C E M E N T and C O N C R E T E RESEARCH.

Vol. 18, pp. 44-54, 1988.

P r i n t e d in the USA.
0008-8846/88
$3.00+00
C o p y r i g h t (c) 1988 P e r g a m o n Journals, Ltd.

CORROSION

RESISTANCE

OF

STEEL

MARINE

Department

FIBRES

IN

CONCRETE

UNDER

EXPOSURE

P.S. M a n g a t and K r i b a n a n d a n G u r u s a m y
of E n g i n e e r i n g , A b e r d e e n U n i v e r s i t y , M a r i s c h a l College,

Aberdeen,

U.K.

( C o m m u n i c a t e d by A.J. Majumdar)
(Received July 16, 1987)

ABSTRACT
T h i s is the final p a p e r of a series (i, 2, 3) w h i c h have r e p o r t e d
d i f f e r e n t a s p e c t s of a long term study on the m a r i n e d u r a b i l i t y of steel
fibre r e i n f o r c e d c o n c r e t e (sfrc) . T w o mixes, one w i t h and one w i t h o u t
pfa were r e i n f o r c e d w i t h t h r e e ty?es of steel fibres.
The cement c o n t e n t
of the m i x e s was 430 and 590 k g / m ~ r e s p e c t i v e l y .
P r i s m specimens of these
m i x e s w e r e c u r e d u n d e r m a r i n e exposure, b o t h in the l a b o r a t o r y and at
A b e r d e e n beach, for u p to 2000 w e t - d r y cycles (12OO days).
The state of
c o r r o s i o n of the steel fibres was i n v e s t i g a t e d v i s u a l l y and b y e l e c t r o chemical a n a l y s i s of fibres e x p o s e d at f r a c t u r e d surfaces of specimens
after flexural testing.
r e s u l t s show that the g e n e r a l l y a c c e p t e d
b y w e i g h t of c e m e n t does not a p p l y to sfrc.
The

value of O.61
of Corrosion,

level of 0.4% Cl
the t h r e s h o l d

for the --(Cl-----~)ratio, as p r o p o s e d b y H a u s e m a n n for i n i t i a t i o n

(OH-)
is not v a l i d to steel fibre r e i n f o r c e d concrete.
No corrosion

of fibres e m b e d d e d
exceeding

activation
Similarly,

in c o n c r e t e was e v i d e n t

at C1

(CI-)

and ~

levels g r e a t l y

the a b o v e values.

Introduction
C o n c r e t e n o r m a l l y p r o v i d e s r e i n f o r c i n g steel w i t h e x c e l l e n t c o r r o s i o n p r o t e c t i o n
due to its h i g h alkalinity.
In addition, c o n c r e t e mixes can be d e s i g n e d to have
low p e r m e a b i l i t y w h i c h m i n i m i s e s the d i f f u s i o n of c o r r o s i o n i n d u c i n g s u b s t a n c e s
such as CI-, CO 2 and 0 2 . L o w p e r m e a b i l i t y also i n c r e a s e s the e l e c t r i c a l resist i v i t y of concrete,

w h i c h i m p e d e s the flow of e l e c t r o c h e m i c a l

corrosion

currents.

In d e s i g n i n g for durability, codes of p r a c t i c e s t i p u l a t e s t r i n g e n t r e q u i r e m e n t s

r e g a r d i n g c o n c r e t e c o v e r in a d d i t i o n to the use of i m p e r m e a b l e concrete.
In the
case of steel fibre r e i n f o r c e d concrete, the fibres are u n i f o r m l y and r a n d o m l y
d i s t r i b u t e d w i t h some at the surface of the c o m p o s i t e b e i n g d i r e c t l y e x p o s e d to
the o u t s i d e e n v i r o n m e n t .
C o n s e q u e n t l y the m i n i m u m cover to fibres is e f f e c t i v e l y
zero.

44

Vol.

18, No.

45
CORROSION RESISTANCE,

STEEL FIBERS,

SEA E X P O S U R E

A t the splash zone of m a r i n e s t r u c t u r e s the s u p e r i o r m e c h a n i c a l p r o p e r t i e s of sfrc

can be of g r e a t e s t a d v a n t a g e (4).
However, it is also here that the c o m b i n a t i o n
of salt w a t e r and oxygen, w a v e a c t i o n and ice r e s u l t s in an e x t r e m e l y a g g r e s s i v e
e n v i r o n m e n t for fibre corrosion.
F i b r e s in the v i c i n i t y of c o n c r e t e s u r f a c e are
p a r t i c u l a r l y v u l n e r a b l e and c o n c l u s i v e p r o o f of their c o r r o s i o n r e s i s t a n c e is
r e q u i r e d b e f o r e this i m p o r t a n t area of a p p l i c a t i o n s can be o p e n e d for sfrc.
P r e v i o u s d u r a b i l i t y r e s e a r c h on sfrc has c o n c e n t r a t e d on e x p o s u r e c o n d i t i o n s
such as an i n d u s t r i a l a t m o s p h e r e a n d d e i c i n g salts (5), sewage o u t f a l l and a
c o a s t a l site (remote from splash and tidal zones) (6) and f r e e z e - t h a w cycles (7).
The r e s u l t s of these i n v e s t i g a t i o n s have g e n e r a l l y i n d i c a t e d s a t i s f a c t o r y
d u r a b i l i t y of sfrc.
A r e s e a r c h p r o g r a m m e was i n i t i a t e d at A b e r d e e n U n i v e r s i t y some years ago in o r d e r
to make a f u n d a m e n t a l study of c o r r o s i o n of steel fibres in concrete.
Specimens
of sfrc i n c o r p o r a t i n g d i f f e r e n t types of
fibres
were i n t r o d u c e d to long term
m a r i n e e x p o s u r e (I, 2, 3).
C h e m i c a l a n a l y s e s w e r e c a r r i e d out at r e g u l a r i n t e r v a l s
to e s t a b l i s h the d i f f u s i o n c h a r a c t e r i s t i c s of acid soluble c h l o r i d e s (i, 2) and
the c o m p o s i t i o n of p o r e fluid w i t h r e s p e c t to Cl- and OH- c o n c e n t r a t i o n (3).
In
this p a p e r e v i d e n c e r e g a r d i n g the state of c o r r o s i o n of the v a r i o u s types of steel
fibres is p r e s e n t e d and the r e s u l t s g i v e n in e a r l i e r p a p e r s (i, 2, 3) are r e l a t e d
to these d a t a in o r d e r to gain an u n d e r s t a n d i n g of the c o r r o s i o n mechanism.
Experimental
Mixes

and M a t e r i a l s

T w o types of m i x e s of steel fibre r e i n f o r c e d c o n c r e t e were used.

The first m i x
(mix A) was b a s e d on OPC and in the second m i x (mix B) 26 p e r cent of c e m e n t was
r e p l a c e d b y pfa.
The p r o p o r t i o n s , b y weight, of mix A were 1 . O : 1 . 5 : O . 8 6 w i t h a
w a t e r / c e m e n t r a t i o of 0.4.
The cement c o n t e n t was 590 k g / m 3. The p r o p o r t i o n s ,
b y weight, of m i x B were 0.26 (pfa) :0.74 (OPC) :1.51:0.84 w i t h a w a t e r / ( O P C + pfa)
r a t i o of 0.4.
The c e m e n t c o n t e n t of this m i x was 430 k g / m 3 . Four m i x e s w i t h
d i f f e r e n t steel fibre r e i n f o r c e m e n t were m a n u f a c t u r e d for each of the above m i x
proportions.
D e t a i l s of t h e s e are g i v e n in T a b l e i.
O r d i n a r y P o r t l a n d cement, fine a g g r e g a t e c o n f o r m i n g to zone 2 of BS 882 and iO m m
n o m i n a l size g r a n i t e coarse a g g r e g a t e were used.
F u r t h e r d e t a i l s of m a t e r i a l s
are g i v e n in the e a r l i e r p a p e r s (i, 2).
Casting,

Curing

and T e s t i n g

iOO x iOO x 500 m m p r i s m s p e c i m e n s were m a d e as d e s c r i b e d p r e v i o u s l y (i, 2) and

were d e m o u l d e d after 24 hours.
T h e y w e r e then c u r e d in the l a b o r a t o r y air for one
or f o u r t e e n days as i n d i c a t e d in T a b l e i.
S u b s e q u e n t l y the s p e c i m e n s were transferred e i t h e r to a sea w a t e r s p r a y c h a m b e r in the l a b o r a t o r y or to A b e r d e e n beach.
F u r t h e r d e t a i l s of m a r i n e c u r i n g have b e e n g i v e n p r e v i o u s l y (i, 2).
T e s t s were c o n d u c t e d a f t e r 2000 cycles (for m i x A specimens) and 12OO cycles
(for m i x B specimens) of w e t t i n g and d r y i n g u n d e r m a r i n e exposure.
These
c o r r e s p o n d e d to ages of about 1250 and 640 days r e s p e c t i v e l y .
Three prism specimens
per m i x of T a b l e 1 were first t e s t e d in f l e x u r e and the b r o k e n h a l v e s w e r e u s e d to
o b t a i n s a m p l e s for c h e m i c a l a n a l y s i s as d e s c r i b e d p r e v i o u s l y (i, 2, 3).
For s p e c i m e n s of m i x A only, the e l e c t r o d e p o t e n t i a l of steel fibres e x p o s e d at
the f r a c t u r e d faces of p r i s m s p e c i m e n s was also m e a s u r e d b y c o m p a r i s o n w i t h a
s t a n d a r d c a l o m e l e l e c t r o d e (half cell).
The a r r a n g e m e n t u s e d for t h e s e m e a s u r e m e n t s
is shown in Fig. i. An e l e c t r i c a l c o n n e c t i o n was m a d e b e t w e e n a steel fibre on
the f r a c t u r e d face and the c a l o m e l e l e c t r o d e v i a a h i g h i m p e d e n c e v o l t m e t e r .
The
p o t e n t i a l d i f f e r e n c e b e t w e e n the steel fibre and the half cell was r e c o r d e d b y

46

Vo].
P.S. Mangat

18, No.

and K. Gurusamy

placing the calomel electrode either

being the side faces during casting.

on face 3 or face

1 of the prism,

these

The p o t e n t i a l of the fibres at O, 15, 30, 40 and 50 m/n depth relative to face 1 and
3 was then obtained by m a k i n g e l e c t r i c a l contact with fibres at these depths.
The
p o t e n t i a l s were taken, as far as possible, through fibres located at the centre
line of the fractured face of the specimen, which is indicated in Fig. i.
Results
Corrosion

Threshold

Level

of

and Discussion

(CI-)

(OH-)
Hausmann

(8) suggested a threshold ratio of chloride ion activity to hydroxyl ion

(Cl-)
activity, (OH-)' of O.61 in solution at the iron-matrix interface, above which

corrosion is initiated.
In order to check the validity of this threshold value
to sfrc, the data on free CI- and OH- concentrations in specimens of this investigation are considered.
These results have been p u b l i s h e d separately (3) and were
(Cl-)
used to calculate the (OH_------~ratios at different depths into concrete.
These
values

of

(cl-)

(OH_--------~lfor mixes A and B, are plotted

The vertical

scales

of Figures

2a and 3a are enlarged

TABLE

Details

of Mixes,

Fibres

in Figures

2 and 3 respectively.

in Figures

2b and 3b in order

and Curing

Fibre details
Mix

(ram)

(ram)

(~)

1
vf ~

vf

Fibre
type

Curing*
conditions

Shl4,

Bhl4

AME

25

O.51

147

Melt extract

Shl4,

Bhl4

AMS

28.2

0.48

2.5

147

Low carbon

Shl4,

Bhl4

ACR

40

0.60

2.2

145

Corrosion

Shl4,

Bhl4

resistant

Sh

BME

26.5

0.44

1.7

iOO

Melt extract

BMS

28.2

0.48

1.7

iOO

Low carbon

BCR

40

0.60

1.7

i12

Corrosion

* Shl,
Bhl4

Shl4

marine

shower

curing

beach curing under

curing.

(MC) after

tidal

cycles

I,

Shl4,

Bhl4

Shl4
resistant

1 or 14 days
(TC) after

Shl4

laboratory

14 days

air curing.

laboratory

air

Vol.

18, No.

47
CORROSION

RESISTANCE,

STEEL FIBERS,

SEA EXPOSURE

High impedence
votfmeter-----.~

,/C a[ome[ electrode

sponge
crete prism

fe~Z
Steel

acel or 3

fibres

Fractured
face of

Fig.

Electrochemical

Ni

potential

I
measurement

of steel

fibres.

to indicate clearly H a u s m a n n ' s t h r e s h o l d value of O.61 in relation to the data of

this investigation.
Figure 2b shows that this t h r e s h o l d value is exceeded at
depths of up to 29 mm and 32 mm in concrete exposed to tidal cycles and laboratory
marine cycles respectively.
Similar trends are evident in Figure 3b.
The results
in Figures 2 and 3, therefore, show that in the surface zones of specimens, the
(CI-)

ratios were

several

orders

of m a g n i t u d e

higher

than Hausmann's

threshold

(OH-)
level of 0.61.
A c c o r d i n g l y , extensive corrosion of steel fibres should have
o c c u r r e d in these zones.
The fact that no such corrosion was evident suggests
either that this t h r e s h o l d value is not applicable to small diameter steel fibres
e m b e d d e d in concrete or that one or more of the other r e q u i r e m e n t s for corrosion
to p r o c e e d is not present.
H a u s m a n n d e r i v e d the t h r e s h o l d level of O.61 on the
basis of studies u n d e r t a k e n with "model" electrolytes.
Page and V e n n e s l a n d (9)
have e m p h a s i s e d the u n r e l i a b i l i t y of p r e d i c t i n g corrosion b e h a v i o u r of steel
in
concrete by such methods, as it is impossible to simulate the effects w h i c h may
arise either from oxygen d e p l e t i o n or from the limited m o b i l i t y of chloride ions
in the cement matrix.
The t h r e s h o l d levels are, therefore, likely to be m u c h
higher than the value s u g g e s t e d by H a u s m a n n (iO, ii, 12).
(Cl-)
It is also clear from Figures 2 and 3 that, within the surface zones, the (OH------~
ratios are much higher in m a r i n e shower cured specimens (Sh 1 and Sh 14) as
c o m p a r e d to beach cured specimens (Bh).
This is due to the higher salt concentra-_
(CI)
tions in the l a b o r a t o r y marine shower (2, 3).
Figure 3 also shows that (OH-------~
ratios are higher in specimens Sh 1 w h i c h were exposed to marine cycles after
1 day of air curing in c o m p a r i s o n with specimens Sh 14 which were exposed to
m a r i n e cycles after 14 days of air curing.
Corrosion

Activation

Level

of Cl-

V a r i o u s a c t i v a t i o n levels of acid soluble CI- above w h i c h c o r r o s i o n of steel

r e i n f o r c e m e n t is c o n s i d e r e d to initiate are used in design (13, 14, 15).
The
h i g h e s t value q u o t e d for design is 0.4 per cent Cl- by w e i g h t of cement.
If
this a c t i v a t i o n level is e x c e e d e d then, in the presence of oxygen and moisture,
c o r r o s i o n of steel in concrete is assumed to be initiated.
Acid

soluble

Cl- d i f f u s i o n

curves

for m a r i n e

shower

cured and beach

cured

48

Vol.
P.S. Mangat

18, No.

and K. Gurusamy

350

300

Mix A (1: 1'50:0"86:0"4)

250

20
18

P
200
"i-

16
14

.~arine spray cydes

i Exposure to
spray cycles

i'~
12
-r

.~. 150

100

/\ \

50

Tidal cycles
,....._/
..,
"~-------i,~ ;
10
20
30
Depth (ram)into concrete

Ex osure t o ~

tidatcyc,es ~

2
@61

(a) & (b)

\:

Conventional
reinforcement

. _ _--__~T_h~_,_sh_~d_ tenet

10
20
30
Oepth(mm) into concrete

(a)
Fig.

~
~

(b)
The v a r i a t i o n

of

(CI-)/(OH-)

with depth

after

2 OOO MC or TC

400
350
300
250

Mix B (0"26:0.74:151:084:0.4)

20
18

200

16
Shl

T~

150

k
,,

~
s
~

100

1&
12

10

spray
Bh

Shl

8
6

50
....

o-61 ......

~ . ~
io

2n

3 (a) &

(b)

The v a r i a t i o n

of

...~_~_ _'q~_~e_,~_?d Level

10
20
30
40
Depth into concrete(ram)
(b)

~o

Depth into concrete(ram)

(al
Fig.

: ......

(CI-)/(OH-)

with depth after

1 200 MC or TC

Vol.

18, No.

49
CORROSION RESISTANCE,

STEEL FIBERS,

SEA E X P O S U R E

s p e c i m e n s of this i n v e s t i g a t i o n w e r e g i v e n in e a r l i e r p a p e r s (1, 2).

The CIw a s e x t r a c t e d from p o w d e r s a m p l e s of c o n c r e t e b y d i l u t e acid (i).
The r e s u l t s
s h o w e d that in the s u r f a c e zones of s p e c i m e n s C1
c o n c e n t r a t i o n w e r e a l m o s t an
o r d e r of m a g n i t u d e g r e a t e r than the a s s u m e d a c t i v a t i o n level of 0.4 per cent.
D e s p i t e this t h e r e w a s no v i s u a l e v i d e n c e of c o r r o s i o n of fibres w h i c h were
e m b e d d e d in the s u r f a c e zones of specimens.
The above a c t i v a t i o n level, therefore,
a p p e a r s to be m e a n i n g l e s s for sfrc.
Corrosion

Resistance

of S t e e l F i b r e s

All s p e c i m e n s w e r e v i s u a l l y i n s p e c t e d b e f o r e any m e c h a n i c a l t e s t i n g was undertaken.

It was o b s e r v e d that n o r u s t i n g of fibres e x p o s e d at the c o n c r e t e surface was
e v i d e n t in the case of m e l t e x t r a c t (ME) fibre r e i n f o r c e d specimens.
This was due
to the fact that m e l t e x t r a c t fibres are of s t a i n l e s s steel w h i c h is less p r o n e
to c o r r o s i o n u n d e r d i r e c t e x p o s u r e to sea water.
The c h e m i c a l a n a l y s i s of steel
fibres are g i v e n in T a b l e 2 w h i c h i n d i c a t e a h i g h Cr and Ni c o n t e n t of m e l t e x t r a c t
fibres.
The c o r r o s i o n r e s i s t a n t fibres (CR) e x p o s e d at the s u r f a c e of c o n c r e t e
w e r e also u n s t a i n e d at e a r l y ages of u p to 1 year of exposure.
Such fibres are
c o a t e d w i t h a layer of zinc w h i c h p r o v i d e s a n o d i c p r o t e c t i o n to steel.
A t later
ages, however, a l i m i t e d n u m b e r of rust spots a p p e a r e d at the e x p o s e d s u r f a c e of
such fibres p r o b a b l y at p o i n t s w h e r e the zinc c o a t i n g had b e e n d a m a g e d or d e p l e t e d
due to the p r e f e r e n t i a l c o r r o s i o n of zinc.
E x t e n s i v e corrosion, however, was
e v i d e n t in the case of low c a r b o n steel fibres (MS) e x p o s e d at the surface of
s p e c i m e n s w h i c h w e r e c u r e d u n d e r m a r i n e exposure.
T h e c o r r o s i o n o c c u r r e d well
w i t h i n 150 cycles of exposure.
C o r r o s i o n , h o w e v e r , was l o c a l i s e d at the s p e c i m e n
s u r f a c e and there was no e v i d e n c e of its p e n e t r a t i o n into the e m b e d d e d p a r t s of
the fibres even after 2 O O O cycles (i 250 days).
TABLE 2
Chemical Composition

of S t e e l F i b r e s

Steel Fibre

Elements
C

(%)

si

Mn

Cr

Mo

Ni

Zn

Melt extract

(ME)

0.20

2.77

0.38

0.02

O.O1

17.6

0.07

0.58

<O.O1

Low carbon

(MS)

0.09

O.O1

0.36

0.03

O.O1

0.04

<O.O1

0.06

<O.O1

Corrosion
resistant

iCR)

0.05

O. iO

O.41

0.03

<O.O1

<O.O1

<O.O1

0.03

<2.49

T h e f r a c t u r e d faces of p r i s m specimens, a f t e r f l e x u r a l testing, w e r e also c l o s e l y

e x a m i n e d for a n y e v i d e n c e of fibre corrosion.
In addition, some fibres w e r e
r e t r i e v e d at r a n d o m from the zones close to the s p e c i m e n s u r f a c e s for f u r t h e r
visual examination.
In o r d e r to r e t r i e v e the fibres, the m a t r i x was s o f t e n e d b y
l o a d i n g it in c o m p r e s s i o n .
T h e r e t r i e v e d fibres were c l o s e l y e x a m i n e d for any
signs of c o r r o s i o n b o t h b e f o r e and after c l e a n i n g t h e i r s u r f a c e of any a d h e r i n g
c e m e n t matrix.
F r o m all these o b s e r v a t i o n s , no trace of fibre c o r r o s i o n w i t h i n
the m a t r i x was e v i d e n t for the three types of steel fibres used.
Electrode

Potential

Measurements

T h e p o t e n t i a l s of low c a r b o n steel fibres (MS) in s p e c i m e n s e x p o s e d to 2 O O O tidal

c y c l e s are shown in F i g u r e 4. A l l the p o t e n t i a l r e a d i n g s p l o t t e d are for i n d i v i d u a l
measurements.
It is c l e a r t h a t the v a l u e s i n c r e a s e w i t h i n c r e a s i n g d e p t h of u p to
30 mm, b e y o n d w h i c h the p o t e n t i a l r e m a i n s a p p r o x i m a t e l y c o n s t a n t at -300 mY.
The
free c h l o r i d e c o n c e n t r a t i o n p r o f i l e and pH v a l u e s of the p o r e f l u i d (3) are also
i n c l u d e d in Fig. 4.

50

Vol.
P.S.

(i) 35 500ppmCF

(ii)

PH of pore
e
so[ution{OH-)
Free chloride{d.~_
in pore solution
Potential~"
13"30
(my SCELIoo

40

noCF

}.iooo~
-__

r_.

0 2 ~ 6 8 10 12 lZ~

-500

corrosion

Ol , ph

(iii)
L, , orroslon

(OH') ~ ~,

13.20

-300
-z.O0

6 ,

355ppr.[["

Ic-i....

Genera[ " ] - - - - . .
Corroslon. ~

-200

18, No.

M a n g a t and K. G u r u s a m y

8 P0fenfial

-~

"- -

~,soo

Lo

J
]mmTt~'-'~" t 1000~o
.
,
,
. . , . .0 2 4 6 8 10 12 14ph
Pourbaixdiagrams
at different depths
(i) surface
(ii) 35mr.
(iii)38-50mr.

(r.V SCE)
Mix A ( 1 : 1 ' 5 1 : 0 S 6 : O k )

co

F i b r e : Low c a r b o n

13.00

steel IMS)

-600 30
-700

12.60

-800

-900

~kppr.103

20'

10

1'o

2'o

~o

Depth(mr.) into concrete

Fig.

Electrode

potentials

io

s'o

a f t e r 2 O O O TC, w i t h P o u r b a i x diagrams.

With this i n f o r m a t i o n it is p o s s i b l e to d r a w the t y p i c a l P o u r b a i x d i a g r a m s (16) at

s e l e c t e d d e p t h s into concrete, w h i c h r e p r e s e n t the t h e r m o d y n a m i c e q u i l i b r i u m of
steel in concrete.
In u s i n g P o u r b a i x diagrams, c e r t a i n l i m i t a t i o n s must be apprec i a t e d (17).
Firstly, the e l e c t o c h e m c i a l e q u i l i b r i u m d i a g r a m s w e r e o b t a i n e d by
P o u r b a i x by r e c o r d i n g the b e h a v i o u r of pure m e t a l s in aqueous solutions.
Secondly,
the pH v a l u e g i v e n a l o n g the x - a x i s of the P o u r b a i x d i a g r a m s is the pH of the solution w h i c h is in d i r e c t c o n t a c t w i t h the m e t a l surface.
The d i v e r g e n c e b e t w e e n
local pH v a l u e s and bulk pH v a l u e s can be c o n s i d e r a b l e , p a r t i c u l a r l y in cases of
l o c a l i s e d corrosion.
F u r t h e r m o r e , P o u r b a i x h i m s e l f has w a r n e d that the e l e c t r o c h e m i c a l e q u i l i b r i u m d i a g r a m s m u s t always be u s e d in c o n j u n c t i o n w i t h o t h e r m e a n s
of i n v e s t i g a t i o n .
T h e s e l i m i t a t i o n s n o t w i t h s t a n d i n g , the use of P o u r b a i x d i a g r a m s
p r o v i d e s a v a l u a b l e i n s i g h t into the e l e c t r o c h e m i c a l state of steel fibres in
concrete.
T h r e e t y p i c a l P o u r b a i x d i a g r a m s have, therefore, been i n c l u d e d in
F i g u r e 4.
T h e s e r e p r e s e n t the t h e r m o d y n a m i c e q u i l i b r i u m of steel in c o n c r e t e contamin a t e d w i t h 35,500 ppm, 355 p p m and zero p p m Cl- r e s p e c t i v e l y .
A t the s u r f a c e of
s p e c i m e n s w h e r e Cl- c o n c e n t r a t i o n a p p r o x i m a t e s 2 7 , 0 0 0 ppm, P o u r b a i x d i a g r a m
(i) in
Fig. 4 a p p r o x i m a t e l y r e p r e s e n t s the state of steel fibres.
If the pH at the surface
is taken as a p p r o x i m a t e l y 12.3 from Fig. 4, then it is a p p a r e n t that the fibres at the
s u r f a c e are in the r e g i o n of i m p e r f e c t p a s s i v i t y (IP) in the P o u r b a i x d i a g r a m '(I) '
A t a d e p t h of 35 m m from the surface, w h e r e the CI- c o n c e n t r a t i o n is a p p r o x i m a t e l y
355 ppm, P o u r b a i x (ii) r e p r e s e n t s the state of steel fibres in concrete.
The potential and pH v a l u e s of these fibres i n d i c a t e t h e i r p o s i t i o n to be in the r e g i o n of
imperfect passivity.
A t d e p t h s b e y o n d a b o u t 38 mm, w h e r e free c h l o r i d e is n o t
present, P o u r b a i x d i a g r a m (iii) r e p r e s e n t s the t h e r m o d y n a m i c e q u i l i b r i u m of steel
fibres.
In this case the fibres are c o m f o r t a b l y w i t h i n the p a s s i v e r e g i o n and,
therefore, there is no risk of corrosion.
The v a l u e s of e l e c t r o d e p o t e n t i a l (E) g e n e r a l l y a c c e p t e d as r e p r e s e n t i n g the a c t i v e
and p a s s i v e state of steel r e i n f o r c e m e n t are s h o w n in T a b l e 3.
More r e c e n t l y A r u p
has d e f i n e d four states of c o r r o s i o n of steel, the t y p i c a l p o t e n t i a l s for i n i t i a t i o n
of p i t t i n g c o r r o s i o n b e i n g b e t w e e n
- 200 and
- 500 m V (19).
In Fig. 4 the elect r o c h e m i c a l p o t e n t i a l s of steel fibres at all d e p t h s into c o n c r e t e and e s p e c i a l l y in

Vol.

18, No.

51
C O R R O S I O N RESISTANCE,

STEEL FIBERS,

SEA E X P O S U R E

the surface zones are m o r e n e g a t i v e than

- 250 mY.
It is a p p a r e n t from T a b l e 3
that at these p o t e n t i a l s , steel fibres should have corroded.
As already discussed
above no such c o r r o s i o n of the fibres w a s apparent.
The p o s s i b l e r e a s o n s for this
are:(i)
The e l e c t r o d e p o t e n t i a l v a l u e s shown in T a b l e 3 were o b t a i n e d by u s i n g an
e x p e r i m e n t a l a r r a n g e m e n t w h e r e an e l e c t r i c a l c o n n e c t i o n was made to a c o n v e n t i o n a l
r e i n f o r c e m e n t bar at a c o n v e n i e n t p o s i t i o n e n a b l i n g e l e c t r o d e p o t e n t i a l s to be
m e a s u r e d at the surface of concrete.
By m o v i n g the r e f e r e n c e e l e c t r o d e about on
the surface, the e l e c t r o d e p o t e n t i a l of steel e m b e d d e d at a g i v e n cover could be
m e a s u r e d at any point.
The t e c h n i q u e u s e d to m e a s u r e e l e c t r o d e p o t e n t i a l s in this
i n v e s t i g a t i o n , however, was quite d i f f e r e n t as shown in Fig. i.
In this case the
r e f e r e n c e e l e c t r o d e was fixed at the surface and the p o t e n t i a l s of steel fibres
m e a s u r e d at d i f f e r e n t d e p t h s into concrete.
(ii)
T h e p o t e n t i a l m e a s u r e m e n t s were t a k e n on steel fibres e x p o s e d at the fractured face of p r i s m
s p e c i m e n s a f t e r t e s t i n g in flexure.
These electrode potential
v a l u e s i n d i c a t e the state of steel after p h y s i c a l d i s r u p t i o n of fibres during p u l l
out and not of u n d i s t u r b e d steel fibres e m b e d d e d in the matrix.
(iii)
The p o t e n t i a l m e a s u r e m e n t s were u s u a l l y t a k e n after b e t w e e n 1 to 3 hours
from the time of m e c h a n i c a l testing.
Low carbon steel fibres (MS) e x p o s e d at the
f r a c t u r e d faces of s p e c i m e n s and left u n d e r u n c o n t r o l l e d c o n d i t i o n s in the
l a b o r a t o r y air, s h o w e d signs of rust s t a i n i n g a f t e r about 24 hours.
It is likely,
therefore, that p o t e n t i a l m e a s u r e m e n t s taken even after a few m i n u t e s of m e c h a n i c a l
t e s t i n g m a y n o t be the actual p o t e n t i a l s of u n e x p o s e d steel fibres.
The e l e c t r o d e p o t e n t i a l m e a s u r e m e n t t e c h n i q u e shown in Fig. 1 assumes that fibres
are i s o l a t e d and not in e l e c t r i c a l c o n t a c t w i t h a d j a c e n t fibres.
A check was m a d e
by m e a s u r i n g the r e s i s t a n c e b e t w e e n a d j a c e n t fibres, u s i n g a s t a n d a r d meter.
This c o n f i r m e d that the fibres w e r e not in e l e c t r i c a l contact.
The p o t e n t i a l m e a s u r e m e n t s for s p e c i m e n s r e i n f o r c e d w i t h c o r r o s i o n r e s i s t a n t fibres
(CR) and m e l t e x t r a c t fibres (ME) are shown in Fig. 5.
The p o t e n t i a l v a l u e s show
a s i m i l a r trend of less n e g a t i v e v a l u e s at g r e a t e r depths from the surface as was
p r e v i o u s l y n o t e d for low carbon steel fibres (MS).
B e y o n d a d e p t h of about 30 m m
the p o t e n t i a l r e a d i n g s are fairly c o n s t a n t at m e a n v a l u e s of about - 250 m V for ME
fibres and
- 600 m V for C R fibres.
It is not p o s s i b l e to c o m p a r e these p o t e n t i a l
v a l u e s w i t h P o u r b a i x d i a g r a m s w h i c h are v a l i d only for s t a n d a r d steels.
TABLE
Interpretation

of C o r r o s i o n P o t e n t i a l
E

Measurements

(mY vs SCE)

> - 220
b e t w e e n - 220 and - 270
< - 270

Availability

3
(18)

C o n d i t i o n of Steel

Passive
Active

or P a s s i v e

Active

of O x y g e n

In the m a r i n e e n v i r o n m e n t w h e r e c h l o r i d e ions are likely to d i s r u p t the stable oxide

layer even at h i g h pH, the a v a i l a b i l i t y of o x y g e n at the steel surface is likely
to b e the c r i t i c a l c o n t r o l l i n g factor for c o r r o s i o n to occur.
It has b e e n shown
(20) that o x y g e n d i f f u s i o n near the surface of m o i s t c o n c r e t e is v e r y high.
Hence
it is r e a s o n a b l e to a s s u m e that at least in the s u r f a c e zones of sfrc specimens
s u f f i c i e n t o x y g e n w a s a v a i l a b l e to s u p p o r t corrosion.

52

Vol.
P.S. M a n g a t

18, No.

and K. G u r u s a m y

PH of pore
solution (OH')
Z'Free chloride(CF}
in pore solution
Potential
7o 13.30

Corrosion resistant fibre(CR]

A Melt extract fibre(ME)

",,,,, Mix A(1:1.50:0.86:0 4)

,"'

(mV SEE)I00

(OH-)

60
-200

13,20

-300

(mY SEE)

50

-400
~,0
"500

13'00

-600

30

-700-

20-

-B00 "

Potential

.,
II

(mV SCE)

12-60-

~ppmx103

10-90012.00-1000

Fig.

1o

20

30

Depth(mm)

Electrode potentials

s'o

after 2 OO0 MC.

It is g e n e r a l l y a c c e p t e d that oxygen c o n s u m e d d u r i n g the c a t h o d i c r e a c t i o n has to

be in a d i s s o l v e d state (21).
The e f f e c t of salt c o n c e n t r a t i o n on oxygen s o l u b i l i t y
in pore fluid and c o n s e q u e n t l y rate of c o r r o s i o n is d e m o n s t r a t e d in F i g u r e 6 (21).
It is e v i d e n t that the CI- c o n c e n t r a t i o n of about 78,000 ppm w h i c h o c c u r r e d in the
surface zones of s p e c i m e n s e x p o s e d to 2 O O O MC c o r r e s p o n d s a p p r o x i m a t e l y to the
m a x i m u m rate of corrosion.
The pore fluid in the surface zones, therefore, offers
an ideal e n v i r o n m e n t for corrosion.
Hypothesis

for F i b r e P a s s i v i t y

A c c o r d i n g to s t a n d a r d c o r r o s i o n theory, steel e m b e d d e d in c o n c r e t e is l a r g e l y
in a p r o t e c t e d state b e c a u s e of the a l k a l i n i t y of the matrix.
This a l k a l i n i t y

~o ~

Fig.

i I
I I
I
I
L I

I
i
i
i

36"5 7()'S I02 132 159 185 210 232

Satinify ppmxl03

E f f e c t of sodium
chloride concentration
on c o r r o s i o n rate,
after G r i f f i n and
H e n r y (21).

Vol.

18, No. i

53
CORROSION RESISTANCE,

STEEL FIBERS,

SEA EXPOSURE

results in the formation of a dense oxide layer which prevents current flowing
from anode to cathode, thereby maintaining passivity of steel.
This passivity,
however, can be broken down in the presence of chloride anions, resulting in
pitting corrosion (19).
From the results and observations of this investigation,
it is apparent that no such breakdown has taken place in the steel fibre
reinforced concrete specimens.
In addition, no deterioration in mechanical
properties of both uncracked and precracked specimens of sfrc at small crack
widths was evident after long term marine exposure (22, 23).
Page (24, 25) has suggested an alternative view of passivation.
With the aid of
scanning electron micrographs, he has shown that the interfacial zone separating
concrete and embedded steel is composed largely of segregated lime.
For reinforced
concrete which is permanently submerged in a chloride-bearing aqueous environment,
this lime rich layer effectively screens the metal from direct access of oxygen (24)
Therefore, although the ingress of CI- from sea water destroys the passive film on
steel thus creating anodic sites, the large polarization of the cathodic reaction
effectively stifles the corrosion process.
Hence, the limited occurrence of
corrosion in permanently submerged marine structures is not on account of anodic
passivation but due to the unavailability of oxygen to stimulate the cathodic
reaction.
In conditions other than those of total immersion, however, the supply
of oxygen to embedded steel is unlikely to be a limiting factor (24), more so in
the case of sfrc where the cover to steel is effectively zero.
It is, therefore,
the availability and rates of replenishment of chloride and hydroxyl ions which
are liable to govern the anodic behaviour of metal.
In this connection the
influence of the lime-rich layer in intimate contact with steel
is likely to be
significant.
This is because the surrounding lime provides a reservoir of OH-,
thereby buffering the anodic sites at high pH.
Additionally, the mobility of
chloride ions and, therefore, their supply to the anodic pits is likely to be
restrained by this lime rich layer (12, 26).
This restraint on the diffusion of
chloride ions whilst maintaining a buffered alkaline environment at the surface
of steel will tend to repassivate pits once formed.
The small diameter fibres,
with their large surface area to volume ratio, are even more effectively screened
by the lime rich layer than the large diameter bars used in conventionally
reinforced concrete.
This enhanced protection of the steel fibres provides an
explanation for their apparent passivity in concrete even though chloride is
available

in abundance,

and the

higher than the threshold

(CI'____~)
(OH-) ratios are several orders of magnitude

levels suggested by Hausmann.

Corrosion is characterised by the electro-chemical reaction which takes place

between a confined "pit" (the anode) where steel is depassivated and the
adjacent area of passive steel which acts as cathode (19).
The corrosion rate
depends on the ratio of the cathodic area to the anodic area (27).
Owing to
their discrete nature, the maximum cathodic area available for steel fibres
is limited.
Therefore, even if corrosion is initiated it is probable that the
subsequent rate of corrosion will be very small.
Conclusions
The following conclusions

are based on experimental

results given in this paper:-

i.

Low carbon steel and corrosion resistant (galvanised) steel fibres which
are exposed at concrete surface are prone to corrosion under marine exposure.
Melt extract (stainless steel) fibres exposed at concrete surface did not
show signs of corrosion after 2 OOO cycles of marine exposure.

2.

The activation level of 0.4 per cent CI- by weight of cement does not apply
to steel fibres embedded in concrete since corrosion was not initiated

54

Vol.

18, No ....

P.S. Mangat and K. Gurusamy

at CI- concentrations
activation level.
3.

almost an order of magnitude greater than the above

(Cl-)
The threshold value of O.61 for the (OH_----~ratio does not apply to steel fibres
(Cl-)
embedded in concrete since corrosion was not initiated even when ] - ~ c ~ ratios
were as high as 320.
Acknowledgements

The authors gratefully acknowledge the financial support from the SERC Marine
Technology Directorate for the research project on marine durability of steel
fibre reinforced concrete.
The authors also gratefully acknowledge the advice
and facilities made available by Prof. F.P. Glasser of the Chemistry Department,
Aberdeen University.
References
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12.
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15.
16.
17.
18.
19.
20.
2i.
22.
23.
24.
25.
26.
27.

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