Materials Science, Vol. 49, No. 3, November, 2013 (Ukrainian Original Vol. 49, No.

3, MayJune, 2013)

ANTICORROSION PROPERTIES OF THE EXTRACT OF RAPESEED OIL CAKE AS

A VOLATILE INHIBITOR OF THE ATMOSPHERIC CORROSION OF STEEL
O. E. Chyhyrynets1,2 and V. I. Vorobiova1

UDC 620.197

We study the composition of the volatile fractions of the isopropanol extract of rapeseed (Brassicaceae
family) oil cake by the chromatography-and-mass spectrometry method. It is shown that their main ingredients are glycosides, ketones, aldehydes, saturated and unsaturated fat acids, and steroids. It was
discovered that the extract provides a high level of corrosion protection of the metal as a volatile corrosion
inhibitor under the conditions of periodic condensation of moisture. It is demonstrated that the corrosion
rate of steel decreases as its concentration increases, and the process of formation of films from the vapor phase has a long-term character. The film formed on the surface of steel from the gasvapor phase
of the extract gives an aftereffect on a level of 90% under the conditions of periodic moisture condensation for 504 h.
Keywords: isopropanol extract, rapeseed oil cake, volatile inhibitor, atmospheric corrosion, steel.

At present, volatile atmospheric corrosion inhibitors (VACI) occupy a special place among the inhibitors of
atmospheric corrosion because they can protect products of complex shapes made of both ferrous and nonferrous metals. As VACI, several thousands of compounds of various chemical classes have been investigated and
recommended but most of them do not meet the contemporary ecological and economic requirements. Moreover, new requirements are imposed on the methods of their manufacturing.
The organization of the process of multistage synthesis is a complex and high-cost process. This is why the
VACI whose preparation, in the ideal case, is reduced to simple mixing of the components prove to be most
promising. Hence, it is important to develop volatile inhibitors of atmospheric corrosion characterized not only
by high efficiency and environmental safety but also by a simple procedure of preparation.
As promising raw materials for the development of VACI, we can mention organic substances of vegetable
origin because, as a rule, natural raw materials contain a large number of biologically active substances and the
process of extraction is, as a rule, more cost-efficient than chemical synthesis [16].
Thus, in [2, 3], it was shown that the wastes of the production of oil from rapeseeds (Brassicaceae family)
can be a source of natural organic compounds for the preparation of VACI. Despite the wide complex of bioactive substances, rapeseed oil cake can hardly find any application. In most cases, it is simply burned or disposed
in one or another way. In the literature, one can also find no information about possible applications of the oil
cake and its extracted compounds for the development of anticorrosion materials. For this reason, we study the
chemical composition of volatile fractions of the extract of rapeseed oil cake and its inhibiting efficiency.
1
2

KPI, National Technical University of Ukraine, Kyiv, Ukraine.

Corresponding author; e-mail: corrosionlife@yandex.ru.

Translated from Fizyko-Khimichna Mekhanika Materialiv, Vol. 49, No. 3, pp. 3945, MayJune, 2013. Original article submitted November 30, 2012.
318

1068-820X/13/49030318

2013

Springer Science+Business Media New York

ANTICORROSION PROPERTIES OF THE EXTRACT OF RAPESEED OIL CAKE AS A VOLATILE INHIBITOR

319

Materials and Methods

We study the anticorrosion efficiency of the extract of rapeseed oil cake formed by cold squeezing. For the
extraction of chemically active substances from vegetable raw materials, we used isopropyl alcohol. The extract
was prepared by holding preliminarily ground vegetable raw materials in isopropyl alcohol at a ratio of 1 g of
rapeseed oil cake per 10 ml of the solvent for 24 h. We obtained a light-brown liquid with a smell of isopropyl
alcohol. The pressure of saturated vapor of the extract was 8371.24 at 20.
The composition of volatile substances of the extract was studied by the method of chromatography-andmass spectrometry by using a FINIGAN FOCUS gas chromatograph with an -5MS capillary column 30 m in
length and 0.25 mm in diameter under the following conditions: temperature of injector + 250; temperature
of detector + 280; thickness of the phase 0.25 m; helium as a carrier gas; flow of the carrier gas
1.5 mliter/min; the temperature conditions of chromatographic analysis (program) were as follows: an initial
temperature of the column of 100 and a heating rate of the column (temperature gradient) of 10/min up to
280; the mass range was 30500 a.m.u.; the sample was introduced with a split flow of 15 mliter/min; the
volume of the sample was 2 l. The components were identified by comparing the peak retention times in the
chromatogram and the complete mass-spectra of individual components with the corresponding results for pure
compounds in the NIST-5 Mass Spectral Library. The relative contents of the chemical components of the extract were found by the method of internal normalization of the areas of peaks without correcting the sensitivity
coefficients.
The anticorrosion efficiency of the extract was evaluated by the method of accelerated tests under the condition of moisture condensation both in the solution and on the paper carrier. According to the first technique,
samples of St3 steel were placed in a hermetically sealed vessel with distilled water and a tank with the volatile
inhibitor in a heat chamber, in which a mode of periodic moisture condensation (a test cycle at 40 for 8 h and
at 25 for 16 h) was maintained. The total test time was 21 days. According to the second technique, the
VACI was used in the composition of inhibited paper. For this purpose, we impregnated craft paper with the
inhibitor, wrapped samples by it and then by a polyethylene cover, and held them under room conditions for 3
days to form a protective film. The testing conditions were identical to the aforementioned testing conditions.
Prior to investigation, samples 50 20 1 mm in sizes were cleaned with emery paper of different grit, degreased, and held in an atmosphere of vapor of inhibitors for three days. We assessed visually the efficiency of
corrosion protection and calculated the negative mass index of the corrosion rate K m and degree of protec-

tion Z [7, 8]. The change in the mass of samples was found by weighing. Corrosion products were removed
by etching in an inhibited 10% HCl solution for 1 min.
The adsorption dynamics of the protective film of volatile substances on the surface for 5 days was assessed
according to the changes in the electrochemical behavior of the metal held in vapors of the volatile compounds
of the extract. As a model electrolyte for atmospheric corrosion, we used 1 N Na2SO4. For the polarization electrochemical investigations, an installation consisting of a PI-50-1 potentiostat, a PR-8 programmer, and a -5
mixer was used.

An St3 sample with an area of 0.385 cm 2 pressed into Teflon served as a working electrode, a sulfurprotoxide electrode served as a reference electrode, and a platinum electrode was used as an auxiliary electrode.
The values of potentials were converted to the normal hydrogen scale. Prior to taking polarization curves, we
treated the electrode with emery paper of different grit, degreased with acetone, and held for 2496 h in a tightly
closed tank with a volume of 200 ml over a weighing bottle with 2 ml of the isopropanol extract of rapeseed oil
cake.

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V. I. VOROBIOVA

Table 1. Component Composition of the Volatile Substances of the Isopropanol Extract

of Rapeseed Oil Cake
Name of the component

Holding time t , min

Guanosine

8.41

Saccharose

8.57

Xanthosine

8.62

3,5-dimethoxyacetophenone

9.28

Syringaldehyde

10.21

Acetic acid

10.56

n -cyclohexyl-4-hydroxybutyramide

15.14

Hexadecanoic acid

16.63

Octadecadienoic acid

16.67

Oleic acid

17.81

Pyrrolidine, 1-(1-oxo-7, 10-hexadecadienyl)

18.23

2-pyrrolidine, 1-(9-octadecenyl)

19.66

Ethanamine, 2,2-oxy-bis[N,N-dimethyl]-

22.97

Dihydrodiosgenin

23.01

Campesterol

23.37

-sitosterol

23.93

-sitosterol

24.56

Ergosta-5,22-dien-3-ol

25.73

Results and Discussion

By the chromatography-and-mass spectrometry method, in the volatile fraction of the isopropanol extract of
the rapeseed oil cake, we detected 20 compounds (see Table 1 and Fig. 1).
Among these, we can mention glycosides (they are predominant and constitute 27% of all identified volatile
compounds), namely, saccharose, guanosine, and xanthosine; syringaldehyde (12%), ketone-3,5-dimethoxyacetophenone (11%), steroids ( - and -sitosterol, campesterol, etc.), and saturated and unsaturated fat acids

(34%) represented by palmitic, oleic, linoleic, and acetic acids. We also detected small amounts (3%) of alkaloids (pyrrolidine, 1-(1-oxo-7,10-hexadecadienyl), and 2-pyrrolidine, 1-(9-octadecenyl)) and, in addition, some
terpenes (dihydrodiosgenin and ergosta-5,22-dien-3-ol; their amount was close to 4%).
Most of these substances are known as corrosion inhibitors in various media and often as main components
of the compositions.

ANTICORROSION PROPERTIES OF THE EXTRACT OF RAPESEED OIL CAKE AS A VOLATILE INHIBITOR

321

Fig. 1. Chromatogram of the isopropanol extract of rapeseed oil cake ( Rab is relative abundance).
The analysis of the results of accelerated corrosion tests (Table 2) shows that the volatile fractions of the extract protect steel from corrosion under the conditions of periodic moisture condensation when the extract is
used both from the vapor phase and in the form of inhibited paper with degrees of protection of about 94 and
93%, respectively. It should be noted that the treatment of specimens in the vapor phase of individual isopropanol does not improve the corrosion resistance of the metal.
We recorded the formation of the first signs of corrosion on the metal surface on the fifth day in the absence
of treatment. At the same time, these signs appeared only after 10-day holding in the case of treatment by the
volatile fractions of rapeseed oil cake from the vapor phase and after 15-day holding in the case of wrapping in
the inhibited paper. It is worth noting that the efficiency of volatile substances of the extract also depends on the
volume ratio of the inhibiting component in the closed space or in the carrier, i.e., in the inhibited paper.
It was shown that the corrosion rate of steel decreases as the volume ratio of the isopropanol extract of rapeseed oil cake increases (Table 2). To provide the reliable protection of the metal, a ratio of the volume of the
inhibitor to the volume of the closed space of 1:100 is sufficient. According to the results of accelerated tests,
a high level (70.4%) of corrosion protection of steel is attained even at a ratio of 0.5:100. However, the first corrosion defects on the surface of the specimens were recorded somewhat earlier, namely, on the eighth day.
As the content of the extract increases to 2, 3, and 4 ml per 100 ml of the closed volume, we do not record any
noticeable increase in the inhibiting efficiency.
To determine an optimal amount of VACI in the packing material, we estimated the anticorrosion properties
of the samples of inhibiting paper with various contents of the isopropanol extract. Insufficient protection was
recorded for the inhibitor : isopropanol ratios equal to 1:1 and 3:1. In this case, the degrees of protection were
equal to 60.8 and 66.4%, respectively. Increasing the volume of the inhibiting component in the paper (6:1 and
1:0), we can prevent the emergence of corrosion damages within the whole time of the experiment (21 days).
The degree of protection was 74.4 and 93.3%, respectively (Table 2).
The electrochemical behavior of steel was investigated in 1 N Na 2 SO 4 after the formation of the protective

film for 48 h for different contents of inhibitor in the closed volume (Fig. 2 and Table 3). In the case of using
the extract of rapeseed oil cake for ratios of the inhibitor to the volume lower than 0.1:100, the kinetics of the
anodic and cathodic electrode reactions remain almost unchanged. As the indicated ratio increases to 0.35:100,
the currentless potential shifts to the positive side by 0.07 V.

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V. I. VOROBIOVA

Fig. 2. Polarization curves of St3 steel in 1 N Na 2SO 4 without protective film (curve 1) and with a film formed after holding for 48 h

in the vapor phase of the isopropanol extract of rapeseed oil cake for different ratios of the inhibitor to the volume (100 ml):
0.1 (2); 0.35 (3); 0.75 (4); 1.0 (5); 1.25 (6); 2.5 (7).

Table 2. Corrosion Rate and Degree of Protection of St3 Steel

(Periodic Moisture Condensation; 40 )
Procedure of application of
VACI

Treatment in the vapor phase

Inhibited paper1

Without inhibitors

Conditions of application of the

inhibitor (ml)

In a closed volume
(100 ml)

For the indicated inhibitor : isopropanol ratios

Corrosion rate K m ,

g/(m 2 h)

Z,%

0.5

0.0734

70.4

0.0196

92.1

0.0189

92.3

0.0159

93.6

0.0150

93.9

1:1

0.0972

60.8

3:1

0.0832

66.4

6:1

0.0634

74.4

1:0

0.0165

93.3

0.2481

Comment: 1. Different concentrations of the inhibitor in the paper were obtained by diluting it with isopropanol and impregnating the paper base.

ANTICORROSION PROPERTIES OF THE EXTRACT OF RAPESEED OIL CAKE AS A VOLATILE INHIBITOR

323

Fig. 3. Polarization curves of St3 steel in 1 N Na 2SO 4 without film (curve 1) and with a film formed after holding for 24; 48; 72, and
96 h (curves 25) in the vapor phase of the isopropanol extract of rapeseed oil cake.

Table 3. Characteristics of the Polarization Curves of St3 Steel in 1 N Na 2 SO 4 with a Film Formed
for 48 h in the Vapor Phase of the Isopropanol Extract of Rapeseed Oil Cake

Amount of the inhibitor (ml) per

100 ml of the closed volume

Currentless
potential, V

Without inhibitor

Tafel coefficients, V

I corr ,

Z,
%

ba

bc

A/cm

0.41

0.09

0.15

9.89

0.1

0.36

0.09

0.16

5.41

45.3

0.35

0.34

0.09

0.16

5.06

48.8

0.75

0.30

0.10

0.16

4.01

59.5

1.0

0.23

0.12

0.16

3.01

69.5

1.25

0.23

0.12

0.16

3.02

69.5

2.5

0.23

0.12

0.16

3.01

69.5

The procedure of treatment of specimens by the volatile fractions of the extract for an inhibitor content
equal to 1:100 promotes a substantial shift of the currentless potential to the positive side ( E = 0.23 V) and
increases the anodic polarization of the electrode (Table 3). As the volume of the inhibitor increases further
(to 1.25 and 2.5 per 100 ml of the closed volume), the kinetics of the electrode reaction remains almost unchanged.
Since the film is formed from the gas-vapor phase for a certain period of time, we studied the influence of
the time of holding of a specimen of St3 steel in the vapor phase of the extract on the kinetics of electrode reactions. As a result of treatment of the metal by the volatile fractions of the extract, the currentless potential shifts
to the positive side ( E = 0.23 V) even after holding for 24 h (Fig. 3 and Table 4).

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V. I. VOROBIOVA

Table 4. Characteristics of the Polarization Curves of St3 Steel in 1 N Na 2 SO 4 After the Formation of
Protective Film from the Vapor Phase of the Isopropanol Extract of Rapeseed Oil Cake

I corr ,

Tafel coefficients, V

Currentless

Holding time,
h

potential, V

ba

bc

A/cm 2

0.45

0.09

0.15

9.89

24

0.27

0.11

0.16

3.54

64.2

48

0.22

0.12

0.16

3.01

69.5

72

0.27

0.11

0.16

3.42

65.4

96

0.34

0.11

0.16

3.81

61.4

Z, %

Table 5. Aftereffect of the Films Formed on St3 Steel from the Vapor Phase of the Isopropanol
Extract of Rapeseed Oil Cake (Time of Formation 120 h; Time of Experiment 504 h)
Testing conditions

Periodic
moisture
condensation

3% NaCl

1 N Na 2 SO 4

Corrosion rate K m ,

g/(m 2 h)

Z, %

In the vapor phase of the extract

of rapeseed oil cake

0.0356

90.3

Without inhibitors

0.3663

In the vapor phase of the extract

of rapeseed oil cake

0.0188

91.8

Without inhibitors

0.2346

The Tafel coefficients ba reveal the change of the mechanism of anodic dissolution of the metal, whereas

the increase in the degree of polarization of the electrode corresponds to the retardation of the anodic corrosion
reaction.
As the time of treatment of the metal by the volatile compounds of the extract increases to 48 h, the increase
in the inhibiting efficiency becomes especially pronounced ( Z = 69.5%), which corresponds to the saturation
of the surface with the inhibitor and the formation of the strongest bonds between the inhibitor and the metal.
The diffusion currents differ insignificantly, which shows that the influence of the inhibitor on the rate of
the cathodic reaction of oxygen reduction is negligible. With further increase in the holding time to 72 and 96
days, the anticorrosion efficiency somewhat decreases. In this case, the degrees of protection (according to the
polarization curves) are equal to 65.4 and 61.4%, respectively. This is probably connected with the competing
character of adsorption of different components of the extractive part, which leads to the desorption of some
compounds from the surface.
As an important characteristic of the films formed on the metal surfaces in the vapor of the volatile inhibitor, we can mention their ability to preserve protective properties (aftereffect) in the course of time in the ab-

ANTICORROSION PROPERTIES OF THE EXTRACT OF RAPESEED OIL CAKE AS A VOLATILE INHIBITOR

325

sence of VACI in corrosive media. For this reason, we investigated the aftereffect of films formed on the metal
surface after preliminary holding of the specimens in the vapor of the isopropanol extract of rapeseed oil cake.
It was shown (Table 5) that these films give the required aftereffect under the conditions of periodic condensation of moisture over 3% NaCl and 1 N Na 2 SO 4 aqueous solutions. In particular, the specimens treated by the

VACI vapor stay without corrosion defects for 5 and 9 days, and the rate of corrosion is equal to 0.0356 and

0.0188 g/(m 2 h) , respectively.

CONCLUSIONS
It is shown that the main components of the gasvapor part of the isopropanol extract of rapeseed oil cake
are glycosides (saccharose, guanosine, and xanthosine), syringaldehyde, ketone-3,5-dimethoxyacetophenone,
steroids, and saturated and unsaturated fat acids (34%) (palmitic, oleic, linoleic, and acetic). The results of accelerated tests performed under conditions of humid atmosphere and polarization investigations in the model
electrolyte enable us to conclude that the analyzed extract guarantees high levels of anticorrosion protection of
the metal in the case of its application both from the vapor phase and on the carrier (inhibiting paper). The corrosion rate of steel decreases as the concentration of the inhibitor increases. A concentration of 1 ml of the in-

hibitor per 100 ml of the closed volume per 10 cm 2 of the metal surface should be regarded as minimal and
sufficient for stable corrosion protection.
The formation of a film with maximum protective characteristics is completed after holding of St3 steel for
48 h in the vapor of volatile compounds of the extract. It is characterized by the aftereffect under the conditions
of periodic condensation of moisture over a 3% NaCl aqueous solution for up to five days and, in 1 N Na 2 SO 4 ,
for up to nine days.

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