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Materials Chemistry and Physics 77 (2002) 831835

Study of weldability of a CrSi modified heat-resisting alloy


Sergio Haro a, , Rafael Cols b , Abraham Velasco c , David Lpez d
a

Universidad Autnoma de Zacatecas, Primavera #306, Centro, Zacatecas, Zac., 98060 Mexico, Mexico
b Universidad Autnoma de Nuevo Len, San Nicols de los Garza, N.L., Mexico, Mexico
c Corporativo Nemak, S.A. de C.V. Garca N.L., Mexico, Mexico
d Instituto Mexicano del Petrleo, Boca del Ro, Veracruz, Mexico, Mexico
Received 21 March 2001; received in revised form 25 March 2002; accepted 27 March 2002

Abstract
A cast heat-resistant alloy able to withstand carburization and metal dusting was developed to be used in the conducting pipes of reformed
gas heaters for the direct reduction process. However, this alloy exhibits serious weldability problems in its as-cast condition and during the
repair of aged pieces. Study of the microstructural and technological factors that affect weldability indicate that the use of low heat input (in
the range of 630950 kJ m1 ) and a maximum interpass temperature of 150 C favors the welding repair of the high CrSi modified HK40
alloy. A solution annealing treatment prior to welding was necessary to obtain acceptable weldments. The commonly known buttering
technique was not successful in this type of alloy. A series of microstructural phenomena, such as precipitation of secondary carbides,
formation of intermetallic compounds (sigma phase and nickel silicide), as well as transformation of primary carbides, were observed to
occur during aging, and they are suspected to be responsible for reducing the weldability of aged parts.
2002 Elsevier Science B.V. All rights reserved.
Keywords: Heat resisting alloys; Castings; Weldability

1. Introduction
Among the various heat-resisting alloys available for use
in gas reforming, HK40 is one of the most commonly used
in direct reduction plants [1], although it may be subjected
to severe carburization and metal dusting while exposed to
the reducing gas (70% H2 , 20% CO and small amounts of
H2 O, CO2 and CH4 ), at temperatures ranging from 450 to
950 C and at pressures of up to 5 atm [2]. In order to avoid
such problems, the content of chromium and silicon were
increased to a nominal composition of 28%Cr, 20%Ni and
2%Si in a modified HK40 alloy. Such an increase was more
than satisfactory since in a 29-month period of continuous
operation, only a limited amount of pitting was observed to
occur in some elbows, bends and HAZ (heat-affected zone)
of welds, whereas the parts made from the conventional
HK40 alloy exhibited higher damage rates in periods as short
as 4 months [3].
However, the modified HK40 alloy exhibited various
problems related to its weldability in its as-cast and aged
conditions in contrast to the good weldability of the standard HK40 alloy. These problems consisted of the de Corresponding author. Tel./fax: +52-492-23634.
E-mail address: haros@cantera.reduaz.mx (S. Haro).

velopment of a series of small cracks near the weld in


the modified as-cast alloy; repair of pipes cast from the
modified alloy and being in service in reformer furnaces
for over a year was very difficult due to severe cracking
[4].
HK40 alloy is welded following a procedure that minimizes heat input and residual stresses. This is done by the
use of small diameter of electrodes, low welding currents,
narrow weld beads and low interpass temperatures [5].
As the material is subjected to high temperature service,
secondary carbide precipitation is observed to take place,
which results in the increase of creep resistance, and a drastic reduction in elongation and ductility [59]. Ductility is
of great interest since the metal should be able to deform
plastically during cooling of the weldment. Some alloys
can lose more than 80% of their original ductility as a result of their high temperature service [10]. It is possible to
weld aged HK40 samples, but it is required that they should
be first subjected to either the buttering technique or to a
solution annealing treatment [5].
The buttering technique is a process that consists of welding one or more layers of ductile metal under minimum
restraint conditions. The layers are then machined and the
bevel face is inspected. Thus, when a more restrictive weld
is applied, sufficiently ductile metal is available to withstand

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S. Haro et al. / Materials Chemistry and Physics 77 (2002) 831835

the plastic deformation produced by solidification and cooling of the weldment [5].
The aim of this work is to describe a series of tests conducted to evaluate the weldability of the modified alloy.
Among the variables studied were the heat input and interpass temperature, as well as a solution annealing treatment,
which was proposed as a solution for aged parts.

2. Experimental procedure
The material used in this study was manufactured by
centrifugal casting into pipes of an external diameter of
177.8 and 19.6 mm wall thickness. The chemical composition of the material is shown in Table 1. Small coupons
were cut from the pipes and, prior to welding, some of
them were aged at 750 C for 2000 h in an electric box
furnace and cooled in air to reproduce the microstructures
observed after service in gas-reforming furnaces, since
most of the repairs that have to be made are from parts
operating within the 650950 C temperature range [11].
Four of the coupons were subjected to a solution annealing
heat treatment, which consisted of holding the samples for
1 h at 1200 C in an electric box furnace. Cooling was by
forced air. Tensile samples were machined and subjected to

Table 1
Chemical composition of the HK40 alloys and of the filler metal applied
Element

HK40 Typical [12]


ASTM A351

Modified HK40
studied alloy

Filler metal
2535 S

C
Si
Mn
Cr
Ni
P
S
Cu
Mo
Fe

0.40
1.25
1.0
25
20

0.040

0.30
Rest

0.38
2.04
0.64
28
20
0.019
0.021
0.18
0.21
Rest

0.350.45
0.81.75
<2.0
2327
3437
<0.03
<0.025

Rest

similar treatments to evaluate the changes in the mechanical


properties.
The welding trials were conducted in three different
types of joints, namely as-cast/as-cast, as-cast/aged, and
as-cast/solution-annealed. Two additional joints were set
apart to test the buttering technique. The joints were machined into 37.5 V grooves. Welding was by the gas
tungsten arc welding, 2.4 mm in diameter direct current
electrode negative (GTAWDCEN) process, with a 2535
S type filler metal, Table 1. Shielding was with 99% pure
argon (0.42 and 0.78 m3 h1 flows for back and shielding).
Welding was performed on site in concordance with Section IX of the ASME Code [13]. Two different heat inputs
tested, and two interpass temperatures were allowed: one
kept to a maximum of 150 C, whereas the other was the
one that resulted from continuous welding.
Metallographic examination of the different samples
was carried out in a conventional optical microscope with
Berahas etchant [14] (15 ml HCl, 60 ml H2 O, 0.6 mg
K2 S2 O5 ); scanning electron microscopy (SEM) observations were made on samples prepared with an electrolytic
etchant (5.6 g KOH, 100 ml H2 O, 1.5 V for 24 s). X-ray
diffraction analysis was used to identify the components in
the as-cast, aged and solution-annealed microstructures. K
radiation from a Cu tube was filtered by Ni, the beam was
accelerated with a 35 kV using 25 mA.
Hardness tests [15] were carried out with a Rockwells
Willson B504-T hardness instrument. The results were converted to Vickers to have a continuous scale.

3. Results
The structure of the as-cast metal consisted of an
austenitic dendritic matrix containing chains of eutectic
carbide that either have a lamellar or a skeleton structure
typical of this type of carbide [16], Fig. 1A. The interior
of the dendritic structure in the aged metal shows precipitation of two types of carbides (granular and acicular). The
austenitic dendrites are defined by the eutectic carbides,

Fig. 1. Microstructure of the modified HK40 alloy in its as-cast (A), aged to 750 C, 2000 h, air cooled (B) and solution annealed to 1200 C, 1 h, forced
air cooled (C) conditions.

S. Haro et al. / Materials Chemistry and Physics 77 (2002) 831835

833

Table 2
Summary of the X-ray diffraction analysis
Base metal condition

Present phases

As-cast
Aged, 2000 h, 750 C
Solution annealing, 1 h, 1200 C

Cr23 C6
Cr23 C6
Cr23 C6

Cr7 C3
phase

which have changed their morphology from the skeleton


type to the continuous type, Fig. 1B. The structure after
solution annealing consists of eutectic primary carbides and
a small number of undissolved secondary carbides, Fig. 1C.
These observations were confirmed by X-ray diffraction
analysis that indicates the presence of different types of
carbides, Table 2.
Hardness of the alloy changed from 190 HV in the as-cast
condition to 340 HV after aging, and back to 205 HV in
the solution-annealed samples. Results from the tensile tests
show the strengthening of the alloy as a result of aging,
although this change reduces its ductility. Both properties
are recovered after annealing, Table 3.
Welding of as-cast/as-cast joints with low heat input and
low interpass temperature was satisfactory. The joints were
subjected to inspections by visual, penetrating liquids and
radiography, in agreement to Section IX of ASME Code
[13]; and all of them were past the inspections. Continuous
welding and high heat input caused cracking. Cracking in the
as-cast/aged joints were present at both levels of heat input

Nickel silicide [Ni31 Si12 ]

(Fe, C) austenite
(Fe, C) austenite
(Fe, C) austenite

and low interpass temperatures. The fracture originated and


extends on the aged coupon by effect of contraction of the
weld bead, Fig. 2. It was not possible to obtain a satisfactory
weld in the as-cast/aged joints, even at the lowest heat input.
The brittleness of the aged alloy was such that it cracked
when the weld bead was applied. The buttering technique
was applied with a minimum heat input in aged coupons,
but cracks developed in all cases.
Solution annealing allowed for the recovery of ductility,
see Table 3, in such a way that welding was satisfactory
when it was made in the as-cast/solution-annealed joints with
low heat input and when the interpass temperature was kept
below 150 C. A series of cracks were detected in the treated
coupon while using continuous welding and high heat input.

Table 3
Mechanical properties of modified HK40 alloy
Condition

Ultimate tensile
strength (MPa)

Elongation in
50.8 mm (%)

Reduction
in area (%)

As-cast
Aged
Aged + solution
annealing

403
449
419

5.1
0.65
4.7

6.6
0.8
5.05

Fig. 2. Cracking in the as-cast/aged joint. Fracture originates and propagates in the aged material.

Fig. 3. Cracking propagation through the primary carbides in an aged sample. The spectrum of one of these particles indicates the presence of silicon
and molybdenum.

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S. Haro et al. / Materials Chemistry and Physics 77 (2002) 831835

The aged coupons that fractured during welding were


subjected to optical and SEM metallographic observations.
Semi-quantitative analysis of X-ray spectra was made on
the different types of particles in as-cast, aged and annealed
samples. It was found that the primary carbides in the as-cast
samples have an approximate composition of 77% Cr, 16%
Fe, 3% Ni, 2% C, 0.75% Si, and 1% Mo. These same particles changed to 38% Cr, 42% Fe, 13% Ni, 4% Si, 2% C
and 1% Mo after the alloy was aged for 2000 h at 750 C.
In both cases the values reported are the average of five independent spot analysis. Fig. 3 shows that cracking in the
aged samples was intergranular and propagation occurred
through the eutectic carbides. The spectrum obtained from
one of these carbides is included.

4. Discussion
Primary carbides are coarse and are able to maintain
their position during solution annealing, Fig. 1c, at the
boundaries of the dendritic arms, although some of them
tend to coalesce and dissolve towards at either longer times
or higher temperatures. Some of the small secondary carbides remain after the annealing treatment, and this may
be due to the saturation of the austenite by carbon. It has
been pointed out [17] that when these alloys are kept at
temperatures above 1200 C and are cooled down at rates
fast enough to hinder precipitation, it was noted that close
to 0.20% of carbon is retained in the austenite.
X-ray diffraction analysis indicates that the phases present
in the as-cast condition are austenite and M7 C3 and M23 C6
carbides. Presence of sigma phase, nickel silicide (Ni31 Si12 )
and M23 C6 is detected; M7 C3 disappears in the aged condition. Some authors [18] indicate that transformation of M7 C3
into M23 C6 takes place at temperatures in the 600900 C
range, the more stable M23 C6 remains up to temperatures
around 1000 C. After M7 C3 has transformed into M23 C6 ,
part of the later one will transform to M6 C at around
950 C.
The modified HK40 alloy is susceptible, due to its chemical composition, to precipitate sigma phase and other complex FeCrSiMo intermetallic compounds that contributes
to the reduction in toughness, and corrosion resistance [17]
when they are kept at temperatures above 540 C. X-ray
diffraction analysis showed the presence of sigma phase in
the aged material, although only in small amounts due to the
short aging times at 750 C. Results [18] of aging conducted
in the normal HK40 alloy indicate that the amount of sigma
phase after aging for 2000 h at 750 C will be of around
0.5%, but since the alloy under study has greater amounts of
Si and Mo that are strong ferrite and sigma phase-forming
elements, and have been reported to be equivalent to three
or four times that of Cr [17], the quantity of sigma phase
in the aged modified HK40 alloy will be greater.
Table 3 shows the tensile properties of the material, in its
various conditions before welding. It is quite interesting to

notice that even the alloy in its as-cast condition does not
exhibit high ductility since its total elongation is around 5%.
This parameter is of paramount importance in welding, since
the material must be able to deform plastically to accommodate the changes of geometry produced by the heating and
cooling cycles of welding. Aging increases the strength of
the material, but the ductility is diminished [510], and in
the present case, it is close to zero.
Results from the welding experiments have shown that
the alloy under study, in its as-cast and solution-annealed
conditions, is weldable only when low heat input is applied
(in the range of 630950 kJ m1 ) and the interpass temperature is kept below 150 C. It is common practice on
site to use continuous welding to join as-cast pieces in order to increase productivity but it has been found in this
work that such a practice will result in small fissures close
to the weld bead, and that should be eliminated by careful
grinding to avoid possible causes of failure during operation. It is possible to keep the interpass temperature below
150 C by welding a series of pipes in an alternate way.
In this case, the productivity will be high, and the quality
of the joints will be assured. Another common practice for
on-site weldments is that of increasing the heat input to reduce the number of weld beads, but this is unacceptable for
the present alloy.
The material in the aged condition was not weldable due
to its high ductility loss and brittleness. Not even when
the buttering technique was performed was the material
weldable. The solution annealing treatment allowed for
an improvement in ductility of the aged material, Table 3,
in such a way that it was possible to obtain satisfactory
as-cast/solution-annealed joints when low heat inputs and
low interpass times were allowed for. Recent work [19]
has also shown that solution annealing is the most critical
step in the repair by welding of aged pieces. From this
study, it is concluded that the minimum ductility of 4%,
in a standard tensile test, is required to obtain satisfactory
joints.
Analysis by optical and electronic microscopy indicated
that cracking during welding in the aged alloy was of the
intergranular type and propagated through the primary eutectic carbides. Analyses of the X-ray spectrum obtained by
SEM showed that not only the morphology of the primary
carbides changed, but also their chemical composition. In
this case, the original CrFe-rich carbides suffer the diffusion of Si and Mo to their interior.
Previous studies [6,19] have shown the adverse effect of
silicon on ductility of aged materials. This element is added
to improve the resistance to carburization and metal dusting
of the alloy; but when it reaches amounts higher than 5%, it
will be able to form fragile intermetallic compounds. In the
present case of having segregated as-cast pieces, these types
of intermetallics will be readily formed even if the nominal
silicon content is low [20]. The effect of molybdenum is
also important, since it contributes to the stability of brittle
intermetallic phases such as Laves, chi and sigma [20].

S. Haro et al. / Materials Chemistry and Physics 77 (2002) 831835

5. Conclusions
It is found that the weldability of a modified HK40
alloy is influenced by both technological and microstructural factors. It may be that the latter are of more importance, however application of an inadequate welding
procedure can make non-weldable an otherwise weldable
alloy.
The results show that extreme caution should be taken
when welding the modified HK40 alloy. The use of low
heat inputs (in the range of 630950 kJ m1 ) and low
interpass temperatures (below 150 C) favor the repairs
by welding. On the other hand, high heat inputs (in the
11001400 kJ m1 range) and continuous welding produce
fissures and cracking. The benefit of a solution annealing
treatment was proven for this alloy due to the recovery of
its mechanical properties. The buttering technique is not
advisable for this alloy.
Precipitation of secondary carbides, formation of sigma
phase and nickel silicide, and the transformation of
primary carbides are the microstructural changes that
take place during the aging of this alloy. Each one of
these changes have a contribution over the embrittlement of the alloy, although is necessary to quantify the
amounts of sigma phase and nickel silicide present. It
was found that cracking in the aged alloy was of the intergranular type propagating through transformed primary
carbides.

Acknowledgements
The authors thank the support of people, institutions and
industry that made this research possible: UAZ, UANL,

835

HYLSA, IMP and CONACyT, especially to Dr. Ezequiel


Haro and Ma. del Refugio Rodrguez.
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