UNIVERSITY OF WATERLOO

Faculty of Engineering

ChE 391 Experiment 4: Corrosion Studies

Data analysis report

Prepared by
Group S: Keunwoo (Paul) Kang
Date of Submission: September 24, 2016
Date of Experiment: September 21, 2016

1.0 Objective
The objective of this experiment is to
-

Develop an understanding of corrosion rate values for a variety of metals

through immersion
Experimentally obtain corrosion rates via a variety of corrosion testing
techniques

2.0 Experimental
2.1
-

PAR VersaStat3-400 Potentiostat w/(2A max.) and Frequency Response

Analyzer (FRA)
Versastudio corrosion software
1L Ametek Corrosion Test Cell (Princeton model K47) inc. 1 Saturated
calomel reference electrode filled with saturated KCl, 2 graphite counter
electrodes, a Teflon sealed working electrode sample holder, salt bridge
tube and gas sparger
2 clean metal (mild steel, stainless steel, aluminium, copper and brass)
cylindrical coupons (9.2mm dia x 12 mm approx. with #3-48 tap)
Paraffin wax and paint
250 ml sample bottles and fishing wire
Incubators (room temp up to 50C)

2.2
-

Equipment

Materials

Metal coupons (mild steel, galvanized steel, 316 stainless

aluminium, or copper)
0.1 1 M NaCl(aq), HCl(aq), NaOH(aq), H3PO4(aq) or H2SO4(aq)

steel,

2.3

Schematic

Figure xx: Schematic of submerged metal sample into solution (Immersion Corrosion Testing)

2.4

Procedures

Part A Preparation of the samples and settings

Preparation of the samples are to be completed prior to the experiment. Six metal
coupons are used as a corrosion sample and the cleaning of these samples follows
ASTM G1-03 (2011) cleaning procedure standards. First cleaning step is to clean
metal coupons in pre-degassed ultra-sonication bath containing distilled water for
30 minutes. Then the coupons are rinsed with distilled water and sanded with 600
grit sand paper to smooth surface followed by rinsing with methanol or acetone to
remove all the remaining grease. The metal coupons are again rinsed with distilled
water and allow to air dried. It is important not to dry with any paper or cloth as lint
can affect the observed corrosion rate. Coupons are placed in oven and desiccator
for accelerated drying and cooling.
All metal coupon samples are weighed and recorded prior to immersion to the
solution. Metal coupons are then suspended into clear glass jar (fully submerged)
with varying concentration of sodium chloride (NaCl) and hydrochloric acid (HCl)
and the glass jar is labeled with necessary information containing metal type,
solution type and concentration. They are left in the incubator in room temperature
(25C) for over 6 days.

Part B Electrochemical Corrosion Testing (EIS, Tafel and LPR)

B.1 Electrochemical Impedance Spectroscopy (EIS)
In this experiment, Versastat potentiostat is used to test the corrosion degree.
Counter electrode is connected together using wire with alligator clips and attach

red lead to one clip. Green lead is attached to working electrode, white lead is
attached to reference electrode, and black lead is not connected to any of the
electrode. Then, the mechanical specification of the electrode is then recorded and
updated into the software. Approximate OCV value for the cell has to be recorded,
which has been resting at least 45 min prior to the testing. Following EIS parameters
are then entered to describe the characteristic of AC voltage/current for testing the
subject.
Start frequency: 10000Hz
End frequency: 0.05Hz
Amplitude: 10Mv
Potential: Ecorr (value available in OCV)
Three windows are appeared: (1) Bode plot, (2) Nyquist plot (3) Dataview table
which shows the data being collected. Using the software, data will be fitted to find
Rs and Rs+Rp values. Then, all the relevant data will be transferred and copied into
the excel file.
B.2 Linear Polarization Resistance (LPR)
It is important to do LPR testing as second corrosion testing run for any sample as
the estimation will depend on the Tafel constants. New LPR scanning window will be
created and related parameter will be set as default. Sample will be scanned and
using the RP fit feature, slope of Potential Vs Current will be obtained at output
value at Ecorr.

B.3 Tafel plots

By creating a new Tafel scan from the corrosion test, OCV range will be set in a
range of 0.2 to -0.2 V vs OCV. Enter set-up data before running scan. Tafel-fit feature
will enable to determine Tafel cathodic, Anodic Beta values, Ecorr and Icorr in a
Potential Vs Log Current plot.

Part C Immersion corrosion testing

Preparation of the testing samples are described in Part A Preparation of the
samples. In the actual lab session (experimental performance), physical appearance
will be observed (qualitative observation: localized pitting, discoloration, surface
film, metal oxidation, and etc.) also test for the solution discoloration or any solid
media suspended. Test condition, date and time of submergence is recorded. Metal
coupons are removed from the solution media and rinsed with de-ionized water and
placed in the oven for 30-minute dry. Metal coupon will be weighed after rinsing
with de-ionized water. Any metal oxide will be removed with sand paper and the
final weight will be recorded for comparison. Surface condition will also be observed
using stereomicroscope. Weight lost over time due to corrosion for each sample will
be determined from comparison of weight values of before and after experiment.

3.0 Results and discussion

Qualitative observation:
The image of the non-corroded mild steel with a acid is shown below. The sample
had been prepared approximately 3 days before the actual lab experiment.
Stereomicroscope image of the physical structure of mild steel has been taken to
compare the corrosion effect to the surface.

Figure 4: Stereomicroscope-Non-Corroded Mild Steel with Dark Resolution

In the figure above, the Non-corroded mild steel shows bumpiness with a white
substance which indicate natural corrosion occurred. The white substance that
forms bumpiness is predicted to be the metal oxide and the thin layer that causes
passivation.

Figure 6: Stereomicroscope-Corroded Mild Steel under Room Temperature

FIgure 7: Stereomicroscope-Corroded Mild Steel under 40C

After corrosion, bumpiness occurs more readily. There is a clear evidence that the
metal oxide has been corroded away and the thin layer starts to disappear. However
the metal oxide crystals are still abundant.
Nyquist plot for mild steel in sodium chloride at 40C is shown below. As shown in
the Nyquist plot, EIS estimates the large R p value which represents high corrosion
rate. First x-intercept (starting point of the semi-circle) represents the solution
resistance and second x-intercept represents the polarized resistance plus the
solution resistance. The Rp value found by extrapolation of the data point gives the
resistance value of 427.8 ohms

Figure xx: Nyquist plot for mild steel in sodium chloride (NaCl) at 40C
LPR test is performed and shows the Rp value to be 128.673 ohms. There is
significant difference of polarized resistance values between EIS and LPR tests. One
of the possible reason for this is when the KCl solution in the reference electrode
contains impurities, bubbles or any sort of substance that causes interference of its
performance disrupts the correct corrosion voltage (E corr) therefore shifts the
sinusoidal wave in a different region. This effect cause i corr value to contain error
therefore cause error in Rp value. Such increment in resistance for the EIS testing
can be also due to any dirt on the electrode connection (alligator clips) that causes
the faulty reading.

Figure xx: LPR plot for mild steel in sodium chloride (NaCl) at 40C
Tafel plot for mild steel in sodium chloride at 40C is shown below. The beta values
for cathodic and anodic current lines will be used to estimate the corrosion current
value, Icorr, along with polarization resistance value to estimate the corrosion rate. In
this Tafel plot, the beta cathodic, cathodic value shows 167.890 (mV/decade) and
anodic value 67.034 (mV/decade). Tafel plot analysis also shows I corr value to be
55.183 A. the beta values are to be used to find the corrosion current I corr for EIS
and LPR tests.

Figure xx: Tafel plot (anodic) for mild steel in sodium chloride (NaCl) at 40C

Figure xx: Tafel plot (anodic) for mild steel in sodium chloride (NaCl) at 40C
In the Tafel plot shown above figure, the Tafel fitting did not give a reasonable fitting
which did not give any intersection points nor any reasonable beta constants.
Instead, the linear fitting for certain range of the data point that represents anodic
and cathodic region is selected and pl,otted. The slope has a unit of mV/decade and
its linear slope is used to represent the beta values for cathodic and anodic current
values. Using these values and the surface area of the bottom side of the mild steel
stick, the corrosion current and its density can be calculated.
The calculation of the corrosion current for EIS and LPR tests is as follows:

I corr=

Where

anodic cathodic
=i A
2.303 ( anodic + cathodic ) R p corr

i corr is corrosion current density, and A is bottom surface area of the mild

steel stick.

Rearranging the equation to get corrosion current density,

i corr =

anodic cathodic
2.303 ( anodic + cathodic ) R p A

For LPR testing,

i corr , LPR, NaCl =0.235001475 mA /c m2

For LPR potentiostat analysis value,

i corr , LPR, device, NaCl =0.250066 mA /c m 2

For EIS testing,

i corr , EIS , NaCl =0.140041345 mA /c m2

To calculate the corrosion rate of the mild steel stick in brine solution at 40C, I am
referring to the corrosion rate equation from the Corrosion Tests and Standards [1]:

CR ( Corrosion Rate )=

K 1 i corr Ew
mildsteel

Where:

K 1=3.27103
Ew =equivalent weight ,

M w 55.845
=
=27.9225 for mild steel
n
2

mild steel=7.85 g/c m3

For LPR test, using the calculated icorr value,

CR LPR , NaCl=2.736885179mm / yr
For LPR test, using the value from software i corr,

CR LPR ,device , NaCl =2.912330355 mm/ yr

For EIS test, using the calculated i corr value,

CR EIS ,NaCl =1.630956068

mm
yr

Since the objective of this experiment is to compare the corrosion rate in a different
environment condition using three different technique, our group chose to compare
the corrosion rate values in a different solution medium, HCl.
Nyquist plot for mild steel in hydrochloric acid at 40C is shown below. In this case,
the semicircle fitting shows the result that solution resistance is 1.12804 ohms and
polarized resistance Rp value to be 30.87396 ohms.

Figure xx: Nyquist plot for mild steel in Hydrochloric acid (HCl) at 40C
As one can notice from this Nyquist plot, there is a significant difference between
the polarized resistance values. The LPR analysis at 40C in hydrochloric acid shows
Rp value of 41.244 ohms with the Icorr value of 0.780145 mA. The LPR plot is shown
below.

+
Figure xx: LPR plot for mild steel in Hydrochloric acid (HCl) at 40C
Tafel plot for mild steel in hydrochloric acid at 40C is shown below. In this Tafel plot,
the beta cathodic, cathodic value shows 154.248 (mV/decade) and anodic value
230.092 (mV/decade). Using the same equation to calculate the corrosion current
value.

Figure xx: Tafel plot for mild steel in Hydrochloric acid (HCl) at 40C

I corr=

anodic cathodic
=i A
2.303 ( anodic + cathodic ) R p corr

For LPR testing,

i corr , LPR, HCl =1.412860231mA /c m

For LPR potentiostat analysis value,

i corr , LPR, device, HCl =1.133766894 mA /c m2

For EIS testing,

i corr , EIS , HCl=1.887416042 mA /c m

Again, the Corrosion rate calculation using the equation from the Corrosion Tests
and Standards [1],
For LPR test, using the calculated icorr value,

CR LPR , HCl=16.43355779 mm/ yr

For LPR test, using the software icorr value,

CR LPR ,device , HCl =10.5203630mm / yr

For EIS test, using the calculated i corr value,

CR EIS ,HCl =21.95331139 mm / yr

Overall overview of this corrosion rate of mild steel in each different solution
medium shows significant corrosion rate difference. In general, corrosion rate of the
HCl is significantly faster than in the brine solution, and this is due to high reactivity
nature of hydrochloric acid. In the Tafel plots, the slopes of the anodic sides of NaCl
is slightly showing interference, which indicates that there is an evidence of the
passivation occurring. Again, the passivation is the process of protecting a metal
through the use of an outer layer coating. In the Tafel plot of brine solution shows
the non-linear region in which caused the Tafel fitting to be unusable. Our group had
to select certain region and fit the linear fitting to get the slope values of the beta
anodic and cathodic values to calculate the estimated value of corrosion current.
Corrosion immersion testing
Before the lab session, our group prepared variety of different solution medium
concentration (with brine solution and HCl). In this experiment, 1M of NaCl and 1 M
of HCl is used to prepare different concentration of solution medium with Mild Steel,
Aluminum and copper. First it is important to focus on the corrosion rate between

different solution medium (but with same molar concentration) of Mild Steel to
validate the result from the EIS, LPR and Tafel testing. Following table represents the
specifications of this experiment.

Table xx: Table of corrosion immersion testing result with different solution medium
Samp
le #

Metal

Acid
Concentration
HCl or NaCl(M)

Mild
Steel

Mild
Steel

1 (NaCl)

Date of
Submergence

2016-0916
1300H
2016-0916
1300H

Initial
Mass of
Metal
(g)

11.11
17
11.11
15

Date of
Measurement

2016-0921
1515H
2016-0921
1515H

Final
Mass of
Metal
(g)

Mass
After
Cleansin
g (g)

7.638
9

7.631
3

11.09
79

11.09
44

From the testing result, we are able to derive the corrosion rate equation applying
the differential of the mass with time. Since the corrosion rate was expressed in a
unit of mm/yr, active surface area must be divided to the volume of the corrosion.
This face yields the following equation:

Corrosion Rate=

Which the

dm
dt

dm 1
dt A
part refers to the mass difference in a certain time duration.

is the density of the Mild steel which is 7.84g/cm 3, and A represents the active
surface area which is in this case 2599.7708 mm 2.
The calculation of the corrosion rate in immersion corrosion testing is as follows:
For 1M of HCl solution medium

time difference=t 2 t 1=110.15 hours

mass difference ( before cleansing )=m2m1=3.4728 g
mass difference ( after cleansing )=m2m1 =3.4804 g
Corrosion Rate ( before cleansing )=13.55027949 mm/ yr
Corrosion Rate ( after cleansing ) =13.579933412mm / yr
For 1M of NaCl solution medium,

time difference=t 2 t 1=110.15 hours

mass difference ( before cleansing )=m2m1=0.0136 g
mass difference ( after cleansing )=m2m1 =0.0171 g
Corrosion Rate ( before cleansing )=0.05306490472 mm/ yr
Corrosion Rate ( after cleansing ) =0.06672131408 mm/ yr
Furthermore, our group differentiated the concentration of the hydrochloric acid to
see the effect of the corrosion rate related to the different concentration of the acid.
Similar procedure has been carried out with Aluminum and copper.

Table xx: Table of corrosion immersion testing result with different solution
concentration, materials
Samp
le #

Metal

Acid
Concentration
(M)

Mild
Steel

0.5

Aluminu
m

Aluminu
m

0.5

Copper

Date of
Submergence

2016-0916
1300H
2016-0916
1300H
2016-0916
1300H
2016-0916
1300H

Initial
Mass of
Metal (g)

11.60
95
4.287
7
4.281
69
14.01
69

Date of
Measureme
nt

2016-0921
1515H
2016-0921
1515H
2016-0921
1515H
2016-0921
1515H

Final
Mass of
Metal (g)

Mass
After
Cleansin
g (g)

8.636
8

8.606
5

2.357
3

2.356
4

3.149

3.149
7

13.35
96

13.35
33

Calculation of the corrosion rate of sample # 3,4,5,6 is same with calculation of the
corrosion rate for sample #1,2. Below table is the summarized table of each
corrosion rate
Table xx: Summary of different corrosion rate with different solution
media, materials

Materials

Solution
media (M)

corrosion rate
(before
cleansing)
mm/yr

corrosion
rate (after
cleansing)
mm/yr

mild steel
1 M HCl
13.550279
13.579933
mild steel
1 M NaCl
0.0530649
0.0667213
mild steel
0.5 M HCl
11.598974
11.717199
aluminum
1 M HCl
21.870972
21.881169
aluminum
0.5M HCl
12.833108
12.825177
copper
1M HCl
2.2440895
2.2655983
As shown in above table, the observed corrosion rate in immersion corrosion testing
turns out to the observation that corrosion rate of HCl is much greater than that of
NaCl using Mild Steel. This is due to high reactivity of the acid therefore the
corrosion of the metal is faster. Furthermore, this information can deliver the
observation that aluminum corrosion rate in HCl is much faster than the other
materials. Furthermore, the higher concentration with the same material shows the
higher corrosion rate, since there are more H+ ions present, lowering the pH value.
The relationship of the material type and the corrosion rate is shown below:
Table xx: Summary of the corrosion rate of different material in same
concentration of HCl
Material
s

Solution
media

corrosion rate
(before
cleansing)
mm/yr

corrosion
rate (after
cleansing)
mm/yr

Densi
ty
g/cm3

mild
1 M HCl
13.55027949
13.579933
7.84
steel
aluminu
1 M HCl
21.87097217
21.881169
2.7
m
copper
1M HCl
2.244089459
2.2655983
8.96
Furthermore, it is apparent that the lower the density value, higher the corrosion
rate. This alludes to the observation that how closely packed the metal atoms
determines the corrosion rate, which may suggest suggests the mechanism that
depending on the oxidation state of the metal ions, the density of specific material
changes, and because of there is a change in oxidation state, the reactivity also
changes along with the line. Figure shown below represents the relationship
between the density and the corrosion rate.

25

20

15

Corrosion rate, mm/yr

10

10

Density, g/cm3
Aluminum, Al

Copper, Cu

Mild Steel, Fe

Figure xx: Relationship between corrosion rate and density of material

chosen
Comparing the EIS, Tafel and LPR results, there is a significant evidence that the
NaCl solution corrosion rate with the mild steel is much lower than that of HCl
solution.
Literature value of the corrosion rate of mild steel in HCl solution varies depending
on the result that other researchers reported. For the sake of simplicity, 2 literature
values are chosen and averaged out to compare the data obtained in this
experiment
Table xx: Literature corrosion rate values of 1M HCl with mild steel
Literature
value

Corrosion
rate,
mm/yr

Osarolube et
al

17.2209

17.98928
57
Table xx: Literature corrosion rate values of 1M NaCl with mild steel
Tang et al

Literature
value
Mehra et al
Acharya et

Corrosion
rate,
mm/yr
3.7819
2.769

al

Table xx: Comparison of values from literature and different testing

methods
Corrosion
Corrosion
rate,
Experiments
rate,
mm/yr,
mm/yr, HCl
NaCl
Immersed
13.5799
0.066721
EIS
16.43356
1.630956
LPR
21.95331
2.736885
Literature
17.2209
3.7819
Value 1
Literature
17.98929
2.769
Value 2
As shown in the above table, NaCl solution shows an extreme difference between
literature values and immersed testing values. Possible reason for this is inaccurate
measurement of time and mass of the sample. This inadequacy can be solved by
having multiple sample and excluding outliers that shows unreasonable data, and
running the test multiple times. On the other hand, EIS and LPR values are showing
close value to the literature value. LPR technique seems to show the closest
corrosion rate value to the literature value.
On the other hand, HCl solution shows fairly accurate results on three different
testing methods. EIS method has the closest value to the literature reported value,
and this is because the EIS takes account of the redox reaction to evaluate the
polarized resistance of the reaction. It shoots out small AC voltage and receives the
current respond, in which is the least destructive for the sample (i.e. least
interference of a redox reaction occurring at the bottom side of the mild steel). LPR
result is showing some deviation and this is possibly due to the large interference of
the redox reaction. Immersion corrosion technique also shows deviation to some
extent, and this is possible due to inaccurate or imprecise measurement of mass
and time.
Corrosion is defined as the degradation of materials by chemical reaction with the
environment in which the material resides. The causes of corrosion are due to
reactivity of metal (oxidation state), presence of impurities, presence of air,
moisture, gases like carbon dioxide or oxygen and presence of electrolytes.
Indeed, that the corrosion has a significant impact to chemical engineering industry.
One of the largest chemical industry is oil and gas processing industry (such as
refinery), and according to the study titled as Corrosion Costs and Preventative
Strategies in the US (conducted in 2001, approximately there is 5.7 billion dollars
of potential value loss annually only in oil and gas industry. As this study suggests,
there are large costs related to the corrosion with the chemical engineering industry.

Corrosion effect and its negative impact to the industry can be prevented. There are
three methods that controls the corrosion; Protective coating, Cathodic protection
and Strategic engineering design and material selection methods to control
corrosion.
Corrosion Inhibitors
Corrosion can be controlled by foreign compounds which are known as inhibitors.
They get adsorbed on to the active site of redox reaction and forms one molecular
layer of the metal surface. The other way that inhibitors can inhibit the corrosion is
to increase the electrode potential. It may block the anode and cathode site that
restricts the corrosion. For example, Hexylamine or sodium benzoate are used to
inhibit for anodic process. Nitrite, Chromate, red lead, amines and etc are used as
corrosion inhibitors.
Cathodic protection
This method is to alter the electrode potential of the metallic surface structure so
that they can stay in a region where metal is in the stable oxidation state that the
redox reaction is not possible to occur.
Strategic engineering design and material selection
Proper selection of a material selection that corrosion does not occur is another way
that corrosion can be controlled.

4.0 Conclusion
As discussed in the results and discussion section, EIS, Tafel and LPR demonstrates
great deal of error that shows certain degree of deviation from the literature
reported value. This phenomenon is vividly shown when solution media was NaCl,
and as the literature value demonstrates as well, the reactivity of the sodium
chloride with the mild steel is very low. Such low corrosion rate trend is observable
with this experiment, but the numerical value of the actual corrosion rate contains a
lot of error. This is due to faulty performance of each testing device (EIS, Tafel and
LPR). Immersion corrosion testing might cause such deviation (by degree factor of
10) because of the faulty measurement of the mass.
Furthermore, difference of the density among the metal material is also related to
the corrosion rate. Observation from this experiment proves the fact that the higher
density of the metal has lower corrosion rate, and vice versa. This observation
alludes to the fact that the oxidation state of the metal and how closely packed the
metal ion are key factors that affects the corrosion rate
Concentration variation and its corrosion rate has been also studied. Higher the
concentration of the whichever the solution media (in this experiment, NaCl and
HCl) shows the higher corrosion rate. Presence of ions cause the redox reaction
vigorously and since the higher concentration of solution refers to large number of
ions present, the reaction will be much faster and prominent

5.0 Nomenclature
I corr=Corrosion current

=beta constant for cathodicanodic currents ( alsocalled SternGeary Constant )

RP = polarization resistance
A=active surface area

i corr =corrosion current density

CR=corrosion rate
Ew =equivalent weight
=density of the material

M w =molecular weight
n=normal oxidation state
m=mass of the material

t=time

6.0 References
[1] Noor, E. A., & Al-Moubaraki, A. H. (2008, May 29). Corrosion Behavior of Mild
Steel in Hydrochloric Acid Solutions.
[2] Baboian, R. (2005). Corrosion tests and standards: Application and
interpretation. West Conshohocken, PA: ASTM International.
[3] Mehra, R., & Soni, A. (2001, June 23). Mild steel deterioration with time in various
aqueous salt solutions.
[4] Effect of sodium chloride on corrosion of mild steel in CO2-saturated brines.
(n.d.). Retrieved September 27, 2016, from
http://link.springer.com/article/10.1007/s10800-011-0290-3
[5] Pritzker, M. (2015). Corrosion. In Elctrochemical Engineering: Course Notes (pp.
6.1-6.44).
Waterloo, Ontario: University of Waterloo.
[6] CORROSION Uniform Corrosion. (2010, February 12). Retrieved October 8, 2015,
from
http://www.scribd.com/doc/26756949/CORROSION-UniformCorrosion#scribd
[7] Corrosion Costs by Industry Sector. (2000). In Corrosion Costs and Preventative
Strategies in the United States (pp. 3-8). Houston, Texas: NACE International.

7.0 Appendicies
7.1 Sample Calculation
Using Tafel constants, calculation of i corr

I corr=

I corr=

anodic cathodic
2.303 ( anodic + cathodic ) R p

=i corr A

67.034167.890
=i corr 0.6881 c m2
2.303 ( 67.034 +167.890 ) 128.673

i corr , LPR, NaCl =0.235001475 mA /c m2

Using icorr, calculation of corrosion rate (NaCl, LPR)

CR ( Corrosion Rate )=

K 1 i corr Ew
mildsteel

K 1=3.27103
Ew =equivalent weight ,

M w 55.845
=
=27.9225 for mild steel
n
2

mild steel=7.85 g/c m3

CR LPR , NaCl=2.736885179mm / yr

Immersion corrosion testing, corrosion rate calculation (1M of HCl with mild steel)

time difference=t 2 t 1=110.15 hours

mass difference ( after cleansing )=m2m1 =3.4804 g
Corrosion Rate ( after cleansing ) =13.579933412mm / yr