Corrosion Engineering

Lecture 6
CHE 311
Corrosion electrochemistry
 Metallic corrosion has been defined in Note 2 as an electrochemical reaction,
involving the transfer of electrons.
Corrosion Rate for an alloy:
 Definitions
 ai = the atomic weight of the (i) species in the alloy
 ni = the number of electrons exchange of the (i) species in the alloy
 f i = mole fraction of the (i) species in the alloy

f ni
= number of equivalent of the (i) species in the alloy
i

a i

f n fi
 i i
 a =N = total number of equivalent
a i ni
EQ
i

1
The equivalent number, EW 
N EQ
Corrosion Rate for an alloy:
 Definitions
 ai = the atomic weight of the (i) species in the alloy
 ni = the number of electrons exchange of the (i) species in the alloy
 f i = mole fraction of the (i) species in the alloy

The corrosion rate of any alloy may be estimated

(i) (EW)
C.R. = C
D av

D av   fi Di

i = the current density in A / cm2 , C: constant

Two common equations for the corrosion rates of an alloy are:

1- C.R. in mpy = 1.287 x 105 (i) (EW) / Dav

1- C.R. in mmy = 3.27 x 103 (i) (EW) / Dav

Corrosion Rate for an alloy: Example 1
 A specimen has a surface area of 100 in2. Weight loss = 7.3216 grams for 50 days.
Find the C.R. in mdd
Corrosion Rate for an alloy: Example 1
 A specimen has a surface area of 100 in2. Weight loss = 7.3216 grams for 50 days.
Find the C.R. in mdd.
 Solution:

2
(100) (2.54) (2.54) cm 2
 A = 100 in2 =  6.4516 dm
(10) (10) cm 2 dm 2

 W = 7.3216 gram = 7321.6 milligrams

W
 C.R. = (A) (T)

7321.6 mg
 22.6970 mdd
 C.R. = (6.4516 dm 2) (50 days)
Corrosion Rate for an alloy: Example 2
 What is C.R. in mpy if the specimen in Example 1 is from steel?
Corrosion Rate for an alloy: Example 2
 What is C.R. in mpy if the specimen in Example 1 is from steel?
 Solution:

1.437 ), gm
 (
C.R. = mdd D for steel, D = 7.87 cm3

1.437
 C.R. = (22.6970) 7.87 = 4.1443 mpy

To get mdd To get mpy

Multiply by Multiply by
mpy 0.696 D mdd 1.437/D
ipy 696 D ipy 1000
mmy 27.4 D mmy 39.4
Corrosion Rate for an alloy: Example 3
 What is the corrosion current density in A/cm2 for zinc corresponding to a corrosion
rate of 0.05 ipy.
Corrosion Rate for an alloy: Example 3
 What is the corrosion current density in A/cm2 for zinc corresponding to a corrosion
rate of 0.05 ipy.
 Solution:  

 ipy = 1.287  102 i M/n  D

 Required data: M = 65.37 g/mole

 n=2 , D = 7.14 g/cm3

0.05 = 1.287  102 (4.57773)(i)

i = 0.8487  10-4 A/cm2 = 0.8487 A/m2

Corrosion Rate for an alloy: Example 4
 A zinc specimen exposed to an acidic solution loses 25 milligrams during 12 hours
exposure:
 (a) What is the equivalent current flowing due to corrosion?
 (b) If the specimen area is 200 cm2, what is the corrosion rate in mdd?
 (c) What is the corrosion rate in mpy?
 Solution:
 a)  m = kIt k= M
nF
 Δm = (net mass produced or consumed) in grams
 I = current in amperes (A)
Metal n Mwt K (g/C)
 k = electrochemical equivalent
Fe 2 55.84 2.893E-4
 t = time (seconds)
Zn 2 65.38 3.39E-4
 F = Faraday = 96500 C/eq
Al 3 17.98 6.21E-5
 M = molecular weight
Corrosion Rate for an alloy: Example 4
 A zinc specimen exposed to an acidic solution loses 25 milligrams during 12 hours
exposure:
 (a) What is the equivalent current flowing due to corrosion?
 (b) If the specimen area is 200 cm2, what is the corrosion rate in mdd?
 (c) What is the corrosion rate in mpy?
 Solution:
 a)  m = kIt k= M
nF
3
 m = 2510 grams

 M = 65.37 g/mole, t = (12 hr)(3600 s/hr) = 43200 s, n = 2, F = 96500 C/ eq

 k = 3.387E-4
 I = 1.707E-3 A
Corrosion Rate for an alloy: Example 4
Weight loss
 b) C.R.= (Time) (Area)
 To obtain C.R. as mdd, we need the following data
 Weight loss = (mg) = 25 mg
 Time in days = 12/24 = 0.5 day
 Area in dm2 = 2 dm2
 Answer C.R. (mdd) = 25 mdd
Corrosion Rate for an alloy: Example 4
 c) mpy = 1.287  105 i M/n  D
 
3
I 1.707 10 xD
i= = = 8.55  103 A cm2
A 200

M = 65.37 g/mole , n=2 , D = 7.14 g/cm3

C.R. (mpy) = 5.04 mpy

Corrosion Rate for an alloy: Example 5
 Calculate the C.R. for 304 SS alloy in mpy equivalent to 1 µA/cm2 ?
 The alloying elements of SS 304 are
 19% Cr, 9.25 % Ni balance = Fe (other elements are small <1% )

Element fi ni ai Di (g/ cm3)

Cr 0.19 3 52 7.1
Ni 0.0925 2 58.71 8.9
Fe 0.717 2 55.85 7.87
Corrosion Rate for an alloy: Example 5
 Calculate the C.R. for 304 SS alloy in mpy equivalent to 1 µA/cm2 ?
 The alloying elements of SS 304 are
 19% Cr, 9.25 % Ni balance = Fe (other elements are small <1% )
Element fi ni ai Di (g/ cm2)
Cr 0.19 3 52 7.1
Ni 0.0925 2 58.71 8.9
Fe 0.717 2 55.85 7.87

 Solution:
0.19*3 0.0915*2 0.717*2
N EQ  52

58.71

55.85
 0.03981

1 1
EW = N EQ  0.03981  25.12 1- C.R. in mpy = 1.287 x

D av
 (0.19  7.1)  (0.0925  8.9)  (0.7175  7.87)  7.82 g/cm

6 2
5 (1  10 A cm ) (25.12)
C.R =1.28  10
7.82
C.R = 0.413 mpy
Guidelines for the Corrosion Rate
 For handling chemical media whenever the attack is uniform, metals are classified
into three groups according to their corrosion rates and intended application.
 These classifications are as follows:
 a) When the C.R. < 0.15 mm/y (<0.005 ipy) — Metals in this category have good corrosion
resistance to the extent that they are suitable for critical parts, for example: valve seats,
pump, shafts , impellors and springs.
 b) When the C.R. is in the range of 0.15 to 1.5 mm/y (0.005 to 0.05 ipy). Metals in this
group are satisfactory, if a higher rate of corrosion can be tolerated, for example: Tanks,
piping, valve bodies, and bolt heads.
 c) When the C.R >1.5 mm/y (> 0.05 ipy) — usually not satisfactory.
Corrosion rate
 Faraday's Law:  m = kIt

k= M
nF
 Where:
 m = (net mass produced or consumed) in grams
 I = current in amperes (A)
 k = electrochemical equivalent
 t = time (seconds)
 F = Faraday constant = 96500 C/eq
 M = molecular weight

 Few values for k

Metal n Mwt K (g/C)
Fe 2 55.84 2.893E-4
Zn 2 65.38 3.39E-4
Al 3 17.98 6.21E-5
Corrosion rate
 Faraday’s equation
 G = E * (- n F)
 Where:
  G = Free energy change of the corrosion process.
 E = Potential (Volts)
 n = The number of electrons transferred in the corrosion reaction.
 F = Faraday = 96484 C/eq.
 1 mole of metal of valence n converted into ions gives n x 96494 C.
Corrosion Rate Calculations
 Corrosion rate can be expressed in different ways. The most common ways are:
 Weight loss.
 Penetration loss.
 Corrosion current.

 1- Weight Loss: The initial and final weight of a coupon is measured. The corrosion
rate (C. R.) expression is based on this weight loss, the time of exposure and the
area of the coupon. The rate expression
Weight is
loss
C.R.= (Time) (Area)

 The weight loss gives the average corrosion rate.

 Two common units
 1. Milligrams per day per square decimeter (mdd)
 2. Grams per square meter per day (gmd)

 Conversion factor: 10 mdd = 1 gmd.

Corrosion Rate Calculations
 2- Penetration loss: This method is based on the loss of thickness. The
corrosion rate expression is
Thickness loss
C.R.= Time
 The most common used units are mils per year (mpy), inches per year
(ipy), and millimeters per year (mmy).
 Some conversion factors between the weight loss and penetration loss are
presented

To get mdd To get mpy

Multiply by Multiply by
mpy 0.696 D mdd 1.437/D
ipy 696 D ipy 1000
mmy 27.4 D mmy 39.4

 1 mil = 0.001'' = 0.025mm

 40 mils = 1mm
 D is the density in g/cm3


Corrosion Rate Calculations

   Corrosion current: The corrosion current (Icorr.) can be obtained from
3-
the knowledge of the theoretical weight loss ( m) and the time (t) of exposure
according to Faraday's law:

m = (k) (t) (Icorr)

 Where m in grams, t, in seconds, k is the electrochemical equivalent in
grams per coulomb (g/C). Few relations are obtained between corrosion rates
and current.

Where, I is the current density in A/cm2, M is the atomic weight and n is the
oxidation state.