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
entwickelt.
Die fur den Standardansatz geforderten Bedingungen erfullt
u. E. waarige Salzsaure a m besten. Wir haben deshalb die Auf-
losungsgeschwindigkeit von 0,2 g Aluminium in Salzsaure un-
terschiedlicher Konzentration untersucht. Uber das Ergebnis
orientiert Abb. 8.
200
160
120
80
LO
Abb. 8. Auflosungsgescliwindigkeit von 0,2 g Aluminium in 120 ml
Salzsaure unterschiedlicher Konzentration bei Zusatz von jeweils
2,5% NaCl unter Stickstoff. a) 1,5n HCI; b) I n HCI; c ) 0,5n HC1;
d) 0,2n HC1
Fig. 8. Dissolution rate of 0.2 g aluminium in 120 ml hydrochloric
acid of different concentrations with addition of 2.5% NaCl under
nitrogen
b) unter Sauerstoff bzw. Stickstoff
c) in Abhangigkeit von der Art und Oberflachenbeschaffen-
heit des Aluminiums
d) bei Zusatz von Fremdionen.
Bei der Korrosion von Aluminium unter Sauerstoff wird ei-
nerseits Sauerstoff verbraucht und andererseits Wasserstoff
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
Anwendungsgrenzen dieses Meaverfahrens werden angegeben.
Zur Durchfuhrung routinemafiiger Inhibitionsversuche
wird ein Standard-Ansatz entwickelt, der unter Stickstoff als
Schutzgas reproduzierbare Werte liefert.
Dank
Der Deutschen Forschungsgemeinschaft danken wir fur die
finanzielle Forderung unserer Untersuchung auf dem Gebiet
der Korrosion des Kupfers und Aluminiums. Herr Prof. Dr.
G. Winkhaus, Vereinigte Aluminium-Werke, hat uns freund-
licherweise Aluminiumfolie (99,99/al) zur Verfugung gestellt,
wofur wir bestens danken.
(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-
saure mit einem Zusatz von 2,5% NaCl unter Stickstoff
empfohlen. Uber das Prufungsergebnis von mehr als 400 or-
ganischen Verbindungen unterrichtet eine spatere Veroffent-
lic hung.
Zusammenfassung
Die Korrosion des Aluminiums wird untersucht:
a) in Abhangigkeit vom pH ohne und mit Zusatz von NaCl
1. 21. Mitteil. L. Horner und Chr. L. Horner: Werkstoffe u. Korro-
sion29 (1978) 101.
2. Auszug aus der Diplomarbeit K. Meisel, Universitat Mainz 1977.
3. L. Horner, F. Rdttger, H. Hinrichs und H. Ertel: Werkstoffe u.
Korrosion 16 (1965) 36.
4 . Vgl. den zusammenfassenden Bericht von L. Horner: Chemiker
Ztg. 100 (1976) 247.
5. L. Horner, E. Pliefke und K. Meisel: Werkstoffe u. Korrosion 28
(1977) 607.
6 . G. Winkhaus und W. Griihl: Chemiker Ztg. 97 (1973) 311.
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
Up to this time all the methods to measure the corrosion
rate of reinforcing steels embedded in hardened concrete have
been o f the destructive type, which requires much time and
materials and makes the full scale study o f th e phenomenon
difficult. The authors have applied the polarization resistance
method to bars embedded in hardened mortar and immersed
in Ca(OHj2-saturated solution, and have f o u n d an acceptable
agreement between the gravimetric and th e electrochemical
weight loss data.
*) Frau Dr. C . Andrade, Chemical Dept. of IETCC and Corrosion
Dept. of CENIM, Centro Nacional de Investigaciones hletalikgicas,
Ciudad Universitaria, Madrid-3.
Kurzfassung
Alle bisherigen Methoden zur Bestimmung der Korrosions-
geschwindigkeit von Bewehrungsstahl in gehartetem Beton
waren destruktiv und erforderten betrachtlichen Zeit- und
Materialaufwand, wodurch eine umfassende Untersuchung
dieser Korrosionserscheinungen erklart wurde. Bei Verwen-
dung der Polarisationswiderstundsmethode wurde an in ge-
hartetem Beton eingebetteten Stangen, wobei die Proben in
gesaftigter Calciiimhydroxidliisung gelager f wurden. eine an-
nehmbare Ubereinstimmung zwischen den gravimetrisch
und elektrochernisch ermittelten Gewichtsverlusten gefun-
den.
**) Dr. J. A . Gonzdlez, Corrosion Dept. oTCENIM.
5 16 Andrade and Gonzalez
1. Introduction
In concrete, the electrolyte is represented by t h e liquid
phase that fills t h e pores; it is, fundamentally, a Ca(OH)*-
saturated solution which, according t o Peguin and coll. ( l ) ,
who have extracted t h e solution by strongly compressing
concrete specimens, contains SO4', K',Na+, S = and, some-
times, also other ions, if they have been added as additives;
according t o these authors, the pH is > 13.
At this high pH, and at t h e corrosion potentials of t he
reinforcements, t h e steel is in t h e passivity zone of Pourbaix's
diagram (2). Therefore, it is indefinitely protected provided
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
reinforcement into t h e corrosion zone (2), are relatively fre-
quent, and have been described by numerous authors (3-6).
So, carbonation concrete decreases t h e pH, and produces a
general corrosion t h e magnitude of which depends mainly o n
the coincidence with other corrosion factors e. g. enough
moisture. T h e presence of depassivating ions o r cracks pro-
duces localized attack and, finally, t h e simultaneous action
of mechanical stress and aggressive factors can be t h e origin
of stress corrosion cracking. In any case, the corrosion of re-
inforcing steel can cause very important damage.
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
weight loss; complemented with data o n t h e percentage of
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.
T h e electrochemical techniques, which were applied for
the first time in 1959 by Kuesche (7), Baurnel ( 8 ) and Baumel
and Engell(9) t o hardened concrete specimens immersed in
Ca(OH)2-solutionopened up a promising field, that has later
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 providing quantitative kinetic indications are well-known.
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-
tives which destroy the inherent passivity of steel in strong
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-
mining the instantaneous corrosion rate is laborious and, as
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.
Thus, t h e quantitative methods investigated so far t o deter-
mine th e corrosion rate of reinforcing steels are, more o r less,
destructive and require a long and tedious work, so that t o have
a non-destructive test method would b e a desirable progress,
not only for the laboratory studies but also t o control the
structures a t working sites.
For this purpose. the polarization resistance technique has
been studied which was first described by Wagner and Truud
( 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.
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-
chemical techniques t o concrete because of the high electrical
resistivity of the medium, t h e impossibility of direct observa-
tion of t h e electrodes and the heterogeneity of the concrete
itself, which makes necessary t h e preparation of series of identi-
cal specimens. Therefore, t h e electrochemical techniques have
Werkstoffe und Korrosion 29,515-519 (1978)
not been applied as widely t o concrete as t o other materi-
als. When it was actually applied, either the limitations were
ignored, so that erroneous results were obtained or, saturated
Ca(0H)z solutions were used only, so that though t h e ther-
modynamic properties (potential and pH) are similar t o those
of the hardened concrete, the kinetic properties are very
different (3, 24, 25).
The most important of t h e above limitations, and the errors
which they may introduce into t h e final result, are:
a) the IR-drop between t h e bars due to the high resistivity of
the concrete, which results in a smaller I,,,, than the true
one, and
values of I,,,,.
For several years, the authors of the present report have
tried t o measure the corrosion rate of steel reinforcement em-
bedded in hardened concrete and they have only attained a
semi-quantitative relation between t h e R p indications and
t h e visual observations of t h e steel in t h e broken concrete
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
electrochemical ones).
The present paper reports the results of a n investigation
into t h e relation between the gravimetric and the electrochemi-
reinforcing steel bars embedded in hardened mortar and im-
mersed in Ca(OH)z-saturated solution.
2. Experimental Method
2.1. Materials
The bars used as test materials were of high strength pre-
stressed steel, cold drawn, 7 m m dia. and 8 cm long. The bars
in water and degreased in acetone. The tests had a duration
of about 30 days after which the bare steel was cleaned in
inhibited HCl and the galvanized steel in 20% NH4C1 solution.
The mortar was prepared according t o Spanish Standard
RC-75 (26) with a w/c ratio of 0.5 and a cement:sand ratio
over 90% of relative humidity at 20 f 2' C during t h e first
24h and then kept in polyethylene bottles, with a 2 cm depth
across it. Several types of cements were used: normal Port-
land cement (P-350), Slag cement (S-111-250) and Pozzolanic
cement (PUZ-1-350) (25)
The cements were used without and with additives (analy-
tical grade): CaClz up t o 2% (all the proportions are in rela-
tion t o cement weight) and Ca(HC00)z up t o 3% as depas-
sivating agents, and NaNOz up t o 4% as inhibitor. Calcium
formate, used as a curing accelerator in place of CaCI2, has
been considered a depassivating agent because when it is added
t o a saturated Ca(OH)z solution a rise of' breakdown poten-
carried out with mortar specimens the passivation layer did
Two sets of experiments were carried out:
1) In the first set, the corrosion rate of the steel bars (bare
and galvanized) immersed in a saturated Ca(OH)z solution
is measured using a polyethylene corrosion cell (more re-
sistant than glass t o alkaline attack) as shown in Fig. I ,
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

Fig. 1. Polyethylene corrosion ccll for the experiments in saturated
Ca(OH), solution
Abb. 1. Fiir die Versuche mit gesattigter Calciumhydroxidlosung
verwendete Korrosionszelle aus Polyethylen
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-
inforcing steel bars embedded in hardened mortar.
Each point represents only one bar. The large differences
in the total attack are due to t h e different additives in the
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
corrosion rate of reinforcing steel embedded in hardened con-
crete, and it presents t h e invaluable advantages of rapidity and
non-destructive nature; if up to now it has been used in labo-
ratory experiments only it should be possible t o apply it t o
structures a t t h e working site or t o specimens specifically
placed to this purpose.
Acknowledgments
T h e authors are grateful d o Dr. Feliu, Head of Corrosion
and Protection Department of CENIM, and Dr. Fullea, for their
suggestion at t h e initiation of t h e work, and t o the Chemical
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)
(Eingegangen: September 1977)
References
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.
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.
3. C. Andrade: Doctoral Thesis, Madrid, July 1973.
4.J. Calleja: Mat. de Const, No 150-151 (1973) 153.
5 . Rilem (12-CRC Committee): Mater et Const, No 51 (1976) 187.
6. I$. Kaesche: Archiv Eisenhiittenwesen 36 (12) (1965) 91 1.
7. H. Kaesche: Zement-KalkCips 12 (7) (1959) 289.
8. A. Baumel: Zement-Kalk-Gips I 2 (7) (1959) 294.
9. A. Baumel and H. J. Engell. Archiv. Eisenhhttenwesen 30 (7) (1959)
417.
10. K. S. Rajagopalan, N. S. Rengaswmy and T.M.Balasubramanian:
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).
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
Res5 (1975) 1.
15. C. Wagner and W. Traud: 2. Elektrochem 44 (1938) 391.
16. M.Stern and A. L. Geary: J . Electrochem. SOC104 (1957) 56
1280.
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
(1976) 132.
23. M. Prafciik: Werk. u. Korr. 25 (1974) 104.
25. J. A. Gonzdlez and C. Andrade: Mat. de Const., 165 (1977) 69.
de cemento. MOP 1975, Madrid.
27. C. Andrade, A. J. Va2quez and J. A. GonzPez: Rev. de Met. CENIM
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
mit der Anwesenheit eines Kohlenstoffilms an der Oberflache
von Kupfer verbunden sein kann.
Durch Rontgenpulveraufnahmen konnte im oberflach-
lichen Belag von gegluhten Kupferrohren, die durch Lochfrafi
vum Typ I korrodiert waren, Malachit, Atakamit, Kupfer (I)-
Chlorid, Tenorit und Cuprit nachge wiesen werden.
Rontgeninduzierte Photoelektronenspektroskopie-Unter-
suchungen und lonen-Beschuj3 haben bewiesen, dap Verbin-
dungen, die Kupfer(II] enthalten, nur in den obersten Schich-
ten vorliegen und daj3 der Belag hauptsachlich aus Cuprit be-
steht. Kohlenstoff ist zwar varhanden, aber die Abtragung
der auj3eren Schichten durch Ionenbeschufi zeigt, da$ Koh-
lenstoff nicht lediglich einen Film bildet, sondern in der gan-
zen Dicke des Oxidbelags verbreitet ist.
I t is usually accepted that pitting I isgenerally connected
with the presence o f a carbon f i l m on the inner surface o f cop-
per pipes. Samples o f annealed copper pipes showing pitting
corrosion o f type Z have been examined and the solid products
scraped o f f f r o m the surface have been submitted to X-ray
diffraction. Malachite, atacamite, cuprous chloride, tenorite
and cuprite have been detected. Significant amounts o f carbon
were found by chemical analysis. X-ray induced photoelectron
spectroscopy studies and ionic etching o f the coatings on the
inner surface of the pipes have shown that copper11compound.r
occur only in the outer layer. Cuprite is the main constituent.
Removal o f successive layers by ionic etching proves that car-
bon does not form a continuous film b u t is almost evenly dis-
tributed across the whole thickness of the oxide coating.

*) 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.)