Materials Characterization 49 (2003) 219 229

Microstructural characterization of modified 25Cr35Ni

centrifugally cast steel furnace tubes
Luiz Henrique de Almeidaa, Andre Freitas Ribeiroa, Iain Le Maya,b,*
a
COPPE/UFRJ, C.P. 68508, Rio de Janeiro, R.J., 21945-970, Brazil
b
Metallurgical Consulting Services Limited, P.O. Box 5006, Saskatoon, Canada S7K 4E3
Received 1 December 2002; accepted 15 December 2002

Abstract

HP steels modified with Nb and Nb-plus-Ti, produced in the form of centrifugally cast tubes, were
characterized by means of light optical microscopy, scanning electron microscopy (SEM) with secondary and
backscattered electron imaging, and transmission electron microscopy (TEM) with energy-dispersive
spectroscopy (EDS) and selected area diffraction. A complete description of the phases present in the as-
cast, welded, and aged condition was made as a function of the modifying elements. The chromium carbide
stoichiometry, secondary precipitation, NbC instability at elevated temperatures, the G-phase transformation,
and the effect of Ti on this reaction are discussed. It is indicated that partial transformation of G-phase in
the alloy modified with Ti is one of the explanations for the superior creep properties observed in this
material.
D 2003 Elsevier Science Inc. All rights reserved.

Keywords: Microstructural characterization; Modified 25Cr 35Ni; Centrifugally cast steel furnace tubes

1. Introduction number of studies were conducted subsequently to

The petrochemical industry has been using cast
steel of the 25% Cr 20% Ni type (HK type steel)
since the early 1960s in reformer and pyrolysis
furnaces. This class of steel had replaced the tra-
ditional superalloys with a reduction in costs and has
similar properties under conditions of creep, which is
one of the principal degradation mechanisms leading
to failure in service at elevated temperature. A
* Corresponding author. Metallurgical Consulting Serv-
ices Limited, P.O. Box 5006, Saskatoon, Canada S7K 4E3.
Tel.: +1-306-934-9191; fax: +1-306-933-1814.
E-mail address: lemayi@metallurgicalconsulting.net
(I. Le May).
evaluate of phase changes during service and the
influence of these changes on the mechanisms of
failure by creep. An improved understanding of this
relationship has been the driving force for the
development of a new generation of this type of
steel approximately every 5 years. The use of the
centrifugal casting technique for tube production has
also contributed to higher performance of these
components. Better creep properties have been
attributed to the morphological modifications intro-
duced in the microstructure and to the presence of
more stable phases during aging while in long-term
service. The base composition has also been ad-
justed with increase in the Ni content to around 35%
to produce the HP type steels. The addition of nio-
bium, and more recently niobium-plus-titanium, has

1044-5803/03/$ see front matter D 2003 Elsevier Science Inc. All rights reserved.
doi:10.1016/S1044-5803(03)00013-5
220 L.H. de Almeida et al. / Materials Characterization 49 (2003) 219229

Table 1 their capabilities for the identification of phases and

Welding parameters used for the HP-Nb and HP-NbTi tube transformation mechanisms, and to show how they
joints (GTAW) contribute to an understanding of the role of additive
Bead Voltage Current Work speed Heat input elements in developing improved mechanical prop-
(V) (A) (mm s 1) (kJ mm 1) erties.
1 15 85 0.80 1.10 In this paper, two modified HP steels with Nb and
2 15 95 0.65 1.50 Nb-plus-Ti, produced in the form of centrifugally cast
3 15 85 1.00 0.80 tubes, have been characterized by means of different
4 15 90 1.00 0.90 techniques in the as-cast, welded, and aged condi-
tions. These techniques are described and their
application to phase identification is illustrated.
promoted the fragmentation of the as-cast micro-
structure and the partial replacement of chromium
carbides by more stable ones [1]. Other elements 2. Experimental procedure
such as molybdenum, zirconium, and vanadium
have been introduced to the chemical composition Two HP-modified steels were produced in the
of these steels with similar effects. The addition of form of centrifugally cast tubes. One was produced
rare-earth elements has also been considered [2]. with the addition of Nb as the modifying element, the
The creep resistance of these alloys is dependent tubes having an external diameter of 102.7 mm and a
on the chemical composition and on the distribution wall thickness of 7.5 mm. This alloy was identified as
of the phases that form during casting or that trans- HP-Nb. The second was produced with the combined
form within them during service. The primary addition of Nb and Ti, and the tubes had an external
eutectic-like carbide network appears to play an diameter of 111.5 mm and a wall thickness of 11.8
important role in preventing grain boundary sliding.
Secondary precipitation in the form of a fine distri-
bution of cube-shaped chromium carbides should act
to restrict the motion of dislocations.
A partial transformation of the primary niobium
carbide to a nickel niobium silicide, identified as the
G-phase, was first observed by Soares et al. [3] at
temperatures between 700 and 1000
C in Nb-modi-
fied HK and HP steels. This transformation also
affects the high-temperature mechanical properties
of these alloys.
During the years covering the development of
improved steels, the experimental procedures for
characterizing the microstructure, including phase
identification, the morphology of primary and sec-
ondary precipitation, as well as studies of phase
transformation, have been well developed and
reported in the literature [3 6]. However, a review
of the results contained in more recently published
papers [7 10] dealing with this type of material
indicates that these characterization techniques
should be discussed more fully in order to clarify

Table 2
Chemical composition of the HP-Nb and HP-NbTi alloys
and weld metal (wt.%)
Alloy C Cr Ni Si Mn Nb Ti
HP-Nb 0.43 24.8 34.1 1.67 1.0 1.34
HP-NbTi 0.41 25.5 34.9 1.91 1.0 0.78 0.04
Weld metal 0.39 26.6 35.8 1.21 0.9 0.79 0.04 Fig. 1. Light optical micrographs of both alloys in the as-cast
Balance: Fe. condition. (a) Alloy HP-Nb; (b) alloy HP-NbTi.
 L.H. de Almeida et al. / Materials Characterization 49 (2003) 219229 221

mm-diameter discs that were mechanically polished

on both sides to a thickness of approximately 60
mm. They were then dished using a dimple
grinder device to approximately 20-mm thickness,
and final polishing was made by ion milling with
a high sputtering angle. This procedure was fol-
lowed to ensure that the large primary carbides
were preserved.
The microstructural characteristics were deter-
mined using bright field images, selected area dif-
fraction and energy-dispersive spectroscopy (EDS)
analysis.

3. Results

Fig. 1 shows the as-cast microstructure as revealed

using reagent 2 for both HP-Nb and HP-NbTi alloys,
after a careful grinding and polishing procedure using
low pressure during grinding. The austenitic matrix
with the dendritic carbide network typical of this type
of material is seen clearly in Fig. 1a, while the less-
continuous nature of the dendritic carbide network for

Fig. 2. Light optical micrographs of both alloys in the as-cast

condition at higher magnification. (a) Alloy HP-Nb; (b)
alloy HP-NbTi.

mm: this material was identified as HP-NbTi. Sec-

tions of the tubes were welded together using the gas
tungsten arc welding process (GTAW). The weld
metal used was similar in composition to the parent
metals, but contained Ti as in the HP-NbTi alloy, and
Table 1 shows the welding parameters. The chemical
compositions of the two alloys and the weld metal are
given in Table 2.
The alloys were submitted to high-temperature
aging for 1000 h at 1173 K. Light optical microscopy
and scanning electron microscopy (SEM) using both
secondary and backscattered electron imaging were
used for metallographic characterization. Observa-
tions were made on unetched samples, and on others
etched with a modified glyceregia chemical reagent
with 45% HNO3, 40% HCl, and 15% glycerol
(reagent 1), or using electrolytic etching with a so-
lution of 64% H3PO4, 15% H2SO4, and 21% H2O
(reagent 2). In the latter case, a stainless steel cath-
ode was used with 5 V direct current at 298 K for
4 s.
Foil samples for examination in the transmission Fig. 3. Light optical micrographs of both alloys in the aged
electron microscope (TEM) were prepared from 3- condition. (a) Alloy HP-Nb; (b) alloy HP-NbTi.
222 L.H. de Almeida et al. / Materials Characterization 49 (2003) 219229

the HP-NbTi alloy is apparent at this relatively low
magnification, Fig. 1b. This latter effect is due to the
presence of titanium. At higher magnification, the
austenite matrix is observed to be free of precipitates
(Fig. 2).
Fig. 3 shows the microstructure etched using
reagent 2 after the aging heat treatment. The sec-
ondary precipitation decorates the austenitic matrix
and is clearly defined at higher magnification. The
figure also illustrates the finer and more evenly
distributed secondary precipitation in alloy HP-
NbTi.
Micrographs taken in the SEM for both alloys in
the as-cast condition are shown in Fig. 4, using
secondary electrons from specimens etched with
reagent 1 and using backscattered electrons from
specimens that were not etched. The same character-
istics as observed by light optical microscopy are
reproduced when the image is obtained from second-
ary electrons. Using backscattered electrons, the dark
phase can be identified as chromium-rich, while the
Nb- or NbTi-rich phases appear as white regions, due
to the fact that Nb has a much greater atomic weight
than Cr.

Fig. 4. SEM images of HP-Nb and HP-NbTi in the as-cast condition. (a) HP-Nb shown using secondary electrons; (b) HP-Nb
shown using backscattered electrons; (c) HP-NbTi shown using secondary electrons; (d) HP-NbTi shown using backscattered
electrons.
 L.H. de Almeida et al. / Materials Characterization 49 (2003) 219229 223

Fig. 5 shows the SEM micrographs using sec-
ondary and backscattered electrons for both alloys
in the aged condition, for specimens etched with
reagent 1. As for the as-cast condition, the same
characteristics are observed when comparing sec-
ondary electron images with light optical micro-
scopy ones. For backscattered electron images, the
Nb- or NbTi-rich phases [NbC, (NbTi)C, and G-
phase] can be distinguished clearly from the prim-
ary and secondary chromium carbide precipitates.
In the aged condition, after exposure for 1000 h at
1173 K, the HP-Nb alloy has only two phases pre-
cipitated, namely, the chromium carbide and the G-
phase that has formed due to the instability of the
niobium carbide at this temperature [3]. On the
other hand, the presence of Ti inhibits the trans-
formation of (NbTi)C to G-phase. For this reason,
three phases are observed in the HP-NbTi alloy in
the aged condition; chromium carbide, G-phase,
and niobium titanium carbide. The G-phase iden-
tification in SEM micrographs using backscattered
electrons is not reliable because the difference in
contrast between it and the Nb or (NbTi)C is very
small.

Fig. 5. SEM images of HP-Nb and HP-NbTi in the aged condition. (a) HP-Nb shown using secondary electrons; (b) HP-Nb
shown using backscattered electrons; (c) HP-NbTi shown using secondary electrons; (d) HP-NbTi shown using backscattered
electrons.
224 L.H. de Almeida et al. / Materials Characterization 49 (2003) 219229

The weld fusion line, as delineated using reagent

2, is shown in Fig. 6 for both HP-Nb and HP-NbTi
welded joints. The typical dendritic structure and the
size difference between this structure in the parent
metal (coarser) and weld metal (finer) are readily
apparent. Fig. 7 shows the microstructure of the weld
metal after aging at two different magnifications as
revealed using reagent 2, and the same microstruc-
tural characteristics can be observed as for the parent
metal, except for the more refined dendritic structure
in the latter.
TEM observations can be important for these
steels where phase identification by electron diffrac-
tion and EDS analysis is required, and these techni-
ques also serve to show fine secondary precipitation
that is not resolved by light microscopy or SEM
examination. Fig. 8 shows an example of the TEM
image obtained for the HP-NbTi alloy in the aged
condition. This is the most complex of the micro-
structures of the four samples examined, and the
coarse primary chromium carbide, the partially trans-
formed primary Nb Ti carbide with the internal part
being (NbTi)C and the external part G-phase, and
finally the fine cuboid-shaped secondary chromium

Fig. 7. Light optical micrographs at two different magnifi-

cations of the weld metal in the aged condition.

carbides, can all be seen. Fig. 9 shows a magnified

Fig. 6. Light optical micrographs of the fusion line in the as-
cast condition. (a) HP-Nb joint; (b) HP-NbTi joint.
view of the G-phase that surrounds the partially
transformed NbTi primary carbide (Fig. 8). This
region contains fine TiC precipitates, indicating that
the G-phase does not dissolve Ti. Fig. 10 reveals
details of the secondary Cr-carbide (M23C6) precip-
itation, showing an orientation relationship with the
matrix defined as [110]carbide//[110]g and with the
quasi-cuboid particles, the classification of the par-
ticles as quasi-cuboid having been demonstrated
previously [3]. The matrix, and the chromium,
niobium, and niobium-plus-titanium carbides, all
have a FCC structure, while NiNbSi has a superlattice
FCC structure with 116 atoms per unit cell.
The matrix and phases cited above have well-
defined EDS spectra. The phase identification can
also be complemented with selected area diffraction
and calculation of the various lattice parameters. Fig.
11 shows the G-phase spectrum with Ni, Nb, and Si
characteristic peaks: the diffraction pattern is also
shown in the Fig. 11 and the lattice parameter was
calculated as 1.122 nm. A previous X ray analysis
had indicated the Ni16Nb7Si6 stoichiometry for this
phase [3].
 L.H. de Almeida et al. / Materials Characterization 49 (2003) 219229
Fig. 8. TEM bright field image, HP-NbTi alloy in the aged
condition. The primary (P Cr) and secondary (S Cr)
chromium carbides, the (NbTi) carbide, and the G-phase
(G) are indicated.
Figs. 12 and 13 show the EDS spectra and the
diffraction patterns for NbC and (NbTi)C precipitates.
The lattice parameters of both phases are similar,
varying from 0.411 to 0.437 nm. The EDS spectrum
Fig. 9. TEM bright field image, HP-NbTi alloy. The G-phase
region shown in Fig. 8 is illustrated, in which it is possible to
observe individual TiC particles (Ti).
225
Fig. 10. TEM bright field image, HP-NbTi alloy, showing
details of the secondary chromium carbide precipitation. The
[110]carbide//[110]g orientation relationship is illustrated.
and the diffraction pattern for the TiC carbide repre-
cipitated during (NbTi)C transformation to G-phase
are shown in Fig. 14. The lattice parameter for this
phase is similar to the previous ones, 0.435 nm. Fig.
15 shows the EDS spectrum and the diffraction
pattern for the primary and secondary chromium
carbide, M23C6. The lattice parameter was calculated
as 1.111 nm. A well-defined orientation relationship
is observed between the secondary chromium car-
bides and the matrix, these particles being coherent
with the matrix. Finally, Fig. 16 shows the EDS
spectrum and the diffraction pattern for the matrix,
the lattice parameter being 0.339 nm.
4. Discussion
The metallographic characterization using light
microscopy, the SEM with backscattered electons,
and the TEM with EDS analysis and selected area
diffraction, allows a complete identification to be
made of the phases in the as-cast, aged, and welded
conditions as a function of the modifying elements
present in HP-modified steels with additions of Nb or
Nb-plus-Ti.
In the as-cast condition, the primary chromium
carbide has the stoichiometric composition, M23C6,
with a lattice parameter of 1.111 nm, Fig. 15. In the
classic HP composition, this precipitate would be
M7C3 [3]. With the addition of Nb-plus-Ti, a sig-
nificant fraction of the total carbon is consumed by
226 L.H. de Almeida et al. / Materials Characterization 49 (2003) 219229

Fig. 11. EDS spectrum, selected area diffraction, and calculated lattice parameter for the G-phase.

the NbC and (NbTi)C precipitation at temperatures
higher than the temperature interval over which the
chromium carbide precipitates. As a consequence, a
higher Cr/C ratio is present during precipitation. The
secondary chromium carbides also have this stoichi-
ometric composition and are coherent with the
matrix.
In the modified alloy containing Nb, NbC is also
present in addition to chromium carbide (Fig. 12),
showing the typical Chinese script morphology,
Figs. 2a and 4a and b. On the other hand, in the alloy
modified by the addition of Nb-plus-Ti, the typical
precipitates, in addition to those based on chromium,
are of (NbTi)C, Fig. 13. TiC is not observed in the as-
cast condition, at least with the present Nb and Ti
concentrations. As the sum of the Nb and Ti atoms in
the HP-NbTi alloy is lower than the number of Nb
atoms in the HP-Nb alloy, a smaller volume fraction

Fig. 12. EDS spectrum, selected area diffraction, and calculated lattice parameter for the niobium carbide.
 L.H. de Almeida et al. / Materials Characterization 49 (2003) 219229 227

Fig. 13. EDS spectrum, selected area diffraction, and calculated lattice parameter for the niobium-plus-titanium carbide.

of these phases is observed in the HP-NbTi alloy, and
the Chinese script morphology is no longer ob-
served, Figs. 2b and 4c and d.
During aging, all NbC particles were fully trans-
formed to G-phase in the HP-Nb alloy as a con-
sequence of the instability of NbC in this temperature
range. In the HP-NbTi alloy, the observations show
partially transformed particles, Fig. 8, where the
center of the particle remains as (NbTi)C and the
outer part has transformed to G-phase. In this region,
it is possible to observe individual TiC particles, Fig.
9. It is important to note that the EDS spectrum of the
G-phase of this aggregate (Fig. 11) shows only Ni, Si,
and Nb peaks, indicating that this phase does not
dissolve Ti. The morphology observed in this par-
tially transformed (NbTi)C particle suggests that the
transformation is an in situ reaction controlled by
carbon and Ti expulsion and by the incorporation of

Fig. 14. EDS spectrum, selected area diffraction, and calculated lattice parameter for the titanium carbide.
228 L.H. de Almeida et al. / Materials Characterization 49 (2003) 219229

Fig. 15. EDS spectrum, selected area diffraction, and calculated lattice parameter for the chromium carbide.

Si and Ni. As the reaction starts from the outside and
continues towards the center of the particle, and the
G-phase does not dissolve Ti, this element controls
the transformation process.
The partial transformation only to G-phase in the
HP-NbTi alloy may be one of the explanations,
together with the finer and more distributed second-
ary precipitation and the less-continuous nature of the
dendritic carbide network, for the superior creep
behavior observed for this alloy as compared to that
for the HP-Nb steel [6]. It is reported that the
interface between the G-phase and the matrix is a
preferential site for the occurrence of creep damage
[5]. During the transformation, there is an increase in
the volume of the phase, causing an increase in the
interfacial energy. This effect is minimized in the HP-
NbTi alloy with the smaller volume fraction of G-
phase.

Fig. 16. EDS spectrum, selected area diffraction, and calculated lattice parameter for the matrix.
 L.H. de Almeida et al. / Materials Characterization 49 (2003) 219229
5. Conclusions
The Nb concentration and the presence of Ti as a
modifier element in HP-modified steels determine the
microstructural morphology in the as-cast and aged
conditions. The concentration of Nb promotes the
primary Chinese script morphology and Ti pro-
motes a finer and more distributed secondary precip-
itation.
Ti inhibits and controls the (NbTi)C transforma-
tion to G-phase. This reaction starts from outside and
continues toward the center of the phase, and the G-
phase does not dissolve Ti. For this reason, a smaller
volume fraction of G-phase is observed in the HP
steel modified with Ti.
A finer and more evenly distributed secondary
precipitation, a less-continuous dendritic carbide net-
work, and a smaller volume fraction transformed to
G-phase observed in the alloy modified with Ti may
be the explanation for the superior creep properties
observed in this steel when compared with steel
having additions of niobium alone.
Acknowledgements
Financial support by CNPq and FAPERJ is
gratefully acknowledged. This project was also
financed by the CTPETRO fund.
References
[1] Shinoda TL, Zaghloul MB, Kondo Y, Tanaka R. The
effect of single and combined additions of Ti and Nb
229
on the structure of the centrifugally cast HK40 steel.
Trans Iron Steel Inst Jpn 1998;18:139 48.
[2] Borges RMT, de Almeida LH. Microstructure of a cen-
trifugally cast modified-HP steel tube with yttrium ad-
ditions. Acta Microsc Suppl A 1999;8:251 2.
[3] Soares GDA, de Almeida LH, da Silveira TL, Le May
I. Niobium additions in HP heat-resistant cast stainless
steels. Mater Charact 1992;29:387 96.
[4] Ibanez RAP, Soares GDA, de Almeida LH, Le May I.
Effects of Si content on the microstructure of modified-
HP austenitic steels. Mater Charact 1993;30:243 9.
[5] de Almeida LH, Emygdio PRO, Le May I, Ferraz FC.
Microstructural characterization and geometrical anal-
ysis of welded joints of high temperature stainless steel
tubes. In: Burke MG, Clark EA, Palmiere EJ, editors.
Microstructural science, vol. 24: understanding micro-
structure: key to advances in materials. Materials Park:
ASM; 1996. p. 193 8.
[6] Ribeiro AF, Borges RMT, de Almeida LH. Phase trans-
formation in heat resistant steel observed by STEM:
(NbTi)C NiNbSi (G-phase). Acta Microsc 2002;11:
59 63.
[7] Rodriguez J, Haro S, Velasco A, Colas R. A metallo-
graphic study of aging in a cast heat-resisting alloy.
Mater Charact 2000;45:25 32.
[8] Wu XQ, Jing HM, Zheng YG, Yao ZM, Ke W, Hu ZQ.
The eutectic carbides and creep rupture strength of
25Cr20Ni heat-resistant steel tubes centrifugally cast
with different solidification conditions. Mater Sci
Eng A 2000;293:252 60.
[9] Wu XQ, Yang YS, Zhang JS, Jia GL, Hu ZQ. Struc-
ture characteristics in industrially centrifugally cast
25Cr20Ni stainless steel tubes solidified under different
electromagnetic field intensity. J Mater Eng Perform
1999;8:525 30.
[10] Haro S, Lopez D, Velasco A, Viramontes R. Micro-
structural factors that determine the weldability of a
high Cr-rich Si HK 40 alloy. Mater Chem Phys 2000;
66:90 6.