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Werkstoffe und Korrosion 29, 515-519 (1978) Quantitative measurements of corrosion rate 515

Overlag Chemie, GmbH, D4940 Weinheim, 1978

in 24 Std. 30 ml und bei Zusatz von 2,5%iger NaCl 50 In1 H 2 b) unter Sauerstoff bzw. Stickstoff
entwickelt. c) in Abhangigkeit von der Art und Oberflachenbeschaffen-
Die fur den Standardansatz geforderten Bedingungen erfullt heit des Aluminiums
u. E. waarige Salzsaure a m besten. Wir haben deshalb die Auf- d) bei Zusatz von Fremdionen.
losungsgeschwindigkeit von 0,2 g Aluminium in Salzsaure un- Bei der Korrosion von Aluminium unter Sauerstoff wird ei-
terschiedlicher Konzentration untersucht. Uber das Ergebnis nerseits Sauerstoff verbraucht und andererseits Wasserstoff
orientiert Abb. 8. entwickelt. Bei pH-statischer Kontrolle unter gleichzeitiger
Beobachtung der Volumenveranderung kann der Anteil der
beiden Konkurrenzreaktionen bei pH 2 und pH 3 mit Hilfe
einer einfachen Apparatur quantitativ bestimmt werden. Die
200 Anwendungsgrenzen dieses Meaverfahrens werden angegeben.
160 Zur Durchfuhrung routinemafiiger Inhibitionsversuche
120
wird ein Standard-Ansatz entwickelt, der unter Stickstoff als
Schutzgas reproduzierbare Werte liefert.
80
LO
Dank
Der Deutschen Forschungsgemeinschaft danken wir fur die
Abb. 8. Auflosungsgescliwindigkeit von 0,2 g Aluminium in 120 ml finanzielle Forderung unserer Untersuchung auf dem Gebiet
Salzsaure unterschiedlicher Konzentration bei Zusatz von jeweils
2,5% NaCl unter Stickstoff. a) 1,5n HCI; b) I n HCI; c ) 0,5n HC1; der Korrosion des Kupfers und Aluminiums. Herr Prof. Dr.
d) 0,2n HC1 G. Winkhaus, Vereinigte Aluminium-Werke, hat uns freund-
licherweise Aluminiumfolie (99,99/al) zur Verfugung gestellt,
Fig. 8. Dissolution rate of 0.2 g aluminium in 120 ml hydrochloric
acid of different concentrations with addition of 2.5% NaCl under wofur wir bestens danken.
nitrogen (Eingegangen: 3. 1.1978)

Fur den Standard-Ansatz zur Uberprufung organischer Ver-


bindungen auf ihre Wirkung als Korrosionsinhibitoren des Alu- Schrifttum
miniums hat sich schliefilich eine wa8rige Losung von 1 n Salz-
1. 21. Mitteil. L. Horner und Chr. L. Horner: Werkstoffe u. Korro-
saure mit einem Zusatz von 2,5% NaCl unter Stickstoff sion29 (1978) 101.
empfohlen. Uber das Prufungsergebnis von mehr als 400 or- 2. Auszug aus der Diplomarbeit K. Meisel, Universitat Mainz 1977.
ganischen Verbindungen unterrichtet eine spatere Veroffent- 3. L. Horner, F. Rdttger, H. Hinrichs und H. Ertel: Werkstoffe u.
lic hung. Korrosion 16 (1965) 36.
4 . Vgl. den zusammenfassenden Bericht von L. Horner: Chemiker
Ztg. 100 (1976) 247.
Zusammenfassung 5. L. Horner, E. Pliefke und K. Meisel: Werkstoffe u. Korrosion 28
(1977) 607.
Die Korrosion des Aluminiums wird untersucht: 6 . G. Winkhaus und W. Griihl: Chemiker Ztg. 97 (1973) 311.
a) in Abhangigkeit vom pH ohne und mit Zusatz von NaCl W 1982

Quantitative measurements of corrosion rate of reinforcing steels


embedded in concrete using polarization resistance measurements
Quantitative Messung der Korrosionsgeschwindigkeit von Bewehrungsstahl in Beton mit Hilfe-der
Polarisa tionswiders tandsmessung
C. Androde*) and J. A . Gonzhlez**)

Summary Kurzfassung
Up to this time all the methods to measure the corrosion Alle bisherigen Methoden zur Bestimmung der Korrosions-
rate of reinforcing steels embedded in hardened concrete have geschwindigkeit von Bewehrungsstahl in gehartetem Beton
been o f the destructive type, which requires much time and waren destruktiv und erforderten betrachtlichen Zeit- und
materials and makes the full scale study o f th e phenomenon Materialaufwand, wodurch eine umfassende Untersuchung
difficult. The authors have applied the polarization resistance dieser Korrosionserscheinungen erklart wurde. Bei Verwen-
method to bars embedded in hardened mortar and immersed dung der Polarisationswiderstundsmethode wurde an in ge-
in Ca(OHj2-saturated solution, and have f o u n d an acceptable hartetem Beton eingebetteten Stangen, wobei die Proben in
agreement between the gravimetric and th e electrochemical gesaftigter Calciiimhydroxidliisung gelager f wurden. eine an-
weight loss data. nehmbare Ubereinstimmung zwischen den gravimetrisch
und elektrochernisch ermittelten Gewichtsverlusten gefun-
*) Frau Dr. C . Andrade, Chemical Dept. of IETCC and Corrosion den.
Dept. of CENIM, Centro Nacional de Investigaciones hletalikgicas,
Ciudad Universitaria, Madrid-3. **) Dr. J. A . Gonzdlez, Corrosion Dept. oTCENIM.
5 16 Andrade and Gonzalez Werkstoffe und Korrosion 29,515-519 (1978)

1. Introduction not been applied as widely t o concrete as t o other materi-


als. When it was actually applied, either the limitations were
In concrete, the electrolyte is represented by t h e liquid ignored, so that erroneous results were obtained or, saturated
phase that fills t h e pores; it is, fundamentally, a Ca(OH)*- Ca(0H)z solutions were used only, so that though t h e ther-
saturated solution which, according t o Peguin and coll. ( l ) , modynamic properties (potential and pH) are similar t o those
who have extracted t h e solution by strongly compressing of the hardened concrete, the kinetic properties are very
concrete specimens, contains SO4', K',Na+, S = and, some- different (3, 24, 25).
times, also other ions, if they have been added as additives; The most important of t h e above limitations, and the errors
according t o these authors, the pH is > 13. which they may introduce into t h e final result, are:
At this high pH, and at t h e corrosion potentials of t he a) the IR-drop between t h e bars due to the high resistivity of
reinforcements, t h e steel is in t h e passivity zone of Pourbaix's the concrete, which results in a smaller I,,,, than the true
diagram (2). Therefore, it is indefinitely protected provided one, and
th e medium conditions are not changed. However, such chang- b) t h e estimated value of constant B which influences also the
es in th e concrete service conditions which shift the steel values of I,,,,.
reinforcement into t h e corrosion zone (2), are relatively fre- For several years, the authors of the present report have
quent, and have been described by numerous authors (3-6).
tried t o measure the corrosion rate of steel reinforcement em-
So, carbonation concrete decreases t h e pH, and produces a
bedded in hardened concrete and they have only attained a
general corrosion t h e magnitude of which depends mainly o n
semi-quantitative relation between t h e R p indications and
the coincidence with other corrosion factors e. g. enough
t h e visual observations of t h e steel in t h e broken concrete
moisture. T h e presence of depassivating ions o r cracks pro-
duces localized attack and, finally, t h e simultaneous action beams (due to the large size of the beams 2 x 0.1 x 0.1 rn -
~

no gravimetric tests can be taken for comparison with the


of mechanical stress and aggressive factors can be t h e origin
electrochemical ones).
of stress corrosion cracking. In any case, the corrosion of re-
inforcing steel can cause very important damage. The present paper reports the results of a n investigation
into t h e relation between the gravimetric and the electrochemi-
Up t o this time t h e method most widely used t o determine cal tests using polarization resistance measurements of several
th e corrosion rate of reinforcements has been t h e gravimetric reinforcing steel bars embedded in hardened mortar and im-
weight loss; complemented with data o n t h e percentage of mersed in Ca(OH)z-saturated solution.
corroded surface and depth and number of pits per unit area.
However, this method is time-consuming, requires a large num-
ber of samples and t h e results frequently lack sufficient accu-
racy. 2. Experimental Method
T h e electrochemical techniques, which were applied for
2.1. Materials
the first time in 1959 by Kuesche (7), Baurnel ( 8 ) and Baumel
and Engell(9) t o hardened concrete specimens immersed in
The bars used as test materials were of high strength pre-
Ca(OH)2-solutionopened up a promising field, that has later
stressed steel, cold drawn, 7 m m dia. and 8 cm long. The bars
been investigated by many authors ( 10--14). Fundamentally,
they used potential-current density and E,,,-time curves. With were polished with abrasive paper up to number 0 0 , washed
regard to the latter, the limitations of t h e corrosion potential in water and degreased in acetone. The tests had a duration
in providing quantitative kinetic indications are well-known. of about 30 days after which the bare steel was cleaned in
inhibited HCl and the galvanized steel in 20% NH4C1 solution.
As far as current density-potential curves are concerned, it has
been shown that they are useful for studying t h e tppe of addi- The mortar was prepared according t o Spanish Standard
tives which destroy the inherent passivity of steel in strong RC-75 (26) with a w/c ratio of 0.5 and a cement:sand ratio
alkaline media and the conditions necessary for this phenome- of 1 : 3 . The specimens were cured in an environment, with
non t o occur. Nevertheless, t h e use of such curves for deter- over 90% of relative humidity at 20 f 2' C during t h e first
mining the instantaneous corrosion rate is laborious and, as 24h and then kept in polyethylene bottles, with a 2 cm depth
very high polarisations are necessary, the use of t h e same elec- of water t o moisten the mortar and decrease the IR-drop
trode for successive experiments involves some risk. across it. Several types of cements were used: normal Port-
land cement (P-350), Slag cement (S-111-250) and Pozzolanic
Thus, t h e quantitative methods investigated so far t o deter-
cement (PUZ-1-350) (25)
mine th e corrosion rate of reinforcing steels are, more o r less, The cements were used without and with additives (analy-
destructive and require a long and tedious work, so that t o have
tical grade): CaClz up t o 2% (all the proportions are in rela-
a non-destructive test method would b e a desirable progress,
tion t o cement weight) and Ca(HC00)z up t o 3% as depas-
not only for the laboratory studies but also t o control the
sivating agents, and NaNOz up t o 4% as inhibitor. Calcium
structures a t working sites.
formate, used as a curing accelerator in place of CaCI2, has
For this purpose. the polarization resistance technique has been considered a depassivating agent because when it is added
been studied which was first described by Wagner and Truud t o a saturated Ca(OH)z solution a rise of' breakdown poten-
( 16) and then developed by Stern and coll. (1 6 , 17) and which tials results. O n the other hand, when it was used in t h e tests
is increasingly used t o nieasure instantaneous corrosion rates. carried out with mortar specimens the passivation layer did
Although, in recent years numerous literature which discusses not fail.
the limitations and modifications of its accuracy and validity
has been published (18-20) and there are still some aspects
to be clarified (2 1 - - 2 3 ) >it is necessary t o admit it has rendered
an outstanding service t o corrosion science because of its sim- 2.2 Experiments
plicity. rapidity and non-destructive nature.
There are many difficulties in t h e application of t h e electro- Two sets of experiments were carried out:
chemical techniques t o concrete because of the high electrical 1) In the first set, the corrosion rate of the steel bars (bare
resistivity of the medium, t h e impossibility of direct observa- and galvanized) immersed in a saturated Ca(OH)z solution
tion of t h e electrodes and the heterogeneity of the concrete is measured using a polyethylene corrosion cell (more re-
itself, which makes necessary t h e preparation of series of identi- sistant than glass t o alkaline attack) as shown in Fig. I ,
cal specimens. Therefore, t h e electrochemical techniques have where t h e electrolyte is covered with an oil layer to avoid
Werkstoffe und Korrosion 29, 515-519 (1978) Quantitative measurements of corrosion rate 517

REFERENCE ELECTRODE simultaneously t h e carbonation of the solution and the


r localized attack along t h e water-line. This procedure is
more effective than shaking, bands, resins and greases, be-
cause these cannot stop the carbonation of the solution.
2) The other set was performed with 2 x 5.5 x 8 cm hard-
ened mortar specimens with embedded bars identical t o
t h e first set, as shown in Fig. 2. Also it was necessary t o
OIL insulate t h e steel in the interphase mortar-air with an
epoxy resin.
~

PO LY ET H Y L E N E
CELL 2.3. Procedure

The R p measurements were taken every day, with an AMEL


CALCIUM H Y D R O X I D E potentiostat. The total weight loss is obtained from the area
S ATU RAT. S 0 L UT I0 N
integration of the I,,,,-time curve.
Up to t h e present time, intensiostatic measurements with
2-electrode systems have been made (3)(24). In the present
work, potentiodynamic measurements were taken by polariz-
SOLID C A L C I U M
' HYDROXIDE ing cathodically from the Eco,, up to -10mV, and then, up to
'10 mV, t o obtain the original slope (26).
By continuously moistening t h e mortar t h e influence of
IR-drop is reduced, but not eliminated.
An intermediate value of the constant B is chosen: 26 m V
for the bare steel in the active state and for galvanized steel,
and 52 ni V for bare steel in the passive state. With these va-
lues the highest possible error is 100%(17).

3. Results

Fig. 3 shows, in logarithmic coordinates, the gravimetric


weight loss against the electrochemical loss calculated from
Rp values for the reinforcing steel bars kept in saturated Ca
(OH), solution, and Fig. 4 shows thc same results for the re-
Fig. 1. Polyethylene corrosion ccll for the experiments in saturated inforcing steel bars embedded in hardened mortar.
Ca(OH), solution Each point represents only one bar. The large differences
Abb. 1. Fiir die Versuche mit gesattigter Calciumhydroxidlosung in the total attack are due to t h e different additives in the
verwendete Korrosionszelle aus Polyethylen mortar, this effect permits the passive and active states of the
steel t o be studied.
T h e effect of each additive in particular can be seen from
the tests carried out both in saturated Ca(OH)2 solution and
in mortar, b y comparing Figs. 3 and 4 with tables 1 and 2,
respectively .
In fig, 4 there is a general tendency for the gravimetric loss
t o be higher than the electrochemical obtained value. This be-
haviour may be explained by the fact that the IR-drop is not
totally eliminated, as is mentioned in paragraph 2. Inspite of
this, a good agreement can b e seen in t h e results of both kinds
of measurements.
Now the authors are performing similar experiments with
a potentiostat with automatic elimination of IR-drop and, in
a future work, they expect t o obtain a greater precision con-
cerning t h e true influence (which is not more than 20-40%
in moist mortar) of this factor o n the Kp measurements, and
also a more approximate value of constant B for steel embed-
ded in hardened mortar.

4. Discussion and Conclusions

The experiments in saturated Ca(0H)z solution have been


mainly performed t o obtain a sufficiently approximate value
of constant B (due t o the high conductivity of thc solution
there is not appreciable IR-drop between the reference and
working electrode) for the steel in very alkaline media, and
to apply this value t o the mortar experiments. From the re-
Fig. 2. Mortar specimen Abb. 2. Mortelprobe sults shown in fig. 3 and other experiments carried out in sim-
5 18 Andrade and Gonzalez Werkstoffe und Korrosion 29,515-519 (1978)

i.
B A R E S T E E L [ A WITH DEPASSIVATING IONS BARE s WITHOUT ADDITIVES
A WITH DEPASSIVATING IONS

$STIZED { o

o
W I T H O U T ADDITIVES
WITH DEPASSIVATING I O N S
WITH DEPASSIVATING A N D INHIBITING IONS
STEEL WITH DEPASSIVATING AND INHIBITING IONS

4
I;/

N
u
f
o
.
*o -1
o a
.; 2 :.z- N na*Io-np
6 0 d d
ELECTROCHEMICAL WEIGHT LOSS ( mg/cmz) ELECTROCHEMICAL WEIGHT LOSS (mg/cm21

Fig. 3. Gravimetric and electrochemical wcight loss of steel bars in Fig. 4. Gravimetric and electrochemical weight loss of the steel bars
saturated Ca(OH), solution. The data for bare steel without additives in the mortar tests
and with depassivating and inhibiting ions have not been included due Abb. 4. Grdvimetrisch und elektrochemisch ermittelte Gewichtsver-
to the reduced attack (a weighing error would be of the same order, luste von in Mortel eingebetteten Stahlstangen
or higher, than the real weight losses)
Abb. 3. Gravimetrisch und elektrochemisch ermittelte Gewichtsver- Table 2. Nature and ratio of additives and type of cement in the hard-
luste von Stahlstangen in gesattigter Calciumhydroxidlosung. Die An- ened mortar experiments
gaben, die fur blanken StaN in Losungen ohne Zusatzstoffe und mit
depassivierenden und inhibiercnden Ionen gefunden wurden, sind Tabelle 2. Art und Mengenanteile der Zusatzstoffe und Zementtyp
wegen des geringen Angriffs nicht aufgefmt (ein Wagefehler w2re bei den Versuchen mit g e h ~ t e t e mBeton
mindestens so groiS wie der tatsachliche Gewichtsverlust)
Number Cement Additives Ratio
in fig. 4 type (26)
Table 1. Nature and ratio of additives and characteristics of steels -
1 P-350 without add.
used for the experiments with saturated Ca(OH),solution
2 P-350 CaCl, 2%
Tabelle 1. Art und Mengenanteile der Zusatzstoffe und Eigenschaf- 3 P-350 CaC1, 3%
ten der fur die Versuche mit der gesattigten Calciumhydroxidlosung 4 S-111-250 CaCl, 2%
verwendeten Stahle 5 PUZ-1-350 CaCl 2%
6 P-350 Ca(&oO), 3%
7 P-350 CaCl, + NaNO, 1%+2%
Number Additives Ratio Steel 8 P-350 CaCl, + NaNO, 2%+ 4%
in fig. 3
9 P-350 without add. -
1 KCL 0,lO mol/l Black 10 P-350 CaC12 2%
Black 11 P-350 CaCl, + CrOx 2% + 100 ppm
2 KC1 0,72 mol/l Black
3 Ca(HCOO), 0,05 mol/l Black
4 Ca(HCOO), 0,30 mol/l Black
ilar conditions (25) (27) it can b e inferred that the values of
5 without addit. ~
Galvanized B = 26 m V for t h e bare steel in the active state and t h e galva-
6 KC1 0,03 mol/l Galvanized nized steel, and 52 m V for t h e bare steel in t h e passive state,
7 KC1 0,72 mol/l Galvanized
Galvanized are acceptable.
8 CrO3 100 ppm
9 KCI + C r 0 3 0.10 mol/l+ Galvanized In t h e case of the mortar experiments, fig. 4, the agreement
+ 100 ppm is not so perfect, b u t if it is considered that such results yield
d a t a which differ b y up to t w o orders of magnitude, and that,
10 without addit. ~
Galvanized with
a pickled ring
excepting some cases, t h e error factor is less t h a n t w o o r three,
11 KCl 0,lO moll1 Galvanized with it is evident that the Rp m e t h o d provides sufficiently approx-
a pickled ring imate values. This situation will improve, undoubtedly, when
t h e IR-drop is eliminated.
12 without addit. - Galvannealing
0,lO mol/l Galvannealing
In spite of t h e limitations mentioned, it is possible to con-
13 KCI
clude that t h e Rp m e t h o d is a technique suitable f o r t h e quan-
Werkstoffe und Korrosion 29, 519-522 (1978) Lochfrai3 an Kupferrohren und oberflachlicher Kohlenstoff 5 19
a v e r l a g Chemie, GmbH, D-6940 Weinheim, 1978

titative and reproducible determination of t h e instantaneous 5 . Rilem (12-CRC Committee): Mater et Const, No 51 (1976) 187.
corrosion rate of reinforcing steel embedded in hardened con- 6. I$. Kaesche: Archiv Eisenhiittenwesen 36 (12) (1965) 91 1.
crete, and it presents t h e invaluable advantages of rapidity and 7. H. Kaesche: Zement-KalkCips 12 (7) (1959) 289.
non-destructive nature; if up to now it has been used in labo- 8. A. Baumel: Zement-Kalk-Gips I 2 (7) (1959) 294.
9. A. Baumel and H. J. Engell. Archiv. Eisenhhttenwesen 30 (7) (1959)
ratory experiments only it should be possible t o apply it t o 417.
structures a t t h e working site or t o specimens specifically 10. K. S. Rajagopalan, N. S. Rengaswmy and T.M.Balasubramanian:
placed to this purpose. J. Scient. Ind. Res. 28 (1969) 382.
11. V. Amicarelli and R. Caromazza: L Indust. Ital. Cement 2 (1968)
67.
12. K. Kishitani: J o f Faculty of Eng. Univ. Tokyo (1970).
Acknowledgments
13. J. Olden and H. Polsfer: Baup-Bauteck 25 ( 8 ) (1971) 371.
14. V. K. Gouda; M.A. Shater andR, Sh. Mikhail: Cement and Concrete
T h e authors are grateful d o Dr. Feliu, Head of Corrosion Res5 (1975) 1.
and Protection Department of CENIM, and Dr. Fullea, for their 15. C. Wagner and W. Traud: 2. Elektrochem 44 (1938) 391.
suggestion at t h e initiation of t h e work, and t o the Chemical 16. M.Stern and A. L. Geary: J . Electrochem. SOC104 (1957) 56
Department of IETCC for t h e facilities to carry o u t t h e tests. 17. M. Stern and E. D. Weisert: Proc. Am. SOC.Test. Mat. 5 9 (1959)
1280.
(Eingegangen: September 1977) 18. F. Mansfeld: J. Electrochem. SOC. 120 (1973) 515.
19. G. A. Marsh: Proc. 2nd. Int. Cong. Met. Corr. N . York (1963) 936.
20. D. A. Jones and N, D. Greene: Corrosion 7 (1966) 198.
21. J. A. Gonzhlez and J. Fullea: Corr. y Prot.5 (5) (1974) 273.
22. L. M. Callow,J. A . Richardson and J. L. Dawson: Br. Corr. J. 3
References (1976) 132.
23. M. Prafciik: Werk. u. Korr. 25 (1974) 104.
1. P. Peguin, M.Rubaud, P. Longuet and A. Zelwer: Cahiers du Centre 24. C. Andrade: Working Paper No 30. IETCC, Madrid.
Sci. et Tech. du B&; No 130, June 1972, cahier 1109. 25. J. A. Gonzdlez and C. Andrade: Mat. de Const., 165 (1977) 69.
2. M. Pourbaix: Atlas d Equilibres Electrochimiques & 25 C, Ed. 26. RC-75: Pliego de prescripciones tBcnicas generales para la recepcion
Gauthiers-Villars, Paris 1963. de cemento. MOP 1975, Madrid.
3. C. Andrade: Doctoral Thesis, Madrid, July 1973. 27. C. Andrade, A. J. Va2quez and J. A. GonzPez: Rev. de Met. CENIM
4.J. Calleja: Mat. de Const, No 150-151 (1973) 153. 13 (3) (1977) 142.
W 1992

Lochfraf3 an Kupferrohren und oberflachlicher Kohlenstoff:


ESCA-Untersuchungen
Pitting corrosion of copper tubes and carbon deposits: ESCS studies

P. Callot*), A . Jaegle**), A . Kalt**) und G. Name***)

Kurzfassung Summary

Es wird gewohnlich angenommen, daj3 LochfraP vom T y p I I t is usually accepted that pitting I isgenerally connected
mit der Anwesenheit eines Kohlenstoffilms an der Oberflache with the presence o f a carbon f i l m on the inner surface o f cop-
von Kupfer verbunden sein kann. per pipes. Samples o f annealed copper pipes showing pitting
Durch Rontgenpulveraufnahmen konnte im oberflach- corrosion o f type Z have been examined and the solid products
lichen Belag von gegluhten Kupferrohren, die durch Lochfrafi scraped o f f f r o m the surface have been submitted to X-ray
vum Typ I korrodiert waren, Malachit, Atakamit, Kupfer (I)- diffraction. Malachite, atacamite, cuprous chloride, tenorite
Chlorid, Tenorit und Cuprit nachge wiesen werden. and cuprite have been detected. Significant amounts o f carbon
Rontgeninduzierte Photoelektronenspektroskopie-Unter- were found by chemical analysis. X-ray induced photoelectron
suchungen und lonen-Beschuj3 haben bewiesen, dap Verbin- spectroscopy studies and ionic etching o f the coatings on the
dungen, die Kupfer(II] enthalten, nur in den obersten Schich- inner surface of the pipes have shown that copper11compound.r
ten vorliegen und daj3 der Belag hauptsachlich aus Cuprit be- occur only in the outer layer. Cuprite is the main constituent.
steht. Kohlenstoff ist zwar varhanden, aber die Abtragung Removal o f successive layers by ionic etching proves that car-
der auj3eren Schichten durch Ionenbeschufi zeigt, da$ Koh- bon does not form a continuous film b u t is almost evenly dis-
lenstoff nicht lediglich einen Film bildet, sondern in der gan- tributed across the whole thickness of the oxide coating.
zen Dicke des Oxidbelags verbreitet ist.

*) Institut des Sciences Exactcs et Appliquies, 4, rue des Frbres LUmihe, F-68093 Mulhouse Cedex
**) Laboratoire de Spectroscopie Electronique, 4, rue des Frkres LumiBre, F-68093 Mulhouse Cedex
***) Office de la Recherche Scientifique et Technique Outre-Mer (0.R. S . T. 0. M.)