Acra mrrd.

Pergamon

0956-7151(95)00041-0

Vol. 43, No. 9, pp. 3403-3413, 1995 Elsevier Scrence Ltd Copyright C 1995 Acta Metallurgica Inc. Printed in Great Britain. All rights reserved 0956-7151195 $9.50 + 0.00

marer.

SPINODAL DECOMPOSITION IN Fe-Cr ALLOYS: EXPERIMENTAL STUDY AT THE ATOMIC LEVEL AND COMPARISON WITH COMPUTER MODELS-II. DEVELOPMENT OF DOMAIN SIZE AND COMPOSITION AMPLITUDE
M. K. MILLER*, M. G. HETHERINGTONT, A. CEREZO, G. D. W. SMITHS and C. M. ELLIOTT3 Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH, England, 2Metals and Ceramics Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831-6376, U.S.A. and School of Mathematical and Physical Sciences, University of Sussex, Falmer. Brighton BNI 9QH, England
(Received 30 Norember 1994)

J. M. HYDE,

thermally aged Fe-Cr alloys have been analysed in terms of scale and composition amplitude. The development of the microstructure scale was found to fit a power law with a time exponent considerably smaller than that predicted by the LSW theory but in agreement with Monte Carlo simulations of the
decomposition. Numerical solutions to the classical non-linear Cahn-HilliarddCook equation were found to tit the classical LSW theory. A model, based on the non-linear theory of spinodal decomposition by Langer et al. is used to quantify the composition amplitude at any stage of the phase separation. A detailed comparison between the atomic scale experimental results and computer simulations of spinodal decomposition is given,

Abstract-The a series of

three-dimensional

interconnected

microstructures

resulting

from

spinodal

decomposition

in

1. INTRODUCTION

In Part I of this series [l], the use of atom probe techniques for analysing the three-dimensional (3D) atomic structure of alloys was discussed. The resulting spinodal decomposition in a series of thermally aged Fe-Cr alloys was compared qualitatively with two computer simulations of the decomposition process: a Monte Carlo model and a numerical solution to the non-linear Cahn-Hilliard-Cook equation. In this paper, the kinetics of phase separation in the binary Fe-Cr system are determined and quantitatively compared with the two computer simulations. Two quantitative parameters are studied: geometrical domain size and composition amplitude.
2. DEVELOPMENT OF SCALE

fractions of particles. the larger particles will grow at the expense of the smaller ones, a process known as Ostwald ripening. Independently, Lifshitz and Slyozov [2] and Wagner [3] developed a theory for the time dependent coarsening of particles, known as the LSW theory. It was assumed that the particles were spherical and widely separated so that interactions between them could be ignored, and that the supersaturation was small (fields quasi-static). As decomposition proceeds, the rate of growth of the particles slows, since the distance or diffusion path between the remaining particles gradually increases. The LSW law predicts the power law growth of the mean precipitate size R(t)

2.1. Theory
At the late stages of spinodal decomposition, the domains reach their equilibrium compositions. The driving force for further decomposition is the reduction of interface area between the domains, since these are associated with excess surface energy. As the domains coarsen, both the area and curvature of the interfaces are reduced. For materials with low volume
+Deceased. j:To whom

all correspondence

should

be addressed.

More recently, Huse [4] generalized the LSW theory to apply to arbitrary volume fractions of the two phases in the late stage limit. In the LSW formulation, the only method of interface motion or growth is by long range diffusion. Clearly. in systems with interconnected microstructures, long range diffusion is coupled with diffusion along the interface. To date, neither a growth law nor scaling formula has been derived directly for the case when both of these mechanisms occur simultaneously. The free energy will be minimized if the diffusing atoms adhere to the interface at points of

3403

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J . M . HYDE

et al.:

SPINODAL DECOMPOSITION IN Fe-Cr A L L O Y ~ - I I

minimal curvature. Atoms adhering at points of higher curvature will either diffuse along the interface or leave the interface and diffuse to another domain. Although this diffusion along the interface does not contribute to domain growth, it can limit the effectiveness of long range diffusion particularly during the early stages of decomposition when high curvatures exist. At the later stages of decomposition, there is less need for further transport of the atoms along the interfaces because the interfaces are smoother. Generally, the thermodynamic driving force for diffusion along the interface will be much greater than the driving force for bulk diffusion. However, when high curvatures exist, local rearrangements are important. This results in a slower coarsening during the early stages of decomposition. Therefore, the growth exponent is expected to increase Io the limiting value of 1,'3. However, the behaviour during early stages of phase separation, before the limit is reached, has not been extensively studied.

2.2. Determination of microstructural scale from atom probe data

For isolated particles, the scale of the microstructure may be defined in terms of the mean particle size and the mean particle separation. The equivalent measures for interconnected morphologies are the mean domain width and the mean distance between domains. In Part I of this series [1], it was shown that a simple composition profile could be used to estimate the microstructural scale. An autocorrelation analysis [5, 6] is useful for quantifying regular modulations in composition and deriving averaged spatial information from the composition fluctuations present in a sample. The one-dimensional (1D) autocorrelation function Rk, at lag k, may be defined as

distribution in an alloy would be large and positive for k = 2 and large and negative for k = 2/2 (where 2 is the wavelength of the modulations). The correlation coefficient for k = 0 is always equal to 1 since the correlation of a value with itself is perfect. The development of the autocorrelation function from 1D atom probe analyses of a series of thermally" aged F e ~ 5 % Cr alloys is shown in Fig. 1. The compositions were calculated using a block size of 33 ions. From the positions of the first minima, k0, and the first maxima, k., and their variation with aging time, it is possible to estimate the wavelength of the composition fluctuations and the rate of decomposition with aging time. The position at which the autocorrelation function crosses zero may also be used to estimate the thickness of the ~' phase. The increase in magnitude of these parameters with aging time indicates the increasing microstructural scale during phase separation. Although the autocorrelation functions are noisy, it is easier to determine the scale of decomposition, from either the position of the first minimum or the first maximum, than from a direct analysis of composition profiles as shown in Part I of this series [1]. The 1D autocorrelation function may be extended to use 3D data by using a radial function
R,~ ~

l rma" -- k 0"~ E (fir) -- Co)(C(r-Fk)r--O

Co)

R, = ~ ,~, ( c , - Co)(C,,+~,- Co)

where C, is the composition of sample i, N the total number of samples, Co the mean composition and cr2 the variance of the compositions C~ given by ~r2=

L(C-Co)2.
1

where C is the composition of a spherical shell at radius r from the chosen centre point, rm,x is the maximal radius at which there is compositional information and er2is the variance of the compositions. Note that the mean Co is the mean of the compositions C,,~which may be slightly different from the mean alloy composition. Since the volume enclosed by a spherical shell of uniform thickness varies as r 2, the number of atoms contributing to each sample volume is not constant. However, the significance of the autocorrelation function is determined only by the number of sample volumes. The shells are therefore made as thin as possible to maximize the number of samples. For the
ECAP 24 h h 500

For each pair of samples situated at a lag k apart, the composition differences between the sample composition and mean value are multiplied together. The sum of these pairs is divided by the variance of the composition values to yield the correlation coefficient R~. Comparison of two low concentration samples or two high concentration samples yields a positive contribution to the correlation coefficient, whereas comparison between a low concentration sample and a high concentration sample yields a negative contribution to the correlation coefficient. If the individual contributions are randomly positive and negative, their sum will be zero. Thus, the correlation coefficient calculated from a sinusoidal composition

1 0.8
0.6-

0.2
0 '

-0.2-0.4 [
0
I I i I I

20

40

60

80

100

Lag, k Fig. 1. Development of autocorrelation function from 1D atom probe analyses of a series of Fe~J,5% Cr alloys thermally aged at 500C.

J. M. HYDE et al.:

SPINODAL DECOMPOSITION IN Fe-Cr ALLOYS

2.3. A t o m probe results

II

3405

a)

0.8~ Rk
0"61111 4 h 0"4~II\\/ 24 h 1/~ 100

1]

PoSAP Analysis F e - 4 5 % Cr

500 h

nm

10

b)
10-

Gradient= 0.28+0.05 First Maximum

J J ....
~/

Gradient= 0.22-+0.05
First Minimum

Y, 1

,i

10

1 O0

1000

Aging (h)

Fig. 2. (a) Development of the 3D autocorrelation function calculated from PoSAP analyses of a series of thermally aged Fe~45% Cr alloys. In (b) the corresponding measurement of scale with time is shown. Multiple points represent results from different experiments.

analysis of the experimental data, a shell thickness of 0.2 nm was chosen, and for the computer simulations, a comparable shell thickness of 0.5 lattice units was used. Samples with large radii have compositions averaged over a wide area, resulting in values roughly equal to the mean composition of the alloy. Thus, R~ tends to zero at large k, and no significance should be placed on the autocorrelation function beyond the first maximum. In order to remove the bias associated with the selection of a central point, many radial autocorrelations may be calculated centred on random positions in the analysed volume and the results averaged. Sampling the data many times is computationally intensive, since for each atom a distance must be calculated from each central point. In the results that follow 200 random central points were chosen and the averaged autocorrelation function was calculated.

After 4 h aging at 773 K, the autocorrelation function does not show any significant phase separation in the F e ~ , 5 % Cr alloy, whereas after 24 h a scale can be measured [Fig. 2(a)]. A measurement of the first maximum, after 24 h aging, gives the wavelength of the composition fluctuations as approx. 2 nm. After aging for 500 h, the wavelength of the composition fluctuations increases to approx. 5 nm. As the aging proceeds the first minimum becomes more pronounced [Fig. 2(a)]. For each series of thermally aged alloys, the scale as a function of time [Fig. 2(b)] was fitted to a power law, R ( t ) v c t , and the time exponent n was measured. A summary of the time exponents for the development of scale derived from the autocorrelation analyses is shown in Table 1. The results refer to the scale measured using the first minimum and first maximum of the autocorrelation function. Due to the low volume fraction of the Cr-enriched ~' phase, insufficient data was obtained from the analysis of the F ~ 1 7 % Cr and F e - 1 9 % Cr for an accurate autocorrelation analysis. Results from all of the other series of thermally aged alloys suggest that the scale of decomposition fits a power law relationship with a time exponent independent of alloy composition. The autocorrelation functions from the energy compensated atom probe show a time exponent of 0.21 and the data from the PoSAP exhibits a time exponent of ~0.25. The results are considerably higher than the exponent determined by Brenner et al. [7] (n ~ 0 . 1 1 ) from composition profiles and F I M micrographs of F e - 3 2 % Cr alloys aged at a lower temperature of 743 K. The results are, however, in general agreement with some recent small angle neutron scattering (SANS) measurements [8, 9, 10]. Bley [8] studied Fe Cr alloys containing 20, 35 and 50 at.% Cr thermally aged at 773 K. In each series of alloys, the characteristic length scales were found to scale with a time exponent of 0.2 for aging longer than 30 h. Harwick [10] found a time exponent of ~0.25 for alloys with Cr contents between 20 and 40% thermally aged at temperatures between 788 and 818 K. LaSalle and Schwartz also used S A N S to study phase separation in F e - 3 2 % Cr alloys aged up to 2 0 0 h at 773 K [9]. They found that the time exponent showed a strong dependence on solutionizing treatment. A time exponent of 0.2 was found for alloys solution treated at 1273 K, whereas a time exponent of 0.12 was found for alloys heat treated at 1123 K.

Table I. Time scaling exponents from the autocorrelation analyses of atom probe analyses of Fe Cr alloys Time scaling exponents from autocorrelation analysis Alloys aged at 773 K Analysis Time region (h) First minimum First maximum Fe-24%Cr PoSAP 24-500 0.25 +_0.06 0.30 _+0.04 Fe 32%Cr PoSAP 8-500 0.27 + 0.02 0.29 + 0.04 Fe~,5%Cr PoSAP 4-500 0.22 +_0.05 0.28 + 0.05 Fe~15%Cr ECAP 4-500 0.28 +_0.03 0.21 + 0.02

3406

J . M . HYDE et al.:

SPINODAL DECOMPOSITION IN Fe-Cr ALLOYS--II The a u t o c o r r e l o g r a m s from M o n t e Carlo simulations for a n A - 5 0 % B alloy o n a b.c.c, lattice with second nearest n e i g h b o u r interactions are s h o w n in Fig. 3(a). As aging proceeds, the first m i n i m u m becomes m o r e p r o n o u n c e d a n d its value is observed to increase. After approx. 10,000 MCS, the scale o f the structure produced by the M o n t e Carlo simulation is similar to that observed experimentally after 500 h aging at approximately the same temperature. The first m i n i m a a n d m a x i m a from the autocorrelation functions f r o m the M o n t e Carlo d a t a presented all fitted a power law with a time e x p o n e n t o f ~ 0 . 2 1 [Fig. 3(b) a n d Table 2]. There was no evidence o f logarithmic behaviour. The results are i n d e p e n d e n t o f lattice type, lattice size a n d aging temperature. N o t e t h a t because the M o n t e Carlo a l g o r i t h m is a stochastic process, two simulations performed u n d e r the same conditions m a y yield slightly different results. In each simulation, the time e x p o n e n t m e a s u r e d using the first m i n i m u m o f the a u t o c o r r e l a t i o n function was within error b o u n d s of the experimental results, a n d the time e x p o n e n t m e a s u r e d using the first m a x i m u m was found to be only slightly lower t h a n the experimental results. It has been suggested t h a t the different solutionizing treatments could affect the long term dynamics o f phase separation a n d could explain the dependence o n solution t r e a t m e n t t e m p e r a t u r e reported by LaSalle a n d Schwartz [9]. A c o m p u t e r experiment was performed using the M o n t e Carlo a l g o r i t h m to assess the effect of a solution t r e a t m e n t just a b o v e the miscibility gap. A simulation was performed o n a simple cubic lattice aged at the equivalent t e m p e r a t u r e o f 1000 K for 20,000 M C S a n d then q u e n c h e d to 750 K a n d aged for a further 10,000 MCS. After the q u e n c h into the spinodal region, the time e x p o n e n t for the d e v e l o p m e n t of scale was m e a s u r e d a n d f o u n d to be 0.21 4-0.01. This value agrees with the time exponents m e a s u r e d from simulations q u e n c h e d f r o m a n infinite temperature. T w o further simulations were performed, simulating a controlled cooling from 1000 to 750 K during (a) 100 M C S a n d (b) 1000 MCS. Since d e c o m p o s i t i o n occurred during the quench, the time exponents for s u b s e q u e n t d e c o m p o s i t i o n at 750 K might be expected to be lower. N o t e t h a t time was reset to 0 following the quench. The results (Table 2) show t h a t generally the time exponents are lower, b u t they

a)

1 1 MCS
/

Monte Carlo Simulation (750 K)

O.6-

Rk 0.40.20-0.2 2

100 MCS / 10000 MCS

4 am

10

b)
3O

650K |
[] 750KI
/', 8 5 0 K

First Maximum , ~
~

.=_=
~1o-

3 =~

/ ~ s t
~

Minimum

IO

1oo MCS

IOOO

I#

Fig. 3. (a) Autocorrelation analysis of a Monte Carlo simulations for an A 50% B alloy on a b.c.c, lattice with second nearest neighbour interactions. In (b) the corresponding measurements of scale with time are shown.

2.4. M o n t e Carlo simulations

The time dependence of d o m a i n growth from M o n t e Carlo simulations has been extensively studied. A logarithmic g r o w t h law has been f o u n d at the late stages of aging by M a z e n k o et al. [11, 12] studying spinodal decomposition of the 2D Ising model at 50% concentration. However, most researchers have reported power law behaviour. Both A m a r [13] a n d G r a n t et al. [14] found agreement with L S W theory. O t h e r M o n t e Carlo simulations have s h o w n time exponents of 0.17-0.25 [15-17]. Huse [4] presented M o n t e Carlo results from 2D simulations which yielded a time e x p o n e n t of 0.29. N o n e of the previous simulations have been directly c o m p a r e d with experimental results from spinodal d e c o m p o s i t i o n in the F e - C r system.

Table 2. Time scaling exponents from the autocorrelation analyses of Monte Carlo simulations Lattice Simple cubic Simple cubic Simple cubic Simple cubic Body centred Simple cubic Simple cubic Simple cubic Solution treatment Drop quench from T = :c Drop quench from T = ~ Drop quench from T - ~ Drop quench from T = ~ Drop quench from T = oo 20,000MCS ( 1000 K) Gradual quench from 1000 K over 100 MCS Gradual quench from 1000 K over 1000 MCS Ageing T (K) 650 650 750 850 750 750 750 750 Timeregion (MCS) 10-10,000 10-10,000 10-10,000 10-10,000 10-10,000 10-10,000 10-10,000 I0-10,000 Time scaling exponent from 3D autocorrelation First minimum First maximum 0.21 + 0.02 0.22 __ 0.01 0.20 4- 0.02 0.23 + 0.03 0.20 + 0.01 0.21 + 0.01 0.24 + 0.03 0.17 4- 0.03 0.20 + 0.02 0.21 4- 0.01 0.18 __0.01 0.22 4- 0.01 0.22 + 0.03 0.20 4. 0.02 0.18 4. 0.03 0.18 + 0.03

J. M . H Y D E

et al.:

SPINODAL

DECOMPOSITION

IN Fe Cr ALLOYS--II

3407

a)
1 0.8- \ 0.6- l / 0.4 1' 0.20 -0.2 -0.4 .

Numerical Discretisation of Cahn-Hilliard-Cook Equation lO Time Units / 100 Time Units 1000 Time Units

Rk

nm

lO

b)
30

10

.3

~
! ~- ........ i -, ...... T ........ i

First
Maximum

First Minimum

3~
....... i

10 100 1000 Aging (time units)

104

Fig. 4. (a) Autocorre|ation analysis of the numerical solution to the Cah~Hilliard-Cook equation of an A 50% B alloy. In (b) the corresponding measurements of scale with time are shown.

do not predict the very slow dynamics observed by Brenner et al. [7]. Varying the solutionization treatment did not affect the long term dynamics.
2.5. Numerical discretization of the Cahn-Hilliard Cook equation

The 3D autocorrelograms for the numerical solution to the Cahn Hilliard-Cook equation are shown in Fig. 4(a). In the early stages of aging (10-100 time units) a dominant wavelength forms and the composition amplitude increases, shown by the increasing amplitude of the first minimum. in agreement with the linear theory of spinodal decomposition [18]. Beyond approx. 100 time units, coarsening begins. The simulations were stopped after 3000 time units since further coarsening might have become limited by the volume of the simulation. As the interaction range was increased, both the magnitude of the early stage dominant wavelength and the time before the onset of coarsening increased. The size of

the Cook term had no effect on the magnitude of the early stage dominant wavelength. During the coarsening stage (between 200 and 3000 time units) the scale of the microstructures produced by the numerical solution to the Cahn-Hilliard equation followed a power law with a time exponent close to the value 1/3 [Fig. 4(b) and Table 3] predicted by the classical LSW theory [2, 3] in marked disagreement with both experiment and the Monte Carlo simulations. Neither the Cook term nor the precise value of the interaction range significantly affected the value of the time exponent. Several researchers have assessed numerical models based on the Cahn-Hilliard-Cook equation [19-21] and there is general agreement that the late stage development of scale fits a power law. Rogers et al. [20] used finite difference methods to study a 2D percolating spinodal system with continuous order parameter. They found that at late time the domains coarsen with a time exponent of 1/3 which was independent of thermal noise. Recently, Lacasta et al. [22] studied domain growth, in 2D, at low temperature using a concentration dependent diffusion coefficient. The scaling exponent for the characteristic domain size was found to increase continuously from 1/4 to l/3 with increasing time. The change in time exponent was interpreted as originating from a crossover from interfacial to bulk diffusion mechanisms. Harwick [10] considered the effect of the Cook term on a 1D numerical solution to the Cahn-HilliardCook equation by plotting a characteristic size evolution against time with and without the Cook term present. At low temperatures, its effect was negligible, whereas at higher temperatures ( ~ Tel4) the noise term clearly accelerated the initial growth process, although at later times the two curves converged. The decomposition proceeded more rapidly at higher temperatures ( ~ To/2), but the Cook term had a proportionately smaller effect. There is no substantial evidence for the effect of the Cook term on the long time coarsening behaviour [23]. 3. COMPOSITION AMPLITUDE
3.1. Introduction

Some manipulation of the raw atom probe data is required to determine the magnitude of the composition fluctuations present in an ultrafine fine scale two phase microstructure. Brenner et al. [24] were the first to use composition frequency distributions to detect spinodal decomposition in an Fe-32% Cr alloy.

Table 3. Time scaling exponents from the numerical solution to the C a h n - H i l l i a r d ~ C o o k equation Time scaling exponent from 3D autocorrelation (7/aF I/6 1/3 1 1/3 1/3 Magnitude of C o o k term 0 0 0 0.01 0.0001 T i m e region 200-+3000 200-3000 1000-3000 200-3000 200-3000 First m i n i m u m 0.36 0.35 0.31 0.33 0.36 ,+ + + ,+ 40.01 0.01 0.02 0.01 0.02 First m a x i m u m 0.37 0.36 0,34 0,34 0.35 ,+ 0.01 ,+ 0.02 ,+ 0,0l _+ 0.01 4- 0.02

3408

J.M. HYDE et al.: SPINODAL DECOMPOSITION IN Fe Cr ALLOYS II 3.2. Development d frequency distributions In Fig. 6(a), the development of the frequency distribution using a block size of 27 atoms is shown from a PoSAP analysis of the thermally aged F e ~ 5 % Cr alloys. At the earliest stages, before significant phase separation has occurred, the distributiola follows the binomial form. During aging, -the distribution first broadens and, at the latest stage, begins to show two peaks. A comparison with the frequency distribution obtained from data from the energy compensated atom probe (see Part I [1]) illustrates an important difference between the two instruments. The frequency distributions from the PoSAP experiments are not centred around the mean alloy composition, in contrast to the ECAP analyses. The different positioning efficiencies for Fe and Cr atoms in the PoSAP [32] lead to an inaccurate estimate of the alloy composition. The frequency distributions demonstrate the importance of taking into consideration all experimental limitations when comparing models with experiments. In Fig. 6(b), a composition frequency distribution is shown from a Monte Carlo simulation ofspinodal decomposition at 750 K. Before calculating the distribution, both the detection efficiency and trajectory aberrations were modelled as described in the Part I of this series [1]. The results show a remarkable similarity with the experimental data. During aging up to 10,000 MCS two distinct phases were produced and the scale of the structure was similar to that observed in the Fe-45% Cr alloy after aging for 500 h at 773 K. An equivalent diagram for the development of the frequency distribution for the numerical solution to the Cahn-Hilliard equation is shown in Fig. 6(c). Since the composition is defined in terms of a continuous composition variable, no sampling is required. The initial peak is therefore very narrow, but rapidly broadens retaining symmetry about the mean composition. After 200 time units, phase separation has occurred to such an extent that some of the composition samples have already reached the solid solubility limits and, after 500 time units, the frequency distribution consists of two well defined peaks. A direct comparison can be made with the experimental results by modelling the experimental limitations (as for the Monte Carlo data) and the sampling process. Each vertex in the lattice must first be defined as either an A or B site. This is achieved by interpreting the parameter (u + 1)/2 as the probability that there is an A atom at a site with composition u. The form of the frequency distribution curves, shown in Fig. 6(d), compares favourably with both the experimental results and Monte Carlo simulations, although no phase separation is detected during the first 100 time units. 3.3. Quant~/.~'ing the composition amplitude In the method by Langer et al. [33], for solving the non-linear Cahn-Hilliard Cook equation, the

Several models have been developed to quantify the extent of phase separation by analysing the sampled frequency distribution [25--29]. These models only contain information on the composition amplitude and not wavelength or spatial distribution. A random solid solution will generate a binomial frequency distribution whereas a system in which phase separation has occurred will produce a broadening of this distribution. In the limiting case, a very heavily decomposed sample will yield a distribution with two peaks corresponding to the development of two separate phases. Thus, in a two phase microstructure, the phase separation may be quantified by deconvoluting the two peaks. The choice of block size (N) has caused much debate [30, 31]. If too small a block size is chosen, none of the noise is smoothed out, limiting the significance of the calculated amplitude. In the limit of a block size of 1, the frequency distribution will consist of two delta functions of compositions 0 and 1 corresponding to pure A and pure B. However. if too large a block size is chosen, the composition ttuctuations will be smoothed over. Estimates by Hetherington and Miller [31] for the Oak Ridge National Laboratory AP, using the mean change in composition as a function of block size suggest that the optimum block size ranged from 20 atoms at the early stages of decomposition to 100 atoms per block in the later stages. Since the lateral extent of the region analysed by the PoSAP is much larger than that of the conventional atom probe, a PoSAP experiment may be considered as a series of parallel atom probe experiments, each with an effective square aperture equal to the cell area shown in Fig. 5. Since the positional information for each ion is known, the cell area may be chosen arbitrarily. For an isotropic microstructure, and a given block size (in terms of a number of atoms) a cell size is chosen to give an approximately cubic block. Non-cubic blocks may smooth the microstructural detail in the elongated directions. Variations in detector effciency, local magnification effects and statistics of collection will cause some variation of depth of each cell as shown in Fig. 5.

Cell area

Fixed number of ions per block

Fig. 5. Method of sampling data into approximately cubic blocks each containing the same number of atoms. Local magnification effects and variations in detector efficiency cause a small variation of the depth of each individual cell.

J. M. HYDE et al.:

SPINODAL DECOMPOSITION IN Fe Cr ALLOYS~II

3409

a)
l/ \,, - - c ~ 24 h |

a- o.o2-

+,00

~- 0.0-

probability distribution is assumed to be thc sum of two Gaussian distributions of equal width (s). The Gaussians are centred on #, (1 > / q > x0) and /*2 (0 </~2 < x0), where xo is the mean composition of the alloy as shown in Fig. 7. The parameter/h-#2 is the difference in composition of the two phases and therefore taken as the composition amplitude of the spinodal

0.2

0.4 0.6 Composition

0.8

(xo

#2) exp L

202 ~j

_] -

+ (1'~ - Xo) exp

p[x(r)] =

b)

(~, - ii,)~ v,,'~f~

0.05~ i
^,/ / I

.~ o.,.,,,]
g
2 003i ~

r,~ ',
~,/

/'~,

I
I

o
z~

1 MCS

t 0 MCS

100 MCS
lOOO MCS

I~

10000 MCS I

A- o.0

"

"

0 Fe

0.2

0.4 0.6 Composition

0.8

1 Cr

c)
0.15

Time Units

In this model, there are three time-dependent parameters,/q, #2 and 0. The ratio of the heights of the two Gaussians is pre-determined since the mean composition is fixed. For large values of#l-#2, or o, the tails of the distribution extend beyond the physical limits of 0 and 100%. In this case, the probability distribution needs rescaling, to ensure that the integrated probability between 0 and 100% is equal to 1. In order to model the statistical sampling process that occurs when the atom probe collects atoms, any underlying probability distribution must be convolved with a binomial distribution. The probability of obtaining n solute atoms in a block of N atoms is
P(n) =

0.1

~ j I

x;'(1 - xj) N

I,
0 0 0.2

j',,
0.4 0.6 Composition 0.8 1

o_

d)
=~
~

O.O5
0.04~

I L

o ~

0.0al
0.02

,~

~[

1 Time Units 100 Time Units 200 Time Units 500 mime Units

* 1000VimeUnits

,g

oov J
0 0,2 04 0.6 Composition 0.8 1

Fig. 6. Development of the composition frequency distribution from (a) PoSAP analyses of a series of thermally aged Fe~45% Cr alloys, (b) Monte Carlo simulation of the decomposition process, (c. d) a numerical solution to the non-linear Cahn Hilliard Cook equation. In (c) the exact frequency distribution is shown whereas the sampled distribution is shown in (d). In (a), (b) and (d) the size of each composition block was 27 atoms.

where x, is a discretization of the continuous composition distribution and f = p ( x 3 . In contrast, however, no sampling is required in the analysis of the numerical solution to the Cahn-Hilliard C o o k equation, since in this model the composition is well defined within each lattice cell on a continuous scale. The best value for each parameter in each model is estimated by maximizing the log of the probability of obtaining the set of experimental data, using the method of maximum likelihood. The maximum likelihood technique will always yield the parameters which have the maximum likelihood of being correct. However, if the model is inappropriate, the model frequency distribution may bear no relationship to that observed. The X: statistic can be used to test whether the experimental data could have been obtained from the underlying distribution predicted by a model. A level of significance :~% is chosen to test the hypothesis that the observed distribution is consistent with the model. Since the X 2 follows the Z2 distribution, the null hypothesis can be rejected if the X ~ value exceeds the tabulated ~% percentile with n - 1 degrees of freedom where n is the number of composition bins. In the time regimes studied, the LBM model fitted both the experimental and Monte Carlo frequency

3410

J. M. HYDE et al.: SPINODAL DECOMPOSITION IN Fe-Cr ALLOYS~II

[] o PoSAP ECAP

distributions at the 5% significance level. At short aging times, the composition amplitude is low, whereas at longer times the composition difference between the phases increases with the broadening of the frequency distribution. 3.4. Atom probe results In order to detect the earliest stages of decomposition in an isotropic material, an ideal block would be cubic or spherical, to avoid smoothing over composition fluctuations in any direction. The energy compensated atom probe samples a long, narrow cylinder of material. Because no positional information is available in the lateral directions, the data can only be sub-divided into smaller cylinders with the same diameter. A block size of 33 was chosen so that each of these small cylinders had an approximately equal length and diameter. In the PoSAP, where full 3D information is available, blocks can be made cubic. Specimens from the same material have been analysed in both the PoSAP and ECAP. The results (Fig. 8) show clearly that both instruments measured the composition amplitudes with a similar accuracy. The ECAP results have been calculated using a block size of 33 and the PoSAP results using a block size of 27. 3.5. Monte Carlo results To simulate the loss of data that occurs during a PoSAP experiment, a detection efficiency parameter Ex was introduced, where Ex is the probability of detecting an ion of species X (see Part I [1]). Decreasing the detection efficiency whilst keeping a constant number of detected atoms within each block simply increases the physical volume of each composition cell. This is equivalent to increasing the block size, which has been shown to slightly decrease the measured composition amplitude since some composition fluctuations are smoothed out. Since the loss of positional information is worse for Cr than for Fe, the elements were assigned different detection efficiencies. The results, using detection efficiencies ranging from perfect (all Fe and Cr atoms detected) to a realistic experimental value (only 30% of the Cr atoms and 50% of the Fe atoms detected), are shown in Fig. 9. As predicted, the measured composition amplitude
0.03

=C

0.1

0.01

~ .. . . . . . . .

. . . . . . . .

. . . . . . . .

10

100

1000

Aging (h)
Fig. 8. Composition amplitude as a function of aging time for Fe-45% Cr aged at 773 K. The LBM formulation was used with a block size of 27 for the PoSAP data and 33 for the ECAP analyses. decreases with decreasing detection efficiency. The only exception occurred after 1 MCS, when the atoms were still essentially randomly arranged. The lateral scatter associated with field evaporation will also tend to reduce the measured composition amplitude. The uncertainty in atomic positions will tend to make the interface region appear more diffuse, resulting in the measurement of blocks with compositions nearer the mean in these areas. The effect is more pronounced at shorter aging times since the size of the Cr-rich clusters is small and interface measurements dominate. To model both the trajectory aberrations and spatial resolution of the detector, a Gaussian scatter of width a (measured in atomic spacings) was added to the x, y co-ordinates as described in Ref. [1]. The addition of a large scatter results in the measurement of a lower composition amplitude (Fig. 10). A comparison between experimental results and Monte Carlo simulations shows that a reasonable match occurs when the width of the Gaussian is approx. 1 atomic spacing. 3.6. Numerical discretization of the Cahn-HilliardCook equation Since the composition is defined on each lattice vertex in the numerical simulation, the composition frequency distribution can be obtained directly. There is no need to introduce any sampling, and therefore

g
25

002

xlj/
\

,~

0.1

S
........

EF=I.0, Ect= 1.0I

EFe=0.7, ECr= 0.5~ EFe=0.5, Ecf= 0.31

........

o 0.01 J

of
0

0.01

10

0.2

0.4 0.6 Composition

0.8

1O0 MCS

........

1000

........

104

Fig. 7. Composition distribution for the Langer, Bar-on and Miller (LBM) theory.

Fig. 9. Effect of detector efficiencyon measured composition amplitude for a Monte Carlo simulation at 750 K on a b.c.c. lattice with second nearest neighbour interactions. The block size was 27 atoms. Ex is the effciencyof detecting element X.

J. M. HYDE et al.:
1

SPINODAL DECOMPOSITION IN Fe-Cr ALLOYS--II

3411

Table 4. Time scaling of composition amplitude from experimental data Data series Time region (h) 8-500 24-500 8-500 4-500 Exponent with block size 27 0.41 0.37 0.27 0.35 + 0.14 _ +0.09 _ ___0.03 _4-0.05 Exponent with block size 100 0.35 0.41 0.29 0.38 + 0.08 + 0.10 _+ 0.04 _+ 0.06

=~ 0.1- ~

: -2o;o
0.01
r ........ i

Fe-17% Fe-24% F~32% Fe~45%

Cr Cr Cr Cr

10

100
MCS

1000

104

Fig. 10. Effect of positional resolution on the measurement of composition amplitude for a Monte Carlo simulation of an A 50% B alloy on a b.c.c, lattice with second nearest neighbour interactions aged at 750 K. To simulate a uniform resolution a Gaussian scatter of width s atomic spacings has been added to the atomic co-ordinates. The detection efficiencies of the Fe and Cr atoms were 0.5 and 0.3 respectively.

comparisons can be made directly with the probability distributions predicted by the models. At the early stages of aging, a single narrow peak dominates, which can be fitted to a Gaussian with a very small width. However, at the late stages &aging, when two narrow peaks in the composition distribution have formed, poor fits are observed with the LBM model since the peaks are narrow with respect to the range of observed

a)
1

~ [~e~-Amplitude I f tl Exponential Fit I /

:.'t

compositions. Therefore, in Fig. l l(a), the composition amplitude has been defined as the difference between the maximum and minimum composition observed during the simulation as a function of time. A rapid increase in composition amplitude is observed between 10 and 100 time units during which time little coarsening of the domains was observed [Fig. 4(b)]. The growth in amplitude between 10 and 100 time units is consistent with the linear solution to the Cahn-Hilliard-Cook equation which predicts exponential growth in the very early stages. For comparison, an exponential curve fit through the data is also shown in Fig. 1l(a). In Fig. 1l(b), the results of fitting the LBM model to the sampled data are shown. Since the modelling of trajectory aberrations and detection efficiency of each element reduces the measured amplitude, the rapid increase in amplitude appears to occur at a slightly later time. The results are not, however, consistent with the observed experimental results. Not only is exponential growth predicted by the Cahn-Hilliard-Cook equation, but the composition amplitude growth occurs with only a small increase in wavelength in contrast to the experimental results and Monte Carlo simulations.

3, 7. Time scaling o f the composition amplitude

The time exponents for the development of composition amplitude (experimental data), fitted using the method of least squares, are higher than the time exponents for the development of scale and are also subject to large errors (Table 4). A summary of the effect of detector efficiency and lateral resolution applied to the Monte Carlo simulations are given in Table 5. As both the efficiency of detector and lateral resolution decrease, the measured time exponent increases (Table 5). This reflects the fact that the measured composition amplitude is reduced as both the efficiency and resolution decrease. The effect is more pronounced at the early stages of aging than at

i o::
1

10 1O0 Aging Time (Time Units)

1000

b)
1

0.t~

0.01
Table 5. Time scaling of the composition amplitude for Monte Carlo simulation of an A-50% B alloy on b.c.c, lattice with second nearest neighbour interactions. The effects of block size, detection efficiency (E~, and Ec0 and lateral resolution (a) are shown E~:. I 0.7 0.5 0.5 0.5 Err 1 0.5 0.3 0.3 0.3 a 0 0 0 0.5 1.0 Time exponent (block size 27) 0.19 0.23 0.24 0.25 0.29 _+ 0.00 0.01 + 0.00 _+ 0.00 + 0.02 Time exponent (block size 100) 0.29 0.31 0.35 0.26 0.43 + 0.00 + 0.02 + 0.02 _+ 0.04 + 0.06

0.001 I . . . . . . . . . . . . . . . . ~ ........ , , , ~ I I0 100 1000 104 Aging (Time Units) Fig. 11. Development of composition amplitude for the numerical solution to the non linear Cahn-Hilliard equation. In (a) the maximum variation in composition has been plotted as a function of time and in (b) the LBM model was used to calculated the composition amplitude.

3412

J.M. HYDE et al.: SPINODAL DECOMPOSITION IN F ~ C r ALLOYS--II and morphology over these time regions is examined in Part III in this series [34]. authors would like to thank Professor R. J. Brook for the provision of laboratory facilities. J.M.H. would like to acknowledge the Engineering and Physical Sciences Research Council (EPSRC) and Wolfson College for financial support. A.C. thanks The Royal Society for financial support and Wolfson College for the provision of a Fellowship. This research was funded by the EPSRC under grant number GR/H/38485 and by the Division of Materials Sciences, U.S. Department of Energy, under contract DE-AC05-84OR21400 with Martin Marietta Energy Systems Inc.
Acknowledgements--The
REFERENCES

the later stages. The fact that the gradient is a function of both detection efficiency and detector resolution demonstrates that the composition gradient measured directly from experimental results is not necessarily correct. With a reasonable values of detection efficiency (EF0= 0.5, Ecr= 0.3) and scatter (a = 1), a time exponent of 0.29 +_ 0.02 (with a block size of 27) was measured for the Monte Carlo simulations of an A - 5 0 % B alloy on a b.c.c, lattice. A time exponent of 0.35 _+ 0.05 was measured from comparable PoSAP data. It has been demonstrated that the positioning efficiencies increased with increasing decomposition [32]. This will also have an effect on the measured scaling exponent since the lower detection efficiency at the early stages of aging will tend to push these estimates of the composition amplitude further down.

4. DISCUSSION AND CONCLUSIONS The autocorrelation analyses suggest that a time scaling regime for the development of domain size exists. A best fit to the experimental results yielded a time exponent of 0.25 + 0.03. The Monte Carlo results fitted a power law relationship with a time exponent of 0.21 +_ 0.03 which, although slightly lower than the PoSAP results, is still within the error bounds of the experimental results. Despite the fact that the numerical solution to the C a h n - H i l l i a r d - C o o k equation generated a complex interconnected morphology, a time exponent was observed during coarsening close to the value of 1/3 predicted by the LSW theory for the coarsening of isolated precipitates. This exponent is outside the error bounds of the experimental data. A comparison of the frequency distributions showed good agreement between the experimental data and simulations. The model for measuring composition amplitude based on the theory of Langer et al. has proved successful, finding good fits to both atom probe data and M o n t e Carlo simulations for alloys with a range of compositions and aging treatments. Because of trajectory aberrations and the loss of data associated with atom probe analysis, the composition amplitude calculated is an underestimate of the true extent of decomposition. As a result it is difficult to find true amplitude scaling relationships with aging time. It has, however, been shown by using the M o n t e Carlo data and applying approximately known detection efficiencies and estimates of the resolution, that it is possible to make a good estimate of the effect. Both Monte Carlo simulations, performed for approx. 5000 MCS, and the numerical solution to the C a h n - H i l l i a r d - C o o k equation, aged for 1000 time units, generated a structure with a similar scale and composition amplitude to that observed in the F e ~ 5 % Cr alloy after aging for 500 h. A quantitative comparison of the development of interfacial structure

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SPINODAL DECOMPOSITION IN Fe-Cr A L L O Y S - - I I

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