DOI 10.

1007/s11003-014-9719-2

Materials Science, Vol. 50, No. 2, September, 2014 (Ukrainian Original Vol. 50, No. 2, March–April, 2014)

INFLUENCE OF ORGANIC FERTILIZERS ON THE CORROSION-ELECTROCHEMICAL

CHARACTERISTICS OF LOW-CARBON STEELS

P. V. Popovych,1 L. А. Mahlatyuk,2,3 and R. B. Kupovych2 UDC 620.197.3

It is shown that the media of liquid and mixed manure are characterized by the weak corrosive action
upon St.20 and St.3 steels. The observed insignificant local corrosion damages are caused by sticking of
the suspended particles (straw, seeds, etc.). The corrosion rate of these types of steel for the first day of
holding in the filtered manure does not exceed 0.032–0.040 mm/yr, which is 3–4 times lower than in
the model rainwater solution. The subsequent decrease in the rate to 0.003 mm/yr can be explained by
the inhibiting properties of the chemical components of manure. The corrosion of St.20 and St.3 steels
in both types of manure runs according to the electrochemical mechanism. The stationary potentials of
both steels in these media are shifted toward the region of more negative values as compared with dis-
tilled water and the corrosion currents are 4–5 times weaker. The Tafel constants are higher than their
values in distilled water, which indicates that both electrode reactions are inhibited as compared with
the model medium.

Keywords: organic fertilizers, corrosion rate, depth index, stationary potential, corrosion current, ca-
thodic and anodic reactions, polarization.

The operating reliability of agricultural machines used for the manuring of soils depends on the possibility
of its failure-free operation, designed service life, repairability, and ability to preserve these characteristics. It is
well known that the standby period of agricultural machines can be as large as 80% of the total time [1]. There-
fore, the serviceability of machines is maintained within the period of interseasonal storage by the outdoor or in-
door method whose efficiency depends, first of all, on the high-quality cleaning of the equipment from the rem-
nants of organic fertilizers and soil and the proper rust-preventive treatment. Corrosion damage appears if these
procedures are not realized. The corrosion rate of the equipment made of low-carbon and medium-carbon steels
depends on the aggressiveness of the medium, contact time, temperature, state of the metal and protective coat-
ings, and the quality of the welds and bolted joints. Note that some units of the spreaders of organic fertilizers
suffered point, crevice, and contact corrosion, corrosion cracking, and fretting corrosion [2]. Although in this
case, the total losses of the metal can be insignificant but they are most often discovered in the critical joints of
the components responsible for the serviceability of machines as a whole. Among organic fertilizers, the peat
composts prove to be especially aggressive, whereas the valley peats, high-moor peats, and manure (based of the
excrements of cows) exhibit the lowest level of corrosive activity. In this case, water acts as a kind of catalyst of
the corrosion processes.
Within the working period, the simultaneous action of corrosive media and mechanical stresses proves to be
especially dangerous and, in particular, in the processes of loading and unloading of the fertilizers. As a result,

1
Pulyui Ternopil National Technical University, Ternopil, Ukraine.
2
Karpenko Physicomechanical Institute, Ukrainian National Academy of Sciences, Lviv, Ukraine.
3
Corresponding author; e-mail: maglatyuk@ipm.lviv.ua.

Translated from Fizyko-Khimichna Mekhanika Materialiv, Vol. 50, No. 2, pp. 110–115, March–April, 2014. Original article submitted
September 30, 2013.

284 1068-820X/14/5002–0284 © 2014 Springer Science+Business Media New York

INFLUENCE OF ORGANIC FERTILIZERS ON THE CORROSION-ELECTROCHEMICAL CHARACTERISTICS OF LOW-CARBON STEELS 285

the service life of machines may decrease by 40–60%. The realization of reliable corrosion-preventive treatment
of machines within the interseasonal period and minimization of the number of failures in the process of opera-
tion require reliable data on the corrosion resistance of carbon steels in the media of organic fertilizers and the
understanding of the mechanism of electrochemical corrosion in their aqueous solutions.
The aim of the present work is to study the influence of the time of holding on the corrosion rate of St.20
and St.3 steels and their electrochemical characteristics in the solutions of cattle manure and mixed manure.

Materials and Methods

The corrosion tests were performed on specimens of St.20 and St.3 steels in the as-delivered state prepared
in the form of disks 20 mm in diameter with surface ground up to a roughness Ra = 0.63 µm. The degreased
specimens were weighted in an analytical balance with an accuracy of ± 0.0004 g and stored in a desiccator for
at most 24 h.
The organic fertilizers, namely, liquid cattle manure and mixed manure (their compositions are presented in
Table 1), and distilled water used as a model of condensate or rainwater served as corrosive media. Prior to test-
ing, liquid manure and mixed manure were filtered through the paper filter to remove dispersed components.

Table 1. Contents of the Main Biogenic Substances

Elements
H 2O N total N protein N ammonia P2O 5 K 2O CaO MgO SO 3

Medium Wt.%
Liquid cattle manure 86.7 0.38 – – 0.12 0.22 0.25 – –

Mixed manure 75.0 0.50 0.31 0.15 0.25 0.60 0.35 0.15 0.10

Prior to the corrosion tests and after their completion, we measured the рН values of solutions by using
an I-160M рН-meter. The corrosion rate K m (g/cm 2 ⋅ h) was found by the massmetric method after holding
for 1, 7, 12, and 24 days under the conditions of natural aeration and after removal of the corrosion products [3].
The corrosion rate was computed by well-known formulas from [4].
The degree of corrosion protection of steel Z (%) was determined by the formula

Ki
Z = Km − ⋅100% , (1)
Km

where K m and K i are the corrosion rates of the steel in distilled water and manure media, respectively.
The polarization investigations were performed with the use of an IP-Pro potentiostat equipped with a spe-
cial software. Specimens of St.20 and St.3 steels pressed into fluoroplastic with an area of the working surface
of 0.0628 cm 2 served as the working electrode. Prior to each measurement, the specimens were polished with
an abrasive paper No. 0, washed by acetone, and dried. The role of reference electrode was played by the satu-
rated silver-chloride electrode and the auxiliary electrode was platinum. The sweep rate was equal to 1 mV/sec.
The corrosion current and Tafel constants of the cathodic and the anodic reaction were determined from the rec-
tilinear segments of polarization curves.
286 P. V. POPOVYCH, L. А. MAHLATYUK, AND R. B. KUPOVYCH

Fig. 1. Corrosion rates of St.20 (a) and St.3 steel (b) for various times of holding in different media: H 2O ( ); liquid manure ( );
mixed manure ( ).

The current indices of corrosion rate were converted into the mass indices by the following formula:

ikA
K = , (2)
nF

where i is the corrosion current, A/cm 2 , k is a coefficient ( k = 1, if the testing time is measured in se-
conds and the area is measured in cm 2 ), A is the atomic mass of the metal (for iron and steel, A = 56), n is
the level of oxidation (for iron, 2 or 3), and F is the Faraday constant [5].

Results and Discussion

The chemical analysis of the liquid cattle manure and mixed manure reveals the presence of nitrogen-
containing compounds (Table 1). These compounds often have the properties of corrosion inhibitors. The cor-
rosion tests of St.20 and St.3 steels for different holding times revealed the following facts (Figs. 1a, b):
The corrosion rates of both steels for the first day are 3–4 times lower than in distilled water and 8–10 times
lower than in the media of mineral fertilizers, namely, ammonium phosphate and nitrophoska [6].
St.3 steel corrodes somewhat faster than St.20 steel. The increase in the time of holding leads to a substan-
tial decrease in the corrosion rate and, after 24 days, the corrosion rates of St.20 and St.3 steels in both media
become equal. In fact, for the first day, both liquid and mixed manures exhibit an inhibiting effect on a level of
65–75% as compared with distilled water. After 24 days, the degree of protection becomes as high as 96%.
The difference between the corrosive activities of both types of manure is practically absent. The isolated local
corrosion defects observed on steel after holding in the unfiltered manure are formed as a result of the formation
of galvanic couples caused by the sticking of dispersed solid remnants of straw, seeds, etc. to the surface.
After testing in the media of both types of organic fertilizers for a day, on the surface of steel specimens,
we detect only individual changes in the form of variable colors corresponding to a thickness of the oxide film
of about 460–680 Å. After subsequent tests (7–24 days), the variable colors disappear and the surface becomes
clear and lustrous, without visible changes (Fig. 2).
Prior to the corrosion tests, the рН values of the solutions of liquid and mixed manures were 7.45–7.50. Af-
ter holding of steels in these media for 24 days, the рН values increase to 8.0–8.2.
INFLUENCE OF ORGANIC FERTILIZERS ON THE CORROSION-ELECTROCHEMICAL CHARACTERISTICS OF LOW-CARBON STEELS 287

Fig. 2. General view of a specimen of St.20 steel after holding for 24 days in the cattle manure.

Fig. 3. Character of reaching the steady-state value of the potential for St.20 steel (a) and St.3 steel (b): (1) distilled water; (2) liquid
manure; (3) mixed manure.

The corrosion potentials of St.20 and St.3 steels in the media of both types of manure attain the steady-state
value for 15–20 min and are shifted to more negative values as compared with those in distilled water (Fig. 3).
The polarization curves on specimens of both steels are similar in character (Fig. 4). The cathodic curves of
St.20 steel differ by the range and values of the ultimate diffusion currents: in the liquid manure, within the poten-
tial range (–630)–(– 920) mV, the ultimate diffusion current is 7 ⋅10 −2 mA/cm 2 , whereas in the mixed manure
[within the range (–510)–(– 810) mV], the ultimate diffusion current is equal to 3 ⋅10 −2 mA/cm 2 . The cathodic
curves of St.3 steel in both organic fertilizers differ only by the potential range of the ultimate diffusion current:
(– 680)–(– 1100) mV in the liquid manure and (– 580)–(– 1100) mV in the mixed manure. The ultimate diffu-
sion current is somewhat higher than for St.20 steel and is equal to 9 ⋅10 −2 mA/cm 2 and 7 ⋅10 −2 mA/cm 2 , re-
spectively.
The anodic curves on both steels have a small segment, which can be associated with the inhibition of the
anodic reaction: in the liquid manure, from – 480 to – 530 mV (St.20 steel) and from – 480 to – 540 mV (St.3
steel) and in the mixed manure, from – 250 to – 320 mV (St.20 steel) and from – 350 to – 420 mV (St.3 steel).
The region of inhibition of the anodic reaction in both media is also well visible if the potential is shifted from
–250 mV to less negative potentials for high values of the current (about 10 mA/cm 2 ).
288 P. V. POPOVYCH, L. А. MAHLATYUK, AND R. B. KUPOVYCH

Fig. 4. Polarization curves of St.20 (a) and St.3 steels (b): (1) distilled water; (2) mixed manure; (3) liquid manure.

Table 2. Electrochemical Characteristics of St.20 and St.3 Steels in Solutions of Organic Fertilizers

St.20 St.3

Medium − Est , icorr ⋅10 5 , bc ba − Est , icorr ⋅10 5 , bc ba

mV A/cm 2 mV mV A/cm 2 mV

Liquid cattle manure 610 0.7 33.3 30.0 590 0.9 30.2 28.1

Mixed manure 460 0.6 38.5 32.1 450 0.8 35.0 27.9
Distilled water 372 3.0 25.0 22.3 401 4.1 21.3 18.3

Table 3. Comparison of the Corrosion Rates of St.20 and St.3 Steels Determined Gravimetrically (K m ) ,
Electrochemically (icorr ) , and Computed According to the Current Indices (K i )
in the Media of Organic Fertilizers

H 2O dist. Liquid manure Mixed manure

Medi- 5 9
K m ⋅10 9 , icorr ⋅10 , K i ⋅10 , K m ⋅10 9 , icorr ⋅10 5 , K i ⋅10 9 , K m ⋅10 9 , icorr ⋅10 5 , K m ⋅10 9 ,
um
g/(cm 2 ⋅sec) A/cm 2 cm 2 ⋅sec g/(cm 2 ⋅sec) A/cm 2 cm 2 ⋅sec g/(cm 2 ⋅sec) A/cm 2 cm 2 ⋅sec

St.20 3.25 3.0 5.8 0.94 0.7 1.4 0.8 0.6 1.2

St.3 3.5 4.1 7.8 1.1 0.9 1.7 0.9 0.8 1.5

The corrosion currents of both steels in liquid and mixed manures are 4–5 times weaker than in distilled wa-
ter (Table 2). These instantaneous values of the current indices of corrosion rates converted by using relation (2)
INFLUENCE OF ORGANIC FERTILIZERS ON THE CORROSION-ELECTROCHEMICAL CHARACTERISTICS OF LOW-CARBON STEELS 289

satisfactorily agree with the rates obtained by the massmetric method for the first day (Table 3). The low ag-
gressiveness of both types of manure is also confirmed by the analysis of the Tafel segments of the polarization
curves. The Tafel constants of the cathodic and anodic reactions of St.20 and St.3 steels in these media are
higher than in distilled water (Table 2). This means that both electrode reactions are more inhibited in the ma-
nure media than in water. This results in the low rates of electrochemical corrosion.
Thus, liquid and mixed manures are characterized by the weak corrosion action upon St.20 and St.3 steels.
In these media, the corrosion processes run according to the electrochemical mechanism at much lower rates
than in distilled water (models of distillate or rainwater) under the conditions of natural aeration.

CONCLUSIONS

It is shown that the corrosion of St.20 and St.3 steels in liquid and mixed manures has a local character de-
termined by the formation of galvanic couples formed as a result of sticking of the suspended solid particles
(straw, seeds, etc.).
It is discovered that, after the procedure of filtering of suspended particles, both media exhibit weak corro-
sion actions upon St.20 and St.3 steels. The corrosion rates of these steels held for the first day constitute only
0.032–0.040 mm/yr, which is 3–4 time lower than in distilled water. The subsequent decrease in the rate to
0.003 mm/yr can be explained by the inhibiting properties of the chemical components of manure.
It is also established that the corrosion of St.20 and St.3 steels in both types of manure proceeds by the elec-
trochemical mechanism, as shown by the satisfactory agreement of the current indices of corrosion rates with the
corresponding massmetric indices. The stationary potentials of both steels in these media are shifted to more
negative values as compared with distilled water and the corrosion currents are 4–5 times weaker. The Tafel
constants for both steels are higher than in distilled water, which shows that both electrode reactions are inhibit-
ed.

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