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Cement and Concrete Research, Vol. 25, No. 2. pp. 25%264, 1995 iiiiii!iii!!iiiiiiiiiiiiiiii Copyright 1995 Elsevier Science Ltd !iiiiiiiii!iii!i!i!iii!i!i!i Printed in the USA. All rights reserved !!iiiiiiiiiiiiiiii!ii;!iii!

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COMPARISON OF RATES OF GENERAL CORROSION AND M A X I M U M PITTING PENETRATION ON CONCRETE EMBEDDED STEEL R E I N F O R C E M E N T J.A. Gonz~lez*, C. Andrade**, C. Alonso** and S. Feliu* Centro Nacional de Investigaciones Metal~rgicas (CENIM), Avda. Gregorio del Amot 8, 28040 Madrid, Spain. Fax: 34 1 534 7425 ** Instituto de Ciencias de la Construccidn "Eduardo Torroja" (ICCET), Serrano Galvache s/n, 28033 Madrid, Spain. Fax: 34 1 302 0700
(Comm~icatedbyC.D. Pomcroy)
(ReceivedAugmt~,l~4)

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ABSTRACT Local attack of reinforcement is observed usually in chloride-contaminated concrete. When mechanical w e a k e n i n g of the concrete structure is affected by the bar section loss in the places where corrosion is intensified, the m a x i m u m penetration of the deepest pits happens to be a very relevant datum. In this work average corrosion values are compared with maximum pit depth values. Using natural corrosion tests and accelerated tests, it has been found that the maximum penetration of localized attack on steel embedded in concrete containing chlorides is equivalent to about four to eight times the average general penetration. Key words: Chloride-contaminated concrete, reinforcement deterioration, maximum penetration of pits, average general corrosion, damage prediction. INTRODUCTION It is well known the harmful role that corrosion of reinforcement plays in the service life of reinforced concrete structures (1,2), This calls for routine assessment of any corrosion process developed on them, preferably by using non-destructive techniques. Nowadays, the Continuous or periodic m o n i t o r i n g of corrosion is m a i n l y based on electrochemical measurements. These measurements are referred both to corrosion potential (Eeoc) and Corrosion current (Icon). Eeorris related to the likelihood that reinforcements suffer active corrosion (3), and therefore fails to provide an accurate measurement of corrosion rate. This problem is solved with Ieo measurements (4,5), although other problems arise in this case, ~ such as those related to the correct interpretation of the measurements. The values of Ico= experimentally determined in reinforcements, even the highest ones, do not seem to imply at first sight too much
257

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danger. V a l u e s of 1-3 ~ A / c m 2 are frequent in active c o r r o s i o n and o n l y seldom values of the order of i0 ~ A / c m 2 or h i g h e r are d e t e r m i n e d (6). V a l u e s of 1-3 ~ A / c m 2 are e q u i v a l e n t to c o r r o s i o n rates of 11-33 ~m per year, so that it is d i f f i c u l t to u n d e r s t a n d how from such a low figures a structure b e c o m e s u n u s a b l e in a r e l a t i v e l y short p e r i o d of time, as so happens in some instances. However, such values are only a p p a r e n t l y small. E x t r a p o l a t i n g from an a s s u m e d constant rate of 20 ~ m / y e a r up to 50 years, an a v e r a g e a t t a c k p e n e t r a t i o n of 1 mm will be obtained, w h i c h m e a n s a loss of m a t e r i a l e q u i v a l e n t to the 21 per cent of the c r o s s - s e c t i o n a l area of a rebar of 9 mm diameter, which may exceed the safety coefficient. The p r e s e n c e of l o c a l i z e d corrosion, w i t h pit depths several times g r e a t e r than the average c o r r o s i o n attack, m a k e s the s i t u a t i o n worse, e s p e c i a l l y in p r e s t r e s s e d structures. Similar c o n s e q u e n c e s c o n c e r n l n g structural safety and s e r v i c e a b i l i t y come from the p o i n t of v i e w of the concrete cover cracking. So, it has been e s t a b l i s h e d (7) that the amount of iron oxide g e n e r a t e d d u r i n g the c o r r o s i o n of 10-50 ~m of metal (depending on rebar diameter) is e n o u g h to crack a concrete cover of 2-3 cm. This m e a n s that m a n y c o n c r e t e covers will be c r a c k e d after 1-3 years as a r e s u l t of c o r r o s i o n rates of only 10-30 ~m/year. The values of Ico= are average values r e f e r r e d to the o v e r a l l r e i n f o r c e m e n t surface. The i n t e g r a t i o n of these v a l u e s over the exposure time allows estimate of an a v e r a g e penetration of c o r r o s i o n (Pay), but it does not inform at all about the m a x i m u m penetration (Pmax) of the d e e p e s t pits w h e n the a t t a c k is v e r y have m o r e uneven. For life predictions, this Pmax value m a y i m p o r t a n c e than the a v e r a g e value when the m e c h a n i c a l w e a k e n i n g of the s t r u c t u r e is a f f e c t e d by the bar section loss in t h o s e p l a c e s w h e r e c o r r o s i o n is intensified. P~x could be e s t i m a t e d from Ico n p r o v i d e d that a ratio (R) b e t w e e n Pmax and Pay could be e s t a b l i s h e d . D e s p i t e the p r a c t i c a l interest of the matter, little s y s t e m a t i c w o r k has so far been done to the writers' k n o w l e d g e on p i t t i n g of r e i n f o r c e m e n t s . A study by Tuutti (8), who d e t e r m i n e d values of R = 4-10, m a k e s an exception, a l t h o u g h he did not i n c l u d e the effect of c h l o r i d e a d d i t i o n s to cement and used an e x t e r n a l v o l t a g e source as a c o r r o s i o n accelerator. Some m o r e i n f o r m a t i o n on pit depths is found in a number of papers on a t m o s p h e r i c and soil c o r r o s i o n of bare metals. From these data, values of R = 3-5 for m i l d and l o w - a l l o y steel (9-13) and R = 8-10 for a l u m i n i u m alloys (14), e x p o s e d to d i f f e r e n t atmospheres, as well as v a l u e s of R 3.5-15 for b u r i e d u n c o a t e d steel and c a s t - i r o n pipe samples (15,16), have been estimated. D e t e r m i n a t i o n of R in natural r e i n f o r c e d concrete c o r r o s i o n entails i m p o r t a n t e x p e r i m e n t a l difficulties, such as to have (a) to b r e a k up the concrete sample in order to examine pitting on the r e i n f o r c e m e n t surface, (b) to wait for a long time (many years) to get, t h r o u g h a natural c o r r o s i o n process, a s u f f i c i e n t a t t a c k to f a c i l i t a t e the survey, and (c) to handle concrete samples of large dimensions (big enough for the e x a m i n a t i o n of an e x t e n s i v e r e i n f o r c e m e n t surface) in order to arrive at s t a t i s t i c a l l y sound c o n c l u s i o n s r e g a r d i n g the d i s t r i b u t i o n and size of pits.

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iii:li ii:!i iiiil

:::::::::

:::::::: ~i~iiiiiiijiiiii ::::::::: :::

These d i f f i c u l t i e s have, no doubt, this p a r t i c u l a r aspect.

c o n t r i b u t e d to delays in t e s t i n g
:::::::: i:::: [::i :;::.;..;

Both n a t u r a l and a c c e l e r a t e d c o r r o s i o n t e s t i n g will be u s e d in this investigation, the latter to v e r i f y the f e a s i b i l i t y of u s i n g a small i m p r e s s e d current (of the order of Ico=) to a c c e l e r a t e p i t t i n g in l a b o r a t o r y t e s t i n g of chloride c o n t a i n i n g r e i n f o r c e d c o n c r e t e samples.
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E x P E R IM E N T A

For the natural testing, two types of concrete samples w e r e m a d e of 50 cm x 50 cm x i0 cm and 20 cm x 15 cm x i0 cm d i m e n s i o n s , r e s p e c t i v e l y , h a v i n g e m b e d d e d 0.8 cm d i a m e t e r steel r e i n f o r c e m e n t . The c o n c r e t e used in the first type of samples c o n t a i n e d 3% of CaCI 2 per w e i g h t of cement, in order to p r o v o k e an a c t i v e a t t a c k on r e i n f o r c e m e n t s . This sample was subjected to r e p e a t e d p e r i o d s of w e t t i n g - d r y i n g , by k e e p i n g a w a t e r m o i s t e n e d pad on its surface, w h i c h w e r e f o l l o w e d by d r y i n g periods in the l a b o r a t o r y a t m o s p h e r e (50-60% RH approx.). The second type of concrete samples c o n t a i n e d no admixtures, and were submerged into a natural sea w a t e r t a n k l o c a t e d at the Instituto de Ciencias del Mar (CSIC) of Barcelona. The m e a n s a l i n i t y of w a t e r was 28 g/l, t e m p e r a t u r e v a r i e d from 14-C in w i n t e r to 24-C in summer, and oxygen m e a n c o n t e n t was 5 ppm (17). A f t e r 6 years testing, both types of samples w e r e b r o k e n in o r d e r to assess the c o r r o s i o n suffered by the steel r e i n f o r c e m e n t , i.e. w e i g h t loss, attack m o r p h o l o g y and pit depth d i s t r i b u t i o n . W e i g h t loss was o b t a i n e d by c o m p a r i n g the w e i g h t per unit length of attacked reinforcement (once all a d h e r e d c o n c r e t e and c o r r o s i o n p r o d u c t s w e r e removed), w i t h that of the u n a t t a c k e d r e i n f o r c e m e n t . The d e p t h of p i t t i n g was m e a s u r e d in d i f f e r e n t ways, a c c o r d i n g to convenience. W h e r e pits w e r e big enough a m i c r o m e t e r was d i r e c t l y used. In other cases, the depth was determined from the displacement of an optical m i c r o s c o p e objective f o c u s s i n g the e x t e r n a l surface and the b o t t o m of the pit successively. For the a c c e l e r a t e d testing, two types of samples w e r e also prepared: (a) m o r t a r samples 2 cm x 5.5 cm x 8 cm, w i t h m i l d steel bars e m b e d d e d of 0.6 cm in diameter and a m o r t a r cover of 0.7 cm, and (b) c o n c r e t e samples 15 cm x 15 cm x 40 cm, w i t h bars of 1.6 cm in d i a m e t e r and concrete covers of 2 to 5 cm. Both series w e r e p r e p a r e d w i t h 2 and 3% by w e i g h t of a d m i x e d CaCl2 to p r o v o k e a c t i v e c o r r o s i o n from the b e g i n n i n g of test. A n o d i c currents r a n g i n g from i0 to I00 ~ A / c m 2 w e r e a p p l i e d to the r e i n f o r c e m e n t . A central g r a p h i t e bar in samples "a" and an external m e t a l l i c p l a t e p l a c e d on the c o n c r e t e surface (through a wet pad) in samples "b" w e r e u s e d as c o u n t e r e l e c t r o d e s . At the end of the test period, w h e n cracking of m o r t a r or concrete cover occurred due to the a c c u m u l a t i o n of c o r r o s i o n products (oxide), the samples w e r e b r o k e n and pits e x a m i n e d s i m i l a r l y to natural testing. RESULTS Natural testing The e x a m i n a t i o n of the r e i n f o r c e m e n t that had b e e n part of sample of d i m e n s i o n s 50 cm x 50 cm x i0 cm e x p o s e d to the the

....... ......

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laboratory atmosphere disclosed a great number of pits, d i s t r i b u t e d all over their surface, which is normal with highly chloridecontaminated concretes. The study of this specimen was m a i n l y based on two reinforcements: one reinforcement "A" located in front of a crack in the concrete cover (the crack was detected on the third year of testing), and other reinforcement "B" that was all the time under an undamaged concrete cover. In the case of reinforcement "A", the weight loss after the 6 years was equivalent to an average penetration of the attack on all the surface of 0.265 mm (Table i).

Table

i. Values of R obtained in natural conditions, when the concrete samples containing 3% CaCl 2 by weight of cement were submitted to wetting-drying cycles in the atmosphere. Average penetration of attack after 6 years (mm) Maximum pit depth after 6 years (mm) R value

Conditions

Rebar in front of a crack in the concrete cover Uncracked cover

0.265

1.20

4.4

0.085

0.50

5.9

The deepest pits showed penetrations of the order of 1.20 mm. In this bar, pitting was more abundant and deeper along the reinforcement generatrix coincident with the position of the crack on the concrete. If the average value (0.265 mm) is compared with the depth of the deepest pits, a ratio R between P~x and Pay of 4.4 is obtained. In the case of reinforcement "B", the weight loss after the 6 years was equivalent to an average penetration of 0.085 mm, which is lower than for reinforcement "A", most likely due to the higher protecting capacity of the undamaged concrete cover. The deepest pits showed depths in the order of 0.50 mm. In this case, R= 5.9. During the six years of testing, Ieo measurements w e r e highly ~ influenced by wetting and drying conditions of concrete, ranging from about 0.I ~A/cm 2 for dry concrete up to some 7 ~A/cm 2 for very wet concrete. Table 2 summarizes the characteristics of the attack in samples that were continuously submerged in sea water. The average value of R for all the reinforcements examined gave a figure of 4.5 which is of the order of those previously found. Scatter of data seems to be normal in pitting attack. In these samples the value of I~o~ increased gradually with time as the chlorides penetrate into the concrete, reaching values of 10-20 ~A/cm 2 after 5-6 years. The total corrosion estimates from curves Ic~ vs. time gave values in reasonable agreement with the measured weight losses. A c c e l e r a t e d testing Tables 3 and 4 show the values of R obtained when an anodic current is applied. They range from 3.2 to 16.1 with an average value of

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::::::::::

Table

2. v a l u e s of R o b t a i n e d in n a t u r a l c o n d i t i o n s w h e n the c o n c r e t e samples w e r e i m m e r s e d in n a t u r a l sea water.

:::::::::::

Concrete typ e

Reinforc em e n t

Average penetration of a t t a c k after 6 years

M a x i m u m pit depth after 6 years

R value iiZ!iii ii!i!ii iliiii ~ii!i i!!i! i:~?~ 8.9 3.7 3.7 5.0 4.2 2.7 5.3 4.6

(ram)
OPC-400 kg/m 3 IN 2N 3N 5N 17N 19N 20N 28N 0.62 0.41 0.41 0.43 0.53 0.42 0.47 0.38

(mm)
5.50 1.51 1;51 2.15 2.20 1.15 2.50 1.72

ii~iii i iiii i iiii!i iiiiii ~!iii

w/c=0.38 OPC-400 w/c=0.6 OPC-400 w/c=0.5 kg/m 3 kg/m 3

0PC-300 kg/m 3 w/c=0;6

32N 33N

0.54 0.40

2.19 I.I0

4.1 2.8

T a b l e 3. V a l u e s of R o b t a i n e d from a c c e l e r a t e d tests in m o r t a r s a m p l e s c o n t a i n i n g 2% C a C l 2 by w e i g h t of cement. A p p l i c a t i o n of a c u r r e n t of i0 ~ A / c m 2. Conditions Test d u r a t i o n R mean value of 6 r e b a r s

samples immersed in w a t e r Samples exposed to RH > 90%

1-3 m o n t h s

3.2

1-3 m o n t h s

3.7

T a b l e 4. V a l u e s of samples containing Concrete cover (cm) Current (~A/cm 2)

R o b t a i n e d from a c c e l e r a t e d tests in c o n c r e t e 3% of CaCl 2. Test duration, 1 month. Number of bars tested Average penetration of a t t a c k Maximum pit depth R value

(mm)
2 i0 i00 100 I0 I00 2 3 5 1 3 0.095 0.276 0.314 0.090 0.263

(mm)
1.20 1.68 1.86 1.50 2.15 12.6 6.1 5.9 16.1 8.2

3 5

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R = 8.2. In spite of the applied current, surface examination revealed a very uneven corrosion, with areas not corroded and others intensely attacked, reproducing in some way the appearance of natural corrosion of reinforcement in concrete. DISCUSION The frequent obtaining of R = Rmax/Pay values ranging from about 4 to 8 in natural corrosion, and from 5 to 13 in accelerated testing of reinforced concrete, is a fact of a great practical importance for prediction of residual life of concrete structures from electrochemical Ico measurements. Accordingly, it can be expected ~ that pit growth proceeds 4-8 times or so more rapidly than the instantaneous Ico. (average rate) measured. Similarly, the maximum total depth of localized attack will exceed by about 4-8 times the estimated average general penetration deduced from loss in weight after a given exposure time. Certainly, the above conclusions are provisional while a meticulous statistical study on a large number of samples is not accomplished. It is interesting to note that the furnished data appear to agree among themselves and, as mentioned, with other data reported for bare metals in the atmosphere or in the soil. The resemblance among R values in different circumstances recalls other similarities between the mechanisms of concrete corrosion and atmospheric corrosion already emphasized (18). A rigorous approach to pitting corrosion should involve the combined use of a great amount of field measurements, statistical analysis and mechanistically based modelling. Extreme value statistics may provide an approximate method of p r e d i c t i n g the m a x i m u m pit depth in a given area (19). Analysis of many samples is required, where the number of pits and the depths of all of them have to be measured. In the statistical analysis, conflict with the physical limits on pit growth kinetics can exist and significant progress is still needed in the development of realistic models (20). In a general treatment, progress of pits with time should also be considered; especially the effect of time on the number, distribution, total area and volume of all pits. The value of R depends on the penetration rate (Vmax) for the deepest pits and the average corrosion rate (Vav) for the whole exposed surface. The complex nature of the pitting process makes it difficult to predict the effect of the different variables on R. It is foreseeable that Vmax be more or less influenced, according to experimental circumstances, by (i) diffusion of corrosion products and species concerned in the pit propagation process, (ii) activation energies of the anodic and cathodic processes, and (iii) electrical resistance between the anodic and cathodic areas. On the other hand, Vav is a complicated function of (i) presence of heterogeneities that act as nuclei for pit initiation, (ii) alteration of potential distribution around a established pit in a sense unfavourable to the starting of new pits (anodic dissolution of metal within a pit renders the surrounding region insufficiently anodic for the beginning of fresh pitting), (iii) resulting total number of pits on the metal surface and

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CORROSIONRATE,STEEL,PITHNG,CHLORIDES,PENETRATION

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distribution of pit shapes and sizes,

(v) rate of attack of the remaining

(iv) pit growth kinetics,

surface unaffected

and
::::::::::::
:::::::::: ii:i:i:!iii

metal

by the

p it s.
A theoretical justification of the observed values of R should

include a study in depth of all the above points, and for this purpose essential information is lacking. Fortunately, the empirical fact that R values of 4-8 are often obtained, in spite
of life. the number of variables that in theory will affect R, may be

..... ....
://::

used

as

a basis

for

approximate

predictions

of

residual

service

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iiiiiii[ii~i~ : : :::::::::

CONCLUS IONS i. It has been found that the maximum penetration of the localized attack on steel embedded in concrete containing chlorides is equivalent to about four to eight times the average p e n e t r a t i o n of the attack on the overall reinforcement surface. This relation does not differ too much from similar relations reported for the corrosion of metals in the atmosphere or in the soil. 2. The study of pitting corrosion on reinforced concrete can be accelerated by using an impressed anodic current. Values of R rather similar, although slightly higher, to those found under natural conditions have been obtained with the application of i0i00 ~A/cm 2 to reinforcements in concrete containing chlorides. 3. The knowledge of R m a y be useful for estimation of the residual life of concrete structures from on-site Ic~r measurements.

ACKNOWLEDGMENTS This w o r k was suported by the Comisidn Interministerial de Ciencia y Tecnologia (CICYT) of the Ministry of Education and Science of Spain. The authors are indebted to M. Teresa Gutierrez of "E. Torroja" Institute for careful and patient m e a s u r e m e n t of pits in reinforced concrete samples exposed to sea water.

REFERENCES

i.

B. Boyard, C. Warren, S. Somayaji and R. Heidersbach, Corrosion Rates of Steel in Concrete, ASTM STP 1065, N.S. Berke, V. Chaker and D. Whiting, Eds., Philadelphia, P.A. (1990), p. 174. Tranportation Research Board, Strategic Highway Research Program Plans. Final Report. NCHRP Project 20-20. Washington, D.C. (1986). Standard Test Method for Half Cell Potential of R e i n f o r c i n g Steel in Concrete, A S T M C 876-87, Philadelphia, P.A. C. A n d r a d e and J.A. Gonz~lez, J.A. Gonz~lez, 135 (1980). S. Algaba Werks. u. Korr., Br. 29, 515 (1978). Corros. J., 2__55,

2.

3.

4. 5.

and C. Andrade,

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6.

C. Andrade, M.C. Alonso and J.A. Gonz~lez, Corrosion Rates of Steel in Concrete, ASTM STP 1065, N.S. Berke, V. Chaker and D. Whiting, Eds., Philadelphia, P.A. (1990), p. 29. C. Andrade, C. Alonso and J. Molina, Materials and Structures, 26 453 (1994). K. Tuutti, Corrosion of Steel in Concrete. Swedish Cement and Concrete Research Institute, Stockholm (1982). S. Feliu and M. Morcillo, Corrosion and Protection of Metals in the Atmosphere (in Spanish), Ediciones Bellaterra S.A., Barcelona (1982). Materials

7. 8.
9.

I0. C.R. Southwell, J.D. Bultman and A.L. Alexander, Performance, 15, No. 7, 9 (1976). Ii. H.R. Copson, Proceed. ASTM, 52, 1005 (1952).

12. T. Moroishi and J. Satake, J. Iron Steel Inst. (Japan), 59, No. 2, 293 (1973). 13. P. Merino, Metallographic Study of Different Types of Corrosion: Depth of Pits (in Spanish), Doctoral Thesis, Universidad de Santiago de Compostela, Spain, 1987. 14. E. Otero, R. Lizarbe and S. Feliu, Rev. de M e t a l u r g i a (Madrid), !, 359(1971). 15. M. Romanoff, Underground Corrosion. National Bureau of Standards, Circular 579. US. Government Printing Office, W a s h i n g t o n (1957). 16. J.C. Hudson and K.O. Watkins, BISRA Open Report No. MG/B/3/68. 17. C. Andrade, C. Alonso, S. Go~i and J.A. Gonz~lez, Corrosion of Reinforcements in Concrete Immersed in Sea Water, 7th International Congress on Marine Corrosion and Fouling. Universidad Polit6cnica, Valencia, Spain (1988). 18. C. Andrade, C. Alonso, J.A. Gonz~lez and S. Feliu, Corrosion of Reinforcements in Concrete, Ed. C.L. Page, K.W.J. Treadaway, P.O. Bamforth. Society of Chemical Industry, Birmingham, U.K. (1990), p 39. 19. P.M. Aziz, Corrosion, 12, 35 (1956).

20. A. Turnbull, Br. Corros. J., 28, 297 (1993).