18.20.5.

2010,RoznovpodRadhostem,CzechRepublic,EU


THE TWIP ALLOYS RESISTANCE IN SOME CORROSION REAGENTS
Eva MAZANCOV
a
, Petr KOZELSK
a
, Ivo SCHINDLER
a
a
VB-TU OSTRAVA, FACULTY OF METALLURGY AND MATERIAL ENGINEERING,
T. 17.listopadu 15, 708 33 Ostrava Poruba, Czech Republic,
eva.mazancova@vsb.cz, petr.kozelsky@vsb.cz, ivo.schindler@vsb.cz
Abstract
The work deals with corrosion resistance of two high Mn alloys. After cast of the Fe22.3Mn0.5C alloy heat
treated at 1200C/4h/water and forging with total deformation of 25 % were carried out. This represents the
TWIP 1 alloy. The TWIP 2 alloy is the TWIP 1 re-heated at 1150C/3h/air. Final bars corresponded to 12 mm
in diameter. Further the Fe23.1Mn0.73C alloy was laboratory rolled with the final strip thickness of 3 mm
representing the TWIP 3 alloy. Exposition of all variants in the 3.5 % water NaCl solution showed corrosion
on the boundaries of the twins first of all. The TWIP 3 demonstrated higher corrosion resistance. The worst
corrosion attack showed the TWIP 2, where the corrosion traces reached 0.12 mm under surface. After the
TWIP 3 alloy exposition in corrosion solution with bubbled hydrogen sulphide (the HIC test), no hydrogen
cracks were revealed. The results were confronted with austenite grain sizes, formed twins and mechanical
properties.
Keywords: TWIP alloys, heat treatment, rolling, corrosion resistance
1. INTRODUCTION
Some top austenite steels may show high corrosion resistance such as the Ni-Cr stainless steels. Chromium
imparts corrosion resistance and Ni secures high plasticity. Both cardinal elements are expensive due to
their strategic importance. The both mentioned elements can be substituted by cheaper Mn and Al in
materials where not so extreme corrosion resistance is demanded [1, 2]. It is known both Ni and Mn support
austenite area in the iron-carbon equilibrium diagram and are able to stabilize the FCC matrix. The FCC
matrix generally shows high plasticity level being connected with more difficult cleavage crack propagation.
In comparison with the Fe or Ni, the Mn decreases the matrix density which is attractive e.g. in automotive
industry as well as the corrosion resistance, especially in case of the TWIP or TRIPLEX alloys [3, 4]. To the
corrosion resistance of the above mentioned alloys special attention has not been practically paid.
Since the high Mn alloys are promising materials for automotive industry or for gas transport [3, 5] that is
reason why the presented work is focused on corrosion resistance of high manganese alloy of the FeMnC
type being treated in three ways and exposed in two corrosion mediums.
2. EXPERIMENTAL MATERIAL AND TECHNIQUE
For corrosion investigation one high Mn alloy (Fe22.3Mn0.5C) was used. For laboratory heat production a
material of high purity was chosen. Vacuum melting under Ar atmosphere was realized using plasma with
followed cast into four bars of 16 mm in diameter. After homogenizing annealing at the 1200C/4 h/water the
reheated bars (1050C/10) were forged into the diameter of 12 mm in 2 steps with the aim to balance the
temperature. In each deformation stage the diameter reduction by 2 mm (12.5 %) was carried out. For the
forming a multi-stage die was used. One bar was marked as the TWIP 1. The other bar was reheated at
1150C/3h/air and marked as the TWIP 2.
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Another Fe23.1Mn0.73C alloy using plasma metallurgy and Ar of high cleanness was prepared. The 1 kg
ingot was cut up and re-melted in radio frequency induction vacuum furnace and cast to cold graphite ingot
mould 32x13 mm in cross section and of 300 mm in length. The annealing at the 1125C/3h/water followed.
Afterwards the rolling process was realized. The aim of the 1
st
rolling was a thickness decreasing of the cast
ingot. Firstly, the material was reheated at 1100C/20 for an even warming-through and consequently rolled.
After the second reduction the thickness corresponded to 8 mm. After the 1
st
rolling, material was cut in four
sections and subsequently was again reheated at the temperature of 1000C and rolled by one reduction.
The thickness of the strip was 5.5-6 mm. Then, after reheating at the 1000C/1.5 material was again rolled
by two reductions. The final thickness corresponded to 3 mm and the total deformation to 65.1 %. Using
pyrometer the samples temperatures were measured. The rolling process was realized by use of the
laboratory rolling mill of the four-high mill type. The work rolls diameter corresponded to 67 mm reaching 100
revs per minute. The rolled strips were marked as the TWIP 3. Further, at 20C and -20C stacking fault
energies were calculated [5-7].
After expositions in two reagents, metallographic investigation and mechanical parameters determination
followed. Tensile tests were carried out (at 23C) using the INOVA tensile test machine (maximal loading of
50 kN and the crosspiece rate in the range of 0.001-500 mm.min
-1
). In case of the TWIP 3 one
metallographic specimen was also taken. From the bars of the TWIP 1 and 2 two samples were taken in
longitudinal direction with gauge length of 15 mm. One sample of each variant also served for metallographic
analysis by use of the Olympus light microscope X70 as well as the electron microscope SEM J EOL J SM-
6490 LV equipped with the energy dispersion analyser OXFORD INCA Energy 350. The micro-hardness
completed the analysis.
One sample of the TWIP 1, 2 and 3 was used for corrosion test in the 3.5 % water NaCl solution. Four
transverse strips of the TWIP 3 were cut off. The gauge length of one was 33 mm and width of 10 mm and
served for the same corrosion test in the 3.5 % NaCl solution as it was mentioned above. The other three
strips dimensions corresponded to 33x20 mm with the thickness of 3 mm after rolling and were used for the
corrosion test in the H
2
S. Surfaces of all samples were cleaned in alcohol. Those were exposed in 3.5 %
water NaCl solution for 168 hours. Materials were quite dipped into corrosion solution (23C) lengthways
lying on thick glass rods of 3 mm on diameter. The test solution of the other corrosion exposition consisted
of 5 % NaCl, 0.5 % CH
3
COOH in distilled water. The procedure of the experiments was in agreement with
the NACE Standard TM0284-2003, Item No. 21215 for the HIC resistance [6]. The start and finishing
solution pH corresponded to 2.71 and 3.79. The test temperature was kept at the 23C. The hydrogen
embrittlement was evaluated in agreement with the [6]. Metallographically prepared samples were etched in
glycerine, hydrofluoric-, nitric- and hydrochloric acid.
3. RESULTS AND ANALYSIS
The corrosions tests metallographic and mechanical parameters determination of all samples preceded Tab.
1. Samples of the TWIP 1 showed relatively uniform grain size in all cross-sections. The same could be told
about the TWIP 3 samples since the thickness of the 3 mm displayed none differences between central area
(CA) and the sub-surface area (SS) as the Tab. 1 shows. The 68 % austenite grain size (G

) difference was
detected between the TWIP 1 and the TWIP 2 samples. This can be ascribed to the TWIP 2 material
reheating at 1150C. The strength also went down in comparison with the TWIP 1 (Tab. 1). Regarding the
rolled TWIP 3 material, its G

was markedly finer than the grain size of the TWIP 2 alloy. However, it is
surprising the micro-hardness of the both last mentioned materials maximally showed 9.5 % difference. In
18.20.5.2010,RoznovpodRadhostem,CzechRepublic,EU


relation to the reached strengths (46 % difference as the Tab. 1 gives) a higher strength value would be
awaited in the TWIP 3 material. Regarding the proportionalities among strength and reached ductility of all
investigated materials those are in agreement with [7].
Table 1 Mean values of detected parameters (SS=sub-surface area, CA=central area)
alloy HV0.2 G

Re Rm A
[-] [m]
SS CA CA SS [MPa] [%]
TWIP 1 317 301 74 74 429 749 58
TWIP 2 269 243 117 125 406 618 65
TWIP 3 266 266 13 13 468 904 53
a) b) c)

Fig. 1 a, b, c Micrographs of the a) TWIP 1, b) TWIP 2, c) TWIP 3
Microstructures of all studied alloys are presented in Fig. 1a, b and c (transverse sections). After deformation
the microstructure of all samples showed the FCC matrix with more or less developed deformation twins as
the X-ray measurement confirmed [8]. In all materials the thickness of the deformation twins were measured
using the SEM at magnification of 3000x. The TWIP 1 matrix showed the shorter and thinner deformation
twins of 0.762 m in thickness (seldom) and/or of 0.950 m (more frequently), while the maximal strip
thickness corresponded 8.095 m. In the TWIP 2 matrix the thicknesses of twins were lying in extend of
1.143 - 5.3 m, resp. 20 m sporadically. The TWIP 3 matrix showed above mentioned range of 0.566
0.941 m. Those results are quite in agreement with the way of heat treatment and deformation conditions.
The higher deformation and faster cooling is used, the finer grain size is obtained and the finer and shorter
deformation twins are formed [9, 10]. The obtained results confirm this proportionality. Twin boundaries
correspond to special high-angle interfaces representing strong barriers for the propagation of other non-
coplanar deformation twins or for gliding dislocations [11] being also reason of reached different strength
levels of the TWIP 1, 2 and 3 alloys (Tab. 1). A difference in energy per unit fault area between faulted and
perfect structure the SFE expresses. The presented TWIP 1 and 2 alloys show the same calculated SFE
lying on the level of 22.2 mJ .m
-2
at 20C similarly determined like in [12, 13] and 19.2 mJ .m
-2
at -20C
according the concept of the works [13, 14]. In case of the TWIP 3 the SFE was 24.1 mJ .m
-2
(at 20C),
10m 30m 30m
18.20.5.2010,RoznovpodRadhostem,CzechRepublic,EU


respectively 21.1 mJ .m
-2
(at -20C). The differences between the TWIP 1, 2 and the TWIP 3 the chemical
compositions give. The higher Mn-addition of the TWIP 3 alloy makes the SFE higher, while the C-addition
shows much lesser impact [12, 15, 16]. At the temperature of -20C the SFE exceeds 18 mJ .m
-2
. By this, it is
expected the austenite stability of investigated materials under given conditions [13, 14]. Unfortunately, the
calculation does not consider deformation conditions. Deformation and consequently the grain size play an
important part.
a) b) c)

Fig. 2a, b, c Micrograph of the corrosion attack of the a) TWIP 1, b) TWIP 2, c) TWIP 3 matrix

After samples immersion in the 3.5 % water NaCl solution those showed even unnoticable corrosion as the
macrographs of the Fig. 2 present. In the immediate vicinity of few observed sulphides and/or oxisulphides
localized point corrosion was detected unlike the 25Mn6Al high manganese alloy presented by Hamada [17]
who observed pit corrosion in minority BCC phase being more prone to pitting in chloride ion environments
than the FCC matrix. Our materials were fully austenitic. The corrosion attack was observed in the grinded
transverse sections (grinded before exposition) and hardly visible corrosion over the total circumferences. It
can be supposed, an oxides immunizing film protected the material. Using the SEM, corrosion positions were
revealed at the boundaries of deformation twins as the Figs. 2a, b, c show. The longitudinal metallographic
samples observation showed the deepest corrosion attack in case of the TWIP 2 maximally reaching 0.12
mm under surface, then of the TWIP 1 maximally detectable 0.09 mm under surface and the shallowest
corrosion trace was found in the TWIP 3 sample maximally reaching 0.05 mm under surface. Reason of
those differences may lies in number of twins. During the same exposition time the chloride ions were evenly
redistributed among the twins of each matrix. The TWIP 2 showed the thickest, longest and the lowest
number of twins unlike the TWIP 3 where numerous of very narrow and short twins were formed during
intensive rolling process.
The hydrogen susceptibility evaluation [6] was without cracks detection. It is truth, the samples dimensions
for 96 hours hydrogen sulphide exposition should be bigger according the NACE Standard [6], however
hereby the corrosion conditions were much stricter, because in smaller material volume more hydrogen
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atoms could be caught in traps during the exposition. The rolled material showed small grain sizes and a lot
of shorter and very narrow deformation twins. The grains and twins boundaries act as numerous hydrogen
traps and the hydrogen resistant is strongly dependent on equally distributed potential hydrogen traps for
hydrogen catching above all. Moreover, the boundaries of deformation twins represent high-angle interface
for crack propagation [11]. It means each boundary performs hindrance leading to a crack deviation and
being simultaneously attending by a lost of kinetic energy for cleavage crack propagation.
4. CONCLUSIONS
Three TWIP alloys variants marked as TWIP 1, 2 and 3 were investigated. The first material was heat
treated at the 1200C/4h/water after cast and consequently forged with total deformation of 25 %. The
second alloy represented the TWIP 1 heat treated at 1125C/3h/air. The TWIP 3 was annealed at
1150C/water after cast and laboratory rolled at 1000C. Final thickness was 3 mm and the total deformation
corresponded to 65.1%.
Metallographic evaluation showed the FCC matrix with deformation twins. All materials differ in austenite
grain size (for central area 74, 125 and 13 m in sequence TWIP 1, 2 and 3), consequently in number,
length and thickness (the narrowest thickness of 0.762, 1.143 and of 0.566 m again in above mentioned
sequence) of deformation twins in dependence on temperature and faster or slower cooling process.
Strengths were in proportionality with ductility. The lowest strength of 618 MPa connected with 65 % ductility
was found for the TWIP 2, the highest strength of 904 MPa and of 35 % ductility in the TWIP 3 case.
Corrosion influence of the 3.5 % NaCl water solution was the most evident in case of the TWIP 2 (going 0.12
mm under surface) and the least corrosion attack was observed in the TWIP 3 alloy (maximal affected deep
of 0.05 mm). Corrosion was observed in deformation twins interfaces first of all. In the TWIP 3 alloy tested in
the HIC solution none crack were revealed. The fine grains size and the boundaries of deformation twins
acting as numerous hydrogen traps are the reason. The high-angle interfaces of the deformation twins
influence both the formation and the cleavage crack propagation.
ACKNOWLEDGEMENT
Authors acknowledge the Ministry of Education, Youth and Sports of Czech Republic for financial
support of project MSM6198910015 and the RMTVC project CZ.1.05/2.1.00/01.0040
LITERATURE
[1] SCHUMANN, H.: Wesensgleichheit der //-Umwandlung in kohlenstoffarmen austenitischen Mangan und Chrom-Nickel-
Sthlen. Neue Htte, 17, 1972, Heft 4, pp. 203-210.
[2] FLOREEN, S.: An exhibition of chromium substitution in stainless steels. Metal. Trans. 13A, 1982, pp. 2003-2013.
[3] FROMMEYER, G., BRX, U.: Microstructures and mechanical properties of high-strength Fe-M-Al-C light-weight TRIPLEX
steels. Steel Research Int., 77, 2006, No. 9-10, pp. 624-633.
[4] MAZANCOV E.: New material types for automotive industryphysical engineering properties of high strength material alloyed
with manganese and of metal hydrides alloys for hydrogen storage (in Czech). Monography, 1st. ed. Ostrava, VB-TU Ostrava,
2007, 74 p.
[5] KUNZ, M.: Verformungsmechanismen hoch manganlegierter austenitischer TWIP-Sthle. Der Ander Verlag, the 1st ed., 2008,
pp. 97-100.
[6] Evaluation of pipeline and pressure vessel steels for resistance to hydrogen-induced cracking. NACE Standard TM0254-2003,
Item No. 21215, NACE International, Houston, 2003, 13 p.
18.20.5.2010,RoznovpodRadhostem,CzechRepublic,EU


[7] UEJ I, R. et al.: Tensile properties and twinning behaviour of high manganese austenitic steel with fine-grained structure. Scr.
Mater., 59, 2008, pp. 963-966.
[8] MAZANCOV, E. et al.: Microstructural analysis of high manganese alloy. Metallurgical Journal, 2009, LXII, No. 6, pp. 61-65.
[9] INAGATI, M.: Role of annealing twins for grain refinement in controlled rolling of low carbon microalloyed steel. Trans. ISI Jap.,
23, 1983, pp. 1059-1067.
[10] UMEMOTO, M., OHTSUKA, H., TAMURA, I.: Transformation of pearlite from work hardened austenite. Trans. ISI Jap., 23,
1983, pp. 775-784.
[11] SEVILLANO, J .G.: An alternative model for the strain hardening of the FCC alloys that twin validated for twinning induced
plasticity steel. Scr. Mater., 60, 2009, pp. 336-339.
[12] MAZANCOV, E., KURSA, M., MAZANEC, K.: Chosen physical metallurgical parameters of high manganese alloys and their
influence evaluation. Metallurgical Journal, 2008, LXI, No. 7, pp. 71-74.
[13] DUMAY, A. et al.: Influence of addition elements on the stacking fault energy and mechanical properties of an austenitic Fe-Mn-
C steel. Mat. Sci. Eng. A, 483-484, 2008, 483-484, pp. 184-187.
[14] PHIU-ON, K. et al.: Effect of solution treatment and test temperature on tensile properties of high Mn austenitic steels. Steel
Research Int., 80, 2009, No. 1, pp. 29-38.
[15] ALLAIN, S. et al.: Correlations between the calculated stacking fault energy and the plasticity mechanisms on the FE-Mn-C
alloys. Mater. Sci. Eng. A, 2004, 387-389, pp. 307-317.
[16] MAZANCOV, E., MAZANEC, K.: The stacking fault energy evaluation of the TWIP and the TRIPLEX alloys. Metallic Mater., 47,
2009, 6, pp. 1-6.
[17] HAMADA, A.S.: Acta Univ. of Oulu, 2007, C281, htt://herkules.oulu.fi/issm03553213/.