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A polarization behavior of chromium was investigated in H2SO4-Na2SO4 solution of pH 2.0 at 298 K by the potentiostatic oxidation and electrode impedance technique. From the coulometry and the chemical analysis of electrolyte the thickness of the passive films on chromium was estimated to be about 2.1 nm after 3.6 ks potentiostatic oxidation. The frequency response of the electrode impedance were simulated by the equivalent circuit of a cascade connection of two parallel RC in the prepassive (the potential region of the negative loop) and passive region, and of a cascade connection of a parallel RC and a parallel RCL in the active and transpassive region. From the impedance analysis, it was conceivable that the potential drop across the passive film and film/solution interface was constant of about 0.56 V irrespective of the polarization potential in the passive region.

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A study was made of corrosion products and their effects on stress corrosion cracking of austenitic stainless steel. Wedging action by solid corrosion products in notches or cracks induces high stresses and eventual failure of specimens by stress corrosion cracking. Data were obtained from stress-relieved and unloaded (externally) specimens so that wedging by corrosion products provided the only source of stress in the specimen. Pressures were measured in excess of 7000 psi due to wedging action of corrosion products. At the base of a notch these pressures developed stresses of the order of magnitude of the yield strength of the metal. Wedging action can provide all the energy required for stress corrosion cracking. A mechanism is proposed which involves a discontinuous type of propagation, with fluctuations occurring over one or a few atomic distances. A running or mechanical type of crack propagation for more than a few atomic distances is ruled out on the basis of the mechanics of the system. 3.4.3, 3.5.8, 6.2.5

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Metallographic examination of anodically polarized nickel and chromium after long-time exposure at selected active, passive and transpassive potentials in H2-saturated, IN H2SO4 at 25 C (77 F) revealed significant differences in surface topography. Etch figures, present only in the trans-passive state, supported the belief that “active patches” are generated in passive films of these metals at potentials more noble than the passive region. The difference in nature of nickel surface in the early trans-passive region and visible oxygen evolution region is discussed. Effect of temperature on passive nickel (i.e., nickel in passive potential region) over the range 25 to 95 C (77 to 203 F) was determined for H2-saturated 0.5, 1, 5 and ION H2SO4 (pH = 0.85 to −1.05). Apparent activation energies for dissolution of passive nickel were determined. Inflection temperature (Ti) above which “active patches” apparently are formed in passive film was dependent on acid concentration according to the expression 1/Ti × 103 = −0.11 pH+ 3.04 over the pH range investigated and was independent of the direction from which the temperature was approached. The change in apparent activation energy (ΔQ) was a function of direction from which the temperature was approached. Measurements in which temperature was increased stepwise showed that ΔQ is related to pH by the expression ΔQ (kg - cal/mole) = 15,4 pH - 4.7 for acid concentrations studied. Because Ti and ΔQ are dependent on acid concentration, Seeger's activation energy for crystallization of a very thin pseudomorphic film and Kramer's exo-electron emission temperature which are independent of concentration cannot be used to explain fully generation of “active patches” in a passive film as proposed by previous investigators.

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