Materials Science and Engineering A 397 (2005) 195203

Application of ANOVA method to precipitation behaviour studies

Z. Cvijovi a, , G. Radenkovi b , V. Maksimovi c , B. Dim i c c c c cc
a

Department of Metallurgical Engineering, Faculty of Technology and Metallurgy, University of Belgrade, 11120 Belgrade, Karnegijeva 4, Serbia and Montenegro b Faculty of Mechanical Engineering, University of Ni , 18000 Ni , A. Medvedeva 14, Serbia and Montenegro s s c Department of Materials Science, Institute of Nuclear Sciences Vin a, 11001 Belgrade, Serbia and Montenegro c Received 23 August 2004; received in revised form 4 February 2005; accepted 11 February 2005

Abstract The Analysis of variance (ANOVA) method has been used to illustrate the implementation of adaptive numerical (AN) techniques for the prediction of the precipitation behaviour of commercial materials. Case studies involving the analysis of -phase precipitation kinetics in duplex stainless steel (DSS) produced by sand casting and age hardening of 2219 aluminium alloy microalloyed with Ge and/or Si are presented. For each alloy, complex datasets comprised the results obtained from heat treatment trials on a range of commercial processing conditions, so that a single and combined effect of various parameters can be determined. This enabled an estimate of the most inuential parameters to be made, providing an effective means of commercial alloy development and process optimisation. 2005 Elsevier B.V. All rights reserved.
Keywords: Duplex stainless steel; Modied 2219 alloy; Precipitation behaviour; -Phase; SiGe particle; ANOVA method

1. Introduction The precipitation behaviour of metallic alloys is known to depend on many process variables, including composition, cooling rate, temperature, time, etc. Due to the complexity of the relationships between these variables and precipitation kinetics, the optimisation and accurate prediction of the precipitation process and, therefore, the properties are difcult. In order to obtain the desired properties, it is necessary to determine a single and combined effect of various parameters, which would allow the correct choice of the processing parameters. If there are not enough data, a large number of expensive and time-consuming experiments need to be carried out. To solve this problem, the calculation and modelling of the precipitation kinetics would be applied. In the last few years, there has been a constantly increasing interest in adaptive numeric (AN) modelling in different elds of materials science [13]. The physically based approach is only possible in a limited number of cases where a

Corresponding author. Tel.: +381 11 3370 469; fax: +381 11 3370 387. E-mail address: zocvij@tmf.bg.ac.yu (Z. Cvijovi ). c

physical understanding of the processes and model parameters/physical constants are accurately known. For more complex situations, with many interrelated variables and where the mathematical relationships between model inputs and the output parameter are not clear, an AN approach to modelling may provide a variety of complex (usually non-linear) mathematical relationships which equally well predict the observed data distributions, although the underlying mechanisms are not easily visualised from these relationships. In addition, the use of various AN modelling techniques enables a successful interpretation of available datasets of different sizes, so that this approach to modelling may have to be performed even with data that are limited, or badly distributed, or both. The examples presented in this paper illustrate how the Analysis of variance (ANOVA) technique can be successful in analysing selected aspects of precipitation behaviour of alloys for different composition/processing combinations. In one case, we consider the dataset on the amount of -phase for duplex stainless steel (DSS) in various microstructural states achieved by different heat treatment regimes, with the objective to predict the kinetics of secondary phases (SP) precipitation in one of the most commonly used DSSs. The

0921-5093/$ see front matter 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.msea.2005.02.021

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modelling was motivated by the desire to provide a more complete understanding of the variations in pitting corrosion resistance under particular microstructural states, which is regarded to be of crucial importance in DSSs applications. Since the severity of corrosion attack depends on the nature and amount of SP precipitates, a thorough knowledge of the kinetics of precipitate formation is important in determining the heat treatment and cooling rates required during production to ensure precipitate-free parts. In another case, we will present results on the prediction of age-hardening response of the commercial 2219 aluminium alloy microalloyed with small additions of Ge and/or Si, using data on the hardness obtained for each alloy variant and different aging treatments. Recent studies of experimental AlSiGeCu alloys designed in such a way as to enhance the articial age-hardening characteristics [4] have shown that the precipitation of SiGe particles can be used to improve the strengthening potential of 2xxx alloys. But, although there are several reports on the precipitation processes in quaternary AlCuSiGe alloy [5,6], further improvement of the mechanical properties of commercial alloys as well as process optimisation require a broad integrated experimental and modelling investigation. Thus, the present work aims at obtaining new knowledge on the precipitation-hardening behaviour of the commercial AlCu-based alloys modied by SiGe additions and applying the ANOVA approach to identify the most inuential parameters.

by the total sum of squares term: SST =

2 yi ,

for i = 1, 2, . . . , n,

(2)

can be given as: SST = SSm + SSe (3)

where SSm = nM2 and SSe = (yi M)2 are the mean sum of squares and the error sum of squares, respectively, with M = 1/n yi (i = 1,2, . . ., n). In the case of two-way ANOVA, when the interaction effect of main factors affects the output values, the total variation may be decomposed into more components: SST = SSA + SSB + SSAB + SSe (4)

2. ANOVA method A novel way to determine the inuence of any given input parameter on the precipitation process from a series of experimental results is to employ the design of experiment (DoE) approach. The decisions, concerning which parameters affect the response of investigated process are made with assistance of various analytical techniques. Analysis of variance will be the predominant statistical method used to interpret experimental data, since this method is most objective [7,8]. It is designed to represent a concept that any high dimensional function may be broken down into a subset of terms from the expansion:
n n n

where SSA = (A1 A2 ) and SSB = (B1 B2 ) are variations due to the factors A and B, respectively, while SSAB = (AB)i 2 /nABi for i = 1, 2, . . ., k is variation due to the interaction of factors A and B, where k represents the number of possible combinations of interacting factors and nABi is the number of data points under this condition. However, for complete ANOVA calculations, degrees of freedom (d.f.) should also be considered together with each sum of squares. As ANOVA studies are in fact experimental studies with certain test error (Err), the determination of error variance is an essential step in such studies. Similarly, the sample variance within the factor levels should be calculated since the sample size establishes the condence level of the results derived from the analysis. These data are subsequently used to estimate the value F of the Fisher test (Ftest). The portion of total variation observed in an experiment attributed to each signicant factor and/or interaction is reected in the percent contribution (P), which indicates the relative power of a factor and/or interaction to reduce variation, i.e. factors and interactions with substantial percent contribution are the most important. A more detailed description of the ANOVA method is given in the literature [7,8].

3. Analysing precipitation behaviours of selected alloys 3.1. Case 1: -phase precipitation in DSS

f (x) = fo +
i=1

fi (xi ) +
i=1 j=i+1

fi,j (xi , xj ) + . . . (1)

+ f1,2, ..., n (x)

where n represents the number of inputs, fo is a constant (bias term) and the other terms on the right hand side represent the univariate, bivariate, trivariate, etc., functional combinations of the input parameters. Analysis of variance (V), namely, is a mathematical technique, which partitions the total variation into its appropriate components. Thus, the total variation of the system, dened

DSSs composed of -ferrite and -austenite offer a great combination of properties, so that they are suitable for many industrial applications [9,10]. During inappropriate heat treatment or prolonged exposure at elevated temperature, the precipitation of various secondary phases, like secondary austenite ( 2 ), chromium carbides, nitrides, -phase and other intermetallic phases [1114] can take place, causing the time-dependent degradation of the material and particularly its pitting corrosion resistance [1517]. Of the SP mentioned above, -phase has the most deleterious effect because of its large volume fraction. Since the tendency

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toward -phase formation, as well as its precipitation kinetics, mechanism and stability range may vary considerably depending on the exact composition and microstructural state of steel [12,1720], it is necessary to clarify the behaviour of -phase precipitation in highly alloyed DSSs. 3.1.1. Material and experimental procedure The steel with main composition in mass% 27Cr6.7Ni 2.1Mo2.8Cu0.12N0.085Cbal Fe was supplied by the manufacturer in the form of a 20 kg sand cast (SC) Y-block. To reveal microstructure, metallographic samples taken from the central region of SC block were prepared for light optical microscopy (LOM) by grinding and polishing, using diamond pastes of 3, 1 and 0.25 m. The polished sections were then electrolytically etched at 13 V for 15 s in 10% NaOH aqueous solution that etches -ferrite blue-light brown, while -austenite remains virtually uncoloured. The initial microstructure of the as-received SC block is presented in Fig. 1a. It consists of the large and elongated platelets inhomogeneously distributed in the -ferrite matrix, although some globular or rod-like particles of intragranular austenite ( i ) are also visible. Additionally, the etchant used, which tints precipitates brownish-red, revealed the presence of SP particles. The rows of these ne particles nucleated along the slightly curved / -interfaces and thin lms of secondary austenite ( 2 ) immediately adjacent to them are consistent with a proposed model for the cooperative precipitation of Cr-rich M23 C6 carbide and 2 [2124]. The low cooling rate of the order 101 to 101 K/s, related to conventional casting process [25], and a C content higher than that of most duplex grades makes investigated steel more feasible for carbide to precipitate. The total amount of precipitates was determined by means of image analysis. The volume fraction of phases present, VV , was measured by line-intercept method using the Kontron semi-automatic system attached to a Reichert MeF3 light microscope. A condence interval of 95% was used for measurements taken at a magnication of 500 times. The obtained data show that after casting the microstructure of investigated steel consists of a -ferrite matrix with 33.5 vol.% , 2.1 vol.% (M23 C6 + 2 ) mixed structure and small amounts of non-metallic inclusions. In order to eliminate the SP precipitation and produce a duplex ( + ) microstructure, the base SC material was solution treated (ST) at 1150 C for 60 min, followed by water quenching. After this heat treatment, the only phases present, except non-metallic inclusions, are and . At the same time, the transformation occurred, so that a ratio of : = 70.5:29.5 was obtained. Subsequently, this steel in both as-cast and as-cast with 1-h long solution-treatment states was subjected to isothermally annealing at 800, 850, 900 and 950 C for 15 and 60 min, followed by water quenching. The microstructural changes that occur on annealing are determined using image analysis.

Fig. 1. Micrographs of sand cast block before (a) and after 60 min of annealing at 800 C (b) and 950 C (c), showing the presence of austenite ( ) platelets, intragranular austenite ( i ), -phase and mixed constituent (M) of M23 C6 carbide and secondary austenite ( 2 ) in the matrix of -ferrite.

198 Table 1 The results of image analysis Microstructural state

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Volume fraction of -phase (vol.%) 800 C 15 min 60 min 24.34 16.72 850 C 15 min 1.61 1.52 60 min 33.16 30.96 900 C 15 min 1.19 0.82 60 min 21.47 11.66 950 C 15 min 0.31 60 min 1.29 0.97

As-cast ST

0.14 0.25

3.1.2. Microstructural data During annealing the 2 , M23 C6 carbide and -phase were formed (Fig. 1b and c). The precipitation proceeds extensively causing a drastic decrease in the volume fraction of retained -ferrite. At each temperature, the rst transformation product is M23 C6 . This was particularly evident in the ST material. At later stages, the -phase formation was observed to occur. Although the nucleation of carbide is more favourable and faster than the nucleation of -phase, the vast majority of particles precipitated on the curved / -boundaries as the highly preferred sites for nucleation [26] are found to be -phase. The -phase formation mechanism changes with annealing temperature [11,18,24,27]. At temperatures up to 900 C, the -phase forms by the eutectoid reaction + 2 (Fig. 1b), while at higher temperatures by an in situ transformation (Fig. 1c). This observation is supported by the fact that the composition of -phase varies over a wide range of concentrations of its component elements [28], so that at 950 C, the shorter the time needed for the -phase to achieve equilibrium of the chemical composition. As a consequence, an in situ transformation of the - to -phase is favoured. The extent and kinetics of -phase precipitation vary signicantly with annealing condition and with the initial microstructural state of DSS. The volume fractions of -phase after annealing treatments (VV ), measured for 16 microstructural state-annealing treatment combinations, are presented in Table 1. The most inuential parameter is determined by applying the AN modelling approach. Namely, the datasets on the volume fraction of -phase contained up to 32 data lines were further analysed using the ANOVA method.

3.1.3. ANOVA analysis The ANOVA analyses were done with software package Design of experiment V1.0 CIM College. The univariate terms shown in Fig. 2 reect relations between annealing temperature, annealing time and initial microstructural state of the steel on the one hand and -phase fraction on the other. It may be seen that for a given set of inputs (microstructural state whose levels are as-cast and solution treated, four levels for temperature, namely from 800 to 950 C in steps of 50 C, and two levels of time, namely 15 and 60 min), the constructed model selected the annealing time as the main parameter inuencing -phase precipitation behaviour, whilst to a much lesser extent the annealing temperature can play a role. However, the inuence of the annealing temperature varies with different levels. On the other hand, the process kinetics are only slightly affected by variations in matrix homogeneity. Namely, the inuence of single parameter is stronger as the slope of the targed line is larger.The results of the analysis of variance presented in Table 2 show that a bivariate term combining annealing temperature and time, along with an univariate term for temperature had a statistically signicant inuence in the nal fraction of -phase. It should be noted that the P-value obtained for annealing time is almost twice that for the annealing temperature or the combination of annealing temperature and time. A combined effect of annealing temperature and time on -phase fraction is presented in Fig. 3. As can be seen, the -phase fraction was unaffected by the annealing time increase up to 15 min, due to the sluggish kinetics of the reaction at all temperatures in the investigated range. When the annealing time was increased to

Fig. 2. Univariate subfunctions, showing the inuence of (a) annealing temperature, (b) annealing time and (c) initial microstructural state of steel on the -phase fraction.

Z. Cvijovi et al. / Materials Science and Engineering A 397 (2005) 195203 c Table 2 Summary of the results obtained by the ANOVA analysis used for the -phase precipitation investigated Source Temperature Time State Temperature time Temperature state Time state Temperature time state Err Total SS 1061.56 2269.02 53.10 904.02 29.74 46.51 30.14 0.02 4394.10 d.f. 3 1 1 3 3 1 3 16 31 V 353.85 2269.02 53.10 301.34 9.91 46.51 10.05 0.00 F 316782.60 2031317.00 47533.30 269771.20 8874.14 41639.75 8995.39 P

199

24.16 51.64 1.21 20.57 0.68 1.06 0.69 0.00 100.0

Fig. 3. Bivariate subfunction, showing a combined inuence of annealing temperature and time on the -phase fraction.

60 min, the temperature is much more important. It is further noted that this model can be applied to predict the maximum volume fraction of -phase, which is reached after 60 min of annealing as-cast DSS in the temperature range from 850 to 880 C. 3.2. Case 2: age-hardening of modied 2219 Al-alloy The AlCu alloys of the 2xxx series have been widely studied due to their excellent mechanical properties developed by age-hardening. Upon aging, the 2219 alloy displays the well-known precipitation sequence [29]: Supersaturated solid solution GP zones (Al2 Cu).
Table 3 Chemical compositions of modied 2219 alloys used in the present study Alloy designation Element (mass%) Cu 2219S 2219SG 5.91 5.90 Ge 0.69 Si 0.51 0.28 Fe 0.24 0.26 Mn 0.28 0.29

Si, Mn, Be, Sn, Ag and Cd additions are known to inuence metastable phase formation and can, therefore, have a large effect on the precipitation kinetics and mechanical properties [3033]. Renewed interest in this system was stimulated by studies of the rapid hardening that occurs in base AlSiGe alloys and the observation that this effect is enhanced by Cu additions. Recently, it has been shown that the resultant AlCuSiGe alloys show very fast aging response, high peak hardness and better microstructural stability after prolonged aging [4,6]. This was attributed to the formation of SiGe precipitates which act as heterogeneous sites for nucleation of phase. Mitlin et al. [4] identied precipitates by high-resolution electron microscopy (HREM) in contact with multiply twinned SiGe particles after aging for 3 h at 190 C. SiGe particles nucleate quickly and they were detected after as little as 30 min at 190 C [6]. The comparison of the hardening curves for the two laboratory AlCuSiGe alloys aged at 190 C with that of the commercial alloy 2219 or of the alloy 2014 in their T6 peak-aged condition showed that both AlCuSiGe alloys with different Cu level and (Si + Ge) content on equiatomic proportions possess signicantly higher peak hardness [4]. Additionally, they achieved maximum hardness at a shorter aging time (for example, after 3 h instead of the 8 h required for 2219 alloy), while overaged at a rate similar to 2219 alloy. In contrast, alloy 2014 which is not known to display high-temperature stability overaged relatively quickly. These observations indicate that microalloying with Si and Ge may be used to produce higher precipitation hardening than that which occurs in the commercial 2xxx alloys, and it is important to investigate the effect of various parameters on the precipitation behaviour of these alloys. 3.2.1. Selection of alloys and experimental details For this purpose, two laboratory alloys were prepared by adding small amounts of Ge and/or Si to the 2219 commer-

Mg 0.01 0.01

Zn 0.05 0.06

Ti 0.08 0.08

Zr 0.12 0.13

V 0.09 0.09

Cr 0.007 0.007

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Fig. 4. Hardnesstime curves for the 2219S and 2219SG alloys aged at 190 C.

cial base alloy produced by Kaiser Aluminium Company, i.e. one alloy (designated as 2219S) with about 0.5 at.% Si and another alloy with 0.27 at.% Si and 0.26 at.% Ge (designated as 2219SG). The equiatomic proportions of Si and Ge were chosen because the Si and Ge solute atoms have mists of opposite sign in Al, thus, contributing signicantly to the reduction of the elastic strains produced in the matrix and the precipitate [34]. The chemical compositions of the investigated alloys are given in Table 3. The alloys were hot-rolled from 27 to 2 mm in thickness after homogenisation for 48 h at 500 C and subsequently subjected to annealing for 24 h at 500 C, water quenching and holding at room temperature for 9 days. Two different articial aging treatments followed after the natural aging: (1) the samples were aged at 190 C for times ranging from 10 min to 200 h; (2) the samples were kept at 50, 75 and 100 C for 30 min, 1 and 2 h after which they were aged at 190 C for times ranging from 15 min to 256 h. Aging at 190 C was chosen as the main temperature of investigation due to its relevance to commercial applications. The age-hardening response of the alloys was evaluated by Vickers hardness measurements using a load of 98.1 N load. The microstructures of the samples in the underaged, peak hardness and overaged conditions were examined with JEOL 200CX and PHILIPS CM200-FEG analytical electron microscopies operated at 200 kV. Transmission electron microscopy (TEM) samples were prepared by grinding slices to a thickness between 125 and 150 m, then by twin-jet electropolishing using a 25% nitric acidmethanol solution at temperature of 25 C. In order to estimate the chemical composition of precipitates, the EDS microchemical analyses were done in a CM200-FEG microscope. 3.2.2. Characterisation of alloys aged at 190 C Fig. 4 shows the variation in hardness of each alloy as a function of the aging time at 190 C. Note that the hardness of both alloys initially decreased to a minimum, which may

Fig. 5. TEM bright-eld image of microstructure (a) and corresponding SAED pattern recorded near the [0 0 1]Al zone axis (b) of 2219SG alloy aged for 3 h at 190 C.

be ascribed to reversion and then increased until a peak hardness followed by overaging. However, the hardness values of the 2219S alloy are smaller at all times monitored, whereas the stage of hardening involved a gradual rise to peak hardness. Thus, a 2219SG alloy displays a maximum hardness of 100 HV after 8 h of aging, whereas the Si-containing alloy peaks at 80 HV after 24 h of aging, which is three times longer than for 2219 alloy modied by Si and Ge. After the maximum, the hardness of 2219S alloy signicantly decreases with prolonged aging, approaching the level of about 73 HV. This is in contrast to the case of the 2219SG alloy, where the overaged samples show an initial period of constant hardness from the peak hardness condition before reaching a nal hardness of 90 HV after 200 h of aging. These results indicate that the articial aging response of the 2219SG alloy is nearly the same as that in the quaternary AlCuSiGe alloy. This means that there is the benecial age-hardening effect due to the early onset of SiGe particles precipitation.

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Fig. 6. TEM micrograph of SiGe particles in microstructure of overaged 2219SG alloy with the typical EDS spectrum obtained from them.

Fig. 5a and b shows a representative TEM bright-eld (BF) image and a [1 0 0] selected-area electron diffraction (SAED) pattern obtained from the 2219SG alloy aged for 3 h at 190 C. As can be seen in Fig. 5a, the equiaxed SiGe particles with diameters less than 100 nm are present in relatively large amounts. The EDS analysis of such particles (Fig. 6), which are observed to be in the majority even in the grossly overaged samples, conrmed that they contain both Si and Ge. Since the diffraction pattern, as provided in Fig. 5b, exhibits streaking from the face-on precipitates, it seems reasonable that these precipitates act as nucleation sites for SiGe particles. The BF image shown in Fig. 7a demonstrates that after 8 h of aging, the main contributor to the hardness increase is the precipitates. The early onset of precipitation in

the peak-aged 2219SG alloy is indicated by the very faint reections detected in the SAED pattern shown in Fig. 7b. Since a mixture of and precipitates is present at the maximum hardness of 2219SG alloy, it is obvious that the addition of Ge in a commercial 2219 alloy promotes faster aging kinetics than in alloy without Ge. Namely, thin edgeon plates appear in the matrix of 2219S alloy after 24 h of aging (peak-aged condition). Fig. 7c illustrates the presence of these precipitates in the 2219SG alloy after 150 h of aging. The BF image shows edgeon plates together with equiaxed SiGe particles. The spots from the edge-on precipitates can be discerned in the corresponding SAED pattern, as can be seen in Fig. 7d. The precipitates are found to be associated with the SiGe particle/ Al interfaces arrowed in Fig. 7c, owing to the positive volume

Fig. 7. TEM bright-eld images of microstructure (a, c) and corresponding SAED patterns recorded near the [0 0 1]Al zone axis (b, d) of 2219SG alloy aged at 190 C for 8 h (a, b) and 150 h (c, d).

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Table 4 Summary of the results obtained by the ANOVA analysis used for the modied 2219 alloys hardening response investigated Source Composition Temperature (t1 ) Time ( 1 ) Time ( 2 ) Composition t1 Composition 1 Composition 2 Err Total SS 147.00 72.93 2.90 2592.10 30.93 22.19 27.92 276.79 3167.64 d.f. 1 2 2 2 2 2 2 50 63 V 147.00 36.46 1.45 1296.05 15.47 11.10 13.96 5.54 F 26.55 6.59 0.26 234.12 2.79 2.00 2.52 P 4.47 1.95 0 81.48 0.63 0.35 0.53 10.59 100.00

mist between the SiGe precipitate and Al matrix. This may also be correlated with the average thickness and diameter of the precipitates [35]. 3.2.3. Response to two-step aging When the naturally aged 2219S and 2219SG alloys are subjected to two-step articial aging, a variety of microstructures develop. Assessment of hardness for each variation in the temperature and time of rst stage aging and second stage aging time provides a complex dataset, leading to precipitation process optimisation that can generally be obtained by

any AN modelling technique. The present dataset contains a total of 54 alloy-aging treatment combinations and the following input parameters: two levels of alloy composition, three levels for rst stage aging temperature (t1 ), three levels of rst stage aging time ( 1 ), and three levels of second stage aging time ( 2 ), namely, 15 min, 16 and 256 h, was analysed using the ANOVA approach which handles smaller datasets more consistently. The results obtained from a statistical analysis of these data are summarised in Table 4. They reveal the second stage aging time ( 2 ) and the (Si + Ge) addition as the main parameter inuencing precipitation hardening of these alloys. The P-values clearly show that the duration of second stage aging is the most inuential parameter, in agreement with known physical behaviour. As is further illustrated in Fig. 8a, the composition x versus 2 dependency shows that the 2219SG alloy displays faster hardening response and a higher peak hardness than the other alloy. This result supports the earlier observation, indicating that the precipitation of ne SiGe particles enhances the aging kinetics in 2219SG alloy. On the other hand, the hardening response of both alloys is almost unaffected by the rst stage aging conditions as shown in Fig. 8b. Hence, two-step aging treatment of commercial 2219 alloys modied by (Si + Ge) additions is not economically viable. Instead, by control of the duration of aging at 190 C, the optimum hardening effect can be easily obtained.

4. Conclusions The precipitate formation in a cast DSS and commercial 2219 aluminium alloy modied with Ge and/or Si has been analysed by combining the microscopical methods for qualitative and quantitative characterisation of structure with the experimental design approach adapted for prediction of the precipitation behaviour of selected alloys which display various structures over a wide range of heating temperature and time. The intention was not to describe solely the structural characteristics of heated alloys, but rather to verify the capability of the ANOVA method to predict the effect of chosen variables and their interaction affecting the precipitating characteristics of these alloys. The obtained results clearly showed that databases of different sizes can all be analysed success-

Fig. 8. Bivariate subfunctions, showing a combined inuence of (a) alloy composition and second stage aging time, and (b) alloy composition and rst stage aging temperature on the hardening response of modied 2219 alloys.

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fully providing a means for process optimisation and alloy development. Furthermore, the physical-based microstructural parameter used together with empirical capability of the applied modelling technique can be used to control the amount of deleterious SP precipitates, enabling a useful balance of properties to be attained.

Acknowledgments This work is supported by the Ministry of Science and Environmental Protection, Republic of Serbia through the Project No. 1261. All TEM experiments were performed at the National Center for Electron Microscopy, Lawrence Berkeley National Laboratory, University of California. The authors are grateful to Dr. V. Radmilovic for very useful discussions, and to Dr. A.J. Tolley for carrying out the TEM experiments. References
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