Materials Science Forum Vols.

455-456 (2004) pp 290-294

Online available since 2004/May/15 at www.scientific.net
© (2004) Trans
Citation & Tech Publications, Switzerland
doi:10.4028/www.scientific.net/MSF.455-456.290
Copyright (to be inserted by the publisher )

Soft Annealing of High Chromium White Cast Iron

P. Amorim1, H. Santos1, J. Santos2,*, S. Coimbra2, C. Sá3

1
DEMM/FEUP, R. Dr. Roberto Frias s/ nº, 4200-465 Porto, Portugal
2
FERESPE, Brasiela, Fradelos, 4764-908 Ribeirão, Portugal
3
CEMUP, R. Campo Alegre, 832, 4150-180 Porto, Portugal

Keywords: high chromium white cast iron, soft annealing, phase transformations, dilatometry,
microstructure, x-ray microanalysis, metal processing.

Abstract. The objective of the present work is to establish the heat treating parameters necessary to
impose to a pair of high chromium white cast irons a hardness figure in the range from 35 to 40
HRC, acceptable to guarantee a reasonable machinability of the material. Samples of two high
chromium white cast irons have been isothermally annealed under different conditions. The
evolution of the phase transformations during the annealing process has been evaluated by
dilatometry, supported by optical and scanning electron microscopy, x-ray microanalysis (EDS) and
hardness evaluation. The results from this work demonstrate that the recommended procedure for
the soft annealing treatment of the high chromium white cast irons consists of a destabilizing step in
the austenitic domain followed by an isothermal decomposition of the austenite in the ferritic
domain.

Introduction
High Cr white cast iron is used in applications where high wear strength is required, particularly
under abrasion conditions. High Cr white cast irons contain not only a strong Cr addition, between
12 and 30 percent in weight, but also other carbide forming elements like Mo (not higher than 3.5
percent), V and W in smaller contents; they also receive currently Ni and Cu additions (up to 2
percent); Si content is kept lower than 1 percent, as higher figures are claimed to enhance pearlite
formation and decrease hardenability [1,2].
The objective of the carbide forming elements, in the presence of a C content around 3 percent, is
the formation of a high fraction of complex carbides, which ensure the high wear resistance.
The non carbide forming elements improve the hardenability of the austenite, which may change its
nature depending on the rate of cooling imposed to the parts after solidification. These elements are
also said to inhibit the pearlite formation [3], although this character is hard to accept mainly for Cu,
given that this elements is used in cast iron foundries to promote pearlitic microstructures.
This cast iron family is nowadays the optimum response to industrial activities where high wear
resistance is required, such as crushing, grinding, milling, pumping and moving aggressive materials
like ore, coal, sand and cement [4]. The suppliers of these industries are interested in offering
components with the highest economic added value. Sometimes they must impose some machining
operations to the cast components, a task requiring a previous soft annealing, followed by a re-
hardening treatment when the machining is concluded. The definition of the soft annealing
procedure is quite delicate, due the high hardenability of the material. The objective of this work is
to establish thermal cycles capable of imposing to a pair of high Cr white cast irons a hardness
figure in the range from 35 to 40 HRC.

*
corresponding author: ferespe@ferespe.pt

All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of TTP,
www.ttp.net. (ID: 130.194.20.173, Monash University Library, Clayton, Australia-05/12/14,23:08:07)
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Materials and Procedures

This work has been devoted to the soft annealing of two high Cr white cast irons, produced in an
iron and steel foundry, with the following chemical composition (in weight percent):

3.08C - 0.66Si - 0.57Mn - 0.022P - S<0.010 - 26.20Cr - 0.47Ni - 0.20Mo - 0.22Cu

2.91C - 0.45Si - 0.67Mn - 0.017P - S<0.010 - 19.10Cr - 0.25Ni - 1.36Mo - 0.62Cu
The soft annealing cycles have been run in a dilatometer Bahr model 801L. The test pieces were
cylindrical in shape, with the dimensions 50mm for the length and 8mm for the diameter.
A scanning electron microscope equipped with an energy dispersive spectrometer has been used to
characterize the microstructure of the test pieces and run the microanalysis. A SEM/EDS (JEOL
JSM6301F / NORAN - Voyager) has been used for this purpose. The microanalysis has been
conducted using 20 keV excitation voltage and the acquisition time has been 100 seconds. The
weight percent of each element has been calculated using a program accounting for ZAF
corrections. The C content has not been evaluated, so the figures presented in the following sections
do not account for C presence – nevertheless the ratio between the content of the different elements
in each alloy has been preserved.

Results
As cast material characterization. The 26% Cr alloy presents an as cast microstructure, shown in
figure 1, mainly composed of coarse carbides (C) and well developed austenite dendrites (A) in an
eutectic matrix (E). The as cast microstructure of the 19% Cr alloy is presented in figure 2 and
reveals an important fraction of primary dendritic austenite (A) in an eutectic matrix (E) – coarse
carbides are not detected. As a first approach, one may say that the higher Cr content in the 26% Cr
alloy has induced a stronger carbide fraction, what seems reasonable; this issue will be revisited in
the next section, since the apparent occurrence of two primary phases in the microstructure of the
26% Cr alloy needs to be discussed. The hardness of both materials was 52 HRC.

A E
E
A
C

50 Fm 50 Fm

Fig. 1. Optical microstructure of the 26% Cr cast Fig. 2. Optical microstructure of the 19% Cr cast
iron in the as cast state iron in the as cast state
(A – austenite; C – carbide; E – eutectic) (A – austenite; E – eutectic)

Several microanalysis were run on the 19% Cr alloy in the as cast state to evaluate the partition of
the alloying elements between the austenite and the carbide phase; the results are shown in table 1.
It is clear that Cr and Mo partition to the carbide phase, whilst Si, Ni and Cu prefer the austenite,
whatever in the eutectic or in the dendritic nature.
Soft annealing and dilatometry tests. Two different kinds of isothermal annealing were imposed
to the cast irons: a one-step annealing (in the ferritic domain) and a two-step annealing, composed
of a destabilizing stage in the austenitic domain plus a decomposition stage in the ferritic domain.
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To determine the limiting temperature of the stable ferritic domain, dilatometric tests have been
imposed to a test piece of each cast iron; the upper and lower critical points on cooling for the
austenite into ferrite transformation were respectively 707 and 614°C for the 26% Cr alloy and 718
and 627°C for the 19% Cr alloy; since Cr is a stabilizer of the ferrite phase, the relative hierarchy of
the critical points seems acceptable: increased Cr content decreased the critical points.
Data obtained from dilatometry applying the soft annealing are shown in figure 3 and table 2.
Table 1 – Average data from microanalysis for the 19% Cr alloy
Element Content Eutectic Eutectic Dendritic
in the alloy carbide austenite austenite
Si 0.45 0.1 0.7 0.5
Mo 1.36 2.9 1.5 0.4
Cr 19.10 48.0 8.7 12.0
Ni 0.25 0.2 0.4 0.5
Cu 0.62 0.2 0.9 1.0

0.30 0.25
h
c g
dl/l (%)

dl/l (%)
0.20 0.15
b f
0.10 0.05
a
e
d
0.00 -0.05
0 150 300 450 600 0 300 600 900 1200
time at 710°C (minutes) time in the ferritic domain (minutes)

Fig. 3. Relative change in length versus time curves during soft annealing
of 26% Cr (left) and 19% Cr (right) cast irons under conditions described in table 2
Table 2. Parameters for the soft annealing of the alloys and respective final hardness
26% Cr cast iron 19% Cr cast iron
Label Conditions for Label Conditions for
in fig. 3 soft annealing HRC in fig. 3 soft annealing HRC
710°C/12 hours 625°C/20 hours
a) 42-44 d) 48-50
(one-step annealing) (one-step annealing)
710°C/12 hours 725°C/20 hours
b) 34-37 e) 39-41
(after 880°C/5 hours) (one-step annealing)
710°C/08 hours 700°C/24 hours
c) 36-38 f) 40-42
(after 880°C/2 hours) (after 800°C/1 hour)
720°C/6 hours
g) 39-40
(after 830°C/3 hours)
700°C/6 hours
h) 38-41
(after 830°C/5 hours)
From figure 3 one may see that, for both cast irons, the one-step isothermal annealing in the ferritic
domain presents “dl/l versus t” curves with a smaller slope than the ones resulting from the two-step
isothermal annealing. Accepting that the transformation of austenite in the ferritic domain causes an
expansion of the test piece proportional to the extent of the transformation, one may then assume
that the softening process has been accelerated by the destabilizing stage in the austenitic domain.
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Discussion
As cast microstructure. The literature is not unanimous in the description of the solidification of
the high Cr cast iron. Matsubara et al. [5] claim that the alloy presents a solidification sequence
starting by the proeutectic M7C3 carbide precipitation, which is followed by the eutectic formation.
Tabrett et al. [3], supported by more recent studies on the solidification of Fe-Cr-C alloys, sustain
that hypoeutectic alloys like the ones under experiment (with Cr content up to 30% and C from 2 to
3.3%) start the solidification segregating austenite dendrites from the liquid and later suffer the
eutectic reaction, giving place to the “austenite plus M7C3 carbide” eutectic product.
Cast iron with 19% Cr agrees with Tabrett’s opinion; the one with 26% Cr does not, because one
may see both well developed austenite dendrites and coarse carbides in an eutectic matrix (see
figure 1); one possible explanation for the apparent proeutectic occurrence of the carbides is that
this phase is in fact post eutectic, resulting from a solid state reaction of austenite desaturation,
made possible by the relative slow cooling in the sand; fluctuations of Cr, Mo and C in the austenite
dendrites could be responsible for the local enrichment in these elements and cause the carbide
nucleation; at temperatures around 1000°C, particles could grow up to 1 micrometer, their
dimension in figure 1.
Alloying elements partition. The literature claims that the majority of Cr in this cast iron family is
precipitated in the carbides, the remaining Cr content in the matrix being quite low; a Cr matrix
content of 12.5% has been measured in a cast iron with 3.2% C and 29% Cr [3,6] – this figure is in
good agreement with this work’s determinations, presented in table 1. Using literature data, Tabrett
[3] provides partition ratio values for different elements, defined as the content of one element in
the carbide divided by the content of that same element in the matrix. One should know however
what is meant by the content of one element in the matrix, since it may be evaluated in the
proeutectic austenite or in the eutectic austenite and these values are different. Table 3 presents data
for the partition ratio in the case of a cast iron with the composition 3C-20Cr-2Mo-1Cu (quite close
to the 19% Cr microanalysed in this study), together with the values obtained in this study.
Table 3. Partition ratio for several elements (M) in a 19-20% Cr alloy
Partition ratio Cr Mo Si Ni Cu
Data from the literature [3] 4.5 2.2 0.0 0.0 0.0
(M carbide / M matrix)
Data from this work 5.4 2.0 0.2 0.6 0.2
(M carbide / M eutectic austenite)
Data from this work 4.0 7.8 0.2 0.5 0.2
(M carbide / M proeutectic austenite)

Now one may see that the good agreement of the partition ratio between the figures from this work
and from the literature is questioned. The elements without carbide forming tendency, like Si, Ni
and Cu, are present in the carbides, possibly replacing substitutionally the iron atoms; this is a very
common behavior at least for Si, which forms the silicon-carbides in ductile iron during the
austempering reaction [7]. Cr and Mo, the elements with a strong carbide character, partition mainly
to the carbide phase; one should expect the eutectic austenite to be poorer in these elements than the
proeutectic, in view of the shorter diffusion distances in the first case; but proeutectic austenite is
more depleted in Mo than the eutectic, the opposite being true for Cr. This behavior indicates that
partition is far from equilibrium conditions, reinforcing the idea previously advanced that solid state
segregation may be responsible for coarse carbide particles in the as cast microstructure; in fact, one
should expect higher Cr gradients in the 26% Cr alloy, making acceptable that the coarse
precipitation detected has a secondary and not a primary nature.
Soft annealing. It may be concluded from the critical points evaluation that the ferritic domain for
the 26% Cr alloy exists up to a temperature higher than 707°C and for the 19% Cr alloy this figure
is higher than 718°C – note that the dilatometric determinations were made on cooling at 20°C per
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hour, so the equilibrium points should be higher. The isothermal temperatures for the austenite
transformation in the ferritic domain were selected in accordance with this information.
The results obtained for the 26% Cr alloy, presented in figure 3 (left), show that the two-step
annealing is clearly more efficient to soften the cast iron than the one-step annealing; the final
hardness is lower and the increase in length, indicating the austenite transformation, is more intense
for the treatments labeled b) and c). A final trial has been run on samples subjected to heat treatment
in a muffle furnace with subsequent air cooling, with the following results: a two-step annealing
composed of 2 hours at 880°C plus 8 hours at 710°C resulted in a final hardness of 36 to 39 HRC;
this is a reasonable compromise to soften this material, as the dilatometric test pointed out.
For the 19% Cr alloy, the dilatometric data for the one-step annealing indicate clearly a very
incomplete transformation; but 40 HRC for the hardness of the test labeled e) in figure 3 (right) was
a surprise, quite close to the results of the two-step annealing tests. Anyhow the duration of this
process (20 hours) is too long, compared with the two-step annealing; the tests labeled g) and h)
have attained similar final hardness in about 10 hours. A procedure similar to the one referred above
was used to select the final sequence: a two-step annealing in a muffle furnace composed of 3 hours
at 830°C plus 6 hours at 720°C confirmed a final hardness in the range from 38 to 41 HRC.

Conclusions
High Cr white cast iron with 19 and 26% Cr may be efficiently soft annealed by a double-step
procedure, consisting of a first step devoted to the austenite destabilization and a second step during
which the destabilized austenite transforms into ferrite plus carbides. The best procedure for the
26% Cr alloy has been determined as the following: 2 hours at 880°C plus 8 hours at 710°C,
resulting in a final hardness in the range 36 to 39 HRC. For the 19% Cr alloy, the best procedure
was: 3 hours at 830°C plus 6 hours at 720°C, resulting in a final hardness of 38 to 41 HRC.
The as cast microstructure analysis showed that the 19% Cr alloy is composed of proeutectic
austenite plus eutectic, whilst the 26% Cr alloy presents coarse carbides, dendritic austenite and
eutectic; these coarse carbides were proposed to be secondary carbides.
The microanalysis results for the 19% Cr alloy in the as cast state showed a disagreement with
partition data in the literature; unlike the literature states, non carbide forming elements are in fact
present in the carbides; the partition of the carbide forming elements to the carbides is predominant,
but their residual content in the eutectic and proeutectic austenite was shown to be quite different.

References
[1] G. Laird II, G. Powell: Metallurgical and Materials Transactions Vol. 24A (1993), p. 981.
[2] F. Maratray, A. Poulalion: Transactions AFS Vol. 90 (1982), p. 795.
[3] C.P. Tabrett, I.R. Sare, M.R. Ghomashchi: International Materials Review Vol. 41, no. 2
(1996), p. 59.
[4] O.N. Dogan, J.A. Hawk, G. Laird II: Metallurgical and Materials Transactions A Vol. 28, no.
6 (1997), p. 1315.
[5] Y. Matsubara, N. Sasaguri, K. Shimizu, S.K. Yu: Wear Vol. 250 (2001), p. 502.
[6] G. Laird II: Transactions AFS Vol. 101 (1993), p. 497.
[7] J.M. Schissler, J. Saverna: Journal of Heat Treating Vol. 4, nº 2 (1985), p. 167.
Advanced Materials Forum II
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Soft Annealing of High Chromium White Cast Iron

10.4028/www.scientific.net/MSF.455-456.290

DOI References
[1] G. Laird II, G. Powell: Metallurgical and Materials Transactions Vol. 24A (1993), p. 981.
doi:10.1007/BF02656520
[5] Y. Matsubara, N. Sasaguri, K. Shimizu, S.K. Yu: Wear Vol. 250 (2001), p. 502.
doi:10.1016/S0043-1648(01)00599-3
[7] J.M. Schissler, J. Saverna: Journal of Heat Treating Vol. 4, nº 2 (1985), p. 167.
doi:10.1007/BF02833136