 mV was found for mos of the rns. All cues showed a cathodic current plateau. Discussion Polarization Curves With the mechanism given in Equations (3) for the anodic

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