Solidification of an Alloy 625 Weld Overlay

J.N. DuPONT

The solidification behavior (microsegregation, secondary phase formation, and solidification temper-
ature range) of an Alloy 625 weld overlay deposited on 2.25Cr-1Mo steel by gas metal arc welding
was investigated by light and electron optical microscopy, electron microprobe, and differential
thermal analysis techniques. The overlay deposit was found to terminate solidification at '1216 7C
by a g/Laves eutectic-type reaction. The Laves phase was highly enriched in Nb, Mo, and Si. The
solidification reaction and microsegregation potential of major alloying elements in the overlay de-
posit are compared to other Nb-bearing Ni base alloys and found to be very similar to those for
Alloy 718. Solidification cracks observed in the overlay were attributed to the wide solidification
temperature range ('170 7C) and formation of interdendritic (g 1 Laves) constituent. Reasonable
agreement is obtained between the calculated and measured volume percent (g 1 Laves) constituent
with the Scheil equation by treating the overlay system as a simple g-Nb ‘‘binary’’ and using an
experimentally determined kNb value from electron microprobe data.

I. INTRODUCTION Nb was found to be the major solute controlling the solid-

ALLOY 625 is a Ni-Cr-Mo-Nb alloy which was devel-
oped primarily for high-temperature turbine applications.
The solidification and weldability of this alloy has been
thoroughly investigated by Cieslak et al.[1,2] In those studies,
alloys were evaluated which contained factorially designed
variations in Nb, Si, and C. These elemental additions were
based on previous results[3,4] which indicated they exhibited
a strong propensity to form secondary phases at the ter-
minal stages of solidification. The solidification behavior
was studied with differential thermal analysis (DTA) and
various microscopy techniques for phase identification.[1]
Weldability was assessed using the varestraint test.[2] Ad-
ditions of all three minor elements were found to increase
the melting and solidification temperature range. Multiple
regression analysis was performed on the DTA data to yield
values for the Nb, Si, and C liquidus and solidus slopes as
well as the equilibrium distribution coefficients. Niobium-
free alloys used in the study solidified by a simple L → g
transformation without any eutectic-like reaction and ex-
hibited a relatively narrow solidification temperature range.
In contrast, Nb-bearing alloys terminated solidification by
a eutectic-type reaction between g and various Nb-rich
phases such as NbC and Laves (A2B). Carbon additions
generally promoted the formation of NbC while Si pro-
moted the Laves phase. Weldability (solidification cracking
resistance) decreased with increasing total minor element
(Nb 1 Si 1 C) content, which was generally attributed to
the increased solidification temperature range and tendency
to form secondary phases at the terminal stages of solidi-
fication. Niobium was noted to be most detrimental with
regard to these effects.
A similar study was conducted on Alloy 718 by Kno-
rovsky et al.,[5] an alloy which is of interest to the present
work since its chemical composition can be similar to that
produced in dissimilar welds between Alloy 625 and Cr-
Mo steels in weld overlay applications. As with Alloy 625,
J.N. DuPONT, Research Scientist, is with the Energy Research Center,
Lehigh University, Bethlehem, PA 18015.
Manuscript submitted February 8, 1996.
ification behavior of Alloy 718. The alloy exhibits L → (g
1 NbC) and L → (g 1 Laves) eutectic-type reactions. The
L → (g 1 NbC) reaction occurs at a higher temperature
('1250 7C) and produces relatively small amounts of NbC,
while solidification is terminated with the L → (g 1 Laves)
reaction at '1200 7C and produces higher amounts of the
Laves phase. Neglecting the small amount of NbC forma-
tion, Knorovsky developed a pseudo-binary solidification
diagram for Alloy 718 based on Nb segregation and the L
→ (g 1 Laves) eutectic reaction. Weldability evaluations
indicated the alloy was quite susceptible to solidification
cracking compared to other nickel-base alloys due to a wide
solidification temperature range ('160 7C) and presence of
interdendritic Laves phase.
Because of its good resistance to wear[6,7] and corro-
sion,[8,9] Alloy 625 is utilized extensively as a weld overlay
on carbon steel and Cr-Mo steel components. Just as in
applications where the alloy is used in wrought or cast
form, the solidification behavior of the Alloy 625/Cr-Mo
steel dissimilar weld is of considerable importance with re-
spect to understanding solidification cracking susceptibility.
Although the solidification and weldability of wrought Al-
loy 625 compositions have been thoroughly investigated,[1,2]
little work[10,11] has been published on the solidification be-
havior of dissimilar metal welds between Alloy 625 and
Cr-Mo steels. In this work, the previous studies conducted
on Alloy 625 (and Alloy 718) and dissimilar welds involv-
ing Alloy 625 are extended by investigating the solidifica-
tion behavior (microsegregation, secondary phase
formation, and solidification temperature range) of a dis-
similar weld between Alloy 625 and 2.25Cr-1Mo (A387
Grade 22) steel.
II. EXPERIMENTAL PROCEDURE
A. Welding and Materials
The chemical composition of the Alloy 625 consumable
electrode and Cr-Mo substrate are given in Table I. The 1.14-
mm-diameter electrode was deposited onto a 6.4-mm-thick
Cr-Mo steel substrate using the gas metal arc welding process

3612—VOLUME 27A, NOVEMBER 1996 METALLURGICAL AND MATERIALS TRANSACTIONS A

Table I. Chemical Composition of Alloy 625 Electrode and lytically in a 10 pct chromic acid/90 pct water solution at
2.25Cr-1Mo Steel (All Values in Weight Percent) '3 V. Scanning electron microscopy was conducted in the
Element 625 Filler Alloy 2.25Cr-1Mo Substrate
secondary electron and backscattered electron modes at an
accelerating voltage of 20 kV. After observation by LOM
Iron 4.12 balance and SEM, small areas of parallel dendrites were bracketed
Nickel balance ,0.01 for EPMA by microhardness indentations and the sample
Chromium 21.32 2.06
Silicon 0.23 0.27
was repolished to a 0.04-mm finish and carbon coated. An
Niobium 2.84 — EPMA trace was also conducted across the entire overlay
Molybdenum 8.57 0.90 thickness from the fusion line area to the weld metal sur-
Manganese 0.24 0.43 face. Electron probe microanalysis was conducted at an ac-
Titanium 0.22 — celerating voltage of 15 kV and beam current of '20 nA.
Carbon 0.024 0.132 The Ka lines were used for elements Fe, Ni, Cr, and Si,
Phosphorus 0.017 0.024 while La lines were used for Mo and Nb. Considering the
Sulfur ,0.001 0.014 EPMA voltage and the average atomic number, atomic
weight, and density of the overlay deposit, the electron
probe will have an interaction diameter of '1 mm.[12] Raw
data were reduced to weight percentages using the ZAF
algorithm.[13]
A small sample of all weld metal was obtained by ma-
chining away the substrate. The sample was used for bulk
chemical analysis and DTA. The DTA was conducted on
a Netzsch STA 409 thermal analyzer using argon cover gas
and an alumina crucible. The sample size was 0.65 g and
pure Ni was used as the reference material. The sample was
heated to 1000 7C at a rate of 20 7C/min and then heated
through the melting range to 1440 7C at a rate of 5 7C/min.
The alloy was then cooled at a faster rate of 20 7C/min
through the solidification temperature range to simulate no-
nequilibrium solidification as closely as possible within the
equipment cooling rate capacity. The weight of the sample
was simultaneously monitored by a thermogravometric bal-
ance to ensure no weight change occurred during the test.
The DTA system was calibrated by determining the melting
temperature of pure Ni and found to be within 2 7C of the
literature value. Reaction temperatures were taken as de-
viations from the local baseline. Light optical microscopy,
SEM, and EPMA were conducted on the DTA specimen
by the procedure described previously. The area fraction of
minor constituent in the DTA sample was determined on a
LECO* 2001 quantitative image analysis (QIA) system.
*LECO is a trademark of LECO Corporation, St. Joseph, MI.

The area fraction was assumed to be equal to the volume

Fig. 1—LOM photomicrograph of the overlay deposit in the region of a
solidification crack.
at 30 V, 225 A (165 mm/s electrode velocity), and 16 mm/s
travel speed with argon shielding gas. Voltage was measured
between the torch contact tube and substrate and thus rep-
resents the combined voltage drops between the arc and
electrode. Multiple passes were applied with a 50 pct over-
lap between passes and an interpass temperature of 100 7C
to 150 7C.
B. Microstructural Characterization
A sample was sectioned from the middle of the overlay
and mounted for observation by light optical microscopy
(LOM), scanning electron microscopy (SEM), and electron
probe microanalysis (EPMA). The sample was polished to
a 0.04-mm finish using colloidal silica and etched electro-
fraction.
III. RESULTS
A. Microstructural Characterization
Solidification cracks were observed in the overlay de-
posit upon observation by LOM. Figure 1 shows an LOM
photomicrograph of the overlay deposit in the region of a
solidification crack. A secondary constituent is observed in
the interdendritic areas and grain boundaries. The observed
solidification cracks were always associated with this con-
stituent. The crack shown in Figure 1 is presented at higher
magnification in Figure 2 where the secondary constituent
exhibits a lamellar eutectic-type morphology. The DTA
specimen showed the same behavior as the weld overlay
deposit in which a single interdendritic constituent was ob-
served of essentially identical morphology (Figures 3 and
4) but was coarser due to the slower cooling rate. The back-

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 27A, NOVEMBER 1996—3613

Fig. 2—SEM photomicrographs of the solidification crack shown in Fig. 1.
Fig. 3—LOM photomicrograph of the second-phase constituent observed
in the DTA specimen.
scattered electron image shown in Figure 4 indicates the
second phase is enriched in elements of high atomic num-
ber (e.g., Mo and Nb) relative to the matrix.
3614—VOLUME 27A, NOVEMBER 1996
Fig. 4—Backscattered SEM photomicrograph of the second-phase
constituent observed in the DTA specimen.
Figure 5 shows an EPMA trace conducted across several
dendrites within the overlay deposit. The position of the
dendrite cores (example marked with arrow and labeled
DC) and interdendritic areas (example marked with arrow
and labeled ID) are noted in the plot. The dendrite cores
METALLURGICAL AND MATERIALS TRANSACTIONS A
 (a)
(b)
Fig. 5—EPMA trace conducted across several dendrites within the overlay
deposit: (a) Fe, Ni, and Cr; and (b) Mo and Nb.
are depleted in Nb and Mo and slightly enriched in Fe, Ni,
and Cr. Figure 6 shows an EPMA trace conducted from the
fusion line region to the overlay surface. All elements ex-
hibit random variations in concentration which can be at-
tributed to the dendritic microsegregation which was
displayed in Figure 5. Inspection of the main alloying el-
ements (most notably Cr), which show a low tendency for
dendritic microsegregation, indicates there is no significant
macrosegregation within the overlay deposit which may re-
sult from incomplete mixing between the Cr-Mo steel sub-
strate and Alloy 625 consumable electrode. Figure 7 shows
the results expanded about the fusion line area. The tran-
sition region where mixing is incomplete is seen to be only
'20 mm. Once the electron probe exits this transition re-
gion, there is no systematic variation in composition with
distance (Figure 6). Thus, the weld metal composition is
homogeneous on a macroscopic scale. Table II lists the re-
sults of chemical analysis conducted on the all weld metal
sample. The average values of elements analyzed by EPMA
(Figure 6) and estimated from the geometrical measurement
METALLURGICAL AND MATERIALS TRANSACTIONS A
(a)
(b)
Fig. 6—EPMA trace conducted from the fusion line region to the overlay
surface: (a) Fe, Ni, and Cr; and (b) Mo and Nb.
of dilution directly on the metallographic sample are also
listed for comparison. The geometrical dilution is given by
D 5 Asub/(Asub 1 Aol) where Asub is the cross-sectional area
of melted substrate and Aol is the cross-sectional area of
deposited overlay. The geometrical measurement of dilu-
tion yielded a value of 28 pct, which is in reasonable agree-
ment with the bulk chemical analysis of '25 pct. In
addition, the bulk chemical analysis results are within the
range of the average EPMA values. The agreement between
these results further confirms that the weld metal compo-
sition is homogeneous on a macroscopic scale.
The second phase within the eutectic-type constituent of
the DTA sample contained regions which were large
enough ('4 mm) to analyze by EPMA (interaction volume
'1 mm). Table III summarizes the results of EPMA con-
ducted at five different locations on the second phase within
the DTA specimen. The morphology of this eutectic-type
constituent and the composition of the second phase within
the constituent (most notably Nb) have been identified pre-
VOLUME 27A, NOVEMBER 1996—3615
 Table III. Chemical Composition of Laves Phase in Alloy
625 Weld Overlay Deposit (All Values in Weight Percent)

Element 1 2 3 4 5 Average
Iron 17.6 19.5 17.7 17.8 17.6 18.0 5 0.8
Nickel 30.0 29.4 30.7 29.4 31.3 30.2 5 0.8
Chromium 11.7 11.6 11.6 11.6 11.4 11.6 5 0.1
Molybdenum 16.9 15.4 16.7 17.4 17.3 16.7 5 0.8
Niobium 22.5 22.6 22.1 22.1 21.1 22.1 5 0.6
Silicon 1.1 1.2 1.0 1.4 1.0 1.1 5 0.2

viously as a g 1 Laves mixture in studies on Alloy 625[2]

and 718.[5] The Laves phase is significantly enriched in Nb,
Mo, and Si. The amount of g 1 Laves constituent was
measured to be within the range of 1.3 to 2.2 vol pct. The
volume fractions of g and Laves within the mixture were
determined by conducting QIA on six backscattered elec-
tron photomicrographs similar to that shown in Figure 4
with the following results: g 5 25 5 4 pct and Laves 5
(a) 75 5 4 pct.

B. Differential Thermal Analysis

Figure 8 shows the heating and cooling portions of the
DTA scan. Upon heating above 1000 7C at 5 7C/min, an
endothermic peak associated with liquation of the g/Laves
constituent is observed at '1213 7C. The large endothermic
peak shows an initial deviation from the baseline which is
rather gradual. This effect is probably caused by nonuni-
form melting of the cored g dendrites, where the extremities
of the dendrites begin melting first due to a higher concen-
tration of segregants. Because the g is inhomogeneous, no
attempt was made to determine a solidus temperature for
the g matrix. Upon further heating, the liquidus is reached
at 1388 7C. On cooling at 20 7C/min, solidification of the
g dendrites is initiated at 1357 7C (31 7C undercooling) and
solidification is terminated by the g/Laves reaction at
'1216 7C. The rather large degree of undercooling is likely
to result from the relatively fast cooling rate used during
the cooling portion of the thermal cycle.
(b)
Fig. 7—EPMA results expanded about the fusion line area showing the
transition region: (a) Fe, Ni, and Cr; and (b) Mo and Nb.
IV. DISCUSSION
A. Solidification Cracking
Although the relative susceptibility of this particular
Table II. Chemical Composition of Alloy 625 Weld
Overlay Deposit (All Values in Weight Percent)
weld overlay deposit to solidification cracking has not been
quantified in this work, general inferences can be made by
Estimated from considering the solidification results described above and
Average Geometrical comparing these results with other alloy systems. The
Chemical of EPMA Dilution* cracking tendency of weld metals is well known to increase
Element Analysis Data (28 Pct) with the increasing solidification temperature range and the
Iron 28.14 27.2 5 5.8 29.90 formation of terminal secondary constituents in small quan-
Nickel 44.91 46.7 5 5.0 44.93 tities.[14] When an interdendritic liquid forms in large quan-
Chromium 16.67 17.5 5 0.8 15.93 tities, backfilling of hot cracks can occur and cracking
Molybdenum 6.78 6.8 5 0.9 6.42 susceptibility can often begin to decrease.[15,16]
Niobium 2.07 2.4 5 2.1 2.04 The formation of the g/Laves constituent results in a sub-
Silicon 0.24 — 0.24 stantial widening of the solidification temperature range.
Titanium 0.17 — 0.16
Carbon 0.050 — 0.05
The difference between the on-heating liquidus and g/Laves
Phosphorus 0.017 — 0.018 reaction temperature provides a reasonable estimate of the
Sulfur ,0.004 — 0.005 weld metal solidification range. The on-heating liquidus
temperature is utilized since the weld metal solidifies epi-
*Geometrical measurement of dilution, D 5 Asub/(Asub 1 Aol).
taxially from the base metal and requires little undercool-

3616—VOLUME 27A, NOVEMBER 1996 METALLURGICAL AND MATERIALS TRANSACTIONS A


(a)
(b)
Fig. 8—(a) Heating and (b) cooling portions of the DTA scan.
ing[17] (assuming undercooling due to the dendrite radius of
curvature effects during growth is negligible). Thus, the
weld overlay deposit solidifies over a temperature range of
'170 7C and forms 1.3 to 2.2 vol pct g/Laves. This soli-
fication temperature range is rather wide in comparison to
other Ni base alloys such as, for example, HASTELLOY*
*HASTELLOY is a trademark of Stoody Deloro Stellite, Industry, CA.
C4 (DT ' 70 7C),[18] which has been shown to exhibit very
good weldability. In addition, the presence of 1.3 to 2.2 vol
pct (g 1 Laves) is high enough to aggravate cracking but
insufficient to promote any backfilling of hot cracks.[13,14] By
additional comparison, Alloy 718, which is relatively crack
sensitive[5] and possesses a composition somewhat similar to
the Alloy 625 overlay in this study (Table IV), solidifies over
a range of '160 7C and forms about 6 to 10 vol pct g/Laves.
Thus, considering the relatively wide solidification temper-
ature range and amount of interdendritic constituent, the for-
mation of hot cracks in the overlay are not surprising.
The presence of solidification cracks does not completely
preclude the use of Alloy 625 as an overlay for protection
METALLURGICAL AND MATERIALS TRANSACTIONS A
of carbon and Cr-Mo type steels. The effect of such cracks
on the overlay performance will generally depend on the
degradation mechanism which is operable. For example,
under conditions of wear and solid particle erosion (where
this alloy has shown good performance[6,7]), it is only nec-
essary to provide a physical barrier between the substrate
and mechanical force of the abrasive media. Under these
conditions, small cracks generally do not compromise the
overlay integrity. In corrosion applications, solidification
cracks will be detrimental if they traverse through the entire
overlay thickness, in which case they will provide a path
for aggressive gases to reach the underlying substrate. All
the solidification cracks observed under the current set of
conditions were isolated below the overlay surface. The sig-
nificance of solidification cracks must generally be consid-
ered with regard to the intended application.
B. Solidification Reaction
The solidification of the overlay deposit begins with the
formation of g dendrites which are depleted in Mo and Nb
at their cores. As solidification proceeds outward from the
dendrite centers, these elements continue to partition to the
liquid phase while the main elements (Fe, Ni, and Cr) seg-
regate slightly to the solidifying g dendrites. This process
continues until the interdendritic liquid becomes enriched,
most notably in Nb, to the g/Laves eutectic composition, at
which point solidification terminates with the formation of
the g 1 Laves constituent. The solidification sequence can
be written as L → L 1 g → L 1 g 1 Laves → g 1 Laves.
This solidification sequence is consistent with other Nb-
bearing iron- and nickel-base alloys. Both Laves and NbC
phases have been observed in welds of Alloys 625,[1,2]
718,[5,19] and IN519[20] and Alloy 625 weld overlays.[10] The
relative amounts of each phase formed during solidification
are known to be quite sensitive to the C and Si contents,
where NbC is generally favored by C and Laves is favored
by Si additions. It should be noted that the Laves phase will
not form in simple Ni-Nb binary alloys[21] but requires the
presence of other alloy additions such as Fe. In fact, Fe-Nb
binary alloys do form a Laves phase.[21] The role of Fe is of
particular importance here since the 625 overlay composition
is significantly enriched in Fe due to dilution from the sub-
strate (Table II) and only the Laves phase was observed.
Zhao et al.[10] identified both NbC and Laves phase in
625 overlays on carbon steel. Although the resultant over-
lay composition was not reported, the carbon content of the
steel substrate (0.25 wt pct) was nearly twice that of the
Cr-Mo substrate used in this work. The relatively low C
content of the Cr-Mo steel substrate apparently accounts,
at least in part, for the absence of NbC in the 625 overlay
studied here. Although Laves was the predominant second
phase identified in Alloy 718,[5] small amounts of NbC were
also reported. As shown by the comparison in Table IV (C0
values, where C0 is the nominal elemental content), Alloy
718 has a chemical composition similar to that of the Alloy
625 overlay deposit (the values of Cs,i , dendrite core com-
position, and ki, equilibrium coefficient, in the table are dis-
cussed subsequently). The Si and C contents are very
similar, but there is about an even exchange between Fe
and Ni. Thus, the increased Fe addition apparently favors
the Laves phase to the point where NbC formation is com-
pletely suppressed. A similar type of trend is observed if a
VOLUME 27A, NOVEMBER 1996—3617
 Table IV. Comparison of Compositions (Weight Percent) they cause an extension of the solidus to the point where a
and Equilibrium Distribution Coefficients of Alloy 625 Weld eutectic-type reaction occurs to form a g 1 Laves mixture.
Overlay Deposit and Alloy 718 Each of these microsegregation-induced phenomena (wid-
625 Overlay Deposit Alloy 718[19] ening of solidification temperature range and secondary
phase formation), in turn, have a deleterious effect on weld-
Element C0 Cs,i ki C0 ki ability. The tendency of each element to segregate during
Iron 28.14 28.6 1.02 18.10 1.04 solidification can be quantified by use of the EPMA data
Nickel 44.91 46.7 1.04 53.20 1.00 and basic solidification theory.
Chromium 16.67 17.6 1.05 18.18 1.03 If it is assumed that dendrite tip curvature effects and
Molybdenum 6.78 5.83 0.86 3.12 0.82 solid-state diffusion are each negligible, thermodynamic
Niobium 2.07 0.97 0.46 5.25 0.48 equilibrium is maintained at the solid/liquid interface, and
Silicon 0.24 — — 0.21 0.67
Carbon 0.05 — — 0.04 —
diffusion is infinitely fast in the liquid, then the instanta-
neous solid composition, Cs, forming at any solid fraction,
fs, is given by the well-known Scheil equation:[22]
comparison is made between results reported for Alloys 625
Cs 5 kC0 (1 2 fs)k21 [1a]
(Ni-21.65Cr-9.68Mo-3.57Nb-2.26Fe)[1] and IN519 (Fe-
24.63Ni-24.01Cr-2.14Nb-0.01Mo).[20] The Ni-rich 625 Al- where k is the equilibrium coefficient, defined as the ratio
loy (Alloy 7 of Reference 1) contained only 0.008 wt pct of solid to liquid composition at any temperature, and C0
C and 0.38 wt pct Si but still formed the NbC phase. In is the nominal composition of the alloy. A similar equation
contrast, the Fe-rich IN-519 alloy (Alloy SV-20 in Refer- is obtained for the liquid composition (Cl) and liquid frac-
ence 19) contained 0.02 wt pct C and 1.02 wt pct Si and tion (fl)
formed only the Laves phase. Although detailed compari-
sons cannot be made since the Si (and other) contents are C1 5 C0 (f1)k21 [1b]
not equivalent, the general effect of Fe on promoting Laves The value of k provides a measure of an element’s micro-
phase is apparent. Last, Cieslak et al.[4] also reported the segregation potential, where lower k values segregate
presence of only Laves (of very similar composition to that strongly to the liquid phase and widen the solidification
shown in Table III) in a dissimilar metal weld between temperature range by suppressing the solidus temperature.
Alloy 625 and 304 stainless steel. Brody and Flemings[23] have considered the effect of back
The relative amounts of NbC formers (i.e., carbon) and diffusion into the solid during solidification and, assuming
Laves formers (iron and silicon) in the overlay are impor- a parabolic growth rate, derived an expression of the form
tant to consider in terms of solidification cracking suscep- k21
tibility. It is well established that g/NbC forms at higher Cs 5 kC0 [1 2 (122ak)fs]1 2 2ak [2]
temperatures than g/Laves.[1,2,5,19,20] Thus, if the overlay
composition can be adjusted so that solidification is ter- where
minated with the L → g 1 NbC reaction rather than the L
Dstf
→ g 1 Laves reaction, the solification temperature range a5 [3]
will decrease and possibly produce a concomitant decrease L2
in cracking susceptibility. Variations in the overlay com- Here, Ds is the diffusivity of solute in the solid (assumed
position can arise from three sources: (1) variations in the constant in the derivation of Eq. [2]), tf is the local solidi-
Alloy 625 filler alloy composition, where small deviations fication time, and L is half the dendrite spacing. The local
in Fe, Si, and C (which are permitted within specification) solidification time is given by the ratio of solidification tem-
have a significant effect on the type of terminal solidifica- perature range to cooling rate. When a ,, 1, solid-state
tion reaction;[1] (2) variations in the steel substrate compo- diffusion is considered negligible and Eq. [2] reduces to the
sition, most notably C; and (3) variations in dilution due to Scheil equation.
changes in processing parameters.[28] In terms of the filler An order-of-magnitude estimate of the overlay cooling
alloy and substrate, compositions with relatively high C and rate during solidification can be obtained with the solution
low Fe and Si contents would be preferred. Dilution would presented by Rosenthal[24] for three-dimensional heat flow
seem to have the largest effect since significant amounts of which, at the weld centerline, reduces to
Fe can be transferred to the overlay from the substrate. A
quantitative method for predicting dilution has recently ]T 2plS (T 2 T0)2
5 [4]
been proposed by DuPont and Marder.[28] From that work, ]t haVI
maximizing the filler metal feed rate–to–arc power ratio
will minimize the Fe content in the overlay by minimizing where l is thermal conductivity, S is the travel speed, T is
dilution. Careful control of these composition and process- the temperature at which the cooling rate is estimated, T0
ing factors may aid in reducing solidification cracking in is initial temperature, ha is the arc efficiency, and VI is the
this substrate/overlay system. arc power. Using a value of l ' 0.02 W (mmz7C)21 for the
solid at 700 7C as an estimate from a survey of several Ni-
base alloys with similar composition,[25] ha 5 0.84,[26] and
C. Elemental Segregation
the values of S, T0, and VI noted in Section II–A, the cool-
As shown in the preceding results, microsegregation has ing rate at 1350 7C is '550 7C/s. For a solidification range
a significant effect on the solidification sequence of the of 170 7C, this cooling rate results in a solidification time
overlay deposit. As minor alloy additions (most notably Nb of 0.30 seconds. The half dendrite arm spacing was esti-
and to a lesser extent Mo and Si) segregate to the liquid, mated from multiple LOM photomicrographs as '5 mm.

3618—VOLUME 27A, NOVEMBER 1996 METALLURGICAL AND MATERIALS TRANSACTIONS A

This information is used to calculate the a parameter for
the solute Nb in order to assess the possible effect of back
diffusion. No literature data could be found for Ds values
of Nb in a Ni matrix. As an estimate, Ds for Nb in an fcc
Fe matrix is calculated from Reference 27 as 2.7 3 1027
mm2/s. With these values, a 5 0.003. Thus, under the so-
lidification conditions here, solid-state diffusion can be ne-
glected with little error and Eq. [1] can be used.
Values of k at the initiation of solidification can be de-
termined by noting that, in Eq. [1], Csi 5 kiC0 at fs 5 0,
where Csi is the dendrite core composition, ki is the distri-
bution coefficient at the start of solidification, and C0 is the
nominal composition. The value of Cs,i is measured by
EPMA at the dendrite cores where the concentration is at
a minimum (for k , 1) and, as demonstrated previously
the results from chemical analysis of the all weld metal
deposit can be used as C0 since the overlay composition is
uniform on a macroscopic scale. These values are sum-
marized in Table IV, where comparison is made by the
results previously reported by Cieslak et al. on Alloy
718.[19] The data show that the microsegregation potentials
of elements in the two alloy systems are very similar. The
behavior of Nb is of particular interest since it segregates
rather strongly (k 5 0.46) and promotes the Laves phase.
This value of k for Nb is also very close to that measured
by other workers on Alloy 625 (kNb ' 0.50)[1] and INCO-
LOY 909 (kNb ' 0.49).[19]
With k known, it is possible to use Eq. [1] to assess
microsegregation. Although this relationship is developed
for a simple binary system, it can be applied here by mod-
eling the weld overlay as a binary between the g matrix
and Nb. The selection of Nb as the solute is based on its
strong propensity to segregate and form Laves. An addi-
tional assumption required by the use of Eq. [1] is that k
does not vary significantly during solidification. The valid-
ity of this assumption is supported by (1) the consistency
in kNb as measured in multiple alloy systems where the bulk
Nb content varies and (2) the data reported by Knorovsky
et al.[5] on Alloy 718 where k was shown to be equivalent
at the beginning and end of solidification.
A particularly useful application of Eq. [1b] is in deter-
mining the amount of eutectic which forms in the binary
system. When the liquid composition is enriched to the eu-
tectic composition, Cl → Ce, the eutectic composition, and
fl → fe, the eutectic fraction.
~ !
Ce 1 V.
fe 5 k21
[5]
C0
In order to estimate the value of Ce for this system, advan-
tage is again taken of the previous results reported on Alloy
718 and the similarities between the systems. Table V sum-
marizes the similarities between g/Laves constituents and kNb
values in this study and Alloy 718.[19] The g composition
within the g/Laves constituent in Alloy 718 was determined
by analytical electron microscopy. Considering the similari-
ties in the two systems, it is reasonable to assume that the g
within the g/Laves mixture in the 625 overlay will also have
a composition of '9.3 wt pct Nb, for a eutectic composition
of 18.9 wt pct Nb. (The g/Laves composition and reaction
temperature need not be truly invariant in this multicomponent
system.) Using Ce 5 18.9 wt pct Nb, C0 5 2.07 wt pct Nb,
and kNb 5 0.46 in Eq. [5] yields a value of fe 5 1.7 vol pct.
METALLURGICAL AND MATERIALS TRANSACTIONS A
Table V. Summary of Similarities between g /Laves
Constituents and kNb Values in This Study and Alloy 718
Alloy 625/
Cr-Mo Steel Alloy 718[19]
g/Laves eutectic reaction '1213 7C '1200 7C
temperature
Volume percent laves in g/Laves 75 5 4 73 5 12
eutectic
Volume percent g in g/Laves 25 5 4 27 5 12
eutectic
Laves composition in g/Laves 22.1 5 0.6 22.4
eutectic
g composition in g/Laves eutectic — 9.3
kNb 0.46 0.48
(The densities of g, g/Laves, and Laves are very similar.[5]
Thus, the calculated weight fraction fe is essentially equivalent
to volume fraction.) This calculated value of fe is within the
range of g/Laves constituent measured in the DTA sample
(1.3 to 2.2 vol pct). Although some dissolution of the Laves
phase may be expected during solidification and cooling of
the DTA specimen due to the relatively slow cooling rate used
(20 7C/min), a review of some experimental results suggests
this effect is insignificant. The k value of Nb determined by
EPMA on a gas tungsten arc weld (cooling rate '500 7C/s)
in Alloy 718 yielded a value of 0.50.[5] By comparison, a
statistically equivalent value of 0.48 was reported from EPMA
data for the same composition when the results were deter-
mined from a DTA specimen cooled at 20 7C/min.[19] If dif-
fusion was significant in the DTA sample, a higher value for
k would have been obtained on the DTA sample due to dif-
fusion of Nb to the dendrite cores during solidification and
postsolidification cooling. The fact that the k values were es-
sentially equivalent indicates diffusion of Nb is insignificant
even at the relatively slow DTA cooling rates.
It must be emphasized that the results in this study were
obtained on a single weld overlay composition. The overlay
composition can obviously vary significantly with changes
in processing parameters which affect the dilution level.
The dilution level of this overlay is '25 pct (Table II).
Both the substrate composition and overlay dilution level
must be carefully considered when assessing the solidifi-
cation behavior of any weld overlay.
CONCLUSIONS
A study was conducted on the solidification behavior of
an Alloy 625 weld overlay deposited on Cr-Mo steel sub-
strate at a dilution level of '25 pct. The following can be
concluded from this work.
1. Solidification occurs over a temperature range of '170 7C
via L → L 1 g → L 1 g 1 Laves → g 1 Laves, where
the terminal Laves phase exists in a eutectic-type mor-
phology with g. The formation of solidification cracks at
this dilution level can be attributed to this relatively wide
solidification temperature range and the presence of
g/Laves. Selection of filler alloys and substrate composi-
tions with relatively high C and low Fe and Si contents,
along with reductions in dilution through control of pro-
cessing parameters, may serve to reduce this cracking
problem.
VOLUME 27A, NOVEMBER 1996—3619
2. The secondary phase formation and microsegregation
behavior of main alloying elements (Fe, Ni, Cr, Mo, and
Nb) are very similar to those previously reported for
Alloy 718 in particular and other Nb-bearing Ni-base
alloys in general.
3. Agreement is obtained between calculated and measured
volume percent g 1 Laves constituent with the Scheil
equation by treating the overlay system as a simple g-
Nb binary and using the experimentally determined kNb
value from the EPMA data.
ACKNOWLEDGMENTS
The author acknowledges financial support of this work
by Pennsylvania Power and Light Co., Public Service Elec-
tric and Gas, Virginia Power, and Ohio Edison. Technical
assistance with the EPMA work by Kathy Reppa and re-
view of the manuscript by Professor A.R. Marder are also
appreciated.
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METALLURGICAL AND MATERIALS TRANSACTIONS A