Determination and comparison of the corrosion rate of 100Cr6 steel when protected

with Anticorit BG21 mineral oil applied using the spray technique.

K. Mojarro-Saad, 1L.G. Alvarado-Montalvo, 1C. J. Rodríguez-Rodríguez, 2G. Vázquez-

1

Rodríguez, 1M. M. Salazar-Hernández, 1J. E. Valtierra-Olivares, 3B. Ruiz Camacho, 1R.

Solís-Rodríguez, *1J. C. Baltazar Vera.

1
Departamento de Ingeniería en Minas, Metalurgia y Geología, División de Ingenierías,
Universidad de Guanajuato, Campus Guanajuato. Ex. Hda. San Matías S/N, Col. San
Matías, C. P. 36020, Guanajuato, Gto., Méx.
2
Departamento de Ingeniería Civil y Ambiental, División de Ingenierías, Universidad de
Guanajuato, Campus Guanajuato. Juárez 77, Col. Centro, C. P. 36000, Guanajuato, Gto.,
Méx.
Departamento de Ingeniería Química, División de Ciencias Naturales y Exactas,
3

Universidad de Guanajuato, Campus Guanajuato. Noria Alta S/N, Col. Noria Alta, C. P.
36050, Guanajuato, Gto., Méx.
E-mail: *jc.baltazarvera@ugto.mx

Abstract

The corrosion of various materials represents a problem in the manufacturing industry that
directly affects the productivity of companies, which is why technology has been developed
and implemented that allows slowing down the rate of corrosion, mainly of iron-based
materials (steels). In the present work, the results obtained by evaluating the corrosion rate
by electrochemical methods (Open circuit potential, linear resistance to polarization, Tafel
test, electrochemical impedance spectroscopy) as well as by physicochemical methods (jar
test in saline chamber), these data indicate that the corrosion rate in 100Cr6 steel is
considerably inhibited when protected with mineral oil, likewise the results show that the
best impregnation condition corresponds to 3 bar as it is the case study that presents greater
reduction of the corrosive process, having that the case of 2.5 bar yielded data close to that
of 3 bar, for which it can be inferred that this condition can be considered for its
application.

Keywords: Corrosion, Steel 100Cr6, Mineral oil, Electrochemical tests, Physicochemical

test.

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Introduction.

100Cr6 steel is a material that is widely used in various applications such as through
hardening bearings intended for roller contact application and high fatigue process; This is
due to its high hardness, high strength, and cleanliness, which provides this material with
adequate properties to withstand high-cycle and high-stress fatigue [1,2]. Another
application of this material is for the manufacture of other machine components that require
high tensile strength and high hardness [3,4]. Due to the wide spectrum of applications of
the various types of steel, these materials present deterioration processes due to corrosion
caused by the environment to which they are exposed, which is why there are works that
develop technologies focused on the inhibition of the corrosive process such as it can be the
deposition of hard and epoxy coatings [5, 6], coating with organic films [7-9], cathodic
protection by means of macrogalvanic cells [10], among others.

A method widely used today for the corrosion protection of parts and accessories made of
steel is by coating them with mineral oil, this alternative, in addition to its anticorrosive
benefits, helps to reduce material wear due to friction and stress. mechanics inherent to the
operation of the machine of which they are a part [11]. Anticorit BGI 21 is a nitrite, barium
and zinc-free anti-corrosion oil specially developed for the conservation of bearings, which
consists of a solvent-refined base oil that, thanks to its excellent combination of corrosion
prevention even on surfaces not completely coated; It also meets the extremely demanding
requirements of the bearing industry in terms of storage, transportation, and compatibility
[12]; There are various techniques for impregnating mineral oil on metal surfaces, among
the most common are impregnation by the spray method [13,14], sprinkling method [15,
16], flooding method [17, 18], among others. These techniques generally show the
impregnation conditions and do not address their effect on the degree of anticorrosive
protection of the material, which is why this work focuses on the analysis of the effect of
impregnation pressure using the technique by spraying in the inhibition of the degree of
corrosion of 100Cr6 steel.

Methodology

Materials and method of impregnation of the anticorrosive material

The test tube was made of 100Cr6 steel with a cylindrical shape 10 cm long and 1 cm base
diameter. Anticorit mineral oil BGI21 of the Fuchs brand was used as an anticorrosive
agent. The test tube was protected with mineral oil using the spray impregnation technique,
varying the application pressure at 2, 2.5 and 3 bar.

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Electrochemical tests

Electrochemical tests were carried out in order to know the rate of corrosion and its
possible mechanism, among the tests carried out are: Open Circuit Potential (OCP), Tafel
Test, linear polarization resistance (LPR) and electrochemical impedance spectroscopy; a
solution of 3.5% by weight of reagent grade NaCl of the Sigma Aldrich brand in deionized
water was used as a support electrolyte, platinum electrodes and Ag/AgCl were used as
counter electrode and reference electrode, respectively, 100Cr6 steel tube test were used As
working electrodes; the tests were carried out on a Gamry potentiostat, Interfase 1010T
model, the physical conformation of the cell is shown in figure 1.

Figure 1 Physical conformation of the electrochemical cell

The OCP test was carried out in an interval of 900 s at a sweep of 0.25 mV/s, normalizing
the contact area of the working electrode with the electrolyte; the Tafel test was carried out
taking as reference potential the value produced by the OCP test with a speed of 0.167
mV/s. The LPR test was performed taking as reference potential the value produced by the
OCP test with a speed of 0.25 mV/s and an interval of 660 s; for the impedance test,
19000Hz and 0.001Hz were taken as the initial and final frequencies, respectively, with a
jump of 10 Hz, taking the value obtained by the OCP test as the initial value.

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Physicochemical corrosion test

Physicochemical corrosion tests were carried out to know the degree of corrosion that the
specimens can reach, these tests were carried out in a Felisa model FE-291AD brand
equipment at a temperature of 60 °C for 3 hours exposed to a saline solution of 3.5 wt%
NaCl.

Results.

OCP Test

The OCP test measures the potential difference between the metal immersed in an ionic
medium and a reference electrode, giving a first overview of the degree of corrosion of the
material. As this process evolves, the potential decreases due to the decrease in
conductivity in the material because of metal oxide formation [19,20]. Figure 1 shows the
values reported by the OCP test, in which it can be seen that the reference tube test presents
the lowest values with a maximum of -0.54 V and a minimum of -0.55 V followed by the
test tube corresponding to 2.5 bar with a maximum of -0.41 and a minimum of -0.429, the
tube test corresponding to 2 bar registered a maximum of -0.36 V and a minimum of -0.385
V, finally the 3 bar case study registered a maximum of -0.31 V and a minimum of -0.35 V.
The results show that the reference tube test has a considerably shorter OCP time with
respect to the protected samples, this is consistent since the generation of oxide by the
corrosion process interferes in the electronic transfer between the working electrode and the
other elements of the electrochemical cell.

-0.30

-0.35 Reference tube

test
2.5 bar
-0.40
2 bar
OCP (V)

-0.45
3 bar

-0.50

-0.55

-0.60
0.00 200.00 400.00 600.00 800.00 1000.00
Time (s)

Figure 1. Time vs OCP for tube tests with and without protection.

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LPR Test

The LPR test which allows to measure the corrosion rate instantly since it is based on the
relationship between the electrochemical potential and the current generated between
electrically charged electrodes [21,22]. Figure 2 shows the curves corresponding to the
resistance to linear polarization, in which it can be seen that the lowest current density was
obtained by the tube test corresponding to 3 bar with a value of 8.17 x 10 -6µAcm-2, which
suggests that this condition is the one that provides greater inhibition of the corrosive
process, followed by the 2.5 bar and 2 bar tube tests reporting values of 8.20 x 10 -6µAcm-2
and 8.66 x 10-6µAcm-2 respectively; Finally, the reference tube test reported a value of
1.011 x 10-5µAcm-2, which is indicative of a possible more advanced corrosion process.

-0.4

-0.45

-0.5

-0.55
E(mV)/ SCE

-0.6
2 bar
-0.65
3 bar
-0.7
2.5 bar
-0.75 Reference tube test
-0.8

-0.85

-0.9
0.00E+00 1.00E-05 2.00E-05 3.00E-05 4.00E-05 5.00E-05 6.00E-05 7.00E-05
j (µAcm-2)

Figure 2. LPR curves of tube test with and without protection.

Tafel test and calculation of corrosion rate

To estimate the corrosion rate, the Wagner and Traud equation (eq. 1) was used as a basis
[23,24].

i t =i a+i c =i corr exp

[ ( αnF ηa
RT ) (
−exp
−( 1−α ) nF ηc
RT )] (1)

Where T= Absolute temperature, R= Gas constant, F= Faraday constant, n= number of

exchange electrons in the redox process, α and (1-α) = charge transfer coefficients, related

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to the drop in potential across the double layer surrounding the electrode, η= The
polarization (overpotential), ico

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 R1 CPE1

R2

Element Freedom Value Error Error %

R1 Free(+) 61.38 N/A N/A
CPE1-T Fixed(X) 0.00010569 N/A N/A
CPE1-P Fixed(X) 0.86205 N/A N/A
R2 Fixed(X) 9.605 N/A N/A

Data File: C:\Users\mojarkre\Documents\Blanco.txt

Circuit Model File:
Mode: Run Simulation / Freq. Range (0.001 - 1000000)
Maximum Iterations: 100
Optimization Iterations: 0
Type of Fitting: Complex
Type of Weighting: Calc-Modulus

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 = The corrosion current density, in which the anodic and cathodic Tafel slopes represent
rr
the anodic and cathodic branches of the V vs Log(i) graph (Figure 3).

-3

-4

-5
log(I[A/cm2])

Reference tube test

-6
2 bar
2.5 bar
-7
3 bar

-8

-9
-0.67 -0.62 -0.57 -0.52 -0.47 -0.42 -0.37 -0.32
V vs VSHE

Figure 3. Tafel curves of tube test with and without protection

Table 1 shows the values corresponding to the corrosion rate calculated by means of
parameters obtained from the electrochemical tests (Vcorreq) and the corrosion rate calculated
by means of the physicochemical test called jars (Vcorrj); These results indicate that the
Vcorreq data for all the study cases are greater with respect to the V corrj, with the greatest
difference between these two corresponding to the reference tube test and the least
difference being presented by the samples at 2 bar. The sample with the highest V correq
corresponds to the reference tube test with a value of 11.6 mm/year and the lowest was
obtained by the case of 2.5 bar with a value of 1.3 mm/year, likewise, for the Vcorrj the
highest value was obtained by the reference tube test with 3.92mm/year and the lowest was
the sample at 3 bar with 1.57mm/year; These results show that the corrosion rate in the
material is considerably inhibited when carrying out the protection with mineral oil,
considering that the case where it is impregnated with oil at 3 bar is the best option
according to the reported values.

Table 1
Corrosion rates for tube test with and without protection

Sample Vcorreq (mm/año) Vcorrj (mm/año)

Reference tube test 11.6 3.92
2 bar 2.18 2.15
2.5 bar 1.3 1.8
3 bar 3.6 1.57

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Impedance Electrochemical Spectroscopy (EIS)

This test consists of the application of a fixed alternating voltage to an electrode varying the
frequency, in which the current response is obtained and the impedance is calculated at its
respective frequency; Due to the low potentials applied, it is considered a technique with
low disturbance to the system and allows to discriminate and measure resistive, capacitive
and inductive components of an interface; being able to model the electrochemical behavior
by means of equivalent electrical circuits [25, 26]. Figure 4 shows the Bode graph (log f vs
log Z) corresponding to the reference tube test and the protected specimens, in this figure it
can be seen that in all cases the impedance decreases substantially in log f values between 0
and 3000 Hz, this decrease is indicative of the progress of the corrosive process in each
case study; likewise, the sample corresponding to 2.5 bar registered the lowest value of log
Z equal to 190 Ω.cm2, followed by the case at 2 bar with a value of 193.13 Ω.cm 2, later the
reference tube test is located with a value of 194.37 Ω.cm 2 and finally locate the case at 3
bar with a value of 203.94 Ω.cm2.

235
230
225
220
Log Z(Ω.cm2)

215
Reference tube test
210
2 bar
205
2.5 bar
200
3 bar
195
190
185
0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000
Log f (Hz)

Figure 4. Bode graph of tube test with and without protection

Figure 5 shows the Nyquist diagram for the test tubes with and without protection, in this
diagram according to the data trends an adjustment can be made through the equivalent
circuit shown in figure 6, where Rs is the resistance to the electrolyte, Cdl is the capacitive
impedance and Rp is the resistance to polarization [27].

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 13

11

9
Reference tube test
-Zim(KΩ.cm2)

7 Reference tube test FIT

2 bar
5 2 bar FIT
3 2.5 bar
2.5 bar FIT
1 3 bar FIT
3 bar FIT
-1190 195 200 205 210 215 220 225 230

-Zre(KΩ.cm2)

Figure 5. Nyquist diagram of tube test with and without protection

Figure 6. Equivalent circuit of the system subjected to EIS.

Table 2 shows the values obtained by the adjustment to the equivalent circuit; In this table
the resistance to the electrolyte (Rs) is in a similar range of values for all the study cases,
which is consistent since the same type of electrolytic solution was used in all the tests.
Regarding the resistance to polarization (Rp), which indicates the resistance to corrosion,
the sample that presented the highest value was the one at 3 bar, followed by the reference
tube test, then the case at 2 bar and finally the specimen at 2.5 bar, these results are
consistent with the capacitive impedance values (Cdl) which show the same trend as Rp.

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 Table 2
Electrochemical equivalent circuit parameters for tube test with and without protection

Tube test Rs Ω.cm2 Cdl µF Rp Ω.cm2

Reference 62.16 0.43 8.17
2 bar 62.70 0.18 7.62
2.5 bar 61.18 0.11 6.94
3 bar 65.1 0.38 8.44

Conclusions:

With the application of electrochemical tests and physicochemical tests to determine the
corrosion speed of the study material with or without protection, varying the impregnation
conditions of the protective agent, results were obtained that allowed elucidating how,
when protecting the referred material, there is a significant decrease in speed corrosion in
all cases. In general, this work gives an overview of how, by varying the impregnation
pressure conditions of mineral oil as a protection for 100Cr6 steel, it was possible to find
that the best condition was when using an application pressure of 3 bar by the spray
method, this was due to the fact that this case study obtained the largest number of
parameters both in the electrochemical tests as well as the physicochemical tests that
indicate the decrease in the corrosion rate, which provides a solid alternative to carry out a
more efficient protection. of the material of interest.

Acknowledgment

The authors thank the Schaeffler company and the University of Guanajuato for their
support to carry out this research project.

References:

[1] Zbigniew P, Janusz T, Tomasz B, Marcin K, Sylwester S, Konrad L. (2021).

Determination of the critical damage for 100Cr6 steel under hot forming conditions.
Engineering Failure Analysis. 128: 105558.
[2] Kiranbabu S, Tung P, Sreekala L, Prithiv T, Hickel T, Pippan R, Morsdorf L, Herbig M.
(2022). Cementite decomposition in 100Cr6 bearing steel during high-pressure torsion:

PUBLIC
Influence of precipitate composition, size, morphology and matrix hardness. Materials
Science and Engineering: A. 833: 142372.
[3] Ortiz-de-Zarate G, Soriano D, Madariaga A, Garay A, Rodríguez I, Arrazola P (2021).
Experimental and FEM analysis of dry and cryogenic turning of hardened steel 100Cr6
using CBN Wiper tools. Procedia CIRP. 102: 7-12.
[4] López-Uruñuela F, Fernández-Díaz B, Pinedo B, Aguirrebeitia J (2022). Early stages of
subsurface crack and WEC formation in 100Cr6 bearing steel under RCF and hydrogen
influence. International Journal of Fatigue. 155: 106587.
[5] Schröer A, Ensinger W, Wolf G (1991). A comparison of the corrosion behaviour and
hardness of steel samples (100Cr6) coated with titanium nitride and chromium nitride by
different institutions using different deposition techniques. Materials Science and
Engineering: A. 140: 625-630.
[6] Xiang Q, Qiang Y, Guo L (2023). Designing a novel GO@AAP reinforced epoxy
coating for achieving the long-term corrosion protection of steel substrate. Progress in
Organic Coatings. 174:107293.
[7] Liyanage A, Karunarathne D, Nasrazadani S, D'Souza F, Siller H, Golden T. (2022).
Polyphthalocyanine coatings for corrosion protection on additive manufactured steel
materials. Progress in Organic Coatings. 170: 106990.
[8] Ramírez A, Mieres F, Pineda F, Grez P, Heyser C. (2022). Electrosynthesis of
polyindole-carboxylic acids on stainless steel and their corrosion protection at different
temperatures in acidic solution. Progress in Organic Coatings. 172: 107075.
[9] Gapsari F, Hidayatullah S, Setyarini P, Madurani C, Hermawan H. (2022).
Effectiveness of a fish scales-derived chitosan coating for corrosion protection of carbon
steel. Egyptian Journal of Petroleum. 31: 25-31.
[10] Erdogan C, Swain G. (2022). The effect of macro-galvanic cells on corrosion and
impressed current cathodic protection for offshore monopile steel structures. Ocean
Engineering. 265: 112575.
[11] Nitiu E, Sorin A. (2020). Composition for Anticorrosive Cooling and Protection
Emulsion. Procedia Manufacturing. 46: 34-37.
[12] Anticorit BGI 21 (2022) FUCHS, México.
https://www.fuchs.com/mx/es/producto/product/39158-anticorit-bgi-21/
[13] Varansi K, Smith J, Yague J, Jordan B, Hibben C, Xu J, Cong T. (2015). Spray
processes and methods for forming liquid-impregnated surfaces. European Patent Office.
0273518 A1:1-35.
[14] Chen L, Geissler A, Bonnacurso E, Zhang K. (2014). Transparent Slippery Surfaces
Made with Sustainable Porous Cellulose Lauroyl Ester Films. ACS Applied Materials &
Interface. 6(9): 6969-6976.

PUBLIC
[15] Marathe U, Padhan M, Panier S, Bijwe J. (2021). Processing of PAEK-graphite fabric
composites – Pros and cons of film technique over powder sprinkling technique.
Composites Part B: Engineering. 215: 108804.
[16] Martín-Ramos P, Gil F, Martín-Gil J. (2022). Physico-chemical characterisation of
remains from a Bronze Age ochre-burial in Biniadris cave (Menorca, Spain). Journal of
Archaeological Science: Reports. 42: 103362.
[17] Kazaryan P, Agalakova M, Kharitonova E, Gallyamov M, Kondratenko M. (2021).
Reducing the сontact angle hysteresis of thin polymer films by oil impregnation in
supercritical carbon dioxide. Progress in Organic Coatings. 154: 106202.
[18] Medvedovski E, Antonov M. (2020). Erosion studies of the iron boride coatings for
protection of tubing components in oil production, mineral processing and engineering
applications. Wear. 453-454: 203277.
[19] Doménech-Carbó A, Peiró-Ronda M, Vives-Ferrándiz J, Duffó G, Farina S,
Doménech-Carbó M. (2022). Modeling ‘dry’ OCP measurements to characterize
archaeological iron corrosion I: Long-time transients. Journal of Electroanalytical
Chemistry. 913: 116210.
[20] Cheng T, Huang H, Huang G. (2022). Galvanic corrosion behavior between ADC12
aluminum alloy and copper in 3.5 wt% NaCl solution. Journal of Electroanalytical
Chemistry. 927. 116984.
[21] Lijie C, Kai L. (2021). Corrosion rate measurement by using polarization resistance
method for microcell and macrocell corrosion: Theoretical analysis and experimental work
with simulated concrete pore solution. Construction and Building Materials. 267:121003.
[22] Sripriya R, Lakshman N, Radhakrishna G. (2019). Investigation on the polarization
resistance of steel embedded in highly resistive cementitious systems – An attempt and
challenges. Electrochemical Acta. 308: 131-141.
[23] Kumar H, Dhanda, T. (2021). 5-Aminotetrazole a highly efficient corrosion inhibitor
for mild steel in 0.1 N sulphuric acid: Experimental & theoretical study. Chemical Data
Collections, 33:100721.
[24] Alzahrani E, Abo-Die H, Algethami F. (2021). Electrochemical investigations of
hydrochloric acid corrosion for carbon steel and coating effect by Poly (butyl
Methacrylate)-grafted alginate/Fe3O4. Arabian Journal of Chemistry,14 (5): 103100.
[25] Encinas-Sánchez V, Miguel M, Lasanta M, García Martín G, Pérez F. (2019).
Electrochemical impedance spectroscopy (EIS): An efficient technique for monitoring
corrosion processes in molten salt environments in CSP applications. Solar Energy
Materials and Solar Cells. 191:157-163.
[26] Sun F, Wang X, Han P, He B. (2022). Combined EIS and BAS-BP neural network
analysis of electrochemical corrosion on pipeline steel in silty soil in a Salt–Temperature
coupling environment. International Journal of Pressure Vessels and Piping. 200: 104807.

PUBLIC
[27] Amador A. (2005). Análisis de Corrosión con EIS (Electrochemica lmpedance
Spectroscopy). Instituto Tecnológico y de Estudios Superiores de Monterrey.1:1-48.

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