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464 JOURNAL OF THE ELECTROCHEMICAL SOCIETY December 1 9 5 0

A U N I F I E D M E C H A N I S M OF P A S S I V I T Y mates anodically polarize steel, although it seems probable


A N D I N H I B I T I O N , P A R T II that they do. We have noted that when steel is coupled
R. B. M e a r s a n d R. H. B r o w n (pp. 75-82)
to copper and immersed in a chloride solution the potential
of the couple is nearly the same as that of steel indicating
5~ORTIMER C. BLOOMI~ DO single crystals of metals show that steel does not polarize appreciably anodically in
deviations experimentally from the thermodynamically chloride solutions. However, if chromates are added to
calculated electrode potentials? the solution, the potential of the iron-copper couple shifts
R. B. ~IEARS: Yes, single crystals of metals also show in a cathodic direction and is about half way between the
marked deviations experimentally from the thermodynam- open circuit potential of the iron and that of the copper.
ically calculated electrode potentials. See, for example, the This indicates that chromates do polarize the steel anod-
paper by C. J. Walton ~. ically, although this m a y not be the sole effect of the
H. H. UHLIG'2: The authors apparently prefer to look chrom'~tes in inhibiting corrosion of steel.
upon all corrosion reactions from the standpoint of electro- The observed values were as follows:
chemical polarization, neglecting what actually happens
at the electrode sm'faces to bring about such electro- The solution contained 0.01% NaC1 and 1.0%
chemical change. Although this viewpoint is adequate for Na2CrO~. 4H20
obtaining the correct answer, it seems to me that a still Open circuit potential of copper 0.09 volt
more basic approach includes the nature of electrode Open circuit potential of steel 0.39 volt
surfaces and electrode reactions that account for such Potential of couple (copper and steel) 0.16 volt
electrochemical polarization as Messrs. Mears and Brown In sodium chloride solution not containing chromates,
report. Besides providing increased interest in the stud)- the potential of the couple is nearly the same as that of
of corrosion reactions, a stud)" of surface equilibria and steel alone.
kinetics provides new and useful information not obtained M. J. PaYon13: The recent paper by the authors, while
otherwise. being an interesting contribution to the understanding of
I should like to ask l)r. Mears whether any experiment inhibition and passivity, does not, however, get to the
has been performed showing that steels containing a roots of the problem. In fact, the conclusion that the in-
variety of cathodic impurities show a variety of potentials hibiting action of sodium chromate is "mainly the result
when immel'sed in chromate solutions. Were this proved, of polarization of local anodes," is little more than a
it would constitute proof that chromate polarizes steels restatement of the usual definition of an anodic inhibitor.
anodically. Were all potentials the same, however, one In the opinion of the writer, a mechanism of inhibition
would assmne that chromates adsorb generally without should explain, not only the steps leading to this polariza-
regard to anodes or cathodes. tion, but also give some account of the kinetics of the
R. B. ~[EARS: It seems to us that Dr. Uhlig is proposing overall reaction; in the latter case, a study of chemical
that we run before we can walk. We have no objection to a thermodynamics can give no useful information.
fundamental approach which would result in separating In a recent paper 14 the inhibiting action of chromate on
and measuring the individual factors that together make the corrosion of iron was attributed to a heterogeneous
up polarization. In fact, we would like to give encourage- reaction between adsorbed chromate ions and the iron
ment to any such approach. At the present time it is surface, with the result that the iron ions were oxidized,
relatively easy to measure E~ or Er the overall polarization without first passing into solution, to v-Fe20s which formed
at the anode or cathode, respectively. As we pointed out in a thin, continuous surface fihn. This was concluded from
the first paper of this series, these bulk polarizations are the failure to detect any constituent other than v-Fe20s
made up of at least two components. I t would be very during an electron diffraction examination of fihns formed
desirable to measure these components separately. We by the action of 0.0IM potassium chromate solution on
would be glad to see someone make such measurements. originally fihn-free iron. More recent work ~5 has shown
Our fundamental point is, if corrosion is indeed electro- that this same reaction takes place in de-aerated solutions.
chemical, as seems probable, let us express all effects in I t would he interesting to know whether the authors have
electrochemical terms. I t is not sufficient from an electro- any information concerning the nature of the fihn formed
chemical standpoint to say that a film prevents or re- by the action of sodium chromate on aluminium.
duces corrosion since we wish to know how the film be- The authors' conclusions concerning the depolarization
haves electrochemically. Does it introduce a high resistance of the cathodic reaction by chronmte ions are at variance
in the circuit, is it similar to a condenser, or just what is with those of other investigators. Hoar ~6 has pointed out
its electrochemical action? that the reduction of the chromate ion in neutral solutions
Dr. Uhlig inquires if experiments have been performed is very sluggish and experiments by the writer have in-
showing that steels containing a variety of cathodic im- dicated that the cathodic reduction of chromate ions, in
purities show a variety of potentials when immersed in chromate/chloride mixtures, is not appreciable at pH
chromate solutions. Our work with chromates was con- values above 3.0. Similar results have also been obtained
fined to aluminum. We have no direct evidence that chro-
~s National Research Council, Ottawa, Canada.
~0 Naval Research Laboratory, Washington, D. C. 14 ,f. E . O . M A Y N E AND M . J. PaYoR, J. Chem. Soc., 1949,
11 Trans. Electrochem. Soc., 85, 239 (1944). 1831.
~2Department of Metallurgy, Massachusetts Institute of ~' J. E. O. MAYNE AND M. J. PRYOa, Unpublished Work.
Technology, Cambridge, Massachusetts. 16 Trans. Electrochem. Soc., 76, 157 (1939).

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Vol. 97, No. 12 DISCUSSION SECTION 465

with neutral solutions of nitrites ~7. I t may be, therefore, must be almost vertical or coincide with the vertical axis
that the decrease in cathodic polarization w i t h increasing of the figures Dr. Mears has drawn. Interpretation of the
chromate ion concentration (Fig. 1) is due merely to a word passivity is also involved. If the corrosion rate on a
progressive decrease in size of the anodie areas and cor- metal is reduced from 200 to 100 mils per year, I would not
responding enlargement of the cathodic areas; this will interpret this as a result of passivity. The information
lead to a decrease in the cathodic current density and hence presented by Dr. Mears is particularly valuable in the
to a reduction of the cathodic polarization. study of inhibitors.
R. B. MEARS: The authors were interested in Dr. Pryor's We are in complete agreement with Dr. Mears' state-
discussion. They believe, however, that Dr. Pryor does not ment that the single electrode potential is not a measure
understand the real significance of their study of the of passivity. Our work on passivation of stainless steels
mechanism of inhibition by sodium chromate. I t is true, has shown a wide variety of single electrode potentials
as Dr. Pryor indicates, that other workers have suspected (both plus and minus) for steels treated.
that sodium chromate was an anodic inhibitor. As far as R. B. MEARS: The authors wish to thank Dr. Fontana
the authors are aware, however, no one previously has for his discussion. I t can be readily recognized that the
isolated electrically the local anodes and cathodes and formation of a film is not sufficient to account for passivity.
proved by direct measurement that the addition of chro- Tile properties of the fihn are also importani. The proper-
mate to the solution increases the anodic polarization. I t ties of the film which are of most importance are its elec-
can be argued that the electrochemical behavior of an trical or electrochemical properties. For example, it must
inhibitor is of more importance than is the determination be agreed by all that carbon steel in many environments
of the physical or chemical state of the reaction product. forms a fihn of corrosion products (rust). Unfortunately,
Corrosion is an electrochemical phenomenon. The most this film frequently causes little reduction in corrosion
significant information to learn is how the inhibitor affects rate. The reason is that the fihn does not retard the
the electrode reactions. A fihn of reaction product may or electrode reactions. I t can be asked why a lead sulfate
may not appreciably influence the electrode reactions, film reduces corrosion of lead in sulfuric acid. The fact that
depending on the character of this fihn. Just to say that a a film is formed is not sufficient to explaiH the reduction of
fihn of ~-Fe20a is formed does not explain why corrosion is corrosion. Tile film must interfere with electrode processes
reduced. I t is necessary to go further and determine how or corrosion is not retarded. The most accurate way of
this fihn affects the electrode reactions. studying this effect is to determine the influence of the
I t is not believed that the cathodic areas altered appreci- film on the anode and cathode processes separately.
ably as chromates were added for two reasons: While it is true, as Dr. Fontana implies, that the flow
1. The anode area was a single pit that was started by of electric current has not been demonstrated for all
inunersing the aluminum sample in uninhibited sodium types of corrosion reaction, still there is now sufficient
chloride solution. This same pit remained the anode as quantitative and qualitative evidence to make it seem
chromate was added to the solution. probable that corrosion of metals, in aqueous solutions at
2. The area of the cathode, even in the uninhibited solu- least, is electrochemical in nature.
tions, was over one hundred times the area of the anode. I t is our belief that the mechanisms of passivity and
Thus, it would be impossible for the cathode area to in- inhibition are identical. Therefore, if the theory presented
crease by more than 1 per cent. is applicable to inhibitors- it is also applicable to passivity.
M. G. FONTANA18:Dr. Mears has presented his usual HERBERT CHARLES COCKSI~: I feel that a great service
high quality paper and has done a fine job of covering has been performed b y Messrs. Mears and Brown in
some of the fundamentals of electrochemical corrosion. elucidating the part played by oxygen in determining the
With regard to passivity, however, I do not agree that an values of the potentials of metals in salt solutions.
explanation of the anode-cathode relationships is necessary I am of the opinion that this point should be clearly
in all cases. For example, if one postulates that stainless stated in textbooks on electrochemistry and that many
steel is passive because of an oxide layer, an hydrous investigators in the field of electrochemistry, especially
oxide fihn, a chemisorbed film, and/or a physically ad- workers on corrosion, omit consideration of this fact.
sorbed gas thus setting up a barrier between the base M y own view is that the static potentials of nearly all,
metal and the corrosive environment, what further ex- if not all, metals in most solutions are determined not only
planation is required? Lead supposedly becomes passive by the metal/metal ion equilibria but, to some extent, by
in sulfuric acid because of the formation of a lead sulfate the metals behaving as gas electrodes in a similar manner
coating. To draw an almost direct analogy we could ask to the hydrogen electrode. By static potentials I mean, of
the question--why does a paint coating often protect course, those measured when there is no flow of current
steel from corrosion? In addition, all corrosion is not from another electrode. The gas electrode equilibria would
necessarily electrochemical in nature. Unfortunately, the usually be that of the oxygen electrode, but sometimes
determination of anode and cathode potentials is a difficult, that of the hydrogen electrode. In broad terms, the static
if not almost impossible, procedure. potentials of metals in solutions as ordinarily measured
If we assume that passivity involves practically no are to varying degrees partly determined by adsorbed or
corrosion then cathodic and/or anodic polarization must absorbed oxygen or hydrogen on their surfaces as well as
be almost complete. In other words, the polarization lines by the metal/metal ion equilibria. This factor affecting
17 M. COHEN, Private Communication. 10 Royal Aircraft Establishment, Farnborough, Hamp-
is Ohio State University, Columbus, Ohio. shire, England.

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466 JOURNAL OF THE ELECTROCHEMICAL SOCIETY December 1950

the potential would be quite apart from the welLknown posit and a smooth surface from which a second cycle Of
influence of the presence of local anodes and cathodes due growth of elongated crystals begins, and so on repeatedly,
to heterogeneity of the metal surface. thus giving rise to the striated deposit.
Experimental support for these observations was given CLOYDi . SNAVELYAND CHARLESi . FAUST: Mr. Brace's
many years ago by Kahlenburg and French ~~and I found suggestion relating to the accumulation of secondary prod-
some evidence in the case of zinc in zinc sulfate solutions% ucts of electrolysis to affect crystal growth is very interest-
That the potential of magnesium in acid and alkaline solu- ing to the authors. We are unable to offer evidence for or
tions is largely determined by its hydrogen overvoltage against the hypothesis, though our own outlook has been
rather than by the metal/metal ion equilibrium is strongly somewhat different. It should be noted that a considerable
indicated by the work of G. E. Coates 22. change in the character of the plate surface during plating
R. I-I. BROWN:We were very pleased to have Dr. Cocks' is accompanied by equivalent changes in the actual current
views on the nature of electrode equilibria and, in general, density. Possibly, lowering the current density is enough to
it is believed that he is in essential agreement with our cause discontinuance of deposition on the larger crystals.
discussion. There are some minor differences if our under- A. D. Myron4: Would the authors venture to comment
standing of Dr. Cocks' discussion is correct. It is our upon the nature and origin of the striations found on the
feeling that it is of minor consequence whether the oxida- cross-sectional photomicrographs?
tion and reduction reactions occur at separate discreet CLOYD A. SNAVELYAND CHARLES L. FAUST: In answer
areas or whether the areas are indistinguishable. If the to Mr. :Y[uir's question, we have nothing to offer beyond
areas are discreet it may be necessary to keep in mind that the foregoing comments and the discussion in the paper.
the conditions of dynamic equilibria at each area may .-~I. _-~. STERNFELS~S:Have you observed any signs of
differ. It is not clear if we are in agreement with Dr. Cocks' superficial cracking of the deposit arising from heat treat-
discussion regarding the potential of magnesium in acid ing? Hidnert's work 2e on the coefficient of expansion of
and alkaline solutions being largely determined by its chromium shows initial contraction on heating, and the
hydrogen overvoltage rather than by the metal to metal question refers to the possibility that this contraction
ion equilibrium. results in cracking.
If the magnesium to magnesium ion reaction is not CLOYD A. SNAVELYAND CHARLES I.. FAUST: Our inter-
polarized to as great an extent as the hydrogen to hydrogen pretation of the physical causes and significance of the
ion reaction then we would prefer to say that the potential contractile phenomena reported by Hidnert has been de-
is controlled by the hydrogen to hydrogen ion reaction. If tailed in an earlier paper%
on the other hand, the polarization of the magnesium to H. J. WIESNER28: What sort of variation in hardness in
magnesium ion reaction is appreciable relative to that of the chromium plated samples existed before the various
the hydrogen to hydrogen ion reaction, both reactions heat treatments?
would help determine the measured potential of the elec- CLOYD A. SNAVELY AND CHARLES L. FAUST: Careful
trode. Stated in another way, it is our belief that the checks were not made on the hardness of the plate speci-
potential of a single electrode in the solution is determined mens before annealing treatments. The hardness of other
by all possible reactions that could occur and those which plates made under identical conditions varied between
polarize to the greatest extent control the potential of the Knoop numbers of 900 and 1050 when measured on the
electrode. Furthermore, it is felt that the oxidation and cross-section surface.
reduction reactions cannot be considered as occurring J. J. DALE29: I do not agree with the contention of the
independently. It is believed that these two reactions are authors (p. 104) that the exceptional hardness of bright
interdependent. chromium electrodeposits is more reasonably explained
on the basis of fine grain size and internal stress than it is
S T U D I E S ON T H E S T R U C T U R E OF H A R D by the dispersed oxide theory. Actually, al! of these mech-
CHROMIUM PLATE anisms should be considered as complimentary, rather
Cloyd A. Snavely and Charles L. Faust (pp. 99-108) than conflicting, each one contributing its part. The follow-
ing evidence, apparently not considered by the authors,
P. H. BRACE2a:From the authors' remarks I have gained leads me to believe that finely dispersed oxide or hydroxide
the impression that when deposition commences relatively particles confer the greater part of its hardness upon elec-
large elongated crystals grow outward from the surface of
trolytic chromium.
the basis metal. Now, with reference to the striations 1. There is much more oxygen present in deposits than
shown by the photomicrographs, I suggest the possibility that which occurs as oxide in the visible inclusions. Brenner,
that during electrolysis there is an accumulation within et al. 3o, obtained oxygen contents of the order of 0.5 per
the interstices between the initial crystals of secondary
products of electrolysis and that in time these products ~4Ontario Research Foundation, Toronto Canada.
reach concentrations sufficient to cause them to act as do 25 Chromium Corporation of America, Waterbury,
addition agents and give rise to a finely crystalline de- Connecticut.
26 Phys. Rev., 3% 186 (1932).
s0 Trans. Electrochem. Soc., 54, 163 (1928). 27 Trans. Electrochem. Soc., 92, 537 (1947).
21 Trans. Faraday Soe., 26, 525 (1930). ~8Bendix Products Division, South Bend, Indiana.
22 j . Chem. Soc., 1949, 483. 29Defense Research Laboratories, Maribyrnong, Vic-
~3Research Laboratories, Westinghouse Electric Cor- toria, Australia.
poration, East Pittsburgh, Pennsylvania. ~oj . Research Nat. Bur. Standards, 40, 31 (1948).

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