Metallurgicaland Materials Transactions A45 A2014
Metallurgicaland Materials Transactions A45 A2014
Metallurgicaland Materials Transactions A45 A2014
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Universidad Nacional Autónoma de México The Lubrizol Corporation, Brecksville, OH
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Texas A&M University
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Different thermomechanical treatments were applied to a high strength low carbon steel with a
novel chemical composition. As a result, three different microstructures were produced with
dissimilar mechanical and corrosion properties. Subsequently, a tempering heat treatment was
applied to redistribute the phases in the steel. Microstructure A with 56 pct martensite and 32
pct bainite presented high strength but medium ductility; microstructure C with 95 pct ferrite
and 3 pct martensite/austenite resulted in low strength and high ductility, and finally micro-
structure B with 98 pct bainite and 2 pct martensite/austenite resulted in high strength and
ductility. Alternatively the corrosion behavior obtained by polarization curves was character-
ized in 0.1 M H2SO4, 3 M H2SO4, 3.5 wt pct NaCl, and NS4 solutions resulting in similar
magnitudes, while the corrosion behavior acquired by electrochemical impedance spectroscopy
had slightly differences in 3 M H2SO4.
DOI: 10.1007/s11661-014-2320-3
The Minerals, Metals & Materials Society and ASM International 2014
Steel C N Si Mn P S Cr Mo Ni Al Co Cu Nb Ti
A 0.027 0.0060 0.24 1.00 0.003 0.005 0.4 0.180 1.35 0.0451 0.0045 0.0107 0.024 0.154
B 0.020 0.0061 0.24 1.04 0.003 0.003 0.4 0.1700 1.33 0.0515 0.0048 0.0108 0.024 0.154
C 0.031 0.0057 0.23 1.03 0.003 0.002 0.4 0.1674 1.30 0.0520 0.0043 0.0106 0.023 0.149
High strength low carbon steel is widely used due to pct Ni and 0.107 wt pct Cu additions may act on
its high mechanical properties. Nevertheless, it has low austenite transformation kinetics. Ni also promotes an
corrosion resistance.[11,12] Steel degradation has negative increase in energy for crack developments. Microalloy-
consequences upon the economy, the environment, and ing of steel with Nb, Ti, and Al promotes a slowdown in
human safety. Hence, corrosion control needs to be recrystallization and a decrement in grain size as well as
addressed with some methods such as material selection dispersion strengthening. Contents of 0.4 wt pct Cr and
based on the performance characteristics in a specific around 1 wt pct Mn are added to lower the bainitic
environment. Many studies have correlated steel micro- transformation temperature. Mo improves transforma-
structure to its mechanical properties,[13–18] whereas tion hardening through an increased volume fraction of
studies correlating steel microstructure to corrosion acicular ferrite, grain refinement, and precipitation
behavior have not been extensively explored.[19,20] The hardening. Mo also suppresses or retards the formation
design for steel structures should consider the micro- of polygonal ferrite and pearlite. The chemical compo-
structure-mechanical relationship with microstructure- sition of the steel used in this work is not typical of the
corrosion behavior for a specific electrolytic media, commercial microalloyed steels due to the additions of
based on the final application. It has been observed that Ni, Cr, and Mo.
microstructure can affect the corrosion process in
numerous ways, such as the development of carbonate
layers,[21] their porosity and adherence,[22] cathodic B. Thermomechanical Treatments
adsorption sites,[23] anodic adsorption intermediates,[24] The steel slabs were treated thermomechanically as
and stress corrosion cracking.[25] In a prior study, the follows:
microstructure of quenched and tempered (Q & T)
duplex steel was related to better corrosion resistance (1) The plates were reheated and homogenized at
than the annealed structure of the same steel in CO2- 1523 K (1250 C) and then rolled to obtain a
saturated solution at 313 K (40 C), pH = 6, and 5 pct thickness reduction from 4.4 to 2.2 cm (50 pct
NaCl.[22] In addition, corrosion behavior can be related strain) at the same temperature. After that con-
to the distribution of carbon-bearing phases in brine trolled cooling was applied from 1523 K to
solutions under high CO2 pressure.[26] 1193 K (1250 C to 920 C), followed by a second
In this work, relations among chemical steel compo- rolling to decrease the thickness from 2.2 to 1.1 cm
sition, steel processing, microstructure, and corrosion (50 pct strain) at 1193 K (920 C), and then a final
behavior were addressed. Chemical composition and cooling from 1193 K to 298 K (920 C to 25 C)
processes were proposed that would lead to a specific in air with a rate of 0.5 C s1. Finally, a quench-
microstructure, resistance, and corrosion behavior. ing was performed by reheating the plate at
Novel steels were produced and then were thermome- 1223 K (950 C), and then cooling in water at
chanically treated. As a consequence, specific micro- 45 C s1. This thermomechanical treatment can
structures, high strength, and ductility were obtained. be considered like typical controlling rolling with-
The microstructures were modified with thermomechan- out accelerated cooling, followed by annealing–
ical and post-heat treatments to know the effect on both quenching treatment. This was applied to the steel
mechanical properties and corrosion behavior. The A.
corrosion behavior was characterized by time and (2) The plates were reheated and homogenized at
frequency domain electrochemical techniques. 1523 K (1250 C), followed by a thickness reduc-
tion from 5.13 to 2.2 cm (70 pct strain) at 1523 K
(1250 C). After that a controlled cooling from
1523 K to 1153 K (1250 C to 880 C) was per-
II. EXPERIMENTAL PROCEDURE formed, and the steel was rolled again from 2.2 to
1.1 cm (50 pct strain). Finally, the steel was cooled
A. Materials
from 1153 K to 298 K (880 C to 25 C) with
Three slabs were obtained from different steel casts, water sprays and a cooling rate of 20 C s1. This
and their chemical composition is shown in Table I. thermomechanical treatment is considered equiva-
Each cast is identified by a letter. The steel chemical lent as controlling rolling with accelerated cooling.
composition consists in a carbon content from 0.02 to All these steps were applied to the steel B.
0.03 wt pct C with the purpose to achieve high strength, (3) At 1523 K (1250 C), the steel was reheated,
good weldability, and a reduction of segregation in these homogenized, and rolled to decrease the thickness
steels. In an intent to improve the solid solution from 7.32 to 3.66 cm (50 pct strain). Afterward,
strengthening due to the low carbon content, Mn is controlled cooling was applied from 1523 K to
around 1 wt pct. Introduction of approximately 1.3 wt 1273 K (1250 C to 1000 C), and then the steel
NaHCO3 0.483 g/L), 3.5 wt pct NaCl, 0.1 M H2SO4, due to calculations that imply dissolution models on
and 3 M H2SO4. In addition, 3 M H2SO4 was the both sides of the Eq. [1]:
solution employed during EIS testing. The samples used
in the EIS testing were tempered at 473 K, 673 K, and xz þ yð1 zÞ½Ti þ ð1 xÞz þ ð1 yÞð1 zÞ½Nb
873 K (200 C, 400 C, and 600 C) during 300 minutes þ z½Nb þ ð1 zÞ½N ! Tizxþyð1zÞ ½1
after all thermomechanical treatments. All experiments
Nbð1xÞzþð1yÞð1zÞ Cz Nð1zÞ ;
were performed with constant nitrogen bubbling and in
duplicate. These electrolytes were used for different where the bracketed elements denote that they are
reasons which are mention below. dissolved in austenite, while the right compound in the
The NS4 was used, because it is a common electro- Reaction [1] is a complex nitride-carbide of titanium and
lyte that mimics the chemistry for soil conditions of niobium (TiNbCN). The difficulty to obtain the solubil-
buried metallic structures. The 3.5 wt pct NaCl solu- ity constant of this complex precipitates lies in the lack of
tion is common in evaluation of materials exposed to interaction parameters in solid austenite and ferrite of
sea water. The sulfuric acid was used for its simplicity the elements, as well as dissolution models of ceramic
and high aggressiveness, which produces high levels of materials (carbides and nitrides of metals). However,
corrosion of the different steel phases that make assuming that the main elements in the formation of the
possible to record the effect of microstructure on steel precipitates are not affected in their activity for the other
corrosion. components in the steel, and using the solubility con-
The sequence of experiments is described as follows: stants of the simple compounds metal carbide and metal
First, the open circuit potential (Eocp) was measured nitride, the complex precipitate solubility constant could
for 1 hour. Second, the EIS was performed in a be approximated. In this work, the chemical composi-
frequency range from 10,000 to 0.01 Hz with 10 mV tions of the experimental steels were used to obtain the
of applied amplitude, and third, a polarization curve stoichiometry and approximate solubility constant for
was performed in some cases with a scan rate of complex carbonitride of niobium and titanium. The
0.1615 mV s1 from 250 to 250 mV vs corrosion details of the model are described elsewhere.[35] As a
potential (Eocp). result, stoichiometry of the complex carbide-nitride of
titanium and niobium is shown in Table II, while the
solubility constants are presented in Figure 1(a).
The complex carbonitride of titanium and niobium
III. RESULTS AND ANALYSIS stoichiometry results are show in Table II. The stoichi-
ometry is strongly dependant on temperature, and it is
A. Solid Precipitates different from the single TiC, NbC, and NbN. The Ti
The precipitate features that are useful for refining the and N contents rise in the complex precipitate as the
grain size and thus improving the yield strength are temperature increases from 1223 K and 1673 K (950 C
thermodynamic stability at high temperature, small size, and 1400 C). This is an indication of the titanium high
fast kinetic formation, and low alloy quantity (£0.01 wt affinity for nitrogen as well as the influence of the TiN
pct of the alloy).[32] Precipitates that have exhibited on NbC and NbN. The TiN confers higher stability on
these features are mainly carbides and nitrides of NbC and NbN compared with the NbC or NbN
niobium, titanium, vanadium, and aluminum.[33,34] The stability in the absence of TiN.[34]
thermodynamic stability of single carbides or nitrides The solubility constants resulted from the calculations
has previously been obtained.[32] are shown in Figure 1(a). The complex carbonitride
The important precipitates are not only single car- solubility constants are difficult to determine by models
bides or nitrides but also complex precipitates. A in isothermal conditions. Thus, the numerical results are
complex precipitate denotes a combination of single presented, and they could be used in kinetic calculations.[36]
carbides and/or nitrides to form another compound, Previous works claimed that another important com-
which is the result of the mutual solubility of single pound that influences the grain refinement during the
carbides and nitrides at high temperature.[35] The dynamic recrystallization is aluminum nitride (AlN).[37]
prediction of their chemical composition is difficult However, the nitrogen content of the steel used in this
Fig. 2—Optic microscopy of the steel under three different thermomechanical heat treatments.
work is not sufficient for AlN precipitation to occur, bainite microconstituents. The steel B is shown in
because nitrogen in austenitic solid solution is depleted Figure 2(b), the microstructure covers the area by acic-
by the formation of complex NbTiCN. A model previ- ular microstructure form which can be related to the same
ously described[32] was used to obtain the stability among structures founded in A. The grain size is apparently
AlN, TiNbCN, and austenite. For the chemical compo- higher in steel A than in steel B, and it can be observed that
sition of the steel A, the concentrations of [Al] in AIN both steel grain geometries are not equiaxed; in fact some
and [Ti] in TiNbCN were used for the calculation, the grains are irregular. The steel C is presented in
other elements were maintained constant in the complex Figure 2(c), the microstructure is well-defined equiaxed
carbonitride, and the results are displayed in Figure 1(b). grains with dark points among them. This can be related
The thermodynamic calculations for complex to ferrite phase and second microconstituents.
NbTiCN and AlN show that increasing temperature The Nital etching used in this optic microscopy
from 1173 K to 1273 K (900 C to 1000 C): TiNbCN- observation displays the ferrite-bearing phases, while
austenite stability zone expands, austenite-AlN-TiNbCN leaving austenite and cementite intact. Ferrite-based
area shrinks, and AlN-austenite region does not ap- phases, such as bainite ferrite and perlitic ferrite, are
peared when a low pct Ti is presented in the steel. After dissolved and exhibits a typical morphology that gener-
locating the chemical composition of [Al] = 0.0451 and ally allows their recognition, but a problem appears when
[Ti] = 0.154 of steel A in the diagram, it can be seen that a microstructure presents simultaneously martensite and
the AlN is not stable at temperatures greater than austenite as second phases.[28] As a consequence, a
1273 K (1000 C). As a consequence, the formation of microstructure which is made of ferrite, bainite, martens-
AlN is not possible in the steels used in this work. ite, and retained austenite in a very fine structure cannot
be easy to characterize only with Nital. Then, a selective
color etching was used to quantify the phases presented.
B. Optic Microscopy Results
The steel microstructure that is obtained by optic
microscopy following the described thermomechanical C. Color Etching Results
treatments is shown in Figure 2. The steel A is shown in The steels obtained after undergoing thermomechan-
Figure 2(a), the microstructure is mostly an acicular ical treatment are composed of different percentages of
structure that can be associated with martensite and microconstituents. The tinting etching procedure which
Fig. 4—Steel microstructures are shown under the three different thermomechanical treatments. M represents martensite, B bainite, and M/A
martensite/austenite microconstituents.
Grain Size/Steel Temp [K (C)] A (A) 200 (A) 400 (A) 600 B (B) 200 (B) 400 (B) 600 C (C) 200 (C) 400 (C) 600
Small (£120 lm) 134 144 144 40 61 31 46 58 370 414 413 289
Medium (120 to 200 lm) 24 33 32 21 20 14 21 16 19 13 14 34
Large (‡200 lm2) 42 21 21 40 28 49 48 51 4 1 0 9
was described in the Section II–D revealed the ferrite in electron microscope images of each steel are shown in
green–blue, the bainite in brown, and austenite and Figure 4, and they show each phase with more detail
martensite in white.[28] Representative pictures of color than the optic microscopy.
etching are shown in Figure 3. The steel A is shown in
Figure 3(a) and has a microconstituent variety: islands
D. Grain Size Distribution
of marteniste/austenite (M/A) which are small white
grains, martensite (M) denoted in the white acicular The grain area distribution was obtained from SEM
form color inside the grains and bainite (B) in brown images using GIMP and ImageJ freeware software. The
color. The steel B is presented in Figure 3(b) and SEM image was processed in the GIMP software to
includes two main constituents: B in brown color and obtain the grain boundary. A black and white image was
M/A plates among B laths. The steel C is exposed in produced where the grain boundaries are perfectly
Figure 3(c) and contains two phases ferrite (F) and M/A delimitated in black color, while the body of the grains
islands. Afterward, the images were divided in 100 was white. Subsequently, the image was open in the
squares using the GIMP software, if a specific color ImageJ software, and the area of each grain was
appeared in one square, the phase was quantified as 1 obtained. The results are shown in Tables III and IV
pct; if partial zones of one phase appeared in one square, where frequency of ‘‘small,’’ ‘‘medium,’’ and ‘‘large’’
a fraction was given for each phase base on the hue in grains of samples thermomechanically treated and the
the color etching. Subsequently, the quantification of the ones post-tempered during 10 and 300 minutes.
100 squares determined the percentage of the each The procedure described previously was done to obtain
phase. The microconstituent percentages results follow- the area grain distribution, because the grain morphology
ing the thermomechanical heat treatments are: 56 pct M, was neither equiaxial nor homogenous. The ASTM
32 pct B, and 12 pct other phases for steel A; 98 pct B, E-112[38] could be applied to obtain average grain
and 2 pct M/A for steel B; 95 pct F, 3 pct M/A, and 2 size (GS), but the objective in this section is to
pct other phases for steel C. Additionally, the scanning obtain the change in the area distribution due to each
Grain Size/Steel (A) (A) (A) (B) (B) (B) (C) (C) (C)
Temp [K (C)] 473 (200) 673 (400) 873 (600) 473 (200) 673 (400) 873 (600) 473 (200) 673 (400) 873 (600)
Small (£120 lm) 65 62 49 51 38 41 347 289 251
Medium (120 to 200 lm) 15 14 27 26 20 18 19 33 16
Large (‡200 lm2) 44 42 46 49 53 51 5 14 7
thermomechanical and post-tempering process. The 873 K (600 C) at 10 minutes lower than the other two
grain areas distribution comprises all the phases in the tempering temperatures. While the tempering time
steel, and the grains changes are not treated for a specific increases to 300 minutes, the GS distribution changes
phase. to higher frequencies for Me and L areas, specifically,
The grain sizes were categorized like small (S) in an for L area. Steel B exhibits behavior similar to the one
area interval from £120 lm2, medium (Me) from 120 to found in steel A, but the frequency modification is in L
200 lm2, and large (L) ‡200 lm2. The steel A had a area as the tempering time increased. Steel C had only a
frequency of 134 in S areas £120 lm2. This has indicated small variation in its distribution as the tempering time
that the GS is in higher frequency for small sizes. For increased. These results can be summarized as follows:
steel B, the frequency was around 15 in increments of Steel A had a change from small to medium and large
30 lm2 within the area interval from 0 to 300 lm2, and grain sizes in its grain size distribution due to the
the size in the categories (S,Me,L) does not have a big tempering treatment; while steel B had a slight modifi-
frequency difference. It indicates the grain size is cation from small to medium grain sizes. The case of
allocated in S, Me, and L in a similar manner. In the steel C did not have a modification in its grain size
case of steel C, the frequency was 370 for S GS as it is distribution because of the tempering treatment.
shown in Table III. This result denotes that the distri-
bution is extremely high in S sizes in steel C. The
E. SEM Characterization
comparison among the three steels could be summariz-
ing as follows: The steel A had a distribution higher in S The microstructures in steel that underwent three
sizes than steel B did; while the steel C had the highest thermomechanical processes are shown in the scanning
frequency in S sizes. The existence of a GS distribution electron microscopy images of Figure 4. The micro-
(inhomogeneous size) is an indication that dynamic structure for steel A is formed by F and M as it is shown
recrystallization cycles occurred.[39] in Figure 4(a). The microstructure for steel B is consti-
The strain applied in steel A was of 50 pct in a first tuted by B and M/A islands (Figure 4(b)), while the
rolling at 1523 K (1250 C) and 50 pct in a second microstructure for steel C is comprised by F and M/A
rolling at 1193 K (920 C), while the strain applied in areas.
steel B was 70 pct in a first rolling at 1523 K (1250 C) The microstructures in SEM exhibited no consider-
and 50 pct in a second at 1153 K (880 C). Although able difference during the tempering heat treatment.
steel A had a greater grain distribution in S sizes than However, the mechanical properties varied, which could
steel B, the austenite distribution in S sizes before the occur, because the tempering treatment modifications
accelerated cooling was higher in steel B, because the were at molecular level during the first and second stages
higher deformation at high temperature.[39] However, of the tempering, and they could not be revealed by
the quenching which was done in A steel after the scanning electron microscopy. The first stage of tem-
thermomechanical treatment causes the formation of S pering is an aging where carbon has redistributed in the
size martensite grains.[39] As a result, the steel A had a martensite laths interfaces and the dislocations; it has
frequency at approximately 134 for small GS higher been shown by TEM.[40] The second stage is the
than steel B which had a frequency of 61 in the same transformation of austenite to bainite. The bainite is
category. Steel C underwent an initial thickness reduc- formed by ferrite and cementite at high temperature
tion from 7.12 to 3.66 cm (50 pct strain), and a second [473 K to 623 K (200 C to 350 C)], while it is
one from 3.66 to 1.1 cm (70 pct strain). If high constituted by ferrite and transition e- and g-carbide at
deformations are created at approximately the Ac3 low temperature [673 K to 873 K (400 C to 600 C)].[41]
critical temperature, a very fine and homogeneous grain The crystalline structure exhibits a rearrangement, but
size (static recrystallization) will result only if an there is insufficient time that is to attain phase decom-
austenitic–ferritic transformation occurs at medium position in carbides and ferrite. If the transformation-
cooling rates.[39] For that, steel C had a frequency of temperature–time (TTT) diagram could be displayed,
370 for a small grain area which is the highest grain then bainite should be stable at times longer than
refinement in these three steels. 300 minutes because of the influence of the chemical
The area grain distributions which resulted from tem- composition.[39]
pering are shown in Tables III and IV. The analysis was
performed per steel, and the details are described below.
F. TEM Image Results
Steel A has a frequency of 144 for S GS at
temperatures of 473 K and 673 K (200 C and 400 C) Figure 5 exhibits the precipitates found in the
at 10 minutes. Steel A has a frequency of 40 for S GS at steels after they underwent different thermomechanical
treatments and tempering. The images show that the G. Hardness and Toughness Results
precipitate morphologies have cubic crystalline struc- The hardness number, Rockwell C (RC), was
ture. The chemical composition was obtained in cubic obtained, but steel C has a low RC hardness number
precipitates by SEM, and it showed the presence in the that is not acceptable using the standards.[30] Steel C
cubic morphology precipitates of Ti, Nb; see Fig- hardness was taken in RC and Rockwell B (RB) scales,
ures 5(c) and (f). The main precipitates were complex and the numbers are in good agreement if the experi-
carbonitride compounds of niobium and titanium; this mental result and the equivalence between RC and RB
is in agreement with the thermodynamic calculations scales are compared. Steel C is mainly F and has the
that were described in Section III–A. It is important to lowest hardness among these materials. On other hand,
mention that the stoichiometry was only obtained from the microstructure of steel A has M (Figure 5) and has
thermodynamic calculations, and it was associated with the highest hardness. Although material B is containing
the experimental results in TEM images. However, a B and M/A, the microstructure of steel B produces a
specific experimental technique was not used to identify hardness number similar to steel A. The three materials
the precipitate stoichiometry. slightly decreased in hardness as the tempering time
increased at 473 K (200 C). The precipitates and the retained austenitic. During the third stage, ferrite and
phases were not affected, which demonstrates that the cementite are obtained from low carbon martensite and
materials would maintain their strength at this temper- transition carbides. During the fourth step, cementite
ature (Figure 6(a)). On the contrary, the hardness of the coarsening, as well as the polygonization and creation of
steels increased before 10 minutes, and then it dimin- equiaxed grains, occurs.[39]
ished from 10 to 300 minutes at 673 K and 873 K The first stage can be obtained at 473 K (200 C), and
(400 C and 600 C). even if there is a change in carbon distribution, it would
A peculiar observation regarding to steel A is that it not change the hardness at 473 K (200 C), because the
exhibited a larger hardness decrement than steel B for steel that is used in this work is low carbon and thus
tempering times from 3 to 300 minutes at 673 K and would not be affected by the redistribution of this small
873 K (400 C and 600 C). Steel A exhibited a small quantity of carbon. The second stage of tempering is
decrement in HRC number at 10 minutes from 34 to 32 obtained due to the austenite decomposition to cement-
at 673 K (400 C) and from 30 to 26 at 873 K (600 C). ite (or carbides transition) and martensite.[42] This was
As the tempering time increased at 300 minutes, the steel observed in a hardness increment at short time
A hardness was 21 at 673 K (400 C) and 28 at 873 K (£10 minutes) at 673 K and 873 K (400 C and
(600 C); while the steel B hardness decreased from 33 to 600 C), as shown in Figures 6(b) and (c). The third
32 at 673 K (400 C) and from 38 to 32 at 873 K stage consists of the decomposition of martensite in
(600 C) at 10 min; the hardness value stabilized to 31 at bainite, ferrite, and cementite at temperatures, which
673 K (400 C) and 28 at 873 K (600 C) at 300 min- was not observed in the SEM images. However, there
utes. Steel C had a very small reduction of around 2 RB was a hardness reduction at 673 K and 873 K (400 C
units in tempering temperatures and times. The behavior and 600 C) that resulted from the grain size transfor-
and the values described can be attributed to the stages mation-redistribution.
of plain carbon steel tempering. The first stage is Steel A had a decreasing frequency in the S GS, but
described as the formation of transition carbides and steel B did not have a frequency reduction in S GS.
low carbon martensite from the quenching martensite. Thus, the frequencies are almost the same for both
During the second stage, bainite and ferrite form from steels at tempering times at 300 minutes. The phase
Fig. 8—Polarization results in (a) 0.1 M H2SO4 and 3.5 wt pct NaCl, (b) 3 M H2SO4 and NS4 electrolytes.
Table V. Charge Transfer Resistance from Equivalent Circuit in Figs. 11(a) and (b) in Different Electrolytes
Steel: A B C A B C A B C A B C
Electrolyte: 0.1 M H2SO4 3 M H2SO4 3 wt pct NaCl NS4
Rct (X cm2) 37.83 46.67 74.66 14.27 15.55 18.06 12930 13000 16139 27266 29288 33520
Fig. 11—Nyquist diagrams of steels A to C tempered for 300 min at (a) 473 K (200 C), (b) 673 K (400 C), and (c) 873 K (600 C) in 3 M
H2SO4.
Steel: A B C A B C A B C
Tempering Temperature [K (C)]: 473 (200) 673 (400) 873 (600)
Rct (X cm2) 18.97 20.04 15.02 14.75 18.01 11.94 18.92 17.31 15.22
increment is due to the pH change and the products hardness result, while steel B and C did not have a
obtained on the surface. In the NS4 solution, the significant change.
obtained values are higher by three orders of magnitude
for the Rct when compared to the resultant values in
H2SO4. The Rct is approximately 30000 X cm2 for all the IV. CONCLUSIONS
alloys. The Rct value in NaCl (15,000 X cm2) is half of
the Rct in NS4 (30,000 X cm2). The precipitates that improved both strength and
The impedance results were similar to the polarization ductility in the steel are complex carbonitrides of Nb
curve ones. This is the impedance that was higher in and Ti. Aluminum nitride was not obtained in the
H2SO4 than in NaCl or NS4 electrolytes. The corrosion results due to the low N content in the steel used in this
rate increased as the sulfuric acid concentration work.
increased. The behavior between NaCl and NS4 is in The best combination of yield strength and ductility
accordance to that which was recorded by the DC was achieved with a 98 pct bainite and 2 pct martensite/
technique, which demonstrated that the formed layer austenite microstructure (steel B). The highest strength
had better resistance in NS4 than the one formed in with the lowest ductility was attained with a microstruc-
NaCl. ture of 56 pct martensite and 32 pct bainite (steel A).
Impedance test results from the thermomechanical The highest ductility with the lowest strength was
heat treatment reveal that the corrosion resistance Rct obtained with a microstructure of 95 pct ferrite and 3
follows this order: Rct A < Rct B < Rct C in 0.1 M and 3 martensite/austenite(steel C).
M H2SO4. The majority M structure of steel A has the The hardness was found to be in accordance with the
lowest corrosion resistance, followed by the structure of microstructure constituents: steel A was the hardest,
steel B that has 98 pct B and 2 pct M/A. The steel C has while steel B had high hardness comparable to that of
the best corrosion resistance with a microstructure of 95 steel A; the softest steel was C.
pct F and 3 pct M/A. In steel B, the bainite microconstituent was stable at
A new microstructure modification was performed to tempering times of 300 min, this bainite 98 pct ensured
provoke an effect on the corrosion behavior, consisting that this steel maintained its strength over tempering
of a tempering heat treatment for the three steels. The time and temperature.
corrosion behavior was monitored by EIS in 3 M The nanometer-sized carbide precipitate in low car-
H2SO4. The EIS results are shown in Figure 11, while bon steel did not have a significant influence on
the Rct fitting ones are shown in Table VI. The corrosion behavior. For samples that were tempered
tempering effect was previously obtained in carbon steel for 300 minutes, the microstructure difference slightly
immersed in H2SO4 using the mass loss technique,[47] increased the corrosion rate in this order: steel C, steel
and the results showed the corrosion rate decreased as A, and steel B. Therefore, the steel microstructure had a
the tempering temperature increased in quenched and minimal effect on corrosion behavior at short times of
tempered steel with a medium carbon content (0.36 to immersion.
0.44 wt pct). The Rct did not exhibit similar behavior in
this work; the resistance remained at approximately the
same value in the case of the same steel. There was a ACKNOWLEDGMENTS
difference of 2 to 10 X cm2 among the three steel
samples, depending upon the tempering temperature Financial support from Consejo Nacional de Cien-
and the alloy microstructure. cia y Tecnologı́a (CONACYT, México) Ph.D. scholar-
The behavior found for 300 minutes of tempering is ship to J.I.B.-F is gratefully acknowledged. In
shown in Figure 11. The Rct order is C<A<B at 473 K addition, the authors want to thank Ivan Puente Lee
(200 C); C < A < B at 673 K (400 C); and C < B < A from Facultad de Quı́mica, UNAM, for his help in the
at 873 K (600 C). It could be seen that there is a small SEM and TEM work.
impedance change between the thermomechanically
treated samples and the ones that were tempered at
300 min. The corrosion resistance was modified, because REFERENCES
the tempering modified the grain size and phases
distribution in the steels. A phase modification was 1. H. Van Long, D. Jean-François, L.D.P. Lam, and R. Barbara: J.
Constr. Steel Res., 2011, vol. 67, pp. 1001–21.
not recorded in the SEM images; however, the steel A 2. B.H. Smith, S. Szyniszewski, J.F. Hajjar, B.W. Schafer, and S.R.
had a modification in the grain distribution and the Arwade: J. Constr. Steel Res., 2012, vol. 71, pp. 1–10.