SMM 10260 No.

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14 May 2014
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Scripta Materialia xxx (2014) xxx–xxx
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Effect of annealing on point defect population

in cold-drawn pearlitic steel wires
Q1 C. Borchers,a,⇑ A. Lehmberg,a M. Deutges,a J. Cižekb and R. Kirchheima,c,d
a
Institute for Material Physics, University of Göttingen, Göttingen, Germany
b
Department of Low-Temperature Physics, Charles University Prague, Czech Republic
c
Max-Planck-Institut für Eisenforschung, Düsseldorf, Germany
d
International Institute for Carbon–Neutral Energy Research (WPI-I2CNER), Kyushu University, Fukuoka, Japan
Received 15 January 2014; revised 25 February 2014; accepted 19 April 2014

Cold-drawn pearlitic steel wires were subjected to differential scanning calorimetry and resistivity measurements during heat-
ing. Both techniques yield two peaks, one at 500–600 K, the other at 400–450 K. Whereas the peak at 500–600 K can be ascribed to
voids consisting of about 10 vacancies as confirmed by positron annihilation spectroscopy, the low-temperature peak is ascribed to
V1C2 and/or V2C4 complexes.
Ó 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Pearlitic steel; Point defect recovery; Vacancy cluster; Positron annihilation spectroscopy

Cold-drawn pearlitic steel wires possess an
20 excellent combination of ductility and strength. There-
fore, they have great practical importance as, for exam-
ple, cable wire for suspension bridges, steel cord for
automotive tires, engineering springs, or piano strings.
This is why the microstructural evolution of cold-
deformed pearlitic steels has been, for many years, a
topic of considerable scientific research (e.g. [1–14]).
The presence of vacancy clusters or nanovoids in the
as-drawn wires has been shown unequivocally by posi-
tron annihilation spectroscopy (PAS) [15,16]. The pres-
30 ence of monovacancies at or above room temperature in
cold-drawn pearlitic steel wires has been discussed, but
it was not possible to show their existence experimen-
tally [17–19], although in numerous calculations, the
existence of carbon–vacancy clusters, generally in the
form of V1C2 agglomerates, was found to be quite prob-
able [20–23]. Experimentally, V1C1 complexes were
found by PAS in irradiated Fe–C [24–27], but corre-
sponding analysis of cold-drawn pearlitic steel wires is
difficult since the lifetime of a positron trapped at a
40 V1C1 complex is about as short as that of a positron
⇑ Corresponding author. Tel.: +49 551 39 5584; fax: +49 551 39
5012; e-mail: chris@ump.gwdg.de
trapped at a dislocation [15,16,24,25], and V1C2
agglomerates will not be detected by PAS [27].
The material used is a commercial steel wire with
the chemical composition 0.82C–0.20Si–0.50Mn–
0.005P–0.004S (wt.%). The initial material is a wire
which was austenitized at 1223 K and subsequently pat- Q2
ented in a lead bath at 833 K for 20 s. This wire was
heavily strained by wet wire drawing at room tempera-
ture conducted at a drawing speed v of 3.3  102 m s1
with a reduction in area of 20% per pass, corresponding 50
to a strain rate of 3  101 to 102 s1. The tempera-
ture rise during wire drawing did not exceed 100 K.
Wires 138.7 lm in diameter were produced by this draw-
ing process, corresponding to a true strain of 5.0. As-
drawn wires were examined by differential scanning cal-
orimetry (DSC) performed with a Perkin Elmer DSC 7
at a heating rate of 5 K min1. Resistivity measurements
performed with a self-made four-point device at a heat-
ing rate of 1 K min1. Other samples were annealed at
temperatures between 373 and 723 K for 30 min in a 60
high-vacuum furnace to perform subsequent positron
lifetime measurements at room temperature using a dig-
ital PAS spectrometer with a time resolution of 145 ps
(full width at half maximum, 22Na) [28]. Positron life-
time spectra, containing at least 107 positron annihila-
tion events, were decomposed into exponential

http://dx.doi.org/10.1016/j.scriptamat.2014.04.016
1359-6462/Ó 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: C. Borchers et al., Scripta Mater. (2014), http://dx.doi.org/10.1016/j.scriptamat.2014.04.016
 SMM 10260
14 May 2014
2 C. Borchers et al. / Scripta Materialia xxx (2014) xxx–xxx
components using a maximum likelihood based fitting
procedure [29]. Details of the PAS procedure are given
elsewhere [15,16].
70 Figure 1a shows a DSC scan of a wire cold-drawn to
e = 5. It can be seen that the cold-drawn wire shows two
distinct exothermic peaks at T1  416 K and at
T2  577 K with peak areas DH1  130 J mol1, and
DH2  250 J mol1. Figure 1b shows the resistivity dif-
ference DR = R(T)  R0(T) with R0(T) = 0.001T of a
wire cold drawn to e = 5. The curve clearly exhibits
deviations from linear behaviour, indicated by a dashed
horizontal line in the figure, with peak positions at
T1  430 K and at T2  580 K, nearly the same posi-
80 tions as in the DSC scan (see Fig. 1a). Figure 2 presents
the PAS results: three distinct positron lifetimes can be
observed, s1 (Fig. 2a and b) reflecting the presence of
free positrons annihilating in a delocalized state, i.e.
not trapped at defects. This component appears only
after annealing at 523 K with an intensity of 15% at
most. The component s2 (Fig. 2c and d) with an inten-
sity of up to 95% stems from positrons annihilated at
dislocations [15,16]. The component s3 shows the pres-
ence of positrons annihilated at vacancy clusters con-
90 taining 9–10 vacancies [15,16]. This component,
initially exhibiting an intensity of up to 10%, disappears
completely after annealing at 523 K for 30 min, when
the free positron component arises. When comparing
Figures 1 and 2, it is striking that the disappearance of
the component with lifetime s3 coincides with the DSC
and resistivity peak at 500–600 K. The peak temperature
at 577 K merely reflects the fact that the latter measure-
ments were performed at a heating rate of 5 K min1
Figure 1. (a) DSC scan of wires cold-drawn to e = 5. (b) Resistivity
difference DR = R(T)  R0(T) with R0(T) = 0.001T of wires cold-
drawn to e = 5.
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No. of Pages 3
Figure 2. Lifetimes s1 (a), s2 (c) and s3 (e) and corresponding
intensities I1 (b), I2 (d) and I3 (f) as measured by PAS.
(DSC), and a heating rate of 1 K min1 (resistivity),
whereas PAS measurements were performed at room 100
temperature after annealing for 30 min at the respective
temperatures. Therefore, it can be concluded that this
high-temperature DSC (resistivity) peak reflects the
decomposition of vacancy clusters decorated with
carbon. The decoration with carbon was shown by
coincidence Doppler broadening measurements, which
assessed that most positrons annihilated in the presence
of carbon [15,16].
The low-temperature DSC and resistivity peaks are
interesting: in cold-drawn pearlitic steel wires, DSC 110
peaks can be caused by phase transitions, recrystalliza-
tion or recovery of defects. The formation of an appre-
ciable quantity of iron carbides upon annealing of these
wires was shown to happen only after annealing at
temperatures as high as 723 K by high-resolution elec-
tron microscopy [17], and recrystallization happens
simultaneously [17]. The recovery of dislocations sets
in at temperatures >473 K, as can be seen in Figure
2d, and is suggested by post-annealing measurements
of the tensile strength of pearlitic steel wires cold-drawn 120
to e = 5, where the tensile strength is found to decrease
only after annealing at temperatures P523 K [17]. Since
PAS shows that vacancy clusters are stable up to
T = 523 K, this low-temperature peak must be due
to the annihilation of single or perhaps di-vacancies,
present in a species not detectable by PAS, if the
concentration is higher than the detection limit of
vacancies by PAS, 106 [25]. From ab initio calcula-
tions, Först and co-workers predicted that excess carbon
in a-Fe causes greatly enhanced vacancy concentration, 130
present mainly as V1C2 and V2C4 agglomerates when the
vacancy concentration is >106 [21]. It should be noted
that according to these calculations, the populations of
V1C1 and free vacancies do not exceed 1010 irrespective
of the total vacancy concentration.
The low-temperature DSC peak has an enthalpy of
transition of DH  125 J mol1  1.3  103
eV atom1
. Assuming, as a first approximation and in
accordance with the findings of Först et al., that the
binding energy of V1C2 is EB = 1.53 eV and that of 140
 SMM 10260
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C. Borchers et al. / Scripta Materialia xxx (2014) xxx–xxx
V2C4 is EB = 2.43 eV, and assuming further that the
enthalpy of transition is 90% due to V2C4 and 10% to
V1C2 as suggested in Ref. [21], one can calculate concen-
trations of 5  104 of V2C4 and 8.5  105 of V1C2.
These values should be considered to be rough estima-
tions, but give a feeling for the orders of magnitude with
which we are dealing. Other calculations yield similar
binding energies EB  1.5 eV for V1C2 [20,23] and
EB = 3.62 eV for V2C4 [23], values that do not change
150 the above estimates substantially—only the concentra-
tion of V2C4 would fall to 3  104. In a previous
study, the presence of vacancies in high concentrations
interacting with carbon was concluded from accelerated
Ni diffusion in cold-drawn pearlitic steel wires [30,31]. It
was concluded that the presence of carbon leads to a
strongly reduced vacancy formation enthalpy, which is
explained in the framework of the defactant concept
[32–34], which states that defect formation energies
decrease as solute atoms segregate to the defects. These
160 solutes were called defactants [34] in analogy to surfac-
tants that decrease surface formation energies. Using
the equation [35]:
xV ðT Þ ¼ expðS VF =k B Þ expðH VF =k B T Þ; ð1Þ
where xV  104 is the vacancy concentration,
SVF = 1.5 kB atom1 is the formation entropy of a
vacancy in Fe [36], HVF its formation enthalpy, kB is
the Boltzmann constant and T = 300 K is the tempera-
170 ture, the formation enthalpy can be calculated as
HVF = 0.28 eV1. This corresponds well with the activa-
tion enthalpy of defect recovery of 0.3 eV reported in
Ref. [17], where it was presumed that for temperatures
below 523 K this is due to the recovery of small
carbon–vacancy agglomerates.
To summarize, experimental evidence for the
presence of V1C2 and/or V2C4 complexes in cold-drawn
pearlitic steel wires was found for the first time. These
Q3 complexes are present at a concentration of the order
180 of 104, a finding that can be ascribed to a strongly
reduced enthalpy of vacancy formation in the presence
of carbon: HVF fell from 1.4 eV in pure Fe [37] to
0.28 eV in cold-drawn pearlitic steel with a carbon
concentration in ferrite of 0.6 at.% [14].
Q4 This work was supported by the Deutsche
Q5 Forschungsgemeinschaft via the Sonderforschungsber-
eich 602 and the Czech Science Agency (project P108/
12/G043), which are gratefully acknowledged. We
would also like to thank Dr. S. Nishida from Nippon
190 Steel Company for providing the wire specimens used
in this work.
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No. of Pages 3
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