Structural Analysis of Austempered Ductile Iron Obtained by Mössbauer Spectros

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Archives Volume 31 International Scientific Journal

Issue 2 published monthly by the


of Materials Science June 2008 World Academy of Materials
and Engineering Pages 101-104 and Manufacturing Engineering

Structural analysis of austempered ductile


iron obtained by Mössbauer spectroscopy
A. Hanc a,*, F. Binczyk b
a Institute of Materials Science , University of Silesia,
ul. Bankowa12, 40-007 Katowice, Poland
b Chair of Metal Alloys and Composites Engineering, Silesian University of Technology,
ul. Krasiñskiego 8, 40-019 Katowice, Poland
* Corresponding author: E-mail address: ahanc@us.edu.pl
Received 13.04.2008; published in revised form 01.06.2008

ABSTRACT

Purpose: The composition of metallic matrix in ductile iron as-cast and after austempering at temperatures of
280, 330 and 380oC (ADI) was examined.
Design/methodology/approach: The study presents the results of these examinations obtained by Mössbauer
spectroscopy.
Findings: Using calculated values of the parameters of hyperfine interactions (isomeric shift IS, quadrupole
splitting QS and hyperfine effective magnetic field H), isolated by deconvolution of the experimental spectrum,
the constituents of the metallic matrix were identified in terms of both quantity and quality.
Research limitations/implications: The measured values as well as the data compiled in literature indicate
that component Z1 (the, so called, Zeeman spectrum sextet) is related with 57Fe atoms present in the structure
of ferrite α1 (I stage of γo→α1 + γst transformation), component Z2 is typical of ferrite α2 (II stage of γst→α2 +
carbides transformation), while component Z3 has its origin in 57Fe atoms seated in the structure of carbides
(Fe3C, Fe2C or Fe2,4C).
Practical implications: analysis of the parameters of hyperfine interactions describing the non-magnetic
components (L and Q) it has been proved that they are typical of austenite.
Originality/value: In the case of ADI, the determination of the composition of metallic matrix by Mössbauer
spectroscopy is much more precise (the limit is the resolution power), because the experimental spectrum describes
an overall volume of the examined specimen, and not only its surfaces, as does the traditional quantitative
metallography.
Keywords: Austempered ductile iron; Mössbauer effect; Microstructure; Austenite, Ferrite

METHODOLOGY OF RESEARCH, ANALYSIS AND MODELLING

constituents having an adverse effect on the plastic properties of ADI.


1. Introduction
Introduction Therefore it is expected that the results of qualitative and quantitative
examinations of the phase composition may help in determination of
The mechanical properties of ADI (Austempered Ductile the heat treatment parameters optimum for the ductile iron of a given
Iron) depend on microstructure shaped in a two-stage heat chemical composition and primary microstructure. Such possibilities
treatment process, which consists of austenitising and are offered by the Mössbauer Effect spectroscopy, which uses the
austempering [1-3]. Depending on the parameters of this changing capacity to transmit rays and energy emitted during
treatment, the metallic matrix may contain different amounts of nuclear transitions of absorbent, depending on the type of
austenite, ferrite, pearlite and martensite, the latter two chemical bonds and crystal structure [4,5].

© Copyright by International OCSCO World Press. All rights reserved. 2008 101
A. Hanc, F. Binczyk

The extremely high energy resolution of the Mössbauer effect Using this program and a numerical analysis, the
enables detecting a relatively weak effect of the crystallochemical deconvolution of the experimental spectrum into its components
environment on the energy levels of atomic nuclei. Mössbauer (sub-spectra) related with the local environment of Mössbauer
57
spectroscopy is a powerful tool in crystallochemical and structural Fe nuclide was carried out. Due to this, it was possible to
examinations. It helps understand atomic movements in the crystal analysis the phase composition of the examined material. Using a
lattice, the behaviour of dopant atoms, the nature of chemical bonds, set of parameters (IS, QS, H) describing the individual
valency and ionic coordination; it also creates an opportunity for components (sub-spectra), it was possible to identify the
investigation of the internal magnetic field and electric field gradients magnetic and non-magnetic phases, i.e. the IS and QS parameters,
acting on the atomic nuclei in a crystal [6, 7]. or IS only in the case of single lines.
Mössbauer spectroscopy was used to determine the effect of The procedure used for computation of the phase composition from
heat treatment on phase composition of an Fe-Al-C alloy [8] and an experimental Mössbauer spectrum covers the following stages:
on the thermal stability of metastable austenite present in the Initial analysis of the experimental spectrum (carried out by
rapidly solidified tool steel [9]. The same method also served for the method of distribution of magnetic fields and isomeric
determination of structural constituents present in HAZ of the shifts) - it enables qualitative identification of phase
welded, low-carbon, manganese-nickel-molybdenum steel and for composition in the examined material, including the presence
analysis of the precipitates of carbide during the plastic of phases of magnetic and non-magnetic properties.
deformation-induced phase transitions in high-carbon steel Describing each phase with hyperfine parameters - the
[11-16]. Applying Mössbauer spectroscopy it has been noticed preliminary characteristic uses parameters ascribed by
that manganese in compacted graphite cast iron reduces the literature to each of the phases, while computations are made
kinetics of isothermal transformation taking place within the for the percent fraction of each phase in the examined
temperature range of 200 to 400oC [17]. specimen obtained by integration of the surface area covered
by component spectrum corresponding to a given phase.
Having calculated the percent fraction of a given phase,
2. Test
Test material
material and method
method parameters H, IS, and QS are fitted in a way such as to reproduce
exactly the shape of the experimental spectrum, which is the sum
Tests were made on ductile iron containing: 3,75 % C, 2,55% of all sub-spectra describing the individual phases.
Si, 0,19% Mn, 0,08% Mg, 0,62 % Cu, 1,42% Ni as well as 0,08% The last stage consists in determination of parameter S (the
S and 0,03% P. The specimens cut out from a 10 mm casting were intensity of component spectrum), which directly determines
subjected to heat treatment to obtain ADI. The process of the content of a given phase in specimen.
austenitising was carried out for 2h at a temperature of 900oC. The analysis is carried out until a most adequate mode of
Austempering was made in a salt bath (50% KNO3 and describing the shape of an experimental spectrum with a curve,
50%NaNO3) at temperatures of 280, 330 and 380oC, applying which is the sum of all the applied components, is found. The
next CEMS (Conversion Electron Mössbauer Spectroscopy), measure of correctness of the conducted analysis is parameter !2
which enabled examinations of a surface layer about 100 nm with a minimum value of 1. As regards the spectra of the
thick. Gas-filled detector (0.98% He +0.02% Ar) at a pressure of examined material, the value of the parameter describing the
0.9 At was applied. The source of Mössbauer radiation was quality of fit is !2<2.
Co57/Rh of about 10 mCi activity. The measurements were carried On the other hand, Figure 1 shows the same solution applied
out at room temperature. The spectrometer was systematically to a specimen after austempering at a temperature of 330oC. The
calibrated measuring the Mössbauer spectra in a specimen of !- solution so called, Zeeman components Z1, Z2 and Z3 and Z3 and
Fe. The parameters of component spectra were determined by an two non-magnetic components, i.e. a single line L and the, so
MOSDS program, which was used in discrete analysis of the called, quadrupole doublet Q.
experimental Mössbauer spectra. 1,03
exp
Z1
Z2
3. The results
3. The results of
of investigations
investigations Z3
radiation rate, r.u

1,02
Q
The metallic matrix phase composition examined by L
Mössbauer spectroscopy was determined from a discrete analysis
of the experimental Mössbauer spectra using an MOSDS 1,01
program.
In this program, the shape of the Mössbauer spectra is
described by a transmission integer computed according to Gauss-
1
Legandre’a numerical procedure. The program enables very -8 -6 -4 -2 0 2 4 6 8
accurate determination of the following parameters: V, mm/s
isomer shift - (IS),
quadrupole splitting - (QS), Fig. 1. Solution of spectrum with breakdown into individual
hyperfine effective magnetic field - (H), magnetic components Z1, Z2 and Z3 and non-magnetic
intensity of fitted components - (S). components L and Q for specimen after austempering at 330oC

102 102 Archives of Materials Science and Engineering


Structural analysis of austempered ductile iron obtained by Mössbauer spectroscopy

Table 1.
The computed phase compositions of the metallic matrix in the examined specimens ( 20 mm)
Spectrum H IS QS S Structural Fraction
State
component kGs mm/s mm/s - constituent %
Z1 320.6 0.01 0.02 0.11 Ferrite 1 11
After casting
Z3 233.6 0.16 0.11 0.89 Carbides(Pearlite) 89
Z1 317.5 0.01 0.017 0.76 Ferrite 1 76
Austempering
Z2 289.0 0.04 0.003 0.12 Ferrite 2 12
temperature
o Q - 0.21 0.48 0.07
280 C Austenite 12
L - -0.15 - 0.05
Z1 322.8 0.01 0.02 0.62 Ferrite 1 62
Austempering Z2 279.4 0.04 0.001 0.17 Ferrite 2 17
temperature Z3 189.7 0.14 0.03 0.03 Carbides(Pearlite) 3
330oC Q - 0.19 0.48 0.12
Austenite 18
L - -0.14 - 0.06
Z1 326.4 0.016 0.032 0.44 Ferrite 1 44
Austempering Z2 279.3 0.04 0.001 0.17 Ferrite 2 17
temperature Z3 249.3 0.11 0.033 0.05 Carbides(Pearlite) 5
380oC Q - 0.19 0.248 0.28
Austenite 34
L - -0.14 - 0.06

Error estimated from the fitting procedure is equal :


H = +/-0.2 kGs, IS = QS = +/-0.002 mm/s and S = +/-0.2

4. Discussion of
of results
results The Zeeman component Z2 originates from ferrite !2 (the
4. Discussion product of "st!!2 + carbides transformation), while component
The phase compositions of the specimens computed from the Z3 originates from 57Fe atoms present in the structure of carbides
intensities of the spectra of individual constituents were (Fe3C, Fe2C or Fe2,4C). On the other hand, from analysis of the
designated as S and compiled in Table 1. According to the data parameters of hyperfine interactions describing the non-magnetic
given in literature, the magnetic components (Zeeman components (L and Q) it follows that they are typical of the stable
components) characteristic of the phases which should be austenite "st, saturated with carbon, formed during the first stage
expected in the examined material are described by the following of isothermal transformation ("o!!1 + "st). The different values of
values of hyperfine parameters [18]: the parameters H, IS and QS observed in different phase
! for ferrite: field intensity H is from 300 to 330 kGs, isomeric constituents (e.g. Fe3C, Fe2C or Fe2,4C carbides as constituents of
shift IS is up to 0.02 mm/s, pearlite) may be due to differences in their morphology, to
! for martensite: field intensity H is from 240 to 270 kGs, isomeric interactions between the field intensities H originating from ferrite
shift IS is from -0.01 to + 0.04 mm/s, QS is up to 0.02 mm/s, !1 and !2 , and to the presence or absence of austenite in matrix,
! for Fe3C cementite: field intensity H is 200 kGs . e.g. in base cast iron.
! for Fe2C carbide: field intensity H is from 230 to 240 kGs, The compositions of the metallic matrix in as-cast state and
The non-magnetic components for austenite are: IS from -0.1 after austempering, as determined by Mössbauer spectroscopy,
to -0.2 mm/s and QS from 0.2 to 0.4 mm/s. are compared in Figure 2.
The above comparison gives average values typically
describing the individual phases. It is worth mentioning that the 100
89
ferrite 1
value of the hyperfine magnetic field H depends on the number of ferrite 2
76 austenite
Fe atoms present in the local environment of a Mössbauer nuclide 80
pearlite (carbides)
and is the higher, the more of these atoms are present in a given 62
Fraction, %

structure. Due to this fact it is possible to distinguish between the 60


phases of the same crystal structure but different magneto- 44
electronic structure, as it is the case of ferrite 1 and 2. 40 34
Basing on the data given in literature and on the analysis of
the calculated values of the parameters of hyperfine interactions, 20 17 18
17
11 12 12
i.e. isomeric shift, quadrupole splitting and hyperfine magnetic 5
0 0 0 3
field, it has been concluded that the Zeeman component of 0
spectrum Z1 has its source in 57Fe atoms present in the structure after casting 280 330 380

of ferrite !1. In the as-cast specimens, this is the ferrite formed Austempering temperature, oC
during austenite transformation under stable conditions. In
specimens after austempering this is the ferrite formed during Fig. 2. Effect of austempering temperature on metal matrix
stage I of the isothermal transformation (("o!!1 + "st,). composition by Mössbauer spectroscopy

Volume 31 Issue 2 June 2008 103


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