International Journal of Computation and Applied Sciences IJOCAAS, Volume2, Issue 2, April 2017, ISSN: 2399-450
Effect of sensitization on microhardness and corrosion
resistance of austenitic stainless steel
Shukur F. Hasan& Sami I J. Alrubaiey
Abstract-This study presents the results of research for micro
hardness and corrosion behavior of ASTM 304 stainless steel by
investigating and performing the pitting corrosion 1N H2SO4 as a
function of heating temperature (500, 600, 700, 800, 900) C.
Different amounts of carbides precipitated in the austenitic
stainless steel. These precipitates are one of problems with
austenitic stainless steel due to the formation of extreme pitting
corrosion. The current pitting corrosion density for heated
stainless steel at 900 C is greater than that of non-heated
specimen by about 34% in 1N H2SO4. The pitting potential of
heated stainless steel at 900 C is more negative than that of non-
heated specimen by a value of 284 mV. This means that the
increase in heating temperature led to the increase of pitting
intensity.
Keywords:Corrosion resistance,austenitic stainless steel,
sensitization, hardness, Cr-carbides
I. INTRODUCTION
AISI 304 stainless steels are used in a wide range of
applications like chemical, petrochemical, medical and kitchen
equipment because of their good mechanical properties and
excellent corrosion resistance [1, 2]. Most of these
applications are done at higher temperature, which leads to
formation of sensitization phenomena, and the sensitization
generally takes place in the range of temperature (500-900) C.
These phenomena are considered as a susceptible reason for
pitting corrosion [3, 4]. At the sensitization range, the
dissolved carbon in the microstructure would pull the
chromium to forms several chromium carbides, depending on
the annealing temperature along the grain boundaries. At the
same time, a depletion zone of chromium would take place
inside the microstructure. These two phenomena (carbide
precipitation and Cr-depletion zone) are considered as the
main reason for formation of pitting corrosion [5, 6]. A
various of phases may accelerate in the different classes of
stainless steels, particularly AISI 304. Some of these phases,
similar to the Cr7C3, Cr23C6, might be the basic to all classes;
however, some of them are most certainly not [7, 8]. The
corrosion resistance of AISI 304 is analyzed to study the effect
of temperature by using Tafel extrapolation method. It
becomes clear that the best methods to study the
susceptibilities to this form of corrosion are the Tafel
extrapolation method.
II.EXPERIMENTAL METHODS
2.1 Sample preparation
The samples were prepared by cutting into square shape with
1.5 mm and thickness of 2 mm followed by grinding with
different metallographic paper SIC and it has been refined by
polishing paper assistance of cloth Damon and refine oil to
polish the surface of samples. The samples have been clean
and dried. Etching has obtained for the purpose of showing the
microscopic structure using chemical solution, consisting of
50 ml HNO3 and 50 ml HCL. Finally was washed with water
samples and alcohol and then dried by dryer.
2.2 Chemical Compositions
The chemical compositions of stainless steel 304 were carried
out by using oxford instruments product of foundry Master
Xpert Company.
2.3 Heat treatment
Heat treatment was done at rang of temperature in order to
make it sensitive to produce chromium carbides in the
structure. The samples were placed inside the furnace for
heated to several different temperatures from (500, 600, 700
and, 800, 900) oC respectively. Use thermal furnace
(CARBOLITE FURNACE). The installation was for an hour
of time then were cooled slow cooling inside the furnace to
room temperature.
2.4 Corrosion Test
Cyclic Polarization test was performed using Tafel
extrapolation method to investigate pitting corrosion
properties of sensitized specimens. Sulfuric acid solution was
prepared. This acid diluted to 1N aqueous solution of
H2SO4.Equation was used to calculate corrosion rate as
follows: [9].
CR (mpy) =0.13 Icorr. . e/D.(1)
Where:
Icorr : Corrosion current density A/cm2.
e: Equivalent weight (for steel =25.5). g.equivalent
D: Density of metal (for steel =7.9 gm/ cm3) [10]
2.5 Digital Planimeter
To measure the hysteres loop area of cyclic polarization curve.
It represented the energy for pitting corrosion occurrence in
samples of stainless steel. By using a digital planimeter model
(BLCOM-KP-90N-NO.H12556),
2.6 Microhardness Test
Microhardness values were calculated as for receive sample,
sensitive samples and after corrosion. The test force was (9.8
N + 1 Kg) for (20 sec). The average of 3 readings of the
International Journal of Computation and Applied Sciences IJOCAAS, Volume2, Issue 2, April 2017, ISSN: 2399-450

indentation length was taken. The Vickers microhardness
(HV) was calculated according to the following equation [11]:
HV = 1.8544 p/ d2... (1-2)
Where,
boundaries are increased with increasing of the annealing
temperature. This condition can be attributed to the formation
of coherent precipitation of Cr23C6, Cr7C3, Cr2.9C as indicated
in XRD.

P = Applied load, kgf.

d = The mean diagonal of the indentation, mm

III. RESULTS AND DISCUSSION

3.1 Chemical composition

Table (1) represent the chemical composition of samples

which were used in this investigation, and by comparing these
percentages with standard we can conclude that the sample is
austenitic stainless steel type 304.

TABLE 1

CHEMICAL COMPOSITION OF SAMPLE

Fig. 1Microstructures after heat treatment at 400X

3.3 Corrosion behavior results

Table (3) represents the parameter that we got from the

3.2 Effect of Heat Treatment on Microstructure of 304
Stainless Steels
Figure (1) shows the microstructure of 304 stainless steel in
the as received condition. From this figure, it can be seen that
the microstructure has fine and homogenous grains of
austenitic stainless steel. There are no carbides on the grain
boundary.
The effect of temperatures of annealing on the microstructure
of stainless steel showed that as temperature increases, the
microstructure becomes non-homogeneous due to chromium
carbides precipitation at grain boundaries. The small numbers
of coarse chromium carbide precipitations were observed at
the grain boundaries. It is appeared as dark areas in the optical
microstructure. The more carbides get at high annealing
temperature (900 C) as shown in fig. (1). The areas of grain
boundary have different colors. The dark area indicated to
carbides. These areas became darker as the temperature of
annealing was increased. These indicated to more precipitation
carbides. The density and size of precipitation at the grain
polarization curve. The correlation between microstructural
and pitting corrosion resistance proved that unsensitized
structure had low susceptibility to pitting corrosion. It can be
seen that the heating temperature has a great effect on the
corrosion of AISI 304 stainless steel in 1 N H2SO4. As heating
temperature increases, the corrosion current density increases
also. As increase in sensitization temperatures the nucleation
of pitting corrosion increase. When sensitization temperature
increase the surface introduced more pitting corrosion in the
body of grain and in the grain boundary. Show that the surface
interdusing intergranular corrosion when sensitized
temperature increase .The hysteresis loop area of 304 stainless
steel specimen sensitized at 900 C decreased to 9.3simulated
by cm2,which represents the energy required to the emergence
of pitting corrosion which is less than the required energy to
emergence of pitting corrosion the as received, sensitized
specimen.
 International Journal of Computation and Applied Sciences IJOCAAS, Volume2, Issue 2, April 2017, ISSN: 2399-450

Potential [mV]
Potential [mV]

As received AT 800C
As receiv
received ed

Current [mA/cm] Current [mA/cm]

Potential [mV]

Potential [mV]
AT 500C AT 900C

receiv receiv
ed ed

Current [mA/cm] Current [mA/cm]

Fig. 2 Corrosion behavior of austenitic stainless steel sensitized at different

Potential [mV]

condition in 1N H2SO4
AT 600C
receiv C ONDITION As At At At At At
ed PARAMETER reseived 500C 600C 700C 800C 900C

Io mA/cm2 2.6*10-3 9.5*10-3 2.5*10-2 1.3*10-1 1.4*10-1 7.5*10-1

o
E mV -381 -400 -418 -452 -500 -506
Icorr.mA/cm2 2*10-2 3.5*10-1 5.8*10-1 2*100 5*100 9.5*100
E corr. mV -411 -425 -431 -478 -503 -520
Ipit mA/cm2 9*10-1 6*100 1.3*101 6.7*101 9.6*101 2.6*102
E pit mV 1010 978 946 886 811 726
Area under 26.7 20.1 17.9 15.9 15.1 9.3
the curve
Current [mA/cm]
corrosion 0.0083 0.1468 0.2433 0.8390 2.097 3.985
rate (mpy)
Potential [mV]

AT 700C 3.4 Microhardness Results

receiv
Figure (1.3) exhibits the microhardness results for austenitic
ed stainless steel AISI 304 samples sensitized with various heat
treatment conditions, that shown in blue coloure.And, the
microhardness results for samples after corrosion test are
shown in red coloure. The microhardness of as-received
specimen has an average value of 164.3Hv. The average
microhardness was increaseto171.4Hv, 176.3Hv and 184.6Hv
for sensitized specimen at 500 C, 600 C, and 700 C,
recpectively. The increase on microhardness can beascribes
Current [mA/cm] the formation of carbide chromium in boundary of sensitized
specimen at this teamperature. The precipitated of chromium
International Journal of Computation and Applied Sciences IJOCAAS, Volume2, Issue 2, April 2017, ISSN: 2399-450

carbide imped movement of dislocation and reduce the flaw Reference

within crystals lattice.
Moreover, the movement of flaw is often indicate as the
predominant carriers of plasticity and materials ductility
hugely be based on the easiness of crystal lattice flaw could be
propagate. However,the average microhardness was riseseto
186.02Hv and 187.4Hv for sensitized specimen at 800 C
and900C, recpectively. This increase in micro hardness could
be attributing to increase the amount of carbides and
chromium depletion in zone.
The average microhardness results for as received samples
decrease after corrosion. Its value is 161.1Hvdue to the
occurrence of pitting corrosion. The average microhardness
for sensitized specimen after corrosion test decrease to
167.8Hv,170.9Hv,179.5Hv,183.22Hv and 183.9Hv at 500 C,
600 C,700 C, 800 C and 900 C, recpectively. This decrease
caused by intergranular and pitting corrosion and for
chromium depletion zones that became weak.
190 184.6 186.02 187.4
180 176.3
171.4
170 164.3
160
Hardness [Hv]
[1] J. R. Davis, "Heat-Resistant Materials", ASM Specialty Handbook,
ASM International, 1997.
[2] W. Ozgowicz, A. Kurc, and M. Kciuk, "Effect of deformation-induced
martensite on the microstructure, mechanical properties and corrosion
resistance of XCrNi18-8 stainless steel", International Scientific
Journal, vol.43, pp. 42-53, 2010.
[3] A. Philip, P. E.Schweitzer,"Metallic Materials: Physical, Mechanical,
and Corrosion Properties", Marcel Dekker, Inc, 2003.
[4] ASM Specialty Handbook": Steels 2- Volume Set Description Your
Single Resource for Stainless, Sep.21-25, 2009.
[5] R. K. Singh, R. Kumer, "Study of corrosion and corrosion protection of
stainless steel in phosphate fertilizer industry", American Journal of
Mining and Metallurgy, vol. 2, No. 2, pp. 27-31, 2014.
[6] P. de lima-Neto, J. P. Farias, L.Flavo, G. Herculano, C. Helio, W. S.
Araujo, J.Jorence and N.Pebere, "Determenation of the sensitization
zone extension in welded AISI 304 stainless steel using non-destructive
electrochemical techniques", Corrosion Science, vol. 50, No. 4, pp.
1149-1155, 2008
[7] D. Llewellyn and R.Hud ,"Steels Metallurgy and
Applications",Butterworth-Heinemann, 1998.
[8] N. Srisuwan,"Investigation of chromium carbide precipitation and
corrosion behavior on stainless steel AISI 304 for welding process
development", The 2nd RMUTP International Conference, pp.102- 107,
2010.
[9] Fontana and Green," Corrosion Engineering", McGraw-Hill, 1978.
[10] A. Etor, "Electrochemical measurement of crevice corrosion of type

aisi304 stainless steel", PhD. Thesis, University of Saskatchewan,

150 November, 2009.
140 [11] ASM International, Volume 8, Stainless Steel Grades Mechanical
130 Properties, 2004.
25 500
600 700
800 900
sample conditions [c]

Fig. 3 Microhardness chart results

IV.CONCLUSIONS

1. Temperature affects the nature of the corrosion in stainless

steel 304 in terms of original positions devoid of it and the
formation of chromium depletion zones. The chromium
depletion zones are being corroded. When sensitization
temperature rises (500-900) C, Cr carbides will be
precipitated at grain boundary, therefore pitting corrosion
increases as the temperature increases.
2. The pitting corrosion can be occurred by two mechanisms
as follows:
A) As a result of the interaction of carbon with chromium
at the grain boundaries and depletion of Cr that takes
place depending on the carbides formations.
B) Due to the carbides precipitation on the grain boundary,
a galvanic effect will be occurred between carbides and
matrix due to the difference in the electromotive force
that leads to pitting corrosion.
3. The energy to pitting initiation which is measured by the
area of the loop indicated that the pitting corrosion needs
less energy to occur as temperature increases from 500 to
900 C.
4. Hardness increased as sensitization temperature increased
from 500 to 900 C and increased also after corrosion
during this range of temperatures.