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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.
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
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
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
2θ
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.
rms Strain
Crystallite size 0.30 1600
3.608
In presence of defects, dislocations, faults and pre-
rms strain, %
0.25 1400
3.606
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
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