Review report

on
Microstructure and Strengthening
mechanisms in cold drawn pearlitic steel wire

Submitted by
Shubham Pandey , Anuvrat Singh Hada and
Priyanshi Jain
Undergraduates
Dept. of Materials Science and Metallurgical Engineering
MANIT, Bhopal


Physical Metallurgy of Steels
Course Code: MSM 334
SUMMARY
This review paper deals with the strengthening mechanisms and
strengthstructure relationships which have been analyzed in a cold-
drawn pearlitic steel with a structural scale in the nanometer range and a
flow stress of about 3.5 GPa. The wires have been drawn up to a strain
of 3.7 and the structures analyzed and quantified by transmission
electron microscopy and high resolution electron microscopy. The
mechanical properties have been determined by tensile testing. It is
found that the interlamellar spacing and the thickness of the cementite
lamellae are reduced in accordance with the changes in wire diameter up
to a strain of 2.5. At a higher strain enhanced thinning of the cementite
lamellae points to decomposition of the cementite and carbon
enrichment of the ferrite lamellae.
With respect to the above found results, following three strengthening
mechanisms have been analyzed :-

Barrier or boundary strengthening
Dislocation strengthening
Solid solution hardening



Introduction

Pearlitic Steel
Pearlite is a two-phased, lamellar (or layered) structure composed of
alternating layers of alpha-ferrite (88 wt%) and cementite (12 wt%) that
occurs in some steels and cast irons. In fact, the lamellar appearance is
misleading since the individual lamellae within a colony are connected
in three dimensions; a single colony is therefore an interpenetrating
bicrystal of ferrite and cementite. Some hypereutectoid pearlitic steel
wires, when cold wire drawn to true (logarithmic) strains above 5, can
even show a maximal tensile strength above 6 GPa.

Cold Drawing/Working
Work hardening, also known as strain hardening or cold working, is
the strengthening of a metal by plastic deformation. This strengthening
occurs because of dislocation movements and dislocation generation
within the crystal structure of the material.
[1]
Many non-brittle metals
with a reasonably high melting point as well as several polymers can be
strengthened in this fashion.

Strengthening Mechanisms
Methods have been devised to modify the yield strength, ductility,
and toughness of both crystalline and amorphous materials. These
strengthening mechanisms give engineers the ability to tailor the
mechanical properties of materials to suit a variety of different
applications. Plastic deformation occurs when large numbers
of dislocations move and multiply so as to result in macroscopic
deformation. In other words, it is the movement of dislocations in the
material which allows for deformation. If we want to enhance a
material's mechanical properties (i.e. increase the yield and tensile
strength), we simply need to introduce a mechanism which prohibits the
mobility of these dislocations. Whatever the mechanism may be, (work
hardening, grain size reduction, etc.) they all hinder dislocation motion
and render the material stronger than previously.

Significance of Cold-Drawn pearlitic steel wire
Cold-drawn high-carbon steel wires of approximately eutectoid
composition have the highest strength of all steel products, up to
56 GPa.

They have wide industrial applications, including cables for
suspension bridges, steel cords for automobile tyres and springs.

The high strength is also of interest in new applications, for
example where steel wires may be used as reinforcement in
windmill wings for cleaner energy production.

Objectives
Investigation of five samples at five different cold-drawing strains,
covering different strain hardening stages.
Observation under SEM.
Measurement of ILS (Interlamellar spacing) and cementite
thickness by TEM observation.

Past theories relating strengthening mechanisms
Studies of deformation mechanisms and microstructure in drawn
pearlitic wires date back to the 1960s and 1970s, and seminal papers
have been published by Embury and Fisher and Langford. These
authors primarily related the high strength to the close spacing between
the cementite lamellae (or fragments) on the assumption that the
cementite acts as a barrier to dislocation glide, as do grain boundaries in
polycrystalline iron. They therefore introduced the HallPetch
relationship and related the flow stress of the wires to the reciprocal
square root of the spacing between the cementite lamellae (the
interlamellar spacing or ILS). It was found by transmission electron
microscopy (TEM) examination that this spacing decreases in
accordance with the reduction in wire diameter and a relationship
between the flow stress () and the strain () was formulated :

=
0
+ k
1
exp(/4)
where ,

0
= friction stress of the ferrite
k
1
=constant which can be derived from Hall-Petch slope

This equation is a good approximation of the evolution in flow stress
with increasing drawing strain, as has been shown in many studies.



Fig.1 Summary of mechanical data relating the flow stress to thedrawing
strain.
However, this figure also shows significant deviation from a linear
relationship, especially at large strains, which points to other
strengthening mechanisms in addition to the barrier resistance of
cementite. Such mechanisms could be legion, as the wire structure is
complex, but this paper will focus on dislocation strengthening and solid
solution hardening.

Evolution of Strengthening mechanisms

Our approach follows that of previous studies where strengthening of
drawn pearlitic wires has been considered as the additive effect of more
than one microstructural mechanism. The reason is that it has been
observed that a dislocation structure with a high density of dislocations
evolves in the ferrite lamellar and that these lamellae can be enriched by
carbon in solution, especially at high strains at which the cementite
lamellae start to decompose.

It follows that the following three strengthening mechanisms will be
analyzed: (i) barrier or boundary strengthening; (ii) dislocation
strengthening; (iii) solid solution hardening.

The analysis will be based on characterization of structural morphology
and structural parameters by TEM and high resolution electron
microscopy (HREM) also including Kikuchi diffraction analysis and
spot indexing by collecting nanobeam diffraction patterns by field
emission gun (FEG-)TEM. The wires have been drawn up to a strain of
3.7 giving a flow stress around 3.7 GPa. It is found that all three
mechanisms contribute significantly to the wire strength and that their
sum agrees well with the measured flow stress. This agreement leads to
a more general discussion of strengthening mechanisms in nanoscale
structures.









Fig. 2 General True-Stress strain curves for the wires.




Materials and Experimentation

Five samples at five cold-drawing strains covering the different
strain hardening stages in Fig. 1 of high strength, near-eutectoid
composition steel with a carbon content of 0.8 wt.% were
investigated. These samples represent intermediate steps of the
manufacturing process from the as-patented wire (1.26 mm) to the
final drawn filament (0.2 mm). The sample details are listed in
Table 1.


Table 1 : Summary of wire samples used

Sample Diameter (mm) Strain Area Reduction
(%)
1 1.260 0.00 0
2 0.899 0.68 49
3 0.591 1.51 78
4 0.332 2.67 93
5 0.200 3.68 9


Standard grinding and electropolishing (10% perchloric acid in
ethanol) procedures were used to prepare specimens for
investigationa by scanning electron microscopy (SEM) and TEM.
The wires were examined in the longitudinal section.

For the SEM observations specimens were additionally etched in
4% Nital. The ILS and cementite thickness were measured by
TEM, taking care to ensure edge-on conditions to determine the
cementite thickness.

Additionally, the ILS of wires deformed to low strains (e < 1.51)
was measured by SEM using the method of Gensamer et al. [19].
For each sample data were collected from 30 measurements on
randomly chosen areas. Dislocation configurations and densities
were examined using a JEOL 2000FX TEM at 200 kV and a JEOL
3000 FEGTEM at 300 kV.

Results

a) Morphology and structural parameters :

In agreement with previous findings , it was found that the cementite
plates align with increasing strain to the extent that about 97% are
realigned parallel to the drawing direction when the drawing strain
reached 1.5 with an angular spread of 30
o
. The reduction in thickness of
the ferrite lamellae (F) and thickness of the cementite lamellae (T) have
been measured and related to the drawing strain, shown in Fig. 3 and
Table 2. On the assumption that T is reduced in accordance with the
wire diameter, T can be related to the true strain, which is expressed as:
= ln(A
o
/A) or ln(D
o
/D)
2


where, A
o
and D
o
relate to the cross-sectional area and the diameter of
the initial wire and A and D refer to those of a drawn wire. T can then be
expressed by the relationship :

T= T
o
exp(-/2)
where, T
o
is the original thickness of about 19 nm.





Table 2 : UTS and elongation used in the wires

Strain UTS(MPa) Elongation(%)
0.00 1368 9.0
1.51 1904 2.7
2.67 2674 1.9
3.68 3640 2.1


It can be seen that there is good agreement between the measured and
the calculated ILS, in support of the assumption leading to namely that
this spacing decreases in accordance with the reduction in wire diameter.
In the low strain part of the curve (up to approximately e = 1.5) it is
recognized that there are a number of complications with such an
analysis.

These include the fact that the wire center is likely to deform by plane
strain rather than an axisymmetric deformation mode (as indicated by
the characteristic curling seen in the transverse sections of drawn wire
and also the fact that significant reorientation of the pearlitic structure
takes place as the microstructure evolves towards one where the ferrite
and cementite lamellae are parallel to the drawing axis.

It is believed that these factors are reflected in the larger scatter seen in
thickness measurements at the lowest investigated strain (e = 0.68).
Overall, however, cementite evolution (and ILS) follows the prediction
from the assumption of simple axisymmetric deformation. However, for
a strain above 3 the calculated thickness of cementite is 2.9 nm, whereas
the measured thickness is about 2.1 nm. This difference points to a
decompositionof about 30 wt.% cementite with about 1.1 at.% carbon
enriching the ferrite based on the original concentration of 3.63 at.% (0.8
wt.%) carbon.

b) Dislocation configuration and density :

The mechanical properties of deformed metals are dominated by
dislocation storage, and the dislocation density in the ferrite lamella is an
important factor in understanding the strain hardening and its
contribution to the flow stress of drawn pearlitic steel wires.
The random dislocation lines can be observed as a result of the phase
transformation. Dislocation configurations in the ferrite lamellae parallel
to the drawing direction at a strain of 0.68 are shown in the above
figures. Most of the dislocations are spread in the ferrite lamellae, with
the two ends of the line located at the steps in the ferrite/cementite
boundaries. Calculation of the dislocation density gives a value of 7
*10
14
m
-2
, which is in accordance with the results of crystallographic
orientation measurements.


Analysis of structure and strength

The relationship between microstructure and strength will be analyzed
on the basis of the structural observations pointing to three strengthening
mechanisms contributing to the wire strength:

boundary strengthening related to the distance between he
cementite lamellae (r(b));

dislocation strengthening related to the dislocation density in the
ferrite lamellae (r(q));

solid solution hardening related to the carbon concentration in the
ferrite lamellae (r(ss)).


I. Boundary Strengthening :-

The contribution of cementite lamellae to the strength is estimated based
on the HallPetch equation relating the yield stress () to the distance
between barriers which can act as obstacles to dislocation glide. This
relationship had been shown to be valid in the case of polycrystalline
metals where the barrier distance is equal to the grain size. In applying
this equation to pearlite the barrier spacing is taken to be equal to the
mean free path of dislocations, which is estimated to be twice the width
of the ferrite lamellae (d), i.e
=
o
+ k(2d)
-0.5

This application of the relationship is based on the assumption that the
lamellae as grain boundaries can act as barriers to dislocation glide and
that yield takes place when the stress ahead of a pile-up of dislocations
reaches the strength of the barrier or the stress to operate a dislocation
source in the neighboring grain. It is also an interesting result that the
resistance of cementite lamellae is almost constant with increasing
strain, as such an increase leads to a significant change in both the
dimensions and structure of the cementite lamellae . This problem is,
however, for future research as it involves not only characterization of
the cementite but also the cementiteferrite interface, taking into account
both the distribution of dislocations and carbon atoms in solution which
may enhance the interfacial resistance to glide.

II. Dislocation Strengthening :-

Dislocation strengthening has in the present analysis been based on
microscopical characterization and quantification of the dislocation
structure in the ferrite lamellae. The dislocation density has been
estimated based on TEM and HREM investigations and a supplementary
analysis has been carried out to measure the change in the
crystallographic orientation in the narrow ferrite lamellae using
nanobeam diffraction patterns . The contribution of dislocation density
to the wire strength has been estimated as forest hardening proportional
to the square root of the dislocation density. As an alternative to this
mechanism it has been suggested that the flow stress of fine laminated
structures as multilayers and drawn wires is controlled by the
propagation of single dislocation loops in the volume between interfaces
and the deposition of dislocations at or near the interface.
The controlling stress may then be the stress to propagate a dislocation
(Orowan stress) and/or the stress to push a dislocation through the
interface. Inherent in this alternative mechanism is that dislocations are
only stored at or near the interfaces and not in the interior volume. For
drawn pearlitic wires the present observations show that this is not the
case, as both the dislocation density is very high both in the ferrite
lamellae and at the ferritecementite interface.

III. Solid Solution Hardening :

Solid solution hardening has in this analysis been analyzed based on
measurements of the thickness of the cementite lamellae. This estimate
shows that at the highest strain (e = 3.68) the cementite has started to
decompose, which agrees with previous observations showing that
carbon enrichment of the ferrite may take place when the strain is large.
Carbon enrichment of the ferrite is expected to lead to hardening due to
interaction between carbon atoms and dislocations. To study this
strengthening mechanism future investigation may therefore try to
correlate atom probe and TEM observations of both interior volumes
and volumes near the ferritecementite interface.

Conclusions

The microstructure of drawn pearlitic steel wires has been quantified by
TEM and HREM and strength structural relationships have been
analyzed for wires drawn at strains up to 3.7, where the interlamellar
spacing is about 20 nm and the strength is about 3.5 GPa. The
conclusions are as follows:-

The interlamellar spacing and the thickness of the cementite
lamellae are reduced in accordance with the change in wire
diameter up to a strain of 2.5. At a higher strain (e = 3.7) enhanced
thinning of the cementite lamellae points to decomposition of the
cementite and carbon enrichment of the ferrite lamellae.
Dislocations are stored in the interior of the ferrite lamellae and
their density increases to about 2*10
16
m
-2
at the highest strain. A
high dislocation density is also observed at the ferritecementite
interface.

The microstructural analysis suggests that three strengthening
mechanisms are major contributors to the strength of the pearlitic
steel wire: (i) boundary strengthening, which increases with
decreasing spacing between the cementite lamellae; (ii) dislocation
strengthening, which increases with the density of dislocations in
the ferrite lamellae; (iii) solid solution hardening, which increases
with the carbon concentration in the ferrite lamellae.

The individual contributions from the three strengthening
mechanisms to the wire strength have been estimated based on
structural parameters, which were quantified experimentally, and
on the assumption that these contributions are linearly additive.
Good agreement has been found between the estimated and the
measured flow stresses, which is underpinned by a discussion of
the three strengthening mechanisms in nanoscale structures.

Limitations

The observation of morphological changes and the detailed
analysis show that the structural evolution is not homogeneous
during wire drawing. At small and medium strains the cementite
reorients, a process which involves shear banding and grain curling
Such heterogeneities change the structural morphology but may
also affect the density and arrangement of dislocations in the ferrite
lamellae. However, the characterization of such heterogeneities is
for further research, as it will require a fairly detailed
characterization of microstructural parameters at different positions
in the wire. The following analysis will therefore be based on the
assumption of a fibrous structure where the ferrite and cementite
lamellae are parallel to the drawing direction and values for the
interlamellar spacing and the dislocation density will be the
average values for all structures.

Quantification of the degree of misorientation of ferrite lamellae
by TEM is still a challenge. For example it has been found by
dislocation strengthening that misorientations of at least several
degrees exist over a distance of about 100 nm at a strain of 3.68,
which gives a minimum value for the dislocation density in the
ferrite of about
min
= 1.4*10
15
m
-2
. However, this value is a lower
bound of the density, as dark field TEM investigations suggest that
misorientation changes take place over a much smaller distance
than 100 nm, in accordance with a previous TEM observation
showing slightly different crystal orientations within the ferrite
lamellae and also the presence of dislocations and internal strains
in these lamellae.

There is still some debate over the extent (and onset strain) of
cementite dissolution during the wire drawing process, partly due
to experimental difficulties with obtaining such data.