Wheeling 7-2016_Layout 1 6/9/16 5:16 PM Page 229

WELDING RESEARCH
SUPPLEMENT TO THE WELDING JOURNAL, JULY 2016
Sponsored by the American Welding Society and the Welding Research Council

Solidification Cracking Susceptibility of

Ni­30Cr Weld Metals with Variable
Niobium and Molybdenum
A crack healing effect was observed with additions of Nb above 4 wt­%

BY R. A. WHEELING AND J. C. LIPPOLD

7) and 52 (ERNiCrFe-7) were devel-

ABSTRACT oped for welding these high-Cr alloys,
such as Alloy 690. Niobium and
Ni­30Cr alloys such as Alloy 690 and compatible filler metals are used extensively in
molybdenum have been added to this
the nuclear power industry to avoid problems with primary water stress corrosion
cracking (PWSCC). Depending on composition, these alloys can be susceptible to both class of filler metal, in some cases to
solidification and ductility­dip cracking. In this study, the effect of niobium (Nb) and reduce susceptibility to DDC (Refs.
molybdenum (Mo) additions to a base Ni­30Cr alloy (Alloy 690) on solidification cracking 2–7). While this approach has been
susceptibility was evaluated. Both computational and experimental techniques were quite successful in mitigating DDC, in-
used to determine the effect of composition modifications on solidification behavior and creased susceptibility to solidification
cracking susceptibility. Nb additions from 0 to 8 wt­% and Mo additions from 0 to 4 wt­% cracking has been reported, as the so-
were evaluated. The addition of Nb resulted in an increase in the fraction eutectic that lidification temperature range expands
forms at the end of solidification, with 8 wt­% Nb resulting in over 20 vol­% eutectic con­ and supports a eutectic reaction at the
stituents. The addition of Mo had virtually no effect on the fraction eutectic. The cast pin end of solidification (Refs. 6–8).
tear test (CPTT) was used to measure solidification cracking susceptibility. With this test,
It is well documented that niobium
a peak in cracking susceptibility was observed at 4 wt­% Nb. The addition of Nb above
4 wt­% resulted in a decrease in cracking due to a crack healing effect. The addition of additions in Ni-based alloys result in
Mo resulted in a decrease in cracking susceptibility in the higher Nb alloys. Characteriza­ an interdendritic eutectic reaction
tion performed using SEM/EDS verified the crack healing effect at high Nb levels and dif­ consisting of  (fcc) and Nb-rich phas-
ferentiated the eutectic constituents that formed along the solidification grain es such as NbC and Laves (A2B) at the
boundaries. end of solidification, but little re-
search has focused on additions in Al-
loy 690, due to a greater interest in
KEYWORDS corrosion resistance of the alloy
(Refs. 9–12). Niobium is a common
• Solidification Cracking • Stress Corrosion Cracking • Alloy 690 • Nuclear Industry addition of choice for improving
• Filler Metal • Cast Pin Tear Test weldment quality in terms of increas-
ing room temperature strength as
well as increasing corrosion resist-
Introduction tions and coal-gasification units (Ref. ance, but the effect of Nb on weld-
1). In efforts to combat the observed ability has been limited to maximum
Nuclear power generation, petro- ductility dip cracking (DDC) that can additions of up to 5 wt-% (Ref. 12).
chemical, and many other industries occur when these alloys are welded, al- Reports regarding molybdenum
rely on high chromium (25–30 wt-%), loying additions such as niobium and suggest that additions may increase
Ni-based alloys due to the corrosion molybdenum have been introduced, the solidification temperature range
and stress corrosion cracking resist- but may result in an increased suscep- and promote the formation of a low
ance imparted by the high chromium tibility to solidification cracking due to melting eutectic phase, similar to Nb
content, as well as good mechanical a widened solidification temperature (Refs. 7, 13). Molybdenum has been
properties at elevated temperatures. range. shown to improve resistance to DDC
Other applications include the han- Compatible high-chromium weld- in Nb-bearing filler metals such as
dling of nitric/hydrofluoric acid solu- ing filler metals such as 152 (ENiCrFe- 52MSS (ERNiCrFe-13), and there is

R. A. WHEELING and J. C. LIPPOLD are with the Welding Engineering Program, The Ohio State University, Columbus, Ohio.

JULY 2016 / WELDING JOURNAL 229-s

Wheeling 7-2016_Layout 1 6/9/16 5:16 PM Page 230

WELDING RESEARCH

Fig. 1 — Four curves that compare

cracking susceptibility or “sensitivity”
as a function of alloying content in Al
alloys (Ref. 36).

some evidence that it reduces suscep-

tibility to solidification cracking in
fully austenitic stainless steels (Refs.
4, 5, 14).
It has been reported that in some
materials, a large fraction of liquid of
eutectic composition present at the
end of solidification may promote a
backfilling or “crack healing” effect
(Refs. 7, 15–17). Backfilling is defined
as a partial or entire healing of solidifi-
Fig. 2 — Percentage of circumferential cracking for the Alloy 690 base composition and
cation cracks due to the flow of liquid the Nb­bearing alloys. Each point and error bar represents the average of at least 4 ac­
metal into newly formed cracks or ceptable pins. The red circles indicate the critical cracking threshold or longest pin at
voids (Ref. 18). Both volume fraction which no cracking was observed.
eutectic and liquid phase characteris-
tics such as viscosity, surface tension,
and wettability of eutectic films deter- creases, cracking susceptibility initially is associated with the fraction of eu-
mine whether the liquid will “heal” a increases to a peak value and then de- tectic liquid present at the end of so-
forming crack (Ref. 19). It is known creases, presumably due to a crack lidification at a given composition. At
that some Nb-bearing, Ni-based alloys, healing effect. The variation in the lo- the peak, the liquid completely wets
such as Alloy 625, are resistant to so- cation of the peak cracking susceptibil- the solidification grain boundary and
lidification cracking, presumably due ity in these different Al-based systems promotes cracking, while at composi-
to a backfilling (crack healing) effect
(Refs. 5, 7, 9, 20–23). The amount of
Table 1 — Calculated Composition (wt­%) of Alloys Evaluated in this Study
eutectic constituent necessary to pro-
mote crack healing is likely alloy de-
pendent, but in one study of Alloy 625 Composition Ni Cr Fe Nb Mo C
weld metal, an increase in the fraction Alloy 690 60.51 29.45 9.13 – – 0.0290
of Nb-rich eutectic from 7 to 11.5 2Nb0Mo 59.29 28.86 8.95 2.00 – 0.0284
vol-% resulted in a significant decrease 2Nb2Mo 58.09 28.27 8.76 2.00 2.00 0.0278
in cracking susceptibility (Ref. 20). 2Nb4Mo 56.87 27.68 8.58 2.00 4.00 0.0273
Cracking susceptibility curves have 4Nb0Mo 58.09 28.27 8.76 4.00 – 0.0278
been developed for Al alloys (Fig. 1) 4Nb2Mo 56.87 27.68 8.58 4.00 2.00 0.0273
that illustrate a reduction in cracking 4Nb4Mo 55.66 27.09 8.40 4.00 4.00 0.0267
susceptibility at high alloy content due 6Nb0Mo 56.87 27.68 8.58 6.00 – 0.0273
6Nb2Mo 55.66 27.09 8.40 6.00 2.00 0.0267
to the crack healing effect. All of these
6Nb4Mo 54.47 26.51 8.22 6.00 4.00 0.0261
binary (or ternary) systems exhibit a 8Nb0Mo 55.66 27.09 8.40 8.00 – 0.0267
eutectic reaction. As alloy content in-

230-s WELDING JOURNAL / JULY 2016, VOL. 95

Wheeling 7-2016_Layout 1 6/9/16 5:16 PM Page 231

WELDING RESEARCH

Fig. 3 — Cracking susceptibility based on CPTT results compared Fig. 4 — The average circumferential cracking in pins containing
to measured and ThermoCalc­predicted fraction eutectic values. 2 or 4 wt­% molybdenum along with 2, 4, or 6 wt­% niobium ad­
Error bars represent the standard deviation of the measured ditions is compared to that observed in pins with only niobium
fraction eutectic values. additions. Each point represents at least 4 acceptable pins.

Fig. 5 — Optical micrographs of sectioned pins representative of Fig. 6 — Low­ and high­magnification optical micrographs of
the CPTT data in Fig. 2. backfilled cracks. A — 4Nb0Mo; B — 8Nb0Mo pins.

tions beyond the peak, the eutectic liq-
uid has a backfilling, or crack healing,
effect. The crack healing approach has
been shown to be quite effective with
aluminum alloys (Refs. 24–36), but
there is limited data for other alloy
systems.
The cast pin tear test (CPTT) was
used in this investigation since it pro-
vides a more effective means of ac-
counting for the effect of backfilling
on solidification cracking susceptibili-
ty than the Varestraint test, or other
externally loaded tests. Because it is,
in effect, a “self-restraint” test, it pro-
vides a means to determine and obtain
cracking data at imposed strains low
enough as to not overwhelm the back-
filling effect. The CPTT may provide
better predictions regarding cracking
susceptibility in actual practice com-
pared to the Varestraint test since the
test is more effective in identifying the
critical strain required to produce so-
lidification cracking. Field testing in-
volving weldments of varying degrees
of restraint and comparison to CPTT
data may provide insight on the practi-
cal significance of the test, as well as
the backfilling effect in various Ni-
based alloys.
The objective of this study was to de-
termine the effect of variable Nb and
Mo content on the susceptibility of Ni-
30Cr filler metals to solidification crack-
ing as a function of the fraction eutec-
tic. The potential for a reduction in sus-
ceptibility due to a crack backfilling ef-
fect with increasing fraction eutectic
was investigated using an Alloy 690
base alloy that contains no Nb or Mo. A
more fundamental understanding of Nb
and Mo additions in terms of solidifica-
tion cracking will potentially influence
filler metal development for these high-
Cr alloys and allow filler metals to be de-
veloped that are resistant to both DDC
and solidification cracking.
Experimental Methods
and Procedures
Materials and Sample
Preparation
Alloy 690 was used as the base ma-
terial for this study. The composition
(wt-%) of the alloy used was Ni-
29.45Cr-9.13Fe-0.15Mn-0.32Ti-
0.24Al-0.02Mo-0.02Nb-0.029C-
0.002S-0.0048P-0.014N. Additions of
Nb and Mo were made using a button
melting technique. Niobium additions
in this study varied from 0 to 8 wt-%
and were in the form of 99.8% pure
1.0-mm-diameter wire. Molybdenum
additions of 2 and 4 wt-% were made
to select niobium additions and were
in the form of 99.94% pure, annealed
1.0-mm-diameter wire.
The Alloy 690 and pieces of Nb and
Mo wire were carefully weighed and

JULY 2016 / WELDING JOURNAL 231-s

Wheeling 7-2016_Layout 1 6/9/16 5:16 PM Page 232

WELDING RESEARCH

Fig. 7 — Optical micrograph of a network of backfilling and some open cracks in a B

2Nb4Mo pin that exhibited surface cracking.

consolidated using a gas tungsten arc 1) determine an approximate starting

(GTA) button melting process. All melt-
ing was conducted under an argon at-
mosphere, so the introduction of impu-
rity elements (oxygen, nitrogen) was
unlikely. Each button was remelted
three times to ensure homogeneity. The
buttons melted using this procedure
showed little evidence of oxidation. The
nominal composition of Alloy 690 and
resulting compositions after the Nb and
Mo additions are shown in Table 1.
Note that only the major elements are
listed in this table. The compositions of
a select number of buttons were deter-
mined using SEM/EDS and showed that
the calculated compositions in Table 1
were a good approximation of the actual
compositions.
Computational Modeling
The ThermoCalc™ Scheil module
(Ref. 37) was used to do the following:
point for this study in terms of the
levels of niobium, 2) calculate mass
fraction values of eutectic phase for
each composition, and 3) calculate the
average niobium and molybdenum lev-
els at the end of the eutectic reaction.
The TTNi7 database, including liq-
uid, FCC, NbC, and Laves phases, were C
used for the calculation. The Scheil sim-
ulations were run using two values of
fraction solidified as an end point for
the mass fraction calculations, namely
0.95 and 0.98, in order to determine
how the end point affected the calcula-
tions relative to solidification tempera-
ture range and fraction eutectic. These
values of fraction solidified were select-
ed based on the range that is commonly
used by other investigators for deter-
mining solidification temperature range
and/or fraction eutectic (Refs. 38–42). Fig. 8 — SEM micrographs depicting
The mass fractions were determined by crack backfilling in cast pins at crack­
ing threshold. A — 4Nb0Mo; B —
plotting the solid phase fractions as a 6Nb0Mo; C — 8Nb0Mo.

Table 2 — Calculated Solidification Data for Fe­30Cr Alloys with Nb and Mo Additions

Fraction Solid Fraction Solid

0.95 0.98 Measured
Alloy kNb kMo Volume Final Wt. Final Wt.
Mass STR Mass STR Fraction Fraction Fraction
Fraction (C) Fraction (C) Eutectic Nb Mo
Eutectic Eutectic

Alloy 690 0.16 – – 65 0.0192 108 0.003 ± 0.001 – –

2Nb0Mo 0.17 – – 215 0.0255 239.5 0.014 ± 0.006 0.201 –
2Nb2Mo 0.17 0.66 – 225.5 0.0268 254 – 0.191 0.0656
2Nb4Mo 0.17 0.68 – 237.5 0.0287 264.5 – 0.183 0.118
4Nb0Mo 0.18 – 0.0659 212.3 0.0959 221.9 0.075 ± 0.01 0.217 –
4Nb2Mo 0.18 0.67 0.0686 220.8 0.0986 237 – 0.206 0.0700
4Nb4Mo 0.18 0.69 0.0727 228 0.103 247.8 – 0.199 0.124
6Nb0Mo 0.19 – 0.152 191 0.182 199.5 0.144 ± 0.03 0.223 –
6Nb2Mo 0.19 0.68 0.156 201 0.186 216.3 – 0.212 0.0736
6Nb4Mo 0.19 0.69 0.160 207.8 0.190 226.5 – 0.204 0.129
8Nb0Mo 0.20 – 0.253 168.3 0.283 176.3 0.239 ± 0.018 0.227 –

232-s WELDING JOURNAL / JULY 2016, VOL. 95

Wheeling 7-2016_Layout 1 6/10/16 3:22 PM Page 233
Fig. 9 — SEM/EDS analysis of the region around a backfilled crack from Fig. 8. Spots 1–3 represent the composition of the backfilled cracks.
Fig. 10 — SEM/EDS analysis of the region around a backfilled crack in a 6Nb4Mo alloy. Spots 1, 2, and 6 represent the composition of the
backfilled cracks.
function of temperature (Ref. 43). The
average solute solidification profiles cal-
culated by the module and the resulting
mass fractions were compared to Im-
ageJ analyses of the volume fractions
from metallographic analysis and to the
energy dispersive spectroscopy (EDS)
composition data.
The significance of the Scheil simula-
tions in this study was in the correlation
made between the measured volume
fraction eutectic and the calculated
mass fraction eutectic, as well as the rel-
ative composition changes that were
predicted during solidification based on
compositional changes to Alloy 690.
Cast Pin Tear Test
The cast pin tear test (CPTT) can be
used to evaluate susceptibility to solid-
ification cracking through a controlled
variation of restraint levels imposed
by solidification shrinkage. It can be
classified as a “self-restraint” test since
the strain that promotes cracking re-
sults from contraction stresses that ac-
cumulate in the pin during solidifica-
tion. Detailed information regarding
the test as well as the procedure can be
found elsewhere (Refs. 44, 45). Pins
ranging from 0.75 to 1.625 in. in
length were cast at 1460°C after a 90-s
purge in argon gas. The CPTT has been
previously demonstrated to effectively
rank the solidification cracking suscep-
tibility of a number of Ni-based alloys
(Refs. 45, 46).
In this study, the shortest pin
length that exhibited no visible crack-
ing was used to quantify cracking sus-
ceptibility. This value is designated the
threshold pin length for solidification
cracking. At pin lengths above thresh-
WELDING RESEARCH
old, there tends to be more scatter in
the cracking response, making com-
parison among alloys more difficult.
Determination of the threshold pin
length for each alloy was based on a
minimum of four “acceptable” tests.
Acceptable pins were those that exhib-
ited no visible casting defects. Casting
defects result from improper mold fill-
ing and leave behind swirl-like inden-
tations on the pin surface and some-
times visible voids. Casting defects
were minimized through extensive
mold cleaning between casts and by
ensuring that the molten button was
heated to the appropriate casting tem-
perature and dropped properly into
the pin mold. The judgment regarding
“acceptable” pins was based on visual
inspection only. Sectioning of multiple
pins that were considered “acceptable”
did not reveal any subsurface voids.
JULY 2016 / WELDING JOURNAL 233-s
Wheeling 7-2016_Layout 1 6/10/16 3:24 PM Page 234
WELDING RESEARCH
Characterization
The microstructure of each sample
set was characterized using both opti-
cal (Olympus GX51) and scanning
electron (Quanta 200 and Sirion) mi-
croscopy. Sections were taken both
transverse to the pin length (across
the pin diameter) and longitudinally
along the pin length. Serial sectioning
performed by successive grinding was
used to reveal the microstructure
gradient from the pin surface to the
pin center. This technique was particu-
larly useful for determining the extent
of crack backfilling in certain
compositions.
All samples were then polished and
electrolytically etched in a 10%
chromic acid solution for 5–10 s at 5 V
and 2 A with a tungsten anode and
stainless steel cathode. The area frac-
tion eutectic was determined via im-
age analysis using ImageJ software.
The procedure was developed from
work by Payton et. al. (Ref. 47) and
conformed to ASTM E1245-03.
SEM/EDS was used to determine the
composition of the matrix and eutectic
constituents.
An accelerating voltage of 25 kV,
spot size 6, and probe current 10 nA
were utilized at magnifications rang-
ing from 200 to 6000¥. EDS analysis
was performed at 800¥ on samples
that had all been etched in chromic
acid in order to reveal the eutectic con-
stituents and solidification structure
in the samples. Etching prior to EDS
analysis facilitated locating and ana-
lyzing the eutectic constituents.
Results
Solidification Modeling
Results from Scheil simulations for
all compositions are shown in Table 2.
Partition coefficients were calculated
by dividing the composition of the
first solid to form by the initial, nomi-
nal composition in terms of either Nb
or Mo. The available literature does
not report partition coefficients for
Alloy 690, but the calculated values
used seem to be consistent with other
studies of Nb- and Mo-bearing Ni-
based alloys (Refs. 8, 9, 48–51). A
small under/over estimation of the
partition coefficients may decrease the
accuracy of the fraction eutectic calcu-
234-s WELDING JOURNAL / JULY 2016, VOL. 95
lations, but the effect should be minor.
As both the Nb and Mo alloying addi-
tions increase, the partition coeffi-
cients increase slightly (less partition-
ing). The fraction eutectic was predict-
ed to increase with increasing alloy
content, particularly with respect to
Nb. Molybdenum additions produced
only a small change in the calculated
fraction eutectic, but did result in a
large change in the final calculated
composition of the eutectic phase
since Mo partitions to the liquid
during solidification.
The calculated fraction eutectic val- Fig. 11 — Cracking susceptibility versus
solidification temperature range based
ues are reported as mass fraction while
on Varestraint data from DuPont et al.
the measured fraction eutectic values (Ref. 54).
are volume fraction (based on area
fraction measurements). These mass
fraction values are reportedly compa-
rable to volume fraction values as the
densities of the phases involved are
similar (Ref. 9). Regardless, the calcu-
lated fractions correlate well with the
measured values. The calculated aver-
age weight fractions of niobium and
molybdenum were later compared to
Nb and Mo levels measured in back-
filled regions using EDS.
Cast Pin Tear Test
The critical cracking thresholds for Fig. 12 — Cracking susceptibility and
the niobium-bearing samples are predicted solidification temperature
shown in Fig. 2. The base composition, range for the Nb­bearing alloys at 0.95
Alloy 690 with no Nb, and the alloy fraction solidified.
with 8 wt-% Nb exhibited the lowest
susceptibility to solidification cracking,
as indicated by threshold (no cracking) lated mass fractions as a function of
pin lengths of 1.5 and 1.375 in., respec- Nb content is shown in Fig. 3. In order
tively. The alloy with 4 wt-% Nb addi- to be consistent with other data show-
tion showed the highest susceptibility ing the effect of composition on crack-
with a threshold pin length of 0.75 in. ing susceptibility in eutectic systems,
The scatter in the CPTT data tends to such as that shown in Fig. 1, suscepti-
increase with an increase in pin length bility is represented by the reciprocal
above the threshold and with increased of the critical cracking threshold (Refs.
Nb content. This scatter is likely due to 29, 30, 34, 36). The larger this value,
some variation in the amount of eutec- the more susceptible to cracking rela-
tic that is present and the ability of tive to the other plotted compositions.
cracks to heal by a backfilling mecha- This plot clearly illustrates that the
nism when greater stress (pin length) is highest susceptibility is exhibited by
imposed on the system. For that rea- the 4 wt-% Nb composition.
son, the threshold pin length at which When considering the fraction eu-
there is no cracking is used as the most tectic, it appears that the highest
reliable indicator of resistance to solidi- cracking susceptibility occurs at levels
fication cracking. just below 10%. Above 10%, cracking
Samples representing the critical susceptibility decreases due to an ap-
cracking thresholds determined in Fig. parent crack healing effect, as will be
2 were then prepared for image analy- shown by characterization results in
sis. Comparison of their measured vol- the next section. Additional data at 3
ume fraction eutectic as well as calcu- and 5 wt-% Nb are needed to more ful-
Wheeling 7-2016_Layout 1 6/9/16 5:16 PM Page 235
ly develop this curve and more accu-
rately identify the peak in cracking
susceptibility.
The effect of adding 2 and/or 4
wt-% molybdenum to alloys with 2, 4,
or 6 wt-% Nb at the same pin length is
shown in Fig. 4. The pin length, 1.375
in., selected for comparison of the Mo
effect was one in which all three niobi-
um compositions exhibited cracking
prior to molybdenum addition. At the
2 and 4 wt-% Nb levels, there appears
to be little effect from the Mo addi-
tion, and it may actually increase sus-
ceptibility in the 2% Nb alloy. A signif-
icant effect of the Mo addition can be
seen in the 6Nb samples. The 6Nb4Mo
composition results included pins that
did not crack compared to 6Nb0Mo
pins, which exhibited significant
cracking. Thus, there appears to be a
clear beneficial effect of Mo additions
at the higher Nb level. The large error
among circumferential cracking values
in pins of the same composition
makes it difficult to make definitive
comparisons where small trends may
appear, as for the 2Nb and 4Nb com-
positions. The data suggest that the
4Mo samples experienced less cracking
regardless of niobium composition,
but the error in the data will require
more testing before definitive conclu-
sions can be made.
Characterization
As shown in Fig. 5, there is a clear
increase in the fraction eutectic as the
Nb content is increased in the Alloy
690 base alloy. In the base alloy mi-
crostructure, virtually no eutectic
phase is detectable, and only a slight
increase is observed when 2 wt-% Nb
is added, as evidenced by the dark par-
ticles at the solidification subgrain
boundaries. At 4 wt-% Nb, consider-
able eutectic constituent is evident,
and at 8 wt-% Nb, the eutectic con-
stituent is almost continuous.
Evidence of crack backfilling was
detected in the 4, 6, and 8 wt-% niobi-
um pins as well as in the Nb + Mo al-
loys. Optical and SEM micrographs
that demonstrate the backfilling effect
are shown in Figs. 6–8. With the ex-
ception of the 2 wt-% Nb alloys, all mi-
crographs shown are from pin lengths
at the cracking threshold, where no
surface cracking was observed. In the
2 wt-% Nb alloy, evidence of very mi-
nor backfilling was only observed in
pins containing cracks and is at such a
low level that the contribution to crack
healing is minimal.
The backfilled cracks in the
8Nb0Mo pins appeared to contain
fewer voids (cracks) and are more con-
tinuous than in the 4Nb0Mo sample.
The backfilled cracks in the 8Nb0Mo
sample run almost continuously
through the sample, indicating an ex-
tensive crack healing effect in this al-
loy. In the 4Nb0Mo alloy, many open
cracks are evident, indicating that in-
sufficient liquid of eutectic composi-
tion is available to heal the cracks that
form.
Backfilled cracks were difficult to
find in the lower niobium, 2 wt-%
compositions, although some were ob-
served in the 2Nb4Mo alloy, as shown
in Fig. 7. While the beginnings of a
small network of backfilled cracks ap-
pear, many voids remain, and the pin
exhibited surface cracking. The addi-
tion of 4 wt-% Nb to this alloy increas-
es the fraction eutectic from 1.4 to 7.5
vol-% (Table 2), leading to an increase
in cracking susceptibility, as shown
previously in Fig. 4.
Crack healing via a backfilling
mechanism is clearly dependent on
the Nb content. While some crack
healing may occur in the lower 2Nb
and even 4Nb compositions, the level
of backfilling is not sufficient to have a
beneficial effect. In fact, the effect
may actually be detrimental in that
the solidification temperature range of
the 2Nb and 4Nb alloys has increased,
but the amount of eutectic formed is
not enough to adequately fill voids and
cracks to prevent cracking. Again, it is
important to point out that crack heal-
ing is a phenomenon that may not al-
ways increase resistance to solidifica-
tion cracking during welding. High lev-
els of restraint may overwhelm any
crack healing effects, even if the frac-
tion eutectic is high. This is shown in
Fig. 2, where at the longest pin lengths
significant cracking is observed in the
6Nb0Mo and 8Nb0Mo alloys.
The SEM micrographs in Fig. 8 bet-
ter illustrate the difference in crack
backfilling observed based on differ-
ences in Nb. In all cases, the backfilling
occurs along solidification grain
boundaries where preexisting cracks
were present. In the 4Nb0Mo sample,
the width of the backfilled liquid is rel-
WELDING RESEARCH
atively thin with several “breaks” along
the boundary. As Nb increases to 6
and 8 wt-%, the degree of backfilling
increases and the backfilled bound-
aries are much wider. While the back-
filling network in the 8Nb0Mo sample
is quite extensive, some small voids
are still present internally, even
though no cracking was observed on
the surface. Based on prior research,
cracks initiate at the surface and prop-
agate toward the center and pins that
are at or below the threshold do not
contain internal cracks (Refs. 52, 53).
Thus, for the 8Nb0Mo material, the
crack that formed at the surface was
nearly completely healed by
backfilling.
This backfilling results in the sub-
stantial drop in cracking susceptibility
in the 6 and 8 wt-% Nb alloys relative
to the 4 wt-% alloy, as shown in Fig. 2.
Based on the data in Table 2, maxi-
mum cracking at 4 wt-% Nb occurs
when there is ~7.5 vol-% eutectic pres-
ent. By increasing the fraction eutectic
above 15 vol-%, a significant reduction
in cracking occurs, as shown in Fig. 2.
SEM/EDS spot analyses were per-
formed to determine the composition
in the backfilled cracks for 4Nb0Mo,
6Nb0Mo, 8Nb0Mo, 2Nb2Mo,
2Nb4Mo, 6Nb2Mo, and 6Nb4Mo com-
positions. SEM micrographs and the
location of the spot analysis for the
8Nb0Mo and 6Nb4Mo alloys are
shown in Figs. 9 and 10, respectively.
The “nominal” composition refers to
the composition of the Alloy 690 base
alloy used in this study prior to niobi-
um and molybdenum additions, and
the “adjusted” composition is the cal-
culated composition of the new alloys
taking the additions of Nb and Mo
into account.
The partially backfilled crack (spots
1–3) is enriched in Nb to an average of
24.34 wt-% while the matrix (fcc gam-
ma phase) is depleted to an average of
3.56 wt-% Nb. These matrix values
represent locations away from the so-
lidification boundary where no eutec-
tic constituent is present. Thermo-
Calc™ predicted an average niobium
concentration of 23 wt-% for the eu-
tectic reaction that occurs in this alloy,
so the EDS data is in good agreement
with the computed value. It is impor-
tant to point out that the measured
values are average values.
The EDS spot collected data from
JULY 2016 / WELDING JOURNAL 235-s
Wheeling 7-2016_Layout 1 6/9/16 5:16 PM Page 236
WELDING RESEARCH
an ~1 μm diameter. It was determined
that the eutectic lamellae in the back-
filled regions is much less than 1 μm,
so EDS measurements taken in this re-
gion are likely to more closely repre-
sent the average Nb level. Near the
edges, an average representation is
less likely, as lamellae spacing appears
to increase. As such, differences from
predicted values were encountered in
some samples, especially those with a
thinner backfilled region to collect
data from. Depletion of the other ma-
jor elements, Ni, Cr, and Fe coincides
with the Nb enrichment. Similar
trends were seen with the other com-
positions tested.
As with the 8Nb0Mo sample, the
backfilled crack for the 6Nb4Mo pin
also exhibited a large Nb enrichment,
but to a lesser extent with spots 1, 2,
and 6 averaging at 21.2 wt-% Nb.
Molybdenum enrichment of an aver-
age of 7.11 wt-% was measured for the
same spots. ThermoCalc™ predicted a
niobium level around 20 wt-% and a
molybdenum level around 13 wt-% for
this alloy.
While the niobium prediction is
consistent with the measurement, the
molybdenum prediction is overesti-
mated. This may indicate several
things: 1) the calculated partition coef-
ficient is too low, 2) the Scheil simula-
tion predicted a phase with a higher
stoichiometric ratio of molybdenum
than actually occurs, and 3) the EDS
analysis may be inaccurate. Sulfur K-
alpha lines overlap molybdenum L
lines, but since sulfur levels in the Al-
loy 690 base composition were less
than 0.002 wt-%, such a sulfur K-alpha
contribution should be minimal. Coin-
ciding depletion of Ni, Cr, and Fe is
again observed in the backfilled region
of this alloy.
Discussion
The results presented here indicate
for Ni-based alloys that form eutectic
constituents at the end of solidification,
the backfilling effect makes predictions
of cracking susceptibility difficult to de-
termine simply as a function of the so-
lidification temperature range. Previous
data from DuPont et al. (Ref. 54) have
shown a correlation between the solidi-
fication temperature range (STR) and
cracking susceptibility in Ni-based al-
236-s WELDING JOURNAL / JULY 2016, VOL. 95
loys measured using the Varestraint
test, as shown in Fig. 11. While this
data may be relevant, it should be point-
ed out that at the strains used in gener-
ating this data, crack healing is probably
not possible.
When the cracking susceptibility
curve from Fig. 2 is plotted with the
corresponding predicted STR for each
composition, it is apparent that STR is
not the dominating factor affecting
susceptibility at high-alloy additions,
as shown in Fig. 12. Note that cracking
susceptibility and solidification tem-
perature range correlate well with
small additions of Nb, with increased
solidification temperature range re-
sulting in increased susceptibility.
However, as alloying addition increas-
es, a relatively small decrease in STR is
predicted compared to the dramatic
decrease in susceptibility and the cor-
relation is much weaker. This is be-
cause of the following: 1) the liquid
composition has reached the terminal
eutectic point, so further increase in
STR is not possible, and 2) the amount
of eutectic increases allowing for crack
healing to occur. As a result, higher
strains (longer pins) are required to
promote solidification cracking. It
should be noted that the STR values in
Fig. 12 are predicted, not measured.
Ongoing work will determine the
actual STR values using the single
sensor differential thermal analysis
(SS DTA) technique (Ref. 55).
The specific effect of Mo on crack-
ing susceptibility remains unclear. It
has little influence on either expand-
ing the solidification temperature
range or increasing the fraction eutec-
tic. It does segregate to the liquid and
is present in higher than nominal con-
centration in the eutectic liquid. As
shown in Fig. 4, it seems to have no in-
fluence in the 2 and 4 wt-% Nb alloys,
but its effect is dramatic in reducing
cracking susceptibility in the 6Nb4Mo
alloy. One possibility is that the pres-
ence of Mo somehow affects the wet-
ting characteristics of the eutectic liq-
uid and helps promote crack healing.
It should be noted that filler metal
625, which has good solidification
cracking resistance despite a wide solidi-
fication temperature range, contains on
the order of 4 wt-% Nb and 10 wt-%
Mo. Further work is underway to better
understand the effect of Mo in high-Cr,
Nb-bearing Ni-based alloys.
Conclusions
1) The fraction eutectic in Ni-30Cr
weld metals increases dramatically with
increasing niobium content based on
both the measured fraction eutectic and
values calculated with ThermoCalc™.
2) Additions of Nb up to 4 wt-% re-
sult in an increase in cracking suscep-
tibility associated with an increase in
solidification temperature range and
the presence of continuous liquid
films along the solidification grain
boundaries.
3) Niobium additions above 4 wt-%
result in a decrease in cracking suscep-
tibility due to an increase in the frac-
tion eutectic, which promotes crack
healing.
4) The peak in cracking susceptibili-
ty corresponds to a fraction eutectic of
~7.5 vol-%. At levels above ~15 vol-%,
crack healing by eutectic backfilling is
significant.
5) Additions of Mo to alloys con-
taining 6 wt-% Nb resulted in a de-
crease in cracking susceptibility. This
effect was not observed at lower Nb
levels.
6) There was a good correlation be-
tween cracking susceptibility and so-
lidification temperature range at lower
Nb levels. At higher Nb levels (> 4
wt-%), the correlation is not good be-
cause of crack healing effects.
7) The cast pin tear test appears to
be an effective method to evaluate the
influence of backfilling on cracking
susceptibility in materials where suffi-
cient liquid of eutectic composition
forms at the end of solidification.
Acknowledgments
The lead author (RW) would like to
thank the Graduate School at The
Ohio State University for providing a
fellowship during the first year of
graduate studies and to the Depart-
ment of Energy (DOE) Nuclear Engi-
neering University Program (NEUP)
for providing continuing support
through an NEUP Fellowship. Our
thanks to Paul Mason from Thermo-
Calc™ for his prompt and helpful re-
sponses regarding the computational
work performed in this study. Fellow
graduate students Adam Hope, David
Tung, and Daniel Tung are recognized
for their instruction and guidance
Wheeling 7-2016_Layout 1 6/9/16 5:16 PM Page 237
with experimental and computational
techniques. The authors also thank
Ken Copley and Ed Pfeiffer, support
staff in the Welding Engineering Pro-
gram at OSU, for their dedication and
commitment to the development of a
safe and sustainable research environ-
ment.
References
1. Inconel Alloy 690. Special Metal Corp.
Publication No. SMC-079. 2009.
2. Ramirez, A. J., Sowards, J. W., and Lip-
pold, J. C. 2006. Improving the ductility-dip
cracking resistance of Ni-base alloys. Journal
of Materials Processing Technology 179(1–3):
212–218.
3. McCracken, S. 2015. Dissimilar metal
weld issues and repair strategies in the nu-
clear industry. Presentation, Electric Power
Research Institute.
4. Kiser, S. D., Zhang, R., and Baker, B. A.
2008. A new welding material for improved
resistance to ductility dip cracking. Report.
Special Metals Welding Products Co. and
Huntington Alloys/Special Metals Corp.
5. Lippold, J. C., Kiser, S. D., and DuPont,
J. N. 2009. Welding Metallurgy and Weldabili-
ty of Nickel Base Alloys. Noboken, N.J.: John
Wiley & Sons, Inc.
6. Kazuyoshi, S., Bunda, K., Ogiwara, H.,
and Nishimoto, K. 2012. Hot cracking sus-
ceptibility of commercial Alloy 52 filler met-
als in multipass welding of Alloy 690. Trends
in Welding Research, Proceedings of the 9th
International Conference. EDS T. DebRoy, S.
A. David, J. DuPont, T. Koseki, H. K.
Bhadeshia, pp. 322–329. ASM International.
7. Böllinghaus, T., Herald H., Cross, C.,
and Lippold, J., eds. 2008. Hot Cracking Phe-
nomena in Welds II, pp. 166, 169, 208. Berlin:
Springer.
8. Borland, J. C. 1960. Generalized theo-
ry of super-solidus cracking in welds and
castings. British Welding Journal 7: 508–512.
9. DuPont, J. N. 1996. Solidification of
an Alloy 625 weld overlay. Metallurgical and
Materials Transactions 27A: 3612–3620.
10. Cieslak, M. J., Knorovsky, G. A.,
Headley, T. J., and Romig, A. D., Jr. 1989.
The solidification metallurgy of Alloy 718
and other Nb-containing superalloys. Super-
alloy 718 — Metallurgy and Applications. Ed.
E. A. Loria. Sandia National Laboratories.
Albuquerque, N. Mex.: The Minerals, Metals
& Materials Society.
11. DuPont, J. N., and Robino, C. V.
1999. The influence of Nb and C on the so-
lidification microstructures of Fe-Ni-Cr al-
loys. Scripta Materialia 41(4): 449–454.
12. Lee, H. T., Jeng, S. L., and Kuo T. Y.
2003. The microstruture and fracture behav-
ior of the dissimilar Alloy 690-SUS 304L
joint with various Nb addition. Metallurgical
and Materials Transactions 34A: 1097.
13. Nelson, D. E., Baeslack, W. A., III, and
Lippold, J. C. 1987. An investigation of weld
hot cracking in duplex stainless steels. Weld-
ing Journal 66(8): 241-s to 250-s.
14. Lundin, C. D., Chou, C. P. D., and Sul-
livan, C. J. 1980. Hot cracking resistance of
austenitic stainless steel weld metals. Weld-
ing Journal 59(8): 226-s to 232-s.
15. Huang, C., Cao, G., and Kou, S. 2004.
Liquation cracking in partial penetration
aluminum welds: Assessing tendencies to li-
quate, crack, and backfill. Science of Welding
and Joining 9(2): 149–157.
16. Idowu, O. A., Ojo, O. A., and
Chaturvedi, M. C. 2007. Effect of heat input
on heat-affected zone cracking in laser weld-
ed ATI Allvac 718Plus superalloy. Materials
Science and Engineering A 454-455: 389–397.
17. Cieslak, M. J., and Savage, W. F. 1980.
Weldability and solidification phenomena of
cast stainless steel. Welding Journal 59(5):
136-s to 146-s.
18. Savage, W. F., and Dickinson, D. W.
1972. Electron microanalysis of backfilled
hot cracks in Inconel 600. Welding Journal
51(11): 555-s to 562-s.
19. Cao, G., and Kou, S. 2005. Liquation
cracking in full penetration Al-Si welds.
Welding Journal 83(4): 63-s to 71-s.
20. Cieslak, M. J. 1991. The welding and
solidification metallurgy of Alloy 625. Weld-
ing Journal 70(2): 49-s to 56-s.
21. Zhang, R., Kiser, S. D., and Baker, B.
A. 2007. Nickel alloy weld overlays improves
the life of power generation boiler tubing.
Technical Report. Huntington, Special Met-
als Welding Products Co. and Special Metals
Corp.
22. Arata, Y., Matsuda, F., and Katayama,
S. 1977. Solidification cracking susceptibility
in weld metals of fully austenitic stainless
steels — Report 3, Effect of ferrite, P, S, C,
Si, and Mn on ductility properties of solidifi-
cation. Trans. JWRI 6(1): 105–116.
23. Brooks, J. A. 1990. Proceedings of
Weldability of Materials. Eds. R. A. Patterson
and K. W. Mahin, pp. 41–48. ASM
International.
24. Huang, C., and Kou, S. 2003. Liqua-
tion cracking in partial-penetration alu-
minum welds: Effect of penetration oscilla-
tion and backfilling. Welding Journal 82(7):
184-s to 194-s.
25. Tack, W. 1997. Aluminum-scandium
alloys. Patent US 5597529 A. Ashurst Tech-
nology Corp.
26. Kou, S. 2003. Solidification and liqua-
tion cracking issues in welding. JOM 55(6):
37–42.
27. Cross, C. E. 2005. On the Origin of
Weld Solidification Cracking. Hot Cracking Phe-
nomena in Welds. Eds. T. Böllinger and H.
Herald. Springer, pp. 3–18.
28. Lippold, J. C., Nippes, E. F., and Sav-
age, W. F. 1977. An investigation of hot
WELDING RESEARCH
cracking in 5083-O aluminum alloy weld-
ments. Welding Journal 56(6): 171-s to
178-s.
29. Lippold, J. C. 2015. Welding Metallur-
gy and Weldability, p. 107, Hoboken, N.J.,
John Wiley & Sons, Inc.
30. Anderson, T. 2009. Finding an ally al-
loy. Practical Welding Today 12(3).
31. Davis, J. R., ed. 1993. ASM Specialty
Handbook: Aluminum and Aluminum Alloys,
p. 379, ASM International.
32. Kah, P., Martikainen, J., Hiltunen, E.,
Brhane, F., and Karkhin, V. 2011. Hot Crack-
ing Susceptibility of Wrought 6005 and 6082
Aluminum Alloys. Hot Cracking Phenomena in
Welds III. pp. 59–69. Eds. J. Lippold, T.
Böllinghaus, and C. Cross. Berlin: Springer.
33. Bozorgi, S., Haberl, K., Kneissl, C., Pa-
bel, T., and Schumacher, P. 2011. Effect of al-
loying elements (magnesium and copper) on
hot cracking susceptibility of AlSi7MgCu-
alloys. Shape Casting: 4th International Sym-
posium. Eds. M. Tiryakioglu, J. Campbell,
and P. N. Crepeau, Ch. 14. Austrian Foundry
Research Institute.
34. Handbook of Aluminum: Physical Met-
allurgy and Processes. Eds. G. Totten and D. S.
MacKenzie. 2003. Marcel Dekker, Inc.
35. Abbaschian, L., and Sergio Fernandes
de Lima, M. 2003. Cracking susceptibility of
aluminum alloys during laser welding. Mate-
rials Research 6(2): 273–278.
36. Kou, S. 2003. Weld Metal Solidification
Cracking. Welding Metallurgy, p. 272, Hobo-
ken, N.J.: John Wiley & Sons.
37. Andersonn, J. O., Helander, T.,
Hoglund, L., Shi, P., and Sundman, B. 2002.
Thermo-Calc & DICTRA, computational tools
for materials science: Calphad comput. Cou-
pling Phase Diagr. Thermochem 26: 273–312.
38. Ramirez, J. E. 2012. Susceptibility of
IN740 to HAZ liquation cracking and ductili-
ty dip cracking. Welding Journal 91(4): 122-s
to 121-s.
39. DuPont, J. N., Robino, C. V., and
Marder, A. R. 1998. Modeling solute redis-
tribution and microstructural development
in fusion welds of Nb-bearing superalloys.
Acta. Mater. 46(13): 4781–4790.
40. Alexandrov, B. T., Hope, A. T., Sutton,
B. J., Sowards, J. W., Lippold, J. C., and Mc-
Cracken, S. S. 2011. Weldability studies of
high-Cr, Ni-base filler metals for power gen-
eration applications. Welding in the World
55(3/4): 65–76.
41. Rappaz, M., Drezet, J. M., and Gre-
maud M. 1999. A new hot-tearing criterion.
Met. and Mat. Trans. 30A: 449–455.
42. Coniglio, N., and Cross, C. E. 2009.
Mechanisms for solidification crack initia-
tion and growth in Al welding. Met. and Mat.
Trans. 40A: 2718–2728.
43. Private communication with Paul
Mason, ThermoCalc™.
44. Kreuter, V., and Verner, C. 2015. Op-
timization and application of the strain to
fracture test. M.S. thesis. The Ohio State
JULY 2016 / WELDING JOURNAL 237-s
Wheeling 7-2016_Layout 1 6/10/16 3:25 PM Page 238

WELDING RESEARCH

University, Columbus, Ohio.

45. Alexandrov, B. T., and Lippold, J. C.
2013. Use of the cast pin tear test to study
solidification cracking. Weld World 57:
CAN WE TALK?
635–648.
46. Alexandrov, B. T., Hope, A. T., Sutton, The Welding Journal staff encourages an exchange of ideas with you, our readers.
B. J., Sowards, J. W., Lippold, J. C., and Mc- If you’d like to ask a question, share an idea or voice an opinion, you can call, write,
Cracken, S. S. 2012. Susceptibility to solidifi- e-mail, or fax. Staff e-mail addresses are listed below, along with a guide to help you
cation cracking in high chromium nickel- interact with the right person.
base filler metals for nuclear power applica-
tions. Trends in Welding Research, Proceedings
of the 9th International Conference. Eds. S.
Babu, H. K. Bhadeshia, C. E. Cross, and S. A. Editorial Advertising
David. ASM International.
47. Payton, E. J., Phillips, P. J., and Mills, Publisher Manager of Sales Operations
M. J. 2010. Semi-automated characteriza- Andrew Cullison Lea Garrigan Paneca
tion of the  phase in Ni-based superalloys cullison@aws.org, lea@aws.org,
via high-resolution backscatter imaging. Ma- Extension 249, Article Submissions Extension 220,
terials Science and Engineering 527A: Production and Promotion
2684–2692.
48. Valdes, J., Kim, D., Shang, S., Liu, X., Editor
King, P., and Liu, Z. 2008. Investigation of Mary Ruth Johnsen Sr. Advertising Sales Executive
the partition coefficient in the Ni-Fe-Nb al- mjohnsen@aws.org, Sandra Jorgensen
loys: A thermodynamic and experimental Extension 238, sjorgensen@aws.org
approach. Proceedings, Superalloys. Eds. R. C. Feature Articles Extension 254, Advertising Sales
Reed, K. A. Green, P. Caron, T. P. Gabb, M. G.
Fahrmann, E. S. Huron, and S. A. Woodard,
pp. 333–337. TMS. Features Editor Sr. Advertising Sales Executive
49. Kang, S.-H. 2004. Solidification Kristin Campbell Annette Delagrange
process and behavior of alloying elements in kcampbell@aws.org, adelagrange@aws.org
Ni-based superalloy 718. Materials Transac- Extension 257, Extension 332, Advertising Sales
tions 45(8): 2728–2733. News of the Industry,
50. DuPont, J. N., Robino, C. V., Marder, Feature Articles
A. R., and Notis, M. R. 1998. Solidification Sr. Advertising Production Manager
of Nb-bearing superalloys: Part II pseudo- Assistant Editor Frank Wilson
ternary solidification surfaces. Metallurgical Melissa Gomez fwilson@aws.org,
and Materials Transactions 29A(11): mgomez@aws.org, Extension 465,
2797–2806. Extension 275, New Products, Advertising Production
51. Perricone, M. J., and DuPont, J. N. Society News
2006. Effect of composition on solidification
behavior of several Ni-Cr-Mo and Fe-Ni-Cr- Peer Review Coordinator
Mo alloys. Metallurgical and Materials Trans- Assistant Editor Sonia Aleman
actions 37A: 1267–1280. Annik Babinski saleman@aws.org,
52. Lenzo, J. 2016. Evaluation of the ef- ababinski@aws.org, Extension 329,
fect of tungsten and boron additions on the Extension 256, Peer Review of Research Papers
microstructure and solidification cracking Section News
susceptibility of Fe-21Mn-0.18C filler met-
als. M.S. thesis, in progress. The Ohio State
University, Columbus, Ohio. Design and Production
53. Przybylowicz, E. T. 2015. Weldability
evaluation of high-Cr Ni-base filler metals Production Manager
using the cast pin tear test. M.S. thesis. The Zaida Chavez
Ohio State University, Columbus, Ohio. zaida@aws.org,
54. DuPont, J. N., Michael, J. R., and Extension 265,
Newbury, B. D. 1999. Welding metallurgy of Design and Production
Alloy HR-160. Welding Journal 81: 408-s to
415-s.
55. Alexandrov, B. T., and Lippold, J. C. Senior Production Coordinator Welding Journal Dept.
2006. A new methodology for studying Brenda Flores 8669 NW 36th St., #130
phase transformations in high strength steel bflores@aws.org, Miami, FL 33166
weld metal. Trends in Welding Research VII, Extension 330, (800) 443-9353
Proc. of the 7th International Conference. Eds. Design and Production FAX: (305) 443-7404
S. A. David, T. DebRoy, and J. C. Lippold, pp.
975–980. ASM International.

238-s WELDING JOURNAL / JULY 2016, VOL. 95