CORROSION SCIENCE

FIGURE 16. Hydrogen/oxygen reactions at 625 K, pH = 7 for deter-

mination of surface corrosion potentials at ia = ic.

with:

R (zF) (14  (log(%H+ ) –

E oFe3O4 /H2 = (
G T/(zF)–2.3  RT/
++
(7)
6  log(%Fe ) +18.44 + log(pH2 ))))

)GT values are drawn from calculations,21 con-

sidering respective free energy changes of the
individual substances and their molar contribu-
tions at temperature and pressure, with number
of transferred electrons z = 2, F = 96,495 C/mol,
R = 8.3 cal/mol.
—The corrosion currents, charges, and respec-
tive dissolved iron ion contents in the active
zone of the occluded crack tip are calculated for
individual successive time intervals from Tafel
equations and Faraday’s law. Therefore, the to-
tal metal percentages within the active zone add
up continuously. The anodic polarization slope
of the metal surface and the crack tip surface
depends on the thickness and electrical prop-
erties of the precipitated oxide layer following
the “coupling principle” as shown in previous
work5-6 and outlined further below.
—A final crack depth of 5 mm is assumed, which
is equivalent to the through wall cracks of the
FIGURE 15. Principle of local acidification and crack propagation power plant pipe failures mentioned above.1
including above local reactions (1) through (4). The crack starts by anodic dissolution from an
initial surface defect of 0.001 mm microscopic
width, 10 mm length, and za = 0.2 mm depth,
with: representing an initial occluded active zone
depth at some surface defect. The initial crack
R /(zF)  (– log(%Fe++
E o/Fe3O4 = (
G T/(zF) – 2.3  RT +
) + 0.74)) (4) width and active zone depth is maintained
throughout the consecutive calculation steps,
Location 3: magnetite – aqueous solution: which means that the active zone travels down
the crack. Following this local anodic path dis-
++
3 4
4HH2O = Fe 3O 4 8H + 2e – (5) solution, the positive iron ions in the occluded
crack tip solution will accumulate and, by
that can shift to additional equilibrium with H2 gas: further oxidation and reaction with water, pre-
cipitate as iron oxides, in particular, magnetite
++
6 8
8HH 2O = 2 3 1 H+
O 4 14 2 2e
2 e− (6) (Fe3O4) according to the solubility of the oxide.

570 CORROSION—JUNE 2014