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The Effect Of Heat Treatment On The Corrosion And Electrochemical Properties Of

Ferritic-Austenitic Stainless Steel In Sulfuric Acid Solution


Mosaad Sadawy, Taher Shirinov, Rafik Heseinov
Faculty of Metallurgy, Azerbaijan Technical University, Baku, Azerbaijan
e-mail: mosaadsadawy@yahoo.com
Abstract
The effect of heat treatment on the corrosion and electrochemical
properties of Ferritic-Austenitic stainless steel has been investigated in sulfuric
acid solution. The specimens were first heat treated at 1050 0C for 2 hours,
followed by quenching in distilled water, and then specimens were annealed
between 500-800 0C for 2 hours. Weight loss method was used to study the
speed of corrosion. Potential-time and potentiodynamic polarization techniques
were used to investigate the electrochemical properties. The results indicated
that, solution heat treated and as-received specimens gave the best corrosion
resistance, while the annealing process has an adverse effect on ferriticaustenitic stainless steel, indicating that corrosion current increased by
increasing the annealing temperatures.
Introduction
Ferritic-austenitic stainless steels are modern materials characterized by
very good mechanical properties with good corrosion resistance. Therefore,
they find many applications in the petrochemical and offshore structure
industries[1]. Corrosion resistance of this group is determined by the stability
of the passive film, alloy chemistry, heat treatment and precipitation
morphology [2].
The corrosion of stainless steel in acidic solutions is a fundamental academic and industrial
concern that has received a considerable amount of attention. Acidic solution of sulfuric acid
have wide industrial applications, the most important fields being acid pickling,
acid descaling, industrial cleaning and oil-well acidizing [3]. Therefore the objective
of this study is to investigate the effect of heat treatment on the corrosion and electrochemical
properties of ferritic-austenitic stainless steel in acidic solution of 5% wt. H2SO4 .
Experimental work
Material
The present study was carried out using ferretic-austenitic stainless steel. Its chemical
C
0.09

Cr
19.833

Ni
6.833

Mn
0.215

Si
0.603

S
0.001

P
0.023

Ti
0.39

Fe
balance

composition was analyzed by X-ray fluorescence and it is shown in Table 1.


Table 1 Chemical composition (wt %) of the investigated alloy

Heat Treatment Technique


The heat treatment was carried out in a muffle furnace. The temperature of the furnace was
regulated using a temperature regulator of accuracy 100C coupled with thermocouple (K-Type) to
give the actual sample temperature. The received samples were first heat treated at 1050 0C for 2
hours then they removed and directly quenched in the distilled water for 5 minutes at agitation of

500 r.p.m. After that, these samples were tempered at 500, 600, 700, 800 0C respectively for 2
hours and cooled in water.

Weight-Loss Technique
The specimens were cut from sheet to a dimension of 5*5*25 mm. They were then grounded
with silicon carbide abrasive papers of 320, 600, 800 and 1200 grit sizes respectively and finally
degreased in acetone. The coupons were rinsed with distilled water, dried and then weighed before
exposure. Before recording the mass change, the specimens were chemically cleaned according to
ASTM Standards G1 and G31. The acidic solution of 5% wt. H2SO4 was prepared with distilled
water and analytical grade chemicals.
Electrochemical Technique
For electrochemical analysis, the specimens were polished to 1200 grit sizes and then
cleaned with distilled water. Potentiostat-model (PI-50-1) was used in determining corrosion
kinetics and speed of total dissolution in active, transitive and passive areas of potentials. Prior to
electrochemical tests, the specimens were cathodically cleaned for 15 min at -0.60 V Ag/AgCl to
remove the air-formed oxide film. A three-electrode cell composed of a specimen as a working
electrode, Pt counter electrode, and Ag/AgCl reference electrode were used for the tests.
Polarization tests were carried out at a scan rate of 12 mV/min in 5% wt. H2SO4 solution at 25 C.
Specimens with exposed surface area of 0.35 cm2 were used as a working electrode.
Results and Discussions
Weight-Loss Measurements
Figures 1 shows the speed of dissolution of as-received and heat treated specimens in 5%
wt. H2SO4 and solution by weight-loss method. It can be seen from this Figure that the speed of
dissolution of solution heat treated and as-received samples give the lowest speed while it increases
by increasing tempered temperatures. This is due to at temperature above 1035 0C chromium
carbide are completely dissolved in austenitic stainless steels. However, when these steels are
reheated into the range of 500 to 800 0C, chromium carbide precipitates at the grain boundaries and
its concentration increases by increasing temperature [ 3 ]. This precipitation of carbide depletes
chromium adjacent to the grains boundary and the alloy is sensitized to intergranular corrosion or it
forms a concentration cell, in which the depletion zone works as anode and rich chromium zone
works as cathode. Thus, the corrosion attack occurs predominantly.
Electrochemical Behavior
PotentialTime Behavior
Figure 2 shows the change of the open-circuit potential of as-received
and heat treated samples at different conditions in 5% wt. H2SO4 solution. The
recorded results reveal that the corrosion potential of solution heat treated and asreceived are nobler than the tempered specimens which exhibit more negative open circuit potential
values by increasing their tempered temperatures. This behavior for tempered samples is attributed
to a depletion of chromium which causes weakness in the passive film [2]. Comparing the
results in Figure 2, it can be noticed that the corrosion potential increases very
fast towards more noble values. This means that the passive film in this solution stable
thermodynamically [1]. In general, a more positive corrosion potential means that the metal

can be expected to be more resistant to corrosion in that particular electrolyte than one with a more
negative corrosion potential.

-1050/800 0C / 2h
-1050/700 0C / 2h
-1050/600 0C / 2h
-1050/500 0C / 2h
- as-received
-heat treated at 1050 0C

Figure 1 Weight loss-time curves for the corrosion of the investigated alloy in 5wt. %
H2SO4 at different heat treatment

-1050/800 0C / 2h
-1050/700 0C / 2h
-1050/600 0C / 2h
-1050/500 0C / 2h
- as-received
-heat treated at 1050 0C

Figure 2 Potentialtime curves for stainless steel in 5wt. % H2SO4 solution


Electrochemical Polarization Behavior
Figure 3 shows the potentiodynamic polarization curves of austenitic stainless steel in
sulfuric and hydrochloric acid solutions. The cathodic polarization curves show a regular pattern
and the current densities increase in solution heat treated and as-received samples. The curves are

also associated with hydrogen evolution. Therefore, the cathodic reaction was considered to be the
hydrogen evolution reaction, the predominant reaction in acidic solution.
Additionally, the cathodic and anodic polarization curves show that with an increase in
tempered temperatures from 500 to 800 0C the corrosion potential shifted to more active potential
regions and consequently the corrosion current density increased significantly in both solutions.
This is attributed to the precipitation of carbide which depletes chromium [2].
Figure 4 illustrates the anodic dissolution curves of austenitic stainless steel in 5% wt.
H2SO4 for as-received and heat treated samples at different temperatures. The Figure shows that all
anodic curves reveal active, passive and transpassive behavior; however the current densities in the
passive range were much lower for the solution heat treated and as-received samples, indicating the
formation of a more protective film on the solution heat treated and as-received samples than on
those that were tempered samples . It can be seen also from this Figure that, with increase in
tempered temperatures from 500 to 800 0C, the critical current density grows and the active
dissolution region extended.
-1050/800 0C / 2h
-1050/700 0C / 2h
-1050/600 0C / 2h
-1050/500 0C / 2h
- as-received
-heat treated at 1050 0C

Figure 3 Effect of heat treatment on the cathodic- anodic behavior of austenitic


stainless steel in 5% wt. H2SO4 solution

-1050/800 0C / 2h
-1050/700 0C / 2h
-1050/600 0C / 2h
-1050/500 0C / 2h
- as-received
-heat treated at 1050 0C

Figure 4 Effect of heat treatment on the anodic dissolution of austenitic stainless steel
in 5% wt. H2SO4 solution.

Conclusions
From the above given study it could be concluded that:
1-The speed of dissolution and the corrosion current of the tested steel increased by increasing the
tempering temperatures in the tested solution.
2-The region of passivity decreases with increasing in sensitized temperatures in 5% wt. H2SO4
solution.
References
[1] Y. Zhang, X. Zhu, Electrochemical Polarization And Passive Film Analysis of
Austenitic Fe-Mn-Al Steels in Aqueous Solutions, Corro. Sci.,Vol. 41, 1999 ,
p.1817-1833
[2] N.Chermat and R. Kesri, Corrosion-Electrochemical Behavior of 13%
Chromium (Cr) Martensitic Stainless Steel in Hydrochloric Acid (HCl) Solutions,
Protec. of Met., Vol. 43, (No. 4), 2007, p. 344352
[ 3] V. Singh and M. Ray, Effect Of H2SO4 Addition on The Corrosion Behaviour
of AISI 304 Austenitic Stainless Steel in Methanol-HCl Solution,
Int. J.
Electrochem. Sci., Vol. 2, 2007, p. 329 340
[4] A. Aldykiewicz and H . Isaacs, Dissolution Characteristics of Duplex Stainless
Steels in Acidic Environments, Corro. Sci.,Vol. 39, (No.9), 1999 , p.1627-1647

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