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Scripta Materialia 51 (2004) 59–63

www.actamat-journals.com

Characterization of microstructures in Inconel 625 using


X-ray diffraction peak broadening and lattice
parameter measurements
Sanjay K. Rai, Anish Kumar, Vani Shankar, T. Jayakumar *,
K. Bhanu Sankara Rao, Baldev Raj
Metallurgy and Materials Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, India
Received 2 July 2003; received in revised form 10 March 2004; accepted 17 March 2004
Available online 17 April 2004

Abstract
This study demonstrates that, three parameters which are microstrain, lattice parameter and crystallite size, obtained from X-ray
diffraction line profile analysis, can be used in a complementary way to study the precipitation/dissolution of various intermetallics
and carbides in nickel base superalloy Inconel 625, without extracting the precipitates from the matrix.
 2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: XRD; Inconel 625; Precipitation; Intermetallics

1. Introduction phase has also been reported to form directly from the
supersaturated solid solution on ageing at higher tem-
Nickel base superalloy, Inconel 625 is widely used in peratures [3]. Precipitation of M23 C6 , M6 C and MC car-
aeronautical, aerospace, chemical, petrochemical and bides occurs in the temperature range of 1033–1253 K [5].
marine applications. The choice for this material is based Inconel 625 tubes are used extensively in ammonia
upon a good combination of yield strength, tensile cracker units of heavy water plants. During service, the
strength, creep strength, excellent fabricability, welda- alloy is exposed to temperature close to 873 K for pro-
bility and good resistance to high temperature corrosion longed period (60,000 h) leading to substantial de-
on prolonged exposure to aggressive environments. Al- crease in ductility and toughness of the alloy, resulting
though the alloy was initially designed to be used in solid in the failure. The degradation in the mechanical prop-
solution strengthened condition, it is observed that pre- erties has been attributed to the heavy precipitation of
cipitation of intermetallic phases and carbides occurs on intermetallic phases c00 and Ni2 (Cr, Mo) [3,4]. The grain
subjecting the alloy to ageing treatment in the range of boundaries have also been found to be decorated with
823–1023 K [1]. Precipitation hardening in this alloy at continuous network of carbides after the service expo-
elevated temperatures (823–923 K) is mainly derived sure [4,6]. The degraded mechanical properties of such a
from the precipitation of metastable phases c00 [Ni3 (Nb, component can be regained to a significant extent by
Al, Ti)] having ordered body-centered tetragonal DO22 giving the component a resolutionizing heat treatment.
structure and Ni2 (Cr, Mo) phase having orthorhombic A major part of the properties can even be regained by
Pt2 Mo type structure [2–4]. The metastable c00 phase is giving heat treatments in the intermediate temperature
transformed to orthorhombic d phase [Ni3 (Nb, Mo)] range. A few attempts have been made earlier in this
having DOa structure upon prolonged ageing [2,3]. The d direction [4,6]. Understanding the structural changes
during these thermal ageing conditions through sys-
*
Corresponding author. Tel.: +91-411-4280208; fax: +91-411-
tematic studies would provide an opportunity for opti-
4280356. mizing the treatments for proper restoration of service
E-mail address: tjk@igcar.ernet.in (T. Jayakumar). exposed material.
1359-6462/$ - see front matter  2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.scriptamat.2004.03.017
60 S.K. Rai et al. / Scripta Materialia 51 (2004) 59–63

A number of studies have been carried out on lattice bars were then thermally aged at temperatures 923 K for
misfit measurements between precipitates and matrix 1 h and 1123 K for 1, 10 and 500 h. The SE alloy was
in nickel base superalloys [7,8]. Various diffraction tech- also resolutionized at 1423 K for 0.5 h. The selection of
niques such as X-ray and neutron diffraction (XRD and post service heat treatments for this study was based on
ND), and convergent beam electron diffraction (CBED) the TEM study carried out on same specimens earlier by
have been used for lattice misfit measurements. Mea- the authors [3,10].
surements were performed on samples, where the pre-
cipitates were either embedded in the matrix or after 2.2. X-ray diffraction measurements and peak profile
extracting the precipitates by dissolving the matrix [9]. analysis
The fine size of the precipitates does not allow accurate
measurement by CBED. Further, the presence of more The XRD profiles of the samples were recorded using
than one type of precipitate having peaks overlapping MAC Science MXP18 X-ray diffractometer with CuKa
with that of the c matrix complicates the analysis of XRD radiation. The scan was performed in the angular range
patterns from precipitates in the embedded condition. of 20–100 with a step size of 0.02 and counting at each
In the earlier papers by the authors [3,10], micro- step for a duration of 4 s, with X-ray generator power
structure of service exposed (SE) and post service aged set at 4 kW (40 kV and 100 mA). The instrument was set
samples of Inconel 625 were studied using transmission up for Bragg–Brentano geometry with a line focus and a
electron microscopy (TEM). These post service ageing graphite monochromator in diffracted beam arm. Lat-
heat treatments altered the microstructure. TEM studies tice parameter measurements were carried out using the
carried out on the SE alloy showed extensive intra and lattice constant refinement software supplied along with
intergranular precipitation. Some precipitates were the system. All the specimens were polished and elec-
having snowflaky morphology and the others had lens trolytically etched before carrying out the XRD scan.
shape. Further analysis revealed the lens shaped precip- In order to characterize the microstructure in terms of
itates to be c00 (Ni3 (Nb, Al, Ti)) phase and the snowflake the defect parameters such as crystallite (domain) sizes
type precipitates to be Ni2 (Cr, Mo) phase. A continuous and microstrain, it has been experimentally verified that
film of carbides at the grain boundaries could also be crystallite size broadening can be approximated by
seen. Short duration ageing at 923 K for 1 h led to the Cauchy function while the strain broadening is better
dissolution of the Ni2 (Cr, Mo) phase. Ageing the SE described by Gaussian function [12]. In case of both the
alloy at 1123 K for 1 h led to the complete dissolution of components, the crystallite size and the strain, being
both c00 and Ni2 (Cr, Mo) precipitates. Ageing for longer present, it is required to use convolution of both Cauchy
duration at 1123 K led to the precipitation of the d phase and Gaussian functions, which is called Voigt function.
[Ni3 (Nb, Mo)], the volume fraction of which increased In a study, Enzo et al. [15] proposed a convolutive profile
with ageing time. The resolution annealing of the alloy at fitting methodology assuming pseudo-Voigt (pV ) func-
1423 K for 0.5 h dissolved the grain boundary carbides tion of the X-ray profile. In the present study, pV func-
also along with all the intermetallic precipitates, without tion has been used for the peak profiling. This method
affecting the grain size. is considered to be the best in the analysis of materials
TEM is a powerful tool to determine the type and having overlapping peaks. A computer program (sup-
orientation of the precipitates by direct observation. plied by STOE & Cie GmbH, Darmstadt) that employs
However, it is tedious and does not always reflect the pseudo-Voigt function pV ð2hÞ for fitting the diffrac-
information about the sample as a whole. Due to limi- tion peak profile and a fourth order polynomial for
tation of TEM to analyze defect microstructure such as background estimation, was used in this study. Size-
microstrain, crystallite size change and lattice parameter strain measurement was also carried out using size-strain
change, a more detailed microstructural characteriza- software of STOE. This module calculates crystallite size
tion has been attempted in the present study, using well and microstrain from peak widths. The algorithms pro-
established X-ray line profile analysis procedure [11–14]. vided, range from the simple and robust Scherrer and
Wilson formulae to Williamson–Hall (W–H) plots. In
the present study, the classical W–H plots have been used
2. Experimental for separation of size and strain effect using
b cosðhÞ ¼ k=D þ 4  e  sinðhÞ; ð1Þ
2.1. Sample preparation
where b is integral breadth of profile in radians, D is
The chemical composition (in wt%) of the alloy crystallite size, 2h diffraction angle, e is microstrain
investigated is as follows: Cr-21.7, Fe-3.9, Mo-8.8, Nb- component and k is wavelength of incident radiation. By
3.9, C-0.05, Mn-0.14, Si-0.15, Al-0.17, Ti-0.23, Co-0.08 plotting b cosðhÞ vs. 4  sinðhÞ, microstrain can be cal-
and Ni-balance. Bars of size 9 mm · 10 mm · 60 mm culated from the slope of the line and the crystallite size
were machined from the SE Inconel 625 tube and the can be calculated from the ordinate-intercept.
S.K. Rai et al. / Scripta Materialia 51 (2004) 59–63 61

The instrument resolution function was obtained 0.016


SE
using standard LaB6 powder. The pure intrinsic speci- 0.014 SE+923 K/1 h
SE+1123 K/1 h
men broadened profile function was obtained using 0.012 SE+1123 K/10 h
SE+1123 K/500 h
deconvolution and integral breadth b was calculated.

β cosθ
0.010
The W–H plots were generated for each specimen and 0.008
the effective crystallite size and rms mean strain were 0.006
calculated.
0.004

0.002

1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2

3. Results and discussion 4*sinθ

Fig. 2. Williamson Hall plot of service exposed (SE), SE + 923 K for 1


Fig. 1 shows the X-ray diffraction patterns of the h, 1123 K for 1, 10 and 500 h specimens.
service exposed (SE), SE + 923 K for 1 h, SE + 1123 K
for 1, 10 and 500 h treated specimens. Other than the
the specimens SE + 1123 K/1 h, 10 and 500 h do not
peaks from matrix, additional peaks of Nb6 C are also
seem to have any microstrain, as the plots are almost
observed in all the specimens. In the case of SE + 1123 K
parallel to the x-axis. In the service exposed specimen, as
for 500 h treatment, d peaks are also observed. No peaks
both types of coherent precipitates Ni2 (Cr, Mo) and c00
corresponding to Ni2 (Cr, Mo) or c00 (Ni3 (Nb, Al, Ti))
are present, they are straining the matrix by coherency
phase could be recorded in the case of SE specimen. The
strains. In the case of SE + 923 K/1 h specimen, Ni2 (Cr,
peaks of both Ni2 (Cr, Mo) or c00 (Ni3 (Nb, Al, Ti)) could
Mo) gets dissolved in the matrix but the c00 is still present
not be resolved even with the step size of 0.002 and for
and keeps the matrix strained, but to a lesser extent in
counting time of 12 s for each step. As discussed earlier
comparison to the SE condition. In the case of
and emphasized by Li et al. [16], it is very difficult to get
SE + 1123 K/1 h, both c00 and Ni2 (Cr, Mo) get dissolved
XRD peaks from precipitates without extracting them
in the matrix, thus leading to the matrix being free of
from the matrix. However, the presence of the precipi-
microstrain. Further ageing of the SE alloy to longer
tates can be assessed indirectly from the changes in the
durations at 1123 K leads to the precipitation and
XRD pattern of the c matrix. Hence, the peak profile
growth of incoherent d, which does not strain the matrix
analysis and lattice parameter variations evaluated from
and hence the corresponding plots in Fig. 2 show almost
the XRD profiles of the c matrix have been used for the
zero slope. Microstrain values (rms) calculated from the
characterization of precipitation/dissolution of Ni2 (Cr,
W–H plot for each specimen are given in Table 1. It can
Mo), c00 and d precipitates.
be inferred from the comparison of the rms strain values
Fig. 2 shows W–H plots obtained using integral
that Ni2 (Cr, Mo) precipitate strains the matrix more
breadth of XRD peaks, for specimens SE, SE + 923 K
than c00 . The strain values of SE + 1123 K for 1, 10 and
for 1 h, SE + 1123 K for 1, 10 and 500 h. The x-axis of
500 h are 0.03%, 0.02% and 0.013% which are close to
the plot is 4  sin h and the y-axis is b cos h, as per Eq.
zero. These values are comparable to the strain value of
(1). It can be clearly seen from Fig. 2 that, in the case of
0.01% obtained for standard Si powder that is free of
specimens SE and SE + 923 K/1 h, the corresponding
any microstrain. Resolution annealed specimen also
W–H plots show positive slope indicating that the ma-
showed rms strain value of 0.01% which is the same as
trix is experiencing microstrain. Whereas, the plots for
that obtained for Si powder indicating that the matrix is
not experiencing any microstrain.
12000
8000
Table 1 also shows the lattice parameter and crys-
4000 SE+1123 K/500 h
2000 tallite size for each specimen. Fig. 3 shows the changes in
30000
20000 INC 850/ 10 hour the lattice parameter, rms strain and crystallite size for
10000 SE+1123 K/10 h
5000 different specimens. It can be seen from this figure that
Counts

30000
20000 850_1h full the lattice parameter of the service exposed alloy is
10000
5000
SE+1123 K/1 h 3.5989 A.  With the dissolution of Ni2 (Cr, Mo), it in-
12000
ser expo 650-1h full
creases to 3.6015 A. This is attributed to the dissolution
8000
SE+923 K/1 h
4000
2000 of Cr and Mo back in to the matrix. The lattice
8000 parameter further increases to 3.6062 A  with the disso-
5000 service exposed full
(111) (200) SE (311)
3000 (220) lution of c00 in the case of specimen SE + 1123 K/1 h.
1000
(222)
0 This is attributed to the dissolution of Nb in to the
20 30 40 50 60 70 80 90 100
matrix. Increase in the lattice parameter is more when c00

dissolves in comparison to the dissolution of Ni2 (Cr,
Fig. 1. X-ray diffraction patterns of service exposed (SE), SE + 923 K Mo). This can be explained by the fact that, the disso-
for 1 h, 1123 K for 1, 10 and 500 h, in bottom to top sequence. lution of Nb in to the matrix affects the lattice parameter
62 S.K. Rai et al. / Scripta Materialia 51 (2004) 59–63

Table 1
Variation in lattice parameter, rms strain and crystalline size with the microstructural conditions in service exposed and post service heat treated
Inconel 625
Treatment Precipitate present 
Lattice parameter (A) rms Strain (%) 
Crystallite size (A)
(maximum scatter, (maximum scatter, (maximum scatter, ±60)
±0.00125) ±0.01)
Service exposed Ni2 (Cr, Mo), c00 (Ni3 (Nb, Al, Ti)) 3.5989 0.31 353
(SE) and grain boundary carbides
SE + 923 K/1 h c00 (Ni3 (Nb, Al, Ti)) and grain 3.6015 0.12 317
boundary carbides
SE + 1123 K/1 h Only grain boundary carbides 3.6062 0.03 630
SE + 1123 K/10 h d (Ni3 (Nb)) initiates and grain boundary 3.6066 0.02 413
carbides
SE + 1123 K/500 h d saturated and grain boundary 3.5945 0.013 339
carbides
Solution annealed Only primary carbides 3.6089 0.01 1687
*
Intergranular primary carbides were present in all the heat treatment conditions.

3.612 coherently scattering domain size and it is not the same


Lattice parameter, Angstrom

Lattice parameter 0.35 1800


3.610
as the grain size.
Crystallite size, Angstrom

rms Strain
Crystallite size 0.30 1600
3.608
In presence of defects, dislocations, faults and pre-
rms strain, %

0.25 1400
3.606

3.604 0.20 1200 cipitates etc., it is possible to observe crystallite sizes


3.602 0.15
1000 much smaller than the actual grain size. In this case, it
3.600 0.10
800 appears that after all the coherent precipitates got dis-
3.598
0.05
600 solved back in to the matrix, the coherently scattering
3.596 400 domain size increases considerably from 353 to 630 A. 
0.00
3.594
-0.05
200
In the case of SE + 1123 K/10 h specimen, when pre-
Service Exposed 1123K/1h
923K/1h
1123K/500h
1123K/10h Solution annealed
cipitation of d initiates, crystallites size again reduces to
413 A  and it reduces further to 339 A  with increase in
Fig. 3. Variation of lattice parameter, microstrain and crystallite size the amount of d in the case of SE + 1123 K/500 h sam-
with post service treatment. ple. Even though, the change in crystallites size from 413
to 339 A is small in comparison to scatter, the trend is
more than both Cr and Mo [17]. On further ageing of logically explainable as the amount of d increases with
the service exposed alloy at 1123 K for 10 h, there is no ageing at this temperature. In the solutionized sample,
appreciable change in the lattice parameter and also the 
crystallite size was observed to be the highest i.e. 1687 A,
microstrain is close to zero. This behavior is expected as as matrix does not contain any precipitates.
at this stage, initiation of d precipitation at grain As discussed earlier, normally to analyze precipita-
boundaries takes place, the amount of d precipitation is tion behavior of Ni base super alloys using XRD, one
not enough to influence the lattice parameter of the has to extract the precipitates out of matrix by dissolv-
matrix. In the case of SE + 1123 K for 500 h specimen, ing the matrix. However, the extraction of the precipi-
considerable amount of d precipitation takes place (a lot tates from the matrix is a tedious process and also the
of d precipitates are seen in optical micrograph of this XRD study on the extracted precipitates does not pro-
sample as reported in Ref. [10]). Hence, the lattice vide any information about the precipitate–matrix
parameter gets reduced to 3.5945 A,  which is even below interaction. Not much work has been done to analyze
the service exposed alloy. This is expected as a lot of Nb the influence of precipitation in embedded condition,
has come out of the matrix in the form of d (Ni3 Nb) on the XRD pattern of matrix. Liu et al. [17] have re-
which reduces the lattice parameter. The lattice param- lated the changes in lattice parameter of c matrix with
eter of the solutionized specimen is highest at 3.6089 A.  percentage of d precipitation. They have found a rela-
This is attributed to the dissolution of all the precipitates tionship between the percentage of d precipitates and the
including the grain boundary carbides in to the matrix change in the lattice parameter of the matrix due to its
except for a small amount of intragranular primary changed composition. Further, this study also indicated
carbides. that the influence of the lattice volume of the interme-
It is observed from Table 1, that the crystallite size of tallic precipitate on the lattice constant of the matrix is
the service exposed specimen and SE + 923 K/1 h spec- negligible as compared to the changed composition of
imens are of the same order, i.e. 353 and 317 A.  the matrix [17]. In the present study, it has been dem-
Whereas, in the case of SE + 1123 K/1 h specimen, it has onstrated that with the help of the three parameters
increased to 630 A.  Crystallite size is defined as the microstrain, lattice parameter and crystallite size, it is
S.K. Rai et al. / Scripta Materialia 51 (2004) 59–63 63

possible to characterize different stages of microstruc- Variation in the lattice parameter has matched well with
tural changes. A change in the lattice parameter of the the dissolution of the precipitates in the matrix and the
matrix indicates about the occurrence of the precipita- precipitation of d out of the matrix. It has been dem-
tion from the matrix. Presence or absence of microstrain onstrated that even though the XRD peaks from
indicates about the type of the precipitate, i.e. whether it coherent precipitates are not seen separately, their
is coherent or incoherent. When precipitates are coher- presence could be easily detected by analyzing the XRD
ent with the matrix, it is difficult to get XRD pattern patterns of the matrix. Based on this systematic study,
from the precipitates, but W–H plot of matrix XRD the microstructural details of Inconel 625 can be ob-
peak widths reveals the presence of the coherent pre- tained by XRD profile analysis.
cipitates, as coherent precipitates strain the matrix and
presence of microstrain makes the slope of the plot to
deviate from the near zero value. Also, in the situation Acknowledgements
where change in the lattice parameter is not high, the
change in the crystallite size indicates the early precipi- We wish to express our sincere thanks to Dr. S.L.
tation, as was observed in transition from SE + 1123 K Mannan, Associate Director, Materials Development
for 1–10 h. In the case of incoherent precipitates, we get Group and Mr. P. Kalyanasundaram, Head, Division
indication first by reduction in the effective crystallite for PIE and NDT Development for their cooperation.
size, then after sufficient amount of precipitation, The stimulating discussions held with Mr. V.S. Shastry,
change in the lattice parameter as well as the extra XRD Materials Science Division are gratefully acknowledged.
peaks relating to the phase are observed.

References
4. Conclusions
[1] Eiselstein HL, Tillack DJ. In: Loria EA, editor. Superalloy 718,
625 and various derivatives. Warrendale, PA: TMS; 1991. p. 1.
The present study has demonstrated that with the use [2] Brown EE, Muzyka DR. In: Sims CT, Hagel WC, editors. The
of the three parameters microstrain, lattice parameter superalloys II. New York: Wiley; 1987. p. 165.
and crystallite size in a complementary manner, it is [3] Shankar V, Rao KBS, Mannan SL. J Nucl Mater 2001;288
possible to detect the precipitation of any phase and (2–3):222.
[4] Sundararaman M, Kumar L, Prasad GE, Mukhopadhyay P,
identify the nature of precipitates (coherent/incoherent),
Banerjee S. Met Mater Trans A 1999;30:41.
without extracting the precipitates from the matrix. A [5] Muzyka DR. In: Sims CT, Hagel WC, editors. The superalloys.
change in the lattice parameter of the matrix indicates New York: Wiley; 1972. p. 113.
about the occurrence of the precipitation from the ma- [6] Thomas C, Tait P. Int J Press Vess Piping 1994;59:41.
trix. Presence or absence of microstrain indicates about [7] Ecob RC, Ricks RA, Porter AJ. Scripta Metall Mater
1982;16:1085.
the type of the precipitate, i.e. whether it is coherent or
[8] Kuhn HA, Biermann H, Ungar T, Mughrabi H. Acta Metall
incoherent. Further, the crystallite size is useful for the Mater 1991;39:2738.
detection of early precipitation of incoherent phase. [9] Decker RF, Mihalisin JR. Trans AIME 1969;62:481.
With the prior information of the precipitating phases in [10] Kumar A, Shankar V, Rao KBS, Jayakumar T, Raj B. Philos
such alloy systems, with the help of TEM, the precipi- Mag A 2002;82(13):2529.
[11] Rietveld HM. J Appl Crystallogr 1969:65.
tation/dissolution of individual precipitates can be
[12] Warren BE. X-ray diffraction. Reading, MA: Addison-Wesley;
studied using XRD profile analysis. 1969 [Chapter 13].
Microstructural characterization of service exposed [13] Williamson GK, Hall WH. Acta Metall 1953;1:22.
and post service aged specimens of Inconel 625 has been [14] Delhez R, de Keijse TH, Lanford JI, Louer D, Mittemeijer EJ,
carried out using profile analysis of the X-ray diffraction Sonneveld EJ. In: Young RA, editor. The Rietveld method. USA:
Oxford University Press; 1995. p. 132.
matrix peaks. It was found that the strain in the matrix
[15] Enzo S, Fagherazzi G, Benedetti A, Polizzi S. J Appl Cryst
due to Ni2 (Cr, Mo) precipitates is more than that of c00 . 1988;21:536.
After dissolution of both Ni2 (Cr, Mo) and c00 , the c [16] Li RB, Yao M, Liu WC, He XC. Scripta Mater 2002;46:635.
matrix does not show presence of any microstrain. [17] Liu WC, Xiao FR, Yao M. Scripta Mater 1997;37:59.

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