CORRELATION OF THE THERMODYNAMIC PARAMETERS AND THE BASE METAL MICROSTRUCTURES TO THE WELDABILITY OF HR-160 EXPERIMENTAL SUPERALLOYS Maroef

I S and Edwards G R ABSTRACT HAYNES HR-160 (HAYNES and HR-160 are trademarks of Haynes International Inc.) is a Ni-CoCr, single-phase superalloy containing a small amount of Si and Ti. This alloy provides a good high temperature resistance in sulphidising environment, and has found large application as piping in incinerators. To extent the application of this alloy, a study was undertaken to explore the weldability of 4 experimental alloys, with a combination of two levels of Si and two levels of Fe. The focus on Si was to enhance the corrosion resistance in sulphidising environment, while the focus on Fe was to find its application as cladding material on steel substrate. The investigation attempted to correlate various aspects, including chemical composition, thermodynamics, microstructure, and weldability. These correlations were explored in the light of various experimental techniques, including the varestraint testing, differential thermal analysis, and metallography, as well as scanning electron microscopy with both electron microprobe analysis (EPMA) and X-ray energy dispersive analysis (EDS). This study showed that there was no single thermodynamic parameter that predominantly influence weldability. However, in concert, the partitioning coefficient, the bulk concentration, and the solidification temperature range appeared to correlate reasonably well with weldability, indicated as the brittle temperature range. Microstructure (grain size) of the weld metal also appeared to influence weldability. As expected, the weld metal microstructure appeared to be partially governed by thermodynamic parameters; hence its correlation with weldability might have been an indirect influence of thermodynamic parameters. On the other hand, the base metal grain size did not appear to strongly influence the solidification cracking, mainly as a consequence of grain coarsening in the heat affected zone. KEYWORDS Super Alloy, Weldability, Microstructures AUTHORS DETAILS Iman Maroef is a Metallurgical Consultant currently with Connell Wagner in Callaghan, NSW, Australia. Glen R. Edwards attends the Colorado School of Mines in the USA.

1.

INTRODUCTION

The purpose of this study was to investigate the effect of silicon and iron on the weldability of HAYNES HR-160 alloy. HR-160 alloy is a solid solution strengthened Ni-Co-Cr-Si alloy. The alloy is designed to resist corrosion in sulfidizing and other aggressive high temperature environments. Silicon is added (~2.75 wt.pct.) to promote the formation of a protective oxide scale in environments with low oxygen activity. HR-160 alloy has found applications in waste incinerators, calciners, pulp and paper recovery boilers, coal gasification systems, and fluidised bed combustion systems. HR-160 alloy has been successfully used in a wide range of welded applications. However, the alloy can be susceptible to solidification cracking under conditions of severe restraint. A previous study by DuPont, et al. [i] showed that silicon promoted solidification cracking in the commercial alloy. In earlier work conducted at Haynes, and also from published work by DuPont, et al., it was recognized that silicon segregates to the terminal liquid, creating low melting point liquid films on solidification grain boundaries. Solidification cracking has been encountered when using the alloy as a weld overlay on steel, and when joining HR-160 plate in a thickness greater than 19 millimeters with matching filler metal. The effect of silicon on the weldability of HR-160 alloy has been well documented, but the effect of iron is not well understood. Prior experience at Haynes has indicated that iron may be detrimental to the solidification cracking resistance of the alloy. Iron does not segregate to the terminal solidification product in nickel-base alloys, as does silicon [ii], but iron may have an indirect or interactive influence on weldability. A set of alloys covering a range of silicon and iron contents was prepared and characterized to better understand the welding metallurgy of HR-160 alloy. This paper intends to emphasis the correlation between weldability, thermodynamic parameters, and microstructures. Due to space limitation, the experimental procedures are not written in enough details, but can be found in earlier publication of this subject [iii]. 2. 2.1 MATERIALS AND EXPERIMENTAL PROCEDURES Materials

For this study, four HR-160 type experimental alloys with different target levels of silicon (2.3 and 3.9 %) and iron (0.10 and 4.0 %) were prepared. The experimental heats represent a [2 x 2] matrix of high and low silicon and iron. The heat 8727- 7- 7506 was included in this study to represent the standard commercial alloy. The chemical compositions of the experimental and commercial alloys are given in Table 1. The experimental alloys were vacuum melted, cast into electrodes, then electroslag remelted into 102-mm-diam. ingots. The ingots were forged to 44.5 mm, then further hot-rolled to 12.5-mm plate. The materials for varestraint testing were prepared by hot rolling at 1021 C to 3 mm plate. The alloys were annealed at 1021 C for 20 minutes and subsequently water quenched. 2.2 Weldability Tests

Longitudinal varestraint tests were undertaken during gas tungsten arc (GTA) welding 70 Amps DC current and 1.9 mm/s travel speed. Each experimental alloy was tested at four augmented strain levels (nominal values of 1.0 to 3.5) in triplicate. The maximum crack distance (MCD) was taken as an indicator of the cracking susceptibility. The maximum crack distance, MCD, is defined as the perpendicular distance from the fusion boundary to the far-end tip of the crack. A representative weld pool temperature cycle was measured from the commercial alloy by manually harpooning pure Pt/ Pt-13% Re type R thermocouple wires to the weld pool during GTA welding. The average cooling rate, over the temperature range of 1400 and 1000 C and at the trailing edge of the weld pool, was found to be 200 30 C/s.

Table 1. Chemical Compositions of the HR-160 Type Experimental and Commercial Alloys (wt. pct.) Haynes Intl. EN2799Heat # 9-0894 Nominal 2.3% Si Si & Fe Content 0.10% Fe CommerSource cial Element C 0.062 Cb <.01 Co 30.01 Cr 27.61 Fe 0.08 Mn 0.55 Ni 38.65 P 0.002 S <.001 Si 2.34 Ti 0.5 2.3 EN2999-0- 8727-70896 7506 2.3% Si 4.0% Fe Exp. 0.061 0.01 29.99 27.88 4.01 0.53 34.40 <.002 <.001 2.24 0.49 2.8% Si 0.10% Fe Exp. 0.05 <.050 30.1 27.80 <0.10 0.46 37.11 0.002 0.007 2.81 0.46 EN2899- EN3099-99-0895 0897 4.0% Si Exp. 0.062 0.01 29.99 27.60 0.09 0.54 36.72 0.005 <.001 4.09 0.5 4.0% Si Exp. 0.065 0.01 29.74 27.68 3.96 0.52 33.04 0.006 <.001 4.11 0.44 0.10% Fe 4.0% Fe

Microstructural Characterisation

Susceptibility to solidification cracking of a weld metal is frequently related to the quantity of the interdendritic eutectic product and the solidification structure itself. Both are governed by microsegregation, which itself depends on both the partitioning coefficient (k) of the particular elements, in addition to the solidification temperature range. Under an assumption of ideal condition satisfying the Scheil equation (no solid back-diffusion and fast diffusion in solid), the apparent partitioning coefficient (k = kCo/Co = Cs/Co) of an element of interest can be estimated from the ratio of the concentration at the dendrite core (Cs) to that of the bulk material surrounding the core (Co) [iv]. Chemical analysis of the alloys were carried out by energy dispersive spectroscopy (EDS) and by electron probe X-ray micro-analysis (EPMA-WDS). The area for both spot and bulk analyses was selected to be the weld metal adjacent to the HAZ of the sample, where primary dendrite morphology is relatively clear and where the cooling rate near solidification temperature was expected to be the highest. 2.4 Differential Thermal Analysis

To assess the solidification temperature range (STR), differential thermal analysis (DTA) was performed with a Netsch Thermal Analyzer STA 409, using alumina as a reference. As a parameter for solidification susceptibility, the solidification temperature range (STR) assessed from DTA was determined. Alumina crucibles and lids, designed for differential scanning calorimetry (DSC), were used to increase sensitivity of the analysis. During initial analyses (DTA1), a sample mass of 150 20 milligrams was found sufficient for easy detection of reaction peaks. On-heating rate was determined to be 0.083C/s (5 C/min.) to obtain near equilibrium solidus and liquidus temperatures. On the other hand, a rate of 0.33C/s (20C/min.) was selected for on-cooling analysis. In this way, reaction temperatures associated with non-equilibrium solidification can be measured. To detect the liquidus more accurately during cooling cycle, the analyses were repeated (DTA2) with an initial cooling rate of 0.05 C/s to 1250 C, followed by a final cooling rate of 0.33 C/s. The sample mass for DTA2 was determined to be 300 30 mg.

3. 3.1

RESULTS Weldability Data

A common way to analyse data obtained from a strain-based testing, such as the varestraint test, is to plot the augmented strain as a function of the cracking temperature range. This plot is usually termed the ductility curve. Such a plot for the data assessed in this study is shown in Figure 1. below. The temperature range for cracking is deduced from the MCD, taking the temperature of the fusion line as the on-cooling liquidus of the alloy, as assessed by the DTA2 analysis. When considering the epitaxial growth during weld metal solidification, estimating the fusion line temperature from the on-cooling liquidus determined by DTA2 analysis (slow cooling rate) would be quite realistic. The temperature at the crack tip was estimated from knowledge of the cooling rate, over the temperature range of 1400 to 1000 C, and at the trailing edge of the weld pool (an average of 200 30 C/s). Weldability of the alloy is then measured by two parameters: the brittle temperature range (BTR), and the threshold strain to initiate cracking. BTR is defined as the maximum range of cracking temperature covered by the ductility curve. An excellent weldability is then characterised by short BTR and high threshold strain to cracking. In this study, the threshold strain to initiate cracking (an alternate ductility indicator) could not be accurately quantified because strain blocks that could give lower levels of strains were not available. To highlight the trend in the threshold strain to cracking, the cracking temperature range at 1 % augmented strain (CTR1%) of the alloys will be used for comparison purposes. It was assumed that a large value of CTR1% would tend to yield a low value of threshold strain to cracking. As shown in Figure1, the two low-Si HR160 alloys clearly out-performed the other alloys, as signified by their short BTRs, as well as by their short CTR1%. If not for the tendency to yield a lower apparent threshold strain to cracking, the low-Si, high-Fe HR160 alloy would certainly be categorized to be as resistant to cracking as its low-Fe sister. Both the commercial and the high-Si low-Fe HR-160 alloys had similar values of BTR and CTR1%. Both alloys BTRs were also the widest among the alloys studied. In contrast to these two later alloys, the high-Si, high-Fe HR-160 alloy yielded a BTR about 30 C shorter, but cracked at a higher value of CTR1%. In other words, by extrapolation of the ductility curve, the high-Si, high-Fe HR-160 alloy tended to yield a lower apparent threshold strain than do the commercial and the high-Si, low Fe HR-160 alloys.
4,0 3,5
BTR 4Si-0.1Fe BTR 4Si-4Fe BTR HR160 BTR 2.3Si-4Fe

Augmented Strain (%)

3,0 2,5 2,0 1,5 1,0 0,5 0,0 1400

BTR 2.3Si-0.1Fe

HR-160 alloy 4.0 Si 4.0 Fe 2.3 Si 4.0Fe 4.0 Si 0.1Fe 2.3 Si 0.1Fe

1350

1300

1250

1200

1150

1100

1050

Temperature (C)

Figure1. Ductility Curve (response) for the Various HR-160 Alloys upon Rapid Straining during the Longitudinal Varestraint Testing

3.2

Microstructures

Figure 2 shows the volume fraction of interdendritic eutectic as a function of the silicon concentration, estimated from its areal fraction. The non-metallic phase that forms the eutectic has been identified by Dupont as the silicon- rich G phase [(Ni, Co)16(Ti, Cr)6(Si)7], which is known to form during solidification of the HR-160 alloy [i]. The amount of eutectic product appears to be directly proportional to the silicon content of the alloy. it was apparent that iron increased the amount of eutectic terminal liquid. The comparison of the eutectic amount and morphology of the weld metals studied can be seen from Figure 3. The two low-Si HR-160 alloys clearly produced the lowest amount of eutectic upon welding. Their eutectic phases were droplet-shaped and completely isolated. The low-Si, high-Fe alloy produced a notably higher amount of eutectic than did the low-Si, low-Fe alloy. In the commercial HR-160 alloy, the amount and the liquid film network of interdendritic eutectic product were less than in the two high-Si experimental alloys. Between the two high-Si alloys, the liquid film network of the eutectic product was roughly similar. A common feature of all micrographs is the observation that solidification cracks occurred at the dendrite grain boundaries, rather than between dendrites of the same crystal orientation.
12

Interdendritic Eutectic Volume Fraction (fe)

10 8 6 4 2 0 2 2,5 3 3,5 4 4,5

fe

Silicon Concentration (wt.pct)

Figure 2. The Quantity of Interdendritic Eutectic Product in the Weld Metal of HR-160 Type Alloys with different Silicon and Iron Concentrations

50m 20

(a)

(b)

(c )

(d)

(e)

Figure 3. Microstructures of Longitudinal Varestraint Test Specimens a) b) c) d) e) 2.0-wt.-pct.-Si, 0.1-wt.-pct.-Fe HR-160 experimental alloy 2.0-wt.-pct.-Si, 4.0-wt.-pct.-Fe HR-160 experimental alloy 2.8-wt.-pct.-Si, 0.1-wt.-pct.-Fe HR-160 commercial alloy 4.0-wt.-pct.-Si, 0.1-wt.-pct.-Fe HR-160 experimental alloy 4.0-wt.-pct.-Si, 4.0-wt.-pct.-Fe HR-160 experimental alloy 5

The fracture surfaces of the alloys, and their corresponding grain structures, are shown in Figure 4 to Figure 7. These fractographs represents the three dimensional structure of the secondary dendrite arms, which are not readily shown by standard metallography. These observations were documented from specimens, varestraint tested at 1.5 %. strain. The scanning electron fractographs were taken at the high-temperature end of the crack, looking down into the crack opening. The fractographs show that silicon increased the secondary dendrite arm thickness. More importantly, they revealed that iron enhanced the tortuosity of the secondary dendrite arms. The solidification grain structure was considered as an important cracking parameter, since solidification cracks occur at the dendrite grain boundaries. Excluding the observation from the commercial alloy, silicon appeared to increase the width of the dendrite grains, whilst iron slightly narrowed the grains. For a fixed silicon content, iron also appeared to significantly shorten the length of dendrite grains (oriented perpendicular to fusion line). It is worth mentioning that the commercial was not subjected to the same thermo-mechanical process as the experimental alloys. Therefore, the commercial alloy would have given a misleading comparison with the rest of the alloys, especially when considering solidification structure of weld metal is governed by epitaxial growth process.

Figure 4. SEM Fractograph and Optical Micrograph 2.0-wt.-pct.-Si, 0.1-wt.-pct.-Fe HR-160 Experimental Alloy

Figure 5. SEM Fractograph and Optical Micrograph 2.0-wt.-pct.-Si, 4.0-wt.-pct.-Fe HR-160 Experimental Alloy

Figure 6. SEM Fractograph and Optical Micrograph 4.0-wt.-pct.-Si, 0.1-wt.-pct.-Fe HR-160 Experimental Alloy 6

Figure 7. SEM Fractograph and Optical Micrograph 4.0-wt.-pct.-Si, 4.0-wt.-pct.-Fe HR-160 Experimental Alloy 3.3 Partitioning Coefficients of Alloying Elements

The apparent k values for selected elements are listed in Table 2. Partitioning coefficient of the two high-Si and commercial alloys obtained from EDS agreed quite well with the data obtained from EPMA Therefore, the EDS assessment for the two low-Si alloys was considered satisfactory for the correlation purpose of this study (No EPMA was conducted for the two low-Si alloys). The addition of iron to the high-Si HR-160 alloy appeared to decrease the partitioning coefficient of silicon, and implies a stronger segregation of silicon to the terminal liquid phase. As a supporting information, with even higher iron content (32 wt.%) [i,ii], the kSi was further decreased to 0.53. The main alloying elements (Ni,Co,Cr) did not have a strong segregation potential, whilst titanium and manganese segregated strongly to different phases. However, the low levels of Ti and Mn concentration could easily gave inaccurate values, and therefore was not considered in this study. It was however worth mentioning that iron resulted almost the same ratio of reduction in partitioning coefficient for Si, Ti, and Mn. Table 2. Apparent Values of Partitioning Coefficients, k, of Selected Elements in HR-160 Alloys. Cs is the concentration at the dendrite core (at zero fraction of solid) and Co is the bulk composition (all in wt.pct) HR160 alloys Silicon Concentration (wt.%) EDS Co 2Si-0.1Fe 2Si-4.0Fe 2.8Si-.1Fe 4Si-0.1Fe 4Si-4Fe 3.4 2.11 1.70 2.87 3.53 3.68 Cs 1.89 1.19 2.32 3.18 2.39 EPMA Co NA NA 2.81 3.56 3.73 Cs NA NA 2.11 2.74 2.52 Silicon Partitioning Coefficient EDS kSi 0.90 0.87 0.81 0.70 0.65 0.12 0.12 0.22 0.04 0.02 EPMA kSi NA NA 0.75 0.77 0.68 NA NA 0.003 0.004 0.003

Differential Thermal Analysis

As a typical DTA thermogram, Figure 8 exhibits the DTA1 results for the commercial HR-160 alloy, containing both the on-heating and on-cooling thermogram curves. During heating, the sample exhibits a solidus temperature of approximately 1300 C (determined as the onset of a detectable inflection in the endothermic part of the curve) and reaches the liquidus temperature at 1370 C (determined as the peak of the endothermic reaction). The near equilibrium melting range was 70 C, similar to the result reported earlier by DuPont [i]. Upon solidification in alumina crucible, the alloy exhibited a large exothermic peak at an under-cooled temperature of 1340 C, which corresponded to the formation of the primary dendrites. Such an undercooling also occurred at the analyses for the other HR-160 experimental alloys. Solidification was completed with a terminal liquid exothermic reaction at 1150 C. To better approximate weld metal solidification (epitaxial growth), the solidification temperature ranges 1 (STR1) for the alloys were taken as the difference 7

between the on-heating liquidus temperature and the on-cooling terminal liquid reaction temperature. As a complementary data, the solidification temperature ranges 2 (STR2) were also calculated, from the difference between the on-cooling liquidus and the terminal liquid temperatures, assessed during DTA2 analyses described in the experimental procedure. For the HR-160 commercial alloy, the STR1 and STR2 were 219 C and 212 C, respectively. Table 3 lists the reaction temperatures and the STR values of the alloys.
0.4 0.2 DSC (mW/mg) 0 -0.2 -0.4 -0.6 -0.8 -1 1000 1100 1200 1300 1400
exothermic C 1152 o C 2.8% Si, 0.10 % Fe endothermic
oC 1371 1371

On Heating

On Cooling

Temperature (C ( (oC) )

Figure 8. DTA Thermogram of the Commercial HR-160 Alloy During Melting at 0.083 C/s and Solidification at 0.33 C/s Table 3. Results of Differential Thermal Analysis and Apparent Solidification Temperature Ranges Alloy On Heatin g Liquid us (C) * 1378 5 1376 5 1371 5 1340 5 1341 5 On Coolin g Liquid us (C) ** 1350 5 1360 5 1364 5 1330 5 1330 5 Termin al Liquid (C) *** 1280 10 1272 10 1152 5 1125 5 1130 5 Solid.T emp. Range STR1 (C) Solid. Temp. Range STR2 (C) 70 10 88 10 212 5 205 5 200 5

2.3%Si, 0.1%Fe 2.3%Si, 4.0%Fe 2.8%Si, 0.1%Fe 4.0%Si, 0.1%Fe 4.0%Si, 4.0%Fe

98 10 96 10 219 5 215 5 211 5

ND = Not Detected STR1 = On Heating Liquidus TTerminal Liquid T.,values fr. DTA1, STR2 = On Cooling Liquidus Terminal Liquid T, values fr. DTA2. (*) : values were assessed from DTA1 with heating rate of 0.083 C/s to 1500 C and cooling rate of 0.33 C/s, (**): values were assessed from DTA2 with heating rate of 0.33 C/s to 1500 C and initial cooling rate of 0.05 C/s to 1250 C, followed by final cooling rate of 0.33 C/s for detection of terminal liquid temperature, (***): values for terminal liquid temperature was an average of values assessed with DTA1 and DTA2. 4. DISCUSSION Factors that influence solidification cracking susceptibility have been taken into account in different theoretical formulations, although no single one has satisfactorily described the complete picture of the mechanism involved. Two main schools of thought on this subject are: 1) those of the

structural considerations, such as the Clyne-Davis concept [v] and 2) those of the rheological considerations, such the Feurers competitive processes between liquid back-filling and shrinkage [vi]. The validity of each criterion appears to depend strongly on the type of process (welding or casting) and the mechanical testing applied (stress or strain based). However, it is generally accepted that a solidifying metal starts to be vulnerable to solidification cracking when coherency is reached [vii]. Coherency is defined as the condition when adjacent dendrites start to form solid/solid contacts. With respect to hot tearing criteria, the varestraint test may pose some limitation in contrasting the rheological process (liquid back-filling) among different alloys. As highlighted by Matsuda [viii], the major part of a solidification crack in the varestraint test propagates rapidly through a rigid structure, with only dispersed and droplet-like terminal liquid. Accordingly, the varestraint test emphasises the structural factors of solidification cracking as opposed to the rheological factors, particularly at high strain levels. The rheological process, such as back-filling by terminal liquid (vol. Fraction larger than 10 pct.), may take a notable role at augmented strains lower than 1 pct (not conducted in this study). BTR should then be correlated with thermodynamic parameters that govern the solidification structure. Among the many parameters, the predominant effect of k has been well recognised [ix].The correlation between the fractographs and kSi revealed that a decrease in kSi (from 0.78 to 0.68) led to an increase in tortuosity of the dendrites. It follows that an increase in tortuosity implied an increase in coherency of the structure, as the density of solid/solid bridging during solidification should also be increased. The BTR value of the high-Si,high-Fe Hr-160 alloy (smallest kSi), being considerably higher than that of the high-Si,low-Fe alloy, appeared to be due to a possible increase in load bearing capacity when coherency was increased. Figure 9 shows the relationship between BTR and two materials parameters; namely the silicon partitioning coefficient (kSi) and the solidification temperature range (STR). There appeared to be no satisfactory correlation between each of the parameters and BTR. This lack of correlation did not come as a surprise since the effect of the parameters to BTR was very likely to be coupled. Figure 0 examined the possible couplings between the thermodynamic parameters. The first coupling between kSi and STR (kSi STR) started show a better correlation with BTR. A further effort to improve the correlation was done by introducing the volume fraction of eutectic terminal liquid fe. The coupling was determined to be in the formulation of (kSi STR)/ fe because increasing fe was considered to reduce BTR, whilst both increase in kSi and in STR should increase BTR. Figure 10 clearly shows that the correlation was very poor, as expected as rheological factors are not considered to be significant in the value of BTR. The last attempt was to formulate the coupling as (1/(1 kSi ) STR Co. The three parameters have been used simultaneously in several equations to predict the cracking susceptibility. The correlation between this latter parameter and BTR appeared to be the best so far, although it by no means has a proven physical ground. As indicated earlier, coupling of these parameters was experimented to emphasis that no single parameter is predominant in governing solidification cracking.

Solidification Temp. Range STR (C)

200

0.8

150

0.7

0.6 0.5 0.4 0.3 0.2 0.1 0 260

100

Fe

STR k-EPMA k EDS

50

Fe

0 120

140

160

180

200

220

240

BTR (C)

Figure 9. Relationship between Brittle Temperature Range (BTR) and Thermodynamic Parameters ( ksi, and STR)
200 k.STR 160 k.STR/fe (1/(1-k)).STR.Co 120 2500 3000

k.STR and k.STR/fe

Partitioning Coefficient (k)

0.9

2.3Si-4.0Fe

2.3Si-0.1Fe

4.0Si-4.0Fe

2.8Si-0.1Fe 4.0Si-0.1Fe

4.0Si-4.0Fe

2.8Si-0.1Fe 4.0Si-0.1Fe

2000

1500

80

2.3Si-4.0Fe

40

2.3Si-0.1Fe

Fe

1000

Fe

500

0 120

140

160

180

200

220

240

0 260

BTR (C)
Figure 10. Relationship between Brittle Temperature Range (BTR) and Combined Thermodynamic Parameters (kSi STR), (kSi STR)/ fe , and (1/(1 kSi ) STR Co The reasonable correlation between the combined thermodynamic parameters and BTR should be treated with caution, especially when considering that solidification cracks occur along the dendrite grain boundaries rather than arbitrarily at any adjoining dendrites. Recently, several modelling studies have also consider grain boundaries in their prediction to cracking susceptibility. The fact that the base metal grain sizes of the various alloys were not the same, raised a suspicion whether or not the observed solidification cracking was influenced by the base metal grain size, especially when epitaxial growth governs the solidification process. Figure 11 shows the number of grain per unit length (as indicator of grain size) of the alloys as a function of BTR. The number of grains was counted as the intercept with a line longitudinally oriented with the weld metal. As shown for the base metal, there was no meaningful correlation could be identified between the number of grains and BTR. However, the correlation became

10

(1/(1-k)).Co.STR

improved at the fusion line (longitudinal) and further became reasonably significant in the weld metal, half way to the weld centre line. In all cases, the number of grains per unit length of a given alloy continuously decreased from the base metal to the weld metal. This finding confirmed that the solidification process was initially epitaxial, follow by competitive growth. As there was no universal pattern in the reduction of the number of grains, one could question whether or not the weld metal microstructure independent from the base metal grain size. It appeared that grain coarsening in the HAZ proceeded at different rates depending on the initial grain size, resulting a similar final size for various initial grain sizes. Since it is the coarse HAZ grain size that govern epitaxial growth frequency, there may a possibility that the solidification structure was indirectly influenced by thermodynamic parameters, possibly playing roles during the grain growth process. Comparison between thermodynamic parameters and microstructure (weld metal), in their correlation to BTR, was shown in Figure 12. The number of weld metal grains per unit length is now presented as a distance, which is proportional to the width of the dendrites. In addition, the maximum length of dendrite grains is shown in Figure 12, particularly for comparison to the crack distances. There appeared to be no apparent correlation between the longest dendrite and BTR. The maximum crack distances (MCD) of the low-Si alloys were in the order of 1.5 mm, whilst the rest of the alloys were in the order of 2 mm. The maximum lengths of dendrites in the two low-Si alloys were in the order of 0.6-0.8 mm, which was considerably smaller than the maximum crack distance (MCD) of around 1.5 mm. Clearly, the crack must had propagated along a few grains long. On the other hand, solidification cracks in the commercial and high-Si,low-Fe alloys appeared to coincide with the maximum length of dendrite grains (in the order of 2mm). The lack of trends in this correlation was emphasised by the high-Si, high-Fe alloy, with its considerably smaller maximum length of dendrites (0.7 mm) than the crack distance (2 mm). By contrast, the grain width appeared to have a better correlation to BTR. In general, there appeared to be a clear indication that smaller/shorter dendrites resulted in narrower BTR. Smaller dendrite grains were thought to suppress hot cracking by preventing easy path for crack propagation. It is worth noticing that reduction in kSi by the addition of iron has consistently decreased the dendrite grain size (width and length) which was then followed by the narrowing of BTR. kSi might contribute to resistance to solidification cracking by resulting smaller dendrite grains, in addition to the higher tortuosity of the dendrites secondary arms. Both thermodynamic parameters and weld metal grain size may be considered influential in governing solidification cracking. Qualitatively, the thermodynamic parameters exhibited slightly better correlation to BTR than did the weld metal grain size (width). The observation suggested that thermodynamic parameters and weld metal microstructure were not independent factors to the solidification cracking. Such a coupling did not come as a surprise, as both grain coarsening and solidification are usually governed by thermodynamic and kinetic parameters of the alloys. On the other hand, the study has not sufficiently isolated microstructure from thermodynamics to consider that thermodynamic parameters has a predominant influence on solidification cracking. Due to the grain coarsening process in the HAZ, base metal grain size appeared to have no control over the solidification cracking. A stronger influence by the base metal grain size to the solidification cracking might be demonstrated by other class of alloys where grain coarsening is inhibited by stable inter or intra grain particles or precipitates. By the same token, separation of the effect of microstructure from that of thermodynamic parameters might be facilitated by identical base metal grain size (ideally large grains).

11

30
f.ine. dendrites mid dendrites Base Metal

25

Number of grain/mm longitudinal line-intercept

Fe
20

15

Fe
10

2.3Si-4.0Fe

2.3Si-0.1Fe

0 120

140

160

180

4.0Si-4.0Fe

200

220

2.8Si-0.1Fe

4.0Si-0.1Fe
240

260

Brittle Temperature Range (C)

Figure 11. The Correlations between Brittle Temperature Range (BTR) and Microstructures (base metal and weld metal)
3000 250

2.3Si-4.0Fe

(1/(1-k) and max. length o dendrites (m)

Fe

2500

2.3Si-0.1Fe

200

2000

4.0Si-4.0Fe

1500

2.8Si-0.1Fe

4.0Si-0.1Fe

150

1000

Fe

100

(1/(1-k).Co.STR max. length of dendrites mid. WM dendites 50

500

0 120

140

160

180

200

220

240

0 260

BTR (C)
Figure 12. The Comparison between Microstructure and Thermodynamic Parameters in their Correlation to Brittle Temperature Range (BTR) 5. CONCLUSIONS

1. At the level of augmented strain used in this study (1 % and higher), the varestraint test mainly revealed the effect of composition to the structural factor of the solidification cracking susceptibility of the alloys. The rheological factor was not adequately evaluated due to limitation of the strain blocks. 2. Within the alloying levels tested, both silicon and iron additions were proved to increase the susceptibility of the alloy to solidification cracking, with silicon having the predominant influence.

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Mid. WM dendrite thickness (m)

3. At a fixed iron concentration, the addition of silicon increased the brittle temperature range of the HR-160 alloys. 4. At a fixed silicon concentration, the addition of iron decreased the brittle temperature range. However, such an apparently beneficial effect was compromised by a concurrent increase in the cracking temperature range at 1% augmented strain. It is anticipated that iron had the tendency to yield a reduction in the threshold strain to cracking. 5. The addition of iron decreased the partitioning coefficient of silicon, which then contributed to the reduction of brittle temperature range when the concentration of iron is increased. 6. A reduction in partitioning coefficient indirectly contributed to a reduction in brittle temperature range by reducing dendrite grain size, as well as increasing the tortuosity of the dendrite secondary arms. 7. Within the composition limit in this study, an increase in silicon concentration indirectly contributed to an increase in brittle temperature range by increasing the solidification temperature range of the alloys. 8. There was no single thermodynamic parameter that predominantly influence solidification cracking. However, in concert, the partitioning coefficient, the bulk concentration, and the solidification temperature range appeared to correlate reasonably well with the brittle temperature range. 9. Microstructure (grain size) of the weld metal also appeared to influence solidification cracking. As expected, the weld metal microstructure appeared to be partially governed by thermodynamic parameters; hence its correlation with the brittle temperature range might have been an indirect influence of thermodynamic parameters. 10. The base metal grain size did not appear to strongly influence the solidification cracking, mainly as a consequence of grain coarsening in the heat affected zone. 6. ACKNOWLEDGEMENT

This research was conducted at the Colorado School of Mines and Haynes International. The varestraint testing by Mr. Mark Rowe, formerly of Haynes International, was instrumental and greatly appreciated. The financial support of the Fossil Energy Materials Program, U.S. Department of Energy, under Contract Number 19X-SW314C, is gratefully acknowledged. The authors also gratefully acknowledge the support of Dr. Stan David, Materials Division, ORNL and the technical assistance of Ms. Brenda Mulac, formerly of CSM. Ing. J. Kiersch and Ing. C. Kwaakernaak, from the Surface and Interface Research group Delft University of Technology, the Netherlands, are also gratefully acknowledged for their help on the EPMA-WDS measurement. The support from the Netherlands Institute for Metal Researches (NIMR) that enabled the first author to complete part of the study was highly appreciated. 7. REFERENCES

i. DuPont JN, Micheal JR, and Newbury BD (1999) Welding Journal 81, 408 -415s. ii. Dupont JN (1997) J. Materials Science 32, 4101-4107. iii. I.S Maroef, M.D. Rowe, and G.R. Edwards, The Effect of Silicon and Iron on the Weldability of Ni-Co-Cr-Si HR-160 Superalloy, in Hot Cracking Phenomena in Welds (eds. T. Bollinghaus and H. Herold), Berlin, Germany, 2003, 119-140. iv. H.D. Brody and M.C. Flemmings (1966) Trans. AIME 236, 615-623. 13

v. Clyne TW, Davies GJ (1975) British Foundry 68, 238-244. vi. V. Feurer (1976) Giessereiforschung, 28, 75. vii. Borland JC (1960) British Welding Journal 7, 508-512. viii. Matsuda F, Nakagawa H, Sorada K (1982) Trans. JWRI, 11(2), 67-77. ix. Flemming MC (1974), Solidification Processing, McGraw Hill, New York.

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