Materials Today: Proceedings xxx (xxxx) xxx

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Materials Today: Proceedings

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Effect of TiN addition on corrosion behavior of spark plasma sintered

304L austenitic stainless steel in chloride media
Samuel Olukayode Akinwamide a,⇑, Ojo Jeremiah Akinribide a, Marcia Mafafo a, Mjwana Phumlani a,
Babatunde Abiodun Obadele a, Bolanle Tolulope Abe b, Peter Apata Olubambi a
a
Centre for Nanoengineering and Tribocorrosion, School of Mining, Metallurgy and Chemical Engineering, University of Johannesburg, Johannesburg 2094, South Africa
b
Tshwane University of Technology, Pretoria 001, South Africa

a r t i c l e i n f o a b s t r a c t

Article history: The corrosion hazards emanating from industries where the use of stainless steel is inevitable has led to
Received 15 September 2019 the development of materials which are capable of withstanding corrosive environments. In addition to
Accepted 10 October 2019 specimen sectioned from a hot rolled austenitic stainless-steel plate, the effect of different weight per-
Available online xxxx
centages (2, 4 and 6%) of titanium nitride (TiN) reinforcement addition on the corrosion property of sin-
tered austenitic stainless steel were investigated in 3.5 wt% NaCl electrolyte. Chronopotentiometry and
Keywords: potentiodynamic polarization techniques were used in analysing the corrosion resistance of specimens
Corrosion
in the electrolyte. Optical micrographs from a high-resolution microscope showed the formation of more
Stainless steel
Titanium nitride
pits on the substrate surfaces of hot rolled and unreinforced sintered specimens, while fewer or no pits
Chronopotentiometry were observed on specimens with TiN addition. The corrosion potentials and current densities of speci-
Potentiodynamic polarization mens obtained from chronoamperometry and potentiodynamic polarization plots further confirmed an
improvement in the corrosion resistance of specimens with 2 and 4 wt% TiN reinforcement.
Ó 2019 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of ‘‘Peer-review under responsibility of the scientific
committee of the 2nd International Conference on Recent Advances in Materials & Manufacturing
Technologies.

1. Introduction improve the corrosion resistance of the resulting composite. Tita-

Austenitic stainless steel is famous for exhibiting a combination
of improved mechanical properties and corrosion resistance. This
has made them a choice material in chemical, nuclear, automobile
and food industries [1]. Powder metallurgy which is a suitable
technique has been widely adopted for the fabrication of compo-
nents which requires a good surface finish and reduced porosities.
In comparison to other conventional methods such as spray depo-
sition [2] and casting [3], powder metallurgy technique offers sev-
eral advantages which include excellent dimensional precision, net
shape abilities, provision of fabricated material with a refined and
homogenous mixture [4].
The reinforcement of metals using nanoceramics to improve its
corrosion resistance has become a global area of interest which is
currently been explored by researchers. The use of titanium nitride
(TiN) as reinforcement in the metal matrix has been reported to
⇑ Corresponding author.
E-mail address: akinwamidekayode@gmail.com (S. Olukayode Akinwamide).
nium which is a highly reactive metal is known for its excellent
corrosion resistance properties as a result of its ability to form pas-
sive films rapidly in corrosive media. Also, the incorporation of
nitrogen into the bulk of stainless-steel during fabrication has been
reported to improve the corrosion resistance of the resulting mod-
ified stainless steel. Titanium nitride (TiN) exhibits excellent prop-
erties which include high electrical conductivity, hardness,
chemical inertness and good adhesion. This has made it found
extensive usage in applications where properties such as improved
wear and corrosion resistance are required [5,6]. From the ideas
above, it is believed that the corrosion properties of austenitic
stainless steel can be improved through the addition of TiN
nanoparticles into its matrix.
Several investigations have been carried out by researchers to
explain the mechanism of corrosion of sintered austenitic stainless
steel [7,8]. Studies have also been conducted on corrosion resis-
tance of stainless steel which contains varying proportions of sec-
ond phase nanoparticles [9]. The effect of titanium carbide (TiC)
reinforcement addition to the matrix of 304 stainless steel was

https://doi.org/10.1016/j.matpr.2019.10.018
2214-7853/Ó 2019 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of ‘‘Peer-review under responsibility of the scientific committee of the 2nd International Conference on Recent Advances in
Materials & Manufacturing Technologies.

Please cite this article as: S. Olukayode Akinwamide, O. Jeremiah Akinribide, M. Mafafo et al., Effect of TiN addition on corrosion behavior of spark plasma
sintered 304L austenitic stainless steel in chloride media, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2019.10.018
2 S. Olukayode Akinwamide et al. / Materials Today: Proceedings xxx (xxxx) xxx
investigated by Qianlin et al. [8]. Assessment of corrosion resis-
tance conducted using immersion and electrochemical techniques
show that composite with a lower amount of TiC addition exhib-
ited the best corrosion resistance. Addition of more TiC reinforce-
ment resulted in depletion of the chromium-rich layers as a
result of carbide precipitation. Another investigation by Oke et al.
[10] examined the effect of TiN addition on corrosion properties
of sintered duplex stainless steel. Composites with TiN addition
were observed to record a better corrosion resistance as compared
to the unreinforced sintered specimen.
Corrosion behavior of sintered stainless steel can be improved
by various means and the investigation of each is a great task. In
this present study, the corrosion behaviour of sintered 304 auste-
nitic stainless steel reinforced with titanium nitride will be
investigated.
2. Experimental procedure
304L Austenitic stainless steel (average particle size 44 mm: Pur-
ity 99%) supplied by TLS-Technik GmbH &Co in Germany and TiN
powder (average particle size 20 nm: Purity 97%) supplied by
Nanostructured & Amophous Material Inc. Texas, USA were used
as matrix and reinforcements respectively. Chemical composition
of powders is presented in Table 1. Varying proportions of TiN
powders (2,4 and 6 vol%) were weighed and mixed with austenitic
stainless steel powders in a dry environment using a turbula mixer
at a speed of 60 rpm for a duration of 6 hrs. Mixing is done to
ensure homogeneous dispersion of TiN reinforcement in the matrix
of the steel powder. Admixed powders were sintered in a spark
plasma sintering machine model HHPD 25, produced by FCT Ger-
many. A sintering temperature of 1100 °C, holding time of
10 min and heating rate of 100 deg/min were all maintained all
through the experiment. Microstructural analysis of powders and
sintered images were analysed using a Zeiss scanning electron
microscope (SEM). Corrosion test of sintered 304L austenitic stain-
less steel was studied using chronopotentiometry and potentiody-
namic polarization techniques in a corrosive medium containing
3.5 wt% NaCl solution. A Versa studio Potentiostat equipped with
a saturated silver/silver chloride reference electrode, graphite
counter electrode and a working electrode probe was used. Prepa-
ration of the working electrode was performed by attaching an
insulated copper wire to the other end of the sample prior to cold
mounting in resin. Potentiodynamic polarization curve was
obtained by scanning between an initial and final potentials of
1.2 and 1.5 V respectively at a scan rate of 1 mV/s. Tests were
repeated thrice for reproducibility purpose.
3. Results and discussion
3.1. Microstructural studies
Fig. 1 shows the SEM morphologies of the starting powders
(austenitic stainless steel and titanium nitride) and sintered com-
posites respectively. pure sintered 304L austenitic stainless steel
and reinforced composite. From Fig. 1a and b, the shapes of TiN
and austenitic stainless-steel powders are observed to be spherical
in shape. The SEM morphologies of the sintered specimen with 4
and 6 vol% TiN is shown in Fig. 1c and 1d. A loose bonding was
Table 1
Elemental composition of starting powders.
Elements Fe C Cr Ni
304L SS Bal 0.03 19 10
TiN <0.001 0.03 – <0.001
Please cite this article as: S. Olukayode Akinwamide, O. Jeremiah Akinribide, M. Mafafo et al., Effect of TiN addition on corrosion behavior of spark plasma
sintered 304L austenitic stainless steel in chloride media, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2019.10.018
observed between the particles of TiN and 304L austenitic stainless
steel. The distribution of TiN in composite with 6 vol% is also
observed to be predominant. This can be ascribed to adequate mix-
ing of the TiN and austenitic stainless-steel powders. The forma-
tion of irregular pores which are visible over the micrographs is
as a result of settling of the TiN particles along the grain bound-
aries of the austenitic stainless-steel matrix.
3.2. Chronopotentiometry analysis
Fig. 2 shows the chronoamperometric curves which are the
measure of potential against time, is used for predicting the ther-
modynamic stability of specimen in the test electrolyte. The poten-
tials of the specimen with 0% TiN was observed to decline all
through the test. This shows it was unstable in the test electrolyte,
which implies its susceptibility to rapid corrosion. The specimen
with 4 and 6% TiN reinforcement are also observed to undergo
an initial decline in the test electrolyte. However, a slight potential
increase was observed after a duration of 1500 s. Stability of spec-
imens was however observed after the duration of the first 3000 s.
The initial decrease observed in the first 1500 s can be attributed to
rupture of the formed passive layer on the surface of the stainless-
steel matrix, due to adsorption of chloride ions present in the
sodium chloride electrolyte.
Further, the fluctuation of OCP values resulting in a sudden
increase and decrease in potential values of sintered reinforced
composites can also be ascribed to nucleation of pits and occur-
rence of re-passivation. A similar observation was recorded in a
recent study by Aghuy et al. [11]. The low potential values
recorded by the unreinforced sintered stainless steel depicts its
poor resistance in corrosive media, while the high stabilising
potentials recorded by specimen with 4% TiN signifies its improved
corrosion resistance in the test electrolyte.
3.3. Potentiodynamic polarization
Fig. 3 shows the polarization curves obtained for test specimens
in sodium chloride electrolyte. The polarization curves for TiN rein-
forced sintered specimens were observed to show an initial pseu-
dopassivity within the potential range of 0 and 500 mV, before
showing full passivation between the potential range of 500 and
1500 mV. However, specimens with 0% reinforcement are observed
to passivate at a much lower potential between the range of 500
and 500 mV. This passivation was noticeably accompanied by a
decreased current density. Moreover, the small passive currents
observed during the anodic scan is an indication of good corrosion
resistance of the specimens, not only in the passive potential
region but also in the corrosion potential domain. Several reports
have been given on the formation of passive oxide layers on the
surface of austenitic stainless-steel alloy in chloride environments.
One of the researchers assumes that the oxide layer consists of iron
and chromium oxides [12]. A study by Paola et al. [13] however
suggested that other alloying elements of austenitic stainless steel
apart from chromium and iron are regarded as dopant rather than
phase forming alloying elements. The passive regions for the spec-
imens extend to the pitting potential where there is rapid increase
in the current density without the evolution of oxygen. This is a
clear indication the occurrence of pitting corrosion. The specimen
Mo Si Mn S P N Ti
– 1 2 0.03 0.045 – –
– <0.003 – – – 21.91 77.83
 S. Olukayode Akinwamide et al. / Materials Today: Proceedings xxx (xxxx) xxx 3

Fig. 1. Optical micrographs of (a) TiN powder (b) 304 Stainless steel powder (c) sintered 304 + 2%TiN (d) Sintered 304 + 6% TiN.

Fig. 2. Chronopotentiometry plot for sintered specimens with varying TiN

reinforcement.
Fig. 3. Potentiodynamic polarization curves for specimens.

with 0% TiN, however, shows the highest current density in the

anodic region, while the least current density is observed in the
specimen with 4% TiN reinforcement. Therefore, potentiodynamic
polarization plots further validate the observation recorded in
the chronopotentiometry plot.
3.4. Microstructural analysis of corroded surface
Fig. 4 shows the scanning electron micrographs of the rein-
forced and unreinforced alloys in chloride media, with the forma-
tion of pits, were evident in the unreinforced specimen. However,
the surface of specimens with reinforcements was observed to be
covered with corrosion products, thereby preventing an in-depth
penetration of formed pits. The mechanism of pit formation in test
electrolyte containing chloride ions is often initiated by any or a
combination of several factors which includes second phase parti-
cles, casting defect and interaction between the matrix and rein-
forcement [14]. Evidence of protruding TiN particles which are
seen over the micrograph of TiN reinforced composite is an indica-
tion that the stainless-steel matrix has undergone dissolution with
the TiN phase unaffected. The protruding TiN particles can, how-
ever, be ascribed to the preferential dissolution of the austenitic
stainless-steel matrix phase surrounding the TiN particles.

Please cite this article as: S. Olukayode Akinwamide, O. Jeremiah Akinribide, M. Mafafo et al., Effect of TiN addition on corrosion behavior of spark plasma
sintered 304L austenitic stainless steel in chloride media, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2019.10.018
4 S. Olukayode Akinwamide et al. / Materials Today: Proceedings xxx (xxxx) xxx

Fig. 4. SEM micrographs of corroded specimens for (a) sintered 304 + 0% TiN (b) sintered 304 + 4% TiN (c) sintered 304 + 6% TiN.

4. Conclusion References

The corrosion behaviour of sintered 304L austenitic stainless-
steel composite which contains varying proportions of TiN rein-
forcement was investigated. The SEM micrographs confirmed an
even dispersion of TiN reinforcements within the matrix of the sin-
tered austenitic stainless steel. Electrochemical behaviour of spec-
imens in 3.5 wt% NaCl electrolyte was assessed using
chronopotentiometry and potentiodynamic polarization tech-
niques, the effectiveness of TiN nanoparticles in improving the cor-
rosion properties of 304L austenitic stainless steel was further
confirmed. However, sintered specimen with 4% TiN reinforcement
exhibited better corrosion resistance to chloride attack in the cor-
rosive media as compared to other specimens.
Acknowledgements
The authors of this manuscript will like to appreciate Global
Excellence Stature (GES) of University of Johannesburg, South Afr-
tica for funding Akinwamide Samuel Olukayode.
[1] R. Sands, G. Bidmead, D. Oliver, Mod. Dev. Powder Metall. 2 (1966) 73–83.
[2] D.-M. Liu, Q. Yang, T. Troczynski, Biomaterials 23 (2002) 691–698.
[3] S.O. Akinwamide, S.M. Lemika, B.A. Obadele, O.J. Akinribide, B.T. Abe, P.A.
Olubambi, J. Compos. Mater. (2019), 0021998319851198.
[4] M. Patel, R.M. Vaidyanathan, N. Sivaraman, Int. J. Mech. Eng. Technol. 5 (2014)
121–128.
[5] R. Babinova, V. Smirnov, A. Useenov, K. Kravchuk, E. Gladkikh, V. Shapovalov, I.
Mylnikov, J. Phys. Confer. ser. 872 (2017) 012035.
[6] S.O. Akinwamide, Fluid Dyn. Mater. Process 15 (2019) 15–26.
[7] R. Loto, O. Joseph, O. Akanji, J. Mater. Environ. Sci. 6 (2015) 2409–2417.
[8] Q. Wu, W. Li, N. Zhong, Corros. Sci. 53 (2011) 4258–4264.
[9] C. Padmavathi, A. Upadhyaya, D. Agrawal, Corrosion behavior of microwave-
sintered austenitic stainless steel composites, Scr. Mater. 57 (2007) 651–654.
[10] S.R. Oke, O.O. Ige, O.E. Falodun, B.A. Obadele, M.R. Mphahlele, P.A. Olubambi,
Mater. Chem. Phys. 206 (2018) 166–173.
[11] A.A. Aghuy, M. Zakeri, M.H. Moayed, M. Mazinani, Corros. Sci. 94 (2015) 368–
376.
[12] M.A. Ibrahim, S.A. El Rehim, M. Hamza, Mater. Chem. Phys. 115 (2009) 80–85.
[13] A. Di Paola, D. Shukla, U. Stimming, Electrochim. Acta 36 (1991) 345–352.
[14] A. Raman, G. Nnaike, A. Choudhury, C. Das, Corros. sci. 25 (1985) 107–115.

Please cite this article as: S. Olukayode Akinwamide, O. Jeremiah Akinribide, M. Mafafo et al., Effect of TiN addition on corrosion behavior of spark plasma
sintered 304L austenitic stainless steel in chloride media, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2019.10.018