TECHNICAL COMMITTEES

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COMMISSIONS TECHNIQUES

RILEM TECHNICAL COMMITTEE 32-RCA

Subcommittee "Long-time Studies"
RESISTANCE OF CONCRETE TO CHEMICAL ATTACKS
S e a w a t e r A t t a c k on C o n c r e t e
and Precautionary Measures

This "state of the art" guide deals only with the possible
reactions of seawater with maritime concrete structures as
investigated by several concrete Iongtime studies during
the last 70 years ([1] to [23]), completed with regard to
the modern state of knowledge on NaCI penetration into
concrete ([24] to [35]). It does not include other special
attacks on certain harbour structures such as fish fat, oil,
deicing materials, etc.

Chloride ions can penetrate into the concrete and cause

accelerated corrosion of the reinforcement. The chemical
reaction of the cement-paste with the high CI-content of
seawater is generally slight and not a primary cause of
distress.
Sulfate ions cause sulfate attack on the cement-paste.
In spite of the high SO4-- concentration the effect is only
slight or moderate due to the very high CI- concentration.
Magnesium ions cause a weakening action on the
cement-paste by ion exchange Ca + +~- Mg + +
Sodium and potassium ions may produce or intensify
alkali aggregate reaction if reactive aggregates are used.

1. P o s s i b l e p a r a m e t e r s o f attack

1.1. Aggressive ions in seawater

The water of all the open oceans usually has a relatively
narrow range of chemical composition:

g/I

CI-

SOi-

Ca++

Mg ++

Na

North Atlantic. , ,
South Atlantic..
World Average..

17.8
20.5
19.8

2.5
2.9
2.7

0.4
0.4
0.4

1.5
1.3
1.3

11.0
11.4
10.9

0.3
0.5
0.4

1.2. Temperature of seawater

At lower temperatures the intensity of the sulfate attack
is increased. At higher temperatures the intensity of the
sulfate attack is slightly decreased while the intensity of
all the other types of attack is increased.
On the w h o l e seawater attack on reinforced concrete is
much more severe in hot climates.

The pH values are about 8.

Experience of seawater is generally based on oceanic
water of this type. The possibility of reactions other than
described below cannot be excluded in water the salt
concentration of which is much higher (e. g. Dead Sea),
or much lower (e. g. Brackish water).

1.3. Z o n e o f a t t a c k
Seawater has only a slight action on fully immersed
concretes or concrete parts. Concretes which are not in
direct contact with seawater, but are sometimes affected

Mat6riaux r Constructions 0025-5432/85/03 223 04/$ 2.40/ 9 BORDAS-GAUTHIER-VILLARS

223

Vol. 18 - N~ 105 - Mat6riaux et Constructions

by seawater spray may also suffer from a slight attack. The

most severe attack of seawater on concrete and reinforcement takes place within the tidal and splash zone.
1.4. H i s t o r y o f t h e c o n c r e t e b e f o r e e x p o s u r e
Beside the quality and the composition of the fresh
concrete also the climatic conditions before its first exposure to the seawater have an influence on its Iongtime
performance. The most important parameters are temperature and relative humidity during the casting, compacting
and curing of the concrete.
During hot weather the danger of an early excessive loss
of water is predominant. At lower concreting temperatures
down to 5~ this process is not so rapid but the water
has far more time to evaporate before it is bound by the
cement which hydrates much more slowly at these low
temperatures. Hence insufficient curing will have a decisive detrimental effect on permeability, strength, and durability of the concrete during its whole lifetime.
1.5. O t h e r e x t e r n a l p a r a m e t e r s

Other possible types of attack, mostly having the effect

of surface deterioration are frost action in freezing environments, mechanical action of waves (cavitation or surface erosion), and biological attack.
1.6. C o n c r e t e q u a l i t y

Careful construction work and a high quality of the

concrete determine the durability of any maritime concrete
structure. The essential parameters related to good workmanship are low porosity and water tightness of the
concrete, and complete embedding and sufficient cover of
the reinforcement.
Specifications regarding concrete composition, compaction procedures, curing conditions, etc. as well as the
degree of fulfilment of the specifications determine the
quality of concrete before exposure.
1.7. C o n c r e t e c o m p o s i t i o n
Each of the three components of reinforced concrete
can be damaged by seawater action if certain rules for
concrete composition of maritime structures are neglected:
The cement-paste can be attacked by chemical reaction
with the salts in the seawater if its CaO/Si02 ratio and its
C3A content are too high. See 2.5.
The reinforcement can corrode even within the cementpaste having a p H > 1 2 if the concrete cover does not
provide enough protection against the penetration of chloride and oxygen. For this a sufficient content of C3A or
other aluminous components and active siliceous compounds in the paste are favourable. See 2.5.
Deleterious aggregates can react due to the penetrating
Na + if the paste does not provide enough protection
against the diffusion of NaCI and alkali aggregate reaction,
especially if the concrete is submitted to cycles of drying
and wetting. Suitable reactive siliceous compounds in the
paste can prevent this type of attack, See 2.9.1.
The resistance against all these possible forms of deterioration is distinctly improved by decreasing the water/
cement ratio and by using a sufficiently high cement
content.

224

2. P r e c a u t i o n a r y M e a s u r e s
2.1. G e n e r a l rules

The concrete must have a composition and quality

which provides enough protection against the corrosion
of concrete and reinforcement in the intertidal zone and
the splash zone. Concrete of this quality will usually not
be at risk below low-water level.
It is necessary to avoid weak elements in the structural
design such as sharp edges and angles.
It is necessary to assure that the specified concrete
quality is obtained before exposure to seawater.
After an adequate curing the time before immersion in
seawater should be as long as possible for Portland
Cement but it should preferably be short for Blastfurnace
Slag Cement with more than 65 % slag and for Pozzolanic
Cement. Any cracks developed during curing should be
repaired before exposure.
In colder climates the concrete must also be resistant to
frost action. See 2.9.2. In warmer climates with higher
rates of chloride diffusion the concrete must provide more
protection against accelerated chloride attack and corrosion of the reinforcement.
2.2. M i x p r o p o r t i o n f o r r e i n f o r c e d c o n c r e t e
Cement content (').
W/C ratio (").
Cement+fine material (<0.125 mm),

t>350 kg/m 3
~<0.50
preferably
~<0.45
~<450 kg/m 3

(') The cement content is a function of the grading of

aggregates.
(~176In the Code of Practice CP 110 from UK "free water/
cementratio < 0.40".

2.3. A g g r e g a t e s

The aggregates should have a good grading according

to national standards. They must be resistant against
strong chloride solutions and against alkali aggregate reaction. In colder climates they must be frost-resistant as
well,
If alkali-reactive aggregates cannot be avoided, see
2.9.1.
2.4. C o n c r e t e c o v e r o f t h e r e i n f o r c e m e n t
In normal climates the concrete cover must not fall
below 40 mm at any point of the reinforcement. That in
general means a concrete cover of a least 45_+5 mm to
allow for the inevitable irregularities when placing the
steel.
In warmer climates it is sometimes necessary to apply
even thicker covers.
If a concrete of high quality has a markedly high resistance against chloride diffusion it is possible to reduce the
concrete cover.
2.5. C e m e n t s

In principle, if attention is paid to points 2.1 to 2,4 all

cements are suitable for seawater constructions if they
have 28 day compressive strengths >~ 35 N/mm 2 (or 35

32-RCA Committee
MPa) as determined by the ISO test and in the case of
Portland cements ~< 10% C3A ([1], [2]).

to achieve concretes w h i c h are practically impermeable to

the diffusion of chlorides and alkalis of seawater.

Particularly suitable are OPC w i t h ~< 8 % C3A (1) CLK

w i t h I> 60% slag and Pozzolanic Cements.
In certain countries the quantity of S03 is limited in
Portland cements used for massive constructions i. e. 3 %
in USA and 2.5% in France.
Cements w i t h l o w early strengths must be protected
against drying out w h i l e hardening longer than cements
w i t h high early strengths.
2.6. M i x i n g w a t e r
The mixing water should be of suitable quality according
to National Standards w h i c h often contain limits on the
content of chlorine and sulfate ions. Seawater must be
avoided in reinforced concrete structures.
2.7. C o n c r e t e a d d i t i v e s
The addition of hydraulic active materials w h i c h can
increase the density and reduce the content of free lime
and w h i c h provide more siliceous c o m p o u n d s (e. g. pozzolanas, granulated blastfurnace slags, moler earth, silica
fume, fly ash, etc.) often has a favourable effect in reducing possible risks of alkali aggregate reaction or chloride
diffusion. Since excessive addition can be unfavourable
the use of additives must be' submitted to preliminary
compatibility tests.
2.8. C o n c r e t e a d m i x t u r e s
Ordinary concrete admixtures may be used in accordance w i t h National Standards. Their application is always
submitted to a preliminary compatibility test according to
National Standards or recommendations and should be
performed on the site w i t h the materials used.
2.9. P r e c a u t i o n s f o r special cases

A. Concrete Iongtime studies

[1] ECKHARDTA. KRONSBEINW. - Beton und Zement im Seewasset. Deutscher Ausschu~ fL~r Stahlbeton, Heft 102, 1950,
Berlin.
[2] LEA F.M., WATKINS C.M. -- The durability of reinforced
concrete in seawater. National Building Studies Technical,
Paper 30; HMSO, 1960, London (incl. steel corrosion).
[3] KEIL F. - Zwanzig Jahres-Bericht der Langzeit-Versuche
6ber das Verhalten von Zement im Beton. (USA Long-Time
Study), beton, Vol. 16, 1966, pp. 27/35 and 77/83.
[4] LEA F.M. - The behaviour of concretes exposed to seawater
(Topic I-General Report). Bull. RILEM, Nr. 30, 1966, pp.
59/70 (incl. steel corrosion).
[5] LYSE I. - The behaviour o f concretes exposed to seawater
(Topic II-General Report). Bull. RILEM, Nr. 30, 1966, pp.
71/73.
[6]
CAMPUSF. -- The behaviour of concretes exposed to seawater (Topic Ill-General Report). Bull. RILEM, Nr. 30, 1966,
pp. 75/86 (incl. steel corrosion).
[7] DUmEZ M. - R e p o r t on reinforced concrete in seawater.
Palermo, 1965, ref. in [4] (incl. steel corrosion).
[8] RIo A., CELANIA. - Report on reinforced concrete in seawater. Palermo, 1965, ref. in [4] (incl. steel corrosion).
[9] GJORV O.E., GUKILD I., SUNDH H.P. - Investigation o f
concrete piles under varying conditions in seawater. Buli.
RILEM, Nr. 32, 1966, pp. 305/322 (incl. steel corrosion).
[10] DUHOUX L., TESSIERA. - Usine mar~motrice de la Rance.
Composition des b~tons. Bull. RILEM, Nr. 32, 1966, pp.
268/278 (incl. steel corrosion).
[tt] CAMPUS F., DANTIENNE R., DZULYNSKI M. - Constatations
effectu~es apr&s trente ann~es d'immersion marine d'~prouvettes de mortier, des b~tons et des batons arm,s dans la mer
du Nord. Association Fran~:aise de Recherches et d'Essais

{12]

2.9.1.
If reactive aggregates cannot be avoided the national
recommendations for prevention of alkali aggregate reaction must be followed. In addition the procedures recommended b e l o w to reduce permeability must be f o l l o w e d .
See 2.10.

[13]

[14]

2.9.2.

[15]

If there is a danger of severe frost action, not only

should there be a limit to the w a t e r / c e m e n t ratio of the mix
but also concrete should be air entrained if appropriate.

[16]

2.10. P r o t e c t i o n a g a i n s t c h l o r i d e d i f f u s i o n
If markedly improved resistance to chloride diffusion
and steel corrosion is demanded, dense concretes w i t h
additives according to 2.7 or the application of blended
cements (as described in 2.5) w h i c h themselves provide
sufficient contents of siliceous c o m p o u n d s (e. g. BFC w i t h
/> 6 0 % slag or pozzolanic cements) are favourable. It is
even possible by careful selection of admixtures a n d / o r
additives, technics and the use of l o w w a t e r / c e m e n t ratios

(l) C3A is conventionalydeterminedby Bogue calculation but this does

not usually give the true mineralogicalcompositionwhich is better determined by X-ray diffraction.

sur les Mat6riaux et les Constructions, Cahiers de la

recherche, Nr. 27, 1968, pp. 161/174 (incl. steel corrosion).
MATHER B. - Field and laboratory studies of the sulphate
resistance of concrete. Thorvaldson Syrup. Univers. of
Toronto Press, 1968, pp. 66/76.
VERBECK G.J. - Field and laboratory studies o f the sulphate
resistance of concrete. Thorvaldson Symp., Univers. of
Toronto Press., 1968, pp. 113/124 (incl. steel corrosion).
LOCHER F.W. -Untersuchung
des
Betons
von
Uferschutzbauten auf Helgoland. Beton, Vol. 18, 1968, pp.
47/50 und 82/84.
RAPHAELM. SHALON R. - A study o f the influence of climate
on corrosion of reinforcement. Proc. Int. RILEM Symp. on
Concrete and Reinforced Concrete in Hot Countries, BRS
Haifa, Vol. I, 1971, pp. 77/96.
PELTIER R. - R~sultats des essais de Iongue duroc de la
r~sistance des ciments ~ l a m e r au laboratoire maritime de
La Rochelle. Revue des Mat6riaux, Nr. 680, 1973, pp. 31/44.

[17] FULTON F.S., ZtETSMANN C.F. - Corrosion of reinforcement

in marine environments. Portland Cement Inst. Monograph:
The properties of Portland cements containing milled granulated blastfurnace slag, Johannesburg, 1974, p. 36.
[~ 8] MEHTA P.K., HAYNES H.H. - Durability o f concrete in seawater. Journal of Structural Division ASCE, Vol. 101, 1975, pp.
1679/1686.
[19] REGOURD M. - L'action de reau de met sur les ciments.
Annales de rlnstitut Technique du B~timent et des Travaux
Publics, Nr. 329, 1975, pp. 87/102.
[20] SCHI~ODER H.T., HALLAUER O., SCHOLZ W. - Bestandigkeit
verschiedener Betonarten im Meerwasser und in sulfathaltio
gem Wasser. Deutscher Ausschuss fL~rStahlbeton, Heft 252,

1975 (incl. CI-diffusion).

225

Vol. 18 - N ~ 1 0 5 - Mat6riaux et Constructions

[21] International Conference. - Performance of concrete in

marine environment. ACI Special Publication, No. 65, 1980,
Detroit (incl. steel corrosion).
[22] TUKKER A., WIEBENGA J.G., BRUGMAN R., VAN VUGT A.P., VOS
Ch.J. - Duurzaamheid maritieme constructies. CUR-rapport,
No. 100, 1981 (incl. steel corrosion and CI-diffusion).
[23] RILEM 32 RCA. - Summaries of the results of Iongtime
studies. Communicated 1978/1980 by N. Ben-Yair, V. Korac,
M. Liatis, F. Massazza, I. Medgyesi and G. Toroczkay, A.E.
Moore and J.A. Dalziel, R, Nagano, M. Regourd, A. Rio,
H.G. Smolczyk, V. Van den Bosch, A~ Yoda.

B. D i f f u s i o n o f N a C I

[24] COLLEPARDI M., MARCIALtS A., TURRIZlANI R. - - La cinetica di

penetrazione degli ioni cloruro nel calcestruzzo, II Cemento,
Vot, 67, 1970, pp. 157/164.
[25]
SLUIJTER W.L. - - De binding van chloride door cement en
de indringsnelheid van chloride in mortel. IBBC-TNO,
Report, No. BI-73-41, Delft, 1973.
[26] SMOLCZYK H.-G. - Investigation on the diffusion of Naion in concrete. Symposium on Alkali-Aggregate Reaction,
Reykjavik, 1975, Proceed., 1 975, pp, 183/188.
[27] BAKKER R.F.M., THOMASSEN W.I.M. - Diffusiesnelheid van
ionen in beton. Cement, Vol. 29, 1977, pp. 419/421.

~?~

[28] SPRUNG S. - Beton fdr Meerwasserentsalzungsanlagen.

Beton, Vol. 28, 1978, pp. 241/245.
[29] GJORV O.E., VENNESLAND O. -- Diffusion of chloride ions
from seawater into concrete. Cement and Concrete Research,
Vol. 9, 1979, pp. 229/238.
[30] EFESY. - Einflu[3 der Zemente T i t unterschiedlichem H~ittensandgehalt auf die Chloridiffusion im Beton. Betonwerk+ FertigteiI-Technik, Vol. 46, 1980, pp. 224/229, 302/306 and
365/367 (incl. steel corrosion).
[31[ NIEL E.M.M.G. - Durzamheid van beton met hoogovenceTent in het zeewatermilieu fond warme landen. Cement,
1980, pp. 730/735 (incl. steel corrosion).
[32] FELDMAN R.F., RAMACHANDRAN V.S. - New accelerated
methods for predicting durability of cementitious materials.
Durability of Building Materials and Components ASTM STP
691, P.J. SEREDA, C.G. LITVAN, Eds., American Society for
Testing and Materials, 1980, pp. 313/325.
[33] PACE C.L., SHORT N.R., TARRAS A.E. - Diffusion of chloride
ions in hardened cement pastes. Cement and Concrete
Research, Vol. 11, 1981, pp. 395/406.
[34] BRODERSENH.A. - Zur Abhangigkeit der Transportvorg~nge
verschiedener Ionen im Retch von Struktur und Zusammensetzung des Zementsteins. Dissertation, RWTH Aachen,
1982.
[35] BROWNE R.D. - Design prediction of the life for reinforced
concrete in marine and other chloride environments. Durability of Building Materials, Vol. 1, 1982, pp. 113/125.