Corrosion Science, Vol. 39, No. 6, pp.

1137-1139, 1997
Pergamon Elsevier Science Ltd
Printed in Great Britain

PII: 80010-938x(97)00040-1

LETTER TO THE EDITOR

Reply to “The effect of chromium enrichment in the film formed by surface treatments on the
corrosion resistance of type 430 stainless steel” by T. Hong,T. Oguthi and M. Nagumo,
CorrosSci. 38,881 (1996)

J.L. Crolet, Elf-Aquitaine, 64018 Pau (France)

The data presented rn thrs artrcle are very kItereStIng from a SClentlflC point of view Unfortunately. the
paper often uses an ambrguous and therefore improper vocabulary It also makes statements on the
corrosron resstance of stamless steels which are not estabkshed, and thus Induce misleading

conclusrons

Vocabulary

The surface treatments of starnless steel In mtnc actd baths descrrbed In thus paper are called
“passrvabon” by the authors (p 884) Wrth reference to field applrcatron. thus denornrnabon proved to be
very ambrguous Indeed. after prckling or mechanical polishing. the mere rinsrng water already
passrvates stainless steels Then any other treatment would stmply passtvate them drfferently and
supposedly better Therefore, they should not be called “passivabon” but “overpassivatton”’ Also, they
must not be confused with the “decontamrnation” treatments rn cold diluted nrtric acrd’ * e g 15 mm rn
3M HN03 (I e 17 % w % or 25 vol %) The latter are pnmarily armed at cleanrng the metal surface
and drssolvrng non statnless lmpunbes (e g particles of iron or Iron oxrde, soluble non metalkc
rnclustons)

Regarding the “relabonship” between the two measured quantibes, namely the chromium ennchment
and the potential at 50 % pitting probabrkty. it IS frrst “suggested” (p 889) Then, only four lanes later, It
becomes “confirmed”, and It is deftmtely stated In the conclusion, the trtle and the abstract In
companson. the actual experimental mformatron IS just the srmultaneous observatron of vanatrons rn
both quantttres

In the same way polansation reSlStanCeS are not expressed In fL cm*, but In Q (ftg 7). whrch IS

meamngless Nevertheless, It seems that the base value should be 200 kf2 cm2, whrch corresponds to

1 pm/y At thus level. It IS drffrcult to consrder that any varrabon could be srgmfrcant rn terms of
“protective properhes” (p 887)

Furthermore. the reported absolute prttfng probabrlrty (scale O-100 % In frg 3) stnctly refers to the
present expenments and therr detarled expenmental protocol (especrally surface of samples and
potenbal sweep rate) In thus respect. a general charactensabon of the prttrng resrstance of starnless
steel would have requred to report the results In terms of elementary prttrng probabrl$ rn cm-2, or strll
better as a prt generation rata3 ln cm 2h-’

1137
1138 F. Mansfelt and C.C. Lee

Relevance of electrochemical data to corrosion resistance

Thrrty years ago, surface treatments in concentrated or warm nitrtc acrd were extensrvely studted by
J M Defranoux’ under the name of “superpassrvatron” (unpublrshed results) In 1977 however, they
were shown to be very close to an artefact’ at best, they mrght help to prevent unfortunate early

farlures. but they do not basrcally change the long term prttrng resistance of a starnless steel surface

In the present paper, these overpassrvabon treatments were shown to Increase the Cr content of the
passive layers and Improve the curves of plttlng probabrlrty (fig 3) It was then “concluded” that the
latter IS due to the former, which is not necessarily the case In thus respect the drrect observatron of
the actual polansabon curfes would have been of utmost Interest In example, for srmrlar (or related)
treatments, we had observed2 that one important consequence of such a surface condrtronrng was to

remove the strongest prt nuclet from the surface, and therefore decrease the number and frequency of

the so called “repassrvated prW4. I e these transitory drssoluhon peaks starting and abortrng below the
cntrcal prtbng potentral’ (hgure Rl) At a grven potential, this means that the Incubation bme of prttrng IS
Increased By simple mathematrcal denvahon, It IS then easy to appreciate that any Increase of this
rncubatron trme does Increase the potenhokinehc plttrng potentra16 At the end of the day, If thus
rncubatron trme reaches one hour or more, which IS quote easy, and If the trme necessary for drawrng a
polansabon curve up to the domain of oxygen evolution remarns below one hour which IS qurte

common, then the experimental curve wrll no longer drsplay a cntrcal ptttrng potentral From the raw
expenmental fact, one would then conclude that this treated sample “cannot prt”, whereas In
potenttostatrc exposures longer than one hour, rt would strll pit

In the present day method of figure 3. this IS expressed by a decrease of the prthng probabrlrty at
constant potential However, this may correspond to erther a translatron of the curve to the right.. or a
simple rotation around Its ongrn on the x axrs Even 11the appearence of the figure remarns somewhat
smrlar in both cases the practrcal consequences are basrcally different

_=+__,
0.6 - 0.6 1 rAkm2

0.4
4 b
-5
P F
/

E
,i
0
IE

01 I 10
_A 01 1 10
A,D B

Frgure RI polarlsation curves on four heats of type 430 Stainless steels In 0 02 M NaCI, pH 6 6 at
23°C P = “passrvated” 15 mn rn 3M HN03 (17 %) at RT, E = emeri polished , A, 8, C = 0 5 % Mn and
resp 0 002.0 025 and 0 059 % S ;D = 0 1 Mn and 0 024 % S*
 Letter to the editor 1139

Obviously, the curve of prttrng probabilrty IS necessanly drawn from expenmental measurements made

wrth a prt generatron rate3 rn the range of the cm.%’ On the contrary the long term prttrng resrstance
must be assessed from an extrapolation In the range of 10.’ to 10.’ rn-‘y.’ Wrth the present scale of the
y axis, thus would correspond to the very low part of the prttrng probabrlrty curve rn these expenments
Srmrlarly, the 200 mV commonly separating the two ranges of prt generation rate does correspond to
the safety margrn formerly recommended by the ancients rn the comparison between free corrosron
potentral and the “classrcal” pittrng potentral. as It was measured before the multr-prt method’ Then a
translation of the prttrng probabrlrty curves would represent a real Improvement of the prtbng resrstance,
whereas a rotatron just expresses the same short term artefact already reported rn 19772. The present
paper clearly corresponds to the latter case. and It should not generate ~llusor-y expectatrons

In conclusron. the paper of Hong, Ogushr and Nagumo IS very rnteresbng on a screntrfrc basis, but rt
may also be extremely dangerous through what IS rmplrcrtly suggested Therefore this warnrng was felt

necessary for preventing any improper extrapolation of these raw data to misleading industrial

judgements

Reference

1. J.M. Defranoux Corros. Sci. 8. 245 (1968)

2. J -L Crolet. L Seraphin. R Tricot, Mem. Scient Rev. Metall 74, 647 (1977)

3 B. Baroux Corros. Sci. 28, 969 (1988)

4 J M Defranoux Corros. SCI. 3, 75 (1963)

5 C. Boulleret, D. Gorse and B. Baroux Corros. Sci. 38, 999 (1996)

6 J -L Crolet. L Seraphin and R Tncot. Compt-Rend. Acad SCI. T280, serie C, 333 (10 fevrrer 1975)