MT 243 LABRORATORY EXPERIMENTS IN

METALLURGY

REPORT OF OXIDATION OF NICKEL

INSTRUCTOR: ALOKE PAUL

SUBBMITTED BY:

GROUP 5
Akshay Pakhare (12165)
Ankush Raina(12314)
Gollapalli Prince(12303)
Harish Kumar(12079)

Aim :
Oxidation Behavior of Nickel at high temperature.
To determine the Activation energy for growth of Nickel oxide layer by interdiffusion of oxygen and nickel.

Materials and Equipments Used:

Furnace, Polishing machine, Emery papers, Optical microscope, SEM, Aluminum foil,
Carbon tape, Colloidal silica, Nickel sample (99.9% purity), SEM, Mounting machine and
Gold sputtering machine.

Experimental Procedure:
1.) The given Nickel sample was polished on both sides with silicon carbide emery paper
(grid size P800 to P3000).
2.) The sample was cleaned with acetone to remove any grease, dirt etc. and placed in the
furnace.
3.) The furnace temperature was set to 1100 oC and a holding time of 9 hrs.
4.) The sample was cut and mounted for polishing.
5.) Polishing was done on emery paper (grid size P800 to P3000) and lapping was done with
colloidal silica.
6.) The sample was wrapped with Aluminum foil and Carbon tape.
7.) Gold sputtering was done on the sample for Electrical conductivity for SEM analysis.
8.) Sample was observed under SEM and the oxide layer thickness was measured.

Theory:
The high temperature oxidation of nickel is considered as a model system because of growth of
NiO scale assumed to be controlled by the outward diffusion of ion. There is oxygen penetration
and formation of duplex morphology in the diffused layer which generally composed of small
equiaxed grains at the metal oxide interface and columnar grain at external part.The formation of
the duplex morphology as discussed is due to the growth stress led to oxide separation from the
metal due to insufficient oxide plasticity.In another model discussed by Gibbs and Hales oxygen
penetrates the scale via pores,which were formed by vacancy and dissociation of oxide.The
observation of Peraldi says that the formation of oxide was not only due to outward diffusion of
nickel but also due to inward diffusion of oxygen.[1]

The growth of NiO follows the parabolic law. In this interdiffusion process the rate of increase is
inversely proportional to the thickness layer .The amount of flux decreases with the increasing layer
thickness because the diffusing atoms have to travel longer distances.[2]
Therefore

dx 1

dt x

Solving this we get x2 = 2Kpt

Where x = thickness of the oxide layer
T = time of oxidation
Kp = Parabolic rate constant
The parabolic rate constant varies with temperature as an Arrhenius type relation as

Q
RT
()
K p=K 0p exp
Where Q = Activation Energy for oxidation
R = Gas constant
T = Temperature of oxidation.

Results and Discussion:

Fig 1. SEM micrographs of Nickel for 1000 oC

Fig 2. SEM micrographs of Nickel for 1050 oC

Fig 3.SEM micrographs of Nickel for 1100 oC

The average thickness value of oxide layer was calculated for each micrograph and was averaged over all
micrographs at that particular temperature. The thickness is increased as the temperature increases. From
the average layer thickness value we calculated the Kp values for each temperature. The graph of ln Kp vs
1/T was plotted . The slope of the graph gives the - Q/R .Hence we obtain the value of activation energy
Q.
Table 1. Thickness and Calculated Values of Kp
Sr. No.
1
2
3

T (oC)
1000
1050
1100

T (K)
1273
1323
1373

X(m)
26.22
57.42
80.99

Kp(m2/s)
1.06E-14
5.08E-14
1.01E-13

ln(Kp)
-32.177
-30.609
-29.921

1/T(K-1)
0.000785
0.000755
0.000728

Activation Energy Calculation:

Slope Q/R = -39602.25
Activation Energy Q = 39602.5 * 8.314 = 329.255 KJ/mol.
Standard Error = 8017.54 * 8.314 = 66.65 KJ/mol

Ni

Ni

Fig. 4 Oxide Layer formed at 1100 oC at 1000x

The duplex morphology of the nickel oxide is not clearly visible

Conclusions:
The activation energy calculated is 329.255 KJ/mol with standard error of 66.65 KJ/mol.
The duplex morphology is not clearly visible.

References:
1. S. Chevalier ,F.Desserry ,J.P.Larpin, Oxygen Transport during the High Temperature
Oxidation of Pure Nickel, Oxidation of Metals, Vol. 64, Nos. 3/4, October , 2005.
2. Aloke Paul, Tomi Laurila, Vesa Vuorinen, Sergiy V. Divinski , Thermodynamics,
Diffusion
and the Kirkendall Effect in Solids:Springer .