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400 Ericsson Werkstoffe und Korrosion 29,400-403 (1978)

Overlag Chemie, CmbH, D-6940 Weinheim, 1978

The influence of sodium chloride on the atmospheric corrosion of steel

Einflufl von N a t r i u m c hl o r i d auf die at mo s p h ar i s ch e Korrosion von Stahl

R . Ericrson *)
Department of Inorganic Chemistry, Chalmers University of Technology and the University of Goteborg, P.O. Box,
S-402 20 Goteborg 5 , Sweden

Summary Kur zfassung

The influence of sodium chloride on the atmospheric Untersucht wurde der Einjluj3 von Natriumchlorid auf
corrosion o f mild steel has been studied. Samples covered die atmospharische Korrosion von Stahl. Dabei wurden mit
with sodium chloride crystals ( 8 pg NaCl ' c m - 2 ) have been Natriumchloridkristallen (8 pg NaCl . c m - 2 ) bedeckte Pro-
exposed to an SO,-free atmosphere a t different relative ben einer schwefeldioxidfreien A tmosphare verschiedener
humidities. The combined effect of sodium chloride crys- relativer Feuchtigkeit ausgesetzt. Die kombinierte Wirkung
tals on a steel surface and sulphur dioxide in the atmosphere von Natriumchloridkristallen auf der Stahloberflache und
has been investigated at an SO,-supply of Schwefeldioxid in der Atmosphare wurde bei einer Sch wefel-
1 pg SO2 . c m - , . h-' ( 1 ppm SO,). The corrosion attack dioxidzufuhr von 1 pg SO, . c m -2* Std-' ( 1 p p m S O 2 ) uriter-
was followed by periodic weighings. The corrosion products sucht. Der Angriff wurde durch kontinuierliches Wiegen ver-
formed have been studied using the SEM-technique. On ex- folgt, und die Korrosionsprodukte wurden mittels REM-
posure of samples with sodium chloride in an SO2-free at- Technik untersucht. Bei der Bewitterung der mit Natrium-
mosphere the extent o f corrosion increased with increasing chlorid bedeckten Proben in schwefeldioxidfreier Atmospha-
relative humidity f ro m 58% to 9095, interrupted by a sharp re steigt die Korrosion mit der relativen Feuchtigkeit (58 bis
minimum at about 87% relative humidity. The SEM-studies 90x1, wobei die Kurve durch ein scharfes Minimum bei 87%
showed that tower shaped corrosion products were formed rel. Feuchtigkeit unterbrochen ist. Die REM-Bilder zeigen,
at a high relative humidity while filiform corrosion appeared daj3 bei hoher rel. Feuchtigkeit saulenformige Korrosions-
when the relative humidity was lowered. A t 90% relative produkte entstehen, wahrend bei niedriger rel. Feuchtigkeit
humidity more corrosion was observed with clean steelsamp- fadenformige Korrosion auftritt. Bei 90% Feuchtigkeit ist
les and an S02-supply o f I p g . cm-, . h-' than with sodium die Korrosion von sauberen Stahlproben bei einer Schwefel-
chloride crystals on the surfaces ( 8 pg NaCl. c m - 2 ) in the dioxidzufuhr von 1 pg- c m - 2 . Std-' starker als die von
absence of SO2. In the combined influence of sodium chlo- mit Natriumchlorid bedeckten Proben in schwefeldioxid-
ride on the steel surfaces and sulphur dioxide in the atmos- freier Atmosphare. Bei Anwesenheit beider angreifender
phere a synergic effect was noticed at 90% relative humidity. Mittel tritt bei 90% rel. Feuchtigkeit ein synergistischer
A t 70% relative humidity no influence of an S02-supply of Ejyekt auf, wahrend bei 70% rel. Feuchtigkeit die Korrosion
1 ~ . ( gSO, ' c.m-2 . h-' o n the corrosion of steel samples with der mit Natriumchlorid bedeckten Proben durch Schwefel-
sodium chloride crystals on their surfaces could be observed, dioxid nicht beeinflu$t wird.

found that during extended exposures, steel corrodes more
The atmospheric corrosion of steel is influenced by several in a marine environment than in an industrial region.
factors e.g. t h e S02-concentration, t h e temperature, the re- Chlorides deposited on metal surfaces can originate from
lative humidity and t h e amount of precipitation. I n coastal industrial plant. This fact can explain the high chloride con-
regions t h e amount of saline particles in t h e air i s of great tent in the corrosion products of steel exposed far from the
importance t o t h e extent of the atmospheric corrosion. In- sea ( 3 ) . A combined influence of chlorides deposited o n the
vestigations performed by Ambler and Bain ( 1 ) in Nigeria surface and sulphur dioxide in the atmosphere is considered
showed that atmospheric corrosion decreased with decreas- to cause extensive corrosion (7).
ing salt content in the air. In an investigation in Great Britain Laboratory investigations with different salt particles
no correlation between t h e amount of deposited chloride showed that the rate of corrosion increased considerably
particles and the extent of corrosion could be found ( 2 ) . above a certain critical value of the relative humidity ( 8 , 9).
Sereda (3) considers that a threshold value of the chloride This critical value is equivalent t o the relative humidity above
content must be exceeded for t h e corrosion caused b y de- a saturated solution of ;he actual salt. For sodium chloride
posited chloride particles t o increase appreciably. this value is 7 8 % a t 20 C ( 8 ) . However, steel with sodium
The initial corrosion of steel is often higher in industrial chloride particles o n its surface corrodes at below 7 8 %
environments than in coastal regions but t h e rate of corrosion relative humidity. This is probably due to the fact that mois-
decreases more rapidly in industrial atmospheres. After an ture is bound to the yteel surface a t the salt particles by ca-
exposure of two years t o a marine environment carbon steel pillary action (10). Thus, in t h e presence of sodium chloride
corrodes more rapidly than if exposed t o a n industrial en- particles on a steel surface, corrosion can take place at relative
vironment (4, 5 ) . Coburn et a]. ( 6 ) also made a comparison humidities that would not have caused corrosion o n clean
between different types of corrosion environments and surfaces ( 1 1). The extent of corrosion is dependent on the
amount of moisture that has been adsorbed by the salt (1 I ,
*) Present address: Avestl: Jernverk, P.O. Box, S-77401 Avesta 1 , 12). Sea salt particles cause corrosion a t lower relative hu-
Sweden. midities than sodium chloride particles do, which results
Werkstoffe und Korrosion 29, 400-403 (1978) The influence of sodium chloride on the atmospheric corrosion 401

from the fact that sea salt contains very hygroscopic mag- W
nesium salts ( 13). irng cm?
In a laboratory investigation with accurately determined 90 7 0
amounts of sodium chloride on a steel surface the rate of
corrosion increased with increasing relative humidity up to 04 85%
90%, interrupted b y a sharp minimum at 87.5% relative 96 %
humidity ( 14). a 1%
Studies concerning t h e initiation of the sodium chloride 86%
induced corrosion of steel showed that the attacks started
where concentrated salt drops had accumulated ( 1 5 , 16). 03 75%


The mild steel had the following chemical analysis: 02 58%

%C % Si % Mn % 1' %S
0.088 0.1 6 0.50 0.035 0.01 8
% Cr % Ni % Mo %cu %N
0.02 <O.OI <0.01 0.1 0.005

The samples for the weight increase measurements had

the dimensions 40 x 2 5 x 2.0 mm and were polished on
600 emery paper with water and ethanol. They were finally
cleaned in ethanol using ultrasonic agitation and dried with 100 500 time l h l
hot air. The samples for the SEM-study were round with a
Fig. 2. The wcight increase of steel samples with sodium chloride
diameter of 1 1mm. They were treated as described above (8 pg NaCl . exposed to an SOz-free atmosphere at different
but were electrolytically polished and etched in addition. relative humidities
A solution of 1.5 wjo sodium chloride was sprayed on
to the sampie surfaces and the samples were immediately Abb. 2. Gcwichtszunahrne von rnit Natriumchlorid (8 p g NaCl ' cm-')
bedeckten Proben in schwefeldioxidfreier Atmosphkre bci verschie-
dried at 80 C. The sodium chloride crystals o n t h e surfaces denen relativen Feuchtigkeiten
had a size of about 0.01 m m and the amount of salt was
8 1 pg NaCl per cm2 surface area.
The S02-exposures were performed with equipment
shown in Fig. 1. Purified air was saturated with water vapour
irng c d
:lean air
SO? "2
I lrom cylindei

Flow meters


Thermosbled exposure chamber

Fig. 1. The measuring device Abb. 1. Mefhorrichtung

at a temperature that gave a desired relative humidity at
22.0 O C in the exposure chamber. The humid air was mixed
with a gas mixture of 100 ppm SOz inonitrogen. The final
gas mixture was thermostated at 22.0 C and entered the
exposure chamber. The SO2-supply to the samples was
1 pg SO2 per cm2 surface area and hour, which was equiva-
lent to 1 ppm S O 2 . Th: exposures t o humid S02-free air 02
were performed at 22 C above saturated salt solutions in
closed chambers. The corrosion attacks o n the samples were
followed by periodic weighings. The SEM-technique was
used to study the appearance of t h e corrosion products
formed. 50 60 70 80 90 130 R H 1%1

Fig. 3. The weight increase of steel samples with sodium chloride

Results (8 fig NaCl . cm-') exposed to humid S02-free atmospheres for
670 hours
The increases in weight of the samples with sodium Abb. 3. Gewichtszunahrnc von mit Natriumchlorid (8 pg NaCl . ern-*)
chloride crystals have been measured at different relative bedeckten Proben in feuchtcr schwcfeldioxidfreier Atmospharc
humidities. The results are shown in Fig. 2. Each curve in (Versuchsdaucr 670 Stundcn)
402 Ericsson Werkstoffe und Korrosion 29, 400-403 (1978)

Fig. 2 is based o n weight increase measurements of at least

three samples. At all relative humidities except at 58%, the
lowest relative humidity that was used in this investigation,
the rate of corrosion was highest at t h e beginning of the
exposure and decreased as corrosion products were formed
o n the st eel surface.
In Fig. 3 the weight increase after an exposure of 670
hours has been plotted as a function of t h e relative humidity
a t th e exposure. The rate of corrosion increased with in-
creasing relative humidity up t o 85%. After that there was
a sharp minimum at about 87% relative humidity. The
highest rate of corrosion was measured at 90% relative
humidity and above that value the corrosion decreased.
Fig. 5 shows a steel surface with sodium chlorid par-
ticles exposed t o a n S02-free atmosphere at 96% relative
humidity for 4 hours. The surface shows extensive corrosion
attacks. At certain places characteristic tower shaped cor-
rosion products rising perpendicularly t o the surface were
formed. At lower relative humidities this type of attack was
not present but filiform corrosion was observed instead;
see Fig. 6.
The results from the exposures with sulphur dioxide are
shown in Fig. 4. At 90% relative humidity the SOz-induced
corrosion was considerably higher than that induced by
Fig. 5. A steel surface with sodium chloride crystals exposed to
sodium chloride alone. The combined effect of sulphur di- an SO2-free atmosphere at 96% relative humidity for 4 hours
oxide and sodium chloride caused the greatest corrosion.
At 70%)relative humidity t h e SO,-supply had a negligible Abb. 5. Mit Natriumchloridkristallen bedeckte Stahloberflache ndch
effect o n the corrosion of samples with sodium chloride. 4 Std. in schwefeldioxidfrcicrAtrnosphire bei 96% rcl. Feuchtigkeit
Samples without sodium chloride did not corrode measur-
ably o n SOz -exposure at 70% relative humidity.

Img cni*~


Fig. 6. A steel surface with sodium chloride crystals exposed to

an SOz-free atmosphere at 78% relative humidity for 8 hours
1- 100 500 time Ihl Abb. 6. Mit NatriumchloridkriFtalIen bcdcckte Stahlobertliche
Fig. 4. The weight increase of steel samples exposed at different nach 8 Std. in schwcfeldioxidfreier Atmosphkc bei 78% rel. I:euch
corrosive conditions tigkeit
A n: 8 pg NaCl . cm;2 and 1 pg SO, ' cm-2 * h-' (1 ppm SO?)
: 1 pg SO2 . cm-L . h-' (1 ppm SO,)
0 0: 8 pg NdCl. Cm-'
Filled symbols: 90% relative humidity Discussion
Open symbols: 70% relative humidity
The decrease of the rate of corrosion that was found at
Abb. 4. Cewichtszunahme von Stahlproben bei verschiedenen Kor-
about 87% relative humidity according to Fig. 3 has been
A A: 8 pg NaCl . und 1 pg SO2 ' cm-' . h-' (1 pprn SO2) reported earlier ( 1 4). Then it was stated that filiforrn cor-
1 pg SO2 ' cn-2 . h-'
0: (1 ppm SOz) rosion in its most extreme form appears a t about 87% relative
0 0:8 pg NKI . cm-' humidity.
gefiillte Symbolc: 90% rel. E'cuchtigkeit A t 96% relative humidity, characteristic tower shaped
offene Symbole: 70%rel. Feuchtigkeit corrosion products, shown in Fig. 5 , were formed after a
Werkstoffe und Korrosion 29, 403 -408 (1978) Korrosionsschutz in Rohren durch Bctonauskleidungen 403
Overlag Chemie, GrnbH, D4940 Weinheim, 1978

short time of exposure. These products have an appearance A synergic effect of the combined influence of
similar t o t h e corniform attacks that Hill ( 1 7) reported. The 1 pg SOz . crn-' . h-' ( 1 ppm S O z ) and sodium chloride
sodium chloride induced corrosion at 78% relative humidity crystals o n the sample surface could be noticed at an ex-
totally lacked these tower shaped products and caused fili- posure at 90% relative humidity, However, at 70% relative
form corrosion products instead. humidity sulphur dioxide did not affect t h e corrosion of
At 90% relative humidity a synergic effect of the com- steel with sodium chloride particles o n its surface.
bined influence of sulphur dioxide and sodium chloride was
obtained. At 70% relative humidity 1 pg SO, . crn-2 . h-' (Eingegangen: 4. 1 1. 1977)
did not cause a measurable corrosion o n t h e samples without
sodium chloride crystals. It is notable that at 70% relative
humidity with a combined influence of sulphur dioxide and
sodium chloride, the corrosion did not increase compared
to the influence of sodium chloride alone.
This investigation has shown the great importance of 1. H. R. Ambler and A . A. Bain: J. Appl. Chem. 5 (1955) 437.
sodium chloride for t h e atmospheric corrosion of steel. Thus 2. H. R. Ambler: J. Appl. Chem. I0 (1960) 213.
sodium chloride particles o n a steel surface can cause corro- 3. P. J. Sereda: ASTM STP 558 (1974) 7.
sion at relative humidities which have been considered too 4. C. P. Larrabee: Corrosion 9 (1953) 259.
low to start SO,-induced corrosion. 5. C. P. Lurrabee: Trans. electrochem. SOC.87(1945) 161.
6. S. K. Coburn et al.: ASTM STP 435 (1968) 360.
7. H. R. Copson: ASTM Roc. 45 (1945) 554.
Summary 8. A. Bukowiecki: Schw. Arch. 23 (1957) 97.
9. A . Bukowieckiand B. G. foshi: Schw. Arch. 32 (1966) 42.
10. B. Sanyal and D. V. Bhadwar: J. Sci. ind. Res. 2 1 0 (1962) 243.
On exposure of steel samples with their surfaces covered 11. K. A . Chandler: Brit. Corros. J. I (1966) 264.
with sodium chloride crystals (8 p g NaCl cm-') in an SO,- 12. S. f. Duly: J. SOC.Chem. Ind. 6Y (1950) 304.
free atmosphere the amount of corrosion increased with in- 13. L! R. Evans and C. A . J. Taylor: Brit. Corros. J. Y (1974) 26.
creasing relative humidity from 58% to 90% with the excep- 14. T.Berglund: TVF 31 (1960) 325.
tion of a decreased rate of corrosion at about 87% relative 15. W. S. Patterson and f. H. Wilkinson: J . SOC.Chem. Ind. 5 7
humidity. (1938) 445.
At 96% relative humidity the sodium chloride induced 16. J. F. Henriksen: Corros. Sci. 9 (1969) 573.
corrosion resulted in tower shaped products that rose at 17. G. V, G. Hill: Brit. Corros. J. 8 (1973) 128.
right angles from the steel surface. An exposure at 78% re- W 1970
lative humidity caused filiform corrosion.

Korrosionsschutz in Rohren durch Betonauskleidungen")

Corrosion protection in pipelines by concrete linings
Von G. Nagel**)

Kurzf assung Summary

Guj3eiserne Rohre verschiedener Durchmesser sowie Stahl- Cast iron and steel pipes of various diameters may be pro-
rohre konnen durch Auskleidungen aus Zementmortel wir- tected against corrosion b y internal linings o f cement mor-
kungsvoll gegen Korrosion geschutzt werden. Dabei ergibt tar. This lining results in addition in an improvement o f the
sich gleichzeitig eine Verbesserung der mechanischen Eigen- mechanical properties of the composit. Within 28 days the
schaften des Verbundes. Der Mortel erreicht innerhalb von mortar cures to compressive strength between 700 to
28 Tagen Druckfestigkeiten von 700 bis 1000 k g lcm 2 , Bie- 1000 kg/cmz and tensile fle x strength exceeding 100 kgjcm',
gezugfesrigkeit uber 100 kglcm' und vtrmittelt auch bei even when the metal tube is damaged a high pressure resis-
Schaden am Metallrohr hohe Druckfestigkeit. Die Haftung tance is maintained. Adhesion between lining and metal im-
zwischen Ze me n t und Metal1 verbessert sich mit der Zeit: proves with time: green cement is rather porous, so that
der frische Zement ist ziemlich poros, so daf3 Wasser bis z u m water may pmetrate to the metal; calcium hydroxide from
Metall durchdringen kann; das Calciumhydroxid aus d em the cement and ferric hydrates formed on the metal surface
Zement und die Ferrihydrate auf der Metalloberfkiche wer- are incorporated in the concrete so that good adhesion re-
den dann in den Beton eingebaut, so daf3 sich eine gute Ver- sults. Sulfate-resistant special grades have shown to be resis-
zahnung ergibt. Sulfatbestandige Spezialzemente halten in tant in waste water containing up t o 3000 mgfl sulfate and
A bwasserteitungen Sulfatkonzentrafionen bis 3000 mgll having pH-values down to 4,5 for short times.
und kurzfristig auch pH-Werte bis 4,s aus.

*) Vortrag, gehalten auf

der 'Pagung ,,Korrosion durch Meerwasser" **) Ing. grad. Gerhard Nagel, Stadtoberbaurat, Tulpenstr. 1,
an der Fachhochschule Wilhelmshaven, 28. bis 30. April 1977. 75 15 Linkcnheim-FIochstetten.