IBP2097_11

IMMERSION CORROSION TESTS OF CARBON STEEL IN

ANHYDROUS ETHANOL FROM DIFFERENT SOURCES
Célia A. L. dos Santos1; Zehbour Panossian2; Gislaine M. Bragagnolo3; Anna R.
Moreira4; Emerson A. Barbosa5; José Veríssimo S. dos Santos6; Gutemberg de
Souza Pimenta7

Copyright 2011, Brazilian Petroleum, Gas and Biofuels Institute - IBP

This Technical Paper was prepared for presentation at the Rio Pipeline Conference & Exposition 2011, held between September,
20-22, 2011, in Rio de Janeiro. This Technical Paper was selected for presentation by the Technical Committee of the event. The
material as it is presented, does not necessarily represent Brazilian Petroleum, Gas and Biofuels Institute’ opinion or that of its
Members or Representatives. Authors consent to the publication of this Technical Paper in the Rio Pipeline Conference &
Exposition 2011.

Abstract
The aim of this study was to verify the corrosiveness of anhydrous ethanol from different sources against carbon steel.
For this, 21-day corrosion immersion tests were conducted using low carbon steel coupons and four different
commercial anhydrous ethanol (lots A, B, C and D). The tests were performed in aerated (obtained by bubbling dried
synthetic air) and de-aerated (obtained by bubbling ultrapure nitrogen) conditions. For a better control of the tests, a
special test vessel was developed which allowed the maintenance of the established conditions (aerated and de-aerated)
without the absorption of atmospheric humidity by ethanol. The coupons were fixed in two ways: by means of screws
and by fixing them through a crevice-contained holder. In the aerated condition, no signs of corrosion were observed on
any of the tested coupons. In the de-aerated condition, all coupons presented discrete dark corrosion spots preferentially
at the region of attachment of the specimens (site of possible crevice formation) and some scattered dark spots on the
surfaces of the coupons accompanied by a color change of the tested ethanol samples. The lot C ethanol presented a
deep color change at the end of the test period. The black spots were analyzed by scanning electron microscopy (SEM)
associated with an elemental analysis by energy dispersive (EDX). The ethanol samples were analyzed before and after
the immersion tests to determine the acidity and the pHe. At the end of immersion experiments, a trend toward higher
values of the acidity and a decrease of the pHe values were observed. This study showed that ethanol samples from
different sources showed different corrosiveness, although incipient, and this corrosiveness manifested itself in de-
aerated condition and preferably in the crevices.

1. Introduction
The search for renewable energy sources has mobilized research in many countries around the globe aiming at
replacing petroleum derivatives. There are two main reasons for this search. The first is directly related with the current
widespread goal in reducing the production of gases that cause global warming and the second, with geopolitical risks
arising from global high dependence on oil from politically unstable countries.
In Brazil, ethanol has been used successfully for over 30 years as fuel replacing gasoline or as gasoline additive
to increase octane. Internationally, ethanol is presented as an important option in the replacement of petroleum products,
currently being used mainly as a gasoline additive. Besides the fuel market, another highlighted area comes up with:
ethanol derived products. For example, ethylene, a petroleum derivative, is widely used as raw materials for
manufacturing several kinds of resins. This chemical can be obtained from ethanol. Other examples are acetates and
ethyl ether (Bastos, 2007) which also can be obtained from ethanol.
Given the above mentioned importance of ethanol, the knowledge of its corrosivity against metallic materials is
an essential task. Many studies related to this subject have been published, especially in Brazil where the use of ethanol
______________________________
1
Dra., Química, IPT
2
Dra., Física, IPT
3
Msc.,Química, IPT
4
Msc., Química, IPT
5
Técnico em Metalurgia, IPT
6
Técnico em Metalurgia, IPT
7
Msc., Engenheiro, CENPES
 Rio Pipeline Conference & Exposition 2011
as fuel for vehicles is much higher than in other countries. D'alkaine et al. (1980) developed studies with ethanol through
potentiostatic and galvanostatic techniques; Guastaldi et al. (1983) conducted corrosion immersion tests in hydrated
ethanol using weight loss technique and verified that the corrosivity of the hydrated ethanol was changed with time due
to water vapor absorption from the atmosphere where the tests were conducted; Tanaka (1984), in his doctoral thesis,
studied the corrosion of carbon steel by ethanol through immersion and electrochemical tests and emphasized the need
to control the absorption of water by ethanol when performing open-air immersion tests; Athayde et al. (1987) published
an article on the anodic behavior of iron in ethanol containing different amounts of water; Souza et al. (1987) conducted
experiments through electrochemical impedance technique using electrochemical cells with two and three electrodes;
Cavalcanti et al. (1987) studied the effect of the presence of water, sulfate ions and pH on the behavior of low carbon
steel in ethanol. More recently, Grosser and Gill (2008) studied the adsorption of caffeine by zinc immersed in caffeine
containing ethanol.
This study evaluated the corrosivity of different lots of commercial anhydrous ethanol collected from an
ethanol storage facility to low carbon steel through immersion tests. The goal of the study was to verify possible
differences in the corrosivity of different lots of ethanol.

2. Experimental

The corrosivity of the four different lots of commercial anhydrous ethanol (lots A, B, C and D) was studied
adopting 21-day immersion tests, both in aerated and deaerated conditions. Those lots were collected in an ethanol
storage facility during the year of 2009, with almost two-month intervals between collections. The collected samples
were stored in hermetic stainless steel containers aiming at preserving the original characteristics of the ethanol lots.
Low carbon steel panels (60 mm x 20 mm x 1,6 mm) were used as test specimens. The specimens were initially
identified using alphanumeric codes. Then, they were degreased with acetone, blasted with glass bead abrasive up to 20
µm to 25 µm (Ry) profile, followed by a cleaning in ultrasonic bath using analytical grade anhydrous ethanol. Finally,
they were dried under hot air flow. After preparation, the specimens were kept in a desiccator for 24 h and then they
were immersed in the tested ethanol. The specimens were weighed before and after the immersion tests, using an
analytical balance with an accuracy of 0.0001 g.
The immersion tests were conducted in a specially developed test cell (Figures 1 and 2). The cell was sealed
and designed to allow the internal atmosphere control aiming at preventing the contamination of ethanol by water
absorption over time. It consisted of a borosilicate glass vessel and its cover. The cover was provided with three faucets
made of glass and polytetrafluoroethylene (PTFE), which were used to introduce the desired gases. Between the test cell
and its cover, a brand of synthetic rubber and a fluoropolymer elastomeric seal ring were inserted in order to isolate the
test solution from the local atmosphere. A stainless steel belt was used to fix the cover to the cell. An additional faucet
was installed at the bottom of the test cell through which the tested ethanol was introduced.
In the interior of the cell, polytetrafluoroethylene test specimen holders were inserted. These holders permitted
testing three metal specimens simultaneously without any contact among them. Two types of holders were used: one
type uses screws to hold the specimen at its topside (Figure 1) and the other uses gaps to fix the specimen at its
underside (Figure 2). It is important to emphasize that, in both conditions, a crevice was formed at the holding side of
each test specimen due to its contact with the PTFE-made holders.
Lot A was tested by fixing the specimen with a screw-type holder (Figure 1) and Lots B, C and D were tested
by fixing the specimen with a gap-type holder (Figure 2).
To initiate an immersion test, the three specimens were first placed in the test cell. After their positioning, the
test cell was closed and purged with the desired gas (dry synthetic air or nitrogen). The ethanol was transferred to the
immersion bottle through the bottom faucet.
The acidity and conductivity of the studied ethanol lots were measured before and after the immersion tests to
check a possible change in their physicochemical characteristics. The acidity was determined through the potentiometric
method using a Metrohm model 809 Titrator and the conductivity was determined using a Mettler-Toledo model
SevenMulti conductometer.

2
 Rio Pipeline Conference & Exposition 2011

Figure 1. Test cell with Figure 2. Test cell with gap-

screw-type specimen holder. type specimen holder.

3. Results
3.1 Immersion Tests – Visual inspection and Weight Loss Measurements

During the immersion tests, the surface of the tested specimens and the tested ethanol were visually inspected.
Table 1 and Table 2 present the results of this inspection for the tests conducted in dry-synthetic-air atmosphere and in
ultrapure-ultradry-nitrogen atmosphere, respectively. The specimens´ images are also shown in these tables.

Table 1 - Results of visual inspection of the tested specimens and the tested ethanol and specimens’ images after 21
days. Immersion tests performed in dried-synthetic-air atmosphere.

Ethanol Side 1 (after 21 days) Side 2 (after 21 days) Visual inspection

After 21 days: discrete dark spots
on the specimen surface at the
Lot A (screw- crevice formed between the
type holder) specimen and the screw-type
holder (not clearly seen in the
Figure). No changes of the tested
ethanol.

Lot B
No changes of the specimen
(gap-type
surface and of the tested ethanol.
holder)

Lot C No changes of the specimen

(gap-type
surface and of the tested ethanol.
holder)

Lot D No changes of the specimen

(gap-type
surface and of the tested ethanol.
holder)

3
 Rio Pipeline Conference & Exposition 2011

Table 2 - Specimens’ images and results of visual inspection of the tested specimens and the tested ethanol after 21 days
of immersion tests performed in ultrapure-ultradry-nitrogen atmosphere.

Ethanol Side1 Side 2 Visual inspection

After 14 days, the first dark spots
showed up in the vicinity of the
screw-type holder. After 21 days,
Lot A the specimen presented many
(screw- dark spots, some of them
type randomly localized and many of
holder) them close to each other forming
dark lines. Ethanol assumed a
slightly yellow color at the end of
the test.
After 14 days, the first dark spots
showed up in the vicinity of the
gap-type holder. After 21 days,
the specimen presented dark
spots (less than those observed in
Lot B
Lot A) randomly localized. Some
(gap-type
of these spots were very close to
holder)
each other forming a short dark
line apparantly coming from the
crevice. Ethanol assumed a
yellow color at the end of the
test.
After 7 days, the first dark spot
showed up in the vicinity of the
gap-type holder. After 21 days,
the specimen presented dark
Lot C spots (less than those observed in
(gap-type Lot A but more than in Lot B)
holder) randomly localized. Some of
these spots were very close to
each other forming short dark
lines. Ethanol strong yellow at
the end of the test
After 7 days, the first dark spot
showed up in the vicinity of the
gap-type holder. After 21 days,
Lot D the specimen presented some
(gap-type
dark spots (less than in the other
holder)
Lots) randomly localized.
Ethanol was slightly yellow at the
end of the test

From Table 1, it can be observed that, in aerated condition, no changes of the specimen surfaces was observed
after 21 days of immersion in ethanol, except for Lot A. In this case, small dark spots appeared only on the specimen
surface in contact with the holder where a crevice was formed. Additionally, no changes of ethanol color were observed,
including Lot A. All the specimen tested in aerated condition presented negligible weight loss after 21 days of
immersion in all tested ethanol. The obtained weight loss values were within the experimental error associated with the
used analytical balance.
From Table 2, it can be observed that, in deaerated condition, all specimens showed black spots distributed
randomly along the specimen surfaces regardless of the tested Lot. The first black points appeared in the vicinity of the
holder. Later on, dark spots appeared on other central regions of the specimen surfaces. For Lot A, in which the
specimens where fixed with screw-type holder at their top-side, the subsequent dark spots developed in the downward
direction. On the other hand, for lots B, C and D, in which gap-type holders were used at the underside of the specimens,
the dark spots appeared in an upward direction. At the end of the test, the Lot C assumed a strong yellow color, the Lot
B a medium yellow color and Lots A and D slight yellow color. All the described changes, both on the specimen

4
 Rio Pipeline Conference & Exposition 2011
surfaces and in the ethanol, indicate the occurrence of a corrosive process. Comparing the results of Table 1 (aerated
condition) with those of Table 2 (deaerated condition), it is clear that the corrosivity of ethanol increases in the decrease
of oxygen content. Despite this observation, all the specimen tested in deaerated condition presented also negligible
weight loss values after 21 days of immersion.

3.1 Acidity and conductivity measurements

Figures 3 and 4 shows the acidity and conductivity, respectively, of the tested ethanol lots in aerated (dried-
synthetic-air atmosphere) and deaerated (ultrapure-ultradry-nitrogen atmosphere) condition.

Immersion tests performed in dried-synthetic-air atmosphere

70
before
after
60

50
Acidity (mg/L)

40

30

20

10

0
A B C D
Ethanol Lots

(a)

Immersion tests performed in ultrapure-ultradry-nitrogen

atmosphere
70
before
after
60

50
Acidity (mg/L)

40

30

20

10

0
A B C D

Ethanol Lots

(b)

Figura 3. Acidity before and after the immersion tests for ethanol media:
(a) dried synthetic air atmosphere, (b) ultrapure nitrogen atmosphere.
5
 Rio Pipeline Conference & Exposition 2011

Immersion tests performed in dried-synthetic-air atmosphere

140 before
after
120

100
Conductivity (µS/m)
80

60

40

20

0
A B C D
Ethanol Lots

(a)

Immersion tests performed in ultrapure-ultradry-nitrogen

atmosphere
140 before
after
120

100
Conductivity (µS/m)

80

60

40

20

0
A B C D

Ethanol Lots

(b)

Figure 4. Condutivity before and after the immersion tests in ethanol:

(a) dried synthetic air atmosphere, (b) ultrapure nitrogen atmosphere

From Figures 3(a) and 3(b), it can be observed that there was an acidity value increase in the end of immersion
period for both studied atmospheres. Based on the visual inspection results, it can be assumed that a corrosive process in
ethanol increases the acidity. Similar behavior was observed in Figures 4 (a) and 4 (b): the conductivity values were
higher after the immersion tests, except to Lot C, which showed a slight decrease which is within the experimental
deviation range.

6
 Rio Pipeline Conference & Exposition 2011
4. Discussion of Results
The obtained results indicate the importance of the presence of oxygen in the ethanol. When the carbon steel
specimen were tested in oxygen-rich atmosphere (dried-synthetic-air atmosphere), no changes of the specimens´ surfaces
were observed, except for Lot A whose specimens exhibited discrete dark spots in the crevice. When the tests were
conducted in oxygen-depleted atmosphere (ultrapure-ultradry-nitrogen atmosphere), all the specimens showed dark
spots on their entire surfaces. This difference in behavior may indicate that oxygen participates in a very thin film
formation that protects the carbon steel. The ethanol color change, observed with the tests conducted under a nitrogen
atmosphere, is an indication of the presence of iron ions in the medium.
It is important to emphasis that, despite the occurrence of corrosion (dark spots and color changes), the
specimens mass loss was negligible which suggests that the attack on the steel surface was light. These results shows
very low amounts of corrosion products are able to change the color of ethanol.
Another important observation during the tested is related to preferential corrosion: in all aerated-condition
tests, the corrosion started near the crevices and in aerated-condition tests, conducted with Lot A, dark spots appeared
only in the crevices. These observations indicate a susceptibility of crevice corrosion of carbon steel in ethanol.
Acidity and conductivity analyses performed before and after the immersion tests indicated that the ethanol
changed after 21 days in contact with carbon steel: the values of acidity and conductivity of all tested ethanol were
higher at the end of the tests. These data show consistency since both parameters increased, however, there was no
proportionality between the initial and final values.

5. Conclusions
The immersion tests showed that the corrosivity of anhydrous ethanol to carbon steel depends on its oxygen
content. Tests conducted under a dried-synthetic-air showed no significant corrosivity of different lots of ethanol
whereas tests conducted under ultrapure-ultradry-nitrogen atmosphere all the tested lots causes a slight attack to carbon
steel. However the ethanol corrosivity is very low as the values of weight loss obtained in all tests were negligible. The
obtained results also showed that carbon steel is susceptible to crevice corrosion in ethanol.

6. Referências Bibliográficas
ATHAYDE, M. G; MATTOS, O. R.; SATHLER, L. The anodic behaviour of iron in ethanol-water solutions in the
presence and absence of NaClO4, as the supporting electrolyte. Electrochimica Acta, v. 32, n. 6, p. 909-913, 1987.
BASTOS, V. D. Etanol, alcoolquímica e biorrefinarias. BNDS Setorial, Rio de Janeiro, n. 25, p. 5-38, mar. 2007.
CAVALCANTI, E.; WANDERLEY, V. G.; MIRANDA, T. R. V.; ULLER, L. The effect of water, sulphate and pH on
the corrosion behaviour of carbon steel in ethanolic solutions. Electrochimica Acta, v. 32, n. 6, p. 935-937, 1987.
D’ALKAINE, C. V.; RÚVOLO FILHO, A.; BULHÕES, O. S. Estudo da corrosão do sistema etanol aço 1020 parte I –
técnicas potenciostáticas e galvanostáticas. SENACORR, 7, July,1980, Rio de Janeiro, p. 159-168.
D’ALKAINE, C. V.; RÚVOLO FILHO, A.; BULHÕES, O. S. Estudo da corrosão do sistema etanol aço 1020 parte II
– técnicas voltamétricas. SIBEE, 2, June, 1980, São Paulo, p. 139-146.
GROSSER, F. N.; GONÇALVES, R. S. Electrochemical evidence of caffeine adsorption on zinc surface in ethanol.
Corrosion Science, v. 50, n. 10, p. 2934-2938, 2008.
GUASTALDI, A. C.; BENEDETTI, A. V.; RIBEIRO, S. J. L. Ensaios de corrosão por perda de massa do aço AISI
1005 em etanol hidratado. Eclética Química, v. 8, p. 43-53, 1983.
SOUZA, J. P.; MATTOS, O. R.; SATHLER, L; TAKENOUTI, H. Impedance measurements of corroding mild steel in
an automotive fuel ethanol with and without inhibitor in a two and three electrode cell. Corrosion Science, v. 27, n.
21, p. 1351-1364, 1987.
TANAKA, D. K. Carbon steel corrosion by ethanol. 1984. 170 f. Thesis – School of Engeeniring, University of São
Paulo, São Paulo.